Green liquid cosmetic

Abstract

To provide green liquid cosmetics suitable for make-up cosmetics, such as eyeshadow, eyeliner, eyebrow, mascara and the like, which is excellent in green color development (high chroma) and dispersion stability.SOLUTION: The green liquid cosmetic of the present invention is characterized by containing: (A) a Prussian blue dispersion for cosmetics, containing at least Prussian blue, 0.05 to 0.13 of a water-soluble basic substance when the content of Prussian blue is 1 by mass ratio, and water; and (B) a red iron oxide dispersion for cosmetics, containing red iron oxide, an organic acid having a molecular weight of 300 or less, and water, the average particle size of red iron oxide by cumulant method analysis in the scattering intensity distribution being 100 nm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a green liquid cosmetic that is suitable for use in makeup cosmetics such as eyeshadow, eyeliner, eyebrow pencil, and mascara, as it exhibits excellent green color development (high saturation) and dispersion stability. [Background technology]

[0002] Traditionally, Prussian blue has been used as a coloring agent, often mixed with extender pigments, and widely used for coloring cosmetics, paints, writing instrument inks, printing inks, resins, and the like (see, for example, Non-Patent Document 1). This Prussian blue pigment is primarily composed of ferric ferrocyanide, and its chemical structure is generally represented as MFe[Fe(CN)6], M=K,Na,NH4. Commercially available Prussian blue pigments mainly use ammonium ferric iron. While it has a deep blue color unique to Prussian blue and strong coloring power as an inorganic pigment, its stable pH is low at 4-6, and its instability in alkaline conditions is a problem (see, for example, Patent Documents 1 and 2, and Non-Patent Document 2). Under alkaline conditions, discoloration may occur, and there are issues such as discoloration or loss of color when used in combination with alkaline extender pigments such as calcium carbonate and alumina. Furthermore, when Prussian blue is reduced, the blue color may be lost, and if mixed with a vehicle that is easily oxidized and sealed, the Prussian blue may act as an oxidizing agent, causing itself to be reduced and discolored.

[0003] On the other hand, in cosmetics and other applications, Prussian blue has greater coloring power than ultramarine, a blue pigment, and can produce highly saturated blue tones. Furthermore, it can produce highly saturated green when used in combination with legally approved pigments such as red or yellow. For these reasons, there is a high demand for its use as an ingredient in cosmetics. However, due to the aforementioned challenges, its use has been restricted.

[0004] To address these issues with Prussian blue, for example, a surface-treated powder characterized by being treated with either or both of α-oxycarboxylic acid and a coating-forming substance (see Patent Document 1) is known. Furthermore, as an example of using Prussian blue in cosmetics, a pigment dispersion for cosmetics containing black iron oxide, red iron oxide, and Prussian blue is known (see Patent Document 2). However, Patent Document 1 mentioned above has issues such as not exhibiting the true color development of Prussian blue and still lacking sufficient dispersion stability. Furthermore, while Patent Document 2 discloses a related technology to the present invention, it simply involves creating a mixed-color black dispersion by blending three components: black iron oxide, red iron oxide, and Prussian blue. It does not mention the aforementioned problem with Prussian blue, nor does it involve preparing a dispersion of Prussian blue with pre-established dispersion stability and using this dispersion to obtain a green liquid cosmetic, etc. Thus, it differs from the present invention in terms of the problem to be addressed and the technical concept. [Prior art documents] [Patent Documents]

[0005] [Non-Patent Document 1] The Latest Illustrated Guide to the Physical Properties of Powders (Third Edition) (3rd Edition, 1st Printing, June 30, 2004, 343 pages) [Non-Patent Document 2] "Introduction to Pigments: Textbook," Japan Society for Pigment Materials, 1970, pp. 114-118) [Patent Document 1] Japanese Patent Publication No. 2004-91645 (Claims, Detailed Description of the Invention, etc.) [Patent Document 2] Japanese Patent Publication No. 2003-231614 (Claims, Detailed Description of the Invention, etc.) [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In view of the problems and current state of the prior art described above, the present invention aims to resolve these issues and provides a green liquid cosmetic suitable for makeup cosmetics such as eyeshadow, eyeliner, eyebrow pencil, and mascara, which has excellent green color development (high saturation), dispersion stability, and weather resistance. [Means for solving the problem]

[0007] In view of the above-mentioned conventional problems, the present inventors conducted diligent studies and found that the above-mentioned green liquid cosmetic can be obtained by including (A) a Prussian blue dispersion for cosmetic use containing at least Prussian blue, a predetermined amount of a water-soluble basic substance, a dispersant, and water, and (B) a red iron oxide dispersion for cosmetic use containing red iron oxide, an organic acid with specific physical properties, and water, wherein the average particle size of the red iron oxide scattering intensity distribution analyzed by the cumulant method is below a predetermined value. Thus, the present inventors have completed the present invention.

