JP5360847B2 - Transparent oil-in-water emulsified cosmetic - Google Patents

Transparent oil-in-water emulsified cosmetic Download PDF

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JP5360847B2
JP5360847B2 JP2012195587A JP2012195587A JP5360847B2 JP 5360847 B2 JP5360847 B2 JP 5360847B2 JP 2012195587 A JP2012195587 A JP 2012195587A JP 2012195587 A JP2012195587 A JP 2012195587A JP 5360847 B2 JP5360847 B2 JP 5360847B2
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令二 宮原
允人 宇山
裕介 薮崎
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Shiseido Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/63Steroids; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10General cosmetic use
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/21Emulsions characterized by droplet sizes below 1 micron
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26Optical properties
    • A61K2800/262Transparent; Translucent

Abstract

[Problem] To provide an oil-in-water emulsion cosmetic offering excellent salt tolerance, whereby a system in which a di-long chain cationic surfactant has been formulated can be easily produced irrespective of the method, such as high-pressure emulsification, and also translucency can kept stable in low-temperature and high-temperature ranges. [Solution] A translucent oil-in-water emulsion cosmetic containing 0.01-1 mass% of a di-long chain cationic surfactant (A), 0.01-2 mass% of a non-ionic surfactant (B) having a sterol backbone with an HLB of 10-18, 0.01-1 mass% of an oil (C) that is liquid at room temperature, 0.1-10 mass% of a specific alkylene oxide derivative (D) (for example, POE(14) POP(7) dimethyl ether or the like), 0.1-20 mass% of a C1-3 monohydric lower alcohol (E), and water (F), [component (C)/component (A) + component (B)] = 0.60 or lower (mass ratio). The translucent oil-in-water emulsion cosmetic may also contain menthol and/or camphor.

Description

本発明は透明な水中油型乳化化粧料に関する。さらに詳しくは、ジ長鎖型カチオン界面活性剤を配合した系を、低温〜高温の幅広い温度域に亘って安定に透明性を維持することができ、耐塩性に優れる水中油型乳化化粧料に関する。   The present invention relates to a transparent oil-in-water emulsified cosmetic. More specifically, the present invention relates to an oil-in-water emulsified cosmetic that can maintain transparency stably over a wide temperature range from low to high temperature, and has excellent salt resistance, in a system containing a di-long-chain cationic surfactant. .

化粧水をはじめとする水系皮膚化粧料においては、外観が透明系のものが好まれる傾向がある(例えば、特許文献1〜2参照)。化粧水は、皮膚に適度な潤いを与え、皮膚を健康に保つといった本来の機能のほかに、近年、消費者の嗜好の多様化に伴い、冷感・清涼感が得られるようメントール、カンファー等の冷感剤(清涼剤)を配合したものも求められるようになってきた。そして冷感剤(清涼剤)とカチオン型界面活性剤を併用することで、冷感・清涼感効果向上を図る技術が特許文献3に開示されている。   In water-based skin cosmetics including lotion, those with a transparent appearance tend to be preferred (see, for example, Patent Documents 1 and 2). In addition to its original function of moisturizing the skin and keeping it healthy, lotion has recently become menthol, camphor, etc. to provide a cool and cool feeling with the diversification of consumer preferences. The thing which mix | blended this cooling agent (cooling agent) has come to be calculated | required. Patent Document 3 discloses a technique for improving the cooling sensation / cooling sensation effect by using a cooling sensation agent (cooling agent) and a cationic surfactant in combination.

ところでカチオン型界面活性剤を含む皮膚化粧料を特に顔などに適用する場合、安全性等の点から、モノ長鎖型カチオン界面活性剤よりもジ長鎖型カチオン界面活性剤が好ましく用いられる。しかしながら、ジ長鎖型カチオン界面活性剤は水に溶け難いため、これまでジ長鎖型カチオン界面活性剤を配合した透明系の化粧水を、高圧乳化等の方法によらずに簡便に製造することは難しかった。上記特許文献1にはカチオン界面活性剤としてモノ長鎖型カチオン界面活性剤、ジ長鎖型カチオン界面活性剤のいずれも用いられ得ることが開示されているものの([0027])、その調製方法として6×107〜18×107Paの圧力下での高圧乳化法が示されている([0044])。また実施例で実際に用いた例として具体的に記載されているのはモノ長鎖型カチオン界面活性剤を用いた例のみである([0058])。上記特許文献2で実施例等に具体的に示されるカチオン界面活性剤はモノ長鎖型カチオン界面活性剤のみである。 By the way, when skin cosmetics containing a cationic surfactant are applied particularly to the face and the like, a di-long-chain cationic surfactant is preferably used rather than a mono-long-chain cationic surfactant from the viewpoint of safety and the like. However, since di-long-chain cationic surfactants are difficult to dissolve in water, transparent skin lotions formulated with di-long-chain cationic surfactants can be easily produced without using high-pressure emulsification methods. That was difficult. Although Patent Document 1 discloses that either a mono-long-chain cationic surfactant or a di-long-chain cationic surfactant can be used as the cationic surfactant ([0027]), a method for preparing the same Shows a high pressure emulsification method under a pressure of 6 × 10 7 to 18 × 10 7 Pa ([0044]). Further, only examples using a mono long-chain cationic surfactant are specifically described as examples actually used in the examples ([0058]). The cationic surfactant specifically shown in Examples and the like in Patent Document 2 is only a mono-long-chain cationic surfactant.

特開2000−191503号公報(段落番号[0027]、[0044]、[0058])Japanese Unexamined Patent Publication No. 2000-191503 (paragraph numbers [0027], [0044], [0058]) 特開平6−271421号公報JP-A-6-271421 特開2002−114649号公報JP 2002-114649 A

本発明は上記従来の事情に鑑みてなされたもので、ジ長鎖型カチオン界面活性剤を配合した系を低温〜高温の幅広い温度域で安定して透明性を維持することができ、しかも高圧乳化等の方法によらずに混合撹拌等の手段で簡便に製造することができ、耐塩性に優れる水中油型乳化化粧料を提供することを目的とする。   The present invention has been made in view of the above-described conventional circumstances, and can stably maintain transparency in a wide temperature range from low to high temperature in a system in which a dilong chain cationic surfactant is blended. An object of the present invention is to provide an oil-in-water emulsified cosmetic that can be easily produced by means such as mixing and stirring without using a method such as emulsification, and has excellent salt resistance.

上記課題を解決するために本発明は、(A)ジ長鎖型カチオン界面活性剤を0.01〜1質量%、(B)HLB10〜18のステロール骨格を有する非イオン界面活性剤を0.01〜2質量%、(C)常温(25℃)で液状の油分を0.01〜1質量%、(D)下記式(I)で示されるアルキレンオキシド誘導体を0.1〜10質量%、(E)炭素原子数1〜3の一価の低級アルコールを0.1〜20質量%、および(F)水を含有し、(C)成分の配合量が、(A)成分と(B)成分の合計量に対し0.60以下(質量比)である、透明な水中油型乳化化粧料を提供する。   In order to solve the above-described problems, the present invention provides (A) 0.01 to 1% by mass of a di-long-chain cationic surfactant, and (B) a nonionic surfactant having a sterol skeleton of HLB 10 to 18. 01 to 2% by mass, (C) 0.01 to 1% by mass of liquid oil at room temperature (25 ° C.), (D) 0.1 to 10% by mass of an alkylene oxide derivative represented by the following formula (I), (E) 0.1 to 20% by mass of a monovalent lower alcohol having 1 to 3 carbon atoms, and (F) water, and the amount of component (C) is (A) and (B) Provided is a transparent oil-in-water emulsified cosmetic that is 0.60 or less (mass ratio) with respect to the total amount of components.

