JP2016160222A - Eye make-up cosmetics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide eye make-up cosmetics that can be spread smoothly, can form a homogeneous make-up film, are excellent in luster, are hard to bleed, and are excellent in long-lasting make-up properties.SOLUTION: The invention provides an eye make-up cosmetic containing an aqueous polymer emulsion, in which polymer particles obtained by radical polymerization of radical polymerizable monomers into an aqueous medium are dispersed, the radical polymerizable monomers are methyl methacrylate and 2-ethylhexyl acrylate, and the coefficient of variation (CV) of the particle diameter distribution of the polymer particle is 15% or less.SELECTED DRAWING: Figure 7

Description

  The present invention relates to eye makeup cosmetics, and more specifically, by using an aqueous polymer emulsion of monodisperse particles copolymerized with a specific acrylic monomer, a cosmetic film having a smooth and uniform spread is formed. The present invention relates to an eye makeup cosmetic that is excellent in luster and that is resistant to bleeding and has excellent makeup durability.

  Eye makeup cosmetics are used to give attractive impressions by applying to the eye periphery such as eyelashes, eyelashes, eyebrows and adding color and shadows. The eye makeup cosmetic is applied to delicate parts such as the edge of eyelids, the eyelashes, and the vicinity of the eyebrows, and therefore needs to spread and spread smoothly during application. Moreover, in order to obtain a sufficient cosmetic effect, it is important that a decorative film having a uniform and excellent gloss is formed after application. Furthermore, eyelashes, eyelashes, etc. move more than other parts, and sweat and tears also come into contact with each other, so that they are difficult to bleed and are required to have a long-lasting makeup film. As described above, the eye makeup cosmetics are required to have various performances, but it has been difficult to realize a cosmetic having all of these properties.

  Among eye makeup cosmetics, eyelash cosmetics such as mascara are required to have a separation effect for producing natural eyelashes without binding the eyelashes in addition to the above performance. The eyelash cosmetics are blended with film-forming components such as polymer emulsions for the purpose of improving volume effect and curl-up effect. For example, acrylic aqueous polymer emulsions such as alkyl acrylate polymer emulsions are used. (Patent Document 1). However, when this polymer emulsion is used, the adhesion is improved, but the feeling of use at the time of application is impaired, and bundles tend to be easily formed, resulting in an unnatural finish. Moreover, the transparency and uniformity of the formed decorative film are low, and a good gloss cannot be obtained, or the water resistance is low and sufficient makeup persistence may not be obtained.

JP 2006-111536 A

  The present invention has been made in view of the above circumstances, and can provide an eye makeup cosmetic that can form a smooth and uniform makeup film that is smooth and spreads, has excellent gloss, and does not easily bleed and has excellent sustainability of the makeup film. The issue is to provide.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have used a monodispersed aqueous polymer emulsion in which a specific acrylic monomer is copolymerized and its particle size distribution is controlled within a certain range. It was found that it spreads smoothly when applied, forms a uniform coating after drying, gives an excellent gloss, is less likely to bleed due to tears, sweat, etc., and can maintain its cosmetic effect for a long time. It came to do.

  That is, the present invention is an aqueous polymer emulsion in which polymer particles obtained by radical polymerization of a radically polymerizable monomer in an aqueous medium are dispersed, wherein the radically polymerizable monomer is methyl methacrylate and 2-ethylhexyl acrylate. There is an eye makeup cosmetic containing an aqueous polymer emulsion having a coefficient of variation (CV) of the particle size distribution of the polymer particles of 15% or less.

  The eye makeup cosmetic of the present invention spreads smoothly at the time of application, has good usability and feeling of use, forms a uniform makeup film after drying, gives excellent gloss, Since it is difficult to bleed and is excellent in the durability of the cosmetic film, its makeup effect lasts for a long time, and it is difficult for makeup to be lost. Further, when applied to eyelashes, bundling hardly occurs and a natural finish is obtained, and the separation effect is excellent.

3 is an exploded perspective view showing three types of plate structures of the chemical reaction device 1. FIG. 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. 2 is an exploded perspective view showing two types of plate structures of the chemical reaction device 2. FIG. 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. 3 is a perspective view showing a plate structure of the chemical reaction device 3. FIG. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of chemical reaction device 3. It is a disassembled perspective view which shows two types of plate structures of the chemical reaction device 1 in FIG. It is a schematic block diagram which shows typically the manufacturing apparatus used by the manufacture example.

  The aqueous polymer emulsion used in the present invention is obtained by dispersing polymer particles obtained by radical polymerization of a radically polymerizable monomer (hereinafter sometimes simply referred to as “polymer particles”) in an aqueous medium. Methyl methacrylate and 2-ethylhexyl acrylate are used as the radical polymerizable monomer constituting the polymer particles. As described above, by combining methyl methacrylate and 2-ethylhexyl acrylate as the radical polymerizable monomer, it spreads smoothly and a uniform decorative film is formed, and the gloss and makeup sustainability are excellent. Further, when applied to eyelashes, an excellent separation effect can be obtained. The mass composition ratio of the radical polymerizable monomer constituting the polymer particles is not particularly limited, but is preferably 35/65 to 65/35, more preferably 40/60 to 60/40, and 50/50. ~ 60/40 (methyl methacrylate / 2-ethylhexyl acrylate) is particularly preferred. Within such a range, it will be particularly excellent in the spread of use and the separation effect during use. Examples of the aqueous medium include water, lower alcohols such as ethyl alcohol and butyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, 1,2-pentanediol, dipropylene glycol, and polyethylene glycol, glycerin, and diglycerin. Examples thereof include glycerols such as polyglycerin and the like, and one or more can be used. Among these, water is more preferable.

The polymer particles are monodisperse particles, and the coefficient of variation (CV) calculated by the following formula is 15% or less, preferably 14% or less, more preferably 12% or less. The average particle diameter (d) and the standard deviation (SD) of the average particle diameter of the polymer particles are values obtained by measuring with a particle size distribution analyzer (submicron particle analyzer N5 BECKMAN COULTER) by a laser diffraction / scattering method. It is.
Coefficient of variation (CV (%)) = 100 × SD / d
d: average particle diameter of polymer particles, SD: standard deviation of average particle diameter

  The average particle size of the polymer particles is preferably 10 to 800 nm, and more preferably 100 to 400 nm. Such a range is preferable because the stability of the aqueous polymer emulsion is good and a uniform decorative film is formed. The solid content concentration of the aqueous polymer emulsion is preferably 15 to 60% by mass, more preferably 30 to 50% by mass. Within this range, the stability of the aqueous polymer emulsion will be good.

  As the radical polymerizable monomer constituting the polymer particles, a radical polymerizable monomer other than methyl methacrylate and 2-ethylhexyl acrylate can be used, but substantially only methyl methacrylate and 2-ethylhexyl acrylate are used. It is preferable to use it.

  The method for producing the aqueous polymer emulsion is not particularly limited, and a known emulsion polymerization method or the like is used. If necessary, a surfactant or the like is added, and the coefficient of variation of the average particle diameter of the polymer particles is What is necessary is just to prepare so that it may become in the said range. As a suitable method, in the presence of a water-soluble radical initiator in a microtubular channel, a radical polymerizable monomer is emulsion-polymerized to a reaction rate of 0.1 to 50%, and then a reaction provided with a stirring blade. A method of reacting to a reaction rate of 95% or more in the kettle is mentioned. By this method, a polymer emulsion having high monodispersity can be produced without substantially adding a surfactant or the like. It is preferable that the aqueous emulsion polymer used in the present invention contains substantially no surfactant since it hardly bleeds and improves makeup sustainability. In the present specification, “substantially free of surfactant” means that the content of the surfactant in the aqueous polymer emulsion is usually 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.8%. It means 01 mass% or less.

