Cosmetic

Abstract

To provide a novel cosmetic that has excellent fixation, water resistance and sebum resistance, and can suppress application blurring over time.SOLUTION: A cosmetic of the present invention contains core-shell type resin particles, where a core part of the core-shell type resin particle is made of polymers created by at least polymerizing (meth)acrylic acid and / or ester thereof, a shell part of the core-shell type resin particle is made of monomers having a ring structure and polymers created by at least polymerizing (meth)acrylic acid and / or ester thereof, a glass-transition temperature of the core part is -30°C or more and 35°C or less, a glass-transition temperature of the shell part is 50°C or more, and a ratio of the mass of the shell part for the total mass of the shell part and the core part is 0.06 or more and 0.40 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cosmetic preparation. [Background technology]

[0002] Conventionally, makeup cosmetics such as eye shadow, eyeliner, eyebrow pencil, and mascara are generally applied to the skin to form a cosmetic film. This cosmetic film is easily affected by factors such as sweating and sebum secretion from within the skin, external moisture such as rain, snow, and seawater, and friction with hands and clothing, causing makeup to come off and become a major problem.

[0003] In particular, in recent years, sports activities such as tennis and golf have become popular, and there is a demand for makeup cosmetics that not only do not come off during normal activities but are also durable enough for use during sports, i.e., makeup cosmetics that can withstand a lot of sweating and sebum secretion and also a large amount of friction, so that the makeup does not come off and does not stick to objects. To satisfy such demands, core-shell type resin particles have been incorporated into cosmetics.

[0004] Patent Document 1 discloses a makeup cosmetic containing a resin having a core and a shell that coats the core and has a higher glass transition point than the core. The core is made of a copolymer whose main monomer component is an acrylic acid ester and / or a methacrylic acid ester. The shell is made of a copolymer whose main monomer components are styrene and / or α-methylstyrene and one or more selected from acrylic acid, methacrylic acid, and their esters.

[0005] Patent Document 2 discloses an aqueous makeup cosmetic containing (A) a film-forming resin emulsion, (B) a solution-based polymer, (C) a colorant, and (D) a pH adjuster. The solution-based polymer (B) is one or more selected from the group consisting of acrylate copolymer AMP, (acrylic acid diacetone acrylamide) copolymer AMP, and (diacrylamide / hydroxyethyl acrylate / methoxyethyl acrylate) copolymer.

[0006] Patent Document 3 discloses an aqueous polymer emulsion containing polymer particles (A), a polymer emulsifier (B), and water (C). The polymer particles (A) are a polymer of an ethylenically unsaturated monomer (a), the polymer emulsifier (B) is a polymer of an ethylenically unsaturated monomer (b), and at least one of the ethylenically unsaturated monomers (a) and (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 6-239718 [Patent Document 2] Japanese Patent Application Laid-Open No. 2018-188396 [Patent Document 3] Patent Publication No. 2021-066851 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides a novel cosmetic that has good adhesion, water resistance, and sebum resistance, and is capable of suppressing smearing over time after application. [Means for solving the problem]

[0009] The present inventors have conducted extensive research and found that the above problems can be solved by the following means, and have completed the present invention. That is, the present invention is as follows: <Aspect 1> A cosmetic containing core-shell type resin particles, the core of the core-shell type resin particle is made of a polymer obtained by polymerizing at least a (meth)acrylic monomer, the shell portion of the core-shell resin particles is made of a polymer obtained by polymerizing at least a monomer having a cyclic structure and a (meth)acrylic monomer, The glass transition temperature of the core portion is -30°C or higher and 35°C or lower, The glass transition temperature of the shell portion is 50°C or higher, and The ratio of the mass of the shell portion to the total mass of the shell portion and the core portion is 0.06 or more and 0.40 or less. Cosmetics. <Aspect 2> The cosmetic according to Aspect 1, wherein the glass transition temperature of the shell portion is 80°C or higher. Aspect 3: The cosmetic according to aspect 1 or 2, wherein the ratio of the mass of the monomer having a cyclic structure to the total mass of the monomer having a cyclic structure and the (meth)acrylic monomer is 0.1 to 0.7. Aspect 4: The cosmetic according to any one of Aspects 1 to 3, wherein the (meth)acrylic monomer of the core portion includes butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate. Aspect 5: The cosmetic according to Aspect 4, wherein the total content of the butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate is 35% by mass to 80% by mass relative to the mass of the core portion. Aspect 6: The cosmetic according to any one of Aspects 1 to 5, wherein the (meth)acrylic monomer of the core portion includes methyl (meth)acrylate and / or ethyl (meth)acrylate, and butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate. Aspect 7: The cosmetic according to any one of Aspects 1 to 6, wherein the monomer having a cyclic structure includes styrene. Aspect 8: The cosmetic according to any one of Aspects 1 to 7, wherein the content of the monomer having a cyclic structure is 10% by mass or more and 70% by mass or less relative to the mass of the shell portion. Aspect 9: The cosmetic according to any one of aspects 1 to 8, wherein the content of the monomer having a cyclic structure is 2% by mass or more and 12% by mass or less relative to the mass of the core-shell resin particles. Aspect 10: A pen-type applicator containing the cosmetic material according to any one of Aspects 1 to 9. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a novel cosmetic that has good adhesion, water resistance, and sebum resistance, and that can suppress smearing of application over time. [Brief explanation of the drawings]

