Oily cosmetic

Abstract

To provide an oily cosmetic having superior curl effect, transparency, and long-term stability.SOLUTION: An oily cosmetic comprises the following components (A) to (C): (A) 0.5 to 5 mass% of oil-soluble polyurethane, (B) 30 mass% or more of volatile hydrocarbon oil, and (C) a film-forming resin. The oily cosmetic is substantially free of wax and organically modified clay mineral.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an oil-based cosmetic, and more particularly to an oil-based cosmetic excellent in eyelash curling effect, transparency, and stability over time.

Background Art

[0002] Oil-based cosmetics are widely used in makeup cosmetics from the viewpoint of high makeup sustainability. One of the cosmetics in which the advantages of oil-based cosmetics are most utilized is eyelash cosmetics such as mascara. The main functions required for eyelash cosmetics such as mascara include curling the eyelashes upward and making the eyelashes appear thicker and longer. In addition to eyelash cosmetics having these functions, in recent years, there has been an increasing demand for eyelash cosmetics with high transparency from the viewpoints of imparting a natural gloss to the eyelashes and aesthetic appearance.

[0003] As a conventional technique for enhancing the transparency of eyelash cosmetics, an oil-based eyelash cosmetic characterized by containing alcohol-modified beeswax, organically modified clay minerals, dextrin fatty acid ester, and a volatile oil agent (see, for example, Patent Document 1), or a confectionery-shaped silicone resin powder having minute protrusions over the entire surface of the powder surface, a volatile oil component, and an oil-based gelling agent, for use in eyelash cosmetics (see, for example, Patent Document 2) are disclosed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the technique of Patent Document 1 above, although the transparency as a coating film is high Transparency as a cosmetic may have been insufficient due to organically modified clay minerals or the like. Also, in the technology of Patent Document 2 above, although the transparency of the base material is high, since wax or the like is blended as a cosmetic, the transparency may have been insufficient. Further, in the above technology, when organically modified clay minerals or waxes are not blended, although a cosmetic with sufficient transparency can be obtained, functions such as curl strength are impaired, and furthermore, poor stability due to a decrease in hardness may occur.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that by creating an oil-based cosmetic containing an oil-soluble polyurethane, a volatile hydrocarbon oil, and a film-forming resin and substantially free of wax and organically modified clay minerals, high curl strength and stability can be maintained while achieving excellent transparency, leading to the completion of the present invention.

[0007] That is, the present invention is [1] The following components (A) to (C); (A) Oil-soluble polyurethane 0.5 to 5% by mass (B) Volatile hydrocarbon oil 30% by mass or more (C) Film-forming resin An oil-based cosmetic containing the above and substantially free of wax and organically modified clay minerals. [2] The present invention is also the oil-based cosmetic according to [1], wherein the component (C) is one or more selected from an acrylic resin, a rosin resin, and a silicone resin. [3] The present invention is also the oil-based cosmetic according to [1] or [2], containing component (D) dextrin palmitate. [4] The present invention is also the oil-based cosmetic according to [1] or [2], wherein the content mass ratio (A) / (C) of the component (A) to the component (C) is 0.03 to 3. [5] Further, it is the oil-based cosmetic according to [1] or [2] that does not contain a pigment or has a pigment content of 10 mass% or less. [6] It is the oil-based cosmetic according to [1] or [2] for use on eyelashes.

Advantages of the Invention

[0008] According to the present invention, there is provided an oil-based cosmetic having high curling power, stability, and transparency.

Embodiments for Carrying Out the Invention

[0009] In this specification, “%” means “mass%” unless otherwise specified. Also, when representing a numerical range using “~”, the range includes the numerical values at both ends.

[0010] Component (A) used in the present invention is an oil-soluble polyurethane. The oil solubility in the present invention means that it can be dissolved in cetyl 2-ethylhexanoate at least 1 mass% or more at 80°C. The structure of component (A) oil-soluble polyurethane is not particularly limited, but from the viewpoints of high curling power, stability, and transparency, those having a hydrophobic part (a1) and a hydrophilic part (a2) are preferred.

[0011] (a1) The hydrophobic part preferably contains a structural unit derived from an isocyanate compound. Examples of the isocyanate compound include 1,6-hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, etc. Among these, 1,6-hexamethylene diisocyanate is preferred.

[0012] Further, from the viewpoints of high curling force, stability, and transparency, the hydrophobic part (a1) preferably further contains a structural unit derived from a hydrogenated polyolefin polyol. Examples of the hydrogenated polyolefin polyol include hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, etc., and among them, hydrogenated polybutadiene diol is preferable.

