JP4650984B2 - Production method of granules for supporting surfactant - Google Patents

Description

【０１２３】
【表２】

【０１２４】
表１、２の結果より、実施例１〜３で得られた界面活性剤顆粒群２、４、５はいずれも比較例１、２で得られた界面活性剤顆粒群１、３に比べて、顆粒強度に優れ、且つ担持能に優れたものであることがわかる。
【０１２５】
また、ゼオライトの配合量が少ない実施例２、３で得られた界面活性剤顆粒群４、５はいずれも実施例１で得られた界面活性剤顆粒群１に比べて、その担持容量及び担持速度には殆ど変化がないことから、本発明の方法は、無定形アルミノケイ酸塩の量を低減しても十分な担持能を発現しうるものであることがわかる。
【０１２６】
また、実施例１〜３で得られた洗剤粒子群２、４、５はいずれも比較例１、２で得られた洗剤粒子群１、３に比べて、流動性、シミ出し性も同程度に優れたものであることがわかる。
【０１２７】
【発明の効果】
液状の界面活性剤を添加して洗剤粒子を製造するための界面活性剤担持用顆粒群の製法であって、洗剤組成物の性能に影響を与える原料を用いることなく、顆粒の担持能を向上させることが可能となる。さらには洗剤粒子の製法において、該界面活性剤を配合するために必要な吸油担体量を低減することや、洗剤粒子の流動性等の粉末物性を損なうことなく、該界面活性剤を多量配合することが可能となる。
【図面の簡単な説明】
【図１】通常の噴霧乾燥装置で噴霧乾燥して得られた、表面が水溶性成分の被膜で被覆された界面活性剤担持用顆粒のＳＥＭを示す。
【図２】本発明により得られる、内部に中空部を有し、且つ顆粒の表面が開口して内部の中空部と通じた形状を有している界面活性剤担持用顆粒のＳＥＭを示す。
【図３】図３は、蒸気を噴出するホルダーを設置したノズルの概略図である。
【符号の説明】
１ ノズル
２ ホルダー
３ 蒸気噴出溝
４ 調製液噴出孔
５ 調製液供給配管
６ 蒸気供給配管[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a particle group for supporting a surfactant and a method for producing the same. Furthermore, the present invention relates to a method for producing detergent particles using such surfactant-carrying granules.
[0002]
[Prior art]
In order to use a liquid surfactant as a powder detergent, there is a method for producing a powder detergent by supporting a composition containing the surfactant on a powder. As such a powder, it is desirable that the amount of absorption (supporting ability) of the surfactant is large from the viewpoint of suppressing bleed out of the surfactant.
[0003]
JP-A-57-159898 discloses a specific amount of sodium carbonate, sodium bicarbonate, hard water softener, aluminum silicate, sodium silicate, bentonite and / or polyacrylate (molecular weight of 1,000 to 5,000). It is disclosed that a group of granules (beads) for supporting a surfactant is obtained by spray drying. However, this is a method of making the granule surface porous by thermal decomposition of sodium bicarbonate during drying and increasing the supporting ability of the nonionic surfactant, so it is necessary to add a large amount of sodium bicarbonate. However, when it is decomposed in the detergent slurry, the physical properties of the slurry change, and it is difficult to obtain granules having uniform physical properties.
[0004]
In JP-A-62-112697, an effective amount of a crystal growth regulator, which is an organic substance having at least three carboxyl groups in a molecule, is mixed with a surfactant slurry before sodium carbonate, thereby producing crystals. Disclosed is a method of obtaining particles having high supporting ability by forming dried sodium carbonate monohydrate and / or burkeite in a slurry and then spray drying. However, since other polymers that are preferably blended in the detergent composition also act as a crystal growth regulator, when an effective amount of the other polymer is blended as a detergent composition, a film composed of the polymer is formed on the surface of the granules. There is a drawback that it is not possible to obtain a sufficient supporting ability. In this publication, the maximum loading capacity is shown when the amount of polymer in the granule is as small as about 1 to 2% by weight, and there are some restrictions on the blending amount of the water-soluble polymer having the effect of improving the granule strength. I had to add it.
[0005]
In other words, these conventional techniques are aimed at improving the ability of granules to carry a surfactant, but for that purpose, a large amount of substances unnecessary for cleaning performance must be blended or compositional restrictions must be imposed. did not become.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a surfactant-carrying granule group having excellent surfactant carrying ability and excellent granule strength, and a surfactant-carrying granule group obtained by the method and the method The object is to provide a method for producing detergent particles using the surfactant-supporting granules.
[0007]
[Means for Solving the Problems]
That is, the present invention
[1] When a solution or slurry containing a water-soluble polymer and a water-soluble salt is atomized and introduced into a spray drying apparatus, a heat medium is supplied near the liquid outlet of the member to be atomized and the heat from the heat medium is sprayed. A method for producing a surfactant-supporting granule group, which is spray-dried while being introduced into a drying zone in a drying apparatus,
[2] A surfactant-supporting granule group obtained by the production method according to [1] above, wherein a pore volume distribution mode diameter by a mercury porosimeter is 1.5 μm or less, and pores having a pore diameter of 0.01 to 3.0 μm A surfactant-supporting granule group having a volume of 0.3 mL / g or more and a granule strength of 15 to 100 MPa, and
[3] Detergent particles comprising a step of mixing the surfactant-carrying granule group obtained by the production method of [1] or the surfactant-carrying granule group of [2] and a liquid surfactant Group manufacturing method
About.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, when a solution or slurry containing a water-soluble polymer and a water-soluble salt (hereinafter also referred to as a preparation liquid) is spray-dried, a heat medium is supplied in the vicinity of the liquid outlet of a member for atomizing the preparation liquid. Thus, by carrying out spray drying while introducing heat from the heat medium into the drying zone in the spray drying apparatus, it is possible to obtain a granule for supporting a surfactant having the characteristics of excellent supporting ability and excellent granule strength. It can be done.
[0009]
1. Internal structure of granule group for loading surfactant and loading mechanism
When a preparation containing a water-soluble component such as a water-soluble polymer and a water-soluble salt is spray-dried with a normal spray-drying apparatus, water evaporation occurs mainly on the droplet surface. Therefore, as the drying progresses, the dissolved water-soluble component moves to the surface together with moisture and precipitates, and the surface of the resulting granule exhibits a spherical structure covered with a coating of the water-soluble component (for example, FIG. 1). ). This coating reduces the drying speed of the droplets, increases the volume of the hollow part inside the granule, reduces the thickness of the particle layer effective for supporting the surfactant, and only reduces the loading volume of the surfactant. In addition, it becomes a factor that inhibits absorption of liquid in granules obtained by spray drying.
[0010]
Therefore, as a method for suppressing the formation of a film on the surface of the granule, a method for reducing the water content of the preparation solution is conceivable. As a result, the absolute amount of water evaporated from the droplets decreases, and as a result, a reduction in the amount of water-soluble components that form a film on the surface can be expected. However, the formation of a coating on the granule surface can be suppressed only by reducing the water content, but the volume of the space used for supporting the surfactant inside the granule (loading capacity) decreases, and the water solution not dissolved in the preparation solution The amount of salt is increased. Since these undissolved water-soluble salts exist in the preparation solution without dissolving, the particle size depends on the particle size at the time of preparation, and the particle size of commercially available water-soluble salts is relatively large. The supporting effect (supporting force) of the active agent is reduced, and as a result, the supporting ability of the granule group is lowered.
Therefore, in order to increase the carrying ability of the granules, it is necessary to improve both the carrying capacity and the carrying force.
[0011]
In order to improve the carrying capacity, the film formed on the droplet surface in the initial stage of drying is formed early to ensure the volume of the granules themselves, and the formed film is made porous to improve the drying speed. It is necessary to ensure the thickness of the particle layer effective for supporting the surfactant. In the method of the present invention, the surface of the liquid droplet is obtained by supplying a heat medium in the vicinity of the liquid outlet of the member for atomizing the preparation liquid and spray drying while introducing heat from the heat medium into the drying zone in the spray drying apparatus. There is an advantage that the film can be formed early and made porous. Further, in the method of the present invention, since the early formation of the film can be sufficiently achieved even when the concentration of the water-soluble polymer is high, it is possible to further improve the granule strength by highly blending the water-soluble polymer. There are advantages.