[0011] [Figure 1] Fig. 1 is a partial cross-sectional view showing a first embodiment of a liquid cosmetic applicator that contains an aqueous liquid cosmetic of the present invention. The mechanism shown in Fig. 1 is an example of a rotary-type dispenser. [Figure 2] Fig. 2 is a partial cross-sectional view showing a second embodiment of a liquid cosmetic applicator that contains an aqueous liquid cosmetic of the present invention. The mechanism shown in Fig. 2 is an example of a built-in cosmetic applicator type. [Figure 3] Figure 3(a) is a perspective view showing a third embodiment of a liquid cosmetic applicator that contains an aqueous liquid cosmetic of the present invention, and Figure 3(b) is a partial cross-sectional view of the same liquid cosmetic applicator as Figure 3(a). The mechanism of the liquid cosmetic applicator in Figures 3(a) and (b) is an example of a collector-type applicator. DETAILED DESCRIPTION OF THE INVENTION

[0012] Cosmetics The cosmetic of the present invention comprises: A cosmetic containing core-shell type resin particles, the core of the core-shell resin particle is made of a polymer obtained by polymerizing at least (meth)acrylic acid and / or an ester thereof, the shell portion of the core-shell resin particles is composed of a polymer obtained by polymerizing at least a monomer having a cyclic structure and (meth)acrylic acid and / or an ester thereof, The glass transition temperature of the core portion is -30°C or higher and 35°C or lower, The glass transition temperature of the shell portion is 50°C or higher, and The ratio of the mass of the shell portion to the total mass of the shell portion and the core portion is 0.06 or more and 0.40 or less.

[0013] Here, the glass transition temperature (Tg) is a theoretically calculated value determined by the FOX equation shown in the following formula (1). 1 / Tg=W1 / Tg1+W2 / Tg2++Wn / Tgn (1) (In the formula, Tg is the glass transition temperature of the core or shell portion, W1, W2, ..., Wn are the weight fractions of the respective monomers constituting these, and Tg1, Tg2, ..., Tgn are the glass transition temperatures of the homopolymers of the respective monomers constituting these. Furthermore, in the formula, these glass transition temperatures are all in absolute temperature (K).)

[0014] The glass transition temperature of the homopolymer used in the above calculation can be a value described in literature, such as the value described in POLYMER HANDBOOK, FOURTH EDITION (Johannes Brandrup, Edmund Heinz Immergut, Eric A. Grulke Wiley, 2004) or a value in a manufacturer's catalog.

[0015] The Tg of the core portion composed of a polymer obtained by polymerizing at least (meth)acrylic acid and / or its ester is sufficiently low to maintain film-forming properties during application and sufficiently high to obtain sebum resistance. However, when such a core portion resin composition is simply used in the form of particles, it does not disperse well in the liquid, and writing may become smudged over time.

[0016] In contrast, the present inventors have found that by combining the core with a shell comprising a polymer obtained by polymerizing at least a vinyl monomer having a cyclic structure and (meth)acrylic acid and / or an ester thereof, and having the above-mentioned Tg, in a mass ratio that satisfies the above, it is possible to suppress blurring of writing over time without impairing adhesion, water resistance, and sebum resistance. More specifically, by mixing a vinyl monomer having a cyclic structure with a polymer obtained by polymerizing at least (meth)acrylic acid and / or an ester thereof in a ratio that satisfies the above-mentioned Tg, the shell can also provide good adhesion and sebum resistance.

[0017] Furthermore, by setting the ratio of the total mass of the shell and core portions to 0.06 or more, the dispersibility during polymerization is improved, thereby suppressing the generation of coarse particles and enabling stable production of core-shell type resin particles. Furthermore, by setting this ratio to 0.40 or less, the film-forming properties and coating flexibility of the core portion can be obtained despite the presence of the shell portion.

[0018] The cosmetic of the present invention may contain a liquid medium, that is, the cosmetic of the present invention may be a liquid cosmetic.

[0019] The cosmetic of the present invention may also contain other optional components. Examples of such other components include preservatives, antioxidants, neutralizing agents, UV absorbers, chelating agents, pH adjusters, moisturizing agents, cosmetic ingredients, fragrances, viscosity adjusters, dispersants, water-soluble dyes, and coloring materials such as resin particle pigments. The content of the other components may be determined appropriately within a range that does not impair the effects of the present invention. These components may be present either within the core-shell type resin particles or outside the core-shell type resin particles.

[0020] The viscosity of the cosmetic of the present invention may be 2 mPa·s or more and 15 mPa·s or less. From the viewpoint of improving the outflow properties of the cosmetic, this viscosity is preferably 15 mPa·s or less, 12 mPa·s or less, 10 mPa·s or less, 9 mPa·s or less, 8 mPa·s or less, or 7 mPa·s or less. This viscosity may be 2 mPa·s or more, 3 mPa·s or more, or 4 mPa·s or more.

[0021] The viscosity range can be adjusted by adjusting the core-shell type resin particles used, the type and content of each component, and the dispersion method.

[0022] In the present invention, the viscosity is measured at a shear rate of 50 rpm (shear rate: 192 [s -1 ]) and was measured at a temperature of 25° C. This viscosity can be measured using, for example, an ELD type viscometer (manufactured by Toki Sangyo Co., Ltd.).

