WO2013183520A1 - Structural color material and cosmetic using same - Google Patents

Description

Structural color material and cosmetics using the same

The present invention relates to a structural color material composed of resin particles having a structural color (interference color) and a cosmetic using the same.

It is known that the structural color is observed when light enters a regular periodic structure having a wavelength of visible light. This structural color is useful as a material for imparting high designability to various articles because the hue changes greatly depending on the viewing angle. In particular, since cosmetics are required to have excellent color developability, materials having such a structural color are very useful.

As a material having a structural color, for example, a material in which monodisperse resin particles having a particle size in a range of about 150 to 500 nm and a narrow particle size distribution are regularly and periodically arranged is known.

As described above, it is possible to obtain a material having a structural color excellent in design with a simple configuration in which resin particles having a small particle diameter are regularly arranged. However, it is very difficult to easily obtain resin particles having a small particle diameter. It is difficult to. For example, when a material having a structural color is produced using a colloidal dispersion of resin particles having a small particle size, the particles are regularly arranged and the structural color is changed by drying the dispersion medium contained in the colloidal dispersion. The material which has can be obtained. However, the material having the structural color obtained in this manner has a problem in that the regular arrangement is easily broken by applying a slight external force and the structural color is not expressed. Therefore, various special operations have been required to produce a material having a structural color using resin particles.

For example, a soap-free emulsion polymerization method is known as one method for obtaining monodisperse resin particles. In this soap-free emulsion polymerization method, in order to stabilize the polymerization system or to control the particle size to 150 to 500 nm, it is necessary to add a protective colloid such as a water-soluble polymer or a surfactant, The surface of monodisperse resin particles obtained by using them is covered with a surfactant, etc., so that the regular arrangement is easily broken by applying a slight external force, and the structural color is expressed. Since there is a problem that it does not occur, it has been proposed to fix the resin particles together after forming a regular array of resin particles (see, for example, Patent Document 1).

However, in the method described in Patent Document 1, an operation of immobilizing resin particles is required, and a material having a structural color cannot be obtained easily. Therefore, a material having a structural color can be easily obtained, and a material that can be applied to cosmetics and the like has been demanded.

JP 2010-24289 A

The problem to be solved by the present invention is to provide a structural color material made of resin particles having a structural color, which can be manufactured by a simple method, and a cosmetic using the same.

As a result of intensive studies to solve the above problems, the present inventors have partially reacted a radical polymerizable monomer in the presence of a water-soluble radical polymerization initiator in a microtubular channel. After forming the particle nuclei of the resin particles, the resin particles obtained by polymerizing the polymerization reaction liquid containing the obtained particle nuclei using a reaction vessel equipped with a stirrer have an average particle size of 150 to It was found that the absolute value of 400 nm and the absolute value of the zeta potential can be easily controlled in the range of 30 to 80 mV and can be produced by a simple method, has a structural color with high color developability, and can be used in cosmetics. Completed.

That is, the present invention feeds a fluid obtained by mixing an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer into a microtubular channel at a constant flow rate, and instantaneously sets the fluid to a preset temperature. After the temperature is reached, a part of the radical polymerizable monomer is reacted in the presence of a water-soluble radical polymerization initiator to form uniform particle nuclei of resin particles in the microtubular channel. Resin particles obtained by subjecting the polymerization reaction liquid containing the particle nuclei to a polymerization reaction using a reaction vessel equipped with a stirrer, the resin particles having an average particle size in the range of 150 to 400 nm, The present invention provides a structural color material characterized in that the absolute value of the potential is in the range of 30 to 80 mV, and a cosmetic using the same.

The structural color material of the present invention can be produced by a simple method and has a structural color having higher color developability. Therefore, by using this structural color material for cosmetics, it is possible to impart a structural color having unprecedented color development properties to cosmetics.

It is a disassembled perspective view which shows three types of plate structures of the chemical reaction device 1 used for this invention. It is a perspective view which shows the plate structure of the chemical reaction device 1 in FIG. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of chemical reaction device 1 used for the present invention. It is a disassembled perspective view which shows two types of plate structures of the chemical reaction device 2 used for the manufacturing method of this invention. It is a perspective view which shows the plate structure of the chemical reaction device 2 in FIG. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of chemical reaction device 2 used for the present invention. These are monodisperse fine particles used in Example 3.

The structural color material of the present invention feeds a fluid obtained by mixing an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer into a microtubular channel at a constant flow rate, and instantaneously sets a preset temperature. After reaching the fluid temperature, a part of the radical polymerizable monomer is reacted in the presence of a water-soluble radical polymerization initiator to form uniform particle nuclei of resin particles in the microtubular channel. Resin particles obtained by polymerizing the obtained polymerization reaction liquid containing particle nuclei using a reaction vessel equipped with a stirrer, and the average particle diameter of the resin particles is in the range of 150 to 400 nm. The absolute value of the zeta potential is in the range of 30 to 80 mV.

The water-soluble radical polymerization initiator is appropriately selected from various water-soluble radical polymerization initiators conventionally used in radical polymerization according to the type of the radical polymerizable monomer as a raw material. Can do. Examples of such water-soluble initiators include water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates, and the like.

Examples of the water-soluble organic peroxide include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1 3,3-tetramethyl hydroperoxide and the like. Examples of water-soluble azo compounds include 2,2′-diamidinyl-2,2′-azopropane monohydrochloride, 2,2′-diamidinyl-2,2′-azobutane monohydrochloride, 2,2 Examples include '-diamidinyl-2,2'-azopentane monohydrochloride and 2,2'-azobis (2-methyl-4-diethylamino) butyronitrile hydrochloride.

Moreover, examples of the redox initiator include a combination of hydrogen peroxide and a reducing agent. In this case, examples of the reducing agent include metal ions such as divalent iron ions, copper ions, zinc ions, cobalt ions and vanadium ions; ascorbic acid and reducing sugars. Furthermore, examples of the persulfate include ammonium persulfate and potassium persulfate. These water-soluble radical polymerization initiators can be used alone or in combination of two or more. One kind may be used alone, or two or more kinds may be used in combination.

The absolute value of the zeta potential of the resin particles used as the structural color material of the present invention is in the range of 30 to 80 mV. By using this range, the resin is used in cosmetics, mixed with other components, etc. Sedimentation due to aggregation of particles can be avoided, and the balance of long-term dispersion stability can be maintained. Moreover, when using for the cosmetics for hair, since the adhesiveness with respect to hair etc. becomes favorable among these resin particles, a cationic resin particle is preferable. Among these water-soluble radical polymerization initiators, water-soluble azo compounds having an amino group in the molecular structure are preferred in order to obtain resin particles having such an absolute value of zeta potential or cationic resin particles.

The radical polymerizable monomer is a compound having a radical polymerizable unsaturated group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl Alkyl (meth) acrylates having 1 to 30 carbon atoms such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyls such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene Styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, chloromethylstyrene; styrene derivatives such as nitrostyrene, acetylstyrene, methoxystyrene, α-methylstyrene; (meth) acrylic acid, itaconic acid or An unsaturated monomer having a carboxyl group such as monoester, maleic acid or monoester thereof, fumaric acid or monoester thereof, itaconic acid or monoester thereof, crotonic acid, p-vinylbenzoic acid, or a salt thereof; 2 -(Meth) acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, α-methylstyrenesulfonic acid, etc. An unsaturated monomer having a sulfo group or a salt thereof; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinylpyrrolidone, N-methylvinylpyridium chloride, (meth) allyltriethylammonium chloride, 2- Unsaturated monomers having a tertiary or quaternary amino group such as hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono ( Unsaturated monomers having a hydroxyl group such as (meth) acrylate; (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acryl Unsaturated monomers having an amide group such as amide and vinyl lactam; diester compounds of unsaturated dibasic acids such as maleic acid, fumaric acid and itaconic acid; unsaturated monomers having a cyano group such as acrylonitrile and methacrylonitrile Conjugated diolefin compounds such as butadiene and isoprene; divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, trimethylolpropane tri (meth) acrylate, Polyfunctional unsaturated monomers such as glyceryl diallyl ether and polyethylene glycol di (meth) acrylate; vinyl monomers such as ethylene, propylene and isobutylene; vinyl acetate, vinyl propionate, octyl vinyl ester, Veova 9, Veova 10, Veova 11 ("Beova" is a registered trademark of Shell Chemical Company, Inc., which is a vinyl ester derived from neononanoic acid, neodecanoic acid or neoundecanoic acid, respectively. Vinyl ester compounds such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, etc .; allyl ether compounds such as ethyl allyl ether; vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, chlorotrifluoroethylene , Unsaturated monomers having halogen groups such as tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluoro (propyl vinyl ether), perfluoroalkyl acrylate, and fluoromethacrylate; glycidyl (meth) acrylate, glycidyl methacrylate, etc. Unsaturated monomer having epoxy group: vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane Silane compounds having a polymerizable unsaturated group such as γ-methacryloxypropyltrimethoxysilane; acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl butyl ketone, diacetone acrylate, acetonitrile acrylate, acetoacetoxyethyl (meth) acrylate And unsaturated monomers having a carbonyl group such as vinyl acetophenone and vinyl benzophenone. These radically polymerizable monomers can be used alone or in combination of two or more.

