Oily eyelash cosmetic

Abstract

To provide an oily eyelash cosmetic excellent in all of separating effect, volume-up effect, curling effect, curl-retaining effect, and good color development.SOLUTION: There is provided an oily eyelash cosmetic which contains the following components (A) to (F): (A) a cross-linked organosilicon resin, which is a specific addition reactant, in which the amount of a hydrogen gas per mass generated from the cross-linked organosilicon resin is 1.5 mL / g or less in the standard state, (B) an oil-soluble resin of a hydrogenated rosin acid ester, (C) a wax, (D) a volatile oil, (E) an organic modified clay mineral and (F) a coloring pigment.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an oil-based eyelash cosmetic.

Background Art

[0002] There are two types of eyelash cosmetics: a film type (water-in-oil type) that can be easily removed with hot water, etc., and a waterproof type (oil-based type) that has excellent makeup retention. In particular, the oil-based type is globally popular because it is easy to enhance the basic functions required for mascara, such as curl and volume. In recent years, the functions required for mascara have become more multifunctional. In addition to the basic functions such as the length, thickness, and curl of the finished eyelashes, a separate effect that makes each hair look neat and makes the eyes look larger has also come to be required. In particular, in recent years, there has been an increasing demand for simultaneously achieving contradictory functions such as a volume-up effect due to high adhesion and a separate effect where the hairs are neatly separated, and various technical developments have been carried out so far. There is also a trend of changing the color of eyelashes, and the demand for colored mascara is increasing. Therefore, high color development has also come to be required in mascara.

[0003] Examinations for achieving these functions have been carried out conventionally. For example, an eyelash cosmetic containing sugar-loaf-shaped silicone resin powder, a volatile oil, and an oil-based gelling agent gives a volume-up effect to the eyelashes and does not impair the original color tone of the cosmetic base (see, for example, Patent Document 1). A water-in-oil type eyelash cosmetic containing a film-forming polymer emulsion, high molecular weight dimethylpolysiloxane, an oil-soluble resin, a hollow fiber in which a part of the peripheral wall of the hollow part having specific physical properties is missing in the longitudinal direction, carbon black, and polyvinylpyrrolidone has been developed to achieve both a volume-up effect and a separate effect, and at the same time, it is excellent in water resistance, curl effect, etc. (see, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-149525 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-197460 [Disclosure of the Invention] [Problems to be Solved by the Invention]

[0005] However, although the technology of Patent Document 1 can obtain a good eyelash cosmetic with high adhesion of granulated sugar-shaped silicone resin powder to eyelashes, excellent volume-up effect, and good color development without impairing the color tone of the pigment, the separation effect is not sufficient, and since it is necessary to contain a large amount of powder, it is difficult to obtain a sufficient curling effect. In addition, although the technology of Patent Document 2 can achieve both contradictory functions of a volume-up effect and a separation effect, since it is an oil-in-water type preparation, the water resistance, curling effect, and curl retention effect are not sufficient, and in recent years when high-level functions are required, the volume-up effect is not sufficient either. Furthermore, there has been no focus on the development of an eyelash cosmetic that can simultaneously achieve high color development. Therefore, an object of the present invention is to develop an eyelash cosmetic that is excellent in all of a volume-up effect, a separation effect, a curling effect, a curl retention effect, and good color development. [Means for Solving the Problems]

[0006] As a result of intensive studies, the present inventors have found that by containing a specific crosslinked organosilicon resin, an oil-soluble resin of hydrogenated rosin acid ester, wax, a volatile oil agent, an organically modified clay mineral, and a coloring pigment, an oily eyelash cosmetic excellent in a volume-up effect, exhibiting a separation effect, and excellent in a curling effect, a curl retention effect, and good color development can be obtained, and thus the present invention has been completed.

[0007] That is, the present invention is: [1] (A) A crosslinked organosilicon resin which is an addition reaction product of the following components (X) and (Y), and which generates hydrogen gas per unit mass of the crosslinked organosilicon resin at standard conditions in an amount of 1.5 mL / g or less. (B) Oil-soluble resin of hydrogenated rosin acid ester (C) Wax (D) Volatile oil (E) Organically modified clay minerals (F) Coloring pigments [(X) component] An alkenyl-containing organosilicon resin having one or more alkenyl groups in each molecule, represented by the following average composition formula (1): [ka] [In the formula, R 1 are each independently an alkenyl group having 2 to 8 carbon atoms; R 2 are each independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. 3 are each independently an organopolysiloxane-containing group, and the R 2 Each R 3 3SiO 1 / 2 R in units 3 At least one of a1, a2, a3, b, c, and d is an organopolysiloxane-containing group. <a1≦5、0<a2≦400、0≦a3≦400、0≦b≦320、0≦c≦320、0<d≦1,000であり、かつ、0.5≦(a1+a2+a3) / d≦1.5を満たす数である。] [(Y) component] An organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule and represented by the following average composition formula (2): [ka] [In the formula, R 2 is the same as above, and R 4 are each independently a hydrogen atom or the above R 2 and all R 4Two or more of them are hydrogen atoms, e, f, g, and h are 0 or positive numbers, provided that 2 ≦ e + f + g + h < 32 is satisfied. It contains and relates to an oil-based mascara. [2] Furthermore, it relates to the oil-based mascara according to [1] above, wherein the content of the component (C) is 10 to 30% by mass. [3] Furthermore, it relates to the oil-based mascara according to [1] or [2] above, wherein the component (C) is a hydrocarbon having a melting point of 85 to 110°C. [4] Furthermore, it relates to the oil-based mascara according to [1] to [3] above, wherein the component (D) is a hydrocarbon oil. [5] Furthermore, it relates to the oil-based mascara according to [1] to [4] above, wherein the mass ratio (C) / [(A)+(B)] of the component (C) to the total mass of the component (A) and the component (B) is 0.6 to 3.0. [6] Furthermore, it relates to the oil-based mascara according to [1] to [5] above, wherein the mass ratio (C1) / (C) of the component (C1) to the component (C) is 0.3 to 1.0.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide an oil-based mascara that exhibits excellent volume-up effect, separation effect, curl effect, curl retention effect, and good color development.

Embodiments for Carrying Out the Invention

[0009] Details of the present invention will be described below. In this specification, "~" means a range including the numerical values before and after it. Also, in this specification, percentages are expressed by mass unless otherwise specified.

[0010] Hereinafter, the component (A) in the present invention will be described in detail. Component (A) is a crosslinked organosilicon resin which is an addition reaction product of the following components (X) and (Y), and which generates hydrogen gas per unit mass of this crosslinked organosilicon resin in an amount of 1.5 mL / g or less under standard conditions.

[0011] [(X) component] The component (X) of the present invention is an alkenyl-containing organosilicon resin represented by the following average composition formula (1) having one or more alkenyl groups in one molecule, and can be used alone or in combination of two or more types. [ka] [In the formula, R 1 are each independently an alkenyl group having 2 to 8 carbon atoms; R 2 are each independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. 3 are each independently an organopolysiloxane-containing group, and the R 2 Each R 3 3SiO 1 / 2 R in units 3 At least one of a1, a2, a3, b, c, and d is an organopolysiloxane-containing group. <a1≦5、0<a2≦400、0≦a3≦400、0≦b≦320、0≦c≦320、0<d≦1,000であり、かつ、0.5≦(a1+a2+a3) / d≦1.5を満たす数である。]

[0012] [(Y) component] The component (Y) of the present invention is an organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule, represented by the following average composition formula (2), and may be used alone or in combination of two or more. The amount of addition reaction is an amount that results in 0.5 to 2.0 moles of hydrosilyl groups per mole of alkenyl groups in the component (X), preferably 0.5 to 1.2 moles, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. [ka] [In the formula, R 2 is the same as above, and R 4 are, independently of each other, a hydrogen atom or a group represented by the above R 2 , and two or more of all R 4 are hydrogen atoms, and e, f, g, h are 0 or positive numbers, provided that 2 ≤ e + f + g + h < 32 is satisfied.]

