JP6596640B1 - Method for producing composite microemulsions - Google Patents

Abstract

The present invention provides an emulsification technique that can be expected to broaden the range of selection of materials to be emulsified to be emulsified with water in producing a microemulsion. A microemulsion intermediate in which a first oil phase component is dispersed as particles in an aqueous dispersion medium, and the specific surface area of the first oil phase component relative to the microemulsion intermediate is 1. A compounding step of adding and mixing the second oil phase component to be emulsified to the microemulsion intermediate of 0.0 × 104 cm 2 / g or more and mixing the mixture with the first oil phase component. A method for producing a composite microemulsion is provided. [Selection figure] None

Description

  The present invention relates to a method for producing a composite microemulsion.

  Emulsions (emulsions) are particles in which other liquids are dispersed in a liquid dispersion medium, and are used in various fields such as food, cosmetics, pharmaceuticals, adhesives, adhesives, paints, and inks. Widely used. Emulsions are broadly classified into oil-in-water (O / W) emulsions in which oil droplets are dispersed in water and water-in-oil (W / O) emulsions in which water droplets are dispersed in oil.

  As a method for producing an emulsion in which a dispersoid is finely dispersed in a dispersion medium, a shearing force is applied to a mixed liquid to be an emulsion by a mechanical stirring force such as a homomixer or a stirring homogenizer, to form droplets. The method of dispersing as fine particles has become industrially mainstream. As an apparatus used for the production of the emulsion, there are a high-speed homogenizer and an ultrasonic homogenizer in addition to the high-speed agitator using the mechanical agitation force described above (see, for example, Patent Documents 1 to 3).

  In recent years, there has been a demand for an O / W type emulsion in which a dispersoid (oil phase) is dispersed in an aqueous dispersion medium (aqueous phase) in a finer and more uniform state. Generally, in the mechanical emulsification method using the above-mentioned homomixer or homogenizer, it is difficult to reduce the average particle size of the dispersoid in the O / W emulsion to nano size, Often requires enormous energy. On the other hand, as a method that can produce a microemulsion with high efficiency without requiring such long-time treatment and enormous energy, it is possible to dissolve supercritical water or subcritical water with a water-insoluble substance. There have been proposed methods for producing microemulsions (see Patent Documents 4 and 5).

JP 2003-147201 A JP 2009-261929 A JP-A-2015-134341 JP 2013-0395547 A JP 2018-176044 A

  According to the disclosures of Patent Documents 4 and 5, an emulsification method using supercritical water or subcritical water (hereinafter sometimes referred to as “supercritical / subcritical emulsification method”) is 10 seconds to several tens of seconds. Since it is possible to obtain a microemulsion in a very short time such as seconds or even several seconds to several tens of seconds, it can be said that this is a very useful technology in the industry.

  On the other hand, in the supercritical / subcritical emulsification method, water is insoluble because water brought into contact with water insoluble under temperature and pressure conditions near the critical point of water (ie, subcritical to supercritical state). Substances will also be used at very high temperature conditions. In addition, when the treatment for refining the dispersoid to nano size by the mechanical emulsification method described above is performed, heat is gradually applied to the oil phase component forming the dispersoid due to high shear force, high pressure, ultrasonic waves, and the like. If the temperature is accumulated and a sufficient cooling time is not provided for each process, the temperature rises. Therefore, when it is intended to efficiently produce nano-sized microemulsions, there is a situation where it is difficult to use a low heat-resistant substance that decomposes at high temperatures.

  Therefore, the present invention intends to provide an emulsification technique that can be expected to expand the range of selection of materials to be emulsified to be emulsified with water when producing a microemulsion.

According to the present invention, a microemulsion intermediate in which a first oil phase component is dispersed as particles in an aqueous dispersion medium, the specific surface area of the first oil phase component with respect to the microemulsion intermediate. A second oil phase component to be emulsified is added to and mixed with the microemulsified intermediate having a viscosity of 1.0 × 10 ⁴ cm ² / g or more, and is combined with the first oil phase component. A method for producing a composite microemulsion comprising a composite step is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the emulsification technique which can anticipate the breadth of selection of the material used as the emulsification object emulsified with water in manufacturing a microemulsion can be provided.

It is the schematic showing an example of the manufacturing apparatus of the micro emulsion intermediate used in the manufacturing method of the composite micro emulsion of one Embodiment of this invention. It is a typical schematic flowchart of an example of the apparatus which can perform the manufacturing method of the composite microemulsion of one Embodiment of this invention. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained by manufacture example 1. FIG. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained by manufacture example 2. FIG. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained by manufacture example 3. FIG. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained in manufacture example 4. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained by manufacture example 5. FIG. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained by manufacture example 6. FIG. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained by manufacture example 7. It is a figure which shows the particle size distribution of the microemulsion intermediate body obtained in manufacture example 8. It is a figure which shows the particle size distribution of the emulsion intermediate body in the comparative example 5. 1 is a graph showing the particle size distribution of a composite microemulsion obtained in Example 1. FIG. 2 is a graph showing the particle size distribution of the composite microemulsion obtained in Example 2. FIG. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 3. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 4. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 5. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 6. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 7. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 8. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 9. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 10. 6 is a graph showing the particle size distribution of the composite microemulsion obtained in Example 11. FIG. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 12. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 13. It is a figure which shows the particle size distribution of the composite microemulsion obtained in Example 14. It is a figure which shows the particle size distribution of the emulsion obtained in the comparative example 5. It is a figure which shows the particle size distribution of the composite micro resin emulsion obtained in Example 15. It is a figure which shows the particle size distribution of the composite micro resin emulsion obtained in Example 16.

  Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

  The method for producing a composite microemulsion according to one embodiment of the present invention (hereinafter sometimes simply referred to as “the present method”) produces a microemulsion in which an oil phase component is dispersed as particles in an aqueous dispersion medium. On how to do. “Fine” in the fine emulsion means that the particles formed of the oil phase component are fine. The “microemulsions” are emulsions (emulsions) in which the oil phase component is finely dispersed as particles in an aqueous dispersion medium, and preferably nano-sized particles (within an average particle diameter of 1 nm or more and less than 1000 nm). It is a dispersed nanoemulsion.

This method includes the step of adding and mixing the second oil phase component to be emulsified to the microemulsion intermediate in which the first oil phase component is dispersed as particles in the aqueous dispersion medium. In this step, the second oil phase component is added to the microemulsion intermediate in which the specific surface area of the first oil phase component relative to the microemulsion intermediate is 1.0 × 10 ⁴ cm ² / g or more. Mix. The second oil phase is added to the first oil phase component (particles) in the microemulsion intermediate by adding and mixing the second oil phase component to the microemulsion intermediate having the specific surface area. The components can be combined. Therefore, the above process is referred to as a compounding process. By this complexing step, the second oil phase component is finely dispersed (preferably nano-sized) in the aqueous dispersion medium in a state of being complexed with the first oil phase component in the microemulsion intermediate. Can do. Therefore, a composite microemulsion in which particles containing the first oil phase component and the second oil phase component are finely dispersed in the aqueous dispersion medium can be obtained by the above-described complexing step.

  The term “microemulsion intermediate” is a term for distinguishing from a microemulsion obtained by the present method (referred to as “composite microemulsion” in the present disclosure). Represents the former microemulsion used to obtain The “aqueous dispersion medium” means a dispersion medium containing at least water. Furthermore, the “oil phase component” means a component that forms a phase (dispersoid) dispersed in an aqueous dispersion medium, and is a term used for the “aqueous dispersion medium”. It is not a word meaning only what is called. The aqueous dispersion medium and each oil phase component will be described later.

The complexing step in the present method is due to the discovery as a result of the study by the present inventors. That is, according to the study by the present inventors, when the specific surface area of the first oil phase component in the microemulsion intermediate is 1.0 × 10 ⁴ cm ² / g or more, Even if it is not a high temperature condition, specifically, the first oil phase component (particles) in the microemulsion intermediate even at 100 ° C. or lower (for example, 5 to 100 ° C.) or even at room temperature (5 to 35 ° C.) However, it has been found that the second oil phase component efficiently absorbs and grows. From this viewpoint, the microemulsion intermediate having the specific surface area may be referred to as a growth microemulsion. The first oil phase component (particles) in the microemulsion intermediate is more than the second oil phase component (second oil phase component before addition) that is refined (preferably nanosized) by the compounding step. Usually, it is fine (preferably nano-sized) and small in size. When the relatively small size is considered to be absorbed by the relatively large size, the first oil phase component has a larger specific surface area than the second oil phase component. It is considered that the second oil phase component can be absorbed.

  As described above, the second oil phase component to be emulsified in the compounding step can be combined with the first oil phase component without requiring high temperature conditions exceeding 100 ° C. Thereby, it can be finely dispersed (preferably nano-sized) in the aqueous dispersion medium. Therefore, as described above, there are also substances having low heat resistance that are difficult to use in the supercritical / subcritical emulsification method or the method in a case where the miniaturization to the nano size is performed in a short time by the mechanical emulsification method. It can be suitably used as the second oil phase component. Therefore, it can be expected that the range of selection of the material to be emulsified with water is expanded by this method.

In the compounding step, the target to which the second oil phase component is added is a microemulsion intermediate in which the specific surface area of the first oil phase component relative to the microemulsion intermediate is 1.0 × 10 ⁴ cm ² / g or more. Is the body. The specific surface area (cm ² / g) is the surface area (cm ² ) of the first oil phase component dispersed as particles per unit mass (g) of the microemulsion intermediate. This specific surface area (cm ² / g) takes a value calculated theoretically as described below, assuming that the first oil phase component contained as particles in the microemulsion intermediate is a sphere. Can do.