[0008] In other words, the green liquid cosmetic composition of the present invention is characterized by comprising (A) a Prussian blue dispersion for cosmetic use containing at least Prussian blue, 0.05 to 0.13 parts water-soluble basic substance when the Prussian blue content is 1 by mass ratio, and (B) an iron oxide dispersion for cosmetic use containing red iron oxide, an organic acid with a molecular weight of 300 or less, and water, wherein the average particle size of the red iron oxide scattering intensity distribution analyzed by the cumulant method is 100 nm or less. It is preferable that the average particle size of the scattering intensity distribution of Prussian blue in the Prussian blue dispersion for cosmetics described above (A) is 130 nm or less, according to the cumulant method analysis. It is preferable that the organic acid with a molecular weight of 300 or less in the aforementioned (B) iron oxide dispersion for cosmetics is at least one selected from the following group A. Group A: Glycolic acid, lactic acid, tartonic acid, glyceric acid, hydroxybutyric acid, 2-Hydro Roxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, malic acid, tartaric acid, citramal Acids, citric acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, ricinoleic acid, Ricinerized acid, cerebronic acid, quinic acid, shikimic acid It is preferable that the organic acid having a molecular weight of 300 or less in the (B) bengala dispersion for cosmetics is citric acid.

Advantages of the Invention

[0009] According to the present invention, there is provided a green liquid cosmetic suitable for makeup cosmetics such as eyeshadow, eyeliner, eyebrow, and mascara, which is excellent in green color development (high color saturation) and dispersion stability. The objects and effects of the present invention are recognized and obtained by using the components and combinations particularly pointed out in the claims. Both the above general description and the following detailed description are exemplary and explanatory, and do not limit the present invention described in the claims.

Brief Description of the Drawings

[0010] [Figure 1] (a) shows an example of a cation arrangement diagram of dark blue, and (b) is an explanatory diagram for explaining the outline of a mechanism for maintaining the dispersion stability etc. of dark blue in the present invention.

Modes for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, it should be noted that the technical scope of the present invention is not limited to each of the embodiments described in detail below, and extends to the invention described in the claims and its equivalents. The green liquid cosmetic of the present invention comprises (A) at least a dark blue, a water-soluble basic substance of 0.05 to 0.13 when the content of the dark blue is 1 in terms of mass ratio, and water, a cosmetic dark blue dispersion, and (B) bengala, an organic acid having a molecular weight of 300 or less, and water, and a cosmetic bengala dispersion having an average particle size of 100 nm or less in the cumulant method analysis of the scattering intensity distribution of bengala.

[0012] 〈(A) Cosmetic Dark Blue Dispersion〉 The indigo dispersion for cosmetics of the present invention contains at least indigo, 0.05 to 0.13 of a water-soluble basic substance when the content of the indigo is 1 in terms of mass ratio, a dispersant, and water. The chemical structure of the indigo used in this indigo dispersion for cosmetics is generally represented by MKFe[Fe(CN)6] (where M is any one of K, Na, or NH4), and the iron ions include divalent iron (Fe II ) and trivalent iron (Fe III ), and FIG. 1 is a diagram of the cation arrangement of the indigo. The indigo used in the present invention can be used without particular limitation as long as it is generally indigo used in cosmetics. Preferably, those with an average particle diameter of 200 nm or less are desirable. Also, from the viewpoint of easy availability, ammonium congou with M being NH4 is preferable, and those with surface modification may also be used. If there are commercially available products, these can be used. Examples of commercially available products include MILORI BLUE FX-6940 and FX-9050 manufactured by Dainichi Seika Co., Ltd., Iron Blue SC manufactured by Daito Kasei Co., Ltd., and C38-7710 Softex Iron Blue manufactured by Sankyo Chemical Co., Ltd. In the present invention, the "average particle diameter" refers to the average particle diameter by the cumulant method analysis in the scattering intensity distribution, as described later.

[0013] This indigo dispersion has problems such as a low stable pH of 4 to 6 and instability in an alkaline state, and there are problems such as productivity and dispersion stability in the production of the dispersion. However, if it is a dispersion having the blending characteristics of the present invention, the above problems will be solved. From the viewpoints of the stability after dispersion and the convenience of cosmetics production, the content of the indigo used is preferably 5 to 50% by mass (hereinafter, "% by mass" is simply referred to as "%"), more preferably 10 to 30% with respect to the total amount of the indigo dispersion. By setting the content of this indigo to 5% or more, the productivity is excellent, and the green coloring property when added to an aqueous green liquid cosmetic (mixed color with a bengala dispersion) is excellent. On the other hand, by setting it to 50% or less, the dispersibility and stability over time are good.

[0014] According to the inventors' findings, the water-soluble basic substance used in the Prussian blue dispersion for cosmetics, as the dispersion of Prussian blue progresses in the dispersion, changes from Prussian blue to NH4, as shown in Figure 1(b). + It detaches, NH4 + From H + This occurs, causing the dispersion pH to decrease, and the absolute value of the zeta potential of Prussian blue at low pH tends to decrease, but H + This method uses a water-soluble basic substance as an alkaline agent to maintain the surface potential, thereby preserving the dispersion stability and micronization of Prussian blue. Specifically, the water-soluble basic substances that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, ammonia, or compounds having an amino group such as amines such as monomethylamine, dimethylamine, triethylamine, monoethylamine, diethylamine, ethylenediamine, monoethanolamine, diethanolamine, and triethanolamine, basic amino acids such as aminomethylpropanol (2-amino-2-methyl-1-propanol), trishydroxymethylaminomethane, arginine, and lysine, and aminoethylpropanolamine, aminomethylpropanediol, and aminoethylpropanediol, which can be used alone or in combination. In particular, discoloration and aggregation of Prussian blue can be suppressed to the greatest extent possible, and the use of aminomethylpropanol and potassium hydroxide is preferable for achieving further effects of the present invention.