The resin particles as the structural color material of the present invention feed a fluid mixed with an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer at a constant flow rate in a microtubular flow channel, and instantly. Obtained after forming the particle core of the resin particles by allowing the fluid temperature to reach a preset temperature and then partially reacting the radical polymerizable monomer in the presence of a water-soluble radical polymerization initiator. The polymerization reaction solution containing the particle nuclei can be produced by a polymerization reaction using a reaction kettle equipped with a stirring device. That is, in the microtubular channel, the radically polymerizable monomer is partially reacted in the microtubular channel to form particle nuclei of the resin particles, and then the polymerization reaction liquid containing the obtained particle nuclei is Using a reaction kettle equipped with a stirrer, if necessary, it can be produced by a polymerization reaction by further adding a radical polymerizable monomer.

In the polymerization reaction performed in the microtubular channel, an aqueous medium containing a water-soluble radical polymerization initiator and a medium containing a radical polymerizable monomer are separately introduced into the microtubular channel, and both are introduced into the microtubular channel. The reaction product is obtained as an emulsified dispersion in which resin particles are dispersed in water. That is, the polymerization reaction in the microtubular channel is soap-free emulsion polymerization performed without using an emulsifier or a dispersant. By this polymerization reaction in the microtubular channel, it is possible to form stable particle nuclei in which the absolute value of the zeta potential of the resin particles finally obtained is 30 to 80 mV.

The polymerization reaction in the micro tubular channel will be described in more detail. As an apparatus used for production of the resin particles used in the present invention, it is preferable to use a micromixer having a microtubular channel formed therein and a reaction vessel having a microtubular channel formed therein. Here, the microtubular channel may be a simple tube or pipe-shaped one as the reaction channel, or a space formed by combining at least two members may be used as the reaction channel. .

By introducing and mixing an aqueous medium containing a water-soluble radical polymerization initiator and a medium containing a radical polymerizable monomer into the reaction vessel, the oil droplets of the radical polymerizable monomer are converted into water-soluble radical polymerization. After formation in an aqueous medium containing an initiator, the radically polymerizable monomer partially dissolved in the aqueous medium starts to polymerize due to decomposition of the water-soluble radical polymerization initiator in the microtubular channel, and the chain length Due to the increase in hydrophobicity due to the increase in the length of the particles, precipitation and aggregation occur and nuclei of fine particles are formed. The radically polymerizable monomer is supplied to the surface of the particle nuclei from oil droplets of the radically polymerizable monomer finely dispersed in the aqueous phase. As a result, emulsion polymerization proceeds. In this emulsion polymerization, stable resin particles can be obtained without using protective colloids such as water-soluble polymers and surfactants used in conventional soap-free emulsion polymerization.

By using the micromixer, since the mixing of the aqueous medium containing the water-soluble radical polymerization initiator and the medium containing the radical polymerizable monomer becomes a mixture of small segments, the contact area becomes large, and thus small energy is required. However, mixing is promoted, and the radical polymerizable monomer can be finely dispersed in an aqueous medium containing a water-soluble radical polymerization initiator even at a relatively low flow rate. Fine dispersion is preferable because monodisperse particle nuclei grow by supplying radically polymerizable monomers smoothly and uniformly from the oil droplets of radically polymerizable monomers to the surface of the particle nuclei.

In the present invention, a fluid obtained by mixing an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer is fed into a microtubular channel at a constant flow rate. Depending on the area and pump capacity, a range of 5 to 1000 mL / min is preferable, and a range of 10 to 500 mL / min is more preferable. In addition, the constant flow rate in the present invention refers to a flow rate at which the flow rate fluctuation is within ± 5%.

In general, polymer particles obtained by soap-free emulsion polymerization as described above are stabilized by repulsion due to the charge of radical initiator segments and adsorption of by-product oligosoap to the particle surface. In the reaction, it takes time to reach a preset temperature, and since the reaction has already started, it is difficult to obtain particles having a small amount of polymerization initiator segment and having a stable charge. . On the other hand, in a reaction vessel in which uniform oil droplets are formed in a micromixer and a microtubular channel is formed inside, the fluid temperature is instantaneously heated to a preset temperature, so that a radical initiator is usually used. More nuclei can be decomposed, the generation and stabilization of fine particle nuclei are promoted, and the nucleation and growth of monodisperse fine particles having a more uniform particle size usually obtained by batch reaction can be realized.

The preset temperature is a temperature at which the water-soluble radical polymerization initiator is decomposed to generate radicals, and can be set according to the type of the water-soluble radical polymerization initiator. In the present invention, “instantaneous” means a range of 0.5 to 10 seconds, preferably 1 to 4 seconds, until the fluid temperature reaches a preset temperature.

A commercially available micromixer can be used as the above-described micromixer having a microtubular channel formed therein. For example, a microreactor having an interdigital channel structure, an institute, a fule, a micromixer, etc. Technic Mainz (IMM) single mixer and caterpillar mixer; Microglass microglass reactor; CPC Systems Cytos; Yamatake YM-1, YM-2 mixer; Shimadzu GLC mixing tea and tea (T-shaped connector); IMT chip reactor manufactured by Micro Chemical Engineering Co., Ltd .; Micro-High Mixer developed by Toray Engineering Co., Ltd.

Furthermore, as a preferred form of the micromixer system, an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer are circulated in separate flow paths, and the two liquids are mixed at the outlets of the two flow paths. After mixing using a micromixer, a micromixer that promotes mixing by supplying and supplying to a flow path whose flow path cross-sectional area is reduced in the flow direction is preferable. Mixing can be further promoted by a turbulent flow effect caused by further contracting the flow path.

After mixing using a micromixer that mixes two liquids at the outlets of the above two channels, mixing can be promoted by supplying the channel to a channel whose channel cross-sectional area is reduced in the flow direction. By using the mixer, it becomes possible to promote the dispersion of the radical polymerizable monomer in the aqueous medium containing the water-soluble radical polymerization initiator.

The microtubular flow channel in the micromixer may be a tube or pipe shape other than that in which at least two members are combined and the space formed between the members is used as the flow channel. May be used as a flow path.

As a preferred form of a micromixer that mixes two liquids at a junction provided at the outlet of a flow path used in the present invention, for example, a chemical reaction device 1 is exemplified. In addition, as a micromixer that can promote mixing of two liquids by a flow path whose flow path cross-sectional area is reduced in the flow direction, for example, the chemical reaction device 2 is exemplified.