[0013] In the above formula, R 1 are, independently of each other, alkenyl groups having 2 to 8 carbon atoms. More specifically, vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, octenyl group and the like can be mentioned. In particular, vinyl group and allyl group are preferable.

[0014] In the above formula, R 2 are, independently of each other, groups selected from alkyl groups having 1 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, or aralkyl groups having 7 to 30 carbon atoms. Among them, alkyl groups, aryl groups, aralkyl groups, and fluorine-substituted alkyl groups having 1 to 10 carbon atoms are preferable. More specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, etc., trifluoropropyl group and the like can be mentioned. In particular, alkyl groups having 1 to 5 carbon atoms, phenyl group or trifluoropropyl group are preferable. Also, optionally, a part of R 2 may contain one or more groups selected from a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms.

[0015] In the alkenyl group-containing organosilicon resin represented by the above formula (1), a1, a2, a3, b, c, and d satisfy 0 < a1 ≤ 5, preferably 0 < a1 ≤ 4.5, more preferably 1 ≤ a1 ≤ 4, and still more preferably 1 ≤ a1 ≤ 3. When a1 is greater than 5, the possibility of gelation increases and film-forming properties are lacking. 0 ≤ a2 ≤ 400, preferably 0 ≤ a2 ≤ 100, more preferably 0 ≤ a2 ≤ 50. 0 ≤ a3 ≤ 400, preferably 0 ≤ a3 ≤ 100, more preferably 0 ≤ a3 ≤ 50. When a3 is greater than 400, the melting point of the resin becomes low and film-forming properties are lacking. 0 ≤ b ≤ 320, 0 ≤ c ≤ 320, and b = 0 and c = 0 are preferred. 0 < d ≤ 1,000, and it is a number that satisfies 0.5 ≤ (a1 + a2 + a3) / d ≤ 1.5, preferably a number that satisfies 0.7 ≤ (a1 + a2 + a3) / d ≤ 1.2. When the value of (a1 + a2 + a3) / d is less than the above lower limit, the crosslinking degree increases and the molecular weight becomes large, resulting in a gel state. When it exceeds the above upper limit, the molecular weight becomes small and film-forming properties are lacking.

[0016] The alkenyl group-containing organosilicon resin represented by the above formula (1) has Q units (SiO 4 / 2 ), M units (R 2 3SiO 1 / 2 and R 1 R 2 2SiO 1 / 2 ) as essential structures, and D units (R 2 2SiO 2 / 2 ), T units (R 2 SiO 3 / 2 ) as optional structures. It may be in a solid state or a liquid state at 25°C, but a solid state is preferred from the viewpoint of film-forming properties. For example, MQ resin, MTQ resin, MDQ resin, MDTQ resin can be mentioned. Its weight average molecular weight is preferably in the range of 1,000 to 30,000, and more preferably in the range of 3,000 to 15,000 from the viewpoints of performance and workability such as filtration. The weight average molecular weight can be determined as the weight average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis.

[0017] In the organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule represented by the above formula (2), R 4 is, independently of one another, a monovalent hydrocarbon group having no aliphatic unsaturated bond and having 1 to 30 carbon atoms, and two or more of all R 4 are hydrogen atoms.

[0018] In the above formula (2), e, f, g, and h are 0 or positive numbers, and may be selected so as to satisfy 2 ≦ e + f + g + h < 32. Preferably, g = 0 and h = 0, more preferably e = 2, 0 ≦ f < 30, g = 0, h = 0, and still more preferably e = 2, 10 ≦ f ≦ 30, g = 0, h = 0. If the number of silicon atoms contained in the (Y) component is 32 or more, the crosslinked organosilicon resin tends to have a gel-like property by entrapping the solvent. Therefore, it tends to form a sticky film after the solvent has evaporated. If the number of silicon atoms contained in the (Y) component is less than 32, the crosslinked organosilicon resin is likely to dissolve in the solvent, so that the property tends to be liquid. Therefore, it is easy to obtain a non-sticky film after the solvent has evaporated.

[0019] The above R 3 is, independently of one another, an organopolysiloxane-containing group or a group selected from the above R 2 . Examples of the organopolysiloxane-containing group include groups represented by the following general formulas (3) to (6). In each of the R 3 3SiO 1 / 2 units, one or more of the R 3 are organopolysiloxane-containing groups. Optionally, a part of the R 3 may be a hydroxyl group.

Chemical formula

[0020] m is an integer satisfying 0 ≦ m ≦ 5, preferably 0 ≦ m ≦ 2, i is an integer satisfying 0 ≦ i ≦ 500, preferably 1 ≦ i ≦ 100, and more preferably 1 ≦ i ≦ 50. When i is greater than 500, the melting point of the resin becomes low, resulting in a lack of film-forming properties. j1 to j3 are each an integer of 0 or more and 2 or less.

[0021] In the above formula (1), it is preferable that b = 0 and c = 0. When b and c are 0, the alkenyl group-containing organosilicon resin does not contain a flexible skeleton such as a D unit or a T unit, and is composed only of an M unit and a Q unit. By using an alkenyl group-containing organosilicon resin that does not contain a D unit or a T unit as a raw material, the crosslinked organosilicon resin, which is an addition reaction product, can form a strong film.

[0022] In the above formula (2), it is preferable that g = 0 and h = 0. When g and h are 0, the organohydrogenpolysiloxane does not contain a branched component such as a T unit or a Q unit, and becomes a linear molecule composed only of an M unit and a D unit. By using a linear organohydrogenpolysiloxane as a raw material, the crosslinked organosilicon resin, which is an addition reaction product, can form a flexible film.

[0023] Also, two or more kinds of groups represented by the formula (2) may be included. As the group represented by the formula (2) has a longer chain length, it has an effect of imparting flexibility to the organosilicon resin. Therefore, for example, by including two kinds of groups represented by the formula (2) having different chain lengths, the film physical properties can be controlled.

[0024] [Physical Properties of Component (A) Crosslinked Organosilicon Resin] The weight average molecular weight of the crosslinked organosilicon resin of component (A) used in the present invention is preferably 5,000 to 1,000,000, more preferably 8,000 to 500,000, and even more preferably 10,000 to 500,000. Being within such a range is more preferable in terms of performance and workability such as filtration. The weight average molecular weight can be determined as the weight average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis (hereinafter the same).

[0025] The crosslinked organosilicon resin of component (A) used in the present invention may be in a solid state, a gel state, or a liquid state at 25°C. For example, it can be dissolved in a liquid oil agent and volatilized to easily form a film. This film is a strong and brittle film before crosslinking, but after crosslinking, its brittleness is improved, and a non-sticky and flexible film can be obtained. From the viewpoint of film-forming property, a solid state or a gel state is preferable, and a solid state is more preferable. The film-forming ability can be determined by dropping 1.5 g of a solution diluted to 30% by mass with isododecane or decamethylcyclopentasiloxane onto PTFE (fluororesin) and drying it at 105°C for 3 hours to see if a self-supporting film is formed. If a film is not formed, oil will seep out due to cracks in the film, etc., and the oil resistance will be significantly reduced, and the followability with the skin will be low, resulting in an unnatural finish.

