JP4429053B2 - Oily cleaning agent - Google Patents

Description

  The present invention relates to an oil-based detergent, and more particularly to an oil-based detergent having an excellent makeup-removing effect and a feeling of use that does not become cloudy or thicken even when mixed with moisture and does not irritate the mucous membrane such as the eyes. .

Makeup cleansing compositions can be broadly classified into aqueous cleansing and oil cleansing. Aqueous cleansing includes a lotion type comprising a surfactant ethanol aqueous solution, and an aqueous gel type obtained by thickening the surfactant with a polymer. It has been. As oil-based cleansing, there are known a cream type in which an O / W emulsion is phase-shifted by massage and exhibits a cleaning function, an oil type composed of a surfactant oil solution, and the like.
Of these, the oil type is known to have a high cleaning effect. In recent years, makeup directivity has become mainstream in types that prevent secondary adhesion such as foundation and lipstick, and types that contain high molecular weight silicone such as mascara. Is growing.

  The oil-type cleansing composition is composed of a nonionic surfactant, an oil component, and a small amount of water, and the surfactant forms a reverse micelle oil solution in which an aggregate is formed with hydrophilic groups inside in the oil. Water is solubilized in the vicinity of the gathering of the hydrophilic groups to form one phase, and is completely transparent.

The oil type has a limit in its ability to take up water completely, so-called solubilization, because of its microstructure. When water is mixed beyond the solubilized amount, it becomes a coexistence state (two-phase state) with other phases, and thus becomes a white and turbid state as a whole due to the difference in refractive index between the two phases. Depending on the type of coexisting phase, the cleaning performance desired as a cleaning agent cannot be exhibited, or the user is strongly impressed with a decrease in cleansing performance, which is not desirable.
In addition, when water exceeds the solubilized amount, the composition thickens, it cannot be applied smoothly, it is difficult to blend in with make-up, and good massage properties cannot be exhibited. there were.

  From this point, when using an oil-based cleansing material, it can not be used with wet hands, it cannot be used on wet faces after washing in the bathroom, which has been a limitation in use. .

  On the other hand, Patent Document 1 describes a cleansing material that easily blends with makeup even when the skin is wet by using a polyglycerin fatty acid ester of HLB 10 or higher and a trihydric or higher polyhydric alcohol in combination. However, this method cannot prevent white turbidity of the appearance, and since the composition thickens, it is difficult to blend in with make-up and the massage property may not be sufficient.

  Further, Patent Document 2 and Patent Document 3 include cleansing materials having high detergency even in hands wet with water by a combination of a nonionic surfactant and an amphoteric surfactant and a combination of a nonionic surfactant and a glyceryl ether derivative. Although described, it is not sufficient to prevent massage and white turbidity of the appearance, and there has been a problem of irritation to mucous membranes such as eyes.

JP 2000-327529 A JP-A-6-16524 Japanese Patent Laid-Open No. 2001-270809

  The present invention has been made in response to the above-described conventional circumstances, and even when water is mixed during use, it may become cloudy, increase in viscosity, become heavy, and become unfamiliar. It is an object of the present invention to provide a liquid oil-based cleaning agent that does not cause deterioration in massage performance, has a good makeup removal effect, and does not irritate the mucous membrane such as the eyes.

  Under such circumstances, the present inventors have conducted intensive research to solve the above problems, and as a result, liquid oil, a specific nonionic surfactant, a higher fatty acid and / or a higher alcohol, and a polyoxypropylene group in the molecule. The present invention was completed by finding that an oil-based cleaning material combined with a compound having an organic solvent can solve the above problems.

That is, the present invention
(A) 50 to 95% by mass of liquid oil,
(B) a nonionic surfactant having an alkyl chain with 14 or more carbon atoms and an HLB of 9 or more and 16 or less,
(C) higher fatty acids and / or higher alcohols;
(D) An oil-based cleaning agent comprising a compound having a polyoxypropylene group having 5 to 35 added moles in the molecule.

  In the present invention, the compound (d) having a polyoxypropylene (POP) group in the molecule includes POP sorbit, POP diglycerin, POP glycerin, POP butyl ether, or POP · POE (polyoxyethylene) random copolymer. It is preferable that it is 1 type or 2 types or more selected, and it is especially preferable that it is a POP sorbit.