Hereinafter, the chemical reaction device 1 and the chemical reaction device 2 provided with a flow channel in a preferable form used in the present invention will be described in detail. FIG. 1 shows a plate in which a microtubular channel through which a fluid containing a radical polymerizable monomer passes, a plate in which a microtubular channel through which a fluid containing a water-soluble radical polymerization initiator passes, and a fluid in which heat exchange is performed. It is the example of schematic structure of the reaction apparatus formed by laminating | stacking the plate which installed the flow path which flows. FIG. 2 shows a chemical reaction device 1 formed by laminating a plate on which microtubular channels for flowing the mixed liquid in the device of FIG. 1 are arranged and a plate on which a channel for flowing a fluid for heat exchange is installed. This is a schematic configuration example.

The chemical reaction device 1 is configured, for example, by laminating a plurality of first plates (5 in FIG. 1) and second plates (8 in FIG. 1) having the same rectangular plate shape in FIG. Has been. Further, a third plate (3 in FIG. 1) is laminated as shown in FIG. 2 as necessary. Each one first plate is provided with a flow path through which a fluid containing a radical polymerizable monomer passes. The second plate is provided with a flow path (hereinafter referred to as “reaction flow path”) through which a fluid containing a water-soluble radical polymerization initiator passes (hereinafter referred to as a “process plate”). "). The third plate is provided with a flow path for temperature control fluid (hereinafter referred to as “temperature control flow path”) (hereinafter, the plate provided with the temperature control flow path is referred to as “temperature control plate”). .)

As shown in FIG. 3, these supply ports and discharge ports are arranged dispersed in each region of the end surfaces 15b, 15c and side surfaces 15d, 15e of the chemical reaction device 1, and in these regions, a water-soluble radical polymerization initiator is disposed. (In FIG. 2, δ represents a liquid flow of a fluid containing a water-soluble radical polymerization initiator), a fluid containing a radical polymerizable monomer (ε in FIG. 2 is a fluid containing a radical polymerizable monomer) A joint portion 32 including a connector 30 and a joint portion 31 for flowing a temperature-controlled fluid (in FIG. 2, γ indicates a flow of the temperature-controlled fluid) and a joint portion 31 are connected to each other. In addition, the outlet mixing is performed by combining the fluid containing the radical polymerizable monomer and the fluid containing the water-soluble radical polymerization initiator in the space 33 formed by the end face 15c of the chemical reaction device 1 and the connector 30. Mixing of a fluid containing a polymerizable monomer and a fluid containing a water-soluble radical polymerization initiator is achieved.

Through these joint portions, a fluid containing a radical polymerizable monomer and a fluid containing a water-soluble radical polymerization initiator are supplied from the end surface 15b, discharged to the end surface 15c, and a temperature-controlled fluid is supplied from the side surface 15d. And is discharged to the side surface 15e. The planar view shape of the device for chemical reaction 1 is not limited to the rectangular shape as shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 15d and 15e longer than between the end surfaces 15b and 15c. Therefore, in accordance with the illustrated shape, the direction from the end face 15b to the end face 15c is referred to as the longitudinal direction of the process plate and the temperature control plate of the chemical reaction device 1, and the direction from the side face 15d to the side face 15e is referred to as the chemical reaction device. This is referred to as the short direction of the process plate 1 and the temperature control plate.

The chemical reaction device 2 includes, for example, a fourth plate (14 in FIG. 4) having the same rectangular plate shape in FIG. 4, and a temperature control plate (3 in FIG. 4) in FIG. As shown, they are stacked. Each one fourth plate is provided with a flow path through which the fluid mixed in the chemical reaction device 1 passes. Then, as shown in FIG. 6, these supply ports and discharge ports are distributed and arranged in each region of the end surfaces 16b, 16c, and side surfaces 16d, 16e of the chemical reaction device 2, and in these regions, radically polymerizable single units are disposed. In order to flow a fluid containing a monomer, a fluid containing a water-soluble radical polymerization initiator (α in FIG. 5 indicates a liquid fluid), and a temperature adjusting fluid (γ indicates a temperature adjusting fluid in FIG. 5) as necessary. The joint portions 32 each including the connector 30 and the joint portion 31 are connected to each other.

Via these joint portions, a fluid containing a fluid containing a radical polymerizable monomer and a fluid containing a water-soluble radical polymerization initiator is supplied from the end face 16b, discharged to the end face 16c, and the temperature control fluid is turned to the side face 16d. Is discharged from the side surface 16e. At this time, by reducing the flow path width of the process plate 14 from q1 to q2, the degree of mixing of the fluid containing the radical polymerizable monomer and the fluid containing the water-soluble radical polymerization initiator is rapidly increased. Yes. The shape of the chemical reaction device 2 in plan view is not limited to the rectangular shape shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 16d and 16e longer than between the end surfaces 16b and 16c. Therefore, in accordance with the illustrated shape, the direction from the end face 16b to the end face 16c is referred to as the longitudinal direction of the process plate and the temperature control plate of the chemical reaction device 2, and the direction from the side face 16d to the side face 16e is referred to as the chemical reaction device. The short direction of the process plate 2 and the temperature control plate will be referred to.

As shown in FIG. 1, the temperature control plate is provided with a temperature control flow path 6 having a concave groove shape on one surface 3 a at a predetermined interval. The cross-sectional area of the temperature control channel 6 is not particularly limited as long as heat can be transferred to the reaction channel, but is approximately in the range of 1 × 10 ⁻² to 2.5 × 10 ² mm ² . More preferably, it is 0.32 to 4 mm ² . The number of temperature control channels 6 may be an appropriate number in consideration of heat exchange efficiency, but is preferably in the range of 1 to 1000 per plate, and more preferably in the range of 10 to 100. .

As shown in FIGS. 1 and 4, the temperature control channel 6 flows in a plurality of main channels 6 a arranged along the longitudinal direction of the temperature control plate, and upstream and downstream ends of the main channel 6 a, respectively. You may provide the supply side flow path 6b and the discharge side flow path 6c which are arrange | positioned substantially orthogonally to the path | route 20, and are connected to each main flow path 6a. In FIGS. 1 and 4, the supply-side flow path 6b and the discharge-side flow path 6c are bent at right angles twice and open to the outside from the side surfaces 3d and 3e of the temperature control plate. As for the number of each temperature control channel 6, only the main channel 6a portion of the temperature control channel 6 is arranged, and the supply side channel 6b and the discharge side channel 6c are each composed of one. .

The emulsified dispersion according to the present invention promotes the generation and stabilization of fine particle nuclei by emulsion polymerization of a radically polymerizable monomer in a temperature range of 70 ° C. to 200 ° C. in a microtubular channel. Nucleation and growth of smaller monodispersed fine particles obtained by batch reaction can be realized.

Usually, when preparing an emulsified dispersion containing monodispersed resin particles only in a batch reaction kettle, the reaction temperature is set to 50 to 90 ° C. This is set according to the 10-hour half-life temperature of persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate that are usually used in soap-free emulsion polymerization. Since the reaction may run out of control and the boiling point of water may exceed 100 ° C., there is a problem that it is very dangerous except for a batch reaction kettle that has special measures such as pressure resistance setting. On the other hand, in the emulsion polymerization performed in the microtubular channel, it is possible to increase the temperature and pressure safely and easily by providing a pressure regulating valve at the channel outlet. For this reason, even if the temperature of an aqueous medium exceeds 100 degreeC, there exists a merit which does not produce any problem.

In general, the radical decomposition rate constant of the radical polymerization initiator can be obtained by the following formula.
k = A × EXP (-E / RT)
k: radical decomposition rate constant (h-1) of polymerization initiator, A: frequency factor (h-1),
E: activation energy (J / mol), R: gas constant (= 8.314 J / mol · K)
T: Absolute temperature (K)

As is clear from the above calculation formula, radical decomposition increases exponentially with increasing temperature. In a reaction vessel with a microtubular channel formed inside, by increasing the fluid temperature to the range of 70-200 ° C, the amount of initiator slices that contribute to the nucleation and stability of fine particles can be rapidly increased. Can do. Therefore, compared to emulsion polymerization using a normal batch reaction kettle, the absolute value of the zeta potential is 30 to 30 in a safe and simple manner, and without adding a protective colloid such as a water-soluble polymer or a surfactant. Resin particles in the range of 80 mV can be obtained efficiently.