All of the charged radical polymerizable monomer (hereinafter referred to as “charged monomer”) may be added to the microtubular inner flow path, or only a part thereof may be added. Moreover, only 1 type may be added among methyl methacrylate and 2-ethylhexyl acrylate, and 2 types may be added. In the reaction in the microtubule, the reaction is continued until the reaction rate with respect to the charged monomer becomes 0.1 to 50%. Next, this polymerization reaction liquid (primary polymer emulsion) is reacted in a reaction kettle equipped with a stirrer until the reaction rate reaches 95% or more with respect to the charged monomer to obtain an aqueous emulsion polymer. When only a part of the charged monomer is added in the microtubular channel, the remainder of the charged monomer is added and then the reaction is carried out in the reaction kettle. When only a part of the monomer is added to the microtubular channel in this way, the reaction rate in the reaction in the microtubular channel means the reaction rate with respect to the charged monomer. As a water-based polymer emulsion used in the present invention, in the microtubular channel, among the charged monomers, methyl methacrylate is added in whole or in part to the charged amount until the reaction rate becomes 0.1 to 50%. After emulsion polymerization, it is preferable to use a mixture prepared by adding the remainder of the monomer to the polymerization reaction liquid and reacting to a reaction rate of 95% or more in a reaction kettle equipped with stirring blades. A reaction rate is calculated | required from the following formula | equation, for example based on the solid content in the polymerization reaction liquid (primary polymer emulsion or aqueous polymer emulsion) of each step measured according to the measuring method as described in an Example.
Reaction rate (%) = (mass of polymerization reaction solution × solid content (%)) / mass of charged monomer

  There is no restriction | limiting in particular as a water-soluble radical initiator, It can select and use suitably from the various water-soluble radical polymerization initiators conventionally used in radical polymerization. As such a water-soluble initiator, for example, water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates and the like are preferably used.

  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.

  Furthermore, examples of the redox initiator include a combination of hydrogen peroxide and a reducing agent. In this case, as the reducing agent, divalent iron ions, copper ions, zinc ions, cobalt ions, vanadium ions and other metal ions, ascorbic acid, reducing sugars and the like are used. Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate.

  One of these water-soluble radical polymerization initiators may be used alone, or two or more thereof may be used in combination.

  The aqueous polymer emulsion uses a micromixer having a microtubular channel formed therein and a reaction vessel having a microtubular channel formed therein, and in the presence of the water-soluble radical initiator, a radical polymerizable monomer It is preferable to produce it by carrying out the emulsion polymerization to a reaction rate of 0.1 to 50% and then reacting to a reaction rate of 95% or more in a reaction kettle equipped with stirring blades.

  More specifically, the aqueous polymer emulsion uses a micromixer having a microtubular channel formed therein and a reaction vessel having a microtubular channel formed therein, and the microtubular channel is first formed therein. By mixing the aqueous medium containing the water-soluble radical initiator and the fluid of the medium containing the radical polymerizable monomer with a micromixer, the oil droplets of the radical polymerizable monomer are mixed with the water-soluble radical initiator. After being formed in the aqueous medium, the radical polymerizable monomer partially dissolved in the aqueous medium starts to polymerize due to the decomposition of the water-soluble radical initiator in the reaction vessel in which the microtubular channel is formed. , Due to the increase in hydrophobicity due to the increase in chain length, precipitation and agglomeration occur to form fine particle nuclei, and radically polymerizable monomers are formed on the surface of the particle nuclei from oil droplets of radically polymerizable monomers finely dispersed in the aqueous phase. Supply Polymerization proceeds, the radical polymerizable monomer is emulsion-polymerized to a reaction rate of 0.1 to 50%, and the reaction rate of the radical polymerizable monomer is 95% or more in a reaction vessel equipped with a stirring blade. It can manufacture by making it react.

  By using a micromixer, the mixing of the aqueous medium containing the water-soluble radical initiator and the medium containing the radical polymerizable monomer is a mixture of small segments, so the contact area becomes large, so the energy is small. However, mixing is promoted, and the radical polymerizable monomer can be finely dispersed in an aqueous medium containing a water-soluble radical 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 general, polymer particles obtained by soap-free emulsion polymerization are said to be stabilized by repulsion due to the charge of the radical initiator segments and adsorption of the by-product oligo soap to the particle surface. In addition, the generation and stabilization of fine particle nuclei are promoted in a reaction vessel in which a microtubular channel is further formed in the reaction vessel, and the generation and stabilization of fine particle nuclei are promoted. Nucleation and growth of monodisperse fine particles with a small particle size can be realized.

  A commercially available micromixer can be used as the micromixer having a microtubular channel formed therein. For example, a microreactor having an interdigital channel structure, an institute, a fool, a microtechnique, a mainz ( IMM) single mixer and caterpillar mixer; Microglass microglass reactor; CPC Systems Cytos; Yamatake YM-1, YM-2 mixer; Shimadzu GLC mixing tee and tee (T-shaped connector) ); IMT chip reactor manufactured by Micro Chemical Engineering Co., Ltd .;

  Furthermore, as a preferred form of the micromixer system, there is provided a micromixer in which an aqueous medium containing a water-soluble radical initiator and a radical polymerizable monomer are circulated in separate flow paths and mixed at the outlets of both the flow paths. It is preferable to use a micromixer that promotes mixing by supplying and supplying a flow path having a reduced cross-sectional area in the flow direction after mixing. Mixing can be further promoted by a turbulent flow effect caused by further contracting the flow path.

  By using a micromixer that promotes mixing by mixing while using a micromixer that mixes at the outlets of both the flow paths and then supplying the flow path with a reduced cross-sectional area in the flow direction. The dispersion of the radical polymerizable monomer in the aqueous medium containing the water-soluble radical initiator can be promoted.

  After mixing using a micromixer that mixes at the outlets of both channels, the microtubular flow of the micromixer that promotes mixing by flowing through the channel with the channel cross-sectional area reduced in the flow direction. The path may be a combination of at least two members and a space formed between the members is used as a flow path, or a simple pipe or pipe shape may be used as the flow path. .

  An example of a preferable form of the micromixer that mixes at the junction provided at the outlet of the flow path is the chemical reaction device 1. Moreover, the device 2 for chemical reaction is illustrated as a micro mixer which accelerates | stimulates mixing by the flow path by which the flow-path cross-sectional area was reduced in the flow direction.