[0013] From the viewpoints of high curling force, stability, and transparency, it is preferable that the hydrophobic part (a1) further contains a structural unit derived from dimer diol. Examples of the dimer diol include dimer dilinoleyl alcohol, dimer dioleyl alcohol, etc., and dimer dilinoleyl alcohol is preferable, and hydrogenated dimer dilinoleyl alcohol is particularly preferable.

[0014] From the viewpoints of high curling force, stability, and transparency, the hydrophilic part (a2) preferably contains a structural unit derived from a low molecular weight diol. Examples of the low molecular weight diol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, etc., and ethylene glycol and 1,4-butylene glycol are preferable.

[0015] Preferable embodiments of the component (A) oil-soluble polyurethane include the following (i) and (ii). In this specification, "terminal" means "both terminals". (i) (a) A hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R 3 -OH (wherein R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond), and the polyurethane obtained by the reaction with a glycol represented by (ii) (c) A hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO-R 3 -OH (wherein R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond), and the polyurethane obtained by the reaction with a glycol represented by

[0016] (a) is not particularly limited as long as it is a hydrogenated polybutadiene having an isocyanate group at the terminal. For example, a compound represented by the following general formula (1) is shown.

[0017]

Chemical formula

[0018] (In the formula, R 1 , R 2 each independently represents a C1-C6 alkylene group, n represents an integer of 10-100, and n1 and n2 each independently represent 0 or 1)

[0019] R 1 , R 2 each independently represents the same or different C1-C6 alkylene groups, and the alkylene may be linear or branched. Examples of the C1-C6 alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, etc. The alkylene group of R 1 is preferably a C1-C2 alkylene group. The alkylene group of R 2 is preferably a C5-C6 alkylene group. The alkylene group is preferably linear. n represents an integer of 10-100, and a more preferable range of n is 15-55. n1 and n2 each independently represent the same or different 0 or 1.

[0020] The hydrogenated polybutadiene moiety of general formula (1) (the structure of the repeating unit "C4H8" in the following general formula (2) has various types as shown in the following general formulas (3a)-(3d), for example.

[0021]

Chemical formula

[0022]

Chemical formula

[0023] In the hydrogenated polybutadiene having an isocyanate group at the terminal, the hydrogenated polybutadiene moiety may consist of only one kind of repeating unit as exemplified above, or may contain two or more kinds of repeating units regularly or randomly. The repeating unit "C4H8" constituting the hydrogenated polybutadiene moiety of the general formula (1) (the above general formula (2)) may have the same or different steric structures, and all structures in which the hydrogenated polybutadiene moiety is represented by the general formula (2) are included in the present invention. Examples of the hydrogenated polybutadiene having an isocyanate group at the terminal represented by the general formula (1) include, for example, a compound represented by the following general formula (4).

[0024]

Chemical formula

[0025] (Here, in the formula (4), n represents an integer of 10 to 100) The compound of the general formula (4) is a hydrogenated polybutadiene having an isocyanate group at the terminal of the general formula (1), where R 1 is an ethylene group, R 2 is a hexamethylene group, and corresponds to the case where n1 = n2 = 1.

[0026] (b) Examples of the glycol represented by HO-R 3 -OH (wherein R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond) include, for example, ethylene glycol (HOCH2CH2OH), propylene glycol (HOCH2CH(OH)CH3), 1,3-butylene glycol (HOCH2CH2CH(OH)CH3), 1,4-butylene glycol (HOCH2CH2CH2CH2OH), and diethylene glycol (HOCH2CH2OCH2CH2OH, the following general formula (5)), etc.

[0027]

Chemical formula

[0028] (c) The hydrogenated polybutadiene having a hydroxyl group at the terminal is not particularly limited, and examples thereof include compounds represented by the following general formula (6).

[0029] [Chemical formula]

[0030] (In the formula, n represents an integer of 10 to 100)

[0031] In the general formula (6), the hydrogenated polybutadiene moiety (general formula (2)) has the same meaning as described above.

[0032] (d) Examples of the diisocyanate compound include 1,6-hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Among these, 1,6-hexamethylene diisocyanate represented by the following general formula (7) is preferred.

[0033] [Chemical formula]

[0034] (i): When producing a polyurethane by polyaddition of (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) a glycol represented by HO-R 3 -OH (wherein R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond), it is preferably carried out at a molar ratio of (a):(b) = 1:4 to 4:1, more preferably at a molar ratio of (a):(b) = 2:3 to 3:2, still more preferably 4:5 to 4:3, and even more preferably 9:10 to 10:9. In this case, the weight average molecular weight (Mw) of (a) is preferably 1000 to 3000.