From the above, the reaction temperature of the polymerization reaction of the radical polymerizable monomer in the present invention is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 160 ° C, and further preferably in the range of 90 to 150 ° C. .

Further, in the present invention, the water-soluble radical polymerization initiator is controlled by continuously controlling the Reynolds number of the fluid containing the water-soluble radical polymerization initiator and the radical polymerizable monomer in the reaction vessel from 0.25 to 300. The mixing of the fluid containing the agent and the radical polymerizable monomer is further enhanced by the turbulent effect, so that the particle nuclei grow uniformly and blockage of the flow path due to aggregation can be prevented. It is preferable because it can be manufactured.

The Reynolds number as used in the present invention is calculated according to the following formula (1).

Reynolds number = (D × u × ρ) / μ (1)
Here, D (inner diameter of the flow path), u (average flow velocity), ρ (fluid density), and μ (fluid viscosity).

The ratio of the fluid containing the water-soluble radical polymerization initiator and the fluid containing the radical polymerizable monomer in the microtubule depends on the polymer fine particle concentration of the target emulsified dispersion. In order to promote the generation and stabilization of fine particle nuclei in the tubular channel, an emulsified dispersion having a smaller particle size and a higher solid content concentration than that of a normal batch reaction can be obtained. The ratio of the fluid containing the radically polymerizable monomer in the fluid containing the water-soluble radical polymerization initiator in the microtubule is preferably in the range of 5 to 60% because aggregation and sedimentation of the generated resin particles can be suppressed. The range of 10 to 50% is more preferable, and the range of 15 to 40% is more preferable.

As a reaction apparatus comprising a microtubular flow path for emulsion polymerization of a radical polymerizable monomer used in the production method of the present invention, a reaction apparatus in which the flow path is installed in a heat transfer reaction vessel is preferable. A microtubule is preferred because it allows rapid control of heating. The microtubular channel is preferably of a size that can adjust the time to reach the polymerization reaction temperature in a short time and is sufficiently large to prevent clogging, and has a fluid cross-sectional area of 0.1 to 4 A flow path having a gap size of 0.0 mm ² is preferable because it is easy to adjust the time to reach the polymerization reaction temperature in a short time and is sufficiently large to prevent clogging. In the present invention, “cross section” means a cross section perpendicular to the flow direction in the flow path, and “cross sectional area” means the area of the cross section.

The cross-sectional shape of the channel is a square, a rectangle including a rectangle, a polygon including a trapezoid, a parallelogram, a triangle, a pentagon, etc. (a shape with rounded corners, a high aspect ratio, ie including a slit shape) It may be a star shape, a semicircle, a circle including an ellipse, or the like. The cross-sectional shape of the channel need not be constant.

The method of forming the reaction channel is not particularly limited, but generally, the member (X) having a groove on the surface thereof is laminated, bonded, or the like on the surface having the groove. It is fixed and formed as a space between the member (X) and the member (Y).

The heat exchange function may be further provided in the flow path. In that case, for example, a groove for flowing the temperature adjusting fluid is provided on the surface of the member (X), and another member is bonded or laminated on the surface provided with the groove for flowing the temperature adjusting fluid. What is necessary is just to fix. In general, a member (X) having a groove on the surface and a member (Y) provided with a groove for flowing a temperature-controlled fluid include a surface provided with a groove, and a surface provided with a groove of another member. A flow path may be formed by fixing the opposite surface, and a plurality of these members (X) and members (Y) may be fixed alternately.

At this time, the groove formed on the surface of the member may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the surface of the member. The method of providing the groove on the surface of the member is arbitrary, and for example, methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography (including energy beam lithography), and laser ablation can be used.

The layout of the flow paths in the member may be in the form of a straight line, a branch, a comb, a curve, a spiral, a zigzag, or any other arrangement according to the purpose of use.

The outer shape of the member does not need to be particularly limited, and can take a shape according to the purpose of use. The shape of the member may be, for example, a plate shape, a sheet shape (including a film shape, a ribbon shape, etc.), a coating film shape, a rod shape, a tube shape, and other complicated shapes. External dimensions such as thickness are preferably constant. The material of the member is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, semiconductor, or the like.

The reaction vessel having a microtubular channel formed therein for obtaining the emulsified dispersion of the present invention has a structure in which a heat conductive plate-like structure having a plurality of grooves formed on the surface is laminated. An apparatus can be used.

The reaction vessel having a microtubular channel formed therein has a heat exchange function and a fluid cross-sectional area flowing in a liquid-tight manner in the microtubular channel is 0.1 to 4.0 mm ^2. Those having a microtubular channel having a void size are preferable, and other requirements are not particularly limited. Examples of such a reaction container include a reaction container in which the flow path (hereinafter, simply referred to as “micro flow path”) is provided in a member used as a chemical reaction device.

The polymerization reaction liquid obtained by polymerizing the radical polymerizable monomer in the above microtubular flow path is added with a water-soluble radical polymerization initiator, a radical polymerizable monomer, etc., if necessary. The polymerization reaction is carried out in a conventional batch reaction kettle equipped with

Examples of the water-soluble radical polymerization initiator added as necessary include the water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates and the like exemplified above.

In this case, a radical polymerizable monomer having a specific functional group may be added for the purpose of introducing a functional group to the particle surface. Examples of the radical polymerizable monomer to be added include the radical polymerizable monomers exemplified above.

The reaction temperature in a normal batch reaction kettle equipped with a stirrer can be appropriately set depending on the type of water-soluble radical polymerization initiator used and the pressure in the reaction kettle.For example, persulfate is used as the water-soluble radical polymerization initiator. When used and reacted under normal atmospheric pressure, a range of 50 to 90 ° C. is preferable, and a range of 60 to 85 ° C. is more preferable. In addition, although the reaction time depends on the reaction temperature, it is usually preferably in the range of 0.5 to 10 hours.

As described above, the resin particles used as the structural color material of the present invention are obtained by partially reacting a radical polymerizable monomer in the presence of a water-soluble radical polymerization initiator in a microtubular channel. After the formation of the particle nuclei, the polymerization reaction liquid containing the obtained particle nuclei is obtained by a polymerization reaction using a reaction vessel equipped with a stirring device. In the formation of the particle nuclei, the reaction rate is preferably in the range of 0.1 to 50% based on the radically polymerizable monomer used initially. Further, in the step of polymerizing the obtained polymerization reaction liquid containing particle nuclei using a reaction kettle equipped with a stirrer, the radical polymerizable monomer used initially and the added radical polymerizable monomer were used. The reaction rate is preferably 95% or more based on the total.

The resin particles used as the structural color material of the present invention are manufactured by the above method, and have an average particle size in the range of 150 to 400 nm and an absolute value of zeta potential in the range of 30 to 80 mV. it can. Further, the average particle diameter of the resin particles is in the range of 150 to 400 nm in order to obtain a structural color having high color developability, but is preferably in the range of 180 to 350 nm in order to enhance the effect. The average particle size of the resin particles is measured with a dynamic light scattering particle size distribution meter. In addition, it is preferable that the particle diameter of the resin particles to be the structural color material of the present invention is uniform, and whether or not it is uniform is determined by CV value (standard deviation and standard deviation) obtained by observation using an atomic force microscope. A numerical value obtained by multiplying the ratio of the average particle diameters by 100), and the CV value is assumed to be uniform if it is in the range of 8% or less. The average particle size of the resin particles in the present invention is measured by a dynamic light scattering method.

Furthermore, the absolute value of the zeta potential of the resin particles is adjusted for the particle size of the resin particles, and when used in cosmetics, avoids settling due to aggregation of the resin particles when blended with other components, and long-term dispersion stability Therefore, the range of 30 to 80 mV is preferable, but the range of 35 to 70 mV is preferable in order to further enhance the effect.