[0026] The crosslinked organosilicon resin of component (A) used in the present invention can be more preferably used as a film-forming agent. The organosilicon resin before crosslinking forms a strong and brittle film, while the crosslinked organosilicon resin after crosslinking has improved brittleness and forms a non-sticky and flexible film. This is because the organosilicon resin before crosslinking forms a strong film, but by crosslinking with flexible chains, flexibility is imparted to the film. Generally, a hard film has low flexibility, and a film with high flexibility tends to be soft, so the strength and flexibility of the film have been considered to be in an antinomic relationship. However, the crosslinked organosilicon resin of the present invention has the characteristic of excellent followability due to its high flexibility despite forming a strong film.

[0027] In addition, the film formed from the crosslinked organosilicon resin of component (A) used in the present invention has significantly improved oil resistance against oil agents such as sebum compared to the film formed from the organosilicon resin before crosslinking. Although the oil resistance of organosilicon resins tends to improve as the molecular weight increases, since there is a limit to increasing the molecular weight of organosilicon resins, there is also a limit to the oil resistance. Crosslinking of the organosilicon resin with a crosslinking agent leads to a pseudo-increase in the molecular weight of the organosilicon resin, and thus has the effect of raising that limit point. Therefore, the crosslinked organosilicon resin has oil resistance that cannot be achieved with conventional organosilicon resins.

[0028] The crosslinked organosilicon resin of component (A) in which f in the above formula (2) is an integer satisfying 0 < f < 30 is solid at 25°C, and a crosslinked organosilicon resin with particularly excellent film-forming properties can be obtained.

[0029] In addition, when f in the above formula (2) satisfies 0 ≤ f < 30 and two of R 4 in are hydrogen atoms, the crosslinked organosilicon resin of component (A) is solid at 25°C, and a crosslinked organosilicon resin with particularly excellent film-forming properties can be obtained. When f is 30 or more, or when three or more of R 4 in are hydrogen atoms, there is a high possibility of becoming gel-like when the diluting solvent is removed. In this case, although there is film-forming property, it has the feel derived from gel.

[0030] In the above formula (1), when a1 satisfies 0 < a1 ≤ 3, f in the above formula (2) satisfies 0 ≤ f < 30, and two of R 4 in are hydrogen atoms, the crosslinked organosilicon resin of component (A) is solid at 25°C, and a crosslinked organosilicon resin with particularly excellent film-forming properties can be obtained. The obtained film exhibits particularly excellent flex resistance and oil resistance.

[0031] The amount of hydrogen gas per unit mass generated from the crosslinked organosilicon resin of the above component (A) is 1.5 mL or less under standard conditions. If it exceeds 1.5 mL / g, the generation of hydrogen gas over time, or the reaction of remaining hydroxy groups or alkoxy groups with hydrosilyl groups, may increase the likelihood of thickening over time and deteriorate the stability over time. The amount of hydrogen gas generated is preferably 0.01 to 1.2 mL / g, more preferably 0.02 to 1.0 mL / g.

[0032] The amount of hydrogen gas per unit mass can be calculated from the volume of hydrogen gas generated by the reaction of hydrosilyl groups and a base. For example, the following method can be used, but the calculation method is not limited to this. <Method for Measuring Hydrogen Gas Amount> To a mixed solution of 50 g of the crosslinked organosilicon resin of component (A) diluted to 50% by mass with decamethylcyclopentasiloxane and 10 g of 1-butanol, 10 g of a 20% by mass aqueous sodium hydroxide solution is added dropwise. The amount of hydrogen gas per unit mass is obtained by dividing the volume of the generated hydrogen gas by the pure content of the crosslinked organosilicon resin.

[0033] [Manufacturing Method] The crosslinked organosilicon resin of component (A) used in the present invention can be synthesized by various formulations known in the art. For example, crosslinking can be achieved by reacting an organopolysiloxane having hydroxyl groups at both ends with the surface silanol groups of the organosilicon resin. However, since it is difficult to completely control the amount of silanol groups on the surface of the organosilicon resin, there is a problem that it is difficult to accurately control the amount of the organopolysiloxane to be crosslinked. In addition, synthesis is possible by an addition reaction of an organosilicon resin having a hydrosilyl group and an organopolysiloxane having alkenyl groups at both ends. However, the hydrosilyl groups in the organosilicon resin have low reactivity, and there is a problem that the remaining hydrosilyl groups react over time, causing an increase in viscosity and the generation of hydrogen gas. Therefore, as a method for producing a crosslinked organosilicon resin crosslinked with silicone, a synthesis method by an addition reaction of an organosilicon resin having an alkenyl group and an organopolysiloxane having hydrosilyl groups at both ends is preferable.

[0034] The method for producing a crosslinked organosilicon resin by the above hydrosilylation reaction will be described in more detail below. In the hydrosilylation reaction step of the alkenyl group-containing organosilicon resin represented by the above average composition formula (1) and the organohydrogenpolysiloxane represented by the above formula (2), the molar ratio of the terminal hydrosilyl group / unsaturated group can be selected from the range of 0.5 to 2.0, preferably 0.5 to 1.2 moles, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. If the above ratio is too large, the remaining amount of the hydrosilyl group will increase, and the stability over time may deteriorate.

[0035] This hydrosilylation reaction is preferably carried out in the presence of a platinum catalyst or a rhodium catalyst. For example, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinylsiloxane complex, etc. are preferred. Also, if the amount of the catalyst used is excessive, the sample will be colored. Therefore, the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0036] Furthermore, the addition reaction may be carried out in the presence of an organic solvent as necessary. Examples of the organic solvent include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; short-chain silicone oils such as methyltrimethicone and short-chain dimethicone; aromatic hydrocarbons such as toluene and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane, decane, tridecane, (C9-12) alkane, isooctane, isododecane, isohexadecane, isoparaffin, and cyclohexane; aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. Ethanol, 1-propanol, and 2-propanol are particularly preferred from the viewpoint of reactivity.

[0037] The amount of the solvent used is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, based on the total amount of the reaction solution (system). When within the above range, the reaction system is uniformly maintained and the reaction proceeds efficiently.

[0038] The crosslinked organic silicon resin of component (A) used in the present invention can be dissolved in an organic solvent and used as a pre-dissolved product. The organic solvent used during the addition reaction may be used as it is, or may be replaced after the addition reaction, and the organic solvent to be replaced can be selected according to the application. The replacement solvent is not particularly limited and can be selected from the aforementioned organic solvents. These organic solvents are also described in component (D) which will be described later.

[0039] The addition reaction conditions are not particularly limited, but it is preferable to heat at a temperature of 50 to 150°C, more preferably 80 to 120°C for about 1 to 10 hours under reflux.

[0040] After the addition reaction, it is also possible to include a step of removing the rhodium catalyst or platinum catalyst used with activated carbon. The amount of activated carbon used is preferably 0.001 to 5.0% by mass of the whole system, and more preferably 0.01 to 1.0% by mass. When within the above range, coloring of the sample can be more suppressed.

[0041] After the addition reaction, it is possible to include a step of removing the remaining hydrosilyl groups as necessary. Especially when used in applications such as cosmetics, the hydrosilyl groups may be deactivated by dehydrogenation reaction over time. Since hydrogen gas is generated, there is no problem from the viewpoint of safety, so it is preferable to include a step of removing the hydrosilyl groups.