Hereinafter, the chemical reaction device 1 and the chemical reaction device 2 provided with a flow channel in a preferable form will be specifically described. 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 initiator passes, and heat exchange are 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 the said fluid. 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 includes, for example, a plurality of first plates (5 in FIG. 1) and second plates (8 in FIG. 1) alternately formed in the same rectangular plate shape in FIG. Configured. Further, as required, a third plate (3 in FIG. 1) is laminated as shown in FIG. Each one first plate is provided with a flow path through which a fluid containing a water-soluble radical initiator passes. Further, the second plate is provided with a flow path (hereinafter referred to as “reaction flow path”) through which a fluid containing a radical polymerizable monomer passes (hereinafter referred to as a “process plate”). Called). Further, 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 dispersed and arranged in each region of the end faces 15b, 15c and side surfaces 15d, 15e of the chemical reaction device 1, and a water-soluble radical initiator is placed in these regions. Fluid containing δ (in FIG. 2 indicates a fluid flow of a fluid containing a water-soluble radical initiator), fluid containing a radical polymerizable monomer (ε in FIG. 2 is a fluid flow of a fluid containing a radical polymerizable monomer) , And a joint portion 32 composed of a connector 30 and a joint portion 31 for flowing a temperature control fluid (γ in FIG. 2 indicates the flow of the temperature control fluid). Further, the outlet mixing is achieved by the fluid containing the radical polymerizable monomer and the fluid containing the water-soluble radical initiator joining in the space 33 formed by the end face 15c of the chemical reaction device 1 and the connector 30. .

Via these joints, a fluid containing a radical polymerizable monomer and a fluid containing a water-soluble radical initiator are supplied from the end face 15b, discharged to the end face 15c, and a temperature-controlled fluid is supplied from the side face 15d. It 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 molecules are disposed. For flowing a fluid containing a mer and a fluid containing a water-soluble radical initiator (α in FIG. 5 indicates a liquid fluid) and, if necessary, a temperature adjusting fluid (γ indicates a temperature adjusting fluid in FIG. 5) A joint part 32 composed of a connector 30 and a joint part 31 is connected to each other.

Through these joint portions, a fluid containing a fluid containing a radical polymerizable monomer and a fluid containing a water-soluble radical initiator is supplied from the end face 16b, discharged to the end face 16c, and the temperature control fluid is discharged from the side face 16e. It is supplied and discharged to the side surface 16d.
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 flow path 6 is not particularly limited as long as heat can be transferred to the reaction flow path, but is approximately in the range of 1 × 10 ^{−2 to} 2.5 × 10 ² (mm ² ). is there. More preferably, it is 0.32-4.0 (mm < ² >). The number of the temperature control flow paths 6 can adopt an appropriate number in consideration of heat exchange efficiency, and is not particularly limited, but is, for example, 1 to 1000, preferably 10 to 100 per plate. It is.

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 6 a portion of the temperature control channel 6 is arranged, and the supply side channel 6 b and the discharge side channel 6 c are each composed of one. .
The aqueous polymer emulsion used in the present invention is a reaction vessel in which a radical polymerizable monomer is finely dispersed in an aqueous medium containing a water-soluble radical initiator by the micromixer, and then a microtubular channel is formed therein. The emulsion can be produced by emulsion polymerization to a reaction rate of 0.1 to 50%, and then reacting to a reaction rate of 95% or more in a reaction kettle equipped with a stirring blade.

The flow path used in the manufacturing method can be any micro-tubular flow path, and other requirements are not particularly limited. A simple pipe or pipe shape may be used as the reaction channel. In addition, a space formed between the members can be used as a reaction channel by combining at least two members.
The aqueous polymer emulsion used in the present invention promotes the generation and stabilization of fine particle nuclei by emulsion polymerization of a radical polymerizable monomer in a temperature range of 70 ° C. to 200 ° C. Thus, it is possible to realize nucleation and growth of monodisperse fine particles having a smaller particle diameter, which are usually obtained by batch reaction.

  Usually, when preparing the polymer emulsion containing a polymer monodisperse fine particle only with a batch reaction kettle, reaction temperature is set to 50 to 90 degreeC. This is set together with 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. This may lead to runaway of the water, and the boiling point of water may exceed 100 ° C. Therefore, it is very dangerous except for batch reactors with special measures such as pressure resistance setting. On the other hand, in the microreactor, it is possible to increase the temperature and pressure safely and easily by providing a pressure adjusting valve at the outlet of the flow path. For this reason, no problem occurs even when the temperature of the aqueous medium exceeds 100 ° C.

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 having a microtubular channel formed therein, the fluid temperature is increased to a range of 70 ° C. to 200 ° C., thereby rapidly increasing the amount of initiator slices that contribute to the nucleation and stability of fine particles. be able to. Compared to ordinary batch reaction kettles, it is safe, convenient, efficient, monodisperse fine particles with extremely high dispersion stability and small particle size without the addition of protective colloids such as water-soluble polymers and surfactants. Can also be generated.
The reaction temperature is preferably 70 ° C to 200 ° C, more preferably 90 ° C to 180 ° C, and most preferably 110 ° C to 160 ° C. When the temperature is 70 ° C. or lower, there is no difference from the batch, and when the temperature is 200 ° C. or higher, the initiator is decomposed too quickly, so there is almost no difference in effect. The above-mentioned effect can be most obtained at 70 ° C. to 200 ° C.

Furthermore, by continuously controlling the Reynolds number in the reaction vessel of the fluid containing the water-soluble radical initiator and the radical polymerizable monomer at 0.25 to 300, the water-soluble radical polymerization initiator and the radical polymerization are controlled. When the miscibility of the fluid containing the functional monomer is further enhanced by the turbulent flow effect, it can be manufactured more efficiently.
Here, by controlling the movement of the fluid in the flow path at a value larger than the Reynolds number 0.25, the mixing property of the fluid containing the water-soluble radical polymerization initiator and the radical polymerizable monomer is not significantly lowered. As a result, the particle nuclei are preferably grown uniformly, and problems such as blockage of the flow path due to aggregation can be avoided. In addition, it is difficult to control the Reynolds number to 300 or more, and if the Reynolds number is too large, the collision frequency between particles increases and the repetition frequency of particle coalescence and separation increases. May spread.

The Reynolds number is calculated according to the following formula.
Reynolds number = (D × u × ρ) / μ
D: inner diameter of flow path, u: average flow velocity, ρ: fluid density, μ: fluid viscosity

The ratio of the fluid containing the water-soluble radical initiator and the fluid containing the radical polymerizable monomer in the microtubule depends on the polymer particle concentration of the target aqueous polymer emulsion. In order to promote the generation and stabilization of fine particle nuclei in the channel, it is possible to obtain a polymer emulsion having a smaller particle size and a higher solid content concentration than in a normal batch reaction. The ratio of the fluid containing the radical polymerizable monomer in the fluid containing the water-soluble radical initiator in the microtubule is usually 5 to 60% by mass, preferably 5 to 50% by mass, more preferably 8 to 20%. % By mass. If it exceeds 60% by mass, the particles may aggregate and settle. A stable polymer emulsion can be obtained by setting the ratio of the fluid containing the radical polymerizable monomer in the fluid containing the water-soluble radical initiator to 5 to 60% by mass.
As the reaction apparatus used in the above production method, a reaction apparatus in which a flow path is installed in a heat transfer reaction vessel is preferable, and the flow path is preferably a microtubular because a heating can be quickly controlled. 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 in a direction perpendicular to the flow direction in the flow path, and “cross section” means its area.