[0023] Each component of the present invention will be described below.

[0024] <Core-shell type resin particles> The cosmetic of the present invention contains core-shell type resin particles. The core-shell type resin particles have a core portion and a shell portion.

[0025] The ratio of the mass of the shell portion to the total mass of the shell portion and the core portion is 0.06 to 0.40. This ratio is preferably 0.06 or more, 0.10 or more, or 0.15 or more, from the viewpoints of suppressing the generation of coarse particles and stably obtaining core-shell type resin particles. This ratio is preferably 0.40 or less, 0.35 or less, 0.30 or less, 0.25 or less, or 0.20 or less, from the viewpoints of obtaining film-forming properties and coating flexibility due to the core portion.

[0026] The difference between the glass transition temperature of the core portion and the glass transition temperature of the shell portion may be 80° C. or more and 210° C. or less. This difference may be 80° C. or more, 90° C. or more, 95° C. or more, 100° C. or more, 105° C. or more, 110° C. or more, 115° C. or more, 120° C. or more, 125° C. or more, 130° C. or more, 135° C. or more, or 140° C. or more, and may be 210° C. or less, 200° C. or less, 190° C. or less, 180° C. or less, 170° C. or less, 165° C. or less, or 160° C. or less.

[0027] The average particle diameter of the core-shell resin particles measured by dynamic light scattering may be 50 nm to 300 nm. This average particle diameter may be 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, or 100 nm or more, or may be 300 nm or less, 270 nm or less, 250 nm or less, 230 nm or less, 200 nm or less, 170 nm or less, or 150 nm or less. The average particle diameter here refers to the histogram average particle diameter (D50) value based on the scattering intensity distribution measured by dynamic light scattering.

[0028] The solid content of the core-shell resin particles may be 5% by mass or more and 30% by mass or less relative to the mass of the cosmetic, and may be 5% by mass or more, 7% by mass or more, 9% by mass or more, 10% by mass or more, or 13% by mass or more, and may be 30% by mass or less, 25% by mass or less, 20% by mass or less, or 17% by mass or less.

[0029] (Core part) The core of the core-shell type resin particle is made of a polymer obtained by polymerizing at least (meth)acrylic acid and / or its ester.

[0030] The glass transition temperature of the core is −30° C. or higher and 35° C. or lower. This Tg may be −30° C. or higher, −25° C. or higher, −20° C. or higher, −15° C. or higher, or −10° C. or higher, and may be 35° C. or lower, 33° C. or lower, 30° C. or lower, 25° C. or lower, 20° C. or lower, 15° C. or lower, 10° C. or lower, 5° C. or lower, 0° C. or lower, or −5° C. or lower.

[0031] The core may or may not contain a coloring material.

[0032] (Core: (meth)acrylic monomer) Examples of (meth)acrylic monomers that can be used include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-sulfoethyl (meth)acrylate, phenyl (meth)acrylate, and metal salts thereof. In the present invention, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0033] The carbon number of the (meth)acrylic monomer may be 3 or more and 12 or less. The carbon number may be 3 or more, 4 or more, or 5 or more, and may be 12 or less, 11 or less, or 10 or less.

[0034] These (meth)acrylic monomers may be used alone or in combination. In particular, by using a mixture of (meth)acrylic monomers, the Tg of the core portion can be adjusted.

[0035] In particular, it is preferable that the (meth)acrylic monomer of the core portion contains butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate, and in particular, methyl (meth)acrylate and / or ethyl (meth)acrylate and butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate, from the viewpoint of suppressing smearing of writing over time.

[0036] When the (meth)acrylic monomer of the core portion contains butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate, the total content of butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate may be 35% by mass or more and 85% by mass or less, based on the mass of the core portion. From the viewpoint of film-forming ability, this content is preferably 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and from the viewpoint of sebum resistance, it is preferably 85% by mass or less or 80% by mass or less.

[0037] (shell part) The shell portion of the core-shell type resin particle is made of a polymer obtained by polymerizing at least a vinyl monomer containing a cyclic structure and a (meth)acrylic monomer.

[0038] The glass transition temperature (Tg) of the shell portion may be 50° C. or higher and 180° C. or lower. The Tg may be 50° C. or higher, 60° C. or higher, 70° C. or higher, 80° C. or higher, 90° C. or higher, 100° C. or higher, 105° C. or higher, 110° C. or higher, 115° C. or higher, 120° C. or higher, 125° C. or higher, or 130° C. or higher. The Tg may be 180° C. or lower, 170° C. or lower, 160° C. or lower, 150° C. or lower, 140° C. or lower, or 135° C. or lower.

[0039] (Shell: Monomer with a cyclic structure) As the monomer having a cyclic structure, for example, a styrene-based monomer or a vinylcycloalkane can be used.

[0040] Examples of styrene-based monomers that can be used include styrene and styrene derivatives, such as α-methylstyrene, m-chlorostyrene, p-chlorostyrene, m-fluorostyrene, p-fluorostyrene, p-methoxystyrene, m-tert-butoxystyrene, p-tert-butoxystyrene, p-vinylbenzoic acid, p-chloro-α-methylstyrene, and p-tert-butoxy-α-methylstyrene.

[0041] As the vinylcycloalkane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and the like can be used.

[0042] The monomer having a cyclic structure preferably contains a styrene-based monomer, particularly styrene or α-methylstyrene, from the viewpoint of adhesiveness.