[0042] Examples of the step of removing the hydrosilyl groups include a formulation in which a basic catalyst is added to hydrolyze the unreacted hydrosilyl groups, and then an acidic catalyst equivalent to the molar equivalent of the basic catalyst is added for neutralization. Examples of the basic catalyst include strong basic catalysts and weak basic catalysts. Examples of strong basic catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weak basic catalysts include alkali metal carbonates such as sodium carbonate and calcium carbonate, and alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate. From the viewpoint of promoting the dehydrogenation reaction, it is particularly preferable to use a strong basic catalyst, specifically sodium hydroxide. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and carboxylic acids such as oxalic acid, formic acid, acetic acid, propionic acid, benzoic acid, citric acid, and trifluoroacetic acid.

[0043] In general, it is preferable to use an acid or a base in combination with water and heat at a temperature below the boiling point of water rather than using them alone. By this step, a hydrosilyl group (SiH group) is converted into a hydroxy silyl group (SiOH group). However, when a crosslinked organosilicon resin is treated with a base catalyst, since the physical properties change due to the reaction of silanol groups or alkoxy groups in the organosilicon resin, it is not preferable to remove the hydrosilyl group by this method.

[0044] The content of the component (A) used in the present invention is not particularly limited, and as a solid content, it is preferably 0.3% by mass (hereinafter simply abbreviated as %) or more, more preferably 1.5% or more, and even more preferably 3% or more, based on the total amount of the oil-based eyelash cosmetic. Further, it is preferably 15% or less, more preferably 12% or less, and even more preferably 10% or less. Moreover, 0.3 to 15% is preferable, 1.5 to 12% is more preferable, and 3 to 10% is even more preferable. Within this range, it is more preferable because the separation effect, curl effect, curl retention effect, and color development are more excellent.

[0045] Component (B) used in the present invention is an oil-soluble resin of hydrogenated rosin acid. Rosin acid is a resin acid obtained from coniferous plants such as those containing abietic acid, palustric acid, isopimaric acid, etc. The oil-soluble resin of the ester of hydrogenated rosin acid, which is hydrogenated, is an ester purified and synthesized from hydrogenated rosin acid, is oil-soluble, and forms a film. Note that forming a film means that a solution in which 30% of the component corresponding to component (B) is dissolved in an oily volatile solvent is applied to a glass plate with an applicator having a thickness of 400 μm and a film is formed after drying at room temperature for 24 hours. Examples include esters of hydrogenated rosin acid and pentaerythritol such as pentaerythrityl hydrogenated rosinate, disproportionated rosin glycerin esters obtained by esterifying a disproportionated product mainly consisting of dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid by the disproportionation reaction of hydrogenated rosin with mono-, di-, or tri-glycerin, hydrogenated rosin glycerin esters obtained by hydrogenating abietic acid, which is the main component of rosin acid, to dihydroabietic acid or tetrahydroabietic acid and then esterifying with mono-, di-, or tri-glycerin, and hydrogenated ester gum, which is obtained by hydrogenating a glycerin ester of a mixture mainly consisting of dehydroabietic acid and dihydroabietic acid obtained by disproportionating rosin acid. Commercially available products include ester gum HP, which is pentaerythrityl hydrogenated rosinate, and pink crystal KE-311, which is glyceryl hydrogenated abietate (both are manufactured by Arakawa Chemical Industries, Ltd.).

[0046] The content of component (B) used in the present invention is not particularly limited. As the lower limit, it is preferably 2% or more, more preferably 3% or more, based on the total amount of the oil-based eyelash cosmetic. As the upper limit, it is preferably 15% or less, even more preferably 12% or less. Also, as the range, 2 to 15% is preferable, and 3 to 12% is more preferable. Within this range, it is more preferable because it is more excellent in volume-up effect, curl effect, and color development.

[0047] Component (C) wax used in the present invention is not particularly limited as long as it is a solid oil of animal oil, vegetable oil, synthetic oil, etc. usually contained in cosmetics. For example, carnauba wax, candelilla wax, fructooligosaccharide fatty acid ester, ceresin wax, microcrystalline wax, polyethylene wax, (ethylene / propylene) copolymer, Fischer-Tropsch wax and other synthetic waxes, paraffin wax, etc. can be used alone or in combination of two or more as needed. Component (C) enhances the curling effect and separation effect due to its hardness, and when combined with component (A) and component (B), it exhibits a higher curling effect, separation effect, and also imparts a curl-keeping effect. Among them, component (C1), which is a hydrocarbon with a melting point of 85 to 110°C, is most preferred because of its excellent hardness. For example, as commercially available products, as synthetic waxes, CIREWAX80 (melting point 80 - 85°C), CIREWAX90 (melting point 91 - 96°C) (manufactured by CIREBELLE), as (ethylene / propylene) copolymer, EPS wax (melting point 90 - 99°C) (manufactured by Japan Natural Products Co., Ltd.), as rice wax, rice wax SS-I (melting point 78 - 80°C) (manufactured by Boso Oil & Fat Co., Ltd.), etc. can be mentioned.

[0048] The content of component (C) used in the present invention is not particularly limited, but as a lower limit, 10% or more is preferred, 15% or more is more preferred, and as an upper limit, 30% or less is preferred, 25% or less is more preferred. Also, as a range, 10 - 30% is preferred, 15 - 25% is more preferred. If it is within this range, it is more preferred from the viewpoint of excellent curling effect and curl-keeping effect.

[0049] In the present invention, the content ratio of component (C1) in component (C) is preferably such that the mass ratio (C1) / (C) is 0.3 - 1.0 in the cosmetic, and more preferably 0.5 - 1.0. If it is within this range, it is more preferred in terms of the separation effect, curling effect, and curl-keeping effect.

[0050] In the present invention, the mass ratio of the component (C) to the total mass of the component (A) and the component (B), (C) / [(A)+(B)], is preferably from 0.6 to 3.0, more preferably from 0.8 to 3.0, and still more preferably from 0.9 to 2.5. When it is within this range, it is more preferable in terms of the separating effect and the curling effect.

[0051] The component (D) volatile oil used in the present invention is an oil that is volatile at 1 atm and 25°C and is also used as a solvent for the component (A), component (B), and component (C). There is no particular limitation as long as it can be used in cosmetics, but it is preferable to contain a volatile oil having a boiling point of 240°C or lower. For example, hydrocarbon oils such as light fluid isoparaffin and isododecane, and silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, methyltrimethicone, and low molecular weight dimethylpolysiloxane can be mentioned, and one or more of these can be used as necessary. It can be appropriately selected and combined according to the type of the base agent of the cosmetics. For example, in the case of silicone oil, commercially available products include TMF-1.5 which is methyltrimethicone, KF-995 which is decamethylcyclopentasiloxane, KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs (manufactured by Shin-Etsu Chemical Co., Ltd.), and BELSIL DM 1PLUS (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.). Further, for example, in the case of a volatile hydrocarbon oil, hydrocarbons having side chains such as isooctane, isododecane, isohexadecane, and isoicosene, straight-chain hydrocarbons such as decane, undecane, dodecane, tridecane, and (C9-12) alkane, isoparaffin, or a mixture thereof, isobutene, n-butene, etc. are polymerized or copolymerized (the degree of polymerization is preferably 4 to 6), and then hydrogenated light fluid isoparaffin, etc. can be mentioned. Commercially available products of these volatile hydrocarbon oils include IP Solvent 1620 MU and IP Solvent 2028 MU (both manufactured by Idemitsu Kosan Co., Ltd.), IsoPar (manufactured by ExxonMobil Chemical Co.), Marcol R (manufactured by Maruzen Petrochemical Co., Ltd.), PARAFOL 12 RSPO-MB, PARAFOL 14 RSPO-MB (SASPL Germany GmbH), Shellsol (manufactured by Shell Chemical Co.), isododecane (manufactured by IMCD), etc. One or more of these can be used in combination as necessary. When the component (D) is low molecular weight dimethylpolysiloxane, methyltrimethicone, or a volatile hydrocarbon oil, it is preferable in that it further enhances the drying of the eyelash cosmetics, achieves both a volume-up effect and a separation effect, and is excellent in the curl-keeping effect.