[0015] The amount of water-soluble basic substance used is preferably in a mass ratio of 0.05 to 0.13, and more preferably 0.05 to 0.10, when the mass of Prussian blue is set to 1, from the viewpoint of dispersibility of Prussian blue and viscosity. If the mass ratio of this water-soluble basic substance is less than 0.05, gelation will occur during dispersion, and the effects of the present invention cannot be achieved. On the other hand, if it exceeds 0.13, the viscosity after dispersion will be high, reducing the design flexibility of green cosmetic products and the like.

[0016] Dispersants that can be used in Prussian blue dispersions for cosmetic purposes are included for the purpose of adjusting viscosity and further improving the dispersion stability of Prussian blue, and include, for example, at least one of surfactants and polymeric dispersants. Any commonly used surfactant may be used as the surfactant, such as anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, or polymeric surfactants, or two or more of these may be used in combination. Among these surfactants, nonionic surfactants are preferred because they provide more stable dispersibility of Prussian blue, are less irritating, and do not affect the dispersion state. Preferred nonionic surfactants include polyoxyethylene alkyl ethers such as laureth (polyoxyethylene lauryl ether), ceteth (polyoxyethylene cetyl ether), steareth (polyoxyethylene stearyl ether), and beheneth (polyoxyethylene behenyl ether), which can be used individually or in combination of two or more. Among these, beheneth-30, ceteth-20, and laureth-21 are preferred in terms of their molecular structure and hydrophilicity.

[0017] Furthermore, the polymer dispersant may contain at least one selected from, for example, polyaspartic acid, polyglutamic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and styrene-α-methylstyrene-acrylic acid copolymer, or at least one of these salts. Examples of these salts include alkali salts and ammonium salts such as sodium, potassium, and lithium, and alkanolamine salts such as mono, di, and triethanolamine and triisopropanolamine. Among these polymeric dispersants, polyaspartic acid, polyglutamic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and styrene-α-methylstyrene-acrylic acid copolymer, as well as at least one of their salts, are particularly preferred for their excellent dispersion stability, and sodium polyaspartate (Na) is especially desirable.

[0018] The content of these dispersants is preferably 0-5%, and more preferably 0-3%, relative to the total amount of the Prussian blue dispersion for cosmetics. A dispersant content exceeding 5% is undesirable because it adversely affects the stability of the cosmetic.

[0019] The remainder of the Prussian blue dispersion for cosmetic use is prepared with water (purified water, distilled water, deionized water, pure water, tap water, etc.). The (A) Prussian Blue dispersion for cosmetic use of the present invention contains at least the above-mentioned Prussian Blue, a water-soluble basic substance, a dispersant, and water. However, in order to further improve dispersibility and the solubility stability of each component, viscosity modifiers, chelating agents, pH adjusters, further dispersants, etc., may be used as appropriate as needed.

[0020] The Prussian blue dispersion for cosmetic use used in the present invention can be prepared by blending the above-mentioned Prussian blue, a water-soluble basic substance, a dispersant, and water in the above-mentioned ranges of their respective content, and then uniformly stirring and mixing them. For example, a Prussian blue dispersion for cosmetic use can be prepared by stirring the above-mentioned Prussian blue, a water-soluble basic substance, a dispersant, and a solvent such as water until homogeneous using a general-purpose disperser, then stirring further with a homomixer until homogeneous using a disperser, or by mixing and dispersing using various stirrers and dispersers such as ultrasonic dispersers, planetary mixers, three-roll mills, ball mills, bead mills, and jet mills in addition to dispersers. The most suitable agitator and disperser is selected based on the type and ratio of the above-mentioned components, the viscosity of the resulting dispersion, and other factors. The stirring and dispersion conditions when using these stirrers and dispersers vary depending on the type and quantity of the mixture. For example, when using the LMZ-4 (manufactured by Ashizawa Finetech Co., Ltd.), the peripheral speed is 5 m / s or more and the time is 60 min or more.

[0021] In the Prussian blue dispersion for cosmetic use in the present invention, viscosity measurement using a cone-plate viscometer at 25°C showed a shear rate of 383 s⁻¹. -1 The viscosity is preferably 10 mPa·s or less, and more preferably 2 to 6 mPa·s, from the viewpoint of appropriate viscosity, dispersion stability of Prussian blue, improved blendability in cosmetics, and improved flowability in collector-type pen applicators. The viscosity range described above (10 mPa·s or less) can be adjusted by suitably adjusting the amounts of each component used, the preferred dispersant and its amount, the pH adjusting agent and its amount, and so on.

