JP7208067B2 - Water-in-oil make-up cosmetic - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-in-oil make-up cosmetic, and more particularly to a water-in-oil make-up cosmetic containing a polyurethane gel composition and a polyvinyl alcohol film-forming agent.

In recent years, the number of users of liquid make-up cosmetics such as eye colors has been increasing because they are easier to obtain luster than solid powder types, and spread thinly with a fresh finish. However, liquid make-up cosmetics tend to be double-folded over time, and the amount of powder is small, resulting in a thin cosmetic film. In addition, the glittering powder tends to fall into the double grooves and peel off after drying, and there was a problem in achieving both a feeling of use and makeup longevity.

In order to solve the above-mentioned problems, conventionally, investigations have been made on dosage forms and composition of ingredients. For example, as a technique for improving makeup longevity, there is an oil-based solid cosmetic (Patent Document 1) in which the film-forming property is improved by containing a film-forming agent in the oil-based solid. In addition, oil-based eye makeup cosmetics containing hydrofluoroethers and clay minerals that provide an excellent feeling of use and long-lasting makeup (Patent Document 2), and water using water-based polymers that have excellent water resistance and provide a fresh feeling of use. There was a make-up cosmetic containing (Patent Document 3) and the like.

JP 2014-129294 A JP-A-2005-255625 JP 2013-209315 A

However, in the technique of incorporating a film-forming agent into an oil-based solid cosmetic, although the makeup lasts longer due to the high content of the film-forming agent, it is easy to feel the weight of the spread and spread, and the makeup is not easy to remove. Techniques containing ethers and clay minerals were not satisfactory because they tended to feel powdery and put a burden on the eyelids. On the other hand, although the technology using water-based polymers provides a fresh feel, it tends to be inferior to oil-based makeup cosmetics in terms of longevity. In general, when the make-up lasts longer, it becomes more difficult to remove the make-up, and the use of a specific make-up remover or rubbing off the make-up may cause a burden on the eyelids.

Accordingly, the present invention provides a make-up cosmetic that does not crinkle in two layers, has long lasting make-up, and is excellent in ease of removing make-up.

Under such circumstances, the present inventors have made intensive studies and, as a result, have focused on a polyurethane having an isocyanate group, which has excellent affinity with the skin. A novel polyurethane gel composition obtained by polyaddition of added polybutene and ethylene glycol at a specific molar ratio, and a water-in-oil makeup cosmetic containing polyvinyl alcohol, which forms a film-like film among film-forming agents. We have completed a liquid water-in-oil type make-up cosmetic that can be removed without burdening the skin by improving the resistance to double-folding while maintaining a non-squeaky and non-burdening feeling.

That is, the present invention includes the following.
[1] component (A) and component (B) containing polyvinyl alcohol,
The component (A) is a polyurethane gel composition containing component (A-1) polyurethane and component (A-2) oil,
The component (A-1) is
(i) (a) a hydrogenated polybutadiene having an isocyanate group at the end and (b) HO-R3-OH (wherein R3 is a linear or branched C2-C6 alkylene group optionally having an ether bond) or polyurethane obtained by reaction with a glycol represented by
(ii) (c) a hydrogenated polybutadiene having a terminal hydroxyl group, (d) a diisocyanate compound and (b) HO-R3-OH (wherein R3 is a linear or branched C2- which may have an ether bond) Representing a C6 alkylene group).
The component (A-1) polyurethane may be an oil-soluble polyurethane.
[2] The component (A-1) polyurethane may have a weight average molecular weight (Mw) of 10,000 to 100,000.
[3] The component (A-2) oil agent may be a liquid oil agent at 25°C.
[4] The component (A-2) oil agent may contain an ester oil having 0 or 1 hydroxyl group.
[5] The content of component (A) may be 0.5 to 35% by mass.
[6] The water-in-oil makeup cosmetic according to any one of [1] to [6], wherein the content of the component (B) is 0.05 to 12% by mass.
[7] The content mass ratio (A-1)/(B) of the component (A-1) and the component (B) may be 0.08 to 54.
[8] It may further contain component (C) glittering powder.

The present invention relates to a water-in-oil type make-up cosmetic that gives a uniform make-up film without feeling of burden, reduces the twisting of double layers, makes the make-up long lasting, and is excellent in the ease of removing the make-up.

It is a schematic diagram which shows the method of measuring a self-restoring force in this invention.

Preferred embodiments of the present invention will now be described in detail. However, the present invention is not limited to the following preferred embodiments, and can be freely modified within the scope of the present invention. In this specification, percentages (%) are indicated by mass unless otherwise specified. In addition, in this specification, when a numerical range is expressed using to, the range includes numerical values at both ends.

The component (A) polyurethane gel composition used in the present invention is a polyurethane gel composition containing component (A-1) polyurethane and component (A-2) oil agent. The polyurethane gel composition can be obtained by using the raw material of component (A-1) polyurethane in the presence of component (A-2) oil agent.

Here, the component (A-1) polyurethane is 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 a polyurethane that uses a glycol that
Furthermore, component (A-1) polyurethane preferably contains at least the following polyurethane (i) or (ii).
More preferably, the component (A-1) polyurethane comprises (i) a hydrogenated polybutadiene having an isocyanate group at the end and (b) HO--R ³ --OH (wherein R ³ has an ether bond). Representing a linear or branched C2-C6 alkylene group that may be linear or branched), or (ii) (c) a hydrogenated polybutadiene having a terminal hydroxyl group and ( d) reaction of a diisocyanate compound with (b) a glycol represented by HO--R ³ --OH (wherein R ³ represents a linear or branched C2-C6 alkylene group optionally having an ether bond); It is a polyurethane obtained by

Examples of the (b) glycol represented by HO--R ³ --OH in the component (A-1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, and diethylene glycol.