[0043] The content of the monomer having a cyclic structure may be 10% by mass or more and 70% by mass or less, based on the mass of the shell portion. From the viewpoint of adhesion, this content is preferably 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more. From the viewpoint of sebum resistance, this content is preferably 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less.

[0044] The content of the monomer having a cyclic structure may be 2% by mass or more and 12% by mass or less relative to the mass of the core-shell resin particles. From the viewpoint of adhesion, this content is preferably 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, or 6% by mass or more. From the viewpoint of sebum resistance, this content is preferably 12% by mass or less, 11% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, or 7% by mass or less.

[0045] (Shell: (meth)acrylic monomer) The (meth)acrylic monomer for the shell portion can be any of those listed for the core portion. Among them, the (meth)acrylic monomer for the shell portion preferably contains at least one of (meth)acrylic acid, acrylic acid, methyl methacrylate, and phenyl methacrylate, particularly methacrylic acid, from the viewpoint of satisfying the above-mentioned Tg of the shell portion.

[0046] When the (meth)acrylic monomer of the shell portion contains methacrylic acid, the content of methacrylic acid is preferably 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more, and 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, relative to the mass of the (meth)acrylic monomer, from the viewpoint of satisfying the above-mentioned Tg.

[0047] Other components that can be included in the cosmetic of the present invention will be described below.

[0048] <Liquid medium> The liquid medium may be water, an organic solvent, or the like, and may particularly be an aqueous solvent. That is, the cosmetic of the present invention may be an aqueous liquid cosmetic.

[0049] In this specification, the term "aqueous solvent" refers to a solvent that contains water in the highest mass ratio among the liquid media that constitute the solvent. In particular, the aqueous solvent may contain water in a majority. The water content may be 50% by mass or more and 90% by mass or less, based on the mass of the aqueous solvent. This content may be 50% by mass or more, 55% by mass or more, or 60% by mass or more, or 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less.

[0050] As the water, for example, ion-exchanged water, distilled water, etc. can be used.

[0051] Examples of organic solvents that can be used include polyhydric alcohols such as glycerin, diglycerin, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,3-butylene glycol, and hexylene glycol, and glycol ethers such as propylene glycol monomethyl ether and 3-methoxy-3-methyl-1-butanol.

[0052] <<Method for manufacturing cosmetics>> The cosmetic of the present invention can be produced by a method including preparing core-shell type resin particles and preparing an ink composition.

[0053] Between the preparation of the core-shell resin particles and the preparation of the ink composition, the core-shell resin particles may be isolated.

[0054] <Preparation of Core-Shell Resin Particles> The core-shell type resin particles can be produced by a method including preparing an aqueous phase containing a polymer for the shell portion, adding an oil phase containing a monomer for the core portion to the aqueous phase, and then emulsion polymerizing the resulting mixture.

[0055] (Preparation of aqueous phase) The aqueous phase containing the shell polymer may be prepared by polymerizing the shell monomer in water to obtain the shell polymer, or by drying the polymer thus obtained and dissolving it in water.

[0056] As the monomer for the shell portion, the monomers listed for the shell portion can be used.

[0057] The aqueous phase may further contain water and a polymerization initiator, and can be prepared by mixing these materials.

[0058] As the polymerization initiator, for example, an azo-based initiator, ammonium persulfate, etc. can be used.

[0059] (Creating the core) The dispersion of the core portion can be prepared, for example, by emulsion polymerization, which can be performed by preparing an oil phase, preparing an aqueous phase, mixing the oil phase and the aqueous phase to emulsify the components of the oil phase, and then polymerizing the mixture.

[0060] The oil phase is preferably added gradually with stirring from the viewpoint of suppressing the formation of coarse particles. Here, "gradual addition" means adding the oil phase to the aqueous phase at a substantially constant rate over 2.0 hours or more, 2.5 hours or more, or 3.0 hours or more, i.e., without artificially adjusting the rate during addition.

[0061] (Core: Oil phase) The oil phase may contain a monomer, and can be prepared by mixing the monomers that make up the oil phase.

[0062] As the monomer, the monomers listed for the core portion can be used.

[0063] <Preparation of cosmetics> The cosmetic can be prepared by a conventional method while mixing the produced core-shell type resin particles and other components constituting the cosmetic using a stirring device such as a disper.

[0064] <Applicator> The applicator of the present invention is a pen-type applicator that contains the above-mentioned cosmetic material.

[0065] In particular, the applicator of the present invention may have a front barrel having an application portion, and a barrel portion having a storage portion, in which the above-mentioned cosmetic material is stored (filled).

[0066] The applicator of the present invention is not particularly limited as long as it is an applicator for cosmetics. In particular, the specific embodiment of the applicator described with reference to the drawings can be used as an eyeliner or eyebrow applicator. The applicator of the present invention may also be an applicator for eyeshadow, mascara, etc.

[0067] The applicator of the present invention may be, for example, a rotary dispenser type (FIG. 1), a knock dispenser type (not shown), a cosmetic-incorporated type (FIG. 2), or a collector type (FIG. 3).

[0068] Each component of the applicator of the present invention will be described below.

[0069] 〈Tip section〉 The front barrel portion has an application portion. The front barrel portion may be formed so that a cap can be attached and detached.