[0022] Furthermore, the Prussian blue dispersion for cosmetics used in the present invention preferably has an average particle size of 130 nm or less in the cumulant method analysis of the scattering intensity distribution of dispersed Prussian blue, and more preferably, it is between 80 and 130 nm. By keeping the average particle size of this Prussian blue below 130 nm, further dispersion stability and vivid color development can be achieved. While a lower lower limit for the average particle size is preferable, it is preferable to have a value of 80 nm or higher from the perspective of manufacturability and cost. In the present invention, examples of measurement devices include dynamic light scattering using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), laser diffraction and scattering using Microtrac (manufactured by Nikkiso Co., Ltd.), and image imaging using MacView (manufactured by Mountec Co., Ltd.).

[0023] In the present invention, the Prussian blue dispersion for cosmetics is preferably adjusted to a pH of 7.5 or lower, and more preferably to a pH of 5 to 7, from the viewpoint of improving colorability, preventing skin irritation, and dispersion stability. In the present invention, the pH of the dispersion can be adjusted using an acidic substance such as citric acid or a basic substance such as 2-amino-2-methyl-1-propanol.

[0024] The pigment dispersion for cosmetics used in the present invention, configured in this way, contains at least Prussian blue, a water-soluble basic substance, and water, thereby resolving issues such as a decrease in the absolute value of the zeta potential of Prussian blue, aggregation, and discoloration. This maintains the surface potential of Prussian blue, preserving dispersion stability and micronization, resulting in a Prussian blue dispersion for cosmetics that is excellent in dispersion stability, color development (high saturation), weather resistance, and long-term stability. Furthermore, the resulting Prussian blue dispersion for cosmetics used in this invention provides a new dispersion method for Prussian blue, yielding a highly saturated blue hue, and further improving particle size and dispersion stability. By using it in combination (mixing) with the iron oxide dispersion described later, a highly saturated green (green dispersion) can be obtained.

[0025] (B) Red iron oxide dispersion for cosmetic use The (B) iron oxide dispersion for cosmetics used in the present invention contains at least iron oxide, an organic acid with a molecular weight of 300 or less, and water, and the average particle size of the iron oxide scattering intensity distribution analyzed by the cumulant method is 100 nm or less. Surprisingly, by combining and mixing the above-mentioned Prussian blue dispersion for cosmetics with such a red-colored iron oxide dispersion, the green liquid cosmetic of the present invention was obtained. Various known red iron oxides can be used as the iron oxide pigment, for example, those mainly composed of red α-Fe2O3 (hematite), brown γ-Fe2O3 (magmahite), black Fe3O4 (magnetite), and yellow α-FeOOH. In particular, in this invention, red α-Fe2O3 (hematite) is used in order to obtain a green cosmetic. The content of this red iron oxide [α-Fe2O3 (hematite), etc.] is preferably 10-50%, and more preferably 15-40%, of the total amount of the red iron oxide dispersion, from the standpoint of stability after dispersion and convenience in cosmetic manufacturing. By increasing the content of this red iron oxide [α-Fe2O3 (hematite), etc.] to 10% or more, productivity is improved, and the green coloring when added to green liquid cosmetics (mixed with Prussian blue dispersion) is also improved. On the other hand, by keeping the content at 50% or less, dispersibility and stability over time are improved.

[0026] The organic acid used has a molecular weight of 300 or less and improves the dispersion of the iron oxide solution. Examples include at least one organic acid selected from aliphatic hydroxy acids, aromatic hydroxy acids, and their derivatives, all of which have a molecular weight of 300 or less. Examples of the above-mentioned aliphatic hydroxy acids include glycolic acid, lactic acid, tartaric acid, glyceric acid, hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricineradicic acid, cerebronic acid, quinic acid, and shikimic acid. Examples of the above-mentioned aromatic hydroxy acids and their derivatives include monohydroxybenzoic acid derivatives, salicylic acid, creosote acids [homosalicylic acid, hydroxy(methyl)benzoic acid], vanillic acid, syringic acid, dihydroxybenzoic acid derivatives, pyrocatechuic acid, resorsilicic acid, protocatechuic acid, gentisic acid, orceric acid, trihydroxybenzoic acid derivatives, gallic acid, phenylacetic acid derivatives, mandelic acid, benzyl acid, atrolactinic acid, cinnamic acid, hydrocinnamic acid derivatives, melilotic acid, floretic acid, coumaric acid, umbellic acid, caffeic acid, ferulic acid, and sinapic acid. Preferably, one can be selected from the above-mentioned aliphatic hydroxy acids (Group A), and more preferably, citric acid is desirable from the standpoint of safety as an eyeliner. Furthermore, in this invention, acids with a molecular weight exceeding 300 are undesirable because they increase the tendency for red iron oxide and ultramarine to aggregate.

[0027] The content of these organic acids with a molecular weight of 300 or less is preferably 0.01 to 2.0% by mass, and more preferably 0.1 to 1.0% by mass, relative to the total amount of the red iron oxide dispersion. If the content of this acid with a molecular weight of 300 or less is less than 0.01% by mass, the above effect will be insufficient. On the other hand, if the content exceeds 2.0% by mass, the pH will decrease, which is undesirable.