The novel polyurethane gel composition used in the present invention was found as a result of extensive research and development on gel materials in order to obtain an oil-soluble gel cosmetic film with high luster, elasticity, and resilience. The gel composition that was released.

The inventors have been conducting extensive research using silicone rubber, polysaccharides, and water-based polyurethane as restorative materials. However, these materials have drawbacks to be solved along with their advantages. Specifically, silicone rubber lacks luster and lacks resilience; polysaccharides have weak resilience and resilience; water-based polyurethane is water-based and lacks luster; had.
However, as a result of intensive studies, the inventors found that HO--R ³ --OH (wherein R ³ is a linear or branched C2-C6 alkylene which may have an ether bond) in the presence of an oil agent. A novel gel material was accidentally obtained when a polyurethane was synthesized using a glycol represented by ). The novel gel material had special functions such as high luster, elasticity, and resilience, as shown in Examples below. This was an unexpected effect for the inventors.
Polyurethane is known to be obtained by reacting diisocyanate and polyol. However, there is no example of using polyurethane as an oil-soluble gelling agent, and the polyurethane gel composition of the present invention was discovered based on a new idea of producing it in the presence of an oil agent.

The concept of the polyurethane gel composition used in the present invention is still under intense investigation, but at present the inventors are thinking as follows. (1) The polyurethane in the polyurethane composition forms a plurality of ring-shaped clusters (tufts) by associating with each other at the hydrophilic portions in the molecule, and by contacting the oil agent at the hydrophobic portion in the molecule, it becomes hydrophilic. The inventors believe that it has a group-associated thickening mechanism. (2) The polyurethane has flexibility and oil solubility because the hydrophobic part in the molecule is a low-crystalline hydrocarbon; The inventors believe that it imparts gelling power and restoring force. (3) The inventors believe that the hydrophilic group-associated thickening mechanism allows the three-dimensional steric structure to be finely formed, resulting in a transparent gel. The polyurethane is preferably an oil-soluble polyurethane, and more preferably, the oil-soluble polyurethane can be dissolved in cetyl 2-ethylhexanoate at least 1% by mass or more at 30°C.

The component (A) polyurethane gel composition used in the present invention includes composition 1 and composition 2 below. Among these, compositions 1 and 2 are preferred.

Composition 1: Polyurethane gel composition 1 containing component (A-1) (i) polyurethane and component (A-2) oil agent;
As component (A-1) polyurethane, (i) (a) hydrogenated polybutadiene having an isocyanate group at the end and (b) HO--R ³ --OH (wherein R ³ may have an ether bond A composition containing a polyurethane obtained by reaction with a glycol represented by a linear or branched C2-C6 alkylene group) and component (A-2) an oil agent.
Composition 2: Polyurethane gel composition 2 containing component (A-1)(ii) polyurethane and component (A-2) oil agent;
As the component (A-1) polyurethane, (ii) (c) a hydrogenated polybutadiene having a terminal hydroxyl group, (d) a diisocyanate compound, and (b) HO--R ³ --OH (wherein R ³ has an ether bond Representing a linear or branched C2-C6 alkylene group which may be substituted) polyurethane obtained by reaction with a glycol.
In the present invention, "end" means "both ends".

If the (a) used in the component (A-1) polyurethane of the component (A) polyurethane gel composition (preferably the composition 1) is a hydrogenated polybutadiene having an isocyanate group at its end, , is not particularly limited. For example, a compound represented by the following general formula (1) is shown, and use of the compound is preferable from the viewpoint of the effects of the present invention.

(wherein R ¹ and R ² each independently represent a C1-C6 alkylene group, n is an integer of 10-100, and n ₁ and n ₂ each independently represent 0 or 1)

R ¹ and R ² each independently represent a C1-C6 alkylene group, which may be the same or different, 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 and the like. The alkylene group of R ¹ is preferably a C1-C2 alkylene group. The alkylene group for R ² is preferably a C5-C6 alkylene group. The alkylene group is preferably straight chain.
n represents an integer of 10-100, and a more preferable range of n is 15-55.
n ₁ and n ₂ each independently represent 0 or 1, the same or different.

The structure of the repeating unit “C ₄ H ₈ ” in the hydrogenated polybutadiene portion of general formula (1) (general formula (6) below) may be various, for example, as shown in general formulas (7a) to (7d) below. types exist. From the viewpoint of the effect of the present invention, it is preferable to use the compound.

The hydrogenated polybutadiene portion in the hydrogenated polybutadiene having an isocyanate group at the end used in the present invention may consist of only one type of repeating units as exemplified above, or may consist of two or more types of repeating units. may be included regularly or randomly.
In the present invention, the steric structure of the repeating unit "C ₄ H ₈ " constituting the hydrogenated polybutadiene portion of general formula (1) (general formula (6) above) may be the same or different, and the hydrogenated polybutadiene All structures whose moieties are represented by general formula (6) are included in the present invention.
As the hydrogenated polybutadiene having an isocyanate group at the end represented by the general formula (1), for example, a compound represented by the following general formula (2) is exemplified. preferred.

(Here, in the formula (2), n represents an integer of 10 to 100)
The compound of general formula (2) is a hydrogenated polybutadiene having an isocyanate group at the end of general formula (1), when R ¹ is an ethylene group, R ² is a hexamethylene group, and n ₁ = n ₂ = 1 Equivalent to.

(b) HO--R ³ --OH (wherein R ³ is Representing a linear or branched C2-C6 alkylene group optionally having an ether bond), for example, ethylene glycol (HOCH ₂ CH ₂ OH), propylene glycol (HOCH ₂ CH ( OH)CH ₃ ), 1,3-butylene glycol (HOCH ₂ CH ₂ CH(OH)CH ₃ ), diethylene glycol (HOCH ₂ CH ₂ OCH ₂ CH ₂ OH), and the like. From the viewpoint of the effect of the present invention, it is preferable to use the compound.
The (b) HO--R ³ --OH is a compound represented by the following general formula (5), and the compound is suitable from the viewpoint of the effects of the present invention.