The cosmetic of the present invention contains the structural color material described above. In addition, as other components used in the cosmetic product of the present invention, components usually used in cosmetic products can be used, and vary depending on the type of cosmetic product. For example, pigments, liquid oils, solid oils, waxes, hydrocarbon oils, high grades Fatty acid, lower alcohol, higher alcohol, polyhydric alcohol, ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water-soluble polymer, increase Sticky agent, film agent, UV absorber, sequestering agent, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient, vitamin, antioxidant, antioxidant aid, antiseptic, anti-inflammatory agent , Whitening agents, plant extracts, activators, blood circulation promoters, antiseborrheic agents, anti-inflammatory agents, fragrances, water and the like.

Examples of the pigment include talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, sauroite, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate. , Magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, boron nitride and other inorganic powders: zinc myristate, palmitic acid Metal soap such as calcium oxide, aluminum stearate; polyamide particles, polyethylene particles, acrylic resin particles, polystyrene particles, styrene-acrylic copolymer resin particles, benzoguanamine resin particles, polytetra Resin particles such as fluoroethylene particles and cellulose particles; titanium dioxide, zinc oxide, dial, iron titanate, γ-iron oxide, yellow iron oxide, ocher, black iron oxide, low order titanium oxide, mango violet, cobalt violet, oxidized Inorganic pigments such as chromium, chromium hydroxide, cobalt titanate, ultramarine, bitumen, pearl pigment, aluminum powder, copper powder; red 201, red 202, red 204, red 205, red 220, red 226 Organic pigments such as red 228, red 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404, red 3, red 104, red 106, red 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc. Organic pigments; natural pigments such as chlorophyll, β-carotene, anthocyanins and the like.

Examples of the liquid oil include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanca oil, castor oil, flaxseed Oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, Examples include beef leg fat, mole, and hardened castor oil.

Examples of the wax include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, and reduced lanolin. Jojo wax, hard lanolin, shellac wax, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, polyoxyethylene cholesterol ether, lanolin fatty acid polyethylene glycol, polyoxyethylene hydrogenated lanolin alcohol ether, and the like.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.

Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid. It is done.

Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

Examples of the higher alcohol include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol; monostearyl glycerin ether, 2-decyltetradecinol, lanolin alcohol, Examples thereof include branched alcohols such as cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, and octyl decanol.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2- Dihydric alcohols such as butene-1,4-diol, hexylene glycol and octylene glycol; Trihydric alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol; Tetrahydric alcohols such as pentaerythritol; Xylitol Pentahydric alcohols such as sorbitol, mannitol, etc .; diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglyceride Polyhydric alcohol condensates such as ethylene glycol, triglycerin, tetraglycerin, polyglycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene Glycol mono 2-methyl hexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl Glycol monoalkyl ethers such as ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Examples include glycol monoalkyl acetates such as glycol monopropyl ether acetate and propylene glycol monophenyl ether acetate; glycerin monoalkyl ethers such as xyl alcohol, ceralkyl alcohol, and batyl alcohol.

Examples of the ester oil include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, Myristyl lactate, Lanolin acetate, Isocetyl stearate, Isocetyl isostearate, Cholesteryl 12-hydroxystearate, Ethylene glycol di-2-ethylhexanoate, Dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, Neopentyl glycol dicaprate , Diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-ethylhexanoic acid trimethylolpropane, Trimethylolpropane isostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glyceryl trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oleyl, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L -Glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, myristic acid 2 Hexyl decyl palmitate, 2-hexyldecyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

Examples of the silicone oil include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; Examples include amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and modified polysiloxane such as fluorine-modified polysiloxane.

Examples of the anionic surfactant include fatty acid salts such as sodium laurate and sodium palmitate; alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; polyoxyethylene-sodium lauryl sulfate, polyoxyethylene-lauryl sulfate. Polyoxyalkylene sulfates such as potassium and polyoxyethylene-lauryl sulfate triethanolamine; N-acyl sarcosine acids such as sodium lauroyl sarcosine; N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid methyl tauride sodium, lauryl Fatty acid amide sulfonates such as sodium methyl tauride; phosphoric acids such as sodium polyoxyethylene-oleyl ether phosphate, polyoxyethylene-stearyl ether phosphate Steal salt; sulfosuccinate such as sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate; sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate, Alkylbenzene sulfonates such as dodecylbenzene sulfonic acid; Fatty acid ester sulfates such as hydrogenated coconut oil fatty acid sodium glycerol sulfate; N-lauroyl glutamate monosodium, N-stearoyl glutamate disodium, N-myristoyl-L-glutamate monosodium, etc. N-acyl glutamate; sulfated oil such as funnel oil; polyoxyethylene-alkyl ether carboxylic acid Α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; sodium lauroyl monoethanolamide succinate; N -Palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride; alkylpyridinium salts such as cetylpyridinium chloride; distearyldimethylammonium dialkyldimethylammonium chloride; poly (N , N′-dimethyl-3,5-methylenepiperidinium); alkyl quaternary ammonium salts; alkyldimethylbenzylammonium salts; alkylisoquinolinium salts; dialkyl morpholinium salts; polyoxyethylene-alkylamines; Examples include salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

Examples of the amphoteric surfactant include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy 2 Imidazoline amphoteric surfactants such as sodium salts; betaine amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaines Agents and the like.

As the nonionic surfactant, a lipophilic one or a hydrophilic one can be used. Examples of the lipophilic nonionic surfactant include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta- Sorbitan fatty acid esters such as 2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan; mono-cotton oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, monostearate glycerin, α, α'-oleate glycerin Glycerin fatty acid esters such as glyceryl pyroglutamate, glyceryl monostearate and malic acid malate; propylene such as propylene glycol monostearate Glycol fatty acid ester; hardened castor oil derivative; glycerin alkyl ether and the like.

Examples of hydrophilic nonionic surfactants include polyoxyethylene-sorbitan monooleate, polyoxyethylene-sorbitan monostearate, polyoxyethylene-sorbitan monooleate, and polyoxyethylene-sorbitan monooleate. Oxyethylene-sorbitan fatty acid ester; polyoxyethylene-sorbite monolaurate, polyoxyethylene-sorbitol monooleate, polyoxyethylene-sorbitol monooleate, polyoxyethylene-sorbitol fatty acid ester such as polyoxyethylene-sorbitol monostearate Polyoxyethylene-glycerol monostearate, polyoxyethylene-glycerol monoisostearate, polyoxyethylene-glycerol triisostearate, etc. Polyoxyethylene-glycerin fatty acid esters such as polyoxyethylene-monooleate; polyoxyethylene-fatty acid esters such as polyoxyethylene-distearate, polyoxyethylene-monodiolate, ethylene glycol distearate; polyoxyethylene-lauryl ether, polyoxyethylene -Polyoxyethylene-alkyl ethers such as oleyl ether, polyoxyethylene-stearyl ether, polyoxyethylene-behenyl ether, polyoxyethylene-2-octyldodecyl ether, polyoxyethylene-cholestanol ether; polyoxyethylene polyoxy Propylene-cetyl ether, polyoxyethylene / polyoxypropylene-2-decyltetradecyl ether, polyoxyethylene Polyoxypropylene-monobutyl ether, polyoxyethylene / polyoxypropylene / hydrogenated lanolin, polyoxyethylene / polyoxypropylene / alkyl ether such as polyoxyethylene / polyoxypropylene / glycerin ether; tetrapolyoxyethylene / tetra Polyoxypropylene-ethylenediamine condensate; polyoxyethylene-castor oil, polyoxyethylene-hardened castor oil, polyoxyethylene-hardened castor oil monoisostearate, polyoxyethylene-hardened castor oil triisostearate, polyoxyethylene -Polyoxyethylene-castor oil derivatives such as hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, polyoxyethylene-hardened castor oil maleic acid; polyoxyethylene-sol Polyoxyethylene-beeswax lanolin derivatives such as bit beeswax; alkanolamides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide; polyoxyethylene-propylene glycol fatty acid ester; polyoxyethylene-alkylamine; poly Examples thereof include oxyethylene-fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphoric acid.

Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate. Rate, sodium lactate, bile salt, dl-pyrrolidone carboxylate, short chain soluble collagen, diglycerin ethylene oxide adduct, diglycerin propylene oxide adduct, Izayoi rose extract, yarrow extract, mellilot extract, etc. Is mentioned.

As the water-soluble polymer, any of natural products, semi-synthetic products, and synthetic products can be used. For example, as a natural water-soluble polymer, for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (brown algae extract), starch (rice, rice, Corn, potato, wheat), glycyrrhizic acid, xanthan gum, dextran, succinoglucan, bullulan, collagen, casein, albumin, gelatin and the like.

Examples of semi-synthetic water-soluble polymers include starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, carboxymethylcellulose, Cellulose polymers such as sodium carboxymethyl cellulose, crystalline cellulose and cellulose powder; and alginic acid polymers such as sodium alginate and propylene glycol alginate.

Synthetic water-soluble polymers include, for example, vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, and carboxyvinyl polymer); polyoxyalkylenes such as polyethylene glycol and polyoxyethylene-polyoxypropylene copolymers Polymers; acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide; polyethyleneimine; cationic polymers.

Examples of the thickener include gum arabic, carrageenan, gum karaya, gum tragacanth, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, Hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, laponite, silicic anhydride Etc.

Examples of the ultraviolet absorber include p-aminobenzoic acid, p-aminobenzoic acid monoglycerin ester, N, N-dipropoxy-p-aminobenzoic acid ethyl ester, and N, N-diethoxy-p-aminobenzoic acid ethyl ester. Benzoic acid UV absorption such as ester, N, N-dimethyl-p-aminobenzoic acid ethyl ester, N, N-dimethyl-p-aminobenzoic acid butyl ester, N, N-dimethyl-p-aminobenzoic acid ethyl ester Agents: Anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; Salicylic acid ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate Octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate , Isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p Cinnamic acids such as -methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate System ultraviolet Line absorber: 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4 Benzophenone ultraviolet absorbers such as' -phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone; 3- (4'-methylbenzylidene) -d , L-camphor; 3-ben Redene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) benzo 2- (2′-hydroxy-5′-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4′-tert-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene ) -3-pentan-2-one and the like.

Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetra Examples include sodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, ethylenediamine hydroxyethyl triacetate, and the like.

As the sugar, any of monosaccharide, oligosaccharide, and polysaccharide can be used. Examples of the monosaccharide include tri-monosaccharides such as D-glyceryl aldehyde and dihydroxyacetone; tetra-monosaccharides such as D-erythrose, D-erythrulose, D-threose and erythritol; L-arabinose, D-xylose, L- Lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc. pentasaccharides; D-glucose, D-talose, D-bucose, D-galactose, D-fructose, L-galactose, Hexasaccharides such as L-mannose and D-tagatose; Heptasaccharides such as aldoheptose and heproose; Octasaccharides such as octulose; 2-deoxy-D-ribose, 6-deoxy-L-galactose and 6-deoxy-L -Deoxy sugars such as mannose; D-glucosamine, D-galactosamine, sialic acid, a Nouron acid, an amino sugar such as muramic acid; D-glucuronic acid, D- mannuronic acid, L- guluronic acid, D- galacturonic acid and uronic acid such as L- iduronic acid.

Examples of the oligosaccharide include sucrose, guntianose, umbelliferose, lactose, planteose, isoliquenose, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbus course, and the like.

Examples of the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato. Examples include sulfuric acid, locust bingham, succinoglucan, and caronic acid.

Examples of the amino acid include neutral amino acids such as threonine and cysteine; basic amino acids such as hydroxylysine. An amino acid derivative can also be used, and examples of the amino acid derivative include acyl sarcosine sodium, acyl glutamate, acyl β-alanine sodium, glutathione, pyrrolidone carboxylic acid and the like.

Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol. Etc.

Examples of the polymer emulsion include acrylic resin emulsion, polyvinyl acetate emulsion, and natural rubber latex.

Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Examples of the vitamin include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.

Examples of the antioxidant include tocopherol and its derivatives, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid ester and the like.

Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid, and the like.

Examples of the preservative include ethyl paraben and butyl paraben.

Examples of the anti-inflammatory agent include glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, and the like.

Examples of the whitening agent include placenta extract, yukinoshita extract, arbutin and the like.

Examples of the plant extract include, but are not limited to: buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokoinin, loofah, lily, saffron, senkyu, ginger, hypericum, Examples include extracts from onionis, garlic, pepper, chimpi, toki, seaweed and the like.

Examples of the activator include royal jelly, photosensitive element, cholesterol derivative and the like.

Examples of the blood circulation promoter include nonyl acid valenyl amide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ectamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotine. Nate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol and the like.

Examples of the antiseborrheic agent include sulfur and thianthol.

Examples of the anti-inflammatory agent include tranexamic acid, thiotaurine, hypotaurine and the like.

The cosmetic product of the present invention can be produced by mixing each of the above-mentioned blending ingredients by a usual method. Specific examples of the cosmetics of the present invention include makeup cosmetics such as lipsticks, foundations, teak colors, eye shadows and nail enamels; hair cosmetics such as hair gels, hair waxes, hair treatments and hair manicure gels.

The blending ratio of the structural color material as a solid content in the cosmetic of the present invention is not particularly limited as long as the desired structural color can be imparted to the cosmetic, but is in the range of 0.1 to 50% by mass. The range of 1 to 30% by mass is more preferable.

Hereinafter, the present invention will be described in more detail with reference to examples.

<Micromixer used in Examples>
In this embodiment, the process plates 5 and 8 having the structure shown in FIG. 1 were used as the micromixer as a micromixer for mixing at the junction provided at the outlet of the flow path. Further, as a micromixer that promotes mixing by a flow path whose flow path cross-sectional area is reduced in the flow direction, a process plate 14 having a structure shown in FIG. 4 was used as the micromixer. The structure of the micromixer includes a chemical reaction device in which the temperature control plate 3 is stacked on the top and bottom of the micromixer laminate in which the plate 5 is stacked on the plate 8, and a chemistry in which the temperature control plate 3 is stacked on the top and bottom of the plate 14. A structure in which a reaction device was connected in series was used. Specifically, an aqueous fluid in which a water-soluble radical polymerization initiator is dissolved is introduced into the flow path 20 of the plate 5 into the flow path 21 of the radical polymerizable monomer plate 8, and the respective fluids are combined at the plate outlet. . Thereafter, the radical polymerizable monomer was further finely dispersed in an aqueous fluid in which a water-soluble radical polymerization initiator was dissolved by passing through the flow path 22 of the plate 14. The process plates 5, 8, and 14 and the temperature control plate 3 are made of SUS304, and the plate thicknesses of the plates 5 and 14 are 0.4 mm and the plate 8 is 1 mm. The cross-sectional dimension of the reaction channel 21 is 1.0 mm wide × 0.5 mm deep, the cross-sectional dimension of the temperature control channel 6 is 1.2 mm wide × 0.5 mm deep, and the cross-sectional dimension of the reaction channel 20 is 6 mm wide × The depth is 0.2 mm, and the cross-sectional dimension of the reaction channel 22 is 4 mm wide × 0.2 mm deep at the wide portion and 0.2 mm wide × 0.2 mm deep at the contracted portion.

<Measuring method of average particle diameter>
Measurement was performed using a Microtrac particle size distribution analyzer “UPA-ST150” manufactured by Nikkiso Co., Ltd. In addition, the measured sample used what diluted the obtained emulsified dispersion 100 times.
<Measurement method of CV value>
In the particle image photograph obtained from the result of observation with an atomic force microscope, 20 resin particles are arbitrarily extracted, and the ratio of the average particle diameter of the particle obtained by image analysis to its standard deviation (standard deviation / average particle) Diameter x 100).

<Measurement method of absolute value of zeta potential>
Measurement was performed using a zeta potential / particle size measurement system “ELS-Z” manufactured by Otsuka Electronics Co., Ltd. In addition, the measured sample used what diluted the obtained emulsified dispersion 10 times.