  Moreover, the blending amount of the nonionic surfactant having (b) the alkyl chain with 14 or more carbon atoms, HLB of 9 or more and 16 or less with respect to the total amount of the cleaning agent is 5 to 40% by mass, and (c) the higher grade The compounding amount of fatty acid and / or higher alcohol is 1 to 10% by mass, and the compounding amount of the compound (d) having a polyoxypropylene group having 3 to 35 added moles in the molecule is 1 to 10% by mass. Is preferred.

  Furthermore, the (c) higher fatty acid and / or higher alcohol is preferably a branched higher fatty acid or higher alcohol.

  According to the present invention, even when water is mixed in, high cleaning performance is maintained, there is no white turbidity or thickening on the appearance, no deterioration in massage performance is caused, an excellent feeling of use, and irritation to the eyes An oil-based cleaning agent with a small amount of oil

The best mode of the present invention will be described below.
(A) Liquid oil The liquid oil used in the present invention is not limited as long as it is a liquid oil usually used in cosmetics, and any oil can be used.
Specifically, hydrocarbon oils such as liquid paraffin, squalane, olefin oligomer, light isoparaffin, 2-ethylhexanoic acid triglyceride, 2-ethylhexanoic acid cetyl, 2-ethylhexanoic acid pentaerythritol, 2-ethylhexanoic acid trimethylol Ester oil such as propane, 2-ethylhexyl palmitate, isocetyl isononanoate, isopropyl myristate, cetyl octanoate, tripropylene dineopentanoate polyglycol, jojoba oil, olive oil, macadamia nut oil, cottonseed oil, teaseed oil, safflower oil, rice bran Examples include natural vegetable oils such as oil, silicone oils such as decamethylpentacyclosiloxane, octamethyltetracyclosiloxane, dimethylsiloxane, and methylphenylsiloxane. Or the application of two or more. Preferred liquid oils include liquid paraffin, cetyl 2-ethylhexanoate, decamethylpentasiloxane, and the like.

  The blending amount of the liquid oil is 50 to 95% by mass, preferably 60 to 80% by mass with respect to the entire oil-based cleaning material. When the blending amount of the liquid oil is less than 50% by mass, it is difficult to obtain a sufficient cleaning effect, and when it exceeds 95% by mass, the water washability is impaired.

(B) Nonionic surfactant having an alkyl chain with 14 or more carbon atoms and an HLB of 9 or more and 16 or less Nonionic surfactant used in the present invention with an alkyl chain having 14 or more carbon atoms and an HLB of 9 or more and 16 or less The surfactant is not particularly limited as long as it is usually used in cosmetics, and any surfactant can be used.
For example, POE (10) oleyl ether (HLB = 10), POE (10) hexadecyl ether (HLB = 10), POE (40) glyceryl isostearate (HLB = 17), POE (20) glyceryl isostearate ( HLB = 14), POE (8) glyceryl isostearate (HLB = 9), POE (40) glyceryl triisostearate (HLB = 11), POE (30) glyceryl trioleate (HLB = 10), POE (10 ) Monoisostearate (HLB = 12), POE (30) hydrogenated castor oil (HLB = 11), POE (50) hydrogenated castor oil monoisostearate (HLB = 12), POE (60) hydrogenated castor oil triiso Stearate (HLB = 10), sorbitan monoisostearate (HLB = 9) There is exemplified, in particular POE (8) glyceryl isostearate are preferred.

  When surfactants having 13 or less carbon atoms are used, irritation to mucous membranes such as eyes is strong, and it is not preferable to use these in cleansing oils applied especially to the face and the like. Moreover, HLB is 9-16, Preferably, it is 9-14. If HLB is less than 9, it becomes cloudy when mixed with water, and if it exceeds 16, it is difficult to obtain a uniform composition.

  The compounding amount of the above-described nonionic surfactant is 5 to 40% by mass, preferably 20 to 40% by mass, based on the entire oil-based cleaning material. If the amount of the nonionic surfactant is less than 5% by mass, it becomes cloudy when mixed with water, and if it exceeds 40% by mass, the viscosity increases when mixed with water and the spread becomes heavy.

(C) Higher fatty acid and / or higher alcohol As the higher fatty acid used in the present invention, all of the higher fatty acids used in ordinary cosmetic bases can be applied.
Specific examples include higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; 2-palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, ricinoleic acid, Examples thereof include unsaturated fatty acids such as linoleic acid, linoelaidic acid, linolenic acid and arachidonic acid, and branched fatty acids such as isostearic acid.

  Further, examples of higher alcohols include saturated higher alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol; unsaturated higher alcohols such as oleyl alcohol, branched higher alcohols such as octyldodecanol, hexyldecanol, and isostearyl alcohol. Can be mentioned.