[0035] (ii):(c) Hydrogenated polybutadiene having a hydroxyl group at the end, (d) a diisocyanate compound, and (b) HO-R 3 -OH (wherein R 3 represents a linear or branched C2-C6 alkylene group which may have an ether bond), when producing a polyurethane by reaction with a glycol represented by the formula, it is preferably carried out at a molar ratio of (c):(b) = 1:4 to 4:1, more preferably at a molar ratio of (c):(b) = 2:3 to 3:2, still more preferably 4:5 to 4:3, and even more preferably 9:10 to 10:9.

[0036] Also, the weight average molecular weight (Mw) of the polyurethane obtained in the above (i) or (ii) is 10,000 to 150,000, more preferably 15,000 to 130,000, and still more preferably 20,000 to 110,000.

[0037] The polyurethane of (i) or (ii) forms a plurality of ring-shaped clusters (bundles) by the association of hydrophilic parts within the molecule, and contacts the liquid oil of component (B) described later at the hydrophobic part within the molecule, thus having a hydrophilic group associative thickening mechanism. Based on this mechanism, it is microscopically formed into a three-dimensional structure and transparently gelled. Also, since the hydrophobic part within the molecule is a low-crystalline hydrocarbon, it imparts flexibility and oil solubility, and it is presumed that the polar groups of the hydrophilic parts within the molecule interact to impart gelation force and restoring force.

[0038] Examples of commercially available products of component (A) include Oilkemia 5S polymer (purity 30%) (Rubrizol, INCI name: glyceryl tri (caprylate / caprate), polyurethane-79), Oilkemia 5S CC polymer (purity 30%) (Rubrizol, INCI name: glyceryl tri (caprylate / caprate), hydrogenated polyolefin (C6-20), (HDI / trimethylolhexyl lactone) cross-polymer), etc.

[0039] The content of component (A) in the present invention is not particularly limited, but as a pure component, the lower limit is preferably 0.5% or more, more preferably 1% or more. Also, the upper limit is preferably 5% or less, more preferably 4% or less. Further, 0.5 to 5% is preferable, and 1 to 4% is more preferable. If it is within this range, it is more preferable because of excellent stability, transparency, and curling force.

[0040] The volatile hydrocarbon oil of component (B) used in the present invention is a hydrocarbon oil having a boiling point at normal pressure of 260°C or lower. Such volatile hydrocarbons are not particularly limited, and examples thereof include hydrogenated polyisobutene, light isoparaffin, isododecane, isohexadecane, etc., and one or more of these may be used in combination. Commercially available products include IP Solvent 1620, IP Solvent 2028 (both manufactured by Idemitsu Petrochemical Co., Ltd.), PERMETHYL 99A (manufactured by PRESPERS), etc. Among these, from the viewpoint of stability, one or more selected from the group consisting of isododecane, isohexadecane, hydrogenated polyisobutene, and light fluid isoparaffin are preferable, and it is more preferable that the volatile hydrocarbon is isododecane.

[0041] In the present invention, the content of component (B) has a lower limit of 30% or more, preferably 50% or more, and more preferably 70% or more. The upper limit is preferably 85% or less, more preferably 75% or less. Also, 30 to 85% is preferable, and 50 to 75% is more preferable. If it is within this range, the stability is excellent.

[0042] Component (C) film-forming resin used in the present invention refers to a resin that has the property of forming a film after spreading a solution of component (C) dissolved in a volatile solvent or the like on a petri dish and drying it. There is no particular limitation as long as it is commonly used in cosmetics, and it can be used. However, the obtained film may crack during drying, and it may not be obtained as a single film. Such resins are not particularly limited. For example, acrylic resins such as cyclohexyl methacrylate / ethylhexyl methacrylate copolymer, silicone resins such as trimethylsiloxysilicic acid, hydrocarbon resins such as polypropylene (TOWAX-8B2 (manufactured by Toagosei Co., Ltd.)), rosin resins such as pentaerythritol rosinate (ester gum HP (manufactured by Arakawa Chemical Industries, Ltd.)) and the like can be mentioned, and one or more of these can be used. Among them, one or more selected from acrylic resins, rosin resins, and silicone resins are particularly preferable, acrylic resins are more preferable, and cyclohexyl methacrylate / ethylhexyl methacrylate copolymer is even more preferable.

[0043] The content of component (C) in the present invention is not particularly limited, but as a pure component, the lower limit is preferably 0.5% or more, more preferably 1.5% or more, and even more preferably 3% or more. The upper limit is preferably 15% or less, more preferably 10% or less, and even more preferably 8% or less. Also, 0.5 to 15% is preferable, 1.5 to 10% is more preferable, and 3 to 8% is even more preferable. Within this range, it is excellent in terms of transparency and curling force.

