JP2003260343A - Method for preparing emulsifying dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently prepare a uniform emulsifying liquid of a fine grain size and high concentration in a simplified process step in preparing an emulsifying dispersion and to enable a continuous large volume treatment. <P>SOLUTION: A flow-through tube type tubular emulsifying apparatus 1 formed by disposing one or more sets of static type emulsifying dispersion elements 3 combined with two plate bodies 3a and 3b drilled with a plurality of pores 4a and 4b into flow-through tubes 2 respectively in their thickness direction in such a manner that the area rate of the segments superposed with the bores 4a of the one plate body 3a on the bores 4b of the other plate body 3b attains ≤90% is used. A dispersion, dispersion medium and surfactant are supplied to the flow-through tube type tubular emulsifying apparatus and these fluids are passed at a high velocity through the bores 4a and 4b of the static type emulsifying dispersion elements 3, by which particulates are dispersed into the dispersion medium. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an emulsified dispersion liquid in which a dispersion liquid is dispersed in a dispersion medium in the form of fine particles, and more specifically, it is a uniform dispersion of fine particles having a monodisperse sharp particle size distribution. The present invention relates to a method for producing an emulsion dispersion.

[0002]

2. Description of the Related Art Conventional emulsification methods are generally carried out in a batch system, in which a dispersion liquid, a dispersion medium and a surfactant are supplied to a stirring emulsifying mixer such as a high speed stirrer (dissolver), a homogenizer or a homomixer. Crush the dispersed droplets, collide,
A stable emulsion is obtained by micronizing using shearing action and stabilizing those fine particles with a surfactant. Further, in recent years, instead of the batch type, a continuous type emulsification device for performing an emulsification treatment while continuously supplying a fluid has been developed.

As an example of a batch type emulsifying apparatus, Japanese Patent Application Laid-Open No. 6-58200
In Japanese Patent Laid-Open No. 182175, a non-aqueous substance is first added and stirred by an emulsifying device equipped with an emulsifying stirring blade rotatably arranged in a horizontal direction and a disintegrating blade installed above the emulsifying stirring blade. However, a method for producing an oil-in-water emulsion by adding an aqueous medium thereafter is disclosed.

Further, in Japanese Patent Laid-Open No. 11-57437, an aqueous phase is circulated through a line emulsifier equipped with a stirring blade which rotates at a high speed, and an oil phase is continuously supplied in front of the line emulsifier. Discloses a method for producing an emulsion without phase inversion.

On the other hand, as an example of a continuous emulsifying device, Japanese Patent No. 2515983 discloses an emulsifying device for a liquid sizing agent using an orifice mixer composed of a single plate having a hole.

Further, Japanese Utility Model Laid-Open No. 6-24732 discloses that
Disclosed is an emulsifying apparatus for producing an emulsion-type sizing agent using a static mixer in which right-handed twisting elements and left-handed twisting elements are arranged alternately in the axial direction and the ends of adjacent elements are arranged to intersect.

Further, as another continuous emulsifying apparatus,
There are colloid mills manufactured by Manton Gorin Co., Microfluidizers manufactured by Microfluidex Co., and the like.

[0008]

However, the above-mentioned conventional emulsifying apparatus or method has the following problems.

According to the method described in JP-A-6-182175, it is possible to prepare an oil-in-water type emulsion in which fine particles having an average particle size of about 1 μm are dispersed.
It is necessary to use an emulsifying stirring blade whose space between the bottom surface and the side surface of the emulsification chamber is as narrow as possible, and it is difficult to manufacture a large-scale apparatus capable of mass processing. Furthermore, when preparing an emulsion liquid dispersed in the form of fine particles with this device, a non-aqueous substance is added first, and then the aqueous medium is gradually added with stirring to prepare an oil-in-water type emulsion liquid. is necessary. In this method, a batch method is indispensable, and since the supply rate of the additive on the way is limited, it takes a long time to prepare one batch, and there is a drawback that productivity is deteriorated. In addition, since the liquid viscosity rapidly increases during phase inversion, a high-torque stirring device is required and the device becomes expensive. In addition, the biggest problem in the batch-type phase inversion emulsification method is that it is difficult to always prepare an emulsion having fine particles having the same particle size distribution, and it is difficult to produce an emulsion having stable quality.

The technique described in Japanese Patent Application Laid-Open No. 11-57437 has a drawback that the line emulsification device is a mechanical rotary type, has a high failure frequency, and lacks reliability. Although a line emulsification device is used, the emulsification process is a batch type and has the drawback of poor productivity.

In the apparatus described in Japanese Patent No. 2515983, an orifice mixer consisting of a single plate having perforations is widely used in production sites, but a highly concentrated finely dispersed emulsion is prepared. It is difficult.

Further, with the position-changing static mixer described in Japanese Utility Model Publication No. 6-24732, it is difficult to prepare a high-concentration finely dispersed emulsion.

Further, other continuous emulsifying apparatuses generally have an effect of finely dispersing, but generally 500 to 10,000.
The equipment is expensive because ultra high pressure such as kg / cm ² is required. However, it has a drawback that it is less economical and inferior in economic efficiency. Further, since the through-holes are extremely thin, problems such as clogging during operation are likely to occur, and they are used only for very limited objects, and are not suitable for the production of emulsion dispersion liquids for continuous large-scale processing.

In view of the above-mentioned technical background, the present invention provides an emulsion dispersion which can efficiently produce a uniform emulsion having a fine particle size and a high concentration in a simplified process, and which enables large-scale continuous processing. The purpose is to provide a manufacturing method.

[0015]

In order to achieve the above object, the method for producing an emulsified dispersion of the present invention comprises two sheets, each having a plurality of holes formed in the plate thickness direction inside the flow pipe. One or more sets of static emulsifying and dispersing elements in which plate members are combined so that the area ratio of the portion where the holes of one plate overlap the holes of the other plate are 90% or less are provided. Using a flow tube type tube emulsifying device, the flow tube type tube emulsifying device is supplied with a dispersion liquid as an emulsified particle phase, a dispersion medium as a continuous phase, and a surfactant, and these fluids are subjected to the static emulsification. The basic idea is to circulate the holes of the dispersion element at high speed.