[0070] The front barrel may have a core to assist in the supply of the cosmetic from the barrel to the application part. This core may be made of a capillary material such as a synthetic resin fiber bundle, a natural fiber bundle, or a porous resin body.

[0071] (application part) The applicator part may be in the form of a brush tip, a pen core, or any other applicator body. In particular, when the applicator part is in the form of a brush tip, the applicator of the present invention is useful as an eyeliner or eyebrow applicator.

[0072] When the application part is in the form of another application body, the application part may be made of, for example, rubber, elastomer, or closed-cell foam having resilience.

[0073] When the application part has a brush tip shape, the application part can be obtained, for example, by aligning (sharpening) multiple resin fiber bundles to form a brush shape so that the tip is tapered, and then integrating the rear end by heat welding and expanding the diameter into a flange shape.

[0074] When the application part is in the shape of a pen core, the application part may be made of a fiber bundle or may be made of a porous resin body.

[0075] The fibers constituting the application part may be synthetic fibers or natural fibers. The synthetic fibers may be made of, for example, polybutylene terephthalate (PBT). The fiber thickness may be 0.10 mm or more, or 0.11 mm or more, and may be 0.15 mm or less, or 0.14 mm or less.

[0076] <Shaft cylinder part> The barrel portion has a storage portion in which the cosmetic material is stored.

[0077] (Storage section) The container may be hollow so that it can be filled with a cosmetic, or may be shaped like a batting that can be impregnated with a cosmetic. When the container is hollow, the applicator is sometimes referred to as a "direct liquid applicator." When the container is shaped like a batting, the applicator is sometimes referred to as a "batting-type applicator."

[0078] Furthermore, when the storage section is hollow, the storage section may contain a stirring body. The stirring body may be in the form of a ball, a rod, or the like. The stirring body may be made of metal or resin.

[0079] <cap> The cap is a member for covering the application part when not in use. The cap may have an inner cap and a spring. The inner cap is a cup-shaped member that is arranged to be movable back and forth to increase the airtightness of the application part. The spring is a member for biasing the inner cap backward.

[0080] <Other configurations> Other optional components constituting the applicator of the present invention can be taken into consideration in the following specific embodiments. These components may be resin molded products.

[0081] Specific embodiments of the applicator will be described below with reference to the drawings. Optional configurations of the applicator of the present invention can be referenced as appropriate to the following descriptions.

[0082] Applicator of the First Embodiment: Rotary-Type Dispenser (Fig. 1) As shown in Figure 1, the rotary-type applicator 100 is configured to eject the cosmetic of the present invention into a brush-shaped applicator part 111 by a liquid-pressing mechanism 130. This configuration can be used as a direct-flow eyeliner. In front of the liquid-pressing mechanism 130 is a storage part 121 in which the cosmetic is stored, and in front of that is disposed the applicator part 111.

[0083] The liquid pressing mechanism 130 rotates the delivery member 131, which is arranged at the rear end of the axial tube portion 120, in the circumferential direction relative to the axial tube portion 120, thereby delivering the cosmetic material from the storage portion 121 and supplying it to the application portion 111.

[0084] The liquid pressing mechanism 130 of this applicator 100 has a feeding member 131, a threaded rod 132, a drive cylinder 133, a screw body 134, and a piston body 135. The feeding member 131 is rotatably fitted to the rear end of the axial cylinder portion 120. The drive cylinder 133 can transmit the force of rotation of the feeding member 131 by the user to the threaded rod 132. The screw body 134 is fixed to the axial cylinder portion 120 and is screwed onto the threaded rod 132. A piston body 135 is rotatably engaged with the tip of the threaded rod 132. The piston body slides within the accommodation portion 121 of the axial cylinder portion 120. The rotation of the feeding member 131 is transmitted to the threaded rod 132 via the drive tube 133, and the rotation of the threaded rod 132 causes the threaded rod 132 and the piston body 135 to move forward via the female thread of the nut-shaped screw body 134, thereby discharging the cosmetic from the storage section 121 to the application section 111.

[0085] As shown in FIG. 1, feeding member 131 is rotatably fitted into the rear end of barrel portion 120 and is exposed. Crown 131a is fitted into the rear end, thereby giving feeding member 131 an operable, closed cylindrical shape. Drive tube 133 is fitted into feeding member 131 and fixed in the rotational direction. Threaded body 134 is attached within drive tube 133, and threaded body 134 is fixed to drive tube 133 in the rotational direction and is movable relative to it in the axial direction. Spring member 131b can urge feeding member 131, which serves as a rotating body, rearward.

[0086] Note that "fixed in the rotational direction" means that when one member is attached to another member, the one member is fixed so that it does not rotate relative to the other member.

[0087] In this applicator, seal portion 113, joint member 114, front barrel portion 110, and applicator portion 111 are attached by fitting to front end portion 120a of barrel tube portion 120. A cosmetic is stored in storage portion 121 of barrel body 120. The cosmetic is dispensed from storage portion 121 through a flow path within joint member 114 and ejected into applicator portion 111, where it can be applied. After use, cap 40 can be attached to front barrel portion 110 to cover applicator portion 111 and front barrel portion 110.

[0088] 1, the barrel portion 120 may have a stirring ball 122 in the storage portion 121, which allows the cosmetic to be stirred by reciprocating motion. The cap 140 may have an inner cap 141 provided inside the cap 140, and a spring 142 that can bias the inner cap 141 rearward.