  In the present invention, the component (c) is preferably a branched higher fatty acid or higher alcohol from the viewpoint of system stability. In particular, isostearic acid and isostearyl alcohol are preferably used, and isostearic acid is more preferably used.

  The compounding quantity of these higher fatty acids or higher alcohol is 1-10 mass%, Preferably it is 1-5 mass%. When the blending amount is less than 1% by mass, it is difficult to obtain a uniform composition, and when it exceeds 10% by mass, the washing performance is impaired.

(D) Compound having a polyoxypropylene (POP) group having an addition mole number of 5 to 35 in the molecule Examples of the compound having a propylene oxide group used in the present invention include 2-chain polyalkylene glycols and polychains. Type polyalkylene glycols, 2-chain polyoxyalkylene alkyl ethers, poly-chain polyoxyalkylene alkyl ethers, 2-chain polyoxyalkylene esters, poly-chain polyoxyalkylene esters and other polyoxyalkylene groups Examples include those containing POP groups, and polyoxypropylene sorbite is particularly preferable. When the added mole number of polyoxypropylene is 2 or less, or 40 or more, the stability of the system is impaired.
More specifically, POP (20-35) sorbit, POP (5-10) diglycerin, POP (6-20) glycerin, POP (5-35) butyl ether or POP (5-35) · POE (5- 30) Random copolymers may be mentioned, and POP sorbit is particularly preferable.

Here, the POP / POE random copolymer is a compound having a polyoxypropylene (POP) group having an addition mole number of 5 to 35 in the molecule among those represented by the following general formula (1).
_{^{R 1 O - [(PO)}} m (EO) n] -R 2 ‥ (1)

(In the formula, PO is an oxypropylene group, EO is an oxyethylene group, m and n are average addition moles of oxypropylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n. ≦ a 70, percentage of the oxyethylene groups with respect to the total of oxypropylene groups and oxyethylene groups is 20 to 80 wt%. oxypropylene groups and oxyethylene groups are randomly added form .R ¹ and R ² is the same or different hydrocarbon group having 1 to 4 carbon atoms or hydrogen atom, and the ratio of the number of hydrogen atoms to the number of hydrocarbon groups of R ¹ and R ² is 0.15 or less.)
Details of the production method of the POP / POE random copolymer are described in, for example, JP-A No. 2003-113023.

  (D) The compounding quantity of the compound containing a POP group becomes like this. Preferably it is 1-10 mass%, More preferably, it is 1-5 mass%. When the blending amount is less than 1% by mass, the effect of suppressing cloudiness when water is mixed in during use or the increase in viscosity due to increased viscosity cannot be sufficiently exerted, and the blending exceeds 10% by mass. Then, the stability of the system is impaired.

  In addition to the above-mentioned components (a) to (d), which are essential components of the present invention, the oil-based cleaning material of the present invention is usually blended in the cosmetics and pharmaceutical fields within a range not impairing the effects of the present invention. Various ingredients can be blended. For example, vitamin B group, vitamin C and its derivatives, tranexamic acid, pantothenic acid and its derivatives, water-soluble active substances such as vitamins such as bithione, water-soluble polymers such as guar gum, xanthan gum and polyvinyl alcohol, thickeners, In addition to buffering agents such as arginine, aspartic acid, citric acid, tartaric acid and lactic acid, chelating agents such as EDTA, preservatives, etc., UV absorbers, various powders, various dyes and the like can be mentioned.

  The dosage form of the oil-based cleaning agent of the present invention is not particularly limited and can be used as a liquid preparation, a gel preparation, an aerosol preparation, a sheet-impregnated preparation, etc. A formulation is more preferred.

  The oily detergent of the present invention can be used as a skin cleanser in the cosmetics field, quasi-drug field and pharmaceutical field, for example. In particular, it is preferably used as a makeup cleaning agent.

Next, examples of the present invention will be described.
Examples 1-10, Comparative Examples 1-6
The oil-based detergent (cleansing oil) comprising the composition shown in Tables 1 to 3 below is prepared by a conventional method, the stability of the composition, the transparency when mixed with water, the spread on the skin when mixed with water, The result of evaluating eye irritation was shown. In addition, the unit of a compounding quantity is the mass%.

In the table, polyoxyethylene polyoxypropylene dimethyl ether is obtained by randomly adding oxypropylene groups and oxyethylene groups, and was produced by the method described in JP-A No. 2003-113023.
The evaluation methods performed in each example and comparative example are as follows.