[0028] The remainder of the iron oxide pigment dispersion for cosmetics is prepared with water (purified water, distilled water, deionized water, pure water, tap water, etc.). The (B) iron oxide dispersion for cosmetic use of the present invention contains at least the above-mentioned iron oxide, an organic acid with a molecular weight of 300 or less, and water, and can be manufactured by blending these components within the above-mentioned range of content and then uniformly stirring and mixing them. For example, a dispersion of red iron oxide for cosmetics can be prepared by stirring the above-mentioned red iron oxide, an organic acid with a molecular weight of 300 or less, and a solvent such as water until homogeneous using a general-purpose disperser, then stirring further with a homomixer until homogeneous using a disperser, or by mixing and dispersing using various stirrers and dispersers such as ultrasonic dispersers, planetary mixers, three-roll mills, ball mills, bead mills, and jet mills in addition to dispersers.

[0029] In the present invention, the (B) iron oxide dispersion for cosmetics preferably has an average particle size of 100 nm or less, and more preferably 10 to 50 nm, as determined by cumulant analysis of the scattering intensity distribution of the dispersed iron oxide. By making the average particle size of this red iron oxide pigment 100 nm or less, further dispersion stability and vivid color development can be achieved. Furthermore, while a lower lower limit for the average particle size is preferable, it is preferable to have a value of 10 nm or more from the perspective of manufacturability and cost.

[0030] <Green or dark blue liquid cosmetic> The green liquid cosmetic composition of the present invention is characterized by comprising (A) a Prussian blue dispersion for cosmetic use and (B) an iron oxide dispersion for cosmetic use. Preferred uses for the green liquid cosmetic composition include, for example, skincare cosmetics, makeup cosmetics, and nail cosmetics. Examples of applications for makeup cosmetics such as foundation, eyeshadow, eyeliner, eyebrow products, mascara, blush, nail polish, treatment nails, various gel nails, and lipstick, as well as hair color and body marker compositions, include body paint. There are no particular limitations on the form of the product, but since it is a dispersion (aqueous system), it can be applied to aqueous forms such as liquid, emulsion, cream, paste, gel, mousse, and spray. In particular, due to the dispersion characteristics of the green liquid cosmetic composition of the present invention, it is preferable to use it in water-based liquid cosmetic compositions such as eye makeup cosmetics including eyeshadow, eyeliner, eyebrow products, and mascara, as well as water-based nail polish. The green liquid cosmetic composition of the present invention contains (A) a Prussian blue dispersion for cosmetic use and (B) a red iron oxide dispersion for cosmetic use, and in addition to the above dispersions, eye makeup cosmetics may also contain a dispersant, a film-forming resin, and water as a dispersion medium (including purified water, distilled water, ion-exchanged water, pure water, ultrapure water, etc.). The water content will be the remainder after containing the above components and any optional components described later.

[0031] The dispersant used should further improve the dispersibility of the colorants, such as Prussian blue and red iron oxide, and should contain at least one of the following: one or more selected from polyaspartic acid, polyglutamic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, or styrene-α-methylstyrene-acrylic acid copolymer; one or more compounds selected from acrylic acid, methacrylic acid, or their alkyl esters as raw material monomers; or one or more of the following: a homopolymer or copolymer, or one or more salts thereof. Examples of these salts include alkali salts and ammonium salts such as sodium, potassium, and lithium, and anionic polymer dispersants such as alkanolamine salts such as mono, di, and triethanolamine and triisopropanolamine. Among these dispersants, using at least one of polyaspartic acid, polyglutamic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-α-methylstyrene-acrylic acid copolymer, tert-butyl acrylate, ethyl acrylate, and a copolymer of methacrylic acid, or salts thereof, provides superior dispersion stability, and sodium polyaspartate is particularly preferred. The content of these dispersants is preferably 0.1 to 10.0%, and more preferably 0.2 to 5.0%, relative to the total amount of the green liquid cosmetic, in order to achieve a high degree of balance between the dispersibility of the colorants, such as Prussian blue and red iron oxide, and dispersion stability within a suitable viscosity range.

[0032] Examples of film-forming resins that can be used include aqueous emulsion resins of copolymers selected from one or more monomers from acrylic acid, methacrylic acid or their alkyl esters or derivatives, styrene, and vinyl acetate. The content of this film-forming resin (aqueous emulsion resin) is preferably 2 to 15% of the total amount of the green liquid cosmetic in terms of solid content (resin content), and more preferably 2 to 10%, from the viewpoint of water resistance and application performance.

[0033] Furthermore, in addition to the components mentioned above, the green liquid cosmetic of the present invention may contain optional components commonly used in liquid cosmetics. Specifically, preservatives, antioxidants, neutralizing agents, UV absorbers, chelating agents, moisturizers such as 1,3-butylene glycol, cosmetic ingredients, fragrances, viscosity modifiers, and other dispersants such as polyethylene glycol alkyl ether may be included in appropriate amounts, as long as they do not impair the effects of the present invention.