[0012]
In order to improve the supporting force, it is preferable to precipitate the water-soluble salts as fine crystals effective for supporting the surfactant inside the granules. The method of the present invention has the advantage that the precipitation of fine crystals of water-soluble salts can be promoted by using a heat medium.
[0013]
In order to obtain fine crystals, a method of increasing the number of water-soluble salt particles in the preparation liquid is also effective, for example, wet pulverization of undissolved water-soluble salt particles present in the preparation liquid. And the like. Among them, a method of precipitating water-soluble salts in a dissolved state is preferable, for example, a method of concentrating water-soluble salts in the prepared solution, and a temperature of the prepared solution so that the solubility of the water-soluble salts is lowered. There are a method of changing, a method of precipitating dissolved water-soluble salts by further adding water-soluble salts having strong dissolving strength to the preparation liquid, and the like. In this way, the water-soluble salts precipitated in the preparation solution containing the water-soluble polymer are extremely fine crystals, staying inside the granules without moving to the surface with moisture during drying, and effective in supporting the active agent Further advantages can be obtained by using in combination with other operations that increase the number of water-soluble salt particles in the preparation liquid.
[0014]
The internal structure of the surfactant-carrying granules described above can be confirmed using a mercury porosimeter as the pore volume distribution inside the surfactant-carrying granules. That is, if the size of the re-precipitated water-soluble salt is appropriate, the fine particles inside the granules for supporting the surfactant measured by a mercury porosimeter (for example, “SHIMADZU pore sizer 9320” manufactured by Shimadzu Corporation) are measured. The pore volume distribution per pore diameter (hereinafter referred to as pore volume distribution) is suitable for supporting the surfactant. Here, the larger the pore volume, the larger the surfactant loading site, the higher the liquid absorption capacity, and the smaller the pore diameter, the ability to retain liquid once absorbed by capillary action. (Supporting ability) becomes high. Therefore, when the pore volume is larger and the pore diameter is smaller, the carrying ability of the surfactant is increased, and it is possible to prevent the surfactant from being spotted. Particle structure of surfactant-supporting granules suitable for oil absorption and loading of surfactant and mode diameter of pore volume distribution (pore diameter having the largest pore volume in the obtained pore volume distribution), etc. The preferred physical properties of the supporting granules will be described later.
[0015]
2. Composition of granules for supporting surfactant
The surfactant-supporting granule group contains a water-soluble polymer (A) and a water-soluble salt (B). The water-soluble salt is precipitated as fine crystals in the presence of the water-soluble polymer, and the fine crystals remain in the granules formed by spray drying of the preparation liquid to form sites effective for supporting the surfactant.
[0016]
The water-soluble polymer (A) is an organic polymer having a solubility in water at 25 ° C. of 0.5 g / 100 g or more and a molecular weight of 1,000 or more. For example, carboxylic acid polymers, cellulose derivatives such as carboxymethyl cellulose, One or more types selected from the group consisting of aminocarboxylic acid polymers such as glyoxylate and polyaspartate, soluble starch, saccharides and the like can be exemplified as preferable examples. Among them, the carboxylic acid-based polymer has the effect of refining water-soluble salts and the detergency, specifically the action of sequestering metal ions, the action of dispersing solid particle dirt from the clothes into the washing bath, and the particles as clothes. It is more preferable from the point of the effect | action which prevents reattachment to.
[0017]
Among carboxylic acid polymers, acrylic acid homopolymers and salts of acrylic acid homopolymers (Na, K, NH _Four Etc.), acrylic acid-maleic acid copolymer and acrylic acid-maleic acid copolymer salt (Na, K, NH) _Four Etc.) are particularly excellent. Particularly, those having a molecular weight of 1,000 to 100,000 are preferable, those having a molecular weight of 20,000 to 80,000 are more preferable, and those having a molecular weight of 50,000 to 50,000 are particularly preferable.
Such water-soluble polymers may be used alone or in combination of a plurality of types.
[0018]
The water-soluble salts of component (B) are those having a solubility in water at 25 ° C. of 0.5 g / 100 g or more and a molecular weight of less than 1,000, and are carbonate groups, hydrogen carbonate groups, sulfate groups, sulfite groups, hydrogen sulfate groups, Examples thereof include alkali metal salts, ammonium salts and amine salts having a hydrochloric acid group or a phosphate group. Further, halides of alkali metals and alkaline earth metals can be used. Moreover, the double salt containing these (for example, burkeite, sodium sesquicarbonate, etc.) is also mentioned. Among them, particularly effective water-soluble salts are sodium carbonate, sodium sulfate and sodium sulfite.
[0019]
Further, the water-soluble salts change the crystal form when precipitated in the presence of the component (A), and thus play an important role in improving the supporting ability of the supporting granules. Of these, carbonates and / or sulfates are more preferable as the base for forming the supporting sites of the supporting granules, and a combination of sodium carbonate and sodium sulfate is most preferable. In particular, burkeite, which is sodium carbonate and / or a double salt of sodium carbonate and sodium sulfate, is important as a base for forming the supporting sites of the supporting granules.
[0020]
Salts having a high degree of dissociation, such as potassium sulfate and sodium sulfite, increase the ionic strength of the washing liquid and act suitably for sebum dirt cleaning and the like. The sulfite group has the effect of reducing hypochlorite ions contained in tap water and preventing oxidative deterioration of detergent components such as enzymes and perfumes by hypochlorite ions. Moreover, sodium tripolyphosphate can also be used as a water-soluble salt.
[0021]
Examples of the component (B) include low molecular weight water-soluble organic acid salts, and examples thereof include carboxylic acid salts such as citrate and fumarate. ²⁺ A base having a large and / or large cation exchange capacity is preferred. Specifically, from the viewpoint of detergency, methyliminodiacetate, iminodisuccinate, ethylenediamine disuccinate, taurine diacetate, hydroxyethyliminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methyl Preferred examples include glycine diacetate, glutamate diacetate, asparagine diacetate, and serine diacetate.
[0022]
In addition, when an anion different from a carbonate group such as a sulfate group or a sulfite group or a cation different from sodium such as potassium or ammonium is mixed in the surfactant-carrying granules as a component (B), This is effective in terms of non-paste forming properties.
[0023]
Such water-soluble salts may be used alone or in combination of a plurality of types.
[0024]
The surfactant-supporting granule group may further contain a water-insoluble inorganic substance (C). The water-insoluble inorganic substance is a solid having a solubility in water at 25 ° C. of less than 0.5 g / 100 g, preferably having an average primary particle size of 0.1 to 20 μm, more preferably 0.5 to 10 μm. Examples include crystalline aluminosilicates, amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite, bentonite, etc., and the reasons for not promoting the cleaning ability and the generation of undissolved residues of detergents From the above, crystalline aluminosilicate, silicon dioxide and hydrated silicate compound are preferred.
[0025]
A suitable crystalline aluminosilicate is A-type zeolite (for example, trade name: “Toyo Builder”; manufactured by Tosoh Corporation), which is also preferable in terms of sequestering ability and economy. Here, the value of the oil absorption capacity of the A-type zeolite according to JIS K 5101 method is preferably 40 to 50 mL / 100 g. In addition, P type (for example, trade name: “Doucil A24”, “ZSE064”, etc .; all manufactured by Crosfield; oil absorption capacity: 60 to 150 mL / 100 g), X type (for example, trade name: “WessalithXD”; manufactured by Degussa) An oil absorption capacity of 80 to 100 mL / 100 g), and a hybrid zeolite described in WO 98/42622 is also suitable as a crystalline aluminosilicate.
[0026]
As an amorphous aluminosilicate, from the viewpoint of maintaining high solubility (not denatured) even after long-term storage, SiO ₂ / Al ₂ O _Three (Molar ratio) is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.3 or less. For example, JP-A-6-179799, column 12, line 12 to column 13, line 1, line 17 Columns 34 to 19 include those described in Column 17 and, among them, a volume of pores of 0.015 to 0.5 μm measured with a mercury porosimeter (“SHIMADZU pore sizer 9320” manufactured by Shimadzu Corporation). A material having a volume of 0 to 0.7 mL / g and a pore diameter of 0.5 to 2 μm is preferably 0.30 mL / g or more.