In the present invention, it is preferable that the hole of the plate has a circular cross section and a tapered shape with a reduced diameter portion formed at an intermediate portion in the plate thickness direction.

It is preferable that the fluid is passed through the minimum cross-sectional area of the hole at a speed of 5 m / sec or more.

The two plate bodies are combined at a predetermined distance in the plate thickness direction, or are combined in a contact state in the plate thickness direction.

In the present invention, the dispersion liquid is a liquid non-aqueous substance, the dispersion medium is a liquid aqueous substance, and the surfactant is one of a nonionic surfactant and an anionic surfactant. One or more. Alternatively,
The dispersion liquid is a liquid water-based substance, the dispersion medium is a liquid non-aqueous substance, and the surfactant is one or more of a nonionic surfactant and an anionic surfactant.

It is preferable that the capacity of the dispersion medium is equal to or larger than the capacity of the dispersion liquid.

Further, it is preferable that at least one of the dispersion liquid, the dispersion medium and the surfactant is heated to a temperature exceeding the boiling point under atmospheric pressure and supplied to the flow pipe type tube type emulsification device.

Furthermore, the fluid that has passed through the flow-through pipe type tube emulsifying device can be supplied again to the flow-through pipe type tube emulsifying device.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to FIGS.

As shown in FIG. 1, a flow tube type tube-type emulsifying apparatus (1) used in the present invention has a stationary type emulsifying and dispersing element (3) disposed inside the flow tube (2) in a direction of blocking the flow. The emulsification device (1) is used to continuously perform emulsification and dispersion treatment.

The stationary emulsifying and dispersing element (3) is composed of two plate bodies (3a) (3b) each having a plurality of holes (4a) (4b) formed in the plate thickness direction. Hole in plate (3a)
(4a) is combined so that the area ratio of the portion of the other plate (3b) overlapping the hole (4b) is 90% or less. That is,
The positions and sizes of the holes (4a) and (4b) of the two plates (3a) and (3b) do not exactly match, but a part of the opening of the hole of one plate does not match the other. It is assembled so that the surface of the plate is closed. In FIG. 1, (5) is a supply passage for introducing the dispersion liquid, the dispersion medium, and the surfactant into the flow pipe type tube emulsification device (1), and (6) is the flow pipe type pipe emulsification device ( This is a delivery path for delivering the emulsion dispersion treated in 1).

In the present invention, the overlapping portion of the hole portions (4a) and (4b) of the two plate bodies (3a) and (3b) means the exit side of the hole portion (4a) of the upstream plate body (3a). The opening is defined as a portion that overlaps the inlet opening of the hole (4b) of the plate (3b) on the downstream side, and the ratio of the area of the overlapping portion to the opening area is represented by%. Hereinafter, it is abbreviated as "overlap area ratio". Two plates (3a) (3b)
Are also in contact with each other in the combined state (l)
Since they may be separated from each other, "overlapping" does not indicate only the contact state, but also indicates the overlapping state when projected on the same plane.

Such a static emulsifying and dispersing element (3)
When the dispersion liquid, the dispersion medium, and the surfactant are supplied to the plate at a high speed, these fluids (F) collide with the plate surface in the plate body (3a) on the upstream side and the holes (4a) (4a) It is divided by. Then, due to the positional deviation between the upstream side hole (4a) and the downstream side hole (4b), the flow is disturbed and the downstream side hole (4b)
Shunted to. The plate body (3b) on the downstream side also collides and splits, and then the fluid collects. At this time, two plates (3a)
The droplet breaking force due to the liquid collision generated by the action of the hole portions (4a) and (4b) appropriately formed in (3b) and the plate surface, and the two plate bodies (3
a) Cavitation action due to the jet flow generated when the fluid passes through each hole (4a) (4b) of (3b) at high speed, and the hole
(3a) The continuous emulsification and dispersion treatment is carried out by the dispersing force and the stirring force due to the strong shearing force when the flow is divided in (3b). Furthermore, when two plates (3a) (3b) are combined with a distance (l) between them, strong shear due to flowing at a high speed in a narrow gap between the two plates (3a) (3b). Forces are generated and stronger dispersive and stirring forces act.

The overlapping area ratio of the two plates (3a) and (3b) is set to 90.
% Or less means that the fluid (F) that has passed through the hole (4a) of the plate (3a) on the upstream side surely collides with the surface of the plate (3b) on the downstream side to reduce the droplet breaking force. This is because the dispersion effect is enhanced by generating the flow and complicating the flow. If the upstream hole (4a) and the downstream hole (4b) are completely aligned,
Its dispersion effect is greatly reduced. A particularly preferable overlapping area ratio is 80% or less. The present invention also includes a case where the overlapping area ratio in which both holes do not overlap at all is 0%.

The outer peripheral shape of the plate bodies (3a), (3b) is not particularly limited, but in order to obtain a uniform flow, it has a uniform thickness and has a smooth surface and conforms to the shape of the flow pipe (2). A shape is desirable. When a circular straight pipe is used as the flow pipe (2), it is desirable to use a circular plate. Further, the thickness of the plate (3a) (3b) is not particularly limited as long as it is at least a thickness sufficient to maintain the mechanical strength of the emulsifying disperser, but usually a plate having a thickness of 1 mm or more and 20 mm or less It is preferable to use. If it is less than 1 mm, the holes (4a) and (4b) may have insufficient mechanical strength.
If it exceeds, the equipment cost becomes high due to the excessive weight of the equipment.

There are no particular restrictions on the three-dimensional shape or the like of the holes, and they can be appropriately used. 2 and 3 illustrate a static emulsifying and dispersing element in which two plates are combined.