[0044] In the present invention, the mass ratio (A) / (C) of component (A) to component (C) is not particularly limited, but 0.03 to 3 is preferable, and 0.1 to 1.5 is more preferable. Within this range, it is excellent in terms of stability, curling force, and transparency.

[0045] The oil-based cosmetic in the present invention preferably contains component (D) dextrin palmitate because it is more excellent in terms of transparency and the like. It is not particularly limited as long as it is commonly used in cosmetics, and examples of commercially available products include Rheopearl KL2 (manufactured by Chiba Flour Milling Co., Ltd.). In the present invention, the content of component (D) preferably has a lower limit of 2% or more, more preferably 5% or more. The upper limit is preferably 15% or less, more preferably 12% or less. Also, 2 to 15% is preferable, and 5 to 12% is more preferable. Within this range, it is more excellent in terms of transparency and the like.

[0046] In the oil-based cosmetic in the present invention, from the viewpoints of transparency, stability, and curling power, it substantially does not contain wax and viscous minerals. Substantially not containing means that the content is 1% or less in the cosmetic, preferably 0.5% or less, more preferably 0.1% or less, and even more preferably 0% (not containing).

[0047] In the oil-based cosmetic in the present invention, although not particularly limited, from the viewpoint of transparency and the like, the content of the pigment is preferably 10% or less, more preferably 5% or less, even more preferably 3% or less, even more preferably 1% or less, and even more preferably not containing (0%). Examples of the pigment include known ones commonly used in cosmetics, such as inorganic compounds such as zinc oxide, iron oxide, titanium oxide, zirconium oxide, cerium oxide, chromium oxide, zinc silicate, titanium silicate, silicic anhydride, cerium silicate, and hydrated silicic acid, aluminum hydroxide, mica, talc, kaolin, manganese violet, carbon black, ultramarine blue, and ultramarine.

[0048] The oil-based cosmetic in the present invention can contain components commonly used in ordinary cosmetics as needed, as long as the effects of the present invention are not impaired. For example, oily components, aqueous components, powders, ultraviolet absorbers, polymers, moisturizers, antioxidants, anti-fading agents, preservatives, medicinal components, stabilizers, pigments, fragrances, etc. can be mentioned.

[0049] The properties of the oil-based cosmetic of the present invention are not particularly limited, and for example, it can have any property such as liquid, gel, cream, solid, etc. Among these, from the viewpoint of easy application, liquid, gel, and cream are preferred.

[0050] The oil-based cosmetic of the present invention is not particularly limited, but from the point where the effects of the present invention are significantly exhibited, it is preferably used in eyelash cosmetics such as mascara, eyelash base, and mascara overcoat.

[0051] Incidentally, the present invention can also take the following configuration. [1] The following components (A) to (C); (A) Oil-soluble polyurethane 0.5 to 5% by mass (B) Volatile hydrocarbon oil 30% by mass or more (C) Film-forming resin An oil-based cosmetic that contains them and substantially does not contain wax and organically modified clay minerals. [2] Also, the present invention is the oil-based cosmetic according to [1], wherein the component (C) is one or more selected from an acrylic resin, a rosin resin, and a silicone resin. [3] Also, the present invention is the oil-based cosmetic according to [1] or [2], which contains component (D) dextrin palmitate. [4] Also, the present invention is the oil-based cosmetic according to [1] to [3], wherein the content mass ratio (A) / (C) of the component (A) to the component (C) is 0.03 to 3. [5] Also, the present invention is the oil-based cosmetic according to [1] to [4], which does not contain a pigment or has a pigment content of 10% by mass or less. [6] The oil-based cosmetic according to [1] to [5], which is for eyelashes.

[0052] Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to the following examples and the like at all.

Examples

[0053] (Examples 1 - 10, Comparative Examples 1 - 5): Oil-based cosmetic (clear mascara) Oil-based cosmetics were prepared according to the following manufacturing method using the formulations shown in Tables 1 and 2 below. For the obtained oil-based cosmetics, each evaluation item of stability, transparency, and curling power was evaluated by the following evaluation methods. The results are shown together in Tables 1 and 2.

Table 1

[0054]

Table 2

[0055] (Manufacturing method) A. Ingredients (1) to (13) are uniformly mixed at 110°C. B. A is filled into a container with an applicator to obtain an oil-based cosmetic.