[0027]
Such a water-insoluble inorganic substance may be used alone or in combination of a plurality of types.
[0028]
As the composition of the surfactant-supporting granule group, the content of the component (A) is preferably 2 to 30% by weight, more preferably 5 to 30% by weight, more preferably 6 to 26% by weight, and 8 to 24% by weight. % Is more preferable, and 10 to 22% by weight is most preferable. The content of the component (B) is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, and most preferably 40 to 70% by weight. When the component (C) is contained, the content is preferably 8 to 49% by weight, more preferably 16 to 45% by weight, and most preferably 24 to 40% by weight. Within this range, it is preferable from the viewpoint that both the carrying ability and particle strength of the obtained surfactant-carrying granule group are compatible.
[0029]
In particular, as the granule group for supporting a surfactant of the present invention, the content of the component (A) is 5 to 30% by weight, the content of the component (B) is 20 to 90% by weight, and the content of the component (C) Is preferably 8 to 49% by weight.
[0030]
Moreover, it is also a preferable aspect to mix | blend a microcrystal precipitation agent (D) in the granule group for surfactant carrying | support.
The fine crystal precipitating agent is a substance having an action of precipitating the component (B) which has already been dissolved by blending after the component (B) as fine crystals. Examples of the component (D) include one or more selected from the group consisting of alkali metal halides and alkaline earth metal salts, solvents compatible with water such as ethanol, methanol, and acetone. From the viewpoint of solubility strength, bromide, iodide and the like are preferable, but chloride is preferable from the viewpoint of storage stability of the detergent particles, and alkali metal salt is preferable from the viewpoint of influence on cleaning performance. Among these, sodium chloride is particularly preferable from the viewpoint of economy.
[0031]
The blending amount of the component (D) in the surfactant-supporting granule group is preferably 0.2 to 20% by weight, more preferably 1 to 12% by weight, and 2 to 10% by weight from the viewpoint of sufficient effect and cleaning performance. Is particularly preferred.
[0032]
In addition to the four components (A) to (D), auxiliary components such as fluorescent dyes, pigments, and dyes suitable for the final detergent particle group may be blended in the surfactant-carrying granule group. Absent. The content of the auxiliary component is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 2% by weight or less of the surfactant-supporting granule group.
[0033]
From the viewpoint of supporting ability, it is most preferable that the surfactant is not substantially contained in the surfactant supporting granules. When a surfactant is blended, the content thereof is preferably 5% by weight or less, more preferably 2% by weight or less of the surfactant-supporting granule group. These contents are values based on the solid content of the slurry.
[0034]
3. Production method of granules for supporting surfactant
The method for producing a surfactant-supporting granule group of the present invention includes a step of spray drying a solution or slurry containing (A) a water-soluble polymer and (B) a water-soluble salt. For example, the steps described below ( The thing including a) and a process (b) is mentioned.
Step (a): A step of preparing a solution or slurry (preparation solution) containing the component (A) and the component (B),
Step (b): supplying a heat medium near the liquid outlet of the member for atomizing the preparation liquid obtained in step (a) and introducing heat from the heat medium into the drying zone in the spray dryer, A step of spray-drying the prepared solution.
[0035]
Step (a) is a step of preparing a solution or slurry (preparation solution) containing the component (A) and the component (B), and the preparation solution may be prepared by a known method. All or almost all of the above is added to the mixing vessel, preferably after the water temperature has nearly reached the operating temperature, other components are added sequentially or simultaneously, all components are added into the preparation, and then preferably for 10 minutes or more, More preferably, it can be prepared by mixing for 30 minutes or more. The component (A) and the component (B) may be blended in any order. In addition, as operation temperature, 35-80 degreeC is preferable.
[0036]
In addition, the water-insoluble inorganic substance (C) and auxiliary components may be appropriately added to the preparation liquid in the step (a), and the preparation liquid after the step (a ′) described later, and further obtained in the step (b). You may mix | blend with the obtained granule for surfactant support.
[0037]
It is preferable to further perform the step (a ′) described below for the preparation liquid obtained in the step (a).
Step (a ′): A step of subjecting the preparation solution prepared in step (a) to a treatment for increasing the number of (B) component particles present in the preparation solution.
[0038]
Preferred embodiments of the step (a ′) are roughly divided into three as described below.
(1) A mode of precipitating the component (B) dissolved in the preparation liquid,
(2) A mode in which the particles of the component (B) in the preparation liquid are wet pulverized,
(3) A mode in which the fine particles of the component (B) are added to the preparation solution under conditions that can exist without being substantially dissolved in the preparation solution.
[0039]
Specific methods of the aspect (1) include the following methods.
(1-1) A method of precipitating the dissolved component (B) by blending the component (D) after the components (A) and (B) are dissolved,
(1-2) A method of precipitating the dissolved component (B) by concentrating the preparation solution,
(1-3) A method of precipitating a part of the dissolved component (B) by changing the temperature of the preparation solution so that the amount of the component (B) dissolved is lowered.
[0040]
In said (1-1), the compounding quantity of (D) component is as above-mentioned. Moreover, there is no limitation in particular about conditions, such as temperature at the time of mix | blending (D) component.
In the above (1-2), the preparation solution may be concentrated using a concentrating device.
As the concentrating device, any concentrating device which is generally spread may be used. For example, the liquid rises while boiling in the heating tube inside the evaporator, collects in the central concentrated liquid collecting tube, falls and naturally circulates, or a circulation pump between the evaporator and the heating can. Use this to circulate the liquid at high speed, evaporate the water with an evaporator, or use an externally heated forced circulation evaporator, or let the liquid flow in from the top of the vertical heating can, and flow down the inner wall of the heating tube as a uniform liquid film There are thin film falling evaporators in which evaporation and concentration are performed, and these can be used alone or in multiple effects. A flash type evaporator that evaporates moisture by injecting a liquid heated to a boiling point or higher into a reduced-pressure evaporator is also effective.
[0041]
Since the preparation liquid used in this embodiment produces crystals of water-soluble salts with concentration, the scale is likely to adhere to the concentration apparatus. Therefore, it is more preferable to use a concentrating device having a function capable of removing the attached scale or a concentrating device having a structure in which the scale is difficult to adhere. As the former apparatus, there is an apparatus, for example, a wiper (manufactured by Shinko Pantech Co., Ltd.) provided with the above-described thin film flow-down evaporator and a stirring blade for scraping off the scale. As the latter device, there is a Rosco evaporator (manufactured by Sumitomo Heavy Industries, Ltd.) that performs concentration by holding a plate-type heating element inside the evaporator and flowing a liquid over the surface of the heating element under reduced pressure.
[0042]
In the above (1-3), as a method for changing the temperature of the adjustment liquid, there is a method of using an apparatus provided with an external jacket, an internal coil or the like for preparation of the preparation liquid, and heating / cooling using these. It is done.
[0043]
The temperature of the preparation liquid is preferably set so that the dissolution rate of the water-soluble salts in the preparation liquid is high, and the optimum temperature is preferably determined according to the type and amount of the water-soluble salts to be blended. For example, when using sodium sulfate or sodium carbonate, it is desirable to adjust the preparation solution to about 40 ° C. and adjust the temperature of the obtained preparation solution to 50 to 70 ° C.
[0044]
In addition, it is also a preferable aspect that the prepared solution obtained in combination with changing the temperature of the prepared solution is concentrated by, for example, flash concentration to promote precipitation of dissolved water-soluble salts. .
[0045]
In these aspects (1), the smaller the amount of undissolved water-soluble salts present in the preparation liquid (however, the preparation liquid before mixing when component (D) is added), the more surface activity obtained. Since the supporting ability of the granule group for supporting the agent increases, the dissolution rate of the water-soluble salts in the preparation liquid is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, particularly preferably 90 to 100% by weight. . When the dissolution rate is less than 100% by weight, it is also a preferred embodiment to pulverize the component (B) in the preparation liquid using a wet pulverizer or the like to refine the undissolved product.
[0046]
Here, the dissolution rate of the component (B) is determined as follows.