The surface area per unit mass of a certain object (sphere) (specific surface area of the object) Sm is expressed as Sm = S / (ρ × V) where V is the volume of the object, ρ is the density, and S is the surface area. The The volume V of the sphere is V = (4/3) × π × (D / 2) ³ where the diameter is D, and the surface area S of the sphere is S = 4 × π × (D / 2) ² . Therefore, the specific surface area Sm of the sphere is Sm = 6 / (ρ × D). Therefore, when the first oil phase component dispersed as particles in the microemulsion intermediate is regarded as a sphere, the specific surface area Sm ₁ (cm ² / g) of the first oil phase component is the first oil phase. When the particle diameter of the phase component is D ₁ (cm) and the density of the first oil phase component is ρ ₁ (g / cm ³ ), Sm ₁ = 6 / (ρ ₁ × D ₁ ). Therefore, when the content (concentration) of the first oil phase component having the specific surface area Sm _{1 based} on the total mass of the microemulsion intermediate is C (mass%), the unit of the microemulsion intermediate The surface area of the first oil phase component per mass, that is, the specific surface area Sm _E (cm ² / g) of the first oil phase component relative to the microemulsion intermediate can be calculated from the following formula (1). .
Sm _E = 6 / (ρ ₁ × D ₁ ) × C / 100 (1)

In addition, about the particle diameter D1 of a _1st oil phase component, the average particle diameter of the 1st oil phase component in a microemulsion intermediate body is taken. In the present specification, the “average particle diameter” is a value measured at 25 ° C. by cumulant method analysis using a particle size distribution measuring apparatus using a dynamic light scattering method. Examples of the particle size distribution measuring apparatus using the dynamic light scattering method include a trade name “Dense Particle Size Analyzer FPAR-1000” manufactured by Otsuka Electronics Co., Ltd. Moreover, about the density of a 1st oil phase component, the value measured using the specific gravity cup of a 100 mL capacity | capacitance on the temperature conditions of 23 +/- 2 degreeC based on the prescription | regulation of JISK5600-2-4: 1999. Can be taken.

As shown in the above formula (1), the specific surface area (Sm _E ) of the first oil phase component based on the unit mass of the microemulsion intermediate is inversely proportional to the average particle diameter (D ₁ ) of the first oil phase component. And is directly proportional to the concentration (C) of the first oil phase component in the microemulsion intermediate. As can be seen from this relationship, the first oil phase with respect to the fine emulsion intermediate is obtained by balancing the average particle diameter (D ₁ ) and the concentration (C) of the first oil phase component in the fine emulsion intermediate. The specific surface area (Sm _E ) of the component can be 1.0 × 10 ⁴ cm ² / g or more.

The specific surface area of the first oil phase component with respect to the microemulsion intermediate is 2.0 × 10 ⁴ cm ² / g or more from the viewpoint that the second oil phase component is easily combined with the first oil phase component. It is preferably 3.0 × 10 ⁴ cm ² / g or more, and more preferably 4.0 × 10 ⁴ cm ² / g or more. The upper limit of the specific surface area is not particularly limited, but is preferably 1.0 × 10 ⁷ cm ² / g or less from the viewpoint of production of the microemulsion intermediate.

  Further, from the viewpoint of easily increasing the specific surface area, the average particle size of the first oil phase component in the microemulsion intermediate is preferably nano-sized. On the other hand, since the composite microemulsion obtained by the composite process is also preferably nano-sized, the average particle size of the first oil phase component is preferably in the range of 5 to 500 nm, and 10 to 300 nm. Is more preferably in the range of 10 to 150 nm. The average particle size of the composite microemulsion obtained by the composite process (particles containing the first oil phase component and the second oil phase component) is preferably in the range of 10 to 800 nm, and preferably 20 to 500 nm. More preferably, it is in the range, and further preferably in the range of 20 to 400 nm.

The concentration of the first oil phase component relative to the microemulsion intermediate is not particularly limited as long as the specific surface area of the first oil phase component relative to the microemulsion intermediate is 1.0 × 10 ⁴ cm ² / g or more. From the viewpoint of production of the composite microemulsion, the concentration of the first oil phase component with respect to the microemulsion intermediate is in the range of 1 to 50% by mass based on the total mass of the microemulsion intermediate. Is preferable, it is more preferable to be in the range of 5 to 50% by mass, and it is more preferable to be in the range of 5 to 40% by mass.

  The addition of the second oil phase component to the microemulsion intermediate can be performed, for example, by dropping or flowing the second oil phase component into the microemulsion intermediate. Moreover, you may make it join them in the pre-stage which mixes a microemulsion intermediate body and a 2nd oil phase component. When adding the second oil phase component to the microemulsion intermediate, only the second oil phase component (oil phase component 100% by mass) may be added, or the second oil phase component and other Mixtures with ingredients may be added. As the mixture, for example, an emulsion (pre-emulsion) obtained by emulsifying a mixture containing the second oil phase component, water, and an emulsifier can be suitably used. The average particle size of the pre-emulsion can be, for example, about a micron size, and is preferably in the range of 1 to 100 μm, more preferably in the range of 1 to 50 μm, and still more preferably in the range of 1 to 10 μm. Can do.

  The amount of the second oil phase component added to the microemulsion intermediate is the first oil in the microemulsion intermediate from the viewpoint of efficiently combining the second oil phase component with the first oil phase component. It is preferably in the range of 1 to 1000 parts by mass, more preferably in the range of 10 to 500 parts by mass, with respect to 100 parts by mass of the phase component.

  As described above, since the temperature condition for adding and mixing the second oil phase component does not need to be a high temperature condition, the second oil phase component can be widely used. From this point of view, it is preferable to add and mix the second oil phase component to the microemulsion intermediate under the condition where the temperature is in the range of 5 to 100 ° C. in the compounding step. The temperature condition is more preferably in the range of 5 to 80 ° C., further preferably in the range of 5 to 60 ° C., and particularly preferably in the range of normal temperature (5 to 35 ° C.).

  Further, the pressure condition during the compounding step in this method may be normal pressure (atmospheric pressure), but it does not require high-speed stirring and high shearing force as performed by the above-mentioned mechanical emulsification method. From the viewpoint of enabling the composite process in time, it is preferable to apply pressure in the composite process. Specifically, in the compounding step, it is preferable to add and mix the second oil phase component to the microemulsion intermediate under conditions where the pressure is in the range of 10 to 40 MPa. Thus, the second oil phase component can be applied to the first oil phase component (particles) in the microemulsion intermediate for a short time (specifically several seconds to several tens of seconds) without requiring high-speed stirring and high shearing force. ), And a composite microemulsion having a sharper particle size distribution (a more uniform particle size) can be obtained. Furthermore, when using the microemulsion intermediate obtained by the supercritical / subcritical emulsification method, the critical point (critical pressure of water 22) when the first oil phase component is contacted with supercritical water or subcritical water. .1 MPa) with the pressure in the vicinity of the resulting microemulsion intermediate being cooled, the compounding step can be carried out continuously from the production of the microemulsion intermediate to the production of the composite microemulsion. It becomes easier to do. From these viewpoints, the pressure condition is more preferably in the range of 15 to 40 MPa, and further preferably in the range of 20 to 40 MPa.

  In the compounding step, when the compounding step is performed under normal pressure (atmospheric pressure) without applying pressure, the second oil phase component is added and mixed to the microemulsion intermediate under stirring conditions. It is preferable. More preferably, while stirring the microemulsion intermediate, the second oil phase component is added thereto, and more preferably after the second oil phase component is added, the microemulsion intermediate and Stirring the mixture containing the second oil phase component. These stirring conditions are not particularly limited, and for example, the rotational speed can be in the range of 50 to 5000 rpm.

  The time during which the second oil phase component is combined with the first oil phase component in the microemulsion intermediate (combination processing time in the combining step) is set to a condition where the above pressure is not applied. Is preferably in the range of 0.5 to 5 hours, more preferably in the range of 1 to 3 hours. When applying the above-mentioned pressure in the compounding step, the compounding step can be performed in a shorter time, and the time is preferably, for example, within 5 minutes, more preferably within 1 minute, More preferably, it is in the range of 1 to 30 seconds.

  About a microemulsion intermediate body, you may prepare what was manufactured separately from this method. The microemulsion intermediate may be produced by a mechanical emulsification method using a homomixer and a homogenizer such as a stirring type, a high-pressure type, and an ultrasonic type, or supercritical / subcritical emulsification. What was manufactured by the method may be used. As described above, in this method, since the compounding step can be performed under normal temperature conditions, supercritical / subcritical emulsification performed under extremely high temperature conditions near the critical point (critical temperature of water 374 ° C.). It is preferable to apply the compounding step to the microemulsion intermediate obtained by the method. This is because, when obtaining this microemulsion intermediate, a substance that has been difficult to use by causing thermal decomposition or the like depending on temperature conditions can be used as the second oil phase component to be emulsified. .

  In this method, a microemulsion intermediate produced as a step preceding the compounding step may be used. That is, the method for producing a composite microemulsion according to one embodiment of the present invention can include a step of producing a microemulsion intermediate (a step of preparing a microemulsion intermediate) before the composite step. In the preparation step of the microemulsion intermediate, for example, the microemulsion intermediate is obtained by mechanically emulsifying a mixture containing the aqueous dispersion medium and the first oil phase component using a homomixer or various homogenizers. Can be obtained.

  In the preparation step of the microemulsion intermediate, for example, using supercritical water or subcritical water as the aqueous dispersion medium, the water in that state is compatible with the first oil phase component, By cooling in the presence of an emulsifier, a microemulsion intermediate can be obtained. Specifically, the preparation step is described as a step in which water contained in the aqueous dispersion medium and the first oil phase component are miscible in a supercritical or subcritical state of water (hereinafter referred to as “compatibility step”). And a step of cooling a compatible product of water and the first oil phase component in the presence of an emulsifier (hereinafter sometimes referred to as “cooling step”). . In the compatibilizing step, water and the first oil phase component may be combined in a subcritical state of water (subcritical water) from the viewpoint of expanding the range of selection of materials used as the first oil phase component. preferable. By performing the compounding step after the preparation step of the above-described microemulsion intermediate, the compounding step can be performed continuously and under the above-described preferred conditions of temperature and pressure. Therefore, from the production of the microemulsion intermediate to the production of the composite microemulsion, a continuous flow system is used for a short time (specifically, several tens of hours) without requiring high-speed stirring and high shearing force. Second to several minutes). In addition, a composite microemulsion with a finer particle size is obtained by performing a composite process in a continuous flow system on the microemulsion intermediate obtained by the preparation process including the compatibility process and the cooling process. It becomes easy to obtain.