[0052] The content of component (D) is not particularly limited, but 10 to 70% is preferable, and 30 to 60% is more preferable. If it is within this range, it is preferable because both the volume-up effect and the separation effect are achieved, and the curl-keeping effect is excellent.

[0053] The component (E) organic modified clay mineral used in the present invention is specifically obtained by ion-exchanging a water-swellable clay mineral with a cationic surfactant such as an alkyl quaternary ammonium salt. In the present invention, those exchanged with benzyl dimethyl stearyl ammonium ions and those exchanged with dimethyl distearyl ammonium ions are particularly preferable. The water-swellable clay mineral is a kind of colloidal hydrous aluminum silicate having a three-layer structure, generally represented by the following general formula (1) (X,Y) 23 (Si,Al)4O 10 (OH)2Z·nH2O … (1) However, X = Al, Fe, Mn, Cr Y = Mg, Fe, Ni, Zn, Li Z = K, Na, Ca and is specifically represented by montmorillonite, laponite, and hectorite, etc., natural or synthetic (in this case, those in which (OH) in the above general formula is replaced by fluorine) montmorillonite group, and synthetic mica known as sodium silicic mica and sodium or lithium teniolite, etc. As the water-swellable clay mineral, montmorillonite and hectorite are particularly preferable. As commercially available products of the organic modified clay mineral, for example, Benton 27V and Benton 38V (manufactured by ELEMENTIS) are available. The organic modified clay mineral of component (E) can be used singly or in combination of two or more as needed, and the content is preferably 1 to 8%, and more preferably 3 to 7% in terms of excellent volume-up effect and separation effect.

[0054] The coloring pigment of component (F) used in the present invention is contained for the purpose of controlling the color tone of the eyelash cosmetic and the color tone of the finish. Generally, as long as it can be used in cosmetics, there is no particular limitation, and any shape of particles, particle size, state of the particle surface, etc. can be used. It is not particularly limited by the shape such as plate shape, spindle shape, needle shape, etc., the particle size such as smoke shape, fine particles, pigment grade, etc., the particle structure such as porous, non-porous, etc., and examples include inorganic powders, lustrous powders, organic powders, composite powders, etc. Examples of the coloring pigment of component (F) include inorganic coloring powders such as titanium oxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue, dark blue titanium oxide, black titanium oxide, safflower, ultramarine blue, chromium oxide, chromium hydroxide, carbon black, titanium·titanium oxide sintered product, zinc oxide, cerium oxide, zirconium oxide, barium sulfate, etc., organic pigment powders such as Red No. 201, Red No. 202, Red No. 205, Red No. 226, Red No. 228, Orange No. 203, Orange No. 204, Blue No. 404, Yellow No. 401, etc., organic pigment powders such as zirconium, barium or aluminum lake of Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, etc., lustrous powders such as mica titanium, iron oxide-treated mica, iron oxide-treated mica titanium, organic pigment-treated mica titanium, titanium oxide-treated glass powder, iron oxide titanium oxide-treated glass powder, aluminum powder, etc., or composite powders such as fine particle titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, etc. These can be used alone or in combination of two or more. Further, these powders may be used in a form in which one or more are compounded. These may be surface-treated with a fluorine-based compound, silicone-based compound, metal soap, lecithin, hydrogenated lecithin, collagen, hydrocarbon, higher fatty acid, higher alcohol, ester, wax, rosin, surfactant, etc. as long as the effects of the present invention are not impaired. The coloring pigment of component (F) can be used alone or in combination of two or more as necessary.

[0055] The content of the coloring pigment, the component (F) used in the present invention, is not particularly limited, but in an oil-based cosmetic, as a lower limit, 0.5% or more is preferable, 1% or more is more preferable, and 3% or more is even more preferable. Further, as an upper limit, 30% is preferable, 20% or less is more preferable, and 15% or less is even more preferable. As a range, 0.5 to 30% is preferable, 1 to 20% is more preferable, and 3 to 15% is even more preferable. If it is within this range, it is more preferable because it is more excellent in the separating effect and the color development.

[0056] In addition to the above components (A) to (F), the oil-based cosmetic for eyelashes of the present invention contains components usually used in cosmetics, for example, oil components other than components (A) to (D) as a base material or an emollient component, powder components other than component (F), fibers as components for obtaining a long lash effect, surfactants for powder dispersion and touch adjustment, aqueous components for moisturizing, ultraviolet absorbers, moisturizers, anti-fading agents, antioxidants, defoaming agents, beauty components, preservatives, fragrances, etc. within a range not impairing the effects of the present invention as appropriate.

[0057] Examples of the oil components other than components (A) to (D) include hydrocarbons, oils and fats, hydrogenated oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine-based oils, lanolin derivatives, oil-based gelling agents, etc., regardless of the origin such as animal oils, vegetable oils, synthetic oils, and the properties such as solid oils, semi-solid oils, and liquid oils. Note that components (A), (B), and (C) can be dissolved in any of these oil agents and provided as a dissolved product. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, etc., oils and fats such as olive oil, castor oil, mink oil, macadamia nut oil, etc., esters such as jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tributyrate, diisostearyl malate, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-lauroyl-L-glutamic acid di(cholesteryl·behenyl·octyldodecyl), etc., higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, etc., silicones such as methylphenyl polysiloxane, fluorine-modified organopolysiloxane, etc., fluorine-based oil agents such as perfluorodecane, perfluorooctane, perfluoropolyether, etc., lanolin derivatives such as lanolin, lanolin acetate, isopropyl lanolin fatty acid, lanolin alcohol, etc., oily gelling agents such as sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, calcium stearate, etc. can be mentioned.

[0058] Any powder other than the component (F) may be used as long as it is commonly used in cosmetics and may contain fibers. The fibers are not particularly limited as long as they are generally used in cosmetics. For example, synthetic fibers such as nylon, polyester, and polypropylene, artificial fibers such as rayon, natural fibers such as cellulose, semi-synthetic fibers such as acetate spun silk, or fibers obtained by combining these may be mentioned. The length is not particularly limited, but generally, 0.1 to 10 mm is preferable, and 0.3 to 7 mm is more preferably used. The fineness is generally preferably 0.1 to 25 tex (hereinafter simply referred to as "T"), and more preferably 0.3 to 20 T. One or more of these fibers having different materials, fineness, and lengths can be used. The shape of the cross-section of the fiber is not particularly limited, and any shape such as circular, elliptical, polygonal, well-shaped, T-shaped, Y-shaped, etc. can be used. Further, these fibers are used after being colored with the colored powder of the component (F) or subjected to surface treatment as necessary. The types of surface treatment agents include silicone oil, powder, oil agent, gelling agent, emulsion polymer, surfactant, etc., and are not particularly limited.