1O−[(AO)a(EO)b]−R2 (I)
〔式(I)中、AOは炭素原子数3〜4のオキシアルキレン基、EOはオキシエチレン基を示し;a、bはそれぞれ前記AO、EOの平均付加モル数で、1≦a≦70、1≦b≦70であり;AOとEOの合計に対するEOの割合[EO/(AO+EO)]は20〜80質量%である。R1、R2は、それぞれ独立に、炭素原子数1〜4のアルキル基を示す。〕
R 1 O — [(AO) a (EO) b ] —R 2 (I)
[In the formula (I), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group; a and b are average addition moles of AO and EO, respectively, 1 ≦ a ≦ 70, 1 ≦ b ≦ 70; the ratio of EO to the total of AO and EO [EO / (AO + EO)] is 20 to 80% by mass. R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms. ]

また本発明は、(A)成分が下記式(II)および/または(III)で示される化合物である、上記水中油型乳化化粧料を提供する。   The present invention also provides the oil-in-water emulsion cosmetic, wherein the component (A) is a compound represented by the following formula (II) and / or (III).

Figure 0005360847
Figure 0005360847

〔式(II)中、R3COは、それぞれ独立に、炭素原子数が12〜22で、二重結合を0〜3個有する脂肪族アシル基を表し;pは1〜3の整数を表し;R4はメチル基、または基−(CH2p−OH(但し、pは上記で定義したとおり)を表し;Xはハロゲン原子、メトサルフェート、またはメトホスフェートを表す。〕 [In the formula (II), R 3 CO independently represents an aliphatic acyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; p represents an integer of 1 to 3; R 4 represents a methyl group or a group — (CH 2 ) p —OH (where p is as defined above); X represents a halogen atom, methosulfate, or methophosphate. ]

Figure 0005360847
Figure 0005360847

〔式(III)中、R5は、それぞれ独立に、炭素原子数が12〜22で、二重結合を0〜3個有するアルキル基を表し;R6は、それぞれ独立に、炭素原子数が1〜3で、二重結合をもたないアルキル基を表し;Yはハロゲン原子、メトサルフェート、またはメトホスフェートを表す。〕 [In the formula (III), R 5 independently represents an alkyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; R 6 each independently represents a carbon atom number; 1 to 3 represents an alkyl group having no double bond; Y represents a halogen atom, methosulfate, or methophosphate. ]

また本発明は、L値が95以上である、上記水中油型乳化化粧料を提供する。   Moreover, this invention provides the said oil-in-water type emulsified cosmetics whose L value is 95 or more.

また本発明は、乳化粒子径が100nm以下である、上記水中油型乳化化粧料を提供する。   Moreover, this invention provides the said oil-in-water type emulsified cosmetics whose emulsion particle diameter is 100 nm or less.

また本発明は、メントールおよび/またはカンファーをさらに含有する、上記水中油型乳化化粧料を提供する。   The present invention also provides the oil-in-water emulsion cosmetic further comprising menthol and / or camphor.

本発明により、ジ長鎖型カチオン界面活性剤を配合した系を、低温〜高温の幅広い温度域に亘り安定して透明性を維持することができ、しかも高圧乳化等の方法によらずに混合撹拌等の手段で簡便に製造することができ、耐塩性に優れる水中油型乳化化粧料が提供される。   According to the present invention, a system containing a di-long-chain cationic surfactant can be stably maintained over a wide temperature range from low temperature to high temperature, and mixed without depending on a method such as high pressure emulsification. An oil-in-water emulsified cosmetic that can be easily produced by means such as stirring and has excellent salt resistance is provided.

以下、本発明について詳述する。なお以下において、POEはポリオキシエチレンを、POPはポリオキシプロピレンを、それぞれ示す。   Hereinafter, the present invention will be described in detail. In the following, POE represents polyoxyethylene, and POP represents polyoxypropylene.

(A)成分であるジ長鎖型カチオン界面活性剤としては、下記式(II)および/または(III)で示されるジ長鎖型カチオン界面活性剤が好ましく用いられる。   As the di-long-chain cationic surfactant as the component (A), di-long-chain cationic surfactants represented by the following formulas (II) and / or (III) are preferably used.

Figure 0005360847
Figure 0005360847

〔式(II)中、R3COは、それぞれ独立に、炭素原子数が12〜22で、二重結合を0〜3個有する脂肪族アシル基を表し;pは1〜3の整数を表し;R4はメチル基、または基−(CH2p−OH(但し、pは上記で定義したとおり)を表し;Xはハロゲン原子、メトサルフェート、またはメトホスフェートを表す。〕 [In the formula (II), R 3 CO independently represents an aliphatic acyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; p represents an integer of 1 to 3; R 4 represents a methyl group or a group — (CH 2 ) p —OH (where p is as defined above); X represents a halogen atom, methosulfate, or methophosphate. ]

Figure 0005360847
Figure 0005360847

〔式(III)中、R5は、それぞれ独立に、炭素原子数が12〜22で、二重結合を0〜3個有するアルキル基を表し;R6は、それぞれ独立に、炭素原子数が1〜3で、二重結合をもたないアルキル基を表し;Yはハロゲン原子、メトサルフェート、またはメトホスフェートを表す。〕 [In the formula (III), R 5 independently represents an alkyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; R 6 each independently represents a carbon atom number; 1 to 3 represents an alkyl group having no double bond; Y represents a halogen atom, methosulfate, or methophosphate. ]

上記式(II)で示されるジ長鎖型カチオン界面活性剤として、好ましくはヤシ油脂肪酸系エステルクワットのハロゲン化物またはメトサルフェートが挙げられる。具体的にはジココイルエチルヒドロキシエチルモニウムメトサルフェート(市販品として「DEHYQUART L80」(コグニスジャパン社製)など)等が挙げられる。ただしこれら例示に限定されるものでない。   The di-long-chain cationic surfactant represented by the above formula (II) is preferably a coconut oil fatty acid ester quat halide or methosulphate. Specific examples include dicocoylethylhydroxyethylmonium methosulfate (commercially available product such as “DEHYQUART L80” (manufactured by Cognis Japan)). However, it is not limited to these examples.

上記式(III)で示されるジ長鎖型カチオン界面活性剤としては、例えば、塩化ジベヘニルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム(市販品として「カチオンDSV」(三洋化成工業(株)製)など)、塩化ジセチルジメチルアンモニウム、塩化ジセトステアリルジメチルアンモニウム、ジステアリルジメチルアンモニウムメトサルフェート、ジベヘニルジメチルアンモニウムメトサルフェート、ジセチルジメチルアンモニウムメトサルフェート、塩化ジセトステアリルジメチルアンモニウムメトサルフェート等が挙げられる。ただしこれら例示に限定されるものでない。   Examples of the di-long-chain cationic surfactant represented by the above formula (III) include dibehenyldimethylammonium chloride and distearyldimethylammonium chloride ("cationic DSV" (manufactured by Sanyo Chemical Industries, Ltd.) as a commercial product) ), Dicetyldimethylammonium chloride, dicetostearyldimethylammonium chloride, distearyldimethylammonium methosulfate, dibehenyldimethylammonium methosulfate, dicetyldimethylammonium methosulfate, dicetostearyldimethylammonium methosulfate, and the like. However, it is not limited to these examples.

(A)成分の配合量は、本発明の化粧料全量中に0.01〜1質量%である。好ましくは0.1〜1質量%である。0.01質量%未満では、特に冷感剤(清涼剤)との併用時における冷感効果向上実感がなくなり、一方、1質量%超では保存時の乳化安定性が不良となり、好ましくない。(A)成分は1種または2種以上を用いることができる。   (A) The compounding quantity of a component is 0.01-1 mass% in the cosmetics whole quantity of this invention. Preferably it is 0.1-1 mass%. If it is less than 0.01% by mass, the actual feeling of improving the cooling sensation effect when used in combination with a cooling sensation agent (cooling agent) is lost. (A) component can use 1 type (s) or 2 or more types.