  In the present specification, the supercritical state of water is a state above the critical point of water, that is, the temperature is 374 ° C. (critical temperature of water) or more, and the pressure is 22.1 MPa (critical pressure of water). This state is referred to above, and the water in this state is called supercritical water. The subcritical state of water refers to a liquid state having a temperature slightly lower than the critical point of water, and the water in this state is referred to as subcritical water. The subcritical water is, for example, water having a temperature of preferably 200 ° C. or higher, more preferably 250 ° C. or higher and lower than 374 ° C., and a pressure of preferably 20 to 30 MPa, more preferably 20 to 25 MPa. Subcritical water) can be used.

  In the compatibilizing step in the preparation step, the first oil phase component is mixed with water that has been preliminarily supercritical or subcritical in temperature and pressure conditions, and the water is mixed with the first oil phase. A method of mixing the components and subjecting the obtained mixture to a temperature and pressure condition in which water becomes supercritical or subcritical can be employed. Of these, the former method is preferable, and the first oil phase component is mixed with water that has been preliminarily supercritical or subcritical in temperature and pressure conditions so that the water and the first oil phase component are compatible. A method of maintaining the temperature and pressure is more preferable. This method can be suitably executed using, for example, the apparatus schematically shown in FIG.

FIG. 1 is a schematic view of an example of an apparatus capable of producing a microemulsion intermediate by a supercritical / subcritical emulsification method. The arrow in FIG. 1 represents the direction in which the liquid flows. Manufacturing apparatus 1 of this micro-emulsion intermediates E _M is a water W to be used as the aqueous dispersion medium, and a first oil phase components O1, a mixing unit 5 for compatibility with the supercritical or subcritical state of the water And a cooling unit 6 that cools a compatible material of the water W and the first oil phase component O1 in the presence of the emulsifier S. The above-described compatibility step can be performed by the mixing unit 5 in the apparatus 1, and the above-described cooling step can be performed by the cooling unit 6.

  The mixing section 5 is connected to a merging section 4a where the water W flowing in from the water flow path 2a and the first oil phase component flow path 2b and the first oil phase component O1 merge. The water W and the first oil phase component O1 merged in the merge section 4a flow into the mixing section 5 through the flow path 2c. The water W is pressurized and supplied continuously or intermittently to the heating device 3a having a heating mechanism such as a heating coil in the flow path 2a before being supplied to the junction 4a. In the heating device 3a, a supercritical or subcritical state is obtained and supplied to the merging section 4a and flows into the mixing section 5. As heating temperature, 200-400 degreeC is preferable, for example, 250 degreeC or more is more preferable, and 300 degreeC or more is further more preferable. Moreover, as a pressure of pressurization, it is preferable that it is 10-40 Mpa, for example, it is more preferable that it is 20-30 Mpa, and it is further more preferable that it is 20-25 Mpa. For the heating mechanism, for example, a resistance heater, an oil bath, a molten salt bath, an infrared heater, or the like may be used. For pressurization, for example, a plunger pump, a diaphragm pump, a syringe pump, or the like is used. be able to.

  The first oil phase component O1 supplied to the merging portion 4a may be at room temperature or heated. The supercritical or subcritical water and the first oil phase component merged at the merge portion 4 a continuously flow into the mixing portion 5, and the first oil phase component is supercritical or subcritical in the mixing portion 5. Dissolve in state water. In the mixing part 5, from the viewpoint of compatibilizing water and the first oil phase component in a supercritical or subcritical state of water, the first oil phase component flow path 2b is also provided with a heating mechanism. It is preferable that the heating device 3b is provided, and it is preferable that the joining unit 4a and the mixing unit 5 are also provided with a heating mechanism. In addition, although the confluence | merging part 4a is provided in the apparatus 1, the confluence | merging part 4a is not provided, but the water (supercritical water or subcritical water) W heated and pressurized, and the 1st oil phase component O1 are included. Each may be configured to directly flow into the mixing unit 5.

In the cooling step in the preparation step of the micro emulsion Intermediate E _M, a phase premixture obtained in about phases溶工, after mixing the emulsifier, it is possible to adopt a method of cooling. In this case, in the apparatus 1 shown in FIG. 1, the emulsifier S can be supplied to the merging section 4b provided near the outlet of the mixing section 5 (near the inlet of the cooling section 6) via the flow path 2d. In the cooling step, in the compatibility step, the first oil phase component and the emulsifier are added to water separately or together to obtain a compatible product containing the first oil phase component, the emulsifier, and water. In addition, a method of cooling the compatible material can also be employed. In this case, in the apparatus 1 shown in FIG. 1, it can comprise so that the emulsifier S may be supplied to the confluence | merging part 4a and the mixing part 5. FIG. Cooling in the presence of an emulsifier is preferably rapid cooling, more preferably at a cooling rate of 10 ° C./second or more, and cooling to a temperature of 100 ° C. or less at a cooling rate of 100 to 1000 ° C./second. Is more preferable.

  In the apparatus 1, the residence time from the merging section 4a to the outlet of the mixing section 5 can be set to be in the range of 0.01 to 90 seconds, for example. Moreover, in the apparatus 1, the pressure regulation valve 7 can be provided, for example in the exit of the cooling part 6, The above-mentioned preferable pressure is provided by the pressure regulation valve 7 from the heating apparatus 3a of the water W to the pressure regulation valve 7. It can be kept within range.

  As described above, in this method, it is preferable to carry out a complexing step after the preparation step of the microemulsion intermediate, and this method is suitable using, for example, an apparatus showing a schematic schematic flow diagram in FIG. Can be executed.

FIG. 2 is a schematic schematic flow diagram of an example of an apparatus that can execute the method for producing a composite microemulsion according to an embodiment of the present invention. The arrow in FIG. 2 represents the direction in which the liquid flows. In the manufacturing apparatus 10 of this composite microemulsion E, about each flow path 2a, 2b, 2c, 2d, each joining part 4a, 4b, the mixing part 5, the cooling part 6, and the pressure control valve 7, it shows in FIG. This is as described in the description of the device 1. The apparatus 10 includes a composite unit 11 between the cooling unit 6 and the pressure regulating valve 7. The above-described compounding step can be executed by the compounding unit 11 in the apparatus 10. In other words, content in the composite unit 11, a micro-emulsion intermediate obtained from the cooling section 6 (E _M), and mixed by adding the second oil phase O2, micro emulsion intermediates (E _M) The second oil phase component O2 is combined with the first oil phase component O1.

In the apparatus 10, the microemulsion intermediate (E _M ) that flows into the composite unit 11 from the cooling unit 6 through the flow path 2c and the second oil phase that flows in through the flow path 2e. A junction 4c where the component O2 merges is connected. The microemulsion intermediate (E _M ) and the second oil phase component O 2 merged at the merge section 4 c flow into the composite section 11. The apparatus 10 is provided with the merging part 4c, but is not provided with the merging part 4c, and each of the fine emulsion intermediate (E _M ) and the second oil phase component O2 flows directly into the compounding part 11. You may make it do.

  Examples of the emulsifier used in the production (preparation step) of the microemulsion intermediate described above include nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers, mixtures thereof, and aqueous solutions thereof. One or more of these emulsifiers can be appropriately used depending on the type of the microemulsion intermediate.

  In the preparation process of the microemulsion intermediate, the dispersion particles (first oil phase component) contained in the resulting microemulsion intermediate are combined (a phenomenon in which the dispersed particles are connected to each other to become larger particles). From the viewpoint of easy suppression, it is preferable to use a nonionic emulsifier having a cloud point as the emulsifier. Among these, it is more preferable to use a nonionic emulsifier having a cloud point in the range of 50 to 100 ° C. Here, the cloud point means that when the aqueous solution of the nonionic emulsifier is heated and heated, the nonionic emulsifier which is a solute and the water which is a solvent begin to separate (the transparency of the aqueous solution decreases and the solution becomes white and turbid) Refers to temperature.

  More preferably, the nonionic emulsifier having a cloud point is used under temperature conditions equal to or higher than the cloud point. As described above, the cloud point is 50 to 50 after the heating device 3a and before the cooling unit 6 as in the merging units 4a and 4b and the mixing unit 5 in the apparatuses 1 and 10 shown in FIGS. If a nonionic emulsifier within the range of 100 ° C. is used, the emulsifier can be used under temperature conditions above the cloud point.

  In addition, by obtaining a composite microemulsion using at least one of the first oil phase component and the second oil phase component containing a polymerizable monomer, a polymerization treatment is performed. When obtaining a composite fine resin emulsion, the polymerization treatment is preferably performed at a temperature below the cloud point. Thereby, the resin particle in the composite fine resin emulsion obtained after a polymerization process tends to become finer.

  As the nonionic emulsifier having a cloud point, for example, those having a cloud point can be selected and used from polyoxyethylene alkyl ethers, polyoxyethylene alkylene derivatives, polyoxyalkylene alkenyl ethers and the like. Specifically, polyoxyethylene lauryl ethers, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl Examples include ether, polyoxyethylene polyoxypropylene glycol, and the like. Moreover, the reactive nonionic emulsifier etc. which have reactivity by introduce | transducing a polymerizable unsaturated bond into those molecules can be mentioned. One of these nonionic emulsifiers may be used alone, or two or more thereof may be used in combination.

  Next, the aqueous dispersion medium, the first oil phase component, and the second oil phase component that have been used in the description of the present method will be specifically described. The aqueous dispersion medium is a dispersion medium containing at least water. It may be an aqueous dispersion medium consisting essentially of water, or an aqueous dispersion medium containing a water-soluble organic solvent together with water. The water content relative to the aqueous dispersion medium is preferably 50% by mass or more, more preferably in the range of 50 to 100% by mass, based on the total mass of the aqueous dispersion medium, and 50 to 99% by mass. More preferably, it is in the range. The water-soluble organic solvent is not particularly limited, and examples thereof include lower alcohols such as ethanol and isopropanol; glycols such as ethylene glycol and propylene glycol; and polyhydric alcohols such as glycerin. One kind of water-soluble organic solvent may be used alone, or two or more kinds may be used in combination.

  As the first oil phase component and the second oil phase component, a component that forms a phase (dispersoid) dispersed in the aqueous dispersion medium can be used. “First” and “second” in “first oil phase component” and “second oil phase component” are oil phase components contained in the microemulsion intermediate having the specific surface area. This is a term for distinguishing between the (first oil phase component) and the oil phase component (second oil phase component) to be combined therewith. Therefore, the same thing may be used for the first oil phase component and the second oil phase component, but the first oil phase component has higher heat resistance than the second oil phase component. It is preferable to use an oil phase component.