That is, the prepared solution is filtered under reduced pressure, and the moisture concentration (P wt%) in the filtrate is measured with a far infrared heater moisture meter (manufactured by Shimadzu Corporation). Further, the concentration of component (B) (S wt%) in the filtrate is determined by ion chromatography or the like. When the water content of the preparation liquid is (Q wt%) and the concentration of the component (B) in the preparation liquid is (T wt%), the dissolution rate of the component (B) is calculated by the following formula.
Dissolution rate (% by weight) = (100 × S × Q) / (P × T)
However, if the calculated dissolution rate exceeds 100% by weight, the dissolution rate shall be 100% by weight.
[0047]
Further, when the component (B) dissolved in the preparation liquid is precipitated, the larger the amount of the component (B) to be precipitated, the smaller the pore size of the obtained surfactant-carrying granule group, and the absorbed liquid Therefore, the precipitation amount of the component (B) is preferably 5% by weight or more of the component (B) dissolved in the preparation liquid, and more preferably 8% by weight or more. On the other hand, from the viewpoint of securing the pore volume of the obtained surfactant-carrying granule group and the handling property of the preparation liquid, the precipitation amount of the component (B) is the amount of the component (B) dissolved in the preparation liquid. It is preferably 35% by weight or less, and more preferably 20% by weight or less. Therefore, the amount of the component (B) to be precipitated is preferably 5 to 35% by weight, more preferably 8 to 20% by weight of the dissolved component (B).
[0048]
The amount of precipitation of component (B) is calculated from the difference between the preparation liquids before and after the precipitation operation of component (B), measuring the dissolution rate of component (B) using the method described above.
[0049]
Further, as the component (B) precipitated in the preparation liquid becomes finer, the effect of improving the carrying ability of the surfactant-carrying granule group obtained by spray drying in the step (b) is large. The average particle size of the component (B) present in the preparation liquid after the component (B) precipitation operation is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. . In addition, an average particle diameter is determined by the particle size distribution of the undissolved (B) component in the preparation liquid before precipitation operation, and the particle size distribution of the (B) component which precipitates by precipitation operation. By adjusting to this particle size range, the effect of improving the carrying ability of the surfactant-carrying granule group obtained in the step (b) becomes clearer. The particle size and number of the undissolved component (B) in the preparation solution can be measured by a method using an in-line type particle droplet monitoring system (“TSUB-TEC M100” manufactured by LASENTEC) described below. The average particle diameter and number of the undissolved component (B) described in the present specification are values measured using this “TSUB-TEC M100”.
[0050]
Weigh 1000 g of the prepared solution prepared in step (a) into a 1 L stainless beaker, and stir the stirring blade with three propeller blades of 2 × 4 cm at 200 r / min in the thermostatic bath set to the final preparation temperature of the prepared solution. Rotate at speed and stir. The LASENTEC in-line type particle monitoring system (TSUB-TEC M100) is allowed to enter at a 45 ° angle with respect to the liquid level of the prepared liquid, and is attached at a position 3 cm below the liquid level. Thereby, particles always collide with the window surface when stirring. The software uses "Control Interface for FBRM Ver5.4 Build 58b" (manufactured by LASENTEC), and the focus position is set to the position where the 0.02mm focus is put inside from the window surface. Measurement duration (one measurement time) is 14.5 seconds and Averaging (moving average) is 10. The median code (particle diameter at 50% of the integrated value of the number of particles) at the time of measurement for 5 minutes is the average particle diameter of the undissolved component (B) in the preparation liquid, and the count number is the number.
[0051]
Further, as a specific method of the aspect (2), there is a method of pulverizing the slurry using a wet pulverizer or the like to refine the undissolved material to an average particle size of 100 μm or less.
[0052]
In addition, as a specific method of the aspect (3), the particles of the component (B) that are first precipitated from the preparation liquid are prepared by spray drying or the like, and the obtained particles are refined by a pulverizer to obtain fine particles. Examples thereof include a method of adding the fine particles to the preparation solution.
[0053]
The number of particles of the undissolved component (B) in the preparation liquid that is increased by the step (a ′) as described above is preferably 500 / s or more, more preferably 1000 / s or more as the increase amount. .
[0054]
The temperature of the preparation liquid and the water content of the preparation liquid are preferably 40 to 80 ° C. and 40 to 60% by weight, respectively, from the viewpoint of the dissolution rate of water-soluble salts and the handling property.
[0055]
In the step (b), a heat medium is supplied near the liquid outlet of the member for atomizing the preparation liquid obtained through the step (a) or the step (a ′), and the heat from the heat medium is dried in the spray drying apparatus. In this step, the preparation liquid is spray-dried while being introduced into the zone, and the granule group obtained in this step becomes the surfactant-supporting granule group. A specific method for supplying a heat medium near the liquid outlet of the member for atomizing the prepared liquid and introducing heat from the heat medium into the drying zone in the spray drying apparatus is as follows. Is supplied to the drying zone in the spray dryer.
[0056]
Here, the drying zone refers to a part of the apparatus that dries the sprayed preparation liquid droplets. There is no particular limitation on the size and shape of the drying zone. The preparation liquid and the heat medium are supplied to a spray drying tower having a drying zone. As the spray drying tower, any form of a countercurrent tower and a cocurrent tower can be used, but a countercurrent tower is preferable from the viewpoint of productivity.
[0057]
In general, a preparation solution containing a water-soluble component such as a water-soluble salt or a water-soluble polymer is such that the droplet shrinks until a film mainly composed of the water-soluble component is formed on the surface of the droplet during the drying process. Since there is a tendency to reduce the internal voids of the resulting granule, the drying temperature in the drying zone is preferably higher from the viewpoint of improving the supporting ability. For example, the blowing temperature in the spray drying tower is preferably 200 to 350 ° C. 250 to 330 ° C is more preferable.
The exhaust air temperature is preferably 75 to 125 ° C, more preferably 90 to 115 ° C.
[0058]
For example, the preparation liquid obtained through the step (a) or (a ′) is supplied to the spray drying tower using a pump, and a member for atomizing the preparation liquid installed in the spray drying tower (hereinafter, (Also referred to as atomizing member) and sprayed onto the drying zone. Examples of the atomizing member include a pressurized nozzle and a two-fluid spray nozzle. Among these, a two-fluid spray nozzle is used from the viewpoint of easily supplying the heat medium to the drying zone from the vicinity of the liquid outlet of the atomizing member. preferable. Examples of the two-fluid spray nozzle include JOKI75 (manufactured by Ikeuchi).
[0059]
The characteristics such as the size, structure, material, and nozzle diameter of the atomizing member may be appropriately adjusted depending on the size of the spray drying tower, the composition of the preparation liquid to be sprayed, and the like, and are not particularly limited. The installation position of the atomization member in the spray drying tower may be appropriately adjusted depending on the type of the spray drying tower. The spraying pressure when spraying the preparation liquid using the atomizing member is preferably, for example, about 1 to 5 MPa for a pressurizing nozzle and about 0.05 to 0.5 MPa for a two-fluid spraying nozzle. Also, the spraying conditions such as the temperature of the preparation liquid and the supply speed of the preparation liquid are not particularly limited.
[0060]
When a normal pressure type nozzle is used as the atomizing member, a holder capable of supplying the heat medium is installed around the liquid outlet in order to facilitate supplying the heat medium to the drying zone from the vicinity of the liquid outlet of the atomizing member. Is preferred. The characteristics such as the size, configuration, material, and shape of the heat medium ejection hole of the holder may be appropriately adjusted according to the characteristics such as the size of the pressure type nozzle, and are not particularly limited.
[0061]
Examples of the heat medium include heated air, heated nitrogen, and water vapor. Among these, water vapor is preferable because of its large heat capacity, and superheated steam is particularly preferable. From the viewpoint of increasing the temperature around the droplets sprayed from the atomization member, the temperature of the heat medium supplied to the drying zone is preferably equal to or higher than the temperature of the hot air discharged from the drying tower, specifically 100 ° C or higher. Is preferable, and 120 ° C. or higher is more preferable. The spray pressure of the heat medium supplied to the drying zone is preferably 0.05 to 1 MPa.
[0062]
A method of supplying a heat medium as the atomization medium of the two-fluid spray nozzle is also a preferable aspect. Here, the atomization medium is a medium for making the preparation liquid into droplets when the preparation liquid is sprayed. The type and temperature conditions of the heat medium supplied as the atomization medium may be the same as described above.