(B)成分はHLB10〜18のステロール骨格を有する非イオン界面活性剤である。HLB値は好ましくは12〜18である。なおHLBは下記数1   The component (B) is a nonionic surfactant having a sterol skeleton of HLB 10-18. The HLB value is preferably 12-18. HLB is the following number 1

Figure 0005360847
Figure 0005360847

(ただし、MWは親水基部の分子量を表し、MOは親油基部の分子量を表す)
で表される川上式により算出される。HLBが10未満あるいは18超のものでは乳化粒子径を小さくするのが難しくなる。
(However, MW represents the molecular weight of the hydrophilic base, and MO represents the molecular weight of the lipophilic base)
It is calculated by the Kawakami equation represented by When the HLB is less than 10 or more than 18, it is difficult to reduce the emulsion particle size.

(B)成分としては、POEフィトステロール、POEフィトスタノール、POEコレスタノール等のPOEステロール・水素添加ステロール類が挙げられる。具体的には、POE(10)フィトステロール(HLB12.5)、POE(20)フィトステロール(HLB15.5)、POE(30)フィトステロール(HLB18.0)、POE(30)POP(7)フィトステロール(HLB13.5)、POE(25)フィトスタノール(HLB14.5)、POE(30)コレスタノール(HLB17.0)等が例示される。ただしこれら例示に限定されるものでない。   Examples of the component (B) include POE sterols and hydrogenated sterols such as POE phytosterol, POE phytostanol, and POE cholestanol. Specifically, POE (10) phytosterol (HLB12.5), POE (20) phytosterol (HLB15.5), POE (30) phytosterol (HLB18.0), POE (30) POP (7) phytosterol (HLB13. 5), POE (25) phytostanol (HLB14.5), POE (30) cholestanol (HLB17.0) and the like. However, it is not limited to these examples.

本発明では非イオン界面活性剤の中でも特にステロール骨格を有する非イオン界面活性剤を用いることにより、保存安定性(特に凍結状態の低温域における透明性の安定維持効果)を優れて向上させることができた。またハリ感、弾力感、しっとり感等の効果実感が得られた。市販品として「ニッコールBPS−10」、「ニッコールBPS−20」、「ニッコールBPS−30」「ニッコールBPS−3007」(以上、いずれも日光ケミカルズ(株)製)等が挙げられる。(B)成分は1種または2種以上を用いることができる。   In the present invention, by using a nonionic surfactant having a sterol skeleton among nonionic surfactants, the storage stability (particularly the stability maintaining effect of transparency in a low temperature region in a frozen state) can be improved. did it. In addition, effects such as a feeling of elasticity, a feeling of elasticity, and a moist feeling were obtained. Examples of commercially available products include “Nikkor BPS-10”, “Nikkor BPS-20”, “Nikkor BPS-30”, and “Nikkor BPS-3007” (all of which are manufactured by Nikko Chemicals Co., Ltd.). (B) component can use 1 type (s) or 2 or more types.

(B)成分の配合量は、本発明の化粧料全量中に0.01〜2質量%である。好ましくは0.1〜1質量%である。0.01質量%未満では100nm以下に乳化粒子径を調製することが困難となり、一方、2質量%超では十分な安定性を得ることができず、また、使用感においてべたつきが生じる。   (B) The compounding quantity of a component is 0.01-2 mass% in the cosmetics whole quantity of this invention. Preferably it is 0.1-1 mass%. If it is less than 0.01% by mass, it is difficult to prepare an emulsified particle size of 100 nm or less, while if it exceeds 2% by mass, sufficient stability cannot be obtained, and stickiness occurs in the feeling of use.

(C)成分である常温(25℃)で液状の油分としては、一般に化粧料に用いられ得るものであれば特に限定されるものでなく、例えば、油脂、高級脂肪酸、エステル油、炭化水素油、高級アルコール、シリコーン油等の従来から化粧品に使用されているものを用いることができる。具体例として以下のものが例示される。   The oil component that is liquid at room temperature (25 ° C.) as the component (C) is not particularly limited as long as it can be generally used in cosmetics. For example, fats and oils, higher fatty acids, ester oils, hydrocarbon oils Conventionally used in cosmetics such as higher alcohols and silicone oils can be used. The following are illustrated as specific examples.

油脂としては、例えば、アマニ油、ツバキ油、マカデミアナッツ油、トウモロコシ油、オリーブ油、アボガド油、サザンカ油、ヒマシ油、サフラワー油、キョウニン油、シナモン油、ホホバ油、ブドウ油、ヒマワリ油、アーモンド油、ナタネ油、ゴマ油、小麦胚芽油、米胚芽油、米ヌカ油、綿実油、大豆油、落花生油、茶実油、月見草油等が挙げられる。   Examples of oils and fats include linseed oil, camellia oil, macadamia nut oil, corn oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, kyounin oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, almond oil Rapeseed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil and the like.

高級脂肪酸としては、例えば、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ペンタデカン酸、ヘプタデカン酸、ノナデカン酸、イソステアリン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸等が挙げられる。   Examples of higher fatty acids include heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and the like.

エステル油としては、例えば、テトラオクタン酸ペンタエリスリット、オクタン酸セチル、ラウリン酸ヘキシル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、パルミチン酸オクチル、イソステアリン酸イソプロピル、イソパルミチン酸オクチル、オレイン酸イソデシル、エチルヘキサン酸セチル等が挙げられる。   Examples of ester oils include pentaerythritol tetraoctanoate, cetyl octanoate, hexyl laurate, isopropyl myristate, octyldodecyl myristate, octyl palmitate, isopropyl isostearate, octyl isopalmitate, isodecyl oleate, and ethylhexane. Examples include cetyl acid.

炭化水素油としては、例えば、流動パラフィン、スクワラン、スクワレン、パラフィン、イソパラフィン、オクタン、デカン、ドデカン、イソドデカン、ヘキサデカン、イソヘキサデカン等が挙げられる。   Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, paraffin, isoparaffin, octane, decane, dodecane, isododecane, hexadecane, and isohexadecane.

高級アルコールとしては、例えば、オクチルアルコール、イソステアリルアルコール、オレイルアルコール等が挙げられる。   Examples of the higher alcohol include octyl alcohol, isostearyl alcohol, oleyl alcohol, and the like.

シリコーン油としては、例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン等の鎖状シリコーン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等の環状シリコーン等が挙げられる。   Examples of the silicone oil include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Can be mentioned.

本発明では特に、乳化良好性の点から、エステル油、高級アルコール、炭化水素油等が好ましく用いられる。(C)成分は1種または2種以上を用いることができる。   In the present invention, ester oils, higher alcohols, hydrocarbon oils and the like are particularly preferably used from the viewpoint of good emulsification. (C) A component can use 1 type (s) or 2 or more types.

(C)成分の配合量は、本発明の化粧料全量中に0.01〜1質量%である。好ましくは0.1〜1質量%である。0.01質量%未満では乳化ができず、(A)成分が析出する場合があり好ましくなく、一方、1質量%超では乳化粒子径を小さくするのが難しくなる。   (C) The compounding quantity of a component is 0.01-1 mass% in the cosmetics whole quantity of this invention. Preferably it is 0.1-1 mass%. If it is less than 0.01% by mass, emulsification cannot be carried out and the component (A) may be precipitated, which is not preferred. On the other hand, if it exceeds 1% by mass, it is difficult to reduce the particle size of the emulsified particles.