As shown in FIGS. 2 (A), (B) and (C), the static emulsifying and dispersing element (10) has two diameters (D) corresponding to the inner diameter (D) of the flow pipe (2). Round plate (10a) (10
It is a combination of b). On one plate (10a), four holes (11a) having a circular cross section are formed at equal positions from the center at right angles to the surface of the plate. The hole (1
1a) have the same shape in which the hole diameter (d1) is constant in the plate thickness direction of the plate body (10a), and are formed with a hole interval (X1). The other plate (10b) and the one plate (10a) are holes.
The only difference is that (11b) is provided at a position rotated by 45 ° from the center. Therefore, as shown in FIG.
When these two plate bodies (10a) and (10b) are combined so as to overlap each other, both hole portions (11a) and (11b) do not overlap at all because of their misaligned positions. That is, the overlapping area ratio of the holes (11a) is 0%.

The static emulsifying and dispersing element (20) shown in FIGS. 3 (A), (B) and (C) has two circular plate members (20a) (20).
The shape and the position of the hole formed in b) are different from those of the static emulsifying and dispersing element (10).

That is, one plate (20a) has one hole (21a) at the center and four holes (21a ') circumscribing evenly around the hole (21a). And a total of 5 holes are formed. The other plate (20b) is provided with four hole portions (21b) circumscribing each other at equal positions around the center. Therefore, the hole spacing (X2) is equal to the opening diameter (d3).

Each of the holes (21a) (21a ') (21b) has a circular cross-sectional shape, and a reduced diameter portion having a diameter (d2) at the center in the plate thickness direction.
The holes (22a) and (22b) are formed, and have a so-called punch-shaped structure, which is tapered so that the diameter increases toward the opening having the opening diameter (d3). In the hole portions (21a) (21a ') (22b), the lengths in the thickness direction of the taper portions (not denoted) on the inlet side and the outlet side are equal (y1), and the reduced diameter portions (22a) (22b). The length in the plate thickness direction of () is (y2). In addition, the opening diameter is the same on both the inlet side and the outlet side (d3).

Then, as shown in FIG. 3C, when these two plate bodies (20a) (20b) are combined, the respective hole portions (21a) (21b) become hole portions (21b) (21a). They are arranged so as to be the center of gravity of a square surrounded by the center of
1a) and (21b) partially overlap. These holes (21a) (21a ')
The overlapping area ratio of the four holes on the downstream side is located in the center.
The hole (21a) having an overlapping portion with respect to (21b) is 72.8.
%, A hole having an overlapping portion with two holes (21b)
(21a ') is 36.4%. In this embodiment, only the central hole portion (21a ') overlaps, and the area ratio is 72.8%. However, if holes are appropriately added outside so as to draw concentric circles, it is possible to form a large number of holes having the same area ratio and overlapping with each other in the central portion of the plate body. Of course, the present invention does not limit the number of holes.

Although the present invention is not limited to the shape of the holes and the number of holes in the above example, the punch-type structure shown in FIG. 3 is preferable in view of excellent dispersion efficiency and stirring efficiency. In other words, when the fluid flows at a high speed in the holes (21a) and (21b) of the punch type structure, the structure causes a rapid contraction flow and an expansion flow, which causes the normal dispersion force due to collision, shear, and jet flow. In addition, finer particle dispersions can be obtained due to the more violent turbulent mixing. Furthermore, the pressure loss can be minimized by the structure and arrangement of the drilled holes.

Examples of the shape of the other holes include a tapered shape whose diameter is reduced in the flow direction and a shape which is inclined with respect to the plate thickness direction. Moreover, the cross-sectional shape may be any shape such as a circle, a triangle, a quadrangle, a polygon, a star, and a slit. However, in order to obtain a fine particle dispersion having a narrow particle size distribution, a circular or regular polygonal shape is desirable. A circular shape that can obtain a particularly uniform flow is desirable. Further, it is desirable to provide a plurality of perforation holes having the same size and arranged as evenly as possible over the entire cross section of the flow path.

The size of the holes is not particularly limited as long as the holes can be formed, but in order to obtain a fine particle dispersion having a narrow particle size distribution, a plurality of holes having the same shape and the same size are flowed through a cross section. It is desirable to make the holes evenly. Further, if the size of the minimum cross-sectional area portion in the hole is too small, there is a possibility that fluid may be clogged. From this perspective,
For example, in the case of a circular hole having a sectional shape, the diameter is preferably 0.5 mm or more. Further, when the cross-sectional shape is a polygon having a triangular shape or more, or a hole having a star shape, a slit shape, or other irregular cross-sectional shape, it is desirable that the size is such that a circle having a diameter of 0.5 mm or more can be formed inside. The maximum size of the hole is not limited.

As described above, one set of two plate members (3
A) and (3b) can be combined in contact with each other or separated by a predetermined distance (l). In the latter case, it is desirable that the distance (l) is usually 20 mm or less. When the thickness exceeds 20 mm, each plate (3a) (3b) acts independently, so that the dispersion due to the droplet breaking force and the shearing force caused by the liquid collision caused by the flow between the two plates (3a) (3b) Since the force cannot be fully utilized, it is not possible to obtain a fine particle dispersion having a narrow particle size distribution. Two more plates (3a) (3
It is particularly preferable that the distance (l) in b) is 5 mm or less. The angle at which the two plates (3a) and (3b) are installed is not particularly limited as long as it can block the flow, but it is usually preferable that the plates are installed at an angle perpendicular to the flow. Again 2
It is desirable that the angles of the plates be the same.

There is no particular limitation on the shape or size of the flow pipe (2). A curved pipe or a straight pipe can be used, but it is usually preferable to use a straight pipe. The cross-sectional shape of the pipe may be any of a circular shape, a quadrangular shape, and a polygonal shape, but a circular cross-sectional structure capable of obtaining a uniform flow is preferable, and it is preferable to use a circular straight pipe having an inner diameter of 5 mm or more. If the inner diameter is less than 5 mm, it is difficult to evenly arrange the holes and the area of the holes is small, resulting in insufficient processing capacity.