  As the first oil phase component and the second oil phase component (hereinafter sometimes collectively referred to as “oil phase component”), a monomer having a polymerizable unsaturated bond (hereinafter referred to as “oil phase component”). And a polymerization initiator, a solvent (oil-soluble solvent), and other oil-soluble compounds. One or more of these can be used for each oil phase component. Each of the first oil phase component and the second oil phase component preferably contains at least one compound selected from the group consisting of a polymerizable monomer and an oil-soluble compound.

  As a polymerizable monomer, a (meth) acrylic acid ester monomer, an unsaturated carboxylic acid monomer, an unsaturated monomer having a nitrogen atom, a styrene monomer, and other than these Examples thereof include a polymerizable monomer. One or more of these can be used. In the present disclosure, the term “(meth) acryl” means that both “acryl” and “methacryl” are included. Similarly, the term “(meth) acrylate” includes the terms “acrylate” and “methacrylate”.

  Examples of the (meth) acrylic acid ester monomer include (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid aralkyl ester, and (Meth) acrylic acid aryl esters, and other (meth) acrylic acid esters other than these may be mentioned. One or more of these (meth) acrylic acid esters can be used.

  Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (me ) Acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate Or a (meth) acrylic acid alkyl ester having a branched alkyl group; and cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, And alicyclic (meth) acrylic acid alkyl esters such as dicyclopentenyl (meth) acrylate. One or more of these (meth) acrylic acid alkyl esters can be used. Among these, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms is preferable.

  Examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, etc. Can be mentioned. These 1 type (s) or 2 or more types can be used.

  Examples of (meth) acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, and 2 -Phenoxyethyl (meth) acrylate etc. can be mentioned. These 1 type (s) or 2 or more types can be used.

  Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, and naphthylmethyl (meth) acrylate. These 1 type (s) or 2 or more types can be used.

  Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, tolyl (meth) acrylate, and naphthyl (meth) acrylate. These 1 type (s) or 2 or more types can be used.

  Examples of other (meth) acrylic acid esters include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol-polyethylene glycol (meth) acrylate, and methoxypolyethylene glycol mono (meth) acrylate. Polyalkylene glycol (meth) acrylates; halogens such as 2-chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate (Meth) acrylic acid alkyl ester having an atom; 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, (Meth) acrylic acid ester having an amino group such as 3- (dimethylamino) propyl (meth) acrylate; (meth) acrylic acid having a carboxy group such as carboxyethyl (meth) acrylate and carboxypentyl (meth) acrylate Esters: (meth) acrylic acid esters having an epoxy group such as glycidyl (meth) acrylate, glycerin mono (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like Derivatives; 2-sulfoethyl (meth) acrylate and (meth) acrylates having a sulfonic acid group such as 3-sulfopropyl (meth) acrylate; and phosphoric acid groups such as 2- (phosphonooxy) ethyl (meth) acrylate (me ) Acrylate; (meth) acrylate (meth) acrylate having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate; (meth) acrylate having a heterocycle such as tetrahydrofurfuryl (meth) acrylate; methoxypolyethylene glycol (meth) acrylate And alkyl group or aryl group-terminated polyalkylene glycol mono (meth) acrylate such as phenoxypolyethylene glycol (meth) acrylate. These 1 type (s) or 2 or more types can be used.

  Examples of the unsaturated carboxylic acid monomer include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid; potassium (meth) acrylate, and bis Metal salts of unsaturated carboxylic acids such as zinc (meth) acrylate; anhydrides of unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride; maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, And monoesters of unsaturated carboxylic acids such as itaconic acid monobutyl ester. These 1 type (s) or 2 or more types can be used.

  Examples of the unsaturated monomer having a nitrogen atom include unsaturated monomers having a cyano group such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) Acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- [ Acrylamide monomers such as 2-dimethylaminoethyl] (meth) acrylamide, N- [3-dimethylaminopropyl] (meth) acrylamide, diacetoneacrylamide, 4-acryloylmorpholine, and 4-methacryloylmorpholine; N-vinyl Acetamide, and Acetamide monomers having a vinyl group such as vinyl-N-methylacetamide; N-vinyl-2-pyrrolidone, 4-vinylpyridine, 1-vinylimidazole, 2-vinyl-2-oxazoline, and 2-isopropenyl And nitrogen-containing heterocyclic compounds having a vinyl group such as 2-oxazoline. These 1 type (s) or 2 or more types can be used.

  Examples of the styrene monomer include styrene, α-methylstyrene, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, 4-tert-butylstyrene, o-, m. -, P-hydroxystyrene, o-, m-, p-methoxystyrene, o-, m-, p-ethoxystyrene, o-, m-, p-chlorostyrene, o-, m-, p-bromostyrene O-, m-, p-fluorostyrene, o-, m-, p-chloromethylstyrene, and the like. These 1 type (s) or 2 or more types can be used.

  As other polymerizable monomer, in addition to the unsaturated carboxylic acid monomer, the unsaturated monomer having a nitrogen atom, and the styrene monomer, for example, ethylene, vinyl monomer, It is also possible to use a conjugated diene monomer, an unsaturated alcohol, a vinyl ether monomer, a vinyl ester monomer, an unsaturated monomer having an epoxy group, an unsaturated monomer having a sulfonic acid group, etc. Is possible.

  Examples of vinyl monomers include vinyl chloride and vinyl fluoride. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and 2-chloro-1,3-butadiene. Examples of the unsaturated alcohol include vinyl alcohol and allyl alcohol. Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, phenyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl versatate. Examples of the unsaturated monomer having an epoxy group include allyl glycidyl ether. Examples of the unsaturated monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and 2- (meth) acrylamide-2-methylpropane sulfonic acid. . These 1 type (s) or 2 or more types can be used.

  Furthermore, it is also possible to use a monomer (crosslinkable monomer) that can have a function as a crosslinking agent as the polymerizable monomer. As the crosslinkable monomer, a monomer having two or more polymerizable unsaturated bonds can be used. Examples of the crosslinkable monomer include 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene Bifunctional (meth) acrylates such as recall di (meth) acrylate and glycerin di (meth) acrylate; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate And polyfunctional (meth) acrylates such as allyl (meth) acrylate; divinylbenzene; and diallyl phthalate. Examples of the crosslinkable monomer include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltrimethoxysilane. A silane coupling agent such as acryloxypropyltrimethoxysilane may also be mentioned. It is possible to use one type or two or more types of crosslinkable monomers.

  Examples of the polymerization initiator include persulfates, organic peroxides, peroxides such as hydrogen peroxide, and azo compounds. One or more polymerization initiators may be used. Can do. Moreover, 1 type, or 2 or more types of reducing agents can also be used as a redox polymerization initiator used together with a peroxide, or a polymerization accelerator.

  Examples of the persulfate include potassium persulfate, sodium persulfate, and ammonium persulfate. One or more of these persulfates can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxyisobutyrate. One or more of these organic peroxides can be used. Examples of the azo compound include azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- And oil-soluble azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, and one of these azo compounds. Or 2 or more types can be used.

  Examples of the oil-soluble solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; cyclic hydrocarbon solvents such as cyclohexane; aromatics such as benzyl alcohol Examples thereof include alcohol solvents; ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate. One of these oil-soluble solvents may be used alone, or two or more thereof may be used in combination.

  The oil-soluble compound is an oil-soluble compound other than the polymerizable monomer, the polymerization initiator, and the oil-soluble solvent. Examples of oil-soluble compounds include fat-soluble carotenoids, vegetable oils, animal fats, plant sterols, fat-soluble vitamins, fat-soluble drugs, fatty acids, hydrocarbon oils, ester oils, higher alcohols, essential oils, silicone oils, and fluorine-based compounds. An oil agent etc. can be mentioned. One or more of these can be used.

  The fat-soluble carotenoid may be any of carotenes, xanthophylls, and apocartenoids. Examples of carotene include α-carotene, β-carotene, γ-carotene, and lycopene. Examples of xanthophyll include actinioerythritol, canthaxanthin, capsorubin, cucurbitaxanthin A, cryptocapsin, astaxanthin, fucoxanthin, lutein, zeaxanthin, capsanthin, β-cryptoxanthin, violaxanthin, and derivatives thereof (fatty acid and Monoester or diester) and the like. Examples of apocartenoids include bixin, β-8′-apo-carotenal (apocarotenal), β-12′-apo-carotenal, and derivatives thereof (such as esters with lower or higher alcohols). One of these fat-soluble carotenoids may be used alone, or two or more thereof may be used in combination.

  The fat-soluble carotenoid is not particularly limited in its origin and production method, and may be derived from natural products such as plants, animals, and microorganisms, and is obtained by fermentation or synthesis. Also good. Natural pigments containing fat-soluble carotenoids can also be used. Such natural pigments include, for example, red pepper pigments (paprika pigments, paprika oleoresin), anato pigments, imo carotene, Dunaliella carotene, carrot carotene, shrimp pigment, krill pigment, orange pigment, crab pigment, corn pigment, tomato pigment , Palm oil carotene, Phaffia pigment, Beninoki powder pigment, Haematococcus alga pigment, Marigold pigment and the like.

  As vegetable oils and fats, for example, sesame oil, salad oil, sardine oil, corn oil, soybean oil, rapeseed oil (canola oil), rice oil, coconut oil, wheat germ oil, coconut oil, safflower oil, coconut oil (palm kernel oil), Examples include cottonseed oil, sunflower oil, sesame oil, linseed oil, olive oil, peanut oil, almond oil, avocado oil, hazelnut oil, walnut oil, grape seed oil, mustard oil, lettuce oil, and hardened oils thereof. One kind of these vegetable oils and fats may be used alone, or two or more kinds may be used in combination.

  Animal fats and oils include, for example, fish oil, beef tallow, pork tallow, shark oil, sheep oil, horse oil, chicken oil, whale oil, tallow oil, liver oil, and hardened oils thereof (lard (tallow), het (tallow) , Rosin, sheep fat, horse fat) and the like. One kind of these animal fats and oils may be used alone, or two or more kinds may be used in combination.