  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 in which these corners are rounded, a high aspect ratio, that is, 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 channel may further be provided with a heat exchange function. 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 member surface may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the member surface. 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 need not 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 polymer emulsion used in 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 channel (hereinafter, simply referred to as “microchannel”) is provided in a member used as a chemical reaction device.
Hereinafter, the reaction vessel having a microtubular channel formed therein will be specifically described. FIG. 7 shows a reaction vessel in which a plate provided with a microtubular flow channel for flowing a mixed solution and a plate provided with a flow channel for flowing a fluid that exchanges heat between the mixed solution are alternately stacked. A schematic configuration example of a reaction vessel (chemical reaction device 3) having a microtubular channel having a void size in which a fluid cross-sectional area flowing in a liquid-tight manner in the microtubular channel is 0.1 to 4.0 mm ² It is.

  The chemical reaction device 3 includes, for example, a first plate (process plate) (2 in FIG. 7) and a second plate (temperature control plate) (in FIG. 7) having the same rectangular plate shape in FIG. And 3) are alternately stacked. Each one first plate is provided with a reaction channel. The second plate is provided with a temperature control channel.

  As shown in FIG. 8, these supply ports and discharge ports are dispersed and arranged in each region of the end surfaces 1b, 1c, side surfaces 1d, 1e of the chemical reaction device 3, and in these regions, radical polymerizable monomers are arranged. The joint part 32 including the connector 30 and the joint part 31 for flowing the fluid containing the water-soluble radical initiator and the temperature control fluid is connected to each other.

  Via these joint portions, a fluid containing a radical polymerizable monomer and a water-soluble radical initiator is supplied from the end surface 1b and discharged to the end surface 1c, and a temperature-controlled fluid is supplied from the side surface 1e to the side surface 1d. It is supposed to be discharged.

  The shape of the chemical reaction device 3 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 1d and 1e longer than between the end surfaces 1b and 1c. Therefore, in accordance with the illustrated shape, the direction from the end surface 1b to the end surface 1c is referred to as the longitudinal direction of the process plate and temperature control plate of the chemical reaction device 1, and the direction from the side surface 1d to the side surface 1e is referred to as the chemical reaction device. 3 is referred to as the short direction of the process plate and the temperature control plate.

  As shown in FIG. 9, the process plate is formed by extending a flow path 4 having a concave groove shape in one surface 2a in the longitudinal direction of the process plate and arranging a plurality of the process plates at a predetermined interval p0 in the short direction. It is. Let L be the length of the flow path 4. The cross-sectional shape is a width w0 and a depth d0.

  The cross-sectional shape of the flow path 4 can be appropriately set according to the type of fluid containing the radical polymerizable monomer and the water-soluble radical initiator, the flow rate, and the flow path length L. In order to ensure uniformity, the width w0 and the depth d0 are set in the range of 0.1 to 500 [mm] and 0.1 to 5 [mm], respectively. In addition, description of a width | variety and a depth is a case where a drawing is referred, Comprising: This value can be interpreted suitably so that it may become a wide value with respect to a heat transfer surface. Although it does not specifically limit, For example, 1-1000 pieces per plate, Preferably it is 10-100 pieces.

  The fluid containing the radical polymerizable monomer and the water-soluble radical initiator is caused to flow into each flow path 4 and is supplied from one end face 2b side as indicated by an arrow in FIGS. It is discharged to the end face 2c side.

  The plurality of process plates and temperature control plates are stacked by alternately stacking process plates and temperature control plates in the same direction, and are fixed to each other and stacked.

  Therefore, in the form of the chemical reaction device 3, each flow path 4 and the temperature control flow path 6 are covered with a lower surface of a plate on which the opening surface of the groove is laminated, and a tunnel shape having a rectangular cross section with both ends opened. It is said.

  Each process plate and temperature control plate can be made of an appropriate metal material. For example, a flow path 4 and a temperature control path 6 are formed by etching a stainless steel plate, and the flow path surface is changed. It can be manufactured by electrolytic polishing finish.

  As an apparatus having a chemical reaction device provided with a flow path used in the manufacturing method, for example, a manufacturing apparatus shown in FIG. 10 can be exemplified.

  In FIG. 10, the fluid containing the radical polymerizable monomer is composed of the outlet of the tank 62 (first tank) into which the fluid (61) containing the radical polymerizable monomer and the inlet of the plunger pump 65 are placed. An outlet of a tank 64 (first tank) for containing a fluid containing a water-soluble radical initiator and an inlet of a plunger pump 66 are connected to each other through a piping that passes through the water-soluble radical initiator. It is connected via a pipe through which the fluid (63) it contains passes. Pipes through which a fluid containing a radical polymerizable monomer or a fluid containing a water-soluble radical initiator passes from the outlet of the plunger pump 65 and the outlet of the plunger pump 66 through the plunger pump 65 or the plunger pump 66, respectively. These pipes are connected to the inlet of a micromixer 67 that mixes at a junction provided at the outlet of a flow path exemplified as the chemical device 1 illustrated in FIGS. 1, 2, and 3. Yes.

  In this micromixer 67, a fluid (61) containing a radical polymerizable monomer and a fluid (63) containing a water-soluble radical initiator are mixed, and the chemical device 2 shown in FIGS. The fluid is mixed with the radical polymerizable monomer and the water-soluble radical initiator by being guided to the micromixer 73 that promotes the mixing by the flow path whose flow path cross-sectional area is reduced in the illustrated flow direction. This fluid moves through the pipe connected to the outlet of the micromixer 73 to the inlet 1b of the reaction vessel 40 exemplified as the chemical device 3 shown in FIGS. A temperature control device 68 is connected to the reaction vessel 40. The radical polymerizable monomer is finely dispersed in the aqueous medium containing the water-soluble radical initiator by moving through the micro flow path in the reaction vessel 40 and dissolved in the aqueous medium by the decomposition of the water-soluble radical initiator. The core of fine particles is formed by polymerization precipitation of the radically polymerizable monomer, and the radically polymerizable monomer is supplied to the surface of the particle core from the oil droplets of the radically polymerizable monomer finely dispersed in the aqueous phase. Polymerization proceeds, moves through the micro flow path in the reaction vessel 40, and reaches the outlet 1 c of the reaction vessel 40. Then, it moves to the inflow port of the cooling heat exchanger 70 through the pipe connected to the outflow port. In the reaction container 40 of the manufacturing apparatus of FIG. 10, the residence time can be controlled by connecting several chemical devices 3 described in FIGS. 7, 8 and 9 as a part of the reaction container through the flow path. .

  The residence time is preferably set so that the reaction rate at the outlet of the reaction vessel is 0.1 to 50%, more preferably 0.5 to 30%. When the reaction rate is lower than 0.1%, the monodispersity of the polymer particles cannot be obtained, and in order to react 50% or more, it is necessary to lengthen the flow path. The flow path may be blocked by the adhesion of the polymer component to the path. By controlling to 0.1 to 50%, an aqueous polymer emulsion containing fine particles having high monodispersibility can be obtained, and the flow path can be blocked without causing clogging.

  Such a residence time depends on the reaction temperature, flow rate, and the type of water-soluble radical initiator used, but when using a persulfate as the water-soluble radical initiator, 0.1 to 30 minutes, preferably Is 0.2 to 20 minutes, more preferably 0.5 to 15 minutes.

  The primary polymer emulsion, which is the polymerization reaction liquid obtained from the outlet of the flow path, can be polymerized to a reaction rate of 95% or higher in a normal batch reaction kettle equipped with a water-soluble radical initiator as necessary and equipped with a stirrer. Become.

  As the water-soluble radical initiator to be added, the aforementioned water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates and the like are preferably used.