It is not necessary to change the dimensions of the holes (3a) and (3b) with respect to the variation of the dimensions of the flow pipe (2). Distribution pipe
Even if the size of (2) becomes large, it is possible to use the holes (3a) (3b) of the optimum size, shape, and arrangement obtained in the small-scale experiment. Therefore, it is possible to obtain a fine particle dispersion having the same particle size distribution even when the treatment amount is increased.

Further, the flow pipe (2) and the plate bodies (3a) (3b)
There is no particular limitation on the material of the. It is desirable to select from various iron and steel materials, plastic materials and other materials in consideration of the chemical properties of fluid, wear resistance, operating temperature and pressure, production cost and the like.

In the flow pipe type tube type emulsification device (1),
When two or more sets of static emulsifying and dispersing elements (3) are used, there is no particular limitation on the interval between the sets, and they may be in contact with each other or may be provided with a gap. Further, it is also possible to connect a plurality of flow pipe type tube type emulsification device (1) in series or in parallel, the Kenix type for the purpose of further mixing between the flow pipe type pipe type emulsification device (1) It is also possible to install static mixers of different mixing methods such as. Furthermore, it is also possible to supply the fluid that has passed through the flow tube type tube emulsification device (1) again to the flow tube type tube emulsification device (1) and repeat the treatment with the same device.

In the present invention, the speed at which the fluid passes through the minimum cross-sectional area of the hole is preferably 5 m / sec or more. Further, it is desirable that the speed is 15 m / sec or more. Since this device can generate a fine particle dispersion by utilizing the dispersing force of collision, shear, and jet, it is desirable to flow the fluid at a high speed. Therefore, at a flow velocity of less than 5 m / sec, it is not possible to obtain a sufficient emulsifying / dispersing power to form a fine particle dispersion. On the other hand, as the flow rate is increased, a finer emulsified dispersion can be obtained.
When the flow velocity exceeds 0 m / sec, excessive pressure loss occurs, so 100 m / sec or less is preferable.

As the liquid non-aqueous substance applicable to the present invention, any substance can be used as long as it is insoluble in a liquid aqueous substance used for emulsification, such as a low-viscosity liquid substance, a high-viscosity liquid substance, a semi-solid substance and a hot melt material. Can also be used. For example, hydrocarbon-based oils, natural or synthetic oils such as modified hydrocarbons, vegetable oils such as soybean oil, monomers such as styrene and (meth) acrylic acid ester, plasticizers such as phthalate ester, and phenols Examples thereof include antioxidants, liquid rubbers, liquid resins and the like, but are not particularly limited thereto.

The viscosity of these liquid non-aqueous substances is not particularly limited, but when used as a dispersion liquid which is an emulsified particle phase, in order to obtain a stable fine particle dispersion, 10,0
It is desirable that the pressure is 00 mPa · s or less. When used as a dispersion medium that is a continuous phase, 5,000 mPa ·
It is preferably s or less. If it is 5,000 mPa · s or more, it becomes difficult to supply the liquid at a desired flow rate to the static emulsifying and dispersing element within the operating pressure normally used.

On the other hand, as the liquid aqueous substance applied to the present invention, various kinds of water such as industrial water and ion-exchanged water, and salts containing water as a main component, bases, inorganic acids, organic acids, alcohols and the like are dissolved. An aqueous solution and the like can be mentioned. Any substance can be used as long as it is a liquid substance containing water as a main component which is insoluble in the liquid non-aqueous substance used for emulsification.

Among the surfactants applicable to the present invention, the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxy. Examples thereof include ethylene sorbitan alkyl esters and the like, and mixtures thereof, but are not particularly limited thereto. Examples of the anionic surfactant include fatty acid salts, higher alcohol sulfate ester salts, liquid fatty oil sulfate ester salts, sulfate salts of aliphatic amines and aliphatic amides, fatty alcohol phosphate ester salts, dibasic aliphatic esters. Examples thereof include, but are not limited to, sulfonic acid salts, fatty acid amide sulfonic acid salts, alkylallyl sulfonic acid salts, formalin-condensed naphthalene sulfonic acid salts, and mixtures thereof.

Further, it is possible to use a combination of a plurality of kinds of surfactants and a combination of a nonionic surfactant and an anionic surfactant.

When the dispersion is a liquid non-aqueous substance and the dispersion medium is a liquid aqueous substance, and when an oil-in-water type (O / W type) emulsion dispersion is prepared, a nonionic surfactant is used as a surfactant. One or more agents and anionic surfactants are used. In the case of nonionic surfactants, the HLB value is 8
It is desirable to use the above. On the contrary, when the dispersion is a liquid water-based substance and the dispersion medium is a liquid non-aqueous substance, that is, in the case of preparing a water-in-oil type (W / O type) emulsion dispersion, a nonionic surface active agent is used. At least one of an active agent and an anionic surfactant is used. In the case of a nonionic surfactant, it is desirable to use one having an HLB value of 6 or less. In addition, in any combination, the capacity of the dispersion medium is preferably equal to or larger than the capacity of the dispersion liquid in terms of good dispersion efficiency.

In this emulsification / dispersion operation, the method of mixing the dispersion medium, the dispersion liquid, and the surfactant is not particularly limited. For example, various emulsification methods such as a method of emulsifying and dispersing the dispersion liquid and the surfactant in the dispersion medium, a method of gradually adding the dispersion medium to the mixed liquid of the dispersion liquid and the surfactant and performing phase inversion emulsification are used. You can

In addition to the liquid non-aqueous substance, liquid aqueous substance and surfactant described above, if necessary, such as a defoaming agent, a polymerization inhibitor, and a filler, which do not adversely affect the emulsification operation, and if necessary, It can be added appropriately.