  Plant sterol is a general term for sterols present in plants. Examples of plant sterols include α-sitostanol, β-sitosterol, stigmasterol, campesterol, brassicasterol, brassicasterol, isofucosterol, 7-stigmasterenol, isofucostanol, stigmasteranol, 7- Examples include stigmasteranol, campestanol, cycloartenol, avenasterol, and glycosides thereof. One of these plant sterols may be used alone, or two or more thereof may be used in combination.

  Examples of fat-soluble vitamins and fat-soluble drugs include vitamin A, vitamin D, vitamin E, vitamin F, vitamin K, and derivatives thereof, ascorbyl stearate, ascorbyl palmitate, ascorbyl tetra-2-hexyldecanoate, and dipalmitin. Examples include acid ascorbyl, β-carotene, ubiquinone-10, methyl salicylate, erythromycin, xanthamicin, butylhydroxyanisole, dibutylhydroxytoluene, and catechin. One of these fat-soluble vitamins and fat-soluble drugs may be used alone, or two or more thereof may be used in combination.

  Examples of fatty acids include lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, behenic acid, hexadecatrienoic acid, octadecatrienoic acid, eicosatetraic acid. Examples include enoic acid, docosatetraenoic acid, eicosapentaenoic acid (EPA), docosapentaenoic acid, docosahexaenoic acid (DHA), tetrahexaenoic acid, and isomers thereof. One of these fatty acids may be used alone, or two or more thereof may be used in combination.

  Examples of the hydrocarbon oil include paraffin, petrolatum, ceresin, ozokerite, montan wax, squalane, squalene, and the like. One of these hydrocarbon oils may be used alone, or two or more thereof may be used in combination.

  Examples of ester oils include glycerin monostearate, glyceryl distearate, glycerin monooleate, isopropyl palmitate, isopropyl stearate, butyl stearate, isopropyl myristate, neopentyl glycol dicaprate, diethyl phthalate, Myristyl lactate, diisopropyl adipate, cetyl myristate, cetyl lactate, 1-isostearoyl-3-myristoylglycerol, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, di-2-ethylhexanoic acid Neopentyl glycol, 2-octyldodecyl oleate, glycerol triisostearate, and mono-2-ethylhexanoic acid diparamethoxycinnamate Seryl, and the like. One of these ester oils may be used alone, or two or more thereof may be used in combination.

  Examples of the higher alcohol (higher alcohol having 8 or more carbon atoms) include octyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. One of these higher alcohols may be used alone, or two or more may be used in combination.

  Examples of essential oils include peppermint oil, spearmint oil, bergamot oil, fennel oil, peppermint oil, and lemon peel oil. One of these essential oils may be used alone, or two or more thereof may be used in combination.

  Examples of the silicone oil include octamethylpolysiloxane, tetradecamethylpolysiloxane, methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, trimethylsiloxysilicic acid, Examples thereof include alkyl-modified silicone, polyether-modified silicone, amino acid-modified silicone, amino-modified silicone, fluorine-modified silicone, alkyl glyceryl ether-modified silicone, alkyl, alkenyl or fluoroalkyl-modified silicone. One of these silicone oils may be used alone, or two or more thereof may be used in combination.

  Examples of the fluorinated oil include perfluorodecalin, perfluoroadamantane, perfluorobutyltetrahydrofuran, perfluorooctane, perfluorononane, perfluoropentane, perfluorodecane, perfluorododecane, and perfluoropolyether. Can be mentioned. One of these fluorinated oils may be used alone, or two or more thereof may be used in combination.

  The first oil phase component preferably contains at least a polymerizable monomer from the viewpoint of easily forming fine particles in the microemulsion intermediate. Further, the first oil phase component contains 5% by mass or more of a polymerizable monomer having an SP value in the range of 8.0 to 10.0 based on the total mass of the first oil phase component. It is preferable to do. Thus, for example, when a compound having a low SP value (for example, an SP value of less than 8.0) is used as the second oil phase component, the second oil phase component in the microemulsion intermediate is used. It becomes easy to make a composite with one oil phase component. From the viewpoint that the second oil phase component is easily complexed with the first oil phase component in the microemulsion intermediate, a polymerizable monomer having an SP value in the range of 8.0 to 10.0 is used. It is preferable to contain 5% by mass or more based on the total mass of the oil phase component of 2.

Here, the SP value (solubility parameter) is a physical property value defined by the square root of the cohesive energy density calculated from the following formula (2).
δ (SP value) = (ΣEcoh / ΣV) ^1/2 (2)

  As shown in the above formula (2), the SP value (solubility parameter) is calculated from the molecular structure by Fedors' estimation method, and is calculated based on the cohesive energy density and molar molecular volume. That is, it can be defined as the above formula (2) from the total ΣEcoh of the cohesive energy density of each functional group of the substance and the total ΣV of the molar molecular volume. In many cases, the unit of the cohesive energy is J / mol. In this specification, the SP value of the unit of J / mol is divided by a coefficient of 4.19, and cal / mol is used. The numerical values described in “R. F. Fedors, Polym. Eng. Sci., 14 [2], 147-154 (1974)” can be used for the constants of atomic group, group-specific cohesive energy, and molar molecular volume.

  In the method for producing a composite microemulsion according to an embodiment of the present invention, when at least one of the first oil phase component and the second oil phase component described above contains a polymerizable monomer, the compounding step A composite micro resin emulsion can also be obtained by polymerizing a polymerizable monomer in the composite micro emulsion from the composite micro emulsion obtained later. The composite fine resin emulsion is one in which resin particles are dispersed in an aqueous dispersion medium (resin emulsion). The resin particles are obtained by polymerizing polymerizable monomers used as the first oil phase component and the second oil phase component. The resin particles are preferably (meth) acrylic resin particles in which a monomer component containing at least a (meth) acrylic acid ester monomer as a polymerizable monomer is polymerized. The (meth) acrylic resin particles may be polymer (homopolymer) particles obtained by polymerizing one kind of polymerizable monomer ((meth) acrylic acid ester monomer), or (meth) acrylic acid ester. Polymer (copolymer) particles obtained by polymerization (copolymerization) of two or more kinds of polymerizable monomers including a monomer may be used.

As described above in detail, in the method for producing a composite microemulsion according to one embodiment of the present invention, the microemulsion intermediate in which the specific surface area of the first oil phase component is 1.0 × 10 ⁴ cm ² / g or more. In addition, since the second oil phase component is added and mixed, the second oil phase component can be combined with the first oil phase component even at 100 ° C. or lower (and at room temperature). Accordingly, the second oil phase component combined with the first oil phase component can be finely dispersed in the aqueous dispersion medium, preferably in a nano size. Therefore, in the conventional emulsification technique, a substance that is difficult to finely disperse can be finely dispersed in the aqueous dispersion medium and further nano-sized by using it as the second oil phase component in the present method. Therefore, it can be expected that the range of selection of the material to be emulsified is widened. Therefore, this method is used for producing microemulsions in various fields such as foods, cosmetics, pharmaceuticals, adhesives, pressure-sensitive adhesives, paints, and inks by appropriately selecting the oil phase components to be emulsified. I can expect that.

In addition, the manufacturing method of the composite fine emulsion of one Embodiment of this invention can take the following structures.
[1] A microemulsion intermediate in which a first oil phase component is dispersed as particles in an aqueous dispersion medium, and the specific surface area of the first oil phase component relative to the microemulsion intermediate is 1. A compounding step in which the second oil phase component to be emulsified is added to and mixed with the microemulsion intermediate that is 0 × 10 ⁴ cm ² / g or more, and is combined with the first oil phase component. A method for producing a composite microemulsion comprising
[2] In the complexing step, the second oil phase component is added to the microemulsion intermediate under conditions where the temperature is in the range of 5 to 100 ° C. and the pressure is in the range of 10 to 40 MPa. The method for producing a composite microemulsion according to the above [1], which is added and mixed.
[3] The above [1] or [1], wherein each of the first oil phase component and the second oil phase component contains at least one compound selected from the group consisting of a polymerizable monomer and an oil-soluble compound. The method for producing a composite microemulsion according to [2].
[4] The first oil phase component contains 5 masses of a polymerizable monomer having an SP value in the range of 8.0 to 10.0 based on the total mass of the first oil phase component. The method for producing a composite microemulsion according to any one of the above [1] to [3], which is contained in an amount of at least%.
[5] The second oil phase component contains 5 masses of a polymerizable monomer having an SP value in the range of 8.0 to 10.0 based on the total mass of the second oil phase component. The method for producing a composite microemulsion according to any one of the above [1] to [4], which contains at least%.
[6] The composite microemulsion according to any one of the above [1] to [5], which comprises the step of preparing the microemulsion intermediate, wherein the microemulsion intermediate is produced before the complexing step. Production method.
[7] The preparation step includes a step of dissolving the water contained in the aqueous dispersion medium and the first oil phase component in a supercritical or subcritical state of the water, the water and the first The method for producing a composite microemulsion according to the above [6], comprising a step of cooling a compatible product with the oil phase component in the presence of a nonionic emulsifier having a cloud point.
[8] At least one of the first oil phase component and the second oil phase component contains a polymerizable monomer, from the complex microemulsion obtained after the complexing step, The method for producing a composite microemulsion according to any one of the above [1] to [7], further comprising a step of polymerizing the polymerizable monomer in the composite microemulsion to obtain a composite microresin emulsion.

  Hereinafter, although the manufacture example, an Example, and a comparative example are given and the further specific example of one Embodiment of this invention mentioned above is demonstrated, this invention is not limited to it. In the following text, “parts” and “%” are based on mass (represented as “parts by mass” and “mass%”, respectively) unless otherwise specified.