  When only a part of the charged monomer is added in the microtubule, the remainder of the charged monomer is added and reacted in the reaction kettle. Although the addition method is not particularly limited, it is preferably dropped and polymerized.

  The reaction temperature is not particularly limited, but when a persulfate is used as a water-soluble radical initiator and a batch reaction kettle used under normal atmospheric pressure is used, it is 50 to 90 ° C, more preferably 60 to 85 ° C. Is preferred.

  Although the reaction time depends on the temperature, it is usually 0.5 hours to 10 hours. Thus, in a microtubular channel, in the presence of a water-soluble radical initiator, after radically polymerizing a radical polymerizable monomer to a reaction rate of 0.1 to 50%, in a reaction kettle equipped with a stirring blade By reacting to a reaction rate of 95% or higher, the monodispersed fine particles contained have an average particle size of 300 nm or less, a coefficient of variation CV of particle size distribution of 15% or less, and a solid content concentration of 15% by mass or more. A polymer emulsion containing no surfactant can be obtained.

  In general, polymer particles obtained by soap-free emulsion polymerization are said to be stabilized by repulsion due to the charge of the radical initiator segment and adsorption of by-product oligosoap to the particle surface. In order to promote the generation and stabilization of fine particle nuclei in the microtubular channel, the method described above required to be performed in very dilute conditions to obtain the fine particles or the system became unstable. It is possible to obtain an aqueous polymer emulsion containing a dispersion stabilizer and a surfactant having a smaller particle size and a higher solid content than those in a normal batch reaction.

  The content of the aqueous polymer emulsion in the eye makeup cosmetic of the present invention is not particularly limited, but is preferably 1 to 30% by mass in terms of solid content, more preferably 2 to 25% by mass, and 3 to 3%. 20% by mass is particularly preferred. In such a range, a decorative film having excellent sustainability and smooth spread can be obtained.

  In addition to the aqueous polymer emulsion, the eye makeup cosmetic of the present invention is a component usually used in cosmetics, such as oily components, powders, fibers, surfactants, aqueous components, ultraviolet absorbers, humectants, Antifading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives, fragrances, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

Oily components include hydrocarbons, oils and fats, waxes, hardened oils, ester oils, regardless of the origin, such as animal oils, vegetable oils, synthetic oils, and solid oils, semisolid oils, liquid oils, etc. Fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives, oily gelling agents, and the like.
Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin, hydrogenated microcrystalline, microcrystalline wax, ethylene propylene copolymer, montan wax, Fischer-Tropsch wax, molasses, olive oil, castor oil, mink Oils and fats such as macadamian nut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, trioctanoic acid Glyceryl, glyceryl stearate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, dioctyl Neopentyl glycolate, cholesterol fatty acid ester, esters such as N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, cetostearyl alcohol , Higher alcohols such as behenyl alcohol, silicones such as methylphenylpolysiloxane and fluorine-modified organopolysiloxane, fluorine oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl Lanolin derivatives such as lanolin alcohol, sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, stearin Oily gelling agents such as calcium and the like.

  Among these, it is preferable to use a wax having a melting point of 80 ° C. or higher because smooth elongation spread and gloss are excellent. Further, when applied to eyelashes, the separation effect is excellent. Examples of the wax having a melting point of 80 ° C. or higher include polyethylene wax, carnauba wax (carnauba wax), ethylene / propylene copolymer, microcrystalline wax, Fischer-Tropsch wax, paraffin wax, and ceresin wax. Among these, carnauba Wax, polyethylene wax, ethylene / propylene copolymer and the like are preferably used. Commercially available products include purified carnauba wax No. 1 (manufactured by Celalica Noda, melting point: 80-86 ° C.), PERFORMALENE 500 POLYETHYLENE (melting point: 80-95 ° C., manufactured by New Phase Technology), PERFORMALENE 655 POLYETTHYLENE (melting point: 95-105 ° C., manufactured by New Phase Technology), EP-700 (Baker) Petrolite, Inc. melting point: 90-100 ° C.). The content of the wax having a melting point of 80 ° C. or higher in the eye makeup cosmetic of the present invention is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass. Such a range is preferable because the decorative film has excellent durability.

  As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned. For example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified Examples thereof include organopolysiloxane, polyether-modified organopolysiloxane, and lecithin.

  The aqueous component may be any component as long as it is soluble in water and water, for example, lower alcohols such as ethyl alcohol and butyl alcohol, propylene glycol, 1,3-butylene glycol, 1,2-pentanediol, Examples include glycols such as propylene glycol and polyethylene glycol, glycerols such as glycerin, diglycerin, and polyglycerin, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose. Examples of water-soluble polymers include guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan and other semi-synthetic compounds such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, Synthetic compounds such as alkyl-added carboxyvinyl polymer and sodium polyacrylate can be mentioned. Other humectants such as protein, mucopolysaccharide, collagen, elastin, keratin, etc. can also be contained.

  Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, and oxybenzone. Examples of humectants include protein, mucopolysaccharide, and collagen. , Elastin, keratin, etc., antioxidants such as α-tocopherol, ascorbic acid, etc., cosmetic ingredients such as vitamins, anti-inflammatory agents, herbal medicines, etc., antiseptics such as paraoxybenzoic acid esters, phenoxyethanol, glycol And the like.

  The eye makeup cosmetic of the present invention can be produced by mixing the aqueous polymer emulsion and optional components added as necessary according to a conventional method. The eye makeup cosmetic of the present invention includes mascara, mascara base, mascara top coat, eyebrow, eyeliner, eye color and the like. The dosage form may be any of oily, aqueous, oil-in-water, water-in-oil, and the like, and the oil-in-water type is particularly preferable. Examples of the shape include cream, gel, and liquid. The appearance may be transparent, translucent, or opaque.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, this invention is not limited to these at all.

(Micromixer used in the production example)
In the production example, the process plates 5 and 8 having the structure shown in FIG. 1 were used as a micromixer as a micromixer for mixing at a 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. 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 chemical 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 initiator was dissolved was introduced into the flow channel 20 of the plate 5 into the flow channel 21 of the radical polymerizable monomer plate 8, and the respective fluids were united at the plate outlet. Thereafter, the radical polymerizable monomer was further finely dispersed in an aqueous fluid in which a water-soluble radical initiator was dissolved by passing through the flow path 22 of the plate 14. The material of the process plates 5, 8, 14 and the temperature control plate 3 is SUS304, and the plate thicknesses of the plates 5, 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.

(Device for reaction vessel used in production example)
In the production example, a reaction vessel device having a structure shown in FIG. 7 was used. As a structure, the process plate 2 and the temperature control plate 3 are alternately laminated. A flow path 4 is formed in the process plate, and a temperature control flow path 6 is formed in the temperature control plate.
The reaction vessel device is formed by alternately laminating three temperature control plates with five temperature control channels 6 formed by etching, as well as two process plates with five reaction channels 4 formed by dry etching. Yes. The material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm. The cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm × depth 0.5 mm.