また本発明では、(C)成分が、(A)成分と(B)成分の合計配合量に対し、0.60以下(質量比)となるよう配合する。0.60超では保存安定性に劣り、乳化粒子径も大きくなり、透明性を得ることができない。なお(A)成分と(B)成分の合計配合量に対する(C)成分の配合比の下限値は、特に限定されるものでないが、水に溶け難い(A)成分を含みながら安定に分散させる点から0.05以上とするのが好ましく、より好ましくは0.1以上、特に好ましくは0.15以上である。   Moreover, in this invention, it mix | blends so that (C) component may be 0.60 or less (mass ratio) with respect to the total compounding quantity of (A) component and (B) component. If it exceeds 0.60, the storage stability is inferior, the particle size of the emulsified particles increases, and transparency cannot be obtained. In addition, the lower limit value of the blending ratio of the component (C) with respect to the total blending amount of the component (A) and the component (B) is not particularly limited, but is stably dispersed while containing the component (A) that is hardly soluble in water. From the point of view, it is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.15 or more.

(D)成分は、下記式(I)で示されるアルキレンオキシド誘導体である。   The component (D) is an alkylene oxide derivative represented by the following formula (I).

1O−[(AO)a(EO)b]−R2 (I) R 1 O — [(AO) a (EO) b ] —R 2 (I)

上記式(I)中、AOは炭素原子数3〜4のオキシアルキレン基を示す。具体的にはオキシプロピレン基、オキシブチレン基、オキシイソブチレン基、オキシトリメチレン基、オキシテトラメチン基等が挙げられる。好ましくはオキシプロピレン基、オキシブチレン基が挙げられる。EOはオキシエチレン基を示す。   In the above formula (I), AO represents an oxyalkylene group having 3 to 4 carbon atoms. Specific examples include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group, and an oxytetramethine group. An oxypropylene group and an oxybutylene group are preferable. EO represents an oxyethylene group.

aはAOの平均付加モル数であり、1≦a≦70、好ましくは2≦a≦20である。bはEOの平均付加モル数であり、1≦b≦70、好ましくは2≦b≦20である。a、bが1未満ではしっとり感が落ち、一方、a、bが70超ではべたつき感が出てきて、すべすべ感が十分に得られない。なお(a+b)は、好ましくは8〜100である。(a+b)が大きすぎるとべたつくことがある。   a is an average added mole number of AO, and 1 ≦ a ≦ 70, preferably 2 ≦ a ≦ 20. b is the average added mole number of EO, and 1 ≦ b ≦ 70, preferably 2 ≦ b ≦ 20. When a and b are less than 1, the moist feeling is lowered. On the other hand, when a and b are more than 70, a sticky feeling is produced, and a smooth feeling cannot be sufficiently obtained. (A + b) is preferably 8 to 100. If (a + b) is too large, stickiness may occur.

AOとEOの合計に対するEOの割合[EO/(AO+EO)]は、20〜80質量%であることが好ましい。EOの割合が20質量%未満ではしっとり感に劣る傾向がみられ、一方、80質量%超ではすべすべ感に劣る傾向がみられる。   The ratio of EO to the total of AO and EO [EO / (AO + EO)] is preferably 20 to 80% by mass. When the EO ratio is less than 20% by mass, a moist feeling tends to be inferior, while when it exceeds 80% by mass, a smooth feeling tends to be inferior.

AOおよびEOの付加する順序は特に限定されるものではない。またAOとEOはブロック状に付加していてもよく、あるいはランダム状に付加していてもよい。ブロック状には2段ブロックのみならず、3段以上のブロックも含まれる。好ましくはランダム状に付加されているものが挙げられる。   The order of adding AO and EO is not particularly limited. AO and EO may be added in a block shape or may be added in a random shape. The block shape includes not only two-stage blocks but also three or more stages. Preferably, those added randomly are listed.

1、R2は、それぞれ独立に、炭素原子数1〜4のアルキル基を示す。アルキル基としては、具体的にはメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基等が挙げられる。好ましくはメチル基、エチル基である。炭素原子数5以上のアルキル基では親水性が低下し、しっとり感が低下する。 R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. A methyl group and an ethyl group are preferred. When the alkyl group has 5 or more carbon atoms, the hydrophilicity is lowered and the moist feeling is lowered.

(D)成分の具体例として、POE(14)POP(7)ジメチルエーテル、POE(17)POP(4)ジメチルエーテル、POE(9)POP(2)ジメチルエーテル、POE(36)POP(41)ジメチルエーテル、POE(55)POP(28)ジメチルエーテル等が例示される。ただしこれら例示に限定されるものでない。   Specific examples of the component (D) include POE (14) POP (7) dimethyl ether, POE (17) POP (4) dimethyl ether, POE (9) POP (2) dimethyl ether, POE (36) POP (41) dimethyl ether, POE. (55) POP (28) dimethyl ether and the like are exemplified. However, it is not limited to these examples.

(D)成分は公知の方法で製造することができる。例えば、水酸基を有している化合物にエチレンオキシドおよび炭素原子数3〜4のアルキレンオキシドを付加重合した後、ハロゲン化アルキルをアルカリ触媒の存在下にエーテル反応させることによって得られるが、これに限定されるものではない。(D)成分は1種または2種以上を用いることができる。   (D) component can be manufactured by a well-known method. For example, it is obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting the alkyl halide to an ether reaction in the presence of an alkali catalyst. It is not something. (D) A component can use 1 type (s) or 2 or more types.

(D)成分の配合量は、本発明の化粧料全量中に0.1〜10質量%である。好ましくは0.2〜8質量%である。0.1質量%未満では微細な乳化粒子径を得ることが難しく、一方、10質量%超ではベタツキや油っぽさを生じ、使用感触に劣る。   (D) The compounding quantity of a component is 0.1-10 mass% in the cosmetics whole quantity of this invention. Preferably it is 0.2-8 mass%. If it is less than 0.1% by mass, it is difficult to obtain a fine emulsified particle size, while if it exceeds 10% by mass, it becomes sticky and oily, resulting in poor use feeling.

(E)成分は炭素原子数1〜3の一価の低級アルコールである。(E)成分として、具体的にはメタノール、エタノール、n−プロパノール、イソプロパノール等が挙げられる。炭素原子数が4以上のものでは臭いも悪く、製造に使用するのは現実的でない。(E)成分は清涼感向上、保存安定性(特に凍結状態の低温域における透明性の安定維持効果)向上、微細な微粒子形成等に寄与する。   The component (E) is a monovalent lower alcohol having 1 to 3 carbon atoms. Specific examples of the component (E) include methanol, ethanol, n-propanol, and isopropanol. When the number of carbon atoms is 4 or more, the odor is bad and it is not practical to use in production. The component (E) contributes to improving the refreshing feeling, improving the storage stability (particularly the effect of maintaining the stability of transparency in a low temperature region in a frozen state), and forming fine particles.

(E)成分の配合量は、本発明の化粧料全量中に0.1〜20質量%である。好ましくは0.2〜15質量%である。0.1質量%未満では微細な乳化粒子径を得ることが難しく、一方、20質量%超では(A)成分や(B)成分といった界面活性剤が界面活性能を失い、乳化破壊を起こす。   (E) The compounding quantity of a component is 0.1-20 mass% in the cosmetics whole quantity of this invention. Preferably it is 0.2-15 mass%. If the amount is less than 0.1% by mass, it is difficult to obtain a fine emulsified particle size. On the other hand, if it exceeds 20% by mass, surfactants such as the component (A) and the component (B) lose their surface activity and cause emulsion breakage.

(F)成分は水である。   The component (F) is water.

本発明では上記(A)〜(F)成分を必須成分とし、これら成分を上記特定の配合量範囲で配合することにより、水難溶性成分である(A)成分を、高圧乳化法等によることなく、水中油型乳化型溶媒に可溶化して低温〜高温の幅広い温度域で安定して透明な基剤とすることができる。   In the present invention, the components (A) to (F) are essential components, and these components are blended in the specific blending amount range, so that the component (A) which is a poorly water-soluble component can be obtained without using a high-pressure emulsification method or the like. It can be solubilized in an oil-in-water emulsified solvent and can be made a stable and transparent base in a wide temperature range from low temperature to high temperature.