The (c) hydrogenated polybutadiene having terminal hydroxyl groups used in the component (A-1) polyurethane of the component (A) polyurethane gel composition (preferably composition 2) is not particularly limited. For example, a compound represented by the following general formula (3) is shown, and the compound is suitable from the viewpoint of the effects of the present invention.

(Wherein, n represents an integer from 10 to 100)

In general formula (3), the hydrogenated polybutadiene moiety (general formula (6)) has the same meaning as above. From the viewpoint of the effect of the present invention, it is preferable to use the compound.

Examples of diisocyanate compounds (d) used in component (d): component (A-1) polyurethane (preferably composition 2) include hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1 ,3-bis(isocyanatomethyl)cyclohexane, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Among these, hexamethylene diisocyanate represented by the following general formula (4) is preferred.

In the component (A) polyurethane gel composition (preferably composition 1), (i): (a) hydrogenated polybutadiene having terminal isocyanate groups and (b) HO--R ³ --OH (wherein R ³ represents a linear or branched C2-C6 alkylene group optionally having an ether bond). : 4 to 4:1, more preferably at a molar ratio (a):(b) = 2:3 to 3:2, still more preferably 4:5 to 4:3, still more preferably is 9:10 to 10:9. In this case, the weight average molecular weight (Mw) of (a) is preferably 1,000-3,000. This range is more preferable because the effect of the present invention can be obtained remarkably.

In the component (A) polyurethane gel composition (preferably composition 2), (ii): (c) a hydrogenated polybutadiene having a terminal hydroxyl group, (d) a diisocyanate compound, and (b) HO—R ³ —OH ( In the formula, R ³ represents a linear or branched C2-C6 alkylene group optionally having an ether bond). ) = 1:4 to 4:1, more preferably at a molar ratio (c):(b) = 2:3 to 3:2, still more preferably 4:5 to 4:3, Even more preferably 9:10 to 10:9. This range is more preferable because the effect of the present invention can be obtained remarkably.

The weight average molecular weight (Mw) of the polyurethane obtained in (i) or (ii) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and still more preferably 30,000 to 70,000. This range is more preferable because the effect of the present invention can be obtained remarkably.

The content of component (A-1) polyurethane in component (A) polyurethane gel composition is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 30% by mass. be.
The content of component (A-2) oil agent in component (A) polyurethane gel composition is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, and still more preferably 70 to 90% by mass. be.
This range is more preferable because the effect of the present invention can be obtained remarkably.

The component (A-2) oil agent used in the component (A) polyurethane gel composition can be used without particular limitation as long as it is commonly used in cosmetics. The properties are not particularly limited, but it is preferably an oil that is liquid at 25°C. It is also preferably used as a solvent when producing the polyurethane gel composition of the present invention.
The component (A-2) oil used in the component (A) polyurethane gel composition may be of any origin such as animal oil, vegetable oil, or synthetic oil. or one ester oil), fatty acids, silicone oils, fluorine-based oils, and the like.

Among these, the one with lower polarity tends to increase the strength of the polyurethane gel composition. The use of one or more selected is exemplified, and it is preferable to include one or more of these in the component (A-2) oil agent.
One or two or more selected from these hydrocarbon oils, ester oils and silicone oils can be contained in component (A-2) oil in an amount of preferably 90% by mass or more, more preferably 95% by mass or more. preferred.
In addition, it is preferable to use the component (A-2) oil as a solvent during the production. The properties of the produced polyurethane gel composition are improved by using the oil during production. In addition, the composition hardness can be adjusted by appropriately using an oil agent in the produced polyurethane gel composition.

Component (A) Component (A-2) oil used in the polyurethane gel composition includes, more specifically, hydrocarbons such as liquid paraffin, squalane, polybutene, and polyisobutylene; olive oil, castor oil, mink oil, Fats and oils such as macadamia nut oil; jojoba oil, cetyl isooctanoate (cetyl 2-ethylhexanoate), isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl isostearate, Esters such as diisostearyl malate, glyceryl tribehenate, pentaerythritol rosinate, and neopentyl glycol dioctoate; silicones such as methylphenylpolysiloxane and diphenylpolysiloxane; More than one species can be used.

The component (A) polyurethane gel composition used in the present invention has advantages of not only transparency and luster, but also extremely high elasticity and resilience.
As a result of measuring the penetration load value, 30 parts of this polyurethane gel composition and 70 parts of liquid paraffin (kinematic viscosity at 40°C according to ASTM D445 measurement method is 8 mm2/s) were dissolved by heating at 85°C, and then heated to 30°C. The gel obtained after cooling exhibited excellent characteristics such as a load value of 0.2 to 10 N when a 2 cmφ spherical adapter was inserted 10 mm at 2 cm/min. This hardness property indicates that the component (A) polyurethane gel composition used in the present invention has gel restoring force.
As for transparency, the component (A) polyurethane gel composition used in the present invention has a transmittance of 90% or more at a wavelength of 700 nm. This high transparency indicates that the component (A) polyurethane gel composition used in the present invention has extremely high transparency.

In the method for producing the component (A) polyurethane gel composition of the present invention, the polyurethane is preferably produced in the presence of the (A-2) oil agent. Further, it is more preferable to use a specific polyol as the raw material for the polyurethane in the component (A-1) and to produce the polyurethane in the presence of the oil agent (A-2). The component (A) polyurethane gel composition of the present invention can be produced using a known method for producing polyurethane.