[0089] Furthermore, the applicator of the first embodiment may have a stopper 150 and a seal ball 112 to close the flow path of the cosmetic material toward the applicator part 111 when not in use (during distribution).

[0090] Stopper 150 has a ring-shaped portion that, when not in use, is positioned between the rear end of front barrel portion 110 and the front surface of the stepped portion of front end portion 120a of barrel portion 120. Stopper 150 fixes the positions of seal portion 113, joint member 114, front barrel portion 110, and applicator portion 111, making it possible to close the flow path of the cosmetic toward applicator portion 111.

[0091] This stopper 150 may have a portion of its ring-shaped portion cut away, with a tab integrally formed on the side opposite the cut-off portion. When the tab is pulled, the ring-shaped portion expands in diameter from the cut-off portion, allowing it to be removed from between the rear end of front barrel portion 110 and front end portion 120a of barrel body 120.

[0092] When not in use, the seal ball 112 is fitted into the inner diameter portion of the seal part 113, thereby preventing the cosmetic from flowing into the application part 111 side.

[0093] During use, the user pulls stopper 150 out of barrel portion 120 and pushes front barrel portion 110 toward the rear end, causing the rear end narrow diameter portion of coupling member 114 to abut against seal ball 112, which is then removed from the inner diameter portion of seal portion 113 and pushed into storage portion 121. This causes the cosmetic material in storage portion 121 to flow from the inner diameter portion of coupling member 114 into the liquid flow path of applicator portion 111, and is supplied to applicator portion 111 from its interior, making it possible to apply the cosmetic to the target area.

[0094] Second Embodiment of Applicator: Cosmetic Material-Incorporated Applicator Type (Fig. 2) As shown in FIG. 2, the cosmetic-containing applicator type applicator 200 has a structure that supplies the cosmetic inside the barrel portion 220 to the applicator portion 211. This applicator 200 has a barrel portion 220, a front barrel portion 210, an applicator portion 211, and a retaining member 212. The barrel portion 220 stores the cosmetic in a padded storage portion 221 by impregnation. The applicator portion 211 is provided on the front barrel portion 210 and is capable of applying the cosmetic to an object. The retaining member 212 is a member that covers the outer periphery of the applicator portion 211 on the barrel portion 220 side (base side), leaving only a tip portion 211a of the applicator portion 211. This applicator 200 may have a cap 240 that is configured to be detachable from the front barrel portion 210, thereby covering the applicator portion 211 and the retaining member 212.

[0095] The padded housing portion 221 is housed within the barrel 220 from the center to the front barrel portion 210, and is sealed and supported by a tail plug 222 fitted into the rear end of the barrel 220.

[0096] A core 213 is disposed in the opening of the front barrel section 210. This core may be made of open-cell foam. The rear end of this core 213 is fitted into the front end of the storage section 221. Meanwhile, the front end of this core 213 is fitted into the rear end of the application section 211, thereby allowing ink contained in the storage section 211 to be guided to the application section 211. The front barrel section 210 has a slightly smaller diameter than the barrel section 220 (smaller by the thickness of the cap 240), thereby creating a step between the front barrel section 210 and the barrel section 220. The core 213 is attached within the front barrel section 210 via a substantially cylindrical support body 214. The cylindrical rear end of the retaining member 212 is fitted between the outer periphery of the support body 214 and the inner periphery of the front barrel section 210.

[0097] The tip of holding member 212 is located further forward than front barrel portion 210, and covers outer peripheral surface 211b of applicator part 211. Outer peripheral surface 212a of holding member 212 tapers to a point in the shape of a conical side surface or tapered.

[0098] Third Embodiment of Applicator: Collector-Type Applicator (Fig. 3) As shown in Figure 3(b), collector-type applicator applicator 300 has collector 312 disposed at the front of barrel section 320, with barrel section 320 housing housing section 321. Collector 312 has a shape in which multiple leaf sections are arranged axially in a comb-like pattern. As shown in Figure 3(a), front barrel section 310 and barrel section 320 on the rear side of front barrel section 310 are fitted together.

[0099] The axial tube portion 320 is formed like a pipe with an interior that is connected and open at the front and rear. A tail plug 323 is fitted into the rear portion of the axial tube portion 320, thereby closing the rear portion of the axial tube portion 320. As a result, the axial tube portion 320 sandwiched between the front end of the tail plug 323 and the rear end of the collector 312 forms the storage portion 321.

[0100] No impregnated material such as batting is placed inside this storage section 321, and the cosmetic material is directly stored therein, and a stirring member (such as a ball) 322 for stirring the cosmetic material is also placed therein.

[0101] Collector 312 has a structure in which it is covered and held by front barrel portion 310 and barrel tube portion 320 .

[0102] Tapered brush-like applicator portion 311 projects from the opening at the front end of front barrel portion 310. Front barrel portion 310 is tapered to a point with a substantially conical side surface, and the tip angle of front barrel portion 310 may be formed to be substantially the same angle as the tip angle of applicator portion 311.

[0103] A cap can be removably fitted onto front barrel portion 310, thereby covering application portion 311.

[0104] Inside the hollow, tapered front barrel portion 310, a bellows-shaped collector 312 is arranged behind the application portion 311, and a core 313 is arranged to pass through the hollow portion of this collector 312.