また本発明化粧料は、優れた耐塩性を有し、系中に塩類を配合した場合であっても、同時配合する他成分によって系の安定性が左右されることがない。塩類は水溶性、油溶性のいずれも用いることができる。これら塩類としては、有機酸塩、アミノ酸塩、無機塩などが挙げられる。有機酸塩としては、クエン酸、乳酸、シュウ酸、スルホン酸等の塩酸塩、金属塩(ナトリウム塩、カリウム塩)、アミン塩などが例示される。アミノ酸塩としては、グリシン、アラニン、プロリン、リジン、アスパラギン酸、グルタミン酸等の塩酸塩、金属塩(ナトリウム塩、カリウム塩)、アミン塩などが例示される。無機塩としては、ナトリウム、カリウム、マグネシウム、カルシウム等の炭酸塩、リン酸塩、硝酸塩、ホウ酸塩、硫酸塩、亜硫酸塩、ハロゲン化合物(塩化ナトリウム、塩化カリウム等)等が挙げられる。   The cosmetic of the present invention has excellent salt resistance, and even when a salt is blended in the system, the stability of the system is not affected by other components blended at the same time. As the salts, either water-soluble or oil-soluble can be used. Examples of these salts include organic acid salts, amino acid salts, and inorganic salts. Examples of the organic acid salt include hydrochlorides such as citric acid, lactic acid, oxalic acid and sulfonic acid, metal salts (sodium salt, potassium salt), amine salts and the like. Examples of amino acid salts include hydrochlorides such as glycine, alanine, proline, lysine, aspartic acid, and glutamic acid, metal salts (sodium salt, potassium salt), amine salts, and the like. Examples of inorganic salts include carbonates such as sodium, potassium, magnesium, and calcium, phosphates, nitrates, borates, sulfates, sulfites, and halogen compounds (such as sodium chloride and potassium chloride).

なお塩類として、塩型薬剤も含まれる。塩型薬剤として、例えば、L−アスコルビン酸およびその誘導体の塩、トラネキサム酸およびその誘導体の塩、アルコキシサリチル酸(例えば、3−メトキシサリチル酸、3−エトキシサリチル酸、4−メトキシサリチル酸、4−エトキシサリチル酸、4−プロポキシサリチル酸、4−イソプロポキシサリチル酸、4−ブトキシサリチル酸、5−メトキシサリチル酸、5−エトキシサリチル酸、5−プロポキシサリチル酸など)およびその誘導体の塩、グルタチオンおよびその誘導体の塩などが挙げられる。塩としては、例えば、ナトリウム塩、カリウム塩、カルシウム塩のようなアルカリ金属塩またはアルカリ土類金属塩のほか、アンモニウム塩、アミノ酸塩等の塩が挙げられる。   As salts, salt-type drugs are also included. Examples of the salt-type drug include salts of L-ascorbic acid and its derivatives, salts of tranexamic acid and its derivatives, alkoxysalicylic acids (for example, 3-methoxysalicylic acid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylic acid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid, 4-butoxysalicylic acid, 5-methoxysalicylic acid, 5-ethoxysalicylic acid, 5-propoxysalicylic acid, and the like, and salts of glutathione and its derivatives. Examples of the salt include alkali metal salts or alkaline earth metal salts such as sodium salt, potassium salt, and calcium salt, and salts such as ammonium salt and amino acid salt.

L−アスコルビン酸誘導体としては、例えば、L−アスコルビン酸モノステアレート、L−アスコルビン酸モノパルミテート、L−アスコルビン酸モノリン酸エステル、L−アスコルビン酸−2−硫酸エステル、L−アスコルビン酸ジステアレート、L−アスコルビン酸ジパルミテート、L−アスコルビン酸トリステアレート、L−アスコルビン酸トリパルミテート、L−アスコルビン酸トリリン酸エステル、L−アスコルビン酸2−グルコシド等が挙げられる。   Examples of L-ascorbic acid derivatives include L-ascorbic acid monostearate, L-ascorbic acid monopalmitate, L-ascorbic acid monophosphate, L-ascorbic acid-2-sulfate, L-ascorbic acid distearate, Examples thereof include L-ascorbic acid dipalmitate, L-ascorbic acid tristearate, L-ascorbic acid tripalmitate, L-ascorbic acid triphosphate, L-ascorbic acid 2-glucoside.

トラネキサム酸誘導体としては、例えば、4−(トランス−アミノメチルシクロヘキサンカルボン酸)−4’−ヒドロキシフェニルエステル、2−(トランス−4−アミノメチルシクロヘキシルカルボニルオキシ)−5−ヒドロキシ安息香酸、トランス−4−アミノメチルシクロヘキサンカルボン酸メチルアミド、トランス−4−(p−メトキシベンゾイル)アミノメチルシクロヘキサンカルボン酸等が挙げられる。   Examples of the tranexamic acid derivative include 4- (trans-aminomethylcyclohexanecarboxylic acid) -4′-hydroxyphenyl ester, 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid, trans-4 -Aminomethylcyclohexanecarboxylic acid methylamide, trans-4- (p-methoxybenzoyl) aminomethylcyclohexanecarboxylic acid, etc. are mentioned.

塩類を配合する場合、化粧料全量中に3質量%程度以下とするのが好ましく、2.5質量%以下程度とするのが好ましい。   When blending salts, the total amount of the cosmetic is preferably about 3% by mass or less, more preferably about 2.5% by mass or less.

なお、本発明化粧料において「透明」とは、透明性の指標であるL値が95以上であるものが好ましい。「L値」は色差計〔例えば、COLOR-EYE 7000A(Gretag Macbeth社製)〕等で測定することができる。L値は100に近いほど透明度が高い。   In the cosmetic of the present invention, “transparent” is preferably one having an L value which is an index of transparency of 95 or more. The “L value” can be measured with a color difference meter [for example, COLOR-EYE 7000A (manufactured by Gretag Macbeth)]. The closer the L value is to 100, the higher the transparency.

また本発明の透明な水中油型乳化化粧料では、乳化粒子径が100nm以下の微粒子径が好ましく、より好ましくは70nm以下である。   In the transparent oil-in-water emulsified cosmetic composition of the present invention, the fine particle diameter is preferably 100 nm or less, more preferably 70 nm or less.

本発明では上記必須成分の他に、冷感・清涼感のより一層の効果向上を目的として冷感剤(清涼剤)を配合することができる。冷感剤(清涼剤)としてはメントール、カンファーが好ましく用いられる。冷感剤(清涼剤)を配合する場合、配合量は化粧料全量に対し0.001〜1.0質量%程度とするのが好ましく、より好ましくは0.01〜0.5質量%である。   In the present invention, in addition to the above essential components, a cooling sensation agent (cooling agent) can be blended for the purpose of further improving the effect of cooling sensation / cooling sensation. Menthol and camphor are preferably used as the cooling sensation agent (cooling agent). When a cooling sensation agent (cooling agent) is blended, the blending amount is preferably about 0.001 to 1.0% by mass, more preferably 0.01 to 0.5% by mass with respect to the total amount of the cosmetic. .

本発明化粧料の製造は、従来のように高圧乳化等の手段を必要とせず、混合、撹拌等の手段で製造することができる。例えば、(A)〜(D)成分を加熱混合し、70℃程度の温度で溶解させる(油相)。次いでこの油相に、(E)成分および(F)成分の一部からなる混合水相を添加、撹拌した後、(F)成分の残部(他に水系成分が配合されている場合、それら水系成分も併せて)を添加混合することによって製造することができる。なお(D)成分を上記油相、上記混合水相とにそれぞれ取り分けて使用してもよい。   Production of the cosmetic of the present invention does not require means such as high-pressure emulsification as in the prior art, and can be produced by means such as mixing and stirring. For example, the components (A) to (D) are heated and mixed and dissolved at a temperature of about 70 ° C. (oil phase). Next, after adding the mixed aqueous phase consisting of a part of the (E) component and the (F) component to this oil phase and stirring, the remainder of the (F) component (if other aqueous components are blended, these aqueous systems It can be produced by adding and mixing the components). The component (D) may be used separately for the oil phase and the mixed aqueous phase.

