WO2013183520A1 - Matière colorée structurale et produit cosmétique l'utilisant - Google Patents

Matière colorée structurale et produit cosmétique l'utilisant Download PDF

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Publication number
WO2013183520A1
WO2013183520A1 PCT/JP2013/064908 JP2013064908W WO2013183520A1 WO 2013183520 A1 WO2013183520 A1 WO 2013183520A1 JP 2013064908 W JP2013064908 W JP 2013064908W WO 2013183520 A1 WO2013183520 A1 WO 2013183520A1
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Prior art keywords
acid
water
resin particles
polymerizable monomer
polymerization initiator
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PCT/JP2013/064908
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English (en)
Japanese (ja)
Inventor
寿計 田中
信洋 小江
昌重 朝日
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Dic株式会社
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Publication of WO2013183520A1 publication Critical patent/WO2013183520A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent

Definitions

  • 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.
  • 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.
  • cosmetics are required to have excellent color developability, materials having such a structural color are very useful.
  • 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.
  • a soap-free emulsion polymerization method is known as one method for obtaining monodisperse resin particles.
  • 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).
  • 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.
  • 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.
  • the present inventors have partially reacted a radical polymerizable monomer in the presence of a water-soluble radical polymerization initiator in a microtubular channel.
  • 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.
  • 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.
  • 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.
  • 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.
  • water-soluble initiators include water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates, and the like.
  • water-soluble organic peroxide examples 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.
  • water-soluble azo compounds examples 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.
  • examples of the redox initiator include a combination of hydrogen peroxide and a reducing agent.
  • 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.
  • examples of the persulfate include ammonium persulfate and potassium persulfate.
  • 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.
  • 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.
  • 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, ⁇ -methylstyrene; (meth) acrylic acid, itaconic acid or An unsaturated monomer having a carb
  • 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
  • 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 ( ⁇ -methoxyethoxy) silane Silane compounds having a polymerizable unsaturated group such as ⁇ -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.
  • 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.
  • 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.
  • the micromixer having a microtubular channel formed therein and a reaction vessel having a microtubular channel formed therein.
  • 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. .
  • the oil droplets of the radical polymerizable monomer are converted into water-soluble radical polymerization.
  • 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.
  • emulsion polymerization proceeds.
  • stable resin particles can be obtained without using protective colloids such as water-soluble polymers and surfactants used in conventional soap-free emulsion polymerization.
  • 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.
  • 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.
  • a range of 5 to 1000 mL / min is preferable, and a range of 10 to 500 mL / min is more preferable.
  • the constant flow rate in the present invention refers to a flow rate at which the flow rate fluctuation is within ⁇ 5%.
  • 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.
  • 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.
  • 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.
  • “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.
  • 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.
  • 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.
  • 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.
  • mixing can be promoted by supplying the channel to a channel whose channel cross-sectional area is reduced in the flow direction.
  • 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.
  • a chemical reaction device 1 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.
  • the chemical reaction device 2 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.
  • 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.
  • 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”). .)
  • 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.
  • ⁇ represents a liquid flow of a fluid containing a water-soluble radical polymerization initiator
  • a fluid containing a radical polymerizable monomer ⁇ 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, ⁇ indicates a flow of the temperature-controlled fluid
  • a joint portion 31 are connected to each other.
  • 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.
  • 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.
  • 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
  • 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.
  • a fluid containing a monomer a fluid containing a water-soluble radical polymerization initiator ( ⁇ in FIG. 5 indicates a liquid fluid), and a temperature adjusting fluid ( ⁇ 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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)
  • T Absolute temperature (K)
  • radical decomposition increases exponentially with increasing temperature.
  • 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.
  • 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. .
  • 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).
  • 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.
  • 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.
  • cross section means a cross section perpendicular to the flow direction in the flow path
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • water-soluble radical polymerization initiator added as necessary examples include the water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates and the like exemplified above.
  • 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.
  • 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.
  • the polymerization reaction liquid containing the obtained particle nuclei is obtained by a polymerization reaction using a reaction vessel equipped with a stirring device.
  • the reaction rate is preferably in the range of 0.1 to 50% based on the radically polymerizable monomer used initially.
  • 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.
  • 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.
  • 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.