Further, it is preferable to heat at least one of the dispersion liquid, the dispersion medium and the surfactant to a temperature above the boiling point under atmospheric pressure, and then to supply to the flow pipe type tube type emulsifying apparatus to improve the dispersion efficiency. Can be increased.

[0054]

EXAMPLES Next, the present invention will be described in detail with reference to Examples. Various physical properties were measured according to the following methods.
Further, parts and% mean parts by weight and% by weight unless otherwise specified. [1] Measurement of volume average particle diameter (median diameter); transmittance of 85 with a particle size distribution measuring device LA-300 manufactured by Horiba Ltd.
The volume-based particle size distribution was measured under the conditions of ˜95%, circulation speed 5, and number of data acquisitions 10 times to determine the volume average particle diameter and standard deviation. Unless otherwise stated in the examples, the value obtained by this measuring method is meant. [2] HLB value: The numerical value described by the manufacturer was used. [3] Viscosity: Based on data measured by a B-type viscometer. (Embodiment 1) In the configuration of Manufacturing Process Example-1 shown in FIG. 4, a flow pipe shown in FIG.
In the middle of (2), the holes (21a) (21b) of the punch type structure shown in FIG.
One set of static emulsifying and dispersing element (20), which was a combination of two plate bodies (20a) and (20b) in which was drilled, was installed. The dimensions of each device used are as follows.

Length of flow pipe (2) (L); 150 mm Inner diameter of flow pipe (D); 18 mm Space between plates (l); 0 (contact state) Reduced diameter of holes (21a) (21b) Diameter of (22a) (22b) (d2); 2
mm Opening diameter of hole (21a) (21b) (d3); 6mm Thickness of plate (20a) (20b) (t2); 5mm Hole interval (X2); 6mm Taper of hole (21a) (21b) Length (y1); 2 mm Length of reduced diameter portions (22a) (22b) (y2); 1 mm Minimum cross-sectional area of hole (cross-sectional area of reduced diameter portions (22a) (22b));
Overlapping area ratio of 126 cm ² holes: 72.8% (21a), 36.4% (21
a ') Angle of the stationary emulsifying and dispersing element (20); perpendicular to the flow direction Into the tank T1, 17 L of 25 ° C. ion-exchanged water of a liquid water-based substance is charged as a dispersion medium, and in the tank T2 is a liquid non-aqueous substance as a dispersion liquid. 25 ℃ white squeezing oil (viscosity 50mPa · s) 1
After adding 0 kg, a nonionic surfactant at 25 ° C .; polyoxyethylene sorbitan monooleate (manufactured by Kao Corporation;
Leodol Super TW-O120, HLB value; 15) 3
kg was added and mixed well by stirring.

Ion-exchanged water is supplied to the emulsifying device at a flow rate of 7.9 L / min by the pump P1 and the white squeezing oil and the surfactant mixed solution are similarly emulsified at a flow rate of 6.1 L / min by the pump P2. It was supplied to the apparatus to prepare an O / W type emulsion dispersion liquid. At this time, the flow velocity passing through the minimum cross-sectional area portion (reduced diameter portions (22a) (22b)) of the hole is 18.5 m / se.
c, the differential pressure was 0.5 MPa.

In the prepared emulsified dispersion, the emulsified dispersed particles had a volume average particle size of 4.1 μm and a standard deviation of 3.1 μm.
It was m. (Second Embodiment) The supply flow rate of the pump P1 of the first embodiment is set to 15.
8 L / min, the supply flow rate of the pump P2 was changed to 12.2 L / min, and the emulsified dispersion was prepared under the same conditions. At this time, the flow velocity in the minimum cross-sectional area of the hole is 37 m
/ Sec, the differential pressure was 2 MPa.

The volume average particle diameter of the obtained emulsion dispersion was 2.5 μm and the standard deviation was 1.7 μm. (Third Embodiment) The supply flow rate of the pump P1 of the first embodiment is set to 31.
The emulsified dispersion liquid was prepared under the same conditions except that the supply flow rate of the pump P2 was changed to 6 L / min and 24.4 L / min. At this time, the flow velocity in the minimum cross-sectional area of the hole is 74 m
/ sec, the differential pressure was 6.5 MPa.

The volume average particle diameter of the obtained emulsion dispersion was 1.4 μm, and the standard deviation was 1.0 μm.

Finer particles could be obtained by increasing the flow velocity in the minimum cross-section area. (Examples 4, 5, and 6) Instead of the white squeezing oil of the liquid non-aqueous substance of Example 1, 25 ° C castor oil (viscosity 700 mPa · s) was used, and the others were the same as those of Examples 1, 2 and 3, respectively. An emulsion dispersion was prepared under the conditions. The volume average particle size and standard deviation of each emulsion dispersion are shown in Table 1 together with the results of Examples 1 to 3.

As in the case of white squeezing oil, the particle size becomes smaller as the flow velocity in the minimum cross-section area is increased, and the standard deviation of the volume average particle size is 2 μm or less is small, and a stable emulsion dispersion having a sharp particle size distribution is obtained. I was able to get it. (Example 7) Static dispersive element used in Example 1
Instead of (20), one set of static emulsifying and dispersing element (10), which is a combination of two plate bodies (10a) and (10b) having holes (11a) and (11b) of constant diameter shown in FIG. did. The dimensions of each part are as follows.

Hole spacing (x1); 6 mm Diameter of holes (11a) (11b) (d1); 2 mm Plate thickness (t1) of plates (10a) (10b); 5 mm Plates (10a) (10b) Interval (l); 2 mm Angle of static emulsifying and dispersing element (10); Overlapping area ratio of right-angled holes (11a) with respect to the flow direction; 0% Other than that, emulsifying and dispersing test was conducted under the same conditions as in Example 1. did. The flow velocity in the minimum cross-sectional area at that time is 18.5 m
/ Sec, the differential pressure was 1 MPa. The obtained emulsion dispersion has a volume average particle diameter of 5.2 μm and a standard deviation of 4.3 μm.
It was m. (Embodiment 8) A test was conducted using equipment having the configuration of Manufacturing Process Example-2 shown in FIG. As the flow pipe type emulsification device, the same flow pipe (2) and static dispersion element (20) as in Example 1 were used.