[0056] (Evaluation method) For the following evaluation items from (a) to (c), evaluations were conducted by the following methods respectively. (Evaluation items) a. Stability Each sample was filled with 60 g into a No. 8 standard bottle and stored in a constant temperature bath at 50°C for 1 month. After 1 month, it was taken out from the constant temperature bath and allowed to stand at room temperature (25°C) for 1 hour, and then the appearance state was observed and judged according to the following judgment criteria. 〔Judgment criteria〕: (Judgment): (Evaluation) ◎: No drainage is observed ○: Slight drainage is observed △: Drainage is observed ×: Considerable drainage is visible

[0057] (Evaluation item) II. Transparency Each sample was poured into a glass cell with a depth of 5 mm, left in a thermostat at 25°C for 5 hours, placed on the black-and-white boundary line of the hiding power test paper JIS5400, and the visibility of the boundary was observed and evaluated according to the following criteria. The evaluation was carried out by 10 professional cosmetic evaluators, the average value of the scores of each evaluator was calculated, and the determination was made according to the following criteria. 〔Evaluation criteria〕: (Evaluation result):(Score) Very good (high transparency): 5 points Good: 4 points Average (neither can be said): 3 points Slightly poor: 2 points Poor (low transparency): 1 point 〔Judgment criteria〕: (Average score):(Judgment) Exceeding 4.5: ◎ Exceeding 3.5 and below 4.5: ○ Exceeding 2.0 and below 3.5: △ 2.0 or below: ×

[0058] III. Curling power Each sample was applied to the eyelashes, and the evaluation was carried out according to the following criteria on whether the applied eyelashes were firmly curled. The evaluation was carried out by 10 professional cosmetic evaluators, the average value of the scores of each evaluator was calculated, and the determination was made according to the following criteria. 〔Evaluation criteria〕: (Evaluation result):(Score) Very good: 5 points Good: 4 points Average (neither can be said): 3 points Slightly poor: 2 points Poor: 1 point 〔Judgment criteria〕: (Average score):(Judgment) Exceeding 4.5: ◎ Exceeding 3.5 and below 4.5: ○ Exceeding 2.0 and below 3.5: △ Less than 2.0: ×

[0059] From Tables 1 to 2, the oily cosmetics of Examples 1 to 10 were excellent in stability, transparency, and curling power. On the other hand, in Comparative Example 1 where the content of component (A) was small, satisfactory results were not obtained in terms of stability and curling power. In Comparative Example 2 where component (A) was a water-soluble polyurethane instead of an oil-soluble one, it was inferior in stability and transparency, and satisfactory results were not obtained. In Comparative Example 3 where a volatile silicone oil was used instead of component (B), satisfactory results were not obtained in all of stability, transparency, and curling power. In Comparative Example 4 where a synthetic wax was used instead of component (D), satisfactory results were not obtained in terms of stability and curling power. Also, in Comparative Example 5 containing an organically modified clay mineral, satisfactory results were not obtained in all of stability, transparency, and curling power.

[0060] Example 11: Oily Liquid Mascara An oily liquid mascara was produced according to the following formulation and production method. (Component) (mass%) 1. Hydrogenated polyisobutene balance 2. Cyclopentasiloxane 14 3. Trimethylsiloxysilicate 14 4. Dextrin palmitate (※6) 5 5. Polymethylsilsesquioxane powder 2 6. (Cyclohexyl methacrylate / ethylhexyl methacrylate) Copolymer 10 7. Nylon fiber 2 8. Iron oxide black 8 9. Propylene carbonate 1 10. Hydrogenated polyolefin (C6-20)· (HDI / trimethylolhexyl lactone) cross-polymer· Tri(caprylic acid / capric acid) glyceryl mixture (※1) 6 11. Squalane 8 12. Meadowfoam oil 5 13. Beeswax 0.2 (Manufacturing method) A. Mix components (1) to (13) uniformly at 110 °C. B. Fill A into a container with an applicator to obtain an oil-based cosmetic.

Claims

1. The following components (A) to (C); (A) Oil-soluble polyurethane: 0.5 to 5% by mass (B) Volatile hydrocarbon oil: 30% by mass or more (C) Film-forming resin containing: An oil-based cosmetic substantially free of wax and organically modified clay minerals.

2. The oil-based cosmetic according to Claim 1, wherein the component (C) is one or more selected from an acrylic resin, a rosin resin, and a silicone resin.

3. The oil-based cosmetic according to Claim 1 or 2, further containing component (D) dextrin palmitate.

4. The oil-based cosmetic according to Claim 1 or 2, wherein the content ratio (A) / (C) of the component (A) to the component (C) is 0.03 to 3.

5. The oil-based cosmetic according to Claim 1 or 2, which does not contain a pigment or has a pigment content of 10% by mass or less.

6. The oil-based cosmetic according to Claim 1 or 2, which is for eyelashes.

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