[0063]
As described above, the ambient temperature of the droplets of the atomized preparation liquid is obtained by supplying the heat medium near the liquid outlet of the atomizing member and introducing the heat generated by the heat medium into the drying zone in the spray drying apparatus. And the heat transfer rate is improved, so that the formation of a film mainly composed of a water-soluble component formed on the surface of the droplet is accelerated, and further, the shrinkage of the droplet in the initial stage of drying is suppressed and obtained. The internal voids of the granules can be increased to improve the loading capacity.
[0064]
Furthermore, when a heat medium is used as the atomization medium of the two-fluid spray nozzle, contact between the liquid droplets of the preparation liquid and the heat medium is performed more efficiently, so that the effect of the heat medium is obtained more efficiently. be able to.
[0065]
Further, the obtained granules for supporting a surfactant may be used after adjusting the particle size by a known method and adjusting to a desired particle size distribution.
[0066]
4). Physical properties of surfactant-supporting granules
The average particle size of the surfactant-supporting granule group is preferably 150 to 500 μm, more preferably 180 to 300 μm, from the viewpoint of the solubility of the detergent particle group.
The bulk density of the surfactant-supporting granules is preferably 400 to 1000 g / L, more preferably 500 to 800 g / L, from the viewpoint of obtaining a detergent particle group having a bulk density of 500 g / L or more.
[0067]
In the surfactant-supporting granules suitable for absorbing and supporting the surfactant, the mode diameter of the pore volume distribution by the mercury porosimeter is preferably 1.5 μm or less, more preferably 1.1 μm or less, and particularly preferably 0.9 μm or less. Most preferably, it is 0.8 μm or less. The pore volume depends on the viscosity of the oil mixture to be absorbed, but preferably has a pore volume of 0.01 to 3.0 μm and a pore volume of 0.3 mL / g or more, and a pore volume of 0.01 to 2.0 μm. It is more preferable to have 0.3 mL / g or more, it is more preferable to have a pore volume with a pore diameter of 0.01 to 1.5 μm, 0.3 mL / g or more, and a pore volume with a pore diameter of 0.01 to 1.0 μm is 0.3 mL / g or more. It is particularly preferred. Further, in each of the pore diameter ranges, the pore volume is more preferably 0.35 mL / g or more, and further preferably 0.4 mL / g or more.
[0068]
Moreover, the granule strength of the granule group for carrying the surfactant is such that when the liquid surfactant composition is added to the granule group for carrying, the granule constituting the granule group for carrying is collapsed and the carrying capacity is reduced. From the viewpoint of suppressing this, it is preferably 5 to 200 MPa, more preferably 10 to 150 MPa, still more preferably 15 to 100 MPa, particularly preferably 20 to 80 MPa, and most preferably 25 to 60 MPa.
[0069]
In particular, the surfactant-supporting granule group of the present invention preferably has the above-described preferable pore volume distribution and granule strength. As preferable physical properties, the mode diameter of the pore volume distribution is 1.5 μm or less, the pore volume of the pore diameter of 0.01 to 3.0 μm is 0.3 mL / g or more, and the granule strength is 15 to 100 MPa. More preferable physical properties are a pore volume distribution mode diameter of 1.1 μm or less, a pore volume of 0.01 to 2.0 μm, a pore volume of 0.3 mL / g or more, and a granule strength of 20 to 80 MPa.
[0070]
The loading capacity of the surfactant-supporting granule group is reduced or unnecessary for the amount of oil-absorbing carrier (for example, amorphous aluminosilicate) required when adding a liquid surfactant to the granule group. From this point, it is preferably 0.35 mL / g or more, more preferably 0.40 mL / g or more, particularly preferably 0.45 mL / g or more, and most preferably 0.50 mL / g or more.
[0071]
The water content of the surfactant-carrying granule group is preferably 1 to 8% by weight, more preferably 1 to 5% by weight, from the viewpoint of the handleability of the granule group.
[0072]
In addition, the surfactant-carrying granule group obtained by the present invention has a hollow portion inside, and a shape in which the surface of the granule is open and communicated with the hollow portion inside (the granule surface is depressed) Those having (recessed holes) are included. The granule having the depression hole is particularly excellent in the absorbability of the liquid surfactant. The “having depression holes” included in the surfactant-carrying granule group of the present invention is, for example, a granule having an appearance as shown in FIG. For confirmation of the appearance, for example, SEM such as a digital microscope VH-6300 manufactured by KEYENCE, or a field emission scanning electron microscope S-4000 manufactured by Hitachi, Ltd. can be used.
[0073]
5. Composition and physical properties of detergent particles
The detergent particles according to the production method of the present invention are obtained by supporting a liquid surfactant on a surfactant-supporting granule group. Here, the liquid state includes not only a normal liquid state at the operating temperature but also a fluid state such as a paste.
[0074]
Examples of the liquid surfactant to be supported include one or more surfactants, preferably anionic surfactants and nonionic surfactants. The anionic surfactant and the nonionic surfactant can be used alone, but it is more preferable to use a mixture of both. In particular, when a nonionic surfactant having a melting point at 30 ° C. or lower is used, it is preferable to use a surfactant fixing agent in combination. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose. In addition, when an anionic surfactant such as alkylbenzene sulfonate is blended in the detergent particle group in an amount of 5 to 25% by weight, an effect is exhibited in terms of non-paste-forming properties in water.
[0075]
Examples of surfactants include anionic surfactants such as alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, α-olefin sulfonates, α-sulfo fatty acid salts or esters thereof, alkyl or alkenyl ether carboxyls. Examples thereof include acid salts, amino acid type surfactants, N-acyl amino acid type surfactants and the like. In particular, a linear alkylbenzene sulfonate having 10 to 14 carbon atoms and an alkyl or alkyl ether sulfate having 10 to 18 carbon atoms may be mentioned, and sodium and / or potassium, monoethanolamine, and diethanolamine are preferable as the counter ion.
[0076]
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene glycol represented by the trademark Pluronic, and polyoxyethylene alkylamine. Higher fatty acid alkanolamides, alkyl glucosides, alkyl glucose amides, alkyl amine oxides and the like. Among them, those having high hydrophilicity and / or those having low liquid crystal forming ability when mixed with water or those that do not produce liquid crystal are preferable. Polyoxyalkylene alkyl ether is particularly preferred. Preferably, it is an ethylene oxide (hereinafter referred to as EO) adduct of an alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, an average addition mole number of 4 to 20, preferably 4 to 12, more preferably 6 to 10, In addition, an EO adduct of alcohol having 8 to 18 carbon atoms and a propylene oxide (hereinafter referred to as PO) adduct are preferable. As the addition order, one added with PO after adding EO, one added with PO after adding PO, or one added randomly with EO and PO can be used. Is represented by the following general formula in which EO is added, PO is added, and EO is added, and among these, regarding the relationship of the most preferable average added mole number, X> 0, Z> 0, X + Y + Z = 6 to 14, X + Z = 5 to 12, and Y = 1 to 4.
R-O- (EO) _X -(PO) _Y -(EO) _Z -H
[In the formula, R represents an alkyl group or alkenyl group having 6 to 24 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and X, Y, and Z each represent an average addition mole number. ]
[0077]
Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
Examples of amphoteric surfactants include carbobetaine type and sulfobetaine type.
[0078]
Examples of the immobilizing agent include an anionic surfactant having a carboxylic acid group or a phosphoric acid group (excluding those having a sulfuric acid group or a sulfonic acid group), specifically, fatty acid salts, hydroxy fatty acids. Examples thereof include anionic surfactants such as salts and alkyl phosphates. In particular, at least one member selected from an alkali metal salt such as a sodium salt or potassium salt of a fatty acid having 10 to 22 carbon atoms or a hydroxy fatty acid, or an amine salt such as an alkanolamine is preferred in terms of solubility.
[0079]
The immobilizing agent also includes a compound having a melting point of 35 ° C. or higher and compatible with a nonionic surfactant. Examples thereof include one or more selected from polyoxyalkylene type nonionic compounds having a molecular weight of 3,000 to 30,000, polyether nonionic compounds having a molecular weight of 3,000 to 30,000, and the like. Particularly preferable examples include polyethylene glycol, polypropylene glycol, and polyoxyethylene alkyl ether. Here, the term “compatible” refers to a property that the mixture is well mixed at a temperature equal to or higher than the pour point of the mixture of the nonionic surfactant and the immobilizing agent and is difficult to separate. The fixing agents may be used alone or in combination.