  • components usually used in cosmetic products can be used, and vary depending on the type of cosmetic product.
  • pigment examples include talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, sauroite, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate.
  • liquid oil examples 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.
  • solid fat examples 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.
  • wax examples 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.
  • hydrocarbon oil examples 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.
  • 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.
  • polyhydric alcohol examples 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;
  • ester oil examples 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-ethylhexa
  • silicone oil examples 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.
  • chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane
  • cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
  • anionic surfactant examples 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 sulfon
  • N-acyl glutamate N-acyl glutamate; sulfated oil such as funnel oil; polyoxyethylene-alkyl ether carboxylic acid ⁇ -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.
  • sulfated oil such as funnel oil
  • polyoxyethylene-alkyl ether carboxylic acid ⁇ -olefin sulfonates higher fatty acid ester sulfonates
  • secondary alcohol sulfates higher fatty acid alkylolamide sulfates
  • sodium lauroyl monoethanolamide succinate 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.
  • alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride
  • amphoteric surfactant examples 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.
  • a lipophilic one or a hydrophilic one can be used as the nonionic surfactant.
  • 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, ⁇ , ⁇ '-oleate glycerin Glycerin fatty acid esters such as glyceryl pyroglutamate, glyceryl monostearate and malic
  • 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 / polyoxypropy
  • humectant examples 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.
  • any of natural products, semi-synthetic products, and synthetic products can be used.
  • 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.
  • 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.
  • starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch
  • Cellulose polymers such as sodium carboxymethyl cellulose, crystalline cellulose and cellulose powder
  • 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.
  • thickener examples 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
  • 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.
  • any of monosaccharide, oligosaccharide, and polysaccharide can be used.
  • 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.
  • oligosaccharide examples include sucrose, guntianose, umbelliferose, lactose, planteose, isoliquenose, ⁇ , ⁇ -trehalose, raffinose, lycnose, umbilicin, stachyose verbus course, and the like.
  • polysaccharide examples 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.
  • amino acid examples 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 ⁇ -alanine sodium, glutathione, pyrrolidone carboxylic acid and the like.
  • organic amine examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol. Etc.
  • polymer emulsion examples include acrylic resin emulsion, polyvinyl acetate emulsion, and natural rubber latex.
  • pH adjuster examples include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
  • vitamin examples include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.
  • antioxidants examples include tocopherol and its derivatives, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid ester and the like.
  • antioxidant assistant examples 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.
  • anti-inflammatory agent examples include glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, and the like.
  • whitening agent examples 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 ⁇ -butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ectamol, tannic acid, ⁇ -borneol, nicotinic acid tocopherol, inositol hexanicotine. Nate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, ⁇ -oryzanol and the like.
  • antiseborrheic agent examples include sulfur and thianthol.
  • anti-inflammatory agent examples 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.
  • 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
  • the cross-sectional dimension of the reaction channel 20 is 6 mm wide ⁇
  • the depth is 0.2 mm
  • 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.
  • 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.
  • 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.
  • V-50 2,2′-azobis (2-methylpropionamidine) hydrochloride
  • V-50 a methyl methacrylate
  • 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.
  • 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.
  • 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.
  • 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.
  • MMA methyl methacrylate
  • 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.
  • 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.
  • 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.
  • Example 2 an emulsified dispersion (3) was obtained.
  • the average particle size of the resin particles in the emulsified dispersion (3) was 303 nm
  • the CV value was 7.3%
  • the absolute value of the zeta potential was 35 mV. (Measured value: +35 mV) and solid content was 17.4% by mass.
  • 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.
  • the average particle diameter of the resin particles in the emulsified dispersion (4) was 279 nm
  • the CV value was 6.7%
  • the absolute value of the zeta potential was 42 mV. (Measured value: -42 mV) and solid content was 20.3% by mass.
  • 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.
  • the average particle size of the resin particles in the emulsion dispersion (5) was 235 nm
  • the CV value was 5.9%
  • the absolute value of the zeta potential was 55 mV. (Measured value: -55 mV) and solid content was 19.3% by mass.
  • 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.
  • the average particle size of the resin particles in the emulsified dispersion (6) was 256 nm
  • the CV value was 6.2%
  • the absolute value of the zeta potential was 48 mV. (Measured value: +48 mV)
  • the solid content was 17.4% by mass.
  • 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.
  • the average particle diameter of the resin particles in the emulsified dispersion (7) was 180 nm
  • the CV value was 5.0%
  • the absolute value of the zeta potential was 65 mV. (Measured value: +65 mV) and solid content was 19.3% by mass.
  • 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.
  • the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours to obtain an emulsified dispersion (R1).
  • the average particle size of the resin particles in the emulsified dispersion (R1) was 306 nm
  • the CV value was 9.6%
  • the absolute value of the zeta potential was 8 mV. (Measured value: -8 mV)
  • the solid content was 19.5% by mass.
  • 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.
  • 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