[0059] Any powder other than the component (F) or other than fibers may be used as long as it is normally used in cosmetics, and is not particularly limited by its shape such as plate-like, spindle-shaped, needle-shaped, etc., particle size such as smoky, fine particles, pigment grade, particle structure such as porous or non-porous, etc. Specifically, aluminum silicate, magnesium silicate, aluminum magnesium silicate, mica, synthetic mica, synthetic sericite, sericite, talc, clay minerals such as kaolin, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, silica, fumed silica, silylated silica, silicon carbide, barium sulfate, inorganic powders such as boron nitride, inorganic powders such as bismuth oxychloride, organic powders such as magnesium stearate, zinc stearate, N-acyl lysine, cellulose powder, silk powder, nylon, composite powders such as barium sulfate-coated mica, polyethylene terephthalate·aluminum·epoxy laminate powder, polyethylene terephthalate·polyolefin laminate film powder, polyethylene terephthalate·polymethyl methacrylate laminate film powder, etc. may be mentioned. One or more of these can be used. These may be surface-treated with silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, rosin, surfactants, etc. as long as the effects of the present invention are not impaired. Also, these powders may be used in the form of a composite of one or more kinds.

[0060] As the surfactant, any surfactant generally used in cosmetics can be used, and examples include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. For example, glycerin fatty acid esters and their alkylene glycol adducts, polyglycerin fatty acid esters and their alkylene glycol adducts, sorbitan fatty acid esters and their alkylene glycol adducts, sucrose fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl copolymer-modified organopolysiloxanes, polyether-modified organopolysiloxanes, lecithin, etc. may be mentioned.

[0061] The aqueous components may be any components that are water and water-soluble components. For example, lower alcohols such as ethyl alcohol and butyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, 1,2-pentanediol, dipropylene glycol, and polyethylene glycol, glycerols such as glycerin, diglycerin, and polyglycerol, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose can be mentioned. Examples of water-soluble polymers include natural ones such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, and carrageenan, semi-synthetic ones such as methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, and synthetic ones such as carboxyvinyl polymer, alkyl-added carboxyvinyl polymer, and sodium polyacrylate. It is also possible to contain other moisturizers such as proteins, mucopolysaccharides, collagen, elastin, and keratin.

[0062] Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzone, etc. Examples of moisturizers include proteins, mucopolysaccharides, collagen, elastin, keratin, etc. Examples of antioxidants include α-tocopherol, ascorbic acid, etc. Examples of beauty components include vitamins, anti-inflammatory agents, crude drugs, etc. Examples of preservatives include paraoxybenzoic acid esters, phenoxyethanol, glycols, etc.

[0063] The oil-based mascara of the present invention is characterized by being oil-based or water-in-oil type with oil as the continuous phase, and can be applied to mascara, mascara base, mascara top coat, etc. Examples of the form include cream, gel, liquid, etc., and among them, the gel form is more preferable.

[0064] Hereinafter, the present invention will be described in detail by giving production examples of component (A) and examples of oil-based mascaras using the same. Note that these do not limit the present invention in any way.

Example

[0065] In the following, the alkenyl group-containing organosilicon resin as a raw material is synthesized according to a known production method. In the following production examples, the reaction rate of the alkenyl group was determined by calculation based on the remaining amount of the alkenyl group after the reaction by 1H-NMR spectrum analysis.

[0066] [Production Example 1] Production method of crosslinked organosilicon resin / decamethylcyclopentasiloxane 30% solution 1,000 g of a 50% solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 7,430, vinyl value: 0.229 mmol / g) represented by the following average composition formula (E1), 700 g of decamethylcyclopentasiloxane, 126.9 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E2) (hydrogen gas generation amount: 20.3 mL / g, hydrosilyl group / vinyl group = 1.0), and 0.6 g of a 0.5% 2-propanol solution of chloroplatinic acid were charged into a reactor and reacted by heating at 120°C for 8 hours. Then, the solvent was distilled off by heating under reduced pressure. After adding decamethylcyclopentasiloxane so that the concentration became 30% and adjusting, filtration was performed to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin. Further, the obtained decamethylcyclopentasiloxane solution of the crosslinked organosilicon resin was heated to 120 to 130°C under reduced pressure to remove decamethylcyclopentasiloxane, and the obtained product was a solid powder (weight average molecular weight 221,000). The reaction rate of the alkenyl group was 92%, and the amount of hydrogen gas generated from the remaining hydrosilyl group was 0.8 mL / g. Formula (E1): [Chemical formula] Formula (E2): [Chemical formula]

[0067] [Production Example 2] Method for Producing Crosslinked Organosilicon Resin / Decamethylcyclopentasiloxane 30% Solution 1,000 g of a 50% decamethylcyclopentasiloxane solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 8,050, vinyl value: 0.224 mmol / g) represented by the following average composition formula (E3), 700 g of decamethylcyclopentasiloxane, 53.8 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E4) (hydrogen gas generation amount: 51.3 mL / g, hydrosilyl group / vinyl group = 1.1), and 0.6 g of a 0.5% 2-propanol solution of chloroplatinic acid were charged into a reactor and reacted by heating at 110 °C for 5 hours. Then, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin.

[0068] Further, the obtained decamethylcyclopentasiloxane solution of the crosslinked organosilicon resin was heated to 120 to 130 °C under reduced pressure to remove decamethylcyclopentasiloxane, and the resulting product was a solid powder (weight average molecular weight 154,000). The reaction rate of the alkenyl group was 93%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 1.0 mL / g. Formula (E3):

Chemical formula

Chemical formula

[0069] [Production Example 3] Method for Producing Crosslinked Organosilicon Resin / Decamethylcyclopentasiloxane 30% Solution 1,000 g of a 50% solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 14,860, vinyl value: 0.323 mmol / g) represented by the following average compositional formula (E5) in decamethylcyclopentasiloxane, 700 g of decamethylcyclopentasiloxane, 160.0 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E6) (hydrogen gas generation amount: 22.6 mL / g, hydrosilyl group / vinyl group = 1.0), and 0.6 g of a 0.5% 2-propanol solution of chloroplatinic acid were charged into a reactor and reacted by heating at 110 °C for 3 hours. Thereafter, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin.

[0070] Further, the product obtained by heating the decamethylcyclopentasiloxane solution of the obtained crosslinked organosilicon resin at 120 to 130 °C under reduced pressure to remove decamethylcyclopentasiloxane was a solid powder (weight average molecular weight 168,500). The reaction rate of the alkenyl group was 92%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 0.5 mL / g. Formula (E5): [Chemical formula] Formula (E6): [Chemical formula]

[0071] [Production Example 4] Production method of crosslinked organosilicon resin / 30% decamethylcyclopentasiloxane solution 1,000 g of a 50% solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 11,730, vinyl value: 0.307 mmol / g) represented by the following average compositional formula (E7) in decamethylcyclopentasiloxane, 700 g of decamethylcyclopentasiloxane, 78.5 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E8) (hydrogen gas generation amount: 43.8 mL / g, hydrosilyl group / vinyl group = 1.0), and 0.6 g of a 0.5% solution of chloroplatinic acid in 2-propanol were charged into a reactor and reacted by heating at 120 °C for 5 hours. Thereafter, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a solution of a crosslinked organosilicon resin in decamethylcyclopentasiloxane.