[0080]
The liquid surfactant used in the present invention may be a composition in which the above-mentioned various surfactants and fixing agents are appropriately blended. The amount of the anionic surfactant is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, and particularly preferably 30 to 180 parts by weight with respect to 100 parts by weight of the nonionic surfactant. The blending amount of the fixing agent is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the nonionic surfactant. In this range, the composition has a temperature range in which the viscosity of the composition is 10 Pa · s or less, 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. And in the temperature range lower than the pour point of the composition and higher than the melting point of the nonionic surfactant, the penetration hardness of the composition is 10 kPa or more, preferably 30 kPa or more, particularly preferably 50 kPa or more. Therefore, it is preferable because the handling property at the time of production of the composition and the detergent particle group becomes good and the non-ionic surfactant can be prevented from being smeared when the detergent particle group is stored.
[0081]
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 using a Mettler FP81 (manufactured by Mettler Instrumente AG) with an 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. Calculated under the condition of 60r / min. If the measured value under the above condition exceeds 2 Pa · s and measurement is impossible, the rotor No. 3. Measured under the condition of 12r / min. The penetration hardness is rheometer (NRM-3002D, manufactured by Fudo Kogyo Co., Ltd.), diameter 8 mm, bottom area 0.5 cm. ² The circular adapter (No. 3, 8φ) was used, and the load when the adapter entered the inside of the surfactant composition by 20 mm at an entry speed of 20 mm / min was divided by the bottom area of the circular adapter.
[0082]
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 70 parts by weight is particularly preferable. The addition amount of the surfactant here does not include the addition amount of the surfactant even if the surfactant is added at the time of slurry preparation in the step (a).
[0083]
When adding the surfactant composition to the surfactant-supporting granule group, powder raw materials other than the granule group may be added as desired. The addition amount is preferably 0 to 150 parts by weight with respect to 100 parts by weight of the granule group. Preferable powder raw materials include powder detergency enhancers (builders). Specifically, bases exhibiting sequestering ability such as aluminosilicates and citrates, sodium carbonate, potassium carbonate Examples of such materials include alkaline materials such as crystalline silicates, bases that have both sequestering and alkaline capacities such as crystalline silicates, and other bases that increase ionic strength such as sodium sulfate.
[0084]
Here, as crystalline silicate, Japanese Patent Application Laid-Open No. 5-27913, column 3, line 17 (especially, it is preferably crystallized by firing at 500 to 1000 ° C.), Japanese Patent Application Laid-Open No. 7-89712. Use of 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) as a preferred powder builder. it can. Where alkali metal silicate SiO ₂ / M ₂ Those having O (wherein M represents an alkali metal) of 0.5 to 3.2, preferably 1.5 to 2.6 are more suitably used.
[0085]
The preferred physical properties of the detergent particles in the present invention are as follows.
The average particle size is preferably 150 to 500 μm, more preferably 180 to 400 μm. From the viewpoint of solubility, the average particle size of the detergent particle group is preferably 1.5 times or less, more preferably 1.3 times or less, and particularly preferably 1.2 times or less than the average particle size of the surfactant-carrying granule group. Among them, it is preferable to be a mononuclear detergent particle group having an average particle size in the above range and substantially consisting of one detergent-supporting granule group.
[0086]
The bulk density is preferably 500 to 1000 g / L, more preferably 600 to 1000 g / L, and particularly preferably 650 to 850 g / L.
[0087]
The caking resistance is preferably such that the sieve passing rate is 90% by weight or more, more preferably 95% by weight or more.
[0088]
If the evaluation by the test method described later is preferably 2 ranks or more, more preferably 1 rank, it is possible to prevent the adhesion of liquid surfactant-containing powder to the equipment in the transport system and to prevent the stain from appearing in the container. It is preferable because no device is required.
[0089]
The fluidity is preferably 7 seconds or less, and more preferably 6 seconds or less as the flow time according to the test method described later.
[0090]
6). Manufacturing method of detergent particles
A suitable production method for obtaining the detergent particle group includes the following step (c), and may further include a step (d) as necessary.
Step (c): A step of mixing the surfactant-supporting granules obtained by the production method of the present invention with a liquid surfactant.
Step (d): Step of mixing the mixture obtained in step (c) (ie, detergent particles) and fine powder, and coating the surface of the mixture with the fine powder (however, in this step, crushing is performed) It also includes the case of progressing simultaneously.)
[0091]
The mixer used in step (c) is preferably, for example, a nozzle for adding a liquid surfactant or a jacket for controlling the temperature in the mixer. Can be mentioned. When performing by a batch type, the thing of (1)-(3) is preferable. (1) 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.) , Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), mixing apparatus described in JP-A-10-296064, JP-A-10-296065, etc., (2) Ribbon mixer (manufactured by Nikki Machine Industry Co., Ltd.), Batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.), etc. There is.
[0092]
Among the above-mentioned mixers, preferably, there are a Redige mixer, a Proshear mixer, a mixing apparatus described in JP-A-10-296064, JP-A-10-296065, and the like (d), which will be described later, the same apparatus It is preferable from the viewpoint of simplification of equipment. Among them, the mixing apparatuses described in JP-A-10-296064 and JP-A-10-296065 are preferable because the moisture and temperature of the mixture can be adjusted by aeration, and the disintegration of the particles for supporting the surfactant can be suppressed. A mixing device such as a ribbon mixer, a nauter mixer, and an SV mixer that can mix powder and liquid without giving a strong shearing force is also preferable because it can suppress the collapse of the particles for supporting the surfactant.
[0093]
Further, the surfactant-supporting granule group and the surfactant may be mixed using the continuous apparatus of the above mixer. Moreover, as a continuous type apparatus of a mixer other than the above, there are a flexo-mix type (manufactured by POWREC Co., Ltd.), a turbulizer (manufactured by Hosokawa Micron Co., Ltd.) and the like.
[0094]
More preferably, the temperature in the mixer in the step (c) is mixed at a temperature higher than the pour point of the surfactant composition. The pour point of the surfactant composition is measured by the method specified in JIS K 2269. Here, the temperature to be raised may be higher than the pour point of the surfactant composition, but as a practical range, a temperature exceeding the pour point and 50 ° C. higher than the pour point is preferable, and 10 p.p. A temperature higher by 30 ° C is more preferred.
[0095]
A suitable mixing time (in the case of a batch system) or an average residence time (in the case of a continuous system) is preferably 1 to 20 minutes, and more preferably 2 to 10 minutes.
[0096]
In the step (c), when adding the above-mentioned crystalline silicate as a powder raw material, from the viewpoint of the solubility of the resulting detergent particle group, 25 parts by weight is preferable, and 2 to 15 parts by weight is more preferable.
[0097]
Furthermore, it is preferable to add the process (d) which surface-modifies the detergent particle group after the process (c). By performing the step (d), in addition to the fluidity and caking resistance of the detergent particles, there is a tendency to improve the stain resistance.
[0098]
From the viewpoint of improving the dispersibility of the fine powder to be added, the mixer used in the step (d) is preferably a mixer equipped with both a stirring blade and a crushing blade among the mixers exemplified in the step (c). It is also possible to carry out with the same apparatus as in c).
[0099]
The fine powder used in the step (d) preferably has an average primary particle size of 10 μm or less from the viewpoint of improving the coverage of the detergent particles, improving the flowability and caking resistance of the detergent particles. More preferably, the thickness is 0.1 to 10 μm. The average particle diameter of the fine powder can be measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.) or microscopic observation.
[0100]
The fine powder is preferably an aluminosilicate, silicate compounds such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate, sodium sulfate, tripolyphosphorus pulverized to an average particle size of 10 μm or less An inorganic compound such as sodium acid or a metal soap having primary particles of 10 μm or less can also be used. Among these, from the viewpoint of cleaning performance, the fine powder preferably has high sequestering ability and high alkali ability, and crystalline aluminosilicate and crystalline silicate are preferred. In the case of using crystalline silicate, it is preferable to use it mixed with fine powder other than crystalline silicate for the purpose of preventing deterioration due to moisture absorption or coagulation of crystalline silicate by carbon dioxide gas.