<Measurement method of solid content of emulsion dispersion polymer>
1 g of the emulsified dispersion was weighed in a metal petri dish with a precision balance, diluted with 1 g of ion-exchanged water, and then dried in a dryer set at 110 ° C. for 2 hours. From the solid resin content remaining in the petri dish after drying and the amount of the emulsified dispersion initially weighed, the solid polymer content in the emulsified dispersion was measured.

Example 1
Two syringe pumps and a 2.17 mm tube were connected to the outlet of each syringe via a pressure gauge, a safety valve, a filter, and a check valve. Each tube was similarly connected with a T-connector having an inner diameter of 2.17 mm, and further connected to a 2.17 mm × 12 m tube through a flow path with a reduced cross-sectional area shown in FIG. The 2.17 mm × 12 m tube was immersed in a thermostatic bath so that it could be heated. Further, a 2.17 mm × 2 m tube was connected, and this was immersed in water so that it could be cooled. Finally, a back pressure valve was connected so that the discharged reaction mixture could be received in a container.

In one syringe, 0.1 g of 2,2′-azobis (2-methylpropionamidine) hydrochloride (“V-50” manufactured by Wako Pure Chemical Industries; hereinafter abbreviated as “V-50”) 100 g of ion-exchanged water An aqueous solution dissolved in was prepared and charged. The other syringe was charged with a methyl methacrylate (hereinafter abbreviated as “MMA”) monomer solution. An initiator aqueous solution was introduced into a reaction tube having an inner diameter of 2.17 mm so that the aqueous solution of the initiator was 16 g / min, the MMA solution was 0.8 g / min, and the reaction mixture was flow rate of 16.8 g / min. The temperature of the thermostatic bath was 110 ° C. The emulsified dispersion was produced by receiving the discharged liquid in a receiving container. The pressure in the tube at this time was adjusted to 2 MPa with a discharge valve.

250 g of the obtained emulsified dispersion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle. After adding 37.5 g of MMA to the dropping funnel and preparing for dropping, V-50 was dissolved in 2 g of 0.1 g ion-exchanged water and added to the reaction solution. The internal temperature of the reaction kettle was raised to 80 ° C., the rate of temperature rise increased at around 80 ° C., and heat generation was confirmed. Then, the dropping of MMA was started from the dropping funnel. After dropping MMA over 1 hour, the mixture was held at 80 ° C. for 2 hours to obtain an emulsified dispersion (1). When the obtained emulsion dispersion (1) was analyzed, the average particle size of the resin particles in the emulsion dispersion (1) was 305 nm, the CV value was 7.5%, and the absolute value of the zeta potential was 38 mV. (Measured value: +38 mV) and the solid content was 19.5% by mass.

The emulsion dispersion (1) obtained above was applied to a glass plate using a film applicator and dried with a hot air dryer at 110 ° C. for 1 minute to obtain a coating film of resin particles. When the obtained coating film was irradiated with a fluorescent lamp and visually observed from directly above, it was colored red, and when visually observed from an oblique angle of 45 degrees, it was confirmed to be colored orange-red. Further, the color developability was strong.

(Example 2)
Two syringe pumps and a 2.17 mm tube were connected to the outlet of each syringe via a pressure gauge, a safety valve, a filter, and a check valve. Each tube was similarly connected with a T-connector having an inner diameter of 2.17 mm, and then connected to a 2.17 mm × 12 m tube via a flow path with a reduced flow path cross-sectional area shown in FIG. The 2.17 mm × 12 m tube was immersed in a thermostatic bath so that it could be heated. Further, a 2.17 mm × 2 m tube was connected, and this was immersed in water so that it could be cooled. Finally, a back pressure valve was connected so that the discharged reaction mixture could be received in a container.

In one syringe, an aqueous solution in which 0.075 g of sodium persulfate was dissolved in 100 g of ion-exchanged water was prepared and charged. The other syringe was charged with a methyl methacrylate (hereinafter abbreviated as “MMA”) monomer solution. The initiator aqueous solution was introduced into a reaction tube having an inner diameter of 2.17 mm so that the aqueous solution of the initiator was 16 g / min, the MMA solution was 4 g / min, and the reaction mixture was 20 g / min. The temperature of the thermostatic bath was 95 ° C. The emulsified dispersion was produced by receiving the discharged liquid in a receiving container. The pressure in the tube at this time was adjusted to 2 MPa with a discharge valve.

250 g of the obtained emulsified dispersion was charged into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen inlet tube, and a temperature sensor for measuring the temperature in the reaction kettle while introducing nitrogen, and then sodium perchlorate 0 After adding an aqueous solution in which 0.05 g was dissolved in 2 g of ion-exchanged water, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours to obtain an emulsified dispersion (2). When the obtained emulsified dispersion (2) was analyzed, the average particle diameter of the resin particles in the emulsified dispersion (2) was 297 nm, the CV value was 6.9%, and the absolute value of the zeta potential was 37 mV. (Measured value: -37 mV) and the solid content was 17.5% by mass. Using this emulsified dispersion (2), a resin particle coating film was obtained in the same manner as in Example 1, and the resulting coating film was visually observed from directly above by applying light from a fluorescent lamp. The color was developed in red and visually observed from an oblique angle of 45 degrees, it was confirmed that the product developed in orange-red color. Further, the color developability was strong.

(Example 3)
Instead of the aqueous solution in which 0.075 g of sodium persulfate used in Example 2 was dissolved in 100 g of ion-exchanged water, an aqueous solution in which 0.1 g of V-50 was dissolved in 100 g of ion-exchanged water was charged into a syringe. Further, 250 g of the emulsified dispersion was charged into a 0.5 liter reaction kettle while introducing nitrogen, and then replaced with an aqueous solution in which 0.05 g of sodium perchlorate was dissolved in 2 g of ion-exchanged water. An aqueous solution in which 05 g was dissolved in 2 g of ion-exchanged water was added. Otherwise in the same manner as in Example 2, an emulsified dispersion (3) was obtained. When the obtained emulsified dispersion (3) was analyzed, the average particle size of the resin particles in the emulsified dispersion (3) was 303 nm, the CV value was 7.3%, and the absolute value of the zeta potential was 35 mV. (Measured value: +35 mV) and solid content was 17.4% by mass. Using this emulsified dispersion (3), a resin particle coating film was obtained in the same manner as in Example 1, and the obtained coating film was visually observed from directly above by applying light from a fluorescent lamp. The color was developed in red and visually observed from an oblique angle of 45 degrees, it was confirmed that the product developed in orange-red color. Further, the color developability was strong.

(Example 4)
An emulsified dispersion (4) was obtained in the same manner as in Example 2 except that the temperature of the thermostatic bath was changed from 95 ° C to 110 ° C. When the obtained emulsified dispersion (4) was analyzed, the average particle diameter of the resin particles in the emulsified dispersion (4) was 279 nm, the CV value was 6.7%, and the absolute value of the zeta potential was 42 mV. (Measured value: -42 mV) and solid content was 20.3% by mass. Using this emulsified dispersion (4), a coating film of resin particles was obtained in the same manner as in Example 1, and the resulting coating film was visually observed from directly above by applying light from a fluorescent lamp. It was confirmed that the color was orange and the color was observed to be yellowish green when observed visually at an angle of 45 degrees. Further, the color developability was strong.

(Example 5)
An emulsified dispersion (5) was obtained in the same manner as in Example 2 except that the temperature of the thermostatic bath was changed from 95 ° C to 130 ° C. When the obtained emulsion dispersion (5) was analyzed, the average particle size of the resin particles in the emulsion dispersion (5) was 235 nm, the CV value was 5.9%, and the absolute value of the zeta potential was 55 mV. (Measured value: -55 mV) and solid content was 19.3% by mass. Using this emulsified dispersion (5), a resin particle coating film was obtained in the same manner as in Example 1, and the resulting coating film was visually observed from directly above by applying light from a fluorescent lamp. It was confirmed that the color was colored green and the color was colored blue when observed visually at an angle of 45 degrees. Further, the color developability was strong.