[0072] Further, the solution of the obtained crosslinked organosilicon resin in decamethylcyclopentasiloxane was heated to 120 to 130 °C under reduced pressure to remove decamethylcyclopentasiloxane, and the obtained product was a solid powder (weight average molecular weight 96,500). The reaction rate of the alkenyl group was 97%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 0.9 mL / g. Formula (E7):

Chemical formula

Chemical formula

[0073] Examples 1 to 33 and Comparative Examples 1 to 7: Oil-based mascara (gel-like) Oil-based mascaras having the formulations shown in Tables 1 to 4 below were prepared, and the volume-up effect, separation effect, curl effect, curl-keeping effect, and color development were evaluated by the following methods. The results are also shown in Tables 1 to 4.

[0074]

Table 1

[0075]

Table 2

[0076]

Table 3

[0077]

Table 4

[0078] (Manufacturing method) (Only those with component numbers described are to be blended.) A. Heat components (1) to (20) to about 100 °C and mix uniformly. B. Add components (21) to (30) to A and mix uniformly. C. Fill B into a container to obtain an oil-based mascara.

[0079] (Evaluation method) The following evaluation items were evaluated by the following methods respectively. (Evaluation items) a. Separation effect b. Volume-up effect c. Curl effect d. Curl keep effect e. Color development quality Regarding items a to e, a usage test was conducted on each sample by 20 professional cosmetic evaluation panelists. Each panelist evaluated on a 7-point scale according to the following absolute evaluation, gave a score, and the average value was calculated from the total scores of all panelists for each sample, and the determination was made according to the following 5-point determination criteria.

[0080] a. For the separation effect, the eyelashes after use were observed from the front, and regarding the separation effect, it was evaluated whether the eyelashes were separated from each other and fixed separately without adhering to each other. <Evaluation criteria>: a. Separation effect (Score): (Evaluation) 5: The eyelashes are very easily separated from each other 4: The eyelashes are somewhat easily separated from each other 3: Neither of the above 2: The eyelashes are somewhat likely to stick together 1: Eyelashes are very likely to stick together. <Judgment criterion>: a. Separation effect (Judgment): (Average score) AA: Average score is 4.5 or more and 5.0 or less. A: Average score is 4.0 or more and less than 4.5. B: Average score is 3.5 or more and less than 4.0. C: Average score is 2.5 or more and less than 3.5. D: Average score is less than 2.5.

[0081] b. Regarding the volume-up effect, the evaluation criterion was how much thicker the eyelashes became compared to the natural eyelashes. <Evaluation criterion>: b. Volume-up effect (Score): (Evaluation) 5: Eyelashes look very thick. 4: Eyelashes look slightly thicker. 3: Neither. 2: Slightly less difference in eyelash thickness is felt. 1: Very little difference in eyelash thickness is felt. <Judgment criterion>: b. Volume-up effect (Judgment): (Average score) AA: Average score is 4.5 or more and 5.0 or less. A: Average score is 4.0 or more and less than 4.5. B: Average score is 3.5 or more and less than 4.0. C: Average score is 2.5 or more and less than 3.5. D: Average score is less than 2.5.

[0082] Regarding the curl effect in c, the eyelashes after use were observed from the side, and whether the eyelashes curled up in a natural arc was used as the evaluation criterion. <Evaluation criterion>: c. Curl effect (Score): (Evaluation) 5: Curls up very well. 4: Curls up slightly well. 3: Neither. 2: Slightly difficult to curl up. 1: It is very difficult to curl up <Judgment criterion>: c. Curl effect (Judgment): (Average score) AA: The average score is 4.5 or more and 5.0 or less A: The average score is 4.0 or more and less than 4.5 B: The average score is 3.5 or more and less than 4.0 C: The average score is 2.5 or more and less than 3.5 D: The average score is less than 2.5

[0083] Regarding the curl keep effect of d, each sample was applied to the eyelashes, and after having the panel live a normal life, whether the curled-up eyelashes had dropped after 6 hours was used as the evaluation criterion. <Evaluation criterion>: d. Curl keep effect (Score): (Evaluation) 5: Maintaining a very good curl effect 4: Slightly maintaining a curl effect 3: Neither 2: Slightly reducing the curl effect 1: Greatly reducing the curl effect <Judgment criterion>: d. Curl keep effect (Judgment): (Average score) AA: The average score is 4.5 or more and 5.0 or less A: The average score is 4.0 or more and less than 4.5 B: The average score is 3.5 or more and less than 4.0 C: The average score is 2.5 or more and less than 3.5 D: The average score is less than 2.5

[0084] Regarding the color development quality of e, it was based on whether the color developed beautifully without clouding and a usage test by 20 professional cosmetic panels. <Evaluation criterion>: e. Color development quality (Score): (Evaluation) 5: The color develops very beautifully and is good 4: The color develops somewhat beautifully and is good 3: Neither 2: Slightly poor color development, difficult to develop color 1: Very poor color development, extremely difficult to develop color <Judgment Criteria>: e. Color development quality (Judgment): (Average score) AA: Average score is 4.5 or more and 5.0 or less A: Average score is 4.0 or more and less than 4.5 B: Average score is 3.5 or more and less than 4.0 C: Average score is 2.5 or more and less than 3.5 D: Average score is less than 2.5 Regarding color development, separately, in Example 3 and Comparative Example 1, a coating film was formed on an aluminum plate with a thickness of 200 μm. When measuring the average luminance value in a range of 100 pixels of the photographed image of the coating film one day after coating using PHOTOSHOP, a difference in luminance value of 1.0 or more was confirmed as a difference. It was found that Example 3 had a clearer and darker black color, better color development, and a tendency for a lower luminance value. It was confirmed that Comparative Example 1 had a bleached color development like a slightly white film. Since the difference in luminance value is not particularly limited and visual observation can most clearly recognize the difference, visual evaluation was adopted this time.

[0085] As is clear from the results in Tables 1 to 4, the oil-based mascaras of Examples 1 to 33 of the present invention are compared with Comparative Examples 1 to 7 oil-based mascaras, and were excellent in all aspects of the effect of separating each eyelash, volume-up effect, curling effect, curling retention effect, and color development quality. In Comparative Example 1 where component (A) was changed to trimethylsiloxysilicate, sufficient color development quality could not be obtained, and problems such as the eyelashes not curling up sufficiently due to the characteristics of the changed component, or the curled-up eyelashes dropping over time occurred, and a satisfactory result could not be achieved in terms of the curling effect and curling retention effect. In Comparative Example 2 where component (A) was changed to polymethylsilsesquioxane, sufficient color development quality could not be obtained, and a satisfactory result could not be achieved in terms of the curling effect and separation effect, such as the eyelashes not curling up sufficiently due to the characteristics of the changed component. In Comparative Example 3 where Component (B) was changed to the oil-soluble resin of candelilla wax extract, sufficient adhesion to the eyelashes could not be obtained, and the effects of volume-up, curl retention, and good color development could not be achieved. In Comparative Example 4 where Component (B) was changed to the oil-soluble resin of dextrin isostearate, sufficient adhesion to the eyelashes could not be obtained, all effects were low, and in particular, the effects of volume-up, curl retention, and good color development could not be achieved. In Comparative Example 5 that did not contain Component (C) and Comparative Example 6 that did not contain Component (E), satisfactory results could not be obtained in all aspects. Comparative Example 7 that did not contain Component (F) was not satisfactory in terms of good color development.