[0101]
The amount of fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the detergent particles from the viewpoint of fluidity and feeling of use of the detergent particles. Part by weight is particularly preferred.
[0102]
In the present invention, since the carrying ability of the surfactant-carrying granule group is high, by using such a granule group, a detergent particle group carrying a sufficient amount of surfactant even if the amount of fine powder is reduced can be obtained. Obtainable.
[0103]
7). Method for measuring physical properties of surfactant-supporting granules and detergent particles
The physical property values in this specification were measured by the following methods.
(Bulk density): Measured by the method defined by JIS K 3362.
[0104]
(Average particle diameter): Determined using a sieve specified in JIS Z 8801. For example, using a 9-stage sieve and saucer with openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm, 125 μm, a low-tapping machine (manufactured by HEIKO SEISAKUSHO, tapping: 156 Rotating: 290 times / minute), shaking 100 g sample for 10 minutes and sieving, saucer, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm , 1000μm, 1400μm, 2000μm in order of the weight frequency on the pan and each sieve, the opening of the first sieve where the cumulative weight frequency is 50% or more is αμm, which is one step larger than αμm When the sieve opening is β μm, the total weight frequency from the saucer to the α μm sieve is γ%, and the weight frequency on the α μm sieve is θ%,
(Average particle size) = 10 ^A :
A = (50- (γ-θ / (log β-logα) × log β)) / (θ / (log β-logα))
Can be asked according to.
The sieve to be used is appropriately adjusted so that the particle size distribution of the measured powder can be accurately estimated.
[0105]
(Granule strength): Put 20 g of sample into a cylindrical container with an inner diameter of 3 cm and a height of 8 cm, and tapping 30 times (Tsutsui Riken Instrument Co., Ltd., TVP1-type tapping-type densely packed bulk density meter, tapping conditions; period 36 times / Minute, free fall from a height of 60 mm), and measure the sample height (initial sample height) at that time. Thereafter, the entire upper end surface of the sample held in the container is pressurized at a speed of 10 mm / min with a pressure tester to obtain a load-displacement curve. The value obtained by multiplying the slope of the linear portion at a displacement rate of 5% or less by the initial sample height and dividing by the pressure area is defined as the particle strength.
[0106]
(Liquid surfactant composition loading capacity and loading speed): Put 100 g of sample into a cylindrical mixing tank with an inside diameter of 5 cm x 15 cm equipped with a stirring blade inside and polyoxylated at 30 ° C with stirring at 350 r / min. Ethylene alkyl ether (C ₁₂ / C ₁₄ = 6/4, EO = 7.7, melting point = 25 ° C) at a rate of about 10 g / min, and the amount of polyoxyethylene alkyl ether charged when the stirring power becomes the highest is the weight of the granules (100 g ) Is taken as the loading capacity (mL / g) of the granules. The loading speed is determined by the amount of polyoxyethylene alkyl ether charged at the time when the amount of change per unit time becomes the largest in the process of increasing the stirring power until the stirring power reaches the maximum value. ) Divided by (mL / g), the larger this value, the better the loading speed, that is, the more excellent the loading speed, the more the excess of polyoxyethylene alkyl ether on the granule surface is suppressed. The time until it rises is delayed.
[0107]
(Moisture): The moisture content of the surfactant-supporting granule group (detergent particle group) is measured by an infrared moisture meter method. That is, 3 g of the sample is placed on a sample pan having a known mass, and the sample is heated and dried for 3 minutes by an infrared moisture meter (manufactured by Kett Science Laboratory Co., Ltd. (infrared lamp 185 W)). After drying, weigh the sample pan and dry sample. Divide the difference between the weight of the container before and after drying obtained by the above operation and the sample by the amount of the sample weighed and multiply by 100 to calculate the amount of water in the sample.
[0108]
(Pore volume distribution): The pore volume of the particles for supporting a surfactant is measured using a mercury porosimeter “Pore Sizer 9320 manufactured by SHIMADZU” based on the instruction manual as follows. That is, 200 mg of a surfactant-supporting granule group is put in a cell, and the mercury to be injected is measured by dividing it into a low pressure part (0 to 14.2 psia) and a high pressure part (14.2 to 30000 psia). The measurement data is smoothed by taking the average of the two data before and after, and the mode diameter and the pore volume of 0.01 μm to 3 μm are obtained.
[0109]
(Fluidity): Flow time is the time required for 100 mL of powder to flow out of the bulk density measurement hopper specified by JIS K 3362.
[0110]
(Caking resistance): The top surface of length × width × height = 10 cm × 6 cm × 4 cm using two types of filter papers defined in JIS P 3801 (for example, “Qualitative No. 2 filter paper” manufactured by Toyo Filter Paper Co., Ltd.) Make an open container. A sample of 100 g is put in this box, and a total weight of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon. This is left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 80%, and the caking state is determined after 7 days. The determination is performed by obtaining the passage rate as follows. The higher the pass rate, the higher the caking resistance, which is a preferable physical property as a detergent particle group.
(Passing rate): Gently open the sample after the test on a sieve (aperture 4760 μm defined in JIS Z 8801), weigh the powder that passed through, and determine the passing rate for the sample after the test.
[0111]
(Stain-out property): The top surface of the vertical × horizontal × height = 10 cm × 6 cm × 4 cm using two types of filter papers defined in JIS P 3801 (for example, “Qualitative No. 2 filter paper” manufactured by Toyo Roshi Kaisha, Ltd.) Make an open container. A line with a width of 0.5 to 1.0 mm is drawn in a diagonal direction using an oil-based marker (“Magic Ink M700-T1” manufactured by Hiroyuki Uchida) on the sample filling surface on the bottom of the container. The container is filled with 100 g of a sample, and a total weight of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon. This was put in a moisture-proof container, left in a thermostat at a temperature of 30 ° C., and after 7 days, the bleeding property of the oily marker was visually judged to determine the bleeding property. Judgment criteria are as follows.
Rank 5: Oil marker spreads over 2cm
Rank 4: The spread width of oily marker is 1cm or more
Rank 3: The spread width of oil-based markers is 0.5cm or more
Rank 2: Slight bleeding of oily marker is observed
Rank 1: No bleeding of oily marker is observed.
[0112]
【Example】
In this example, the following raw materials were used unless otherwise specified.
Sodium sulfate: anhydrous neutral sodium sulfate (manufactured by Shikoku Kasei Co., Ltd.)
Sodium sulfite: Sodium sulfite (Mitsui Chemicals)
Sodium carbonate: “Dense ash” (average particle size: 290 μm, manufactured by Central Glass Co., Ltd.)
Sodium chloride: “Baked salt S” (manufactured by Nippon Salt Corporation)
Fluorescent dye: “Chino Pearl CBS-X” (manufactured by Ciba Specialty Chemicals)
40% by weight sodium polyacrylate aqueous solution: weight average molecular weight 10,000 (manufactured by Kao Corporation)
Crystalline sodium aluminosilicate (zeolite): “Toyobuilder” (4A type, average particle size: 3.5 μm) (manufactured by Tosoh Corporation)
Polyoxyethylene alkyl ether: “Emulgen 108KM” (average number of moles of ethylene oxide added: 8.5, carbon number of alkyl chain: 12-14, manufactured by Kao Corporation)
Polyethylene glycol: “K-PEG6000” (weight average molecular weight: 8500, manufactured by Kao Corporation)
Amorphous aluminosilicate: Preparation Example 2 described in JP-A-9-132794 pulverized to an average particle size of 8 μm
[0113]
Comparative Example 1
431 parts by weight of water was placed in a jacketed mixing tank equipped with a stirrer, and the temperature was raised to 35 ° C. To this, 5 parts by weight of sodium sulfite, 103 parts by weight of sodium sulfate, 122 parts by weight of sodium carbonate, 165 parts by weight of a 40% by weight sodium polyacrylate aqueous solution, 2 parts by weight of a fluorescent dye, and 171 parts by weight of zeolite were added successively and stirred for 30 minutes. Thus, a homogeneous preparation solution in which the water-soluble inorganic salt was completely dissolved was obtained. The final temperature of this preparation solution was adjusted to 50 ° C. (preparation solution moisture 53.0 wt%).