60 L of 90 ° C. ion-exchanged water was added to the tank T1 as a dispersion medium, 300 g of KOH was added, and they were sufficiently mixed. Wingstay L (WSL) manufactured by Goodyear Co., which was heated to 120 ° C. and dissolved in tank T2 as a dispersion liquid.
10 kg was added, and 0.5 kg of oleic acid as an anionic surfactant was added and mixed well (viscosity 1,000 m
Pa · s). The ion exchange water is supplied to the emulsifying device at a flow rate of 9.2 L / min by the pump P1, and M
The ion-exchanged water was heated to 120 ° C with 1 steam mixer, and the operation was continued while being cooled to 90 ° C with the C1 cooler, and then 4.8 L / with the pump P2.
The wing stay L (WS
The L) -oleic acid mixed solution was supplied to prepare an O / W type emulsion. The flow velocity in the minimum cross-section area is 18.5 m / s
ec, the differential pressure was 0.5 MPa. As a result, the volume average particle diameter of the obtained emulsion dispersion was 1.8 μm, and the standard deviation was 1.0 μm. The results are shown in Table 2.

Even when the melting point of the non-aqueous substance is higher than the boiling point of the aqueous substance at 100 ° C. under atmospheric pressure, by combining the present emulsifying apparatus with the steam heater and cooler,
The emulsion dispersion could be prepared by a method that is economically advantageous and capable of mass production. (Embodiment 9) Using the equipment having the configuration of manufacturing process example 3 shown in FIG.
The same flow pipe (2) and static dispersion element (20) were used, and the same liquid type and the same amount of the dispersion medium and the dispersion liquid as in Example 1 were introduced into the tanks T1 and T2.

With the pump P1, the ion-exchanged water 31.
After passing through the emulsifier at a flow rate of 6 L / min, the circulation operation returning to T1 was started. After that, the white squeezing oil-surfactant mixed liquid was supplied to the emulsification device at a flow rate of 24.4 L / min by P2 to start preparation of the emulsified dispersion liquid. When the dispersion liquid in the tank T2 is exhausted, P2 is stopped, the flow rate of P1 is increased to 56 L / min, and T1 → P for another 5 minutes.
After continuing the circulation operation of 1 → emulsifier → T1, P1 was stopped and the emulsification / dispersion operation was completed. The flow velocity in the minimum cross-sectional area part was 74 m / sec, and the differential pressure was 6.5 MPa. As a result, the volume average particle diameter of the obtained emulsion dispersion was 0.7.
μm, and the standard deviation was 0.24 μm. The results are shown in Table 2.

It was possible to prepare a very fine and stable emulsion by repeatedly emulsifying the emulsion through the present emulsifying apparatus. (Example 10) In Example 1, two sets of static emulsifying and dispersing elements (20) having the structure shown in FIG. 3 were provided in the center of the flow pipe (2) as a flow pipe type tube-type emulsification device without leaving a space between them. An emulsification dispersion test was performed under the same conditions as in Example 1 except that the apparatus was installed. The flow velocity in the minimum cross-section area is 18.5m /
sec, the differential pressure was 0.8 MPa. As a result, the volume average particle diameter of the obtained emulsion dispersion was 3.5 μm, and the standard deviation was 2.9 μm. The results are shown in Table 2. (Embodiment 11) In the equipment having the configuration of Manufacturing Process Example-4 shown in FIG. 7, the same flow pipe (2) and static emulsification dispersion element (20) as those of the first embodiment are used as a flow pipe type tube type emulsification device.
Was used to carry out an emulsion dispersion test.

5 L of 60 ° C. ion-exchanged water was added to the tank T1 as a dispersion medium, and 60 ° C. as a dispersion liquid in the tank T2.
Castor oil 3 kg (viscosity 60 mPa · s) and nonionic surfactant at 60 ° C .; polyoxyethylene sorbitan monooleate (manufactured by Kao Corporation; Leodol Super TW-O12)
0, HLB value; 15) 0.9 kg was added and thoroughly mixed by stirring. The pump P2 was started, and circulation was started in which the dispersion liquid in the tank T2 was returned to the tank T2 via the emulsifier at a flow rate of 14 L / min. Open the lower cock of the tank T1 slightly, and add 1.5 kg of ion-exchanged water in T1 to about 5
Add to tank T2 over minutes. After the viscosity of the dispersion liquid increased on the way, phase inversion occurred and the emulsion became an O / W type emulsion. While continuing the circulation operation, the remaining 3.5 kg of ion-exchanged water was added to complete the preparation of the emulsion dispersion. The flow velocity in the minimum cross-section area at that time is 18.5 m / se.
c, the differential pressure was 1 MPa. As a result, the volume average particle diameter of the obtained emulsion dispersion was 1.2 μm, and the standard deviation was 0.
It was 62 μm. The results are shown in Table 2.

The differential pressure was 1 MPa during the circulation operation of castor oil alone, but increased before the phase inversion and became around 1 MPa again after the completion of the phase inversion. (Example 12) An emulsion dispersion test was conducted using the same equipment as in Example 1. 9 L of 40 ° C. C heavy oil (180 mPa.sec) of liquid non-aqueous substance as a dispersion medium in tank T1
After adding, a nonionic surfactant (polyoxyethylene nonylphenyl ether, EO addition mole number is 3) 20
0 g was added and thoroughly stirred to dissolve. On the other hand, 1 kg of 40 ° C. ion-exchanged water, which is a liquid water-based substance, was added to the tank T2 as a dispersion liquid. 12.6 L / m by pump P1
A mixture of C heavy oil and a nonionic surfactant is supplied to the emulsification device at a flow rate of in, and 1.4 L /
Ion-exchanged water is supplied to the emulsifier at a flow rate of min, and W /
An O type emulsion dispersion was prepared. At that time, the flow velocity in the minimum cross-section area was 18.5 m / sec, and the differential pressure was 1.2 MPa.
Met. The volume average particle diameter of the emulsified dispersion liquid obtained from the micrograph was 4.8 μm, and the standard deviation was 3.5 μm.
The results are shown in Table 2. (Comparative Example 1) An emulsified dispersion was prepared using the stirring device (40) shown in FIG. The dimensions of the stirring device (40) used are shown below.