<Preparation of emulsion intermediate>
(Production Example 1)
The following AC liquids were prepared as liquid raw materials.
Liquid A: Ion-exchanged water Liquid B: As the first oil phase component, n-butyl acrylate (hereinafter sometimes referred to as “BA”; SP value = 8.82) and cyclohexyl methacrylate (hereinafter referred to as “CHMA”). Mixed liquid consisting of 50:50 mass ratio of SP value = 9.24) C liquid: nonionic emulsifier having a cloud point of 79 ° C. (polyoxyalkylene branched decyl ether; trade name “Neugen XL”) -100 ", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB 14.7) 22.5% aqueous solution

  Using a supercritical water supply apparatus (product name “SFW-E40S”, manufactured by AKICO), a test apparatus having a configuration like the apparatus 1 shown in FIG. 1 was prepared. This test apparatus will be described with reference numerals in FIG. 1 shown in parentheses for reference. This test apparatus (1) includes two liquid raw material A liquid and B liquid flow paths (2a, 2b), and a merger (4a) in which the flowing A liquid (W) and B liquid (O1) merge. The mixer (5) is connected to the merger (4a) via the flow path (2c). In this test apparatus (1), the heating device (3a) is provided in the flow path (2a) of the liquid A, and the liquid A (W) is supplied under pressure continuously or intermittently to be heated (3a ) In a supercritical or subcritical state, is supplied to the merger (4a) and flows into the mixer (5). In this production example, the heating and pressurizing conditions of the liquid A were set in the range of 250 to 370 ° C. and 25 MPa, respectively, and the liquid A flowing into the mixer (5) was subcritical water. A preliminary heating device (3b) is also provided in the B liquid channel (2b). Moreover, this test apparatus (1) is provided with the cooler (6) which cools the liquid which leaves a mixer (5). In front of the inlet of the cooler (6), a junction (4b) that connects the flow path of the liquid exiting the mixer (5) and the flow path of the C liquid (2d) is provided. 6) is configured such that the liquid exiting from the mixer (5) can be cooled in the presence of C liquid (S). Further, this test apparatus (1) is provided with a pressure valve (7) at the outlet of the cooler (6), and the pressure valve (7) is connected to the pressure valve (7 ) Until the pressure is maintained within a substantially constant pressure range.

  Using the above test apparatus, the A liquid and the B liquid were introduced at a rate of 29.5 mL / min and 4.3 mL / min from the flow paths of the A liquid and the B liquid, respectively. Liquid B (first oil phase component) was dissolved in liquid A under conditions of high temperature and high pressure to become subcritical water of 310 to 360 ° C. and 25 MPa. Subsequently, C liquid is allowed to flow from the C liquid flow path at a rate of 5.2 mL / min. In the cooler, in the presence of C liquid (emulsifier), the liquid (A liquid and B liquid) The compatibilized material was cooled to room temperature. In this way, an emulsion intermediate having a first oil phase component concentration of 10% was obtained.

(Production Example 2)
Liquid B used in Production Example 1 may be described as the first oil phase component as n-butyl acrylate (BA), cyclohexyl methacrylate (CHMA), and methacrylic acid (hereinafter “MAAc”. SP value = 10.73) was changed to a mixed solution mixed at a mass ratio of BA: CHMA: MAAc = 50: 45: 5, and the first oil phase component concentration was 10 in the same manner as in Production Example 1. % Emulsion intermediate was obtained.

(Production Example 3)
The B liquid used in Production Example 1 is described as n-butyl acrylate (BA) and methyl methacrylate (hereinafter, referred to as “MMA”, SP value = 10.02) and methacryl as the first oil phase component. The acid (MAAc) was changed to a mixed liquid mixed at a mass ratio of BA: MMA: MAAc = 50: 45: 5, and the high temperature at which the liquid A became subcritical water at 250 to 300 ° C. and 25 MPa in the mixer. An emulsion intermediate having a first oil phase component concentration of 10% was obtained in the same manner as in Production Example 1 except that the high-pressure conditions were used.

(Production Example 4)
The liquid B and liquid C used in Production Example 1 were changed to the following liquid B and liquid C, respectively, and the high-temperature and high-pressure conditions were set so that the liquid A became subcritical water at 250 to 300 ° C. and 25 MPa in the mixer. And the emulsion intermediate body was obtained by the method similar to manufacture example 1 except having changed the inflow rate of AC liquid.
As the liquid B, 100 parts of a mixed solution of BA: MMA: MAAc = 50: 45: 5 (mass ratio) used in Production Example 3 as a first oil phase component was added to a nonionic emulsifier (trade name “Neugen XL”). A mixed solution of 12.5 parts of “-100” (Daiichi Kogyo Seiyaku Co., Ltd.) was used.
As the liquid C, the above nonionic emulsifier (trade name “Neugen XL-100”): anionic emulsifier (polyoxyethylene polycyclic phenyl ether sulfate ester; trade name “New Coal 707SF”, manufactured by Nippon Emulsifier Co., Ltd.) = 3 A 19.9% aqueous solution of an emulsifier mixed at a mass ratio of 1 was used.
And the inflow rate of A liquid, B liquid, and C liquid was 16 mL / min, 19 mL / min, and 14.6 mL / min, respectively. In this way, an emulsion intermediate having a first oil phase component concentration of 32% was produced.

(Production Example 5)
The liquid B and liquid C used in Production Example 1 were changed to the following liquid B and liquid C, respectively, and the high-temperature and high-pressure conditions were set so that the liquid A became subcritical water at 250 to 300 ° C. and 25 MPa in the mixer. And the emulsion intermediate body was obtained by the method similar to manufacture example 1 except having changed the inflow rate of AC liquid.
As the liquid B, 100 parts of a mixed solution of BA: MMA: MAAc = 50: 45: 5 (mass ratio) used in Production Example 3 as a first oil phase component was added to a nonionic emulsifier (trade name “Neugen XL”). A mixed solution of 12.5 parts of “-100” (Daiichi Kogyo Seiyaku Co., Ltd.) was used.
As the liquid C, only ion-exchanged water was used. And the inflow rates of A liquid, B liquid, and C liquid were 16 mL / min, 19 mL / min, and 2 mL / min, respectively. In this way, an emulsion intermediate having a first oil phase component concentration of 43% was produced.

(Production Example 6)
In a poly mug container with a capacity of 1 L, 370 g of ion-exchanged water, 80 g of a mixed solution consisting of n-butyl acrylate (BA) and cyclohexyl methacrylate (CHMA) in a mass ratio of 50:50 as the first oil phase component, nonionic 10 g of an emulsifier (trade name “Neugen XL-100”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added, and the mixture was stirred for 10 minutes with a homomixer at a rotational speed of 3000 rpm under the condition of a temperature of 25 ° C. to carry out an emulsification treatment. In this way, an emulsion intermediate having a first oil phase component concentration of 20% was obtained.

(Production Example 7)
By further subjecting the emulsion intermediate produced in Production Example 6 to a 5-pass refinement with a high-pressure homogenizer (trade name “H-20”, manufactured by Sanwa Kikai Co., Ltd.) at a temperature of 25 ° C. and a pressure of 80 MPa, An emulsion intermediate having a first oil phase component concentration of 20% was obtained.

(Production Example 8)
The liquid B used in Production Example 1 was used as the first oil phase component, hexyl propionate (hereinafter sometimes referred to as “HP”) and dimethyl silicone oil (trade name “KF-96-50cs”, Shin-Etsu Chemical Co., Ltd.) was changed to a mixed liquid in which the mass ratio of HP: dimethylsilicone oil = 82: 18 was changed, and the first oil phase component concentration was 10% in the same manner as in Production Example 1. An emulsion intermediate was obtained.

For each of the emulsion intermediates obtained in Production Examples 1 to 8, after the emulsion intermediate was diluted with water to a concentration suitable for measurement, a particle size distribution measuring device using a dynamic light scattering method (trade name “rich” The particle size distribution was measured at 25 ° C. using a system particle size analyzer FPAR-1000 ”(manufactured by Otsuka Electronics Co., Ltd.), and the average particle size was measured by cumulant method analysis. Moreover, about each emulsion intermediate body obtained by manufacture examples 1-8, the specific surface area (cm < ² > / g) of the 1st oil phase component with respect to an emulsion intermediate body was computed by above-mentioned Formula (1). 3A to H show particle size distribution diagrams. Table 1 shows the first oil phase component used in each production example, the emulsification conditions, the average particle diameter of the obtained emulsion, the oil phase component concentration, the specific surface area, and the like.

  As shown in Table 1 and FIGS. 3A to H, in Production Examples 1 to 5, 7 and 8, the specific surface area of the first oil phase component with respect to the emulsion intermediate is large, and contains fine particles having a uniform nanoparticle size. It was confirmed that a microemulsion intermediate was obtained. On the other hand, in Production Example 6, it was confirmed that an emulsion intermediate containing micron-sized particles was obtained with a small specific surface area of the first oil phase component relative to the emulsion intermediate.

<Production of composite emulsion>
Example 1
In a 1 L four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser, 200 g of the microemulsion intermediate obtained in Production Example 1 was placed, and at 25 ° C. under atmospheric pressure (normal pressure). Stirring was performed at a rotation speed of 170 rpm. As a second oil phase component, 25 g of cyclohexyl methacrylate (CHMA) was added to the microemulsion intermediate under stirring over 30 minutes. After completion of the addition, stirring was continued for 1 hour at a rotational speed of 170 rpm at 25 ° C. under atmospheric pressure (normal pressure) to obtain an emulsion (composite microemulsion) having an oil phase component concentration of 20%.

(Examples 2 to 4)
In Examples 2 to 4, the oil phase component concentration was changed by the same method as in Example 1 except that the microemulsion intermediate and the second oil phase component used in Example 1 were changed as follows. An emulsion (composite microemulsion) of 20% was obtained.
In Example 2, cyclohexyl methacrylate (CHMA) and toluene were mixed as a second oil phase component in a mass ratio of CHMA: toluene = 82: 18 to 200 g of the microemulsion intermediate obtained in Production Example 2. 25 g of mixture was added.
In Example 3, cyclohexyl methacrylate (CHMA) and n-hexane as the second oil phase component were added to 200 g of the microemulsion intermediate obtained in Production Example 3, and the mass of CHMA: n-hexane = 82: 18. 25 g of the mixture mixed in a ratio was added.
In Example 4, to 62.5 g of the microemulsion intermediate obtained in Production Example 4 to 200 g by adding ion-exchanged water, as the second oil phase component, cyclohexyl methacrylate (CHMA) and allyl methacrylate ( Hereinafter, it may be described as “AMA. SP value = 8.99) and 25 g of a mixed solution obtained by mixing toluene with a mass ratio of CHMA: AMA: toluene = 73: 9: 18 was added.