For example, the polyurethane gel composition 1 used in the present invention contains, in component (A-2) oil agent, (a) hydrogenated polybutadiene having an isocyanate group at the end of A and (b) HO--R ³ --OH (in the formula , R ³ represents a straight-chain or branched C2-C6 alkylene group optionally having an ether bond) is added to carry out a polyaddition reaction.
For example, the polyurethane gel composition 2 of the present invention comprises (c) hydrogenated polybutadiene having terminal hydroxyl groups, (b) HO--R ³ --OH (wherein R ³ may have an ether bond Representing a chain or branched C2-C6 alkylene group), the component (A-2) oil agent is charged and uniformly mixed, and (d) a diisocyanate compound is added and allowed to react. can.

In addition to the components (A-1) and (A-2) described above, the polyurethane gel composition of the present invention may contain optional components that can be used in the pharmaceutical or cosmetic fields as long as the effects of the present invention are not impaired. may be included. Optional ingredients include, for example, volatile ingredients, surfactants, oily ingredients, powders, water-soluble polymers, UV absorbers, moisturizers, anti-fading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives, Other ingredients that are usually used in cosmetics to impart various effects, such as fragrances, can be used as appropriate.

The content of the polyurethane gel composition of component (A) used in the water-in-oil makeup cosmetic of the present invention is preferably 0.5 to 35%, more preferably 1 to 30%, particularly 5 to 10%. preferable. The content of (A-1), which is the solid content of polyurethane, is preferably 0.1 to 7%, more preferably 0.2 to 6%, and particularly preferably 1 to 3%. Within this range, the lightness of the spread and the resistance to twisting to the double layer are more excellent, which is preferable.
By setting the amount in this range, good emulsification stability of the water-in-oil type makeup cosmetic is obtained, and spreadability, longevity and composition strength are improved.

The component (B) polyvinyl alcohol used in the water-in-oil makeup cosmetic composition of the present invention is obtained by saponifying polyvinyl acetate and is known as a raw material for cosmetics. Although the properties differ depending on the degree of polymerization and the degree of saponification, any of them can be used. Although not particularly limited in the present invention, the average molecular weight is more preferably 10,000 to 120,000, particularly preferably 30,000 to 105,000. The degree of saponification depends on the degree of saponification of the acetyl groups of polyvinyl acetate during the production of polyvinyl alcohol, and can be broadly divided into a fully saponified type in which saponification is performed almost completely and a partially saponified type in which some acetyl groups remain. Although any saponified type can be used in the present invention, it is preferable to use partially saponified polyvinyl alcohol. These commercial products include PVA-203, PVA-205C, PVA-210, PVA-217C, PVA-220C, PVA-224C (manufactured by Kuraray Co., Ltd.), Gosenol EG-05, EG-40 (manufactured by Nippon Gosei Kagaku Co., Ltd.) and the like.

The content of component (B) in the present invention is preferably 0.05 to 1.2%, more preferably 0.1 to 1.1%, particularly preferably 0.3 to 0.8%.

In the water-in-oil type make-up cosmetic of the present invention, component (A-1) and component (B) are used to form a flexible film and a water-resistant film produced by the polyurethane gel composition of component (A). ) The weight ratio (A-1)/(B) of polyvinyl alcohol is preferably 0.08 to 54. Within this range, in addition to the lightness of the spreadability, there is no burdensome feeling such as creaking, and it is less likely to be twisted into a double layer.

The water-in-oil type make-up cosmetic of the present invention can further contain component (C) glittering powder. Component (C) is not particularly limited, and examples thereof include titanium mica, bismuth oxychloride, organic pigment-treated titanium mica, titanium dioxide-coated mica, iron oxide-coated mica, titanium dioxide-coated synthetic phlogopite, titanium oxide-coated synthetic phlogopite, and dioxide. Titanium coated bismuth oxychloride, iron mica titanium oxide, Prussian blue treated mica titanium, carmine treated mica titanium, fish scale foil, titanium dioxide coated glass powder, polyethylene terephthalate/aluminum/epoxy laminated powder, polyethylene terephthalate/polyolefin laminated film powder, polyethylene terephthalate/ Examples include resin laminate powder such as polymethyl methacrylate laminate film powder, aluminum powder, metal powder such as gold and silver powder, and the like, and these can be used alone or in combination of two or more thereof. Component (C) is one or two of fluorine compounds, silicone compounds, metallic soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc. It may be surface-treated using the above, and if it contains a water-repellent treated one, it is preferable from the standpoint of makeup durability and is also suitable from the standpoint of the stability of the water-in-oil type cosmetic. . The water-repellent treatment is not particularly limited, but includes methylpolysiloxane treatment, methylhydrogenpolysiloxane treatment, perfluorooctyltriethoxysilane treatment, octylsilane treatment and the like, and methylpolysiloxane treatment is particularly preferred.

Component (C) is generally plate-shaped, and from the viewpoint of the effect of imparting shine to the makeup cosmetic, a large particle size is preferred. is easy to peel off from the cosmetic film over time, and may impair the makeup hold. In the present invention, the cosmetic film composed of components (A) and (B) sufficiently exhibits the long-lasting effect even when it contains such glittering powder. For example, the effect is more likely to be exhibited when the particles having an average particle size of 20 μm or more are contained, and the effect is exhibited more when the particles having an average particle size of 50 μm or more, further 100 μm or more are contained.
In the present invention, the average particle size of component (C) is calculated from the result of measuring the particle size of 10 particles in an arbitrary field of view using a scanning electron microscope.

The content of component (C) in the present invention is preferably 0.1 to 40%, more preferably 5 to 35%, particularly preferably 10 to 30%. Within this range, the long-lasting effect of makeup can be sufficiently exhibited.