Inner diameter (r1) of stirring tank (41); 100 mm Height of stirring tank (41) (h1); 250 mm Type of stirring blade (42); Six-disc turbine blade 1-stage blade diameter (r2): 50 mm , Vane size: Length 12 mm x Width 8 mm Blade set height (h2); 12 mm from bottom Baffle condition: 6 mm flat plate baffle x 4 Dispersion medium 25 ° C ion exchange water 300 mL is added to the stirring tank (4
It was added to 1) and stirring was started at a rotation speed of 500 rpm. Non-ionic surfactant polyoxyethylene sorbitan monooleate (manufactured by Kao Co .; Leodol Super TW-O120, HLB value;
5) A liquid of 25 ° C. to which 54 g was added and mixed was slowly added, and after the addition was completed, the rotation speed was increased to 700 rpm and stirring was continued for 5 minutes, and then the test was terminated. As a result, the volume average particle diameter of the obtained emulsion dispersion was 15.8 μm, and the standard deviation was 26.4 μm. The results are shown in Table 3. The obtained emulsion was unstable, and when left standing, phase separation occurred in a short period of time. (Comparative Example 2) The white squeezing oil in Comparative Example 1 was changed to castor oil, and the emulsification and dispersion test was carried out under the same conditions as in Comparative Example 1. As a result, the volume average particle diameter of the obtained emulsion dispersion was 38.3 μm, and the standard deviation was 55 μm. The results are shown in Table 3.

The obtained emulsion was unstable, and when left standing, phase separation occurred in a short period of time. Comparative Example 3 Using the same stirring tank (41) as in Comparative Example 1, an experiment by the phase inversion emulsification method was conducted as follows.

Stirring tank (200 g of white squeezing oil at 25 ° C. was added to 41, 60 g of nonionic surfactant Rheodor Super TW-O120 at 25 ° C. was added, and stirring was started at 500 rpm. 80g out of 340g
Was slowly added, the rotation speed was increased to 700 rpm, and stirring was continued for 5 minutes.

Thereafter, the remaining 260 g of ion-exchanged water was added, stirring was continued for 5 minutes after the addition was completed, and the experiment was terminated.
As a result, the volume average particle diameter of the obtained emulsion dispersion is 1
It was 8.3 μm and the standard deviation was 10.9 μm. The results are shown in Table 3.

The obtained emulsion was unstable, and when left standing, phase separation occurred in a short period of time. (Comparative Example 4) An emulsion dispersion test was conducted under the same conditions as in Comparative Example 3 except that the white squeezing oil in Comparative Example 3 was changed to castor oil. As a result, the volume average particle diameter of the obtained emulsion dispersion was 3.1 μm, and the standard deviation was 1.7 μm. The results are shown in Table 3. (Comparative Example 5) As a flow tube type tube-type emulsifying apparatus in Example 1, plate bodies (20a) having different positions of the holes (21a) (21a ') (21b)
Instead of the set of static emulsifying and dispersing element (20) consisting of (20b), a static emulsifying and dispersing element consisting of two plates (20a) and (20a) of the same structure is used. That is, the overlapping area ratio of the holes is 100%. An emulsification dispersion test was conducted under the same conditions as in Example 1 except for the above.

As a result, the emulsion dispersion thus obtained had a volume average particle diameter of 6.5 μm and a standard deviation of 5.7 μm.
In this example, since the overlapping area ratio is 100%, the standard deviation is large. That is, it became a dispersion liquid containing large particles. Therefore, if left alone, the amount was small in a short period of time, but phase separation occurred. The results are shown in Table 3. At this time, the flow velocity in the minimum cross-sectional area of the hole is 18.5 m / sec,
The differential pressure was 0.3 MPa.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

As described above, according to the method for producing an emulsified dispersion of the present invention, one plate is provided with two plate bodies each having a plurality of holes formed in the plate thickness direction inside the flow pipe. The static emulsifying and dispersing element in which the area ratio of the portion where the hole portion of the body overlaps the hole portion of the other plate is 90% or less is 1
Using a flow pipe type tube emulsification device which is arranged more than one set, in the flow pipe type pipe type emulsification device, a dispersion liquid which becomes an emulsified particle phase,
A continuous phase dispersion medium and a surfactant are supplied, and since these fluids are to flow through the pores of the static emulsification dispersion element at high speed, the droplet breaking force due to liquid collision,
Emulsion dispersion treatment can be performed by the cavitation action by the jet flow and the excellent dispersion force and stirring force due to the shearing force when splitting into the holes, and it is possible to produce a uniform emulsion dispersion having a fine particle size and a high concentration. . Moreover, the apparatus required for the treatment has a simple structure in which a static emulsifying and dispersing element is arranged in the flow pipe, and since it is a simple process of circulating the material fluid at a high speed, mass production of the emulsified dispersion liquid described above. Is possible.

Further, when the hole of the plate has a circular cross section and a taper shape with a reduced diameter portion formed in the middle portion in the plate thickness direction, the fluid becomes more turbulent. Thus, the fine particles can be dispersed more finely.

When the velocity at which the fluid passes through the minimum cross-sectional area of the hole is 5 m / sec or more, a particularly high dispersion force due to the above-mentioned collision, shear, and jet flow can be obtained.