(Example 5)
50 g of the microemulsion intermediate obtained in Production Example 5, 140 g of ion-exchanged water, and 10 g of an anionic emulsifier (trade name “New Coal 707SF”, manufactured by Nippon Emulsifier Co., Ltd.) were mixed to obtain a mixed solution. 200 g of the above mixed solution was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser, and stirred at 25 ° C. and atmospheric pressure (normal pressure) at a rotational speed of 3500 rpm. To the mixture under stirring, as a second oil phase component, 6.9 g of n-butyl acrylate (BA), 52.4 g of methyl methacrylate (MMA), 3.4 g of methacrylic acid (MAAc), allyl methacrylate ( A mixture of 4.4 g of AMA), 9.9 g of n-heptane, and 0.4 g of a polymerization initiator (azobisisobutyronitrile (AIBN)) was added over 10 minutes. After completion of the addition, stirring was continued for 10 minutes at a rotational speed of 3500 rpm at 25 ° C. and atmospheric pressure (normal pressure) to obtain an emulsion (composite microemulsion) having an oil phase component concentration of 36%.

(Example 6)
In Example 6, 100 g of ion-exchanged water was added to 100 g of the microemulsion intermediate obtained in Production Example 7 to give 200 g, and cyclohexyl methacrylate (CHMA) and n-butyl acrylate were used as the second oil phase component. (BA) and dimethyl silicone oil (trade name “KF-96-50cs”, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a mass ratio of CHMA: BA: dimethylsilicone oil = 68: 22: 10, and 25 g of the mixture was carried out. It added by the method similar to Example 1, and obtained the emulsion (complex microemulsion) whose oil phase component density | concentration is 20%.

(Comparative Example 1)
Instead of the emulsified intermediate, 190 g of ion-exchanged water, nonionic emulsifier (trade name “Neugen XL-100”, No. 1) were added to a 1 L four-necked round bottom flask equipped with a stirrer, thermometer, and reflux condenser. 10 g (manufactured by Ichi Kogyo Seiyaku Co., Ltd.) was added and stirred at a rotation speed of 170 rpm under atmospheric pressure (normal pressure). To the liquid under stirring, 25 g of a mixed liquid in which cyclohexyl methacrylate (CHMA) and n-hexane were mixed at a mass ratio of CHMA: n-hexane = 82: 18 was added over 30 minutes. After completion of the addition, stirring was continued for 1 hour at a rotational speed of 170 rpm at 25 ° C. and atmospheric pressure (normal pressure), but a fine emulsion was not obtained, and a separated liquid in which oil droplets were separated was obtained.

(Comparative Example 2)
In a 1 L four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser, 200 g of the emulsion intermediate obtained in Production Example 6 was placed, and 170 rpm at 25 ° C. under atmospheric pressure (normal pressure). With a rotational speed of. 25 g of a mixed solution in which cyclohexyl methacrylate (CHMA) and oleic acid are mixed as a second oil phase component in a mass ratio of CHMA: oleic acid = 70: 30 is added to the emulsion intermediate under stirring for 30 minutes. Added. After completion of the addition, stirring was continued for 1 hour at a rotational speed of 170 rpm at 25 ° C. and atmospheric pressure (normal pressure), but a fine emulsion was not obtained, and a separated liquid in which oil droplets were separated was obtained.

  About each emulsion obtained in Examples 1-6, after diluting an emulsion with water to the density | concentration suitable for a measurement, the particle size distribution measuring apparatus using a dynamic light-scattering method (brand name "concentration type particle size analyzer") Using FPAR-1000 "(manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution was measured at 25 ° C, and the average particle size was measured by cumulant method analysis. 4A to F show particle size distribution diagrams. In Table 2, the properties of the respective emulsion intermediates used in Examples 1 to 6 and Comparative Example 2 are listed again, and the pressure and temperature conditions when the second oil phase component is added (compositing step), And the average particle diameter etc. which were measured about each emulsion obtained in Examples 1-6 are shown.

As shown in Table 2 and FIGS. 4A to 4F, in Examples 1 to 6, the ^second emulsion phase intermediate having a specific surface area of the first oil phase component of 1.0 × 10 ⁴ cm ² / g or more is added to the second emulsion. It was confirmed that by adding and mixing the oil phase component, a microemulsion was obtained in which fine particles having a uniform size and a nano size were stably dispersed in an aqueous dispersion medium. From this result, in Examples 1 to 6, the second oil phase component was complexed with the first oil phase component forming the particles in the microemulsion intermediate, and a composite microemulsion was obtained. Was confirmed.

<Manufacture of composite emulsion by continuous flow method>
Next, a description will be given of an embodiment in which a test apparatus having a configuration such as the apparatus 10 shown in FIG. 2 described above is used to perform a continuous flow system from the production of a microemulsion intermediate to the production of a composite microemulsion.

(Example 7)
The following A to D liquids were prepared as liquid raw materials.
Liquid A: Ion-exchanged water Liquid B: As a first oil phase component, a mixed liquid consisting of a mass ratio of n-butyl acrylate (BA) and cyclohexyl methacrylate (CHMA) 50:50 Liquid C: Cloud point is 79 ° C. Nonionic emulsifier (polyoxyalkylene branched decyl ether; trade name “Neugen XL-100”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB 14.7) 22.5% aqueous solution D solution: cyclohexyl methacrylate as the second oil phase component (CHMA): Dimethyl silicone oil (trade name “KF-96-50cs”, manufactured by Shin-Etsu Chemical Co., Ltd.) = 82:18 (mass ratio) liquid mixture

  A continuous test apparatus having a configuration like the apparatus 10 shown in FIG. 2 was prepared. The continuous test apparatus will be described with reference numerals in FIGS. 1 and 2 shown in parentheses for reference. The continuous test apparatus (10) is provided with an inflow path (2e) for the D liquid (O2) and a composite section (11) continuously from the test apparatus (1) used in the above production example. It has a configuration. Specifically, the continuous test apparatus (10) exits from the cooler (6) between the cooler (6) and the pressure valve (7) in the test apparatus (1) used in the above-described production example. The flow path (2e) of the D liquid that merges with the flow path (2c) of the liquid at the merger (4c), and the liquid and the D liquid (O2) discharged from the cooler (6) merge at the merger (4c). And a composite part (11) that flows in. In the continuous test apparatus (10), the liquid D (O2) can flow under high pressure by the pressure valve (7). In addition, the liquid (emulsion intermediate) that has come out of the cooler (7) flows into the composite section (11) under the conditions of a temperature of 5 to 100 ° C. and a pressure of 25 MPa. Configured.

  In Example 7, the liquid A and the liquid B were allowed to flow in at a rate of 29.5 mL / min and liquid B at a rate of 4.3 mL / min, respectively, in the continuous test apparatus. In the vessel, liquid B (first oil phase component) was dissolved in liquid A under conditions of high temperature and high pressure at which liquid A (water) was subcritical water of 310 to 360 ° C. and 25 MPa. Subsequently, C liquid (emulsifier) is allowed to flow in at a rate of 5.2 mL / min from the flow path of C liquid, and in the cooler, in the presence of C liquid, the liquids (the liquid A and B liquid) The compatible solution) was cooled to room temperature, and the D solution (second oil phase component) was continuously supplied from the D solution channel at a rate of 5.4 mL / min. In this way, an emulsion (composite microemulsion) having an oil phase component concentration of 20% was obtained by a continuous flow method.

(Example 8)
About the D liquid used in Example 7, and its inflow rate, oil phase component density | concentration is 20% by the method similar to Example 7 except having made the following D liquid flow in at the speed | rate of 13.5 g / min. An emulsion (composite microemulsion) was obtained.
Liquid D: Mixture of 90.9 g of cyclohexyl methacrylate (CHMA), 3.7 g of n-butyl acrylate (BA), and 21.2 g of dimethyl silicone oil (trade name “KF-96-50cs”, manufactured by Shin-Etsu Chemical Co., Ltd.) 2nd oil phase component), anionic emulsifier (trade name “New Coal 707SF”, manufactured by Nippon Emulsifier Co., Ltd.) 14.2 g, and ion-exchanged water 101.7 g were stirred at 6000 rpm for 5 minutes to obtain a micron size. Emulsion

(Examples 9 to 12)
The dimethyl silicone oil in the second oil phase component in the liquid D used in Example 8 is oleic acid in Example 9, octyl alcohol in Example 10, benzyl alcohol in Example 11, and in Example 12. An emulsion (composite microemulsion) having an oil phase component concentration of 20% was obtained in the same manner as in Example 8, except that each was changed to styrene (SP value = 9.24).

  In Examples 7 to 12, for the liquid (emulsion intermediate) partially collected from the cooler (6) before adding the D liquid, the average particle diameter was measured by the same method as described above, When the specific surface area of the first oil phase component was calculated, it was confirmed that all were the same as the microemulsion intermediate obtained in Production Example 1.

(Example 13)
The following A to D liquids were prepared as liquid raw materials.
Liquid A: Deionized water Liquid B: As a first oil phase component, a mixed liquid of n-butyl acrylate (BA): methyl methacrylate (MMA): methacrylic acid (MAAc) = 40: 55: 5 (mass ratio) C Liquid: 22.5% aqueous solution of nonionic emulsifier (polyoxyalkylene branched decyl ether; trade name “Neugen XL-100”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB 14.7) having a cloud point of 79 ° C. Liquid D: Volume In a 1 L poly mug container, 144.7 g of ion-exchanged water, 18.9 g of an anionic emulsifier (trade name “New Coal 707SF”, manufactured by Nippon Emulsifier Co., Ltd.), and methyl methacrylate (MMA) as the second oil phase component ) 113.1 g, allyl methacrylate (AMA) 14.2 g, methacrylic acid (MAAc) 6.7 g, dimethyl silicone oil (trade name “ F-96-50cs "(manufactured by Shin-Etsu Chemical Co., Ltd.) 31.2 g and polymerization initiator (AIBN) 2.0 g were added, and the micron size obtained by stirring for 10 minutes with a homomixer at a rotation speed of 6000 rpm Emulsion

In Example 13, from each flow path in the continuous test apparatus, the liquid A was 19 mL / min, the liquid B was 10 mL / min, the liquid C was 7.2 mL / min, and the liquid D was 19.8 g / min. The same method as in Example 7, except that the liquid A was mixed with the liquid A and the liquid B, and the liquid A was subjected to high-temperature and high-pressure conditions at 250 to 290 ° C. and 25 MPa subcritical water. Thus, an emulsion (composite microemulsion) having an oil phase component concentration of 34% was obtained by a continuous flow method. In Example 13, the average particle size of the liquid (emulsion intermediate) partially collected from the cooler (6) before adding the D liquid was measured by the same method as described above, and the first The specific surface area of the oil phase component was calculated, the average particle diameter of the emulsion intermediate was 90 nm, the concentration of the first oil phase component was 26%, and the specific surface area was 1.9 × 10 ⁵ cm ² / g.