(Example 6)
An emulsified dispersion (6) was obtained in the same manner as in Example 3 except that the temperature of the thermostatic bath was changed from 95 ° C to 100 ° C. When the obtained emulsified dispersion (6) was analyzed, the average particle size of the resin particles in the emulsified dispersion (6) was 256 nm, the CV value was 6.2%, and the absolute value of the zeta potential was 48 mV. (Measured value: +48 mV), and the solid content was 17.4% by mass. Using this emulsified dispersion (6), a resin particle coating film was obtained in the same manner as in Example 1, and the resulting coating film was visually observed from directly above by applying light from a fluorescent lamp. A yellow-green color was developed, and when observed visually from an oblique 45 °, it was confirmed that the color was green. Further, the color developability was strong.

(Example 7)
An emulsified dispersion (7) was obtained in the same manner as in Example 3 except that the temperature of the thermostatic bath was changed from 95 ° C to 145 ° C. When the obtained emulsified dispersion (7) was analyzed, the average particle diameter of the resin particles in the emulsified dispersion (7) was 180 nm, the CV value was 5.0%, and the absolute value of the zeta potential was 65 mV. (Measured value: +65 mV) and solid content was 19.3% by mass. Using this emulsified dispersion (7), a coating film of resin particles was obtained in the same manner as in Example 1. The resulting coating film was visually observed from directly above by applying light from a fluorescent lamp. The color was developed in blue, and when observed visually from an oblique angle of 45 degrees, it was confirmed that the color developed in white. Further, the color developability was strong.

(Comparative Example 1)
A 0.5 liter reaction kettle equipped with a stirrer, a nitrogen inlet tube, and a temperature sensor for measuring the temperature in the reaction kettle was charged with 190 g of ion exchange water and 0.02 g of sodium dodecyl sulfate, and then 2.5 g of MMA was added. Stirring was started at 300 rpm. Next, 0.5 g of sodium perchlorate was added and dissolved, and then the polymerization was started by raising the internal temperature of the reaction kettle to 80 ° C. while introducing nitrogen. After confirming the start of polymerization by a rapid rise in the temperature rise curve, 47.5 g of MMA was added dropwise over 1 hour while maintaining the internal temperature of the reaction kettle at 80 ° C. Furthermore, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours to obtain an emulsified dispersion (R1). When the obtained emulsified dispersion (R1) was analyzed, the average particle size of the resin particles in the emulsified dispersion (R1) was 306 nm, the CV value was 9.6%, and the absolute value of the zeta potential was 8 mV. (Measured value: -8 mV), and the solid content was 19.5% by mass. Using this emulsified dispersion (R1), a resin particle coating film was obtained in the same manner as in Example 1, and the resulting coating film was visually observed from directly above by applying light from a fluorescent lamp. It was confirmed that the color developed in red and the color developed in red with an orange color when observed visually at an angle of 45 degrees, but the color developability was weaker than those obtained in Examples 1 to 7. It was.

Table 1 shows the characteristic values, structural color hues, and color development results of the resin particles produced in Examples 1 to 7 and Comparative Example 1 described above.

From the results shown in Table 1, it was found that the structural color materials of the present invention of Examples 1 to 7 had a structural color having high color developability. On the other hand, the material of Comparative Example 1 was confirmed to have a red to orange-colored structural color, but it was found that the color developability was weak.

(Example 8: Preparation and evaluation of makeup cosmetics)
15.38 parts by mass of the emulsified dispersion (1) obtained in Example 1 (3 parts by mass as a solid content), 1.5 parts by mass of ethanol, 3.5 parts by mass of ethylene glycol, and 79.62 parts by mass of purified water. Makeup cosmetics were prepared by mixing uniformly. The obtained makeup cosmetic was applied to the skin, dried, and visually observed. As in Example 1, a red to orange-colored structural color was observed, and the color developability was high. .

(Examples 9 to 14: Preparation and evaluation of makeup cosmetics)
Using the emulsified dispersions (2) to (7) obtained in Examples 2 to 7, makeup cosmetics were prepared according to the blending amounts shown in Table 2. The obtained makeup cosmetic was applied to the skin, dried, and visually observed. The same structural color as in Examples 2 to 7 was observed. Further, the color developability was high.

(Comparative Example 2: Preparation and evaluation of makeup cosmetics)
Using the emulsified dispersion (R1) obtained in Comparative Example 1, makeup cosmetics were prepared according to the blending amounts in Table 2. When the obtained makeup cosmetic was applied to the skin, dried, and visually observed, it was confirmed that it had a red to orange-like structural color, similar to the result obtained in the observation in Comparative Example 1. However, the color development was weak as compared with the makeup cosmetics prepared in Examples 8-14.

δ ... Fluid containing water-soluble radical polymerization initiator ε ... Fluid containing radical polymerizable monomer γ ... Temperature control fluid 5 · · · 1st Plate (process plate)
5a: the surface of the first plate 5b: the end surface of the first plate 5c: the end surface of the first plate 5d: the side surface of the first plate 5e: Side face of the first plate 3 .... Third plate (temperature control plate)
3a: the surface of the third plate 3b: the end surface of the third plate 3c: the end surface of the third plate 3d: the side surface of the third plate 3e: Side surface of third plate 6... Temperature control flow path with cross-sectional groove shape 6 a... Main flow path with cross-section groove shape 6 b.・ ・ ・ ・ ・ Drain-side channel with cross-sectional groove shape 8 ・ ・ ・ ・ ・ ・ Second plate (process plate)
8a: the surface of the second plate 8b: the end surface of the second plate 8c: the end surface of the second plate 8d: the side surface of the second plate 8e: Side of second plate 14 ... Fourth plate (process plate)
14a ... the surface of the fourth plate 14b ... the end surface of the fourth plate 14c ... the end surface of the fourth plate 14d ... the side surface of the fourth plate 14e ... the side surface of the fourth plate 15 ... Chemical reaction device 1
15b .... End face of the device 1 for chemical reaction 15c ... ... End face of the device 1 for chemical reaction 15d ... Side face of the device 1 for chemical reaction 15e ... Side face of the device 1 for chemical reaction 16 .... Chemical reaction device 2
16b... End surface of the chemical reaction device 2 16c... End surface of the chemical reaction device 2 16d... Side surface of the chemical reaction device 2 16e. ··········································································································· q1, q2 ··· width d0 ··· depth L ··· flow Path length 30 ... Connector 31 ... Joint part 32 ... Joint part 33 ... Space formed

Claims (6)

After a fluid mixed with an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer is fed into the microtubular channel at a constant flow rate, the fluid temperature is instantaneously reached to a preset temperature. In the presence of a water-soluble radical polymerization initiator, a part of the radical polymerizable monomer is reacted to form a uniform particle nucleus of resin particles in the microtubular channel, and the obtained particle nucleus is included. Resin particles obtained by polymerizing a polymerization reaction solution using a reaction vessel equipped with a stirrer, the average particle diameter of the resin particles is in the range of 150 to 400 nm, and the absolute value of the zeta potential is 30. Structural color material characterized by being in the range of -80 mV. The structural color material according to claim 1, wherein the microtubular channel has a micromixer and a heat transfer reaction vessel inside. The micromixer has a structure in which an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer can be mixed, and a flow path diameter is reduced in the flow direction of the mixed fluid. The structural color material according to claim 2. 3. The heat transfer reaction vessel in a microtubular channel polymerizes a fluid in which an aqueous medium containing a water-soluble radical polymerization initiator and a radical polymerizable monomer are mixed at a temperature in the range of 70 ° C. to 200 ° C. 3. Structural color material according to 3. The structure according to any one of claims 1 to 4, wherein a fluid obtained by mixing an aqueous medium containing the water-soluble radical polymerization initiator and a radical polymerizable monomer is continuously supplied at a Reynolds number of 0.25 to 300. Color material. A cosmetic comprising the structural color material according to any one of claims 1 to 5.

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