なお(E)成分と(F)成分からなる上記混合水相における両成分の配合比(質量比)は、乳化のしやすさ等の点から、(E)成分:(F)成分=5:5〜8:2が好ましく、より好ましくは5:5〜7:3である。(E)成分に(F)成分を添加した混合水相を用いることで、微小乳化粒子径を調製しやすくなる。(E)成分と(F)成分からなる混合水相に代えて、(E)成分のみを添加した後に(F)成分(全量)を添加すると、微細な乳化粒子が得られない。   In addition, the blending ratio (mass ratio) of both components in the mixed aqueous phase composed of the (E) component and the (F) component is as follows: (E) component: (F) component = 5: 5-8: 2 is preferable, More preferably, it is 5: 5-7: 3. By using the mixed aqueous phase obtained by adding the component (F) to the component (E), it becomes easy to prepare a fine emulsified particle size. If the component (F) (total amount) is added after adding only the component (E) instead of the mixed aqueous phase composed of the component (E) and the component (F), fine emulsified particles cannot be obtained.

本発明の化粧料には、本発明の効果を損なわない範囲で、上記成分のほかに、通常化粧料に基剤として配合される保湿剤、油分(個体油脂、ロウ類等)、粉末成分、水溶性高分子(天然、半合成、合成)、増粘剤、紫外線吸収剤、金属イオン封鎖剤、糖類(単糖、オリゴ糖、多糖)、有機アミン、pH調整剤、ビタミン類、酸化防止剤、酸化防止助剤、その他の配合可能成分等を、必要に応じて適宜配合することができる。ただしこれら例示に限定されるものでない。   In the cosmetics of the present invention, in addition to the above components, a moisturizing agent, oil (solid fats, waxes, etc.), powder components, Water-soluble polymers (natural, semi-synthetic, synthetic), thickeners, UV absorbers, sequestering agents, saccharides (monosaccharides, oligosaccharides, polysaccharides), organic amines, pH adjusters, vitamins, antioxidants Antioxidant assistants, other components that can be blended, and the like can be blended as necessary. However, it is not limited to these examples.

本発明の化粧料の剤型は、皮膚に適用可能であれば特に限定されるものでないが、化粧水、ローション、シート状基剤に含浸させる含浸液等が挙げられる。   The cosmetic dosage form of the present invention is not particularly limited as long as it can be applied to the skin, and examples thereof include skin lotion, lotion, and an impregnating liquid to be impregnated into a sheet-like base.

以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれによってなんら限定されるものではない。配合量は特記しない限りすべて質量%である。   Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. Unless otherwise specified, all the amounts are mass%.

[平均粒子径]
乳化滴の平均粒子径はゼータサイザーNanoZS(sysmex社製)を用い、試料を希釈することなくそのまま測定した。
[Average particle size]
The average particle size of the emulsified droplets was measured as it was without diluting the sample using a Zetasizer NanoZS (manufactured by sysmex).

[L値(透明性)]
調製直後の試料を、COLOR-EYE 7000A(Gretag Macbeth社製)を用いて測定し、コントロールとして蒸留水の透明度を100としてL値を算出した。
[L value (transparency)]
The sample immediately after the preparation was measured using COLOR-EYE 7000A (manufactured by Gretag Macbeth), and the L value was calculated with transparency of distilled water as 100 as a control.

[保存安定性(L値変化)]
試料を−10℃〜50℃において1カ月間放置した後のL値を測定し、製造直後のL値との差を求め、下記評価基準により評価した。
(評価基準)
○:L値変化が±2以内
△:L値変化が±2超〜±5
×:L値変化が±5超
[Storage stability (L value change)]
The L value after the sample was left at -10 ° C to 50 ° C for 1 month was measured, the difference from the L value immediately after production was determined, and evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: L value change is within ± 2 Δ: L value change is more than ± 2 to ± 5
×: L value change exceeds ± 5

(比較例1〜7、実施例1〜4)
下記表1に示す試料を調製した。これら試料を用いて上記評価方法により平均乳化粒子径、L値(透明性)、保存安定性(L値変化)を評価した。結果を表1に示す。
(製法)
1.(1)(ただし一部を取り分けた残部)〜(4)を室温下で混合し、溶解させた(水相)。
2.(5)〜(13)を加熱混合し、70℃で溶解させた(油相)。
3.(14)〜(15)と、(1)(一部)を混合溶解させ、これを上記油相に添加し、成り行き温度で約40℃以下とした(混合相)。
4.上記混合相を十分撹拌させた後、これを上記水相に添加混合して試料を調製した。
(Comparative Examples 1-7, Examples 1-4)
Samples shown in Table 1 below were prepared. Using these samples, the average emulsified particle size, L value (transparency), and storage stability (change in L value) were evaluated by the above evaluation methods. The results are shown in Table 1.
(Manufacturing method)
1. (1) (however, the remaining part) to (4) were mixed and dissolved at room temperature (aqueous phase).
2. (5) to (13) were heated and mixed and dissolved at 70 ° C. (oil phase).
3. (14) to (15) and (1) (part) were mixed and dissolved, and this was added to the oil phase so that the temperature was about 40 ° C. or less (mixed phase).
4). After the mixed phase was sufficiently stirred, this was added to and mixed with the aqueous phase to prepare a sample.

Figure 0005360847
Figure 0005360847

表1に示す結果から明らかなように、本発明の1以上の構成成分の配合を欠く場合、塩類を配合しない系ではほぼ保存安定性(L値変化)が得られたのに対し、塩類を配合した系では保存安定性(L値変化)を十分に得ることができなかった(比較例1、2〜7)。なお比較例4では平均粒子径が大きく、透明性も得られなかったことから、保存安定性評価は行わなかった。比較例5、7の「平均粒子径」欄の「−(*)」は粒子径の測定は不可能であった(ピークが2つ以上あるため。径1000nm以上のものも存在していると推測された)ことを示す。比較例6の「平均粒子径」欄の「−(**)」は油分が乳化されず、(A)成分の粉末が浮いた状態であった。したがって比較例5〜7についても保存安定性評価は行わなかった。 As is apparent from the results shown in Table 1, when one or more constituents of the present invention are not blended, almost no storage stability (L value change) was obtained in the system not blended with salts, whereas In the blended system, sufficient storage stability (L value change) could not be obtained (Comparative Examples 1, 2 to 7). In Comparative Example 4, since the average particle size was large and transparency was not obtained, storage stability evaluation was not performed. Comparative Example 5 and 7 of the "average particle size" column "- (*)" is when the (peak was impossible the measurement of particle size is also present ones there for more than diameter 1000 nm 2 or more. Inferred). “- (**) ” in the “average particle diameter” column of Comparative Example 6 was a state where the oil was not emulsified and the powder of component (A) was floating. Therefore, the storage stability evaluation was not performed for Comparative Examples 5 to 7.

これに対し、本発明の(A)〜(E)成分を含む実施例1〜4では、塩類を含む系であっても、透明性およびその保存安定性に優れ、平均乳化粒子径も微細なものであった。   On the other hand, in Examples 1 to 4 containing the components (A) to (E) of the present invention, even a system containing salts is excellent in transparency and storage stability and has a fine average emulsion particle size. It was a thing.