(Example 14)
The following A to D liquids were prepared as liquid raw materials.
Liquid A: ion-exchanged water Liquid B: As the first oil phase component, hexyl propionate (HP) and dimethyl silicone oil (trade name “KF-96-50cs”, manufactured by Shin-Etsu Chemical Co., Ltd.), HP: dimethyl silicone Liquid mixture C mixed at a mass ratio of oil = 82: 18 Liquid C: Nonionic emulsifier having a cloud point of 79 ° C. (polyoxyalkylene branched decyl ether; trade name “Neugen XL-100”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 22.5% aqueous solution of HLB14.7) Liquid D: Mass ratio 50 of hexyl propionate (HP) and butyl propionate (hereinafter sometimes referred to as “BP”) as the second oil phase component: 50 liquid mixture

  In Example 14, the liquid A and the liquid B were allowed to flow in at a rate of 29.5 mL / min and liquid B at a rate of 4.3 mL / min, respectively, from the A liquid channel and B liquid channel in the continuous test apparatus. In the vessel, liquid B (first oil phase component) was dissolved in liquid A under conditions of high temperature and high pressure where liquid A (water) became supercritical water at 380 ° C. and 25 MPa. Subsequently, C liquid (emulsifier) is allowed to flow in at a rate of 5.2 mL / min from the flow path of C liquid, and in the cooler, in the presence of C liquid, the liquids (the liquid A and B liquid) The compatible solution) was cooled to room temperature, and the D solution (second oil phase component) was continuously supplied from the D solution channel at a rate of 5.4 mL / min. In this way, an emulsion (composite microemulsion) having an oil phase component concentration of 20% was obtained by a continuous flow method. In Example 14, the average particle size of the liquid (emulsion intermediate) partially collected from the cooler before adding the D liquid was measured by the same method as described above, and the first oil phase When the specific surface areas of the components were calculated, it was confirmed that all were the same as the microemulsion intermediate obtained in Production Example 8.

(Comparative Example 3)
The same operation as in Example 7 was performed except that the liquid B used in Example 7 was not used (does not flow). However, a microemulsion was not obtained, and a separated liquid from which oil droplets were separated was obtained.

(Comparative Example 4)
Liquid A, liquid C, and liquid D (second oil phase component) were prepared in the same manner as in Example 14, except that liquid B (first oil phase component) was not used as the liquid raw material. By using it, an emulsion having an oil phase component concentration of 12.3% consisting of the second oil phase component was obtained. However, this emulsion immediately separated into two layers, and the emulsion stability was poor.

(Comparative Example 5)
The following A to D liquids were prepared as liquid raw materials.
Liquid A: Ion-exchanged water Liquid B: As a first oil phase component, a mixed liquid consisting of a mass ratio of n-butyl acrylate (BA) and cyclohexyl methacrylate (CHMA) 50:50 Liquid C: Cloud point is 79 ° C. 1.4% aqueous solution of nonionic emulsifier (polyoxyalkylene branched decyl ether; trade name “Neugen XL-100”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB 14.7) D liquid: cyclohexyl methacrylate as the second oil phase component (CHMA): Dimethyl silicone oil (trade name “KF-96-50cs”, manufactured by Shin-Etsu Chemical Co., Ltd.) = 80:10 mixed liquid (second oil phase component) mixed with a cloud point of 79 Nonionic emulsifier (polyoxyalkylene branched decyl ether; trade name “Neugen XL-100” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB 14.7) Liquid mixture in a weight ratio of 90:10

  In Comparative Example 5, the liquid A and the liquid B were allowed to flow in at a rate of 30.0 mL / min and liquid B at a rate of 0.6 mL / min from the A liquid channel and B liquid channel in the continuous test apparatus, respectively. In the vessel, liquid B (first oil phase component) was dissolved in liquid A under high temperature and high pressure conditions where liquid A (water) was subcritical water of 310 to 350 ° C. and 25 MPa. Subsequently, C liquid (emulsifier) was allowed to flow in from the C liquid flow path at a rate of 24.0 mL / min. In the cooler, in the presence of C liquid, the liquids out of the mixer (the A liquid and B liquid The compatible solution) was cooled to room temperature, and the D solution was continuously introduced from the D solution channel at a rate of 15.4 mL / min. Thus, an emulsion having an oil phase component concentration of 20% was obtained by a continuous flow method. In this emulsion, separation of silicone oil was observed after 1 day at room temperature, and the emulsion stability was poor.

In Comparative Example 5, the average particle diameter was measured by the same method as described above for a liquid (emulsion intermediate) partially collected from the cooler before adding D liquid, and the first oil phase When the specific surface area of the component was calculated, the average particle size of the emulsion intermediate was 107 nm, the concentration of the first oil phase component was 1.0%, and the specific surface area was 6.2 × 10 ³ cm ² / g. Met. A particle size distribution diagram of the emulsion intermediate obtained in Comparative Example 5 is shown in FIG. 3I. Even when a nano-sized emulsion intermediate is used, if the specific surface area of the first oil phase component relative to the emulsion intermediate is less than 1.0 × 10 ⁴ cm ² / g, the second oil phase component Even when added, the accuracy of the composite decreased and the results were easily separated (see FIG. 5I).

  About each emulsion obtained in Examples 7-14 and Comparative Example 5, the particle size distribution and the average particle size were measured by the same method as described above. 5A to I show particle size distribution diagrams. Table 3 shows the properties of each emulsion intermediate obtained during the production by the continuous flow method, the second oil phase component added to the emulsion intermediate, and the pressure when it is added (compositing step). And the temperature condition, and the average particle diameter measured for each of the obtained emulsions.

As shown in Table 3 and FIGS. 5A to H, in Examples 7 to 14, a continuous flow was performed on the microemulsion intermediate in which the specific surface area of the first oil phase component was 1.0 × 10 ⁴ cm ² / g or more. By adding the second oil phase component in the system and mixing them, a microemulsion was obtained in which fine particles with a uniform size and nano size were stably dispersed in the aqueous dispersion medium. Was confirmed. From these results, in Examples 7 to 14, the second oil phase component was complexed with the first oil phase component forming the particles in the microemulsion intermediate, and a composite microemulsion was obtained. Was confirmed.

<Production of composite fine resin emulsion>
(Example 15)
Into a 1 L four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser, 200 g of the composite microemulsion having an average particle diameter of 162 nm obtained in Example 5 was placed in a 75 ° C. hot water bath. The mixture was stirred for 3 hours to polymerize the polymerizable monomer contained in the composite microemulsion as an oil phase component. After this polymerization treatment, the mixture was cooled to obtain a composite fine resin emulsion having a resin concentration of 36%.

(Example 16)
Except that the composite microemulsion used in Example 15 was changed to the composite microemulsion having an average particle diameter of 120 nm obtained in Example 13, the polymerization treatment was performed in the same manner as in Example 15, and after cooling A composite fine resin emulsion having a resin content of 24% was obtained.

About each emulsion obtained in Example 15 and 16, the particle size distribution and the average particle diameter were measured by the method similar to the above. As shown in the particle size distribution diagrams shown in FIGS. 6A and 6B, it was confirmed that a composite fine resin emulsion having a sharper particle size distribution was obtained compared to the composite fine emulsion before polymerization. Further, the average particle size of the composite fine resin emulsion obtained in Example 15 was 186 nm. The average particle size of the composite fine resin emulsion obtained in Example 16 was 131 nm.

Claims (10)

A microemulsion intermediate in which the first oil phase component is dispersed as particles in the presence of an emulsifier in an aqueous dispersion medium, the specific surface area of the first oil phase component with respect to the microemulsion intermediate A second oil phase component to be emulsified is added to and mixed with the microemulsified intermediate having a viscosity of 1.0 × 10 ⁴ cm ² / g or more, and is combined with the first oil phase component. A method for producing a composite microemulsion comprising a composite step.   In the complexing step, the second oil phase component is added to the microemulsion intermediate under conditions where the temperature is in the range of 5 to 100 ° C. and the pressure is in the range of 10 to 40 MPa. The manufacturing method of the composite microemulsion of Claim 1 mixed.   The first oil phase component and the second oil phase component both contain at least one compound selected from the group consisting of a polymerizable monomer and an oil-soluble compound. A method for producing a composite microemulsion.   The first oil phase component contains 5% by mass or more of a polymerizable monomer having an SP value in the range of 8.0 to 10.0 based on the total mass of the first oil phase component. The method for producing a composite microemulsion according to any one of claims 1 to 3.   The second oil phase component contains 5% by mass or more of a polymerizable monomer having an SP value in the range of 8.0 to 10.0 based on the total mass of the second oil phase component. The manufacturing method of the composite microemulsion of any one of Claims 1-4 to do.   The manufacturing method of the composite microemulsion of any one of Claims 1-5 including the preparation process of the said microemulsion intermediate which manufactures the said microemulsion intermediate before the said composite process. The preparation step includes a step of dissolving water contained in the aqueous dispersion medium and the first oil phase component in a supercritical or subcritical state of the water, and the water and the first oil phase. phase premixture with the component, and a step of cooling in the presence of the emulsifier, a manufacturing method of a composite fine emulsion of claim 6. The said emulsifier is a manufacturing method of the composite microemulsion of any one of Claims 1-7 containing the nonionic emulsifier which has a cloud point. In the compounding step, when adding the second oil phase component to the microemulsion intermediate, an emulsion containing the second oil phase component, water, and an emulsifier is added to the microemulsion intermediate. The manufacturing method of the composite microemulsion of any one of Claims 1-8 added and mixed. At least one of the first oil phase component and the second oil phase component contains a polymerizable monomer,
The method according to any one of claims 1 to 9 , further comprising a step of polymerizing the polymerizable monomer in the composite microemulsion to obtain a composite microresin emulsion from the composite microemulsion obtained after the composite step. A method for producing the composite microemulsion according to claim 1.