(Measuring method of average particle diameter and coefficient of variation of polymer particles)
The average particle diameter (d) and the standard deviation (SD) of the average particle diameter of the polymer particles were measured by a particle size distribution measuring apparatus (submicron particle analyzer N5 BECKMAN COULTER) by a laser diffraction / scattering method. CV (%) was calculated using the following formula.
Coefficient of variation (CV (%)) = 100 × SD / d
d: average particle diameter of polymer particles, SD: standard deviation of average particle diameter

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

(Measurement method of residual monomer amount)
Measurement was performed using a GCMS device GCMS-QP5050ACI manufactured by Shimadzu Corporation. The polymerization solution was dissolved in acetone and measured.

Manufacturing 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 connected to the micromixer shown in FIGS. 1 and 4, and further connected to a 2.17 mm × 12 m tube. 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 0.1 g of sodium persulfate was dissolved in 100 g of ion-exchanged water was prepared and charged in one syringe. The other syringe was charged with methyl methacrylate (MMA). A sodium persulfate aqueous solution was introduced into a reaction tube having an inner diameter of 2.17 mm at a flow rate of 16 g / min and a methyl methacrylate solution at a flow rate of 2 g / min so that the reaction mixture had a flow rate of 18 g / min. The temperature of the thermostatic bath was 110 ° C. The viscosity was 1 mPa · s, the Reynolds number in the reaction vessel was 36, and the residence time was 2.3 minutes. The discharged liquid was received in a container. At this time, the pressure in the pipe was adjusted to 2.0 MPa by the exhaust pressure valve.
When the primary polymer emulsion which is the obtained polymerization reaction liquid was analyzed, the particle size was 110 nm, the solid content was 1.2%, and the reaction rate was 10.8%. Further, 241 g of the obtained primary polymer emulsion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle, and then sodium persulfate. An aqueous solution in which 0.15 g was dissolved in 2 g of ion-exchanged water was added, and the internal temperature of the reaction kettle was raised to 80 ° C. After 26.8 g of 2-ethylhexyl acrylate (2EHA) was added dropwise over 1 hour, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours. The characteristics of the obtained aqueous polymer emulsion are shown in Table 1. The mass composition ratio of the radical polymerizable monomer constituting the polymerizable particles in the aqueous polymer emulsion was determined based on the charged amount of each monomer, the charged ratio, and the residual monomer amount measured according to the measurement method. In addition, about the obtained aqueous polymer emulsion, the reaction rate is 95% or more, and it was the same also in the following manufacture examples.

Manufacturing 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 connected to the micromixer shown in FIGS. 1 and 4, and further connected to a 2.17 mm × 12 m tube. 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 0.172 g of sodium persulfate was dissolved in 100 g of ion-exchanged water was prepared and charged. Methyl methacrylate was charged into the other syringe. A sodium persulfate aqueous solution was introduced into a reaction tube having an inner diameter of 2.17 mm at a flow rate of 18 g / min and a methyl methacrylate solution at a flow rate of 3.86 g / min so that the reaction mixture had a flow rate of 21.86 g / min. The temperature of the thermostatic bath was 130 ° C. The viscosity was 1 mPa · s, the Reynolds number in the reaction vessel was 44, and the residence time was 1.9 minutes. The discharged liquid was received in a container. At this time, the pressure in the pipe was adjusted to 2.0 MPa by the exhaust pressure valve.
When the primary polymer emulsion which is the obtained polymerization reaction liquid was analyzed, the particle size was 170 nm, the solid content was 2.6%, and the reaction rate was 14.7%. Further, 241 g of the obtained primary polymer emulsion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle, and then sodium persulfate 0 An aqueous solution in which .17 g was dissolved in 2 g of ion-exchanged water was added, and the internal temperature of the reaction kettle was raised to 80 ° C. After 45.1 g of 2-ethylhexyl acrylate was added dropwise over 1 hour, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours. The characteristics of the obtained aqueous polymer emulsion are shown in Table 1.

Manufacturing example 3
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 connected to the micromixer shown in FIGS. 1 and 4, and further connected to a 2.17 mm × 12 m tube. 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 0.172 g of sodium persulfate was dissolved in 100 g of ion-exchanged water was prepared and charged. Methyl methacrylate was charged into the other syringe. A sodium persulfate aqueous solution was introduced into a reaction tube having an inner diameter of 2.17 mm at a flow rate of 18 g / min and a methyl methacrylate solution at a flow rate of 3.86 g / min so that the reaction mixture had a flow rate of 21.86 g / min. The temperature of the thermostatic bath was 140 ° C. The viscosity was 1 mPa · s, the Reynolds number in the reaction vessel was 44, and the residence time was 1.9 minutes. The discharged liquid was received in a container. At this time, the pressure in the pipe was adjusted to 2.0 MPa by the exhaust pressure valve.
When the primary polymer emulsion which is the obtained polymerization reaction liquid was analyzed, the particle size was 127 nm, the solid content was 2.9%, and the reaction rate was 16.3%. Further, 300 g of the obtained primary polymer emulsion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle. An aqueous solution in which 164 g was dissolved in 2 g of ion-exchanged water was added, and the internal temperature of the reaction kettle was raised to 80 ° C. After 29.4 g of methyl methacrylate and 82.3 g of 2-ethylhexyl acrylate were added dropwise over 1 hour, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours. The characteristics of the obtained aqueous polymer emulsion are shown in Table 1.

Manufacturing example 4
A primary polymer emulsion was obtained in the same manner as in Production Example 3.
Further, 300 g of the obtained primary polymer emulsion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle. An aqueous solution in which 164 g was dissolved in 2 g of ion-exchanged water was added, and the internal temperature of the reaction kettle was raised to 80 ° C. After dropping 65.9 g of methyl methacrylate and 58.7 g of 2-ethylhexyl acrylate over 1 hour, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours. The characteristics of the obtained aqueous polymer emulsion are shown in Table 1.

Manufacturing example 5
A primary polymer emulsion was obtained in the same manner as in Production Example 3.
Further, 300 g of the obtained primary polymer emulsion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle, and then sodium persulfate. After adding an aqueous solution in which 0.164 g was dissolved in 2 g of ion-exchanged water, the internal temperature of the reaction kettle was raised to 80 ° C. After 12.9 g of methyl methacrylate and 98.8 g of 2-ethylhexyl acrylate were added dropwise over 1 hour, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours. The characteristics of the obtained aqueous polymer emulsion are shown in Table 1.

Examples 1-2 and Comparative Examples 1-3
The oil-in-water type eyelash cosmetics with the formulations shown in Table 2 below were prepared, and the evaluation items a to f below were evaluated by the following methods. The results are also shown in Table 1.

(Evaluation item)
a. Smooth expansion b. Separate effect c. Uniformity d. Gloss e. Blurring f. Persistence of cosmetic film (evaluation method)
Each sample is subjected to a use test by 20 specialist panels, and each panel member evaluates the evaluation items a to f according to the following absolute evaluation and gives a score, and the average value is obtained from the total score of all the panel members of each sample. Was calculated and determined according to the following four-step criteria. Evaluation items a to d were evaluated immediately after use, and evaluation items ef were evaluated 4 hours after application.
Each sample was applied once to the eyelashes, then dried for 1 minute, and the sample was applied again. The cosmetic film after repeating this three times was evaluated.
(Absolute evaluation criteria)
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad (4 step criteria)
(Judgment): (Average score)
◎: More than 5 points: Very good ○: More than 3 points, 5 points or less: Good △: More than 1 point, 3 points or less: Slightly poor x: 1 point or less: Bad

(Production method)
A. Components (1) to (14) are heated at 90 ° C. and mixed uniformly.
B. Ingredients (15) to (27) are uniformly mixed at 90 ° C.
C. B is added to A, emulsified, cooled to room temperature, and components (28) and (29) are added and mixed.
D. Fill the container with C to make a product.