[0034] The green liquid cosmetic composition of the present invention preferably has a viscosity of 10 mPa·s or less, and more preferably 2 to 8 mPa·s. If the viscosity exceeds 10 mPa·s, the flowability from the applicator may be significantly reduced, which is undesirable. Furthermore, the average particle size of the green liquid cosmetic composition of the present invention is preferably 80 to 250 nm, and more preferably 100 to 230 nm, in order to further improve the applicability and stability over time. The viscosity range and average particle size can be adjusted by suitably combining the constituent components of (A) Prussian blue dispersion, (B) red iron oxide dispersion, and other raw materials such as dispersants, as well as by combining their respective contents within a suitable range, and by using a suitable dispersion method. For example, a green liquid cosmetic can be obtained by adjusting the dispersion conditions to suit the requirements using a disperser such as a homomixer, sand mill, ultrasonic homogenizer, or high-pressure homogenizer. Preferably, when using a (multi-unit) ultrasonic homogenizer or a high-pressure homogenizer as the disperser, the dispersion conditions can be adjusted, for example, by setting the frequency to 20-30 kHz for the ultrasonic homogenizer and the pressure to 150-245 MPa for the high-pressure homogenizer.

[0035] When using the green liquid cosmetic composition of the present invention configured in this manner, general-purpose applicators used for eye makeup cosmetics and the like can be used. The shape and structure of the applicator used are not particularly limited, and examples include applicators equipped with a knock-type valve device, applicators with a cotton-type porous material and a flow path and applicator with capillary action, applicators equipped with a brush applicator, direct-liquid type applicators with a collector function, tube-type applicators, and applicators equipped with a piston pressing mechanism.

[0036] The green liquid cosmetic composition of the present invention, configured as described above, contains (A) a Prussian blue dispersion for cosmetic use containing at least Prussian blue, 0.05 to 0.13 parts water-soluble basic substance when the Prussian blue content is 1 by mass ratio, and (B) a red iron oxide dispersion for cosmetic use containing red iron oxide, an organic acid with a molecular weight of 300 or less, and water, wherein the average particle size of the red iron oxide dispersion in the scattering intensity distribution is 100 nm or less according to the cumulant method analysis. As a result, the Prussian blue has excellent dispersibility stability, color development (high saturation), and weather resistance. By mixing it with the red iron oxide dispersion, a green liquid cosmetic composition with excellent green color development (high saturation), dispersion stability, weather resistance, and applicability is obtained, making it suitable for makeup cosmetics such as eyeshadow, eyeliner, eyebrow pencil, and mascara. [Examples]

[0037] Next, the present invention will be described in more detail with reference to manufacturing examples, embodiments, and comparative examples, but the present invention is not limited to the following embodiments.

[0038] [Manufacturing Examples 1-7] Ultramarine dispersions A to D were prepared using the following manufacturing examples 1 to 4, and red iron oxide dispersions A to C were prepared using the following manufacturing examples 5 to 7. The pH, viscosity, and average particle size of the obtained ultramarine dispersions A to D and red iron oxide dispersions A to C were measured using the following method. (Method for measuring pH) The pH of each obtained dispersion was measured at 25°C using a glass electrode pH meter. (Method for measuring viscosity) For each of the obtained dispersions, viscosity was measured at 25°C using a cone-plate viscometer (TVE-25, manufactured by Toki Sangyo Co., Ltd.), with a shear rate of 383 s⁻¹. -1 The viscosity was measured under the following conditions. (Method for measuring average particle size) The average particle size of each dispersion (at 25°C) was measured using dynamic light scattering with an FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

[0039] (Manufacturing example 1: Preparation of ultramarine dispersion A: 100% of total volume) Contrast iron (IRON BLUE SC, manufactured by Daito Chemical Industries Co., Ltd.) 20.000% Dispersant: Nonionic surfactant (Ceteth-20, manufactured by Nikko Chemicals Co., Ltd.) 0.075% Water-soluble basic substance: 2-amino-2-methyl-1-propanol 1.000% Water (purified water) remainder Each of the above components was prepared using a bead mill disperser, with the process performed to ensure sufficient dispersibility and fluidity. pH: 6.5, viscosity: 2.2mP·s, average particle size: 80~120nm

[0040] (Manufacturing Example 2: Preparation of Ultramarine Dispersion B: Total volume 100%) Contrast iron (IRON BLUE SC, manufactured by Daito Chemical Industries Co., Ltd.) 20.000% Dispersant: Nonionic surfactant (Ceteth-20, manufactured by Nikko Chemicals Co., Ltd.) 0.075% Water-soluble basic substance: 2-amino-2-methyl-1-propanol 2.000% Water (purified water) remainder Each of the above components was prepared using a bead mill disperser, with the process performed to ensure sufficient dispersibility and fluidity. pH: 6.7, viscosity: 8.1mP·s, average particle size: 80~120nm

[0041] (Manufacturing Example 3: Preparation of Ultramarine Dispersion C) Contrast iron (IRON BLUE SC, manufactured by Daito Chemical Industries Co., Ltd.) 20.000% Water-soluble basic substance: 2-amino-2-methyl-1-propanol 1.000% Water (purified water) remainder Each of the above components was prepared using a bead mill disperser, with the process performed to ensure sufficient dispersibility and fluidity. pH: 6.2, viscosity: 2.2mP·s, average particle size: 80~120nm