(実施例5〜10、比較例8)
下記表2に示す試料を調製した。これら試料を用いて上記評価方法により平均乳化粒子径、L値(透明性)、保存安定性(L値変化)を評価した。結果を表2に示す。
(製法)
1.(1)(ただし一部を取り分けた残部)〜(7)を室温下で混合し、溶解させた(水相)。
2.(8)〜(12)を加熱混合し、70℃で溶解させた(油相)。
3.(13)〜(14)と、(1)(一部)を混合溶解させ、これを上記油相に添加し、成り行き温度で約40℃以下とした(混合相)。
4.上記混合相を十分撹拌させた後、これを上記水相に添加混合して試料を調製した。
(Examples 5 to 10, Comparative Example 8)
Samples shown in Table 2 below were prepared. Using these samples, the average emulsified particle size, L value (transparency), and storage stability (change in L value) were evaluated by the above evaluation methods. The results are shown in Table 2.
(Manufacturing method)
1. (1) (however, the remaining part) to (7) were mixed and dissolved at room temperature (aqueous phase).
2. (8) to (12) were heated and mixed and dissolved at 70 ° C. (oil phase).
3. (13) to (14) and (1) (a part) were mixed and dissolved, and this was added to the oil phase so that the temperature was about 40 ° C. or less (mixed phase).
4). After the mixed phase was sufficiently stirred, this was added to and mixed with the aqueous phase to prepare a sample.

Figure 0005360847
Figure 0005360847

表2に示す結果から明らかなように、[(C)成分/(A)成分+(B)成分](質量比)が0.60を超えた比較例8では透明性が得られず、粒子径も大きく、本発明効果が得られなかったのに対し、上記比率が0.60以下の実施例5〜10では本発明効果を得ることができた。   As is clear from the results shown in Table 2, in [Comparative Example 8] in which [(C) component / (A) component + (B) component] (mass ratio) exceeded 0.60, transparency was not obtained, and the particles Although the diameter was large and the effect of the present invention was not obtained, the effects of the present invention could be obtained in Examples 5 to 10 in which the ratio was 0.60 or less.

(実施例11〜14)
下記表3に示す試料を調製した。これら試料を用いて上記評価方法により平均乳化粒子径、L値(透明性)、保存安定性(L値変化)を評価した。結果を表3に示す。
(製法)
1.(1)(ただし一部を取り分けた残部)〜(8)を室温下で混合し、溶解させた(水相)。
2.(9)〜(13)を加熱混合し、70℃で溶解させた(油相)。
3.(14)〜(15)と、(1)(一部)を混合溶解させ、これを上記油相に添加し、成り行き温度で約40℃以下とした(混合相)。
4.上記混合相を十分撹拌させた後、これを上記水相に添加混合して試料を調製した。
(Examples 11-14)
Samples shown in Table 3 below were prepared. Using these samples, the average emulsified particle size, L value (transparency), and storage stability (change in L value) were evaluated by the above evaluation methods. The results are shown in Table 3.
(Manufacturing method)
1. (1) (however, the remaining part) to (8) were mixed and dissolved at room temperature (aqueous phase).
2. (9) to (13) were heated and mixed and dissolved at 70 ° C. (oil phase).
3. (14) to (15) and (1) (part) were mixed and dissolved, and this was added to the oil phase so that the temperature was about 40 ° C. or less (mixed phase).
4). After the mixed phase was sufficiently stirred, this was added to and mixed with the aqueous phase to prepare a sample.

Figure 0005360847
Figure 0005360847

表3では塩類配合量を変動(1.59質量%まで増加)させた結果を示す。本発明の構成要件を満たす実施例11〜14では、塩類を配合した系においても、いずれも微細な粒子径、L値が得られ、L値の保存安定性に優れた結果が得られた。 Table 3 shows the results of varying the salt blending amount (increase to 1.59 % by mass). In Examples 11 to 14 that satisfy the constituent requirements of the present invention, a fine particle size and L value were obtained even in a system in which salts were blended, and results excellent in storage stability of the L value were obtained.

(実施例15〜18)
下記表4に示す試料を調製した。これら試料を用いて上記評価方法により平均乳化粒子径、L値(透明性)、保存安定性(L値変化)を評価した。結果を表4に示す。
(製法)
1.(1)〜(7)(ただし(1)および(5)は、それぞれ一部を取り分けた残部)を室温下で混合し、溶解させた(水相)。
2.(8)〜(12)を加熱混合し、70℃で溶解させた(油相)。
3.(13)と、(1)(一部)および(5)(一部)を混合溶解させ、これを上記油相に添加し、成り行き温度で約40℃以下とした(混合相)。
4.上記混合相を十分撹拌させた後、これを上記水相に添加混合して試料を調製した。
(Examples 15 to 18)
Samples shown in Table 4 below were prepared. Using these samples, the average emulsified particle size, L value (transparency), and storage stability (change in L value) were evaluated by the above evaluation methods. The results are shown in Table 4.
(Manufacturing method)
1. (1) to (7) (wherein (1) and (5) are the remainders obtained by separating a part of each) were mixed and dissolved at room temperature (aqueous phase).
2. (8) to (12) were heated and mixed and dissolved at 70 ° C. (oil phase).
3. (13), (1) (part) and (5) (part) were mixed and dissolved, and this was added to the oil phase, so that the expected temperature was about 40 ° C. or less (mixed phase).
4). After the mixed phase was sufficiently stirred, this was added to and mixed with the aqueous phase to prepare a sample.

Figure 0005360847
Figure 0005360847

表4では(E)成分配合量を変動させた結果を示す。本発明の構成要件を満たす実施例15〜18ではいずれも微細な粒子径、高いL値が得られ、低温〜高温域においてL値の保存安定性に優れた結果が得られた。   Table 4 shows the results of varying the amount of component (E). In Examples 15 to 18 that satisfy the constitutional requirements of the present invention, a fine particle diameter and a high L value were obtained, and results of excellent storage stability of the L value were obtained in the low temperature to high temperature range.

(実施例19〜22)
下記表5に示す試料を調製した。これら試料を用いて上記評価方法により平均乳化粒子径、L値(透明性)、保存安定性(L値変化)を評価した。結果を表5に示す。
(製法)
1.(1)〜(8)(ただし、実施例19では、(1)は一部を取り分けた残部;実施例20〜22では、(1)および(5)は、それぞれ一部を取り分けた残部)を室温下で混合し、溶解させた(水相)。
2.(9)〜(12)、および(5)の一部(実施例20〜22)を加熱混合し、70℃で溶解させた(油相)。
3.(13)〜(14)と、(1)(一部)を混合溶解させ、これを上記油相に添加し、成り行き温度で約40℃以下とした(混合相)。
4.上記混合相を十分撹拌させた後、これを上記水相に添加混合して試料を調製した。
(Examples 19 to 22)
Samples shown in Table 5 below were prepared. Using these samples, the average emulsified particle size, L value (transparency), and storage stability (change in L value) were evaluated by the above evaluation methods. The results are shown in Table 5.
(Manufacturing method)
1. (1) to (8) (however, in Example 19, (1) is the remaining part of which is separated; in Examples 20 to 22, (1) and (5) are the remaining parts of which are respectively separated) Were mixed and dissolved at room temperature (aqueous phase).
2. A part of (9) to (12) and (5) (Examples 20 to 22) was mixed by heating and dissolved at 70 ° C. (oil phase).
3. (13) to (14) and (1) (a part) were mixed and dissolved, and this was added to the oil phase so that the temperature was about 40 ° C. or less (mixed phase).
4). After the mixed phase was sufficiently stirred, this was added to and mixed with the aqueous phase to prepare a sample.

Figure 0005360847
Figure 0005360847

表5では(D)成分配合量を変動させた結果を示す。本発明の構成要件を満たす実施例19〜22ではいずれも微細な粒子径、高いL値が得られ、低温〜高温域においてL値の保存安定性に優れた結果が得られた。   Table 5 shows the results of varying the amount of component (D). In Examples 19 to 22 that satisfy the constituent requirements of the present invention, a fine particle size and a high L value were obtained, and the results of excellent storage stability of the L value were obtained in the low temperature to high temperature range.