From Table 2, the oil-in-water type eyelash cosmetics of Examples 1 and 2 of the present invention have a smooth spread, separation effect, uniformity, gloss, as compared with the oil-in-water type eyelash cosmetics of Comparative Examples 1-3. It was excellent in bleediness and durability of the cosmetic film.
On the other hand, in Comparative Example 1 in which a copolymer emulsion was blended in place of the polymer emulsion of Production Example 3 or 4 (acrylates / ethyl hexyl acrylate), the separation effect, uniformity, gloss, blurring, and durability of the cosmetic film were satisfactory. I couldn't get anything better. In Comparative Example 2 in which an alkyl acrylate polymer emulsion was blended instead of the polymer emulsion of Production Example 3 or 4, satisfactory results were not obtained in the separation effect, uniformity, and gloss. In Comparative Example 3 in which an alkyl acrylate polymer emulsion was blended instead of the polymer emulsion of Production Example 3 or 4, it was satisfactory in terms of smooth spreading, separation effect, uniformity, gloss, blurring, and durability of the cosmetic film. I couldn't get anything.

Example 3
Oil-in-water mascara (with fiber):
(Ingredient) (mass%)
(1) Stearic acid 2
(2) Palmitic acid 1.5
(3) Carnauba wax (mp 80-86 ° C.) 2
(4) Candelilla wax (mp 70-75 ° C) 1
(5) Dextrin palmitate 4
(6) Polyoxyethylene sorbitan monooleate (20E.O.) 2
(7) Sorbitan sesquioleate 0.5
(8) Polymethylsilsesquioxane * 5 3
(9) Bengala 1
(10) Yellow iron oxide 2
(11) Talc 1
(12) Mica titanium 1
(13) Ceramide 0.1
(14) Triethanolamine 1.5
(15) Glycerin 3
(16) Polyvinyl alcohol 1
(17) Alkali thickening polymer emulsion * 1 0.5
(18) Aqueous polymer emulsion of Production Example 20
(19) Styrene / vinyl pyrrolidone polymer emulsion * 6 10
(20) Nylon (8 denier, 4mm) 0.5
(21) Polypropylene (5.6 denier, 2 mm) 1.5
(22) 1,2-pentanediol 0.2
(23) Hyaluronic acid 0.05
(24) Sodium dehydroacetate appropriate amount (25) Purified water remaining amount * 5: TOPSPEARL150KA (Momentive Performance Materials)
(Made by Japan GK)
* 6: ANTARA430 (manufactured by ISP)
(Production method)
A. Components (1) to (13) are heated at 90 ° C. and mixed uniformly.
B. Ingredients (14) to (25) are uniformly mixed at 90 ° C.
C. Add B to A, emulsify and cool to room temperature.
D. Fill the container with C to make a product.

  The oil-in-water mascara of Example 3 was an eye makeup cosmetic excellent in all the items of smooth spreading, separation effect, uniformity, gloss, blurring resistance, and durability of the cosmetic film.

Example 4
Water-in-oil mascara:
(Ingredient) (mass%)
(1) Isododecane remaining amount (2) Dimethiconol 1
(3) Trimethylsiloxysilicic acid 8
(4) Decamethylcyclopentasiloxane 15
(5) Dipolyhydroxystearic acid PEG-30 * 7 1
(6) Polyethylene wax 2
(7) Carnauba wax (mp 80-86 ° C) 2
(8) Paraffin wax (mp 56-61 ° C.) 2
(9) Distearyldimonium hectorite 5
(10) Hydrogenated glyceryl abietate 2
(11) Propylene carbonate 2
(12) Silicic anhydride 2
(13) Iron oxide 5
(14) Collagen 0.05
(15) Ceramide 0.05
(16) Purified water 10
(17) Aqueous polymer emulsion of Production Example 4
(18) 1,2-pentanediol 0.2
* 7 Cisroll DPHS (manufactured by Croda Japan)
(Production method)
A. Components (1) to (15) are heated at 90 ° C. and mixed uniformly.
B. Components (16) to (18) are added to A and emulsified.
C. B is cooled to room temperature and then filled into a container to obtain a product.

  The water-in-oil mascara of Example 4 was an eye makeup cosmetic that was excellent in all of the smooth extension spread, separation effect, uniformity, gloss, blurring resistance, and durability of the cosmetic film.

Example 5
Mascara overcoat:
(Ingredient) (mass%)
(1) Glyceryl trioctanoate 1
(2) Light liquid isoparaffin 25
(3) Polyoxyethylene (30.E.O.) cetyl ether 2
(4) Collagen 0.05
(5) Polymethylsilsesquioxane * 5 1
(6) Polymethylsilsesquioxane * 8 0.5
(7) Carbon black 0.5
(8) Polyethylene terephthalate / aluminum / epoxy laminated powder 2
(9) Alkali thickening polymer emulsion 5
(10) L-arginine 2
(11) Aqueous polymer emulsion of Production Example 10
(12) Mulberry white skin extract 0.1
(13) Panthenol 0.5
(14) Dipropylene glycol 5
(15) Remaining amount of purified water * 8 TOSPEARL 3000A (Momentive Performance Materiales Japan GK)
(Production method)
A. Ingredients (1) to (4) are heated at 80 ° C. and mixed uniformly.
B. Components (5) to (15) are uniformly mixed at 80 ° C.
C. Add A to B, emulsify, and cool to room temperature.
D. Fill the container with C to make a product.

  The mascara overcoat of Example 5 was an eye makeup cosmetic excellent in all the items of smooth stretch spread, separation effect, uniformity, gloss, blurring resistance, and durability of the cosmetic film.

Example 6
eyeliner:
(Ingredient) (mass%)
(1) Di (C12-15) palace-6 phosphate 0.2
(2) Seths-20 0.3
(3) 1,3-butylene glycol 9
(4) L-arginine 0.1
(5) (Isobutylene / Na maleate) copolymer 0.2
(6) Black iron oxide 15
(7) Black titanium oxide 3
(8) Sericite 0.5
(9) Silica 3
(10) Purified water remaining amount (11) 1,3-butylene glycol 3
(12) Simethicone 0.02
(13) Alkali thickening polymer emulsion * 1 2
(14) L-arginine 0.5
(15) Aqueous polymer emulsion of Production Example 22
(16) Hyaluronic acid 0.1
(17) Ethanol 1
(18) Perfume appropriate amount (production method)
A. Components (1) to (4) are mixed and dissolved, and components (5) to (8) are added and dispersed uniformly.
B. Add components (9) to (18) to A and mix uniformly.
C. Fill B into a container to make a product.

  The eyeliner of Example 6 was an eye makeup cosmetic that was excellent in smooth stretch spread, uniformity, gloss, blurring resistance, and durability of the cosmetic film.