When the two plates are combined at a predetermined distance in the plate thickness direction, a strong shearing force at the time of flowing through the gap is added to the above-mentioned dispersion force due to collision, shearing, and jet flow, Dispersion power can be increased. Further, they may be combined in a contact state in the plate thickness direction.

As an example of a fluid that can be preferably used in the present invention, the dispersion liquid is a liquid non-aqueous substance, the dispersion medium is a liquid aqueous substance, and the surfactant is a nonionic surfactant and an anionic substance. One or more of the ionic surfactants can be exemplified. Alternatively, the dispersion liquid may be a liquid aqueous substance, the dispersion medium may be a liquid non-aqueous substance, and the surfactant may be one or more of a nonionic surfactant and an anionic surfactant. By combining these, it is possible to produce a uniform emulsion dispersion having a fine particle size and a high concentration.

When the volume of the dispersion medium is equal to or larger than the volume of the dispersion liquid, it is possible to produce a uniform emulsion dispersion having a particularly fine particle size and a high concentration.

Further, when at least one of the dispersion liquid, the dispersion medium and the surfactant is heated to a temperature exceeding the boiling point under atmospheric pressure and then supplied to the flow tube type tubular emulsification apparatus,
It is possible to obtain a high dispersion and obtain a uniform emulsion dispersion having a particularly high particle size and a high concentration.

Furthermore, when the fluid that has passed through the flow tube type tubular emulsifying device is supplied again to the flow tube type tubular emulsifying device, a uniform emulsion dispersion having a particularly fine particle size and a high concentration is obtained. Manufacture

[Brief description of drawings]

FIG. 1 is a partially cutaway perspective view showing an example of a flow pipe type tube-type emulsification device used in a method for producing an emulsion dispersion of the present invention.

FIG. 2 is a diagram showing an example of a static emulsifying and dispersing element, (A) is a plan view of an upstream plate and a sectional view taken along line 2A-2A, and (B) is a plan view of a downstream plate. 2B-2
The sectional view taken on the line B, (C) are a plan view and a sectional view taken on the line 2C-2C showing a combined state of the two sheets.

FIG. 3 is a view showing another example of a static emulsifying and dispersing element, (A) is a plan view of an upstream plate and 3A-3A.
A line sectional view, (B) is a plan view of the plate body on the downstream side and 3B-
FIG. 23 is a sectional view taken along line 23C, and FIG. 23C is a plan view showing a combined state of two sheets and a sectional view taken along line 3C-3C.

FIG. 4 is a block diagram showing Example-1 of the manufacturing process of the method for manufacturing an emulsified dispersion according to the present invention.

FIG. 5 is a block diagram showing Example-2 of the manufacturing process of the method for manufacturing an emulsified dispersion according to the present invention.

FIG. 6 is a block diagram showing Example-3 of the production process of the method for producing an emulsified dispersion according to the present invention.

FIG. 7 is a block diagram showing Example-4 of the production process of the method for producing an emulsified dispersion according to the present invention.

FIG. 8 is a view schematically showing a stirring tank for emulsifying and dispersing.

[Explanation of symbols]

1 ... Flow tube type tube emulsifier 2 ... Distribution pipe 3,10,20 ... Stationary emulsifying dispersion element 3a, 3b, 10a, 10b, 20a, 20b ... Plate 4a, 4b, 11a, 11b, 21a, 21a ', 21b ... hole 22a, 22b ... Reduced diameter

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Katsutoshi Koji             2-3-2 Selling Moat, Nishi-ku, Osaka City, Osaka Prefecture F-term (reference) 4G035 AB40 AB54 AC26 AE13 AE15                 4G037 CA11 EA01

Claims (10)

[Claims] 1. A flow tube, wherein two plate members each having a plurality of holes formed in the plate thickness direction are provided in a portion where the hole of one plate overlaps the hole of the other plate. The static emulsifying and dispersing element combined so that the area ratio is 90% or less,
Using a flow tube type tube emulsification device provided with one or more sets, the flow tube type tube type emulsification device is supplied with a dispersion liquid as an emulsified particle phase, a dispersion medium as a continuous phase and a surfactant, A method for producing an emulsified dispersion, wherein these fluids are circulated at high speed through the pores of the stationary emulsion dispersion element. 2. The emulsified dispersion according to claim 1, wherein the hole of the plate has a circular cross-sectional shape and a tapered shape in which a reduced diameter portion is formed at an intermediate portion in the plate thickness direction. Manufacturing method. 3. The method for producing an emulsified dispersion according to claim 1, wherein the fluid is passed through the minimum cross-sectional area of the hole at a speed of 5 m / sec or more. 4. The method for producing an emulsified dispersion according to claim 1, wherein the two plate bodies are combined at a predetermined distance in the plate thickness direction. 5. The method for producing an emulsified dispersion according to claim 1, wherein the two plates are combined in a contact state in the plate thickness direction. 6. The dispersion liquid is a liquid non-aqueous substance, the dispersion medium is a liquid aqueous substance, and the surfactant is at least one of a nonionic surfactant and an anionic surfactant. The method for producing an emulsified dispersion according to any one of claims 1 to 5. 7. The dispersion liquid is a liquid aqueous substance, the dispersion medium is a liquid non-aqueous substance, and the surfactant is at least one of a nonionic surfactant and an anionic surfactant. The method for producing an emulsified dispersion according to any one of claims 1 to 5. 8. The method for producing an emulsified dispersion according to claim 1, wherein the capacity of the dispersion medium is not less than the capacity of the dispersion. 9. The method according to claim 1, wherein at least one of the dispersion liquid, the dispersion medium and the surfactant is heated to a temperature above the boiling point under atmospheric pressure and supplied to the flow tube type tube emulsification device. The method for producing an emulsified dispersion according to. 10. The fluid flowing through the flow-through tube type tube emulsification device is supplied to the flow-through tube type tube emulsification device again.
9. The method for producing an emulsified dispersion according to item 9.