(1) Stability evaluation of the composition The stability of the composition was evaluated by placing the test samples of Examples and Comparative Examples in 50 ml transparent glass bottles with screw caps, and 0 ° C, 25 ° C, and 50 ° C temperatures. This was performed by observing the appearance for one month and evaluated according to the following criteria.

(Evaluation criteria)
○: No change in appearance at each temperature.
Δ: A small amount of precipitate was observed at 0 ° C, but when the sample was returned to 25 ° C and left to stand, the precipitate disappeared and returned to a uniform and normal appearance.
X: A precipitate is formed or two layers are separated at any temperature of 0 ° C., 25 ° C., and 50 ° C.

(2) Transparency evaluation at the time of water mixing The state of the sample when the professional evaluation panel used 2 g of the sample of the example and the comparative example with a hand wet with 1.5 g of water was evaluated according to the following criteria.

(Evaluation criteria)
A: Transparent.
○: Translucent.
Δ: Partly cloudy.
X: It becomes cloudy.

(3) Elongation evaluation on the skin when mixed with water The professional evaluation panel applied the sample 2g of the example and the comparative example to the face with a hand wet with 1.5g of water. Evaluation was made according to the following criteria.

(Evaluation criteria)
A: The spread is light and easy to blend with the make-up.
○: Feels slightly light.
(Triangle | delta): The spread is heavy and it is hard to make it blend with makeup.

(4) Evaluation of eye irritation We asked 10 professional panelists who did eye makeup to use without notifying the purpose of the test, asked the presence or absence of irritation to the eye after use, and evaluated according to the following criteria:

(Evaluation criteria)
○: 1 out of 10 people report that there is eye irritation.
Δ: 2 to 3 out of 10 people reported eye irritation.
×: Four or more of 10 persons reported that there was irritation to the eyes.

Next, the formulation example of the oil-based cleaning material by this invention is given.
Example 11
Liquid paraffin 34.4% by mass
2-ethylhexyl palmitate 20
Sorbitan monoisostearate 35
(HLB = 9)
Isostearyl alcohol 5
POP (7) Diglycerin 5
Tocopherol acetate 0.1
Water 0.5

Example 12
Liquid paraffin 32.6% by mass
Olefin oligomer 5
Glyceryl tri-2-ethylhexanoate 20
Methylphenylpolysiloxane 5
POE (10) oleyl ether 30
(HLB = 10)
Isostearic acid 1
POP (15) Glycerin 5
Tocopherol acetate 0.1
Water 0.3
Alcohol 1

Example 13
Olefin oligomer 37.6% by mass
Safflower oil 5
Dineopentanoic acid tripropylene polyglycol 20
POE (30) hydrogenated castor oil (HLB = 11) 30
2-Octyldodecanol 5
Polyoxypropylene (20) butyl ether 1
Dibutylhydroxytoluene 0.1
Water 0.3
Alcohol 1

Example 14
Liquid paraffin 39.5% by mass
Cetyl octoate 20
Cyclomethicone 5
Macadamia nut oil 0.1
POE (20) glyceryl isostearate 8
(HLB = 14)
POE (20) glyceryl triisostearate 20
(HLB = 7)
Isostearic acid 1
Polyoxyprepropylene (25) Sorbit 5
Tocopherol acetate 0.1
Water 0.3
Alcohol 1

Claims (5)

(A) 50 to 80 % by mass of liquid oil,
(B) 5 to 40% by mass of a nonionic surfactant having an alkyl chain with 14 or more carbon atoms and an HLB of 9 or more and 16 or less,
(C) 1 to 10% by mass of higher fatty acid and / or higher alcohol,
(D) 1 to 10% by mass of a compound having a polyoxypropylene (POP) group having an addition mole number of 5 to 35 in the molecule ;
And (d) is one or more selected from POP sorbit, POP diglycerin, POP glycerin, POP butyl ether and POP / POE random copolymer . Said (d) is POP (20-35) sorbit, POP (5-10) diglycerin, POP (6-20) glycerin, POP (5-35) butyl ether or POP (5-35) -POE (5- 30) The oil-based cleaning material according to claim 1, which is one or more selected from random copolymers . The oil-based cleaning material according to claim 2, wherein (d) is POP (20-35) sorbit .   The oil-based cleaning material according to claim 1, wherein the (c) higher fatty acid and / or higher alcohol is a branched higher fatty acid or higher alcohol. The oil-based cleaning material according to claim 1, which is transparent or translucent.