Example 7
Eyebrow:
(Ingredient) (mass%)
(1) Hydrogenated lecithin 0.2
(2) Polysorbate 80 0.3
(3) 1,3-butylene glycol 2
(4) Methyl paraoxybenzoate 0.05
(5) Purified water 1
(6) Lecithin-treated titanium oxide * 9 0.5
(7) Silicone-treated black iron oxide * 10 1
(8) Silicone-treated Bengala * 10 1.2
(9) Silicone-treated yellow iron oxide * 10 1
(10) Silicone-treated talc * 10 2.3
(11) Aqueous polymer emulsion of Production Example 3
(12) Polyvinyl acetate polymer emulsion * 8 2
(13) Purified water remaining amount (14) Simethicone 0.01
(15) Alkali thickening polymer emulsion * 9 6
(16) Triethanolamine 1.4
(17) Ethanol 18
(18) (Vinylpyrrolidone / VA) copolymer 1.5
* 9: 0.5% lecithin treatment * 10: Silicone treatment of components (7) to (10) KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A. Components (1) to (4) are mixed and dissolved, and components (5) to (10) are added and dispersed uniformly.
B. Add components (11) to (18) to A and mix uniformly.
C. Fill B into a container to make a product.

  The eyebrow of Example 7 was an eye makeup cosmetic excellent in smooth spreading, separation effect, uniformity, gloss, blurring resistance, and durability of the cosmetic film.

Example 8
Eye color:
(Ingredient) (mass%)
(1) Native gellan gum 0.5
(2) Aqueous polymer emulsion of Production Example 4
(3) Purified water remaining amount (4) 1,3-butylene glycol 15
(5) Triethanolamine 0.1
(6) Lecithin 0.2
(7) Polysorbate 80 0.15
(8) Lauroyl glutamate dioctyldodecyl / phytosteryl / behenyl 1
(9) Talc 2.4
(10) Synthetic phlogopite * 11 14
(11) Perfluorooctyltriethoxysilane treated titanium oxide coated mica * 12 2.5
(12) Perfluorooctyltriethoxysilane treated titanium oxide coated glass powder * 13 10
(13) (PET / Al / epoxy resin) laminate * 14 1
* 11: PDM-40L (Topy)
* 12: FLAMENCO ULTRA SPARKLE 4500 (BASF) treated with 3% perfluorooctyltriethoxysilane * 13: Metashine MT1080RG (made by Nippon Sheet Glass) treated with 2% perfluorooctyltriethoxysilane What
* 14: Aluminum flake silver 0.15 mm (manufactured by Kakuhachi Fish Scale)
(Production method)
A. The component (1) is uniformly heated and swollen with a part of the component (3).
B. Add the remaining components (2) and (3) and (4) to (13) to A and mix uniformly.
C. Fill B into a container to make a product.

  The eye color of Example 8 was an eye makeup cosmetic excellent in smooth stretch spread, uniformity, gloss, blurring resistance and durability of the cosmetic film.

  According to the present invention, an eye makeup cosmetic that spreads smoothly during application, has a good feeling of use, forms a uniform decorative film after drying, has an excellent gloss, and does not bleed and has a long-lasting cosmetic effect. Can be obtained.

δ ... Fluid containing water-soluble radical initiator ε ... Fluid containing radical polymerizable monomer γ ... Temperature control fluid 5 ... First plate (Process plate)
5a... First plate surface 5b... First plate end surface 5c... First plate end surface 5d... First plate side surface 5e. Side surface of the first plate 3 ... the third plate (temperature control plate)
3a... Third plate surface 3b... Third plate end surface 3c... Third plate end surface 3d... Third plate side surface 3e. Side surface 6 of the third plate ····· Temperature control flow path 6a with cross-sectional groove shape · Main flow path 6b with cross-section groove shape · Supply-side flow channel 6c with cross-section groove shape・ ・ ・ ・ ・ Drain-side channel 8 with a concave groove shape in the cross section ・ ・ ・ ・ ・ ・ Second plate (process plate)
8a: second plate surface 8b: second plate end surface 8c: second plate end surface 8d: second plate side surface 8e: Side 14 of the second plate ... 4th plate (process plate)
14a ··· the surface 14b of the fourth plate ··· the end surface 14c of the fourth plate ··· the end surface 14d of the fourth plate ··· the side surface 14e of the fourth plate ··· the side surface of the fourth plate 15 ... Chemical reaction device 1
15b .... End face 15c of chemical reaction device 1 ... End face 15d of chemical reaction device 1 ... Side face 15e of chemical reaction device 1 ... Side face 16 of chemical reaction device 1 .... Chemical reaction device 2
16b... End surface 16c of chemical reaction device 2... End surface 16d of chemical reaction device 2... Side surface 16e of chemical reaction device 2. .... Chemical reaction device 3
1b... End surface 1c of chemical reaction device 3... End surface 1d of chemical reaction device 3... Side surface 1e of chemical reaction device 3. .... First plate (process plate)
2a ... the first plate surface 2b ... the first plate end surface 2c ... the first plate end surface 2d ... the first plate side surface 2e ... the first plate side surface 3 ... 2nd plate (temperature control plate)
3a ... Second plate surface 3b ... Second plate end surface 3c ... Second plate end surface 3d ... Second plate side surface 3e ... Second plate side surface 4... Channel having a concave groove shape p0... Predetermined interval w0... Width d0... Depth L. .... Connector 31 ... Joint part 32 ... Joint part 40 ... Reaction vessel (chemical reaction device 3)
61... Fluid 62 containing water-soluble radical initiator... First tank 63... Fluid 64 containing radical polymerizable monomer. Plunger pump 66 Plunger pump 67 Micro mixer 68 Temperature control device 69 Cooling heat exchanger 70・ Temperature control device 71 ...... Exhaust pressure valve 72 ...... Receiving container 73 ...... Micromixer 80 ...... Schematic configuration diagram schematically showing the manufacturing apparatus used in the manufacturing example

Claims (8)

  An aqueous polymer emulsion in which polymer particles obtained by radical polymerization of a radical polymerizable monomer in an aqueous medium are dispersed, wherein the radical polymerizable monomer is methyl methacrylate and 2-ethylhexyl acrylate, and the polymer particles Eye makeup cosmetics containing an aqueous polymer emulsion having a coefficient of variation (CV) in the particle size distribution of 15% or less.   The eye makeup cosmetic according to claim 1, wherein the polymer particles are obtained by radical polymerization of methyl methacrylate and 2-ethylhexyl acrylate at a mass composition ratio of 50/50 to 60/40 (methyl methacrylate / 2-ethylhexyl acrylate).   The eye makeup cosmetic according to claim 1 or 2, wherein the aqueous polymer emulsion contains substantially no surfactant.   The eye makeup cosmetic according to any one of claims 1 to 3, wherein the content of the aqueous polymer emulsion in the eye makeup cosmetic is 1 to 30% by mass in terms of solid content.   The eye makeup cosmetic according to any one of claims 1 to 4, further comprising a wax having a melting point of 80 ° C or higher.   The eye makeup cosmetic according to claim 5, wherein the content of the wax having a melting point of 80 ° C or higher in the eye makeup cosmetic is 1 to 20% by mass.   After the polymer particles are polymerized in the presence of a water-soluble radical initiator in the microtubular channel to a reaction rate of 0.1 to 50%, a polymerization reaction solution obtained is obtained. The eye makeup cosmetic according to any one of claims 1 to 6, which is an aqueous polymer emulsion obtained by a polymerization reaction up to a reaction rate of 95% or more using a reaction kettle equipped with a stirring device. The eye makeup cosmetic according to any one of claims 1 to 7, which is a cosmetic for eyelashes.

Images