The make-up cosmetic composition of the present invention contains, in addition to the above components (A) to (C), components normally used in cosmetics, an oily component, and components other than component (B) within a range that does not impair the effects of the present invention. film-forming polymer, powders other than component (C), surfactants for powder dispersion and texture adjustment, aqueous ingredients for moisturizing, UV absorbers, moisturizing agents, anti-fading agents, antioxidants, defoaming Agents, cosmetic ingredients, preservatives, perfumes, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

Oily components include hydrocarbons, fats, waxes, hydrogenated oils, and ester oils regardless of their origin, such as animal oils, vegetable oils, or synthetic oils, and their properties, such as solid oils, semi-solid oils, or liquid oils. , fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives, oily gelling agents, oil-soluble resins, volatile oils and the like.
Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, montan wax, fishatropus wax, Japanese wax, olive oil, castor oil, mink oil, macadamia Oils and fats such as coconut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, jojoba oil, cetyl isooctanate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, diisostearin Esters such as polyglyceryl acid, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-lauroyl-L-glutamic acid di(cholesteryl behenyl octyldodecyl), Stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol and other higher alcohols, methylphenylpolysiloxane, fluorine-modified organopolysiloxane and other silicones, perfluorodecane, perfluorooctane, perfluoropolyether fluorinated oils such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin octanoate, dextrin laurate, dextrin palmitate, dextrin myristate, dextrin stearate, dextrin behenate, coconut oil fatty acid Dextrin, (palmitic acid/octanoic acid) dextrin, sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, oily gelling agents such as calcium stearate, hydrogenated pentaerythrityl rosinate, specific alkylmethylpolyacrylate Oil-soluble resins such as siloxane esters, hydrocarbon oils such as light liquid isoparaffin and isododecane, volatile oils such as silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, methyltrimethicone, and low polymerization degree dimethylpolysiloxane etc.

Film-forming polymers other than component (B) include, for example, alkyl acrylate copolymers, alkyl acrylate polymers, alkyl methacrylate copolymers, alkyl methacrylate polymers, and alkyl acrylate/alkyl methacrylate copolymers. , organopolysiloxane polymers, and the like.

Further, polymer emulsions in which one or more of the above polymers or copolymers are dispersed in an aqueous solvent include, for example, alkyl acrylate copolymers, alkyl acrylate polymers, alkyl methacrylate copolymers, methacrylic acid alkyl polymers, alkyl acrylate/alkyl methacrylate copolymers, organopolysiloxane polymers, etc., and polymer emulsions in which one or more of these are dispersed in an aqueous solvent include, for example, alkyl acrylates Copolymer emulsion, alkyl acrylate polymer emulsion, alkyl methacrylate copolymer emulsion, alkyl methacrylate polymer emulsion, acrylic acid/alkyl acrylate copolymer emulsion, acrylic acid/alkyl methacrylate copolymer emulsion, methacrylic acid Acid/alkyl acrylate copolymer emulsions, methacrylic acid/alkyl methacrylate copolymer emulsions, organopolysiloxane polymer emulsions, and the like can be mentioned, and one or more of these can be used.

Powders other than the component (C) include spindle-shaped, needle-shaped, fibrous, spherical, etc., particle sizes such as fumes, fine particles, and pigment grades, and particle structures such as porous and non-porous. It is not limited, and examples thereof include inorganic powders, composite powders, and the like. Specifically, inorganic powders such as aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, talc, kaolin, silica, silicon carbide, boron nitride, magnesium stearate, zinc stearate, N-acyl lysine, Organic powders such as nylon, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, and barium sulfate, iron oxide, carbon black, chromium oxide, chromium hydroxide, Prussian blue, ultramarine blue, red iron oxide, and other colored inorganic pigments. Organic pigment powders such as 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, Red No. 3, Red No. 104, Red Organic pigment powders such as zirconium, barium or aluminum lakes such as No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5, Green No. 3, and Blue No. 1, or metal powders such as aluminum powder, gold powder, silver powder, etc. and these can be used alone or in combination of two or more. In addition, these powders may be used in combination of one or two or more, and may be powdered by known methods using fluorine compounds, silicone oils, metallic soaps, surfactants, fats and oils, hydrocarbons, and the like. It may be surface-treated.

As the surfactant blended for the purpose of improving the dispersibility of the powder, any surfactant generally used in cosmetics can be used, including nonionic surfactants and anionic surfactants. , cationic surfactants, amphoteric surfactants, and the like. For example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified Examples include organopolysiloxane, polyether-modified organopolysiloxane, and lecithin.
The aqueous component may be any component as long as it is soluble in water. Examples include lower alcohols such as ethyl alcohol and butyl alcohol, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose. mentioned. Examples of water-soluble polymers include natural ones such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate and carrageenan; semisynthetic ones such as methylcellulose, hydroxyethylcellulose and carboxymethylcellulose; carboxyvinyl polymers; Synthetic ones such as alkyl-added carboxyvinyl polymer and sodium polyacrylate can be mentioned. Other moisturizing agents such as proteins, mucopolysaccharides, collagen, elastin, keratin can also be included.
Examples of UV absorbers include benzophenone, PABA, cinnamic acid, salicylic acid, 4-tert-butyl-4′-methoxydibenzoylmethane, oxybenzone, etc. Moisturizers include proteins, mucopolysaccharides, and collagen. , elastin, keratin, etc. Antioxidants such as α-tocopherol, ascorbic acid, etc. Beauty ingredients such as vitamins, antiphlogistic agents, herbal medicines, etc. Preservatives such as paraoxybenzoic acid ester, phenoxyethanol, 1 , 2-pentanediol, chlorophenesin and the like.