[0105] The core 313 does not protrude from the rear end of the collector 312 into the storage section 321 of the axial tube section 320 (see Figure 3(b)). The rear end surface of the collector 312 and the rear end surface of the core 313 are on approximately the same plane, so that the rear end of the core 313 does not protrude into the storage section 321. This ensures that the volume within the storage section 321 is sufficient. Furthermore, when the agitator 322 is provided within the storage section 321, even if the agitator 322 moves within the storage section 321, it will not collide with the core 313. This prevents deformation of the core 313, resulting in sufficient penetration of the coating liquid. [Example]

[0106] The present invention will be specifically explained with reference to examples and comparative examples, but the present invention is not limited to these.

[0107] <<Preparation of cosmetics>> Preparation of Shell Polymer A 2-liter flask was equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, and 1000 ml separatory funnel for monomer introduction, and placed in a hot water bath. Distilled water, an azo initiator, and ammonia as a pH adjuster were charged into the flask to prepare an aqueous phase. While introducing nitrogen gas into the aqueous phase, the internal temperature was raised to 50°C.

[0108] The composition obtained by mixing the monomers shown in Table 1 in the content ratios shown in Table 1 was added from a separatory funnel to the above aqueous phase, which was kept at a temperature of around 50°C, over a period of 3 hours while stirring, and polymerized. The mixture was then aged for a further 5 hours to complete the polymerization, and then dried to produce powdered shell polymers E1 to E4 (within the scope of the present invention) and C1 (outside the scope of the present invention).

[0109] Using the glass transition temperature (Tg) and content of each monomer, the glass transition temperature (Tg) of the resulting shell portion was calculated from the above FOX equation (Equation (1)).

[0110] [Table 1]

[0111] The glass transition temperature (Tg) of the shell polymer E2 was measured in accordance with JIS K7121 using a Rigaku thermo plus evo DSC8230 (Rigaku Corporation), and the measured value was 140° C. This shows that there is not a large discrepancy between the calculated glass transition temperature (Tg) obtained by the FOX equation and the measured glass transition temperature (Tg) in accordance with JIS K7121.

[0112] <Preparation of aqueous dispersion of core-shell type resin particles> (Core-shell type resin particle dispersion E1) A 2-liter flask was equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, and 1000 ml separatory funnel for monomer introduction, and placed in a hot water bath. 51.4 parts by weight of distilled water, 8.0 parts by weight of shell polymer E1, 0.1 parts by weight of an azo initiator as an initiator, and 0.5 parts by weight of ammonia as a pH adjuster were charged into the flask to prepare an aqueous phase. While introducing nitrogen gas into the aqueous phase, the internal temperature was raised to 50 ° C.

[0113] Separately, an oil phase was prepared by mixing 15.0 parts by weight of methyl methacrylate and 25.0 parts by weight of 2-ethylhexyl acrylate, which are the monomers constituting the core portion. This oil phase was added from the separatory funnel to the aqueous phase, which was kept at a temperature of about 50°C, over a period of 3 hours with stirring, to carry out emulsion polymerization. The mixture was then aged for a further 5 hours to complete the polymerization, yielding 100 parts by weight of a core-shell resin particle dispersion.

[0114] (Core-shell type resin particle dispersions E2 to E11 and C1 to C6) Core-shell type resin particle dispersions E2 to E11 (within the scope of the present invention) and C1 to C6 (outside the scope of the present invention) were prepared in the same manner as core-shell type resin particle dispersion E1, except that the amount and type of each component were changed as shown in Table 2.

[0115] Using the glass transition temperature (Tg) and content of each core monomer, the glass transition temperature (Tg) of the core portion was calculated according to the above FOX formula (formula (1)).

[0116] The presence or absence of coarse particles in the dispersion was judged based on the particle size distribution obtained by laser diffraction / scattering method, according to the following criteria. Present: Particles with a diameter of more than 1 μm were confirmed. None: No particles with a particle size of more than 1 μm were found.

[0117] The average particle size of the core-shell type resin particles was measured by dynamic light scattering.

[0118] [Table 2]

[0119] [Table 3]

[0120] <Preparation of cosmetics> Cosmetics of Examples 1 to 14 and Comparative Examples 1 to 8 were prepared by adding dispersants, dispersions of core-shell resin particles or fixing agents, organic solvents, and water so as to achieve the content ratios shown in Tables 4 to 6 of colorant, dispersant, core-shell resin particles or fixing agent, organic solvent, and water shown in Tables 4 to 6. In Tables 4 to 6, the content ratio of core-shell resin particles or fixing agent indicates the content ratio of solids. Details of the substances shown in Tables 4 to 6 are as follows. Black A: Carbon black (DK Black No. 2, Daito Chemical Industry Co., Ltd.) Black-red: A mixture of iron oxide red pigment (TALOX R-516HP, Titan Kogyo Co., Ltd.) and iron oxide black pigment (TALOX ABL-412HP, Titan Kogyo Co., Ltd.) (mass ratio 1:1) Black B: A mixture of iron oxide red pigment (TALOX R-516HP, Titan Kogyo Co., Ltd.) and carbon black pigment (CHARCOPOWDER, Daito Kasei Kogyo Co., Ltd.) (mass ratio 1:1) Al: aluminum pigment (Cosmicolor® Frost Silver, Toyo Aluminum Co., Ltd.) Dispersant: styrene acrylic resin Adhesive A: Styrene / acrylic film-forming agent (YODOSOL GH41F, Nouryon Japan Co., Ltd.) Fixing agent B: alkyl acrylate copolymer emulsion (Tg: -15°C, solid content 45% by mass, Akzo Nobel) Organic solvent: 1,3-butylene glycol

[0121] "evaluation"

[0122] The following evaluations were carried out by filling each of the obtained cosmetics into a free-flow eyeliner container (UC-76B, Mitsubishi Pencil Co., Ltd.).