[0042] (Manufacturing Example 4: Preparation of Ultramarine Dispersion D) Contrast iron (IRON BLUE SC, manufactured by Daito Chemical Industries Co., Ltd.) 20.000% Dispersant: Nonionic surfactant (Ceteth-20, manufactured by Nikko Chemicals Co., Ltd.) 0.075% Water (purified water) remainder Each of the above components was dispersed using a bead mill disperser, but sufficient dispersibility and fluidity could not be obtained. pH: 6.8 (before dispersion), Viscosity: Unmeasurable due to increased viscosity, Average particle size: 150-250 nm

[0043] (Manufacturing Example 5: Preparation of Red Iron Oxide Dispersion A) Red iron oxide pigment (No. 216P, manufactured by Daito Chemical Industries Co., Ltd.) 20.000% Dispersant: Sodium polyaspartate 3.000% Citric acid 1,500% Water (purified water) remainder Each of the above components was prepared using a bead mill disperser. pH: 7.5, viscosity: 2.5mP·s, average particle size: 20~70nm

[0044] (Manufacturing Example 6: Preparation of Red Iron Oxide Dispersion B) Red iron oxide pigment (No. 216P, manufactured by Daito Chemical Industries Co., Ltd.) 20.000% Dispersant: Sodium polyaspartate 8.667% Citric acid 0.667% Water (purified water) remainder Each of the above components was prepared using a bead mill disperser. pH: 7.5, viscosity: 3.0mP·s, average particle size: 20~70nm

[0045] (Production Example 7: Preparation of Red Iron Oxide Dispersion C) Red iron oxide (No. 216P, manufactured by Daito Kasei Kogyo Co., Ltd.) 20.000% Dispersant: Sodium polyaspartate 3.000% Water (purified water) the balance Each of the above components was prepared using a bead mill disperser. pH: 8.6, Viscosity: 7.5 mPa·s, Average particle size: 150 to 300 nm

[0046] [Examples 1 to 5 and Comparative Examples 1 to 4] Using the konjac dispersions A to D of Production Examples 1 to 4 and the red iron oxide dispersions A to C of Production Examples 5 to 7, green liquid cosmetics were prepared by dispersion according to the composition shown in Table 1 below and the following method. The average particle size (after 3 months (3M) at 25°C after preparation), pH (after 3 months (3M) at 25°C after preparation), the upper and lower concentration difference after 3 months (3M) at 25°C, the spreadability, and the color development property of the obtained green liquid cosmetics were evaluated. These results are shown in Table 1 below.

[0047] (Dispersion Method) Using 0.3 mm zirconia as the beads to be used, dispersion was carried out with a bead mill disperser.

[0048] (pH Measurement Method) The pH (after 3 months (3M) at 25°C after preparation) of each of the obtained green liquid cosmetics was measured at 25°C using a glass electrode pH meter. (Viscosity Measurement Method) For each of the obtained green liquid cosmetics, the viscosity (after 3 months (3M) at 25°C after preparation) was measured at a shear rate of 383 s -1 under the conditions using a cone and plate viscometer (TVE-25, manufactured by Toki Sangyo Co., Ltd.) at 25°C. (Average Particle Size Measurement Method) The average particle size (after 3 months (3M) at 25°C after preparation) of each of the obtained green liquid cosmetics obtained by the dynamic light scattering method using a FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was measured.

[0049] (Method for evaluating the difference in concentration between upper and lower levels) Each green liquid cosmetic was filled into a direct-ink eyeliner manufactured by Mitsubishi Pencil Co., Ltd. (applicator: UC-76B, tip type), and the writing line condition was observed after 3 months at room temperature (25°C) with the applicator in an upward and downward position, and the following evaluation criteria were used for sensory evaluation. Evaluation criteria: ○: Small difference in concentration between upper and lower parts △: There is a difference in density between the top and bottom, but the hue remains unchanged. ×: The difference in density and hue between the top and bottom is clearly visible.

[0050] (Method for evaluating applicability) For each of the obtained green liquid cosmetic compositions, the applicability after time had elapsed (after 3M at 25°C) was evaluated by filling them into a Mitsubishi Pencil UC-76B container and applying them to the eye area, according to the evaluation criteria below. Evaluation criteria: ○: Can be applied without streaking. △: Slightly streaky, but can be applied. ×: It is streaky and cannot be applied.

[0051] (Method for evaluating color development) For each of the obtained green liquid cosmetic compositions, the liquid cosmetic composition after time (after 3M at 25°C) was coated onto Catherine paper (manufactured by Tokushu Tokai Paper Co., Ltd.) using a bar coater, and the hue (a) was measured using a spectrophotometer (manufactured by Suga Test Instruments Co., Ltd., SC-P). * ,b * ) was evaluated.