[0114]
This prepared solution is supplied to a spray drying tower (tower diameter: 3 m, tower height: 10 m, countercurrent type) with a pump, and sprayed at a spray pressure of 2.5 MPa from a pressurized spray nozzle (Evalloy) installed near the top of the tower. went. The hot gas supplied to the spray-drying tower was supplied at a temperature of 233 ° C. from the bottom of the tower and discharged at 101 ° C. from the top of the tower. The water content of the obtained surfactant-carrying granule group 1 was 2%.
[0115]
Next, detergent particle group 1 was produced by the following method using the surfactant-supporting granule group 1.
The surfactant composition (polyoxyethylene alkyl ether / polyethylene glycol / sodium dodecylbenzenesulfonate / water = 21/4/21/4 (weight ratio)) was set to 80 ° C. The pour point of this surfactant was 45 ° C. Next, 100 parts by weight of the surfactant-supporting granule group 1 obtained in a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket) was added and the main shaft (stirring blade, rotation speed: 60 r / s) min, peripheral speed: 1.6 m / s) was started. Incidentally, warm water of 80 ° C. was passed through the jacket at 10 L / min. Thereto, 60 parts by weight of the surfactant composition was added in 3 minutes, and then stirred for 7 minutes. Furthermore, in order to give good fluidity as a detergent particle group, an appropriate amount of amorphous aluminosilicate was introduced, and the main shaft (rotation speed: 120 r / min, peripheral speed: 3.1 m / s) and chopper (rotation speed) : 3600r / min, peripheral speed: 28m / s) for 1 minute, and detergent particle group 1 was discharged.
[0116]
Example 1
The preparation liquid of Comparative Example 1 was spray-dried using a vapor spray type two-fluid nozzle JOKI75 type (manufactured by Ikeuchi) to obtain a granule group 2 for supporting a surfactant. Spraying was performed with the pressure of the prepared liquid being 0.3 MPa and the pressure of the spray vapor being 0.2 MPa, and the blowing temperature was 231 ° C. and the exhaust air temperature was 98 ° C. Next, detergent particle group 2 was obtained in the same manner as in Comparative Example 1 using the obtained surfactant-carrying granule group 2.
[0117]
Comparative Example 2
A preparation solution was prepared in the same manner as in Comparative Example 1. At that time, sodium chloride was added to the preparation immediately before the zeolite was added. The number of particles in the prepared solution before and after the addition of sodium chloride was measured with TSUB-TEC M100. In order to improve the measurement accuracy, the measurement is performed using a preparation liquid prepared without mixing zeolite in a separate mixing tank, and the number of particles in the preparation liquid is 150 / s before and after the addition of sodium chloride. The average particle size of the increased water-soluble salts was 18.5 μm.
[0118]
This preparation solution was spray-dried in the same manner as in Comparative Example 1 to obtain a surfactant-supporting granule group 3. The detergent particle group 3 was manufactured by the method similar to the comparative example 1 using the obtained granule group 3 for carrying | supporting surfactant.
[0119]
Example 2
The preparation solution of Comparative Example 2 was spray-dried in the same manner as in Example 1 to obtain a surfactant-supporting granule group 4. The detergent particle group 4 was manufactured by the method similar to the comparative example 1 using the obtained granule group 4 for carrying | supporting surfactant.
[0120]
Example 3
When the preparation liquid of Comparative Example 2 is spray-dried in the same manner as in Comparative Example 1, the preparation liquid is spray-dried using a nozzle (FIG. 3) provided with a holder for jetting steam to support the surfactant. Granule group 5 was obtained. A detergent particle group 5 was produced in the same manner as in Comparative Example 1 using the obtained surfactant-carrying granule group 5.
Here, FIG. 3 is a schematic view of the nozzle 1 provided with a holder 2 for jetting steam. The nozzle 1 is connected to the preparation liquid supply pipe 5 so that the preparation liquid is supplied. The steam supply pipe 6 is connected to the inside, and the preparation liquid can be spray-dried by spraying the preparation liquid from the preparation liquid ejection hole 4 while ejecting the steam from the steam ejection groove 3.
[0121]
Table 1 shows the composition and properties of the obtained surfactant-carrying granule groups 1 to 5, and Table 2 shows the physical properties of the detergent particle groups 1 to 5.
[0122]
[Table 1]

[0123]
[Table 2]

[0124]
From the results of Tables 1 and 2, the surfactant granule groups 2, 4, and 5 obtained in Examples 1 to 3 are all compared to the surfactant granule groups 1 and 3 obtained in Comparative Examples 1 and 2. It can be seen that the granule strength is excellent and the carrying ability is excellent.
[0125]
Further, the surfactant granule groups 4 and 5 obtained in Examples 2 and 3 with a small amount of zeolite were compared with the surfactant granule group 1 obtained in Example 1 and their loading capacity and loading. Since there is almost no change in the speed, it can be seen that the method of the present invention can exhibit sufficient supporting ability even if the amount of amorphous aluminosilicate is reduced.
[0126]
In addition, the detergent particle groups 2, 4 and 5 obtained in Examples 1 to 3 have the same level of fluidity and blemishes as compared to the detergent particle groups 1 and 3 obtained in Comparative Examples 1 and 2. It turns out that it is excellent.
[0127]
【The invention's effect】
This is a method for producing a surfactant-supporting granule group for the production of detergent particles by adding a liquid surfactant, and improves the ability to support granules without using raw materials that affect the performance of the detergent composition. It becomes possible to make it. Furthermore, in the method for producing detergent particles, a large amount of the surfactant is blended without reducing the amount of the oil-absorbing carrier necessary for blending the surfactant and without impairing powder physical properties such as fluidity of the detergent particles. It becomes possible.
[Brief description of the drawings]
FIG. 1 shows an SEM of a granule for supporting a surfactant, the surface of which is obtained by spray-drying using a normal spray-drying apparatus and whose surface is coated with a coating of a water-soluble component.
FIG. 2 shows an SEM of a granule for supporting a surfactant obtained by the present invention, having a hollow portion inside and having a shape in which the surface of the granule is open and communicated with the hollow portion inside.
FIG. 3 is a schematic view of a nozzle provided with a holder for ejecting steam.
[Explanation of symbols]
1 nozzle
2 Holder
3 Steam ejection groove
4 Preparation liquid ejection hole
5 Preparation liquid supply piping
6 Steam supply piping

Claims (6)

When the medium containing the water-soluble polymer and water-soluble salts atomizes the solution or slurry of the water and introduces it into the spray dryer,
By spraying the solution or slurry with a pressure nozzle provided with a holder capable of supplying a heat medium around the liquid outlet and supplying the heat medium into the holder, or from a two-fluid spray nozzle By supplying the heat medium as the solution or slurry and the atomization medium, while introducing heat from the heat medium into the drying zone in the spray drying apparatus,
A method for producing a granule group for supporting a surfactant, wherein spray drying is performed by supplying a high-temperature gas from the spray drying apparatus. Step (a): a step of preparing a solution or slurry of water containing a water-soluble polymer and water-soluble salts, and
Step (b): A step of spray drying the solution or slurry obtained in step (a) by supplying a high-temperature gas from a spray drying device,
In the step (b), the solution or slurry is sprayed with a pressurized nozzle provided with a holder capable of supplying a heat medium around the liquid outlet in the step (b). By supplying a heat medium into the holder, or by supplying a heat medium as the solution or slurry and the atomizing medium from a two-fluid spray nozzle, heat from the heat medium in the spray drying apparatus The process according to claim 1, wherein the process is introduced into the drying zone.   The process according to claim 1 or 2, wherein the heat medium is water vapor.   A granule group for supporting a surfactant obtained by the production method according to any one of claims 1 to 3, wherein a mode diameter of a pore volume distribution by a mercury porosimeter is 1.5 µm or less, and a pore having a pore size of 0.01 to 3.0 µm A group of granules for supporting a surfactant having a volume of 0.3 mL / g or more and a granule strength of 15 to 100 MPa. The manufacturing method of the detergent particle group including the process of mixing the granule group for surfactant carrying | support obtained by the manufacturing method in any one of Claims 1-3, and a liquid surfactant. A method for producing detergent particles comprising the step of mixing the surfactant-supporting granules according to claim 4 and a liquid surfactant.

Images