以下にさらに実施例を示す。   Further examples are shown below.

(実施例23:透明化粧水)
(配 合 成 分) (質量%)
(1)精製水[(F)成分] 残余
(2)EDTA−2Na・2H2O 0.02
(3)クエン酸 0.02
(4)クエン酸ナトリウム 0.08
(5)グリセリン 1.0
(6)ジプロピレングリコール 1.0
(7)ブチレングリコール 4.0
(8)ポリエチレングリコール1500 0.5
(9)グリチルリチン酸ジカリウム 0.05
(10)キシリトール 3.0
(11)フェノキシエタノール 0.35
(12)イソステアリルアルコール[(C)成分] 0.1
(13)流動パラフィン[(C)成分] 0.05
(14)塩化ジステアリルジメチルアンモニウム[(A)成分] 0.2
(15)POE(30)フィトステロール[(B)成分] 0.6
(16)POE(14)POP(7)ジメチルエーテル[(D)成分] 2.0
(17)エタノール[(E)成分] 8.0
(18)メントール 0.1
<製造方法>
1:(1)〜(11)、(16)、(17)(ただし、(1)、(16)、(17)は、それぞれ一部を取り分けた残部)を室温下で混合し、溶解させた。
2:(12)〜(15)と、(16)(一部)を70℃で溶解混合させた。
3:(1)(一部)と(17)(一部)、(18)を混合溶解させ、2に添加した。
4:上記3.を十分攪拌させた後、1.と混合させた。
(Example 23: Transparent lotion)
(Mixed component) (mass%)
(1) Purified water [component (F)] Residue (2) EDTA-2Na · 2H 2 O 0.02
(3) Citric acid 0.02
(4) Sodium citrate 0.08
(5) Glycerin 1.0
(6) Dipropylene glycol 1.0
(7) Butylene glycol 4.0
(8) Polyethylene glycol 1500 0.5
(9) Dipotassium glycyrrhizinate 0.05
(10) Xylitol 3.0
(11) Phenoxyethanol 0.35
(12) Isostearyl alcohol [component (C)] 0.1
(13) Liquid paraffin [component (C)] 0.05
(14) Distearyldimethylammonium chloride [component (A)] 0.2
(15) POE (30) phytosterol [component (B)] 0.6
(16) POE (14) POP (7) Dimethyl ether [component (D)] 2.0
(17) Ethanol [component (E)] 8.0
(18) Menthol 0.1
<Manufacturing method>
1: (1) to (11), (16), (17) (however, (1), (16), (17) is the remaining part of each part) are mixed and dissolved at room temperature. It was.
2: (12) to (15) and (16) (part) were dissolved and mixed at 70 ° C.
3: (1) (Part), (17) (Part), and (18) were mixed and dissolved and added to 2.
4: Above 3. After sufficiently stirring, 1. And mixed.

得られた化粧水は乳化粒子が31nmであり、L値が97であった。   The obtained lotion had emulsified particles of 31 nm and an L value of 97.

本発明により、ジ長鎖型カチオン界面活性剤を配合した系を、低温〜高温の幅広い温度域に亘り安定して透明性を維持することができ、しかも高圧乳化等の方法によらずに混合撹拌等の手段で簡便に製造することができ、耐塩性に優れる水中油型乳化化粧料が提供される。   According to the present invention, a system containing a di-long-chain cationic surfactant can be stably maintained over a wide temperature range from low temperature to high temperature, and mixed without depending on a method such as high pressure emulsification. An oil-in-water emulsified cosmetic that can be easily produced by means such as stirring and has excellent salt resistance is provided.

Claims (4)

(A)下記式(II)および/または(III)で示されるジ長鎖型カチオン界面活性剤を0.01〜1質量%、
(B)HLB10〜18のステロール骨格を有する非イオン界面活性剤を0.01〜2質量%、
(C)常温(25℃)で液状の油分を0.01〜1質量%、
(D)下記式(I)で示されるアルキレンオキシド誘導体を0.1〜10質量%、
(E)炭素原子数1〜3の一価の低級アルコールを0.1〜20質量%、および
(F)水
を含有し、(C)成分の配合量が、(A)成分と(B)成分の合計量に対し0.60以下(質量比)である、透明な水中油型乳化化粧料。
<式(II)>:
Figure 0005360847
〔式(II)中、R 3 COは、それぞれ独立に、炭素原子数が12〜22で、二重結合を0〜3個有する脂肪族アシル基を表し;pは1〜3の整数を表し;R 4 はメチル基、または基−(CH 2 p −OH(但し、pは上記で定義したとおり)を表し;Xはハロゲン原子、メトサルフェート、またはメトホスフェートを表す。〕
<式(III)>:
Figure 0005360847
〔式(III)中、R 5 は、それぞれ独立に、炭素原子数が12〜22で、二重結合を0〜3個有するアルキル基を表し;R 6 は、それぞれ独立に、炭素原子数が1〜3で、二重結合をもたないアルキル基を表し;Yはハロゲン原子、メトサルフェート、またはメトホスフェートを表す。〕
<式(I)>:
1O−[(AO)a(EO)b]−R2 (I)
〔式(I)中、AOは炭素原子数3〜4のオキシアルキレン基、EOはオキシエチレン基を示し;a、bはそれぞれ前記AO、EOの平均付加モル数で、1≦a≦70、1≦b≦70であり;AOとEOの合計に対するEOの割合[EO/(AO+EO)]は20〜80質量%である。R1、R2は、それぞれ独立に、炭素原子数1〜4のアルキル基を示す。〕
(A) 0.01-1% by mass of a di-long-chain cationic surfactant represented by the following formula (II) and / or (III) ,
(B) 0.01-2% by mass of a nonionic surfactant having a sterol skeleton of HLB 10-18,
(C) 0.01 to 1% by mass of liquid oil at room temperature (25 ° C.),
(D) 0.1 to 10% by mass of an alkylene oxide derivative represented by the following formula (I),
(E) 0.1 to 20% by mass of a monovalent lower alcohol having 1 to 3 carbon atoms, and (F) containing water, and the blending amount of (C) component is (A) component and (B) A transparent oil-in-water emulsified cosmetic that is 0.60 or less (mass ratio) with respect to the total amount of components.
<Formula (II)>:
Figure 0005360847
[In the formula (II), R 3 CO independently represents an aliphatic acyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; p represents an integer of 1 to 3; R 4 represents a methyl group or a group — (CH 2 ) p —OH (where p is as defined above); X represents a halogen atom, methosulfate, or methophosphate. ]
<Formula (III)>:
Figure 0005360847
[In the formula (III), R 5 independently represents an alkyl group having 12 to 22 carbon atoms and 0 to 3 double bonds; R 6 each independently represents a carbon atom number ; 1 to 3 represents an alkyl group having no double bond; Y represents a halogen atom, methosulfate, or methophosphate. ]
<Formula (I)>:
R 1 O — [(AO) a (EO) b ] —R 2 (I)
[In the formula (I), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group; a and b are average addition moles of AO and EO, respectively, 1 ≦ a ≦ 70, 1 ≦ b ≦ 70; the ratio of EO to the total of AO and EO [EO / (AO + EO)] is 20 to 80% by mass. R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms. ]
L値が95以上である、請求項1記載の水中油型乳化化粧料。 L value is 95 or more, claim 1 Symbol placement of the oil-in-water emulsion cosmetic. 乳化粒子径が100nm以下である、請求項1または2記載の水中油型乳化化粧料。 The oil-in-water emulsified cosmetic according to claim 1 or 2 , wherein the emulsified particle diameter is 100 nm or less. メントールおよび/またはカンファーをさらに含有する、請求項1〜のいずれか1項に記載の水中油型乳化化粧料。 The oil-in-water emulsified cosmetic according to any one of claims 1 to 3 , further comprising menthol and / or camphor.
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