The water-in-oil type make-up cosmetic of the present invention can be produced by a generally known method, which is not particularly limited, and includes, for example, the following methods.
The component (B) and other optional ingredients were heated and uniformly dispersed in the oil-based section, in which the components (A), (C), and other optional ingredients were heated and uniformly dispersed, added to the water-based section, emulsified at 70°C, and filled. Can be manufactured by molding. It can be produced by using a mixing and stirring device such as Azidisper or Homodisper.

The water-in-oil type makeup cosmetic of the present invention is not particularly limited, but it can be applied in any form of liquid, semi-solid, or solid, and eye makeup cosmetics such as eye color and eyeliner. . More preferably, it is preferably used for eye color in terms of the effect of not twisting the double layer of the present application.

EXAMPLES The present invention will be described in more detail below with reference to examples, comparative examples, and the like. In addition, these do not limit this invention at all.

[Production Example 1 of Polyurethane Gel Composition of Component (A)]
899 parts of hydrogenated polybutadiene (molecular weight: 2200), 2450 parts of cetyl 2-ethylhexanoate, and 128 parts of hexamethylene diisocyanate were placed in a 3 L three-necked flask and uniformly mixed.
While controlling the temperature at 60° C., 0.9 part of dibutyltin dilaurate was added, and after stirring for 3 hours, 24 parts of ethylene glycol was added.
After the addition, the mixture was stirred at 80° C. for 5 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 10,000 by GPC measurement (converted to polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85°C and cooled to 30°C. It was 2.5N under the conditions of min and 10 mm penetration.

[Production Example 2 of Polyurethane Gel Composition of Component (A)]
899 parts of hydrogenated polybutadiene (molecular weight: 2200), 2450 parts of cetyl 2-ethylhexanoate, and 128 parts of hexamethylene diisocyanate were placed in a 3 L three-necked flask and uniformly mixed.
While controlling the temperature at 60° C., 0.9 part of dibutyltin dilaurate was added, and after stirring for 3 hours, 24 parts of ethylene glycol was added.
After the addition, the mixture was stirred at 80° C. for 10 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 50,000 by GPC measurement (converted to polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85°C and cooled to 30°C. It was 5 N under the conditions of min and 10 mm penetration.

[Production Example 3 of Polyurethane Gel Composition of Component (A)]
899 parts of hydrogenated polybutadiene (molecular weight: 2200), 2450 parts of cetyl 2-ethylhexanoate, and 128 parts of hexamethylene diisocyanate were placed in a 3 L three-necked flask and uniformly mixed.
While controlling the temperature at 60° C., 0.9 parts of dibutyltin dilaurate was added, and after stirring for 3 hours, 24 parts of ethylene glycol was added while diluting with cetyl 2-ethylhexanoate.
After the addition was completed, the mixture was stirred at 80° C. for 15 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 100,000 by GPC measurement (converted to polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85°C and cooled to 30°C. It was 7.5 N under the conditions of min and 10 mm penetration.

[Production Example 4 of Polyurethane Gel Composition of Component (A)]
899 parts of hydrogenated polybutadiene (molecular weight: 2200), 24 parts of ethylene glycol, 0.9 parts of dibutyltin dilaurate, and 2450 parts of cetyl 2-ethylhexanoate were placed in a 3-liter three-necked flask and uniformly mixed.
128 parts of hexaethylene diisocyanate was added while controlling the temperature at 60° C. After the addition was completed, the mixture was stirred at 80° C. for 10 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 50,000 by GPC measurement (converted to polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85°C and cooled to 30°C. It was 3N under the conditions of min and 10 mm penetration.

[Production Example 5 of Polyurethane Gel Composition of Component (A)]
899 parts of hydrogenated polybutadiene (molecular weight: 2200), 24 parts of ethylene glycol, 0.9 parts of dibutyltin dilaurate, and 2450 parts of cetyl 2-ethylhexanoate were placed in a 3-liter three-necked flask and uniformly mixed.
While controlling the temperature at 60° C., 128 parts of hexaethylene diisocyanate was added, and after the completion of the addition, the mixture was stirred at 80° C. for 15 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 100,000 by GPC measurement (converted to polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85°C and cooled to 30°C. It was 4.5N under the conditions of min and 10 mm penetration.

[Production Comparative Example 1]
100 parts of crosslinked silicone gel (KSG-43, manufactured by Shin-Etsu Chemical Co., Ltd.) is used.
[Production Comparative Example 2]
35 parts of dextrin fatty acid ester (Leopal ISK, manufactured by Chiba Flour Mills) and 65 parts of cetyl 2-ethylhexanoate were heated at 90° C. and cooled to prepare a polysaccharide gel.
[Production Comparative Example 3]
35 parts of crystalline polyethylene wax (PERFORMALENE 655 manufactured by New Phase Technology) and 65 parts of cetyl 2-ethylhexanoate were heated at 90° C. and cooled to prepare a wax oil gel.
The silicone gel of Comparative Production Example 1 lacks luster and lacks restoring force. The polysaccharide gel of Production Comparative Example 2 has weak resilience and resilience. The wax oil gel of Production Comparative Example 3 lacks luster.

[Gel evaluation]
Among the polyurethane gels obtained by the above production method, the polyurethane gel composition of Production Example 2 was evaluated with respect to the gel load value for various oil agents commonly used in cosmetics and the transparency of the gel (Test Examples 1 to 1). 6). Table 1 shows the results. Various evaluation methods are as follows. The component (A) polyurethane gel composition of Production Examples 1 to 5 had a gel load value of 2.5 to 7.5 N and a weight average molecular weight of 10,000 to 100,000.