[0086] Example 34: Oil-based Mascara Base (Component) (%) (1) [Production Example 1: Crosslinked Organosilicon Resin 30% Solution / Weight Average Molecular Weight 221,000] A solution of decamethylcyclopentasiloxane substituted for *15 7 (2) Pentaerythrityl Hydrogenated Rosinate *3 12 (3) Carnauba Wax *10 3 (4) Polyethylene *7 7 (5) Dextrin Palmitate 3.5 (6) Light Liquid Isoparaffin *12 Remainder (7) Distearyldimonium Hectorite *16 4.8 (8) Propylene Carbonate 1 (9) Synthetic Fluorphlogopite *22 3 (10) Kunzite 0.05 (11) Iron Oxide Yellow 0.01 (12) Titanium Oxide 5 (13) Silica (Fumed) *20 1.5 (14) Caprylyl Glycol 0.1 (15) Sorbitan Sesquioleate 0.1 (16) Fragrance 0.2 *22: NK-M (manufactured by Nippon Kogaku Kenkyusho Co., Ltd.)

[0087] (Manufacturing Method) A. Heat components (1) to (6) to about 100 °C and mix them uniformly. B. Add components (7) to (16) to A and mix them uniformly. C. Fill B into a container to obtain an oil-based mascara base.

[0088] The oil-based mascara base obtained as described above was excellent in all of the separation effect, volume-up effect, curling effect, curl-keeping effect, and color development.

[0089] Example 35: Water-in-Oil Mascara (Components) (%) (1) [※1: Crosslinked organosilicon resin 50% solution / weight average molecular weight: 221,000] Isododecane solution 12 (2) Glyceryl hydrogenated abietate *4 3 (3) Carnauba wax *10 5 (4) Synthetic wax (melting point 91 - 96 °C) *23 5 (5) Dextrin myristate 2.5 (6) Dipolyhydroxystearic acid PEG-30 *24 0.7 (7) Isododecane *13 Remainder (8) Dimethiconol 0.6 (9) Quaternium-18 hectorite *25 4 (10) Talc treated with 2% dimethiconol·aminopropyltriethoxysilane 4 (11) Iron oxide yellow treated with 2% lauroyl lysine and 1% aluminum distearate 1 (12) Iron oxide red treated with 3% lauroyl lysine and 1% aluminum distearate 1.6 (13) Iron oxide black treated with 2% lauroyl lysine and 1% aluminum distearate 1.8 (14) Silica *26 1 (15) Sericite treated with 3% silicone 5 (16) Sodium stearoyl methyl taurate 0.4 (17) Water 6.2 (18) Methylparaben 0.2 (19) Polyvinyl alcohol 0.1 (20) BG 0.7 (21) Ethanol 1 *23: CIREWAX 90 (manufactured by CIREBELLA) *24: CITHROL DPHS-SO-(JP) (manufactured by Croda) *25: Smection SAN-P (manufactured by Kunimine Industries Co., Ltd.) *26: Cosmesilica CQ4 (manufactured by Fuji Silysia Chemical Ltd.)

[0090] (Manufacturing method) A. Heat components (1) to (8) to about 100°C and mix them uniformly. B. Add components (9) to (16) to A and mix them uniformly. C. Mix components (17) to (21) uniformly. D. Add C to A and emulsify. E. Fill D into a container to obtain a water-in-oil type mascara.

[0091] The water-in-oil type mascara obtained as described above was excellent in all aspects of separation effect, volume-up effect, curl effect, curl-keeping effect, and color development.

[0092] Example 36: Oil-based color mascara (Components) (%) (1) [Production Example 1: Crosslinked organosilicon resin 30% solution / weight average molecular weight 221,000] A solution obtained by substituting the decamethylcyclopentasiloxane solution with *14 20 (2) Polymethylsilsesquioxane *2 2 (3) Glyceryl hydrogenated abietic acid *4 6 (4) Microcrystalline wax (melting point 77 - 82°C) 5 (5) Ethylene-propylene copolymer (melting point 90 - 99°C)*8 5 (6) Beeswax (melting point 60 - 67°C) *11 2 (7) Dextrin palmitate 3.2 (8) Isododecane *13 balance (9) Distearyldimonium hectorite *16 2.2 (10) Propylene carbonate 0.5 (11) Cellulose *27 2.5 (12) Lauroyl lysine *28 1 (13) Carmine 3 (14) Methylcon silica-coated mica 1.8 (15) Titanium oxide-coated synthetic fluorophlogopite 3 (16) Silica-titanium oxide-coated borosilicate (Ca / Na) 2.5 (17) Silica-silver-coated borosilicate (Ca / Al) 2 (18) Phenoxyethanol 0.3 (19) Hydrogenated lecithin 0.2 (20) Water 1 (21) Lysine dilauroyl glutamate Na 0.5 *27: CELLULOBEADS D-5 (manufactured by Rengo Co., Ltd.) *28: Amihope LL (manufactured by Ajinomoto Co., Inc.)

[0093] (Production method) A. Ingredients (1) to (8) are heated to about 100 °C and mixed uniformly. B. Ingredients (9) to (21) are added to A and mixed uniformly. C. B is filled into a container to obtain an oil-in-water type mascara.

[0094] The oil-based color mascara obtained as described above was excellent in all of the separation effect, volume-up effect, curl effect, curl-keeping effect, and color development.

Claims

1. The following components (A) to (F); (A) A crosslinked organosilicon resin which is an addition reaction product of the following component (X) and component (Y), wherein the amount of hydrogen gas generated per mass of this crosslinked organosilicon resin is 1.5 mL / g or less under standard conditions. Crosslinked organosilicon resin (B) An oil-soluble resin of hydrogenated rosin acid ester (C) Wax (D) Volatile oil agent (E) Organically modified clay mineral (F) Coloring pigment An oil-based eyelash cosmetic containing the same. [(X) component] An alkenyl group-containing organosilicon resin represented by the following average composition formula (1) and having one or more alkenyl groups in one molecule 【Chemical 1】 [In the formula, R １ are each independently an alkenyl group having 2 to 8 carbon atoms; R ２ are each independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. ３ are each independently an organopolysiloxane-containing group, and the R ２ Each R ３ ３ SiO １／２ R in units ３ At least one of the above is an organopolysiloxane-containing group. a1, a2, a3, b, c, and d are numbers that satisfy 0<a1≦5, 0<a2≦400, 0≦a3≦400, 0≦b≦320, 0≦c≦320, and 0<d≦1,000, and 0.5≦(a1+a2+a3) / d≦1.

5. [(Y) component] An organohydrogenpolysiloxane represented by the following average composition formula (2) and having two or more hydrosilyl groups in one molecule 【Chemical 2】 [In the formula, R ２ is the same as above, and R ４ are, independently of each other, a hydrogen atom or a group represented by the above R ２ , and two or more of all R ４ are hydrogen atoms, and e, f, g, and h are 0 or positive numbers, provided that 2 ≤ e + f + g + h < 32 is satisfied.]

2. The oil-based eyelash cosmetic according to Claim 1, wherein the content of the component (C) is 10 to 30% by mass.

3. The oil-based eyelash cosmetic according to Claim 1 or 2, wherein the component (C) is a hydrocarbon having a melting point of 85 to 110°C.

4. The oil-based eyelash cosmetic according to Claim 1 or 2, wherein the component (D) is a hydrocarbon oil.

5. The oil-based eyelash cosmetic according to Claim 1 or 2, wherein the mass ratio (C) / [(A)+(B)] of the component (C) to the total mass of the component (A) and the component (B) is 0.6 to 3.

0.

6. The oil-based eyelash cosmetic according to Claim 1 or 2, wherein the mass ratio (C1) / (C) of the component (C1) to the component (C) is 0.3 to 1.0.

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