[0123] <Writing smudges over time> Each cosmetic material filled in the above-mentioned free-flow eyeliner container was stored at 50°C for 2 months, and after storage, the cosmetic material was applied to the eyes to evaluate its applicability. The evaluation criteria were as follows: A: It can be applied without smudging. B: Slight smearing, but can be applied. C: The coating is smudged and cannot be applied.

[0124] <Adhesion> The cosmetic was applied to the skin, and the drawn line was rubbed with the pad of a finger to evaluate adhesion. The evaluation criteria were as follows: A: There was no change in the drawn line due to rubbing with the pad of a finger. B: A slight change was observed in the drawn line when rubbed with the pad of a finger. C: Significant changes were observed in the drawn lines after rubbing with the pad of a finger.

[0125] <Water-resistant adhesion> The cosmetic was applied to the skin, and then water was run toward the drawn line, and the drawn line was rubbed with the pad of a finger to evaluate the water-resistant adhesion. The evaluation criteria were as follows: A: No change in the drawn line when rubbed with the pad of a finger. B: A slight change was observed in the drawn line when rubbed with the pad of a finger. C: Significant changes were observed in the drawn lines after rubbing with the pad of a finger.

[0126] <Sebum resistance> The cosmetic was applied to the skin, artificial sebum was applied to the drawn line, and the drawn line was rubbed with the pad of a finger to evaluate sebum resistance. The evaluation criteria were as follows: A: No change in the drawn line was observed when rubbed with the pad of a finger. B: No slight change was observed in the drawn line when rubbed with the pad of a finger. C: Significant changes were observed in the drawn lines after rubbing with the pad of a finger.

[0127] Tables 4 to 6 show the configurations and evaluation results of the examples and comparative examples.

[0128] [Table 4]

[0129] [Table 5]

[0130] [Table 6]

[0131] It can be seen from Tables 4 to 6 that the cosmetics of the examples containing core-shell type resin particles within the range of the present invention have good adhesion, water resistance, and sebum resistance, and are able to suppress smearing of the application over time. [Explanation of symbols]

[0132] 100, 200, 300 applicator 110, 210, 310 Tip shaft part 111, 211, 311 application section 112 Sticker Ball 113 Seal part 114 Joint members 120, 220, 320 Shaft cylinder part 120a Front end of the shaft cylinder 121, 221, 321 storage unit 122 Mixing Ball 130 Liquid pressing mechanism 131 Feeding member 131a Crown of Heaven 131b Spring member 132 Threaded Rod 133 Drive tube 134 Threaded body 135 Piston body 140, 240 caps 141 Inner cap 142 Spring 150 Stopper 211a Tip of application part 211b Outer surface of application part 212 Retaining member 212a outer surface of holding member 213 Core 214 Support 222 tail plug 312 Collector 313 Core 322 Stirring body 323 tail plug

Claims

1. A cosmetic containing core-shell type resin particles, the core of the core-shell resin particle is made of a polymer obtained by polymerizing at least a (meth)acrylic monomer, the shell portion of the core-shell resin particle is made of a polymer obtained by polymerizing at least a monomer having a cyclic structure and a (meth)acrylic monomer, the glass transition temperature of the core portion is −30° C. or higher and 35° C. or lower; The glass transition temperature of the shell portion is 50°C or higher, and The ratio of the mass of the shell portion to the total mass of the shell portion and the core portion is 0.06 or more and 0.40 or less. Cosmetics.

2. The cosmetic according to claim 1, wherein the glass transition temperature of the shell portion is 80°C or higher.

3. 3. The cosmetic preparation according to claim 1, wherein the ratio of the mass of the monomer having a cyclic structure to the total mass of the monomer having a cyclic structure and the (meth)acrylic monomer is 0.1 to 0.

7.

4. 3. The cosmetic according to claim 1, wherein the (meth)acrylic monomer of the core portion comprises butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate.

5. The cosmetic according to claim 4, wherein the total content of the butyl (meth)acrylate and the 2-ethylhexyl (meth)acrylate is 35% by mass to 80% by mass relative to the mass of the core portion.

6. 3. The cosmetic according to claim 1, wherein the (meth)acrylic monomer of the core portion comprises methyl (meth)acrylate and / or ethyl (meth)acrylate, and butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate.

7. The cosmetic preparation according to claim 1 or 2, wherein the monomer having a cyclic structure includes styrene.

8. The cosmetic according to claim 1 or 2, wherein the content of the monomer having a cyclic structure is 10% by mass or more and 70% by mass or less relative to the mass of the shell portion.

9. The cosmetic according to claim 1 or 2, wherein the content of the monomer having a cyclic structure is 2% by mass or more and 12% by mass or less relative to the mass of the core-shell type resin particles.

10. A pen-type applicator containing the cosmetic material according to claim 1 or 2.

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