[Measurement of load value and evaluation of gel strength]
The polyurethane gel composition of Production Example 2 and various oil agents listed in Table 1 were dissolved by heating at 85° C. and cooled to 30° C. to prepare elastic gels (Test Examples 1 to 6). The load value of the gel was measured using a load measuring machine (manufactured by FUDOH) under the conditions of 2 cmφ spherical adapter, 2 cm/min, and 10 mm penetration. This was used to evaluate gel strength. As a result of Test Examples 1 to 4, it was confirmed that an oil having a smaller number of hydroxyl groups in the molecule tends to have a higher load value. It is considered that the hydroxyl group in the oil agent affected the hydrophilic group part in the hydrophilic group association thickening mechanism of the polyurethane gel, resulting in a decrease in viscosity.

[Transparency measurement and evaluation]
The transparency of various gels shown in Table 1 (Test Examples 1 to 6) was determined by measuring the transmittance at 700 nm using a transmittance meter (manufactured by Shimadzu Corporation). As a result, all the gels of Test Examples 1 to 6 exhibited good transparency (⊚) of 90% or more.

[Measurement and evaluation of self-restoring force]
Using the polyurethane gel composition of Production Example 2 and the dextrin fatty acid ester gel of Production Comparative Example 2, the self-restoring force was evaluated. Each measurement sample was diluted with cetyl 2-ethylhexanoate so that the pure content was 10.5% by mass, heated at 85°C, poured into a jar container, and cooled to 30°C to obtain elasticity. A gel was prepared. Using a texture analyzer (manufactured by Eei Seiki Co., Ltd.), the prepared sample was subjected to a load of 5 g with a 2 cmφ spherical adapter, and then 7 times at a speed of 1 mm / min and a needle penetration of 5 mm. By repeating the same operation, it was confirmed whether the gel structure was not destroyed by the load and had a restoring force. A schematic diagram of the measurement is shown in FIG.
As a result, in the dextrin fatty acid ester gel of Production Comparative Example 2, the gel structure was destroyed by repeated loading, and the same curve was not obtained. Since the same curve was traced without collapsing, it was found that the gel had high restorability. Moreover, the value of the load value itself was also higher than that of the dextrin fatty acid ester gel of Production Comparative Example 2, indicating that the gel had excellent elasticity.

From the above studies, it was found that the component (A) polyurethane gel composition used in the present invention is a highly novel gel having excellent transparency, high elasticity, and excellent self-restoring power.

Examples 1-15 and Comparative Examples 1-3: Water-in-oil eye color

An eye color having the composition shown in Tables 2 to 4 was prepared; Lightness of elongation, b. film uniformity; c. d. Persistence of color (make-up lasting); e. Evaluate how easy it is to remove. The results are also shown in Tables 2-4 .

※１：ＢＥＮＴＯＮ ３８Ｖ（エレメンティス社製）
※２：ケルコゲル ＬＴ１００（大日本住友製薬社製）
※３：クラレポバール ２２４Ｃ（クラレ社製）
※４：シリコン ＫＦ－７３１２Ｊ（信越化学工業社製）
※５：ＴＩＭＩＣＡ ＧＯＬＤ ＳＰＡＲＫＬＥ
（平均粒子径４５μｍ、三好化成社製）
※６：ＨＥＬＩＯＳ Ｒ１００Ｙ（平均粒子径１００μｍ、トピー工業社製）
※７：ＫＦ－６０３８ (信越化学工業社製)

*1: BENTON 38V (manufactured by Elementis)
*2: Kelcogel LT100 (manufactured by Sumitomo Dainippon Pharma Co., Ltd.)
*3: Kuraray Poval 224C (manufactured by Kuraray Co., Ltd.)
*4: Silicon KF-7312J (manufactured by Shin-Etsu Chemical Co., Ltd.)
*5: TIMICA GOLD SPARKLE
(Average particle size 45 μm, manufactured by Miyoshi Kasei Co., Ltd.)
* 6: HELIOS R100Y (average particle size 100 μm, manufactured by Topy Industries, Ltd.)
*7: KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. Components (1) to (6) and (9) to (14) are heated at 70° C. and mixed.
B. Components (7), (8), (15) to (18) are heated at 70° C. and mixed.
C. Add B to A and emulsify.
D. After defoaming, it is filled into a container.

(Evaluation method)
The following evaluation items were evaluated by the following methods.
(Evaluation item)
stomach. Lightness of elongation b. Film uniformity c. It is difficult to move. Lasting color (makeup lasting)
E. Ease of Dropping Each sample was subjected to a usage test by 20 expert panelists for items a to e. Each panelist uses each eye color of Examples 1 to 15 and Comparative Examples 1 to 3 with an application body and a finger, evaluates and scores in 7 stages according to the following absolute evaluation, and totals the scores of all panelists for each sample. The average value was calculated from , and judged according to the following 4-step judgment criteria. After applying each eye color to the upper eyelids with the applicator, the resistance applied when spreading with a finger was measured. Evaluation was made as lightness of spread, and b. whether or not the cosmetic film was evenly applied after application. It was evaluated as film uniformity. C. After 6 hours, whether or not the cosmetic film was doubled and uneven, and whether or not the color developed immediately after application was maintained. d. It was evaluated as the continuation of the applied color (make-up hold). Also, when removing makeup, the following cleansing cosmetics were soaked in a cotton pad and rubbed twice. Evaluated as easy to drop.

(Cleansing cosmetics)
(Component) (%)
1. Remaining amount of water 2. DPG 10
3. BG 5
4. Ethanol 5
5. PEG-8 glyceryl isostearate 2
6. Phenoxyethanol 0.1
7. Disodium edetate 0.1
8. Disodium phosphate 0.01
9. Sodium phosphate 0.01
10. Methylparaben 0.15
(Production method)
Components 1 to 10 were uniformly mixed to obtain a cleansing cosmetic.