[0052] [Table 1]

[0053] As can be seen from the results in Table 1 above, Examples 1 to 5, which fall within the scope of the present invention, were found to be superior to Comparative Examples 1 to 4, which fall outside the scope of the present invention, in terms of upper and lower concentration difference after 3 months at 25°C, coatability, color development, and viscosity stability. Examples 1-5, which fall within the scope of the present invention, maintain a stable apparent average particle size of 210-220 nm, retaining 200-220 nm even after 3M at room temperature (25°C), and the pH is also stable. The color after 3M is also green (a * = -15, b * It maintains =20). In contrast, in Comparative Examples 1 and 2, the content of water-soluble basic substances fell outside the range of the present invention, which was likely due to the unstable dispersion state of the red iron oxide. In Comparative Example 3, where the average particle size of Prussian blue was large, the Prussian blue settled. Conversely, in Comparative Example 4, which used a red iron oxide dispersion with an average particle size of 150-300 nm, the red iron oxide settled. Remarkably, in the present invention (Examples 1-5), a Prussian blue dispersion, with an average particle size of 130 nm or less and a pH set to basic, was used in combination with a red iron oxide dispersion containing an organic acid with a molecular weight of 300 or less to create a green-colored liquid cosmetic (eyeliner). Furthermore, by mixing it with a fine dispersion of red iron oxide (30-100 nm), an eyeliner that retained its green hue even after time had passed was obtained. [Industrial applicability]

[0054] A green liquid cosmetic composition suitable for makeup cosmetics such as eyeshadow, eyeliner, eyebrow pencil, and mascara, exhibiting excellent green color development (high saturation), dispersion stability, and weather resistance, is obtained, as well as a body marker composition suitable for body paint.

Claims

1. A green liquid cosmetic comprising at least (A) a Prussian blue dispersion and (B) an iron oxide dispersion as colorants, wherein (A) is a Prussian blue dispersion for cosmetic use, comprising at least Prussian blue as the colorant, 0.05 to 0.13 parts water-soluble basic substance when the Prussian blue content is 1 by mass ratio, and water, and having a viscosity of 10 mPa·s or less at a shear rate of 383 s⁻¹ as measured by a cone-plate viscometer at 25°C, and (B) is an iron oxide dispersion for cosmetic use, comprising iron oxide as the colorant, an organic acid with a molecular weight of 300 or less, and water, and having an average particle size of 100 nm or less as measured by the cumulant method in the scattering intensity distribution of iron oxide, and having a viscosity of 10 mPa·s or less at a shear rate of 383 s⁻¹ as measured by a cone-plate viscometer at 25°C.

2. The green liquid cosmetic according to claim 1, characterized in that the (A) Prussian blue dispersion for cosmetic further contains a nonionic surfactant selected from the following group A. Group A: Polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether

3. The green liquid cosmetic according to claim 1 or 2, characterized in that the average particle size of the scattering intensity distribution of Prussian blue in the Prussian blue dispersion for cosmetics, as analyzed by the cumulant method, is 130 nm or less.

4. The green liquid cosmetic according to any one of claims 1 to 3, characterized in that the organic acid with a molecular weight of 300 or less in the aforementioned (B) iron oxide dispersion for cosmetics is selected from the group A below. Group A: Glycolic acid, lactic acid, tartaric acid, glyceric acid, hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricineradicic acid, cerebronic acid, quinic acid, shikimic acid

5. The green liquid cosmetic according to claim 4, characterized in that the organic acid with a molecular weight of 300 or less in the aforementioned (B) red iron oxide dispersion for cosmetics is citric acid.

6. A method for producing a green liquid cosmetic comprising at least (A) a Prussian blue dispersion and (B) an iron oxide dispersion as a coloring agent, (A) The Prussian Blue dispersion is prepared by adding Prussian Blue and a water-soluble basic substance in a mass ratio of 1:0.05 to 0.13, and further adding water, and using a disperser, the viscosity at a shear rate of 383 s⁻¹ measured with a cone-plate viscometer at 25°C is 10 mPa·s or less. Step A is to produce a Prussian Blue dispersion for cosmetic use. (B) The red iron oxide dispersion includes step B, which involves dispersing red iron oxide, an organic acid with a molecular weight of 300 or less, and water using a disperser to produce a red iron oxide dispersion for cosmetics. A method for producing a green liquid cosmetic, characterized by mixing only the Prussian blue dispersion for cosmetics obtained in step A and the red iron oxide dispersion for cosmetics obtained in step B, and further mixing in cosmetic components other than the coloring agent.

7. A method for producing a green liquid cosmetic comprising at least (A) a Prussian blue dispersion and (B) an iron oxide dispersion as a coloring agent, (A) The Prussian Blue dispersion is prepared by adding Prussian Blue and a water-soluble basic substance in a mass ratio of 1:0.05 to 0.13, and further adding a nonionic surfactant and water, and using a disperser, the viscosity at a shear rate of 383 s⁻¹ measured with a cone-plate viscometer at 25°C is 10 mPa·s or less. Step A is to produce a Prussian Blue dispersion for cosmetic use. (B) The red iron oxide dispersion includes step B, which involves dispersing red iron oxide, an organic acid with a molecular weight of 300 or less, and water using a disperser to produce a red iron oxide dispersion for cosmetics. A method for producing a green liquid cosmetic, characterized in that the coloring agent is obtained by mixing only the Prussian blue dispersion for cosmetics obtained in step A and the red iron oxide dispersion for cosmetics obtained in step B, and further mixing in cosmetic components other than the coloring agent.

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