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Abstract

L'invention concerne une matière colorée structurale comprenant des particules de résine ayant une couleur structurale, les particules de résine étant obtenues en : introduisant un fluide obtenu par mélange d'un monomère polymérisable par voie radicalaire et d'un milieu aqueux comprenant un amorceur de polymérisation radicalaire soluble dans l'eau, à un débit constant, dans un minuscule trajet d'écoulement tubulaire ; en amenant instantanément la température de fluide à une température réglée précédemment, puis en faisant réagir partiellement le monomère polymérisable par voie radicalaire en présence de l'amorceur de polymérisation radicalaire soluble dans l'eau, provoquant ainsi la formation de noyaux de particule de particules de résine uniformes à former à l'intérieur du minuscule trajet d'écoulement tubulaire ; et en conduisant une réaction de polymérisation d'une solution de réaction de polymérisation comprenant les noyaux de particule résultants, à l'aide d'un réservoir de réaction comportant un dispositif d'agitation ; et la dimension moyenne de grain des particules de résine se situant dans la plage de 150 à 400 nm et la valeur absolue du potentiel zêta se situant dans la plage de 30 à 80 mV. L'invention concerne également un produit cosmétique utilisant cette matière colorée.
PCT/JP2013/064908 2012-06-07 2013-05-29 Matière colorée structurale et produit cosmétique l'utilisant WO2013183520A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015163194A1 (fr) * 2014-04-25 2015-10-29 国立大学法人東京大学 Puce d'analyse de réticulum endoplasmique extracellulaire, procédé d'analyse de réticulum endoplasmique extracellulaire, et dispositif d'analyse de réticulum endoplasmique extracellulaire
JP5971392B1 (ja) * 2015-09-29 2016-08-17 東洋インキＳｃホールディングス株式会社 ビニル系重合体の製造方法並びに製造装置
CN109363959A (zh) * 2018-11-08 2019-02-22 广东轻工职业技术学院 一种含结构色粒子的眼影及其制备方法
WO2023199972A1 (fr) * 2022-04-14 2023-10-19 三菱ケミカル株式会社 Dispersion, structure, et procédé de fabrication de structure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010242054A (ja) * 2009-03-17 2010-10-28 Sekisui Plastics Co Ltd カチオン性アクリル系重合体粒子の製造方法及びその製造方法により得られたカチオン性アクリル系重合体粒子
JP2012012550A (ja) * 2010-07-05 2012-01-19 Dic Corp 乳化分散体、および乳化分散体の製造方法
JP2012166125A (ja) * 2011-02-10 2012-09-06 Tokyo Institute Of Technology ２色性微小液滴の製造方法およびその装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010242054A (ja) * 2009-03-17 2010-10-28 Sekisui Plastics Co Ltd カチオン性アクリル系重合体粒子の製造方法及びその製造方法により得られたカチオン性アクリル系重合体粒子
JP2012012550A (ja) * 2010-07-05 2012-01-19 Dic Corp 乳化分散体、および乳化分散体の製造方法
JP2012166125A (ja) * 2011-02-10 2012-09-06 Tokyo Institute Of Technology ２色性微小液滴の製造方法およびその装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015163194A1 (fr) * 2014-04-25 2015-10-29 国立大学法人東京大学 Puce d'analyse de réticulum endoplasmique extracellulaire, procédé d'analyse de réticulum endoplasmique extracellulaire, et dispositif d'analyse de réticulum endoplasmique extracellulaire
JP5971392B1 (ja) * 2015-09-29 2016-08-17 東洋インキＳｃホールディングス株式会社 ビニル系重合体の製造方法並びに製造装置
CN109363959A (zh) * 2018-11-08 2019-02-22 广东轻工职业技术学院 一种含结构色粒子的眼影及其制备方法
CN109363959B (zh) * 2018-11-08 2022-03-11 广东轻工职业技术学院 一种结构色粒子及其制备方法
WO2023199972A1 (fr) * 2022-04-14 2023-10-19 三菱ケミカル株式会社 Dispersion, structure, et procédé de fabrication de structure

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