JP2002066297A - Multilayered composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multilayered composition comprising an emulsified layer and other layer to stably form a cloudy emulsified layer in an emulsified state and restoring the original clean multilayered state in a short time when the composition is allowed to stand after the multilayered structure thereof is destructed by shaking. SOLUTION: This multilayered composition comprising the emulsified layer and other layer contains a phosphate diester represented by formula (1) (wherein, R1 and R2 are each independently hydrogen atom or methyl group), an oily component and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a multilayer composition comprising an emulsifying layer and other layers. More specifically, when shaken, the cloudy emulsified layer that has been separated is uniformly dispersed throughout and becomes entirely cloudy, and when it is allowed to stand, the cloudy emulsified layer separates again to form the original multilayer, It relates to a multilayer composition.

[0002]

2. Description of the Related Art In many cases, a multilayer composition comprising two or more layers is composed of an oil layer-aqueous layer or an aqueous layer-powder layer. Each of them becomes uniform emulsion liquid and powder dispersion by shaking, and when they are allowed to stand, the dispersed oil and powder are collected at the upper or lower part to form a multilayer again.

[0003] Of these, in the case of a multilayer composition formed from an oil layer and a water layer, the appearance of both layers is almost transparent, and it is difficult to see at a glance that the composition is a multilayer type. There are problems such as being incorrect or the features of the product being difficult to understand from the appearance. This problem can be solved if at least one layer is an opaque emulsified layer. For this reason, conventionally, there have been attempts to form an emulsified layer by blending a surfactant, but in any case, the emulsified layer is immediately separated into water and oil, and it is difficult to make it stably exist. When the emulsion containing the emulsified layer was shaken and allowed to stand still, it did not return to the original multi-layer containing the emulsified layer or a satisfactory one could not be obtained.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to form an emulsified layer that stably forms a cloudy emulsified layer while maintaining the emulsified state. To provide a multilayer composition composed of layers, and further to provide a multilayer composition that restores the original multilayer shape in a short time when the composition is shaken, the multilayer is broken, and then allowed to stand still. It is in.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the use of a certain phosphoric diester salt as an emulsifying composition-forming agent makes it possible to stabilize the emulsified layer. It is found that a multilayer composition having excellent properties and a clean appearance can be obtained, and when the composition is shaken and allowed to stand, a multilayer composition that separates and restores the original multilayer in a short time can be obtained. The present invention has been completed.

That is, the present invention relates to a multilayer composition comprising an emulsifying layer and another layer, which is represented by the following formula (1):

Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group.) A multilayer composition comprising a phosphate diester salt, an oily component and water. It is.

[0007] The other layer forming the multilayer composition is preferably at least an aqueous layer.

The content of the salt of the phosphoric diester represented by the chemical formula 2 is 0.001 to 1% by weight based on the total amount of the composition.
In this range, the emulsified state of the emulsified layer and the state of separation from other layers are particularly excellent, and the restoration to a multilayered state after shaking is prompt.

It is preferable that the phosphate diester salt represented by Chemical Formula 2 is α-tocopherol-2-L-ascorbic acid phosphate diester salt.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.

The multilayer composition of the present invention is a composition comprising an emulsified cloudy emulsified layer and another layer.
It contains the salt of a phosphoric acid diester represented by these, an oil component, and water.

The phosphoric acid diester salt used in the present invention has the following general formula (1)

Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group). Examples of the phosphoric acid diester salt represented by Chemical Formula 3 include α-tocopherol-2-L-ascorbic acid phosphoric acid diester salt, β-tocopherol-2-L-ascorbic acid phosphoric acid diester salt, and γ-tocopherol-2.
-L-ascorbic acid phosphoric acid diester salt, δ-tocopherol-2-L-ascorbic acid phosphoric acid diester salt, and the like. Of these, α-tocopherol-
2-L-ascorbic acid phosphoric acid diester salt is preferred. Examples of the salt include alkali metal salts such as sodium and potassium, and alkaline earth metal salts such as calcium and magnesium. Of these, alkali metal salts are preferred, and potassium salts are most preferred. In the present invention, one or a combination of two or more of the phosphoric acid diester salts represented by Chemical Formula 3 can be used.

In the present invention, the content of the salt of the phosphoric diester represented by the formula (3) is 0.001 to 0.001 in the total amount of the composition.
A range of 1% by weight is preferred. When the content is in this range, a clean separation state and sufficient stability of the emulsified layer can be obtained, and the speed of restoration into a multilayered structure is fast and sufficient. Also,
The usability of the multilayer composition is also excellent. A more preferable content range of the salt of the phosphoric diester represented by Chemical Formula 3 is 0.005 to 0.5% by weight based on the total amount of the composition.
Most preferably, it is from 0.01 to 0.2% by weight.

As the oily component used in the present invention, any oily component which is usually used in pharmaceuticals, quasi-drugs, cosmetics, toiletries, sundries and the like can be used. These oily components include olive oil, avocado oil, evening primrose oil, jojoba oil, camellia oil, macadamia nut oil, sunflower oil, rapeseed oil, sesame oil, wheat germ oil, castor oil, safflower oil, cottonseed oil, soybean oil, jojoba oil And the like; solid fats and oils such as cacao butter, coconut oil, molle kernel oil, palm oil, hydrogenated oil, molle, and hydrogenated castor oil;
Beeswax, candelilla wax, carnauba wax, lanolin,
Waxes such as jojoba wax; hydrocarbon oils such as squalane, liquid paraffin, polybutene, vaseline, paraffin, microcrystalline wax, polyethylene wax, and ceresin;

Glyceryl tri-2-ethylhexanoate,
Isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate,
Trimethylolpropane tri-2-ethylhexanoate,
Trimethylolpropane triisostearate, pentaerythritol tetraoctanoate, glyceride tri-2-heptylundecanoate, diisobutyl adipate, 2-hexyldecyl sebacate, isopropyl myristate, myristyl myristate, 2-hexyldecyl palmitate, olein Ester oils such as oleyl acid, diisostearyl malate, neopentyl glycol dioctanoate;

Chain silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and diphenylpolysiloxane; cyclic silicone oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexanesiloxane; oleic acid, stearic acid, Behenic acid, 12-hydroxystearic acid, isostearic acid, eicosapentaenoic acid,
Higher fatty acids such as docosahexaenoic acid; higher alcohols such as cetyl alcohol, behenyl alcohol, batyl alcohol, cholesterol, phytosterol, and isostearyl alcohol;

UV absorbers such as octyl paramethoxycinnamate and benzophenone; anti-inflammatory agents such as L-menthol and camphor; vitamins such as vitamin A and tocopherol acetate. These oily components can be used alone or in combination of two or more.

In the present invention, the content of the oily component is preferably 1 to 70% by weight, and more preferably 2 to 40% by weight based on the total amount of the composition.
Is more preferred. Particularly, 5 to 30% by weight is preferable.

The content of water used in the present invention is as follows:
It is preferably from 1 to 99% by weight based on the total amount of the composition, and particularly preferably from 40 to
80% by weight is preferred.

In the multilayer composition according to the present invention, in addition to the above essential components, if necessary, ordinary pharmaceuticals, quasi-drugs, cosmetics, toiletries, miscellaneous goods as