Absolute Evaluation Criteria (Rating): (Rating)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad

4-step judgment criteria (judgment): (average score)
◎: More than 5 points: Very good ○: More than 3.5 points and 5 points or less: Good △: More than 1 point and 3.5 points or less: Slightly poor ×: 1 point or less: Poor

As is clear from the results in Tables 2 to 4 , the water-in-oil type eye colors of Examples 1 to 15 of the present invention are lighter in elongation, uniform in film, less prone to wrinkling, and It was excellent in all of the persistence of applied color (make-up hold) and ease of removal. On the other hand, Comparative Example 1 in which distearyldimonium hectolacto was blended instead of the polyurethane gel composition of component (A), Comparative Example 2 in which gellan gum was blended, and polyvinyl alcohol of component (B) was substituted. Comparative Example 3, in which trimethylsiloxysilicate is blended in, tends to have uneven bulk due to poor compatibility. It was inferior in terms of mochi).

Example 17: Eye color (water-in-oil type)
(Component) (%)
1. Polyurethane gel composition production example 4 12
2. Polyvinyl alcohol 0.6
3. Powder in which aluminum powder is coated with silicic anhydride, tin oxide, silver, and silicic anhydride in this order *1 1.5
4.3% methylpolysiloxane 0.5% methylhydrogenpolysiloxane coated red iron oxide coated mica titanium*2 10
5. Titanium mica *3 15
6. (styrene/acrylates) copolymer *4 5
7. Polyglyceryl tetraisostearate 2 *5 8
8. Isododecane 5
9. Mineral oil *6 5
10. Triethylhexanoin 6
11. cetyl ethylhexanoate 5
12. Remaining water 13. Ethanol 5
14. sodium chloride 0.1
15. Methylparaben 0.3
*1: COSMICOLOR CE. TECLA GR (manufactured by Toyo Aluminum Co., Ltd.)
*2: FLAMENCO SPARKLE BLUE 620J (manufactured by BASF)
*3: FLAMENCO GOLD 220C (manufactured by BASF)
*4: 42% isododecane solution *5: Cosmol 44V (manufactured by Nisshin Oillio Group)
*6: KLEAROL WHITE MINERAL OIL (manufactured by SONNEBOR)
(Production method)
A. Components (1), (3) to (11) are heated at 70° C. and mixed.
B. Components (2) and (12) to (15) are heated at 70° C. and mixed.
C. Add B to A and emulsify.
D. After defoaming, it is filled into a container.
The eye color of Example 17 is a water-in-oil type makeup cosmetic that is excellent in all of light spreadability, uniformity of film, resistance to wrinkling, longevity of applied color (makeup longevity), and ease of removal. rice field.

Example 18: Eyeliner (water-in-oil type)
(Component) (%)
1. Polyurethane gel composition production example 2 5
2. Mixture of paraffin and microcrystalline wax *1 1
3. Candelilla wax *2 1
4. polyvinyl alcohol 1
5. iron oxide 15
6. Mica Titanium 4
7. Hydrogenated polyisobutene *3 45
8.2% methyl polysiloxane treated mica *4 2
9. Mineral oil *5 5
10. Triethylhexanoin 6
11. Phenoxyethanol 0.05
12. Remaining water 13. BG 3
14. DPG 2
15. sodium chloride 0.1
16. Methylparaben 0.3
*1: Synthetic ceresin JNP-81 (manufactured by Japan Natural Products Co., Ltd.)
*2: Refined candelilla wax SR-3 (manufactured by Japan Natural Products)
*3: IP Solvent 1620MU (manufactured by Idemitsu Kosan Co., Ltd.)
*4: JS-1 (manufactured by Sanshin Kogyo Co., Ltd.) treated with 3% methylpolysiloxane *5: CARNATION (manufactured by SONNEBORN)
(Production method)
A. Components (1) to (3) and (5) to (11) are heated at 70° C. and mixed.
B. Components (4) and (12) to (16) are heated at 70° C. and mixed.
C. Add B to A and emulsify.
D. After defoaming, it is filled into a container.
The eyeliner of Example 18 is a water-in-oil makeup cosmetic that is excellent in all of light spreadability, uniformity of film, resistance to wrinkling, longevity of applied color (makeup longevity), and ease of removal. rice field.

Claims (6)

A water-in-oil makeup cosmetic containing the following components (A) and (B),
The component (A) is a polyurethane gel composition containing component (A-1) polyurethane and component (A-2) oil,
The component (A-1) is
(i) (a) a hydrogenated polybutadiene having an isocyanate group at the end and (b) HO--R ³ --OH (wherein R ³ is a linear or branched C2-C6 alkylene optionally having an ether bond) a polyurethane obtained by reaction with a glycol represented by
(ii) (c) a hydrogenated polybutadiene having a terminal hydroxyl group, (d) a diisocyanate compound, and (b) HO--R ³ --OH (wherein R ³ is a linear or branched chain optionally having an ether bond). Representing a C2-C6 alkylene group) is a polyurethane obtained by reaction with a glycol represented by
The component (B) is polyvinyl alcohol ,
The content of the component (A) is 0.5 to 35% by mass,
The content of the component (B) is 0.5. 05 to 1.2% by mass of a water-in-oil makeup cosmetic. The water-in-oil type makeup cosmetic according to claim 1, wherein the component (A-1) polyurethane is an oil-soluble polyurethane. 3. The water-in-oil makeup cosmetic according to claim 1, wherein the component (A-1) polyurethane has a weight average molecular weight of 10,000 to 100,000. The water-in-oil type makeup cosmetic according to any one of claims 1 to 3, wherein the component (A-2) oil is liquid at 25°C. The water-in-oil according to any one of claims 1 to 4 , wherein the content mass ratio (A-1)/(B) of the component (A-1) and the component (B) is 0.08 to 54. Mold make-up cosmetics. 6. The water-in-oil type makeup cosmetic according to any one of claims 1 to 5 , further comprising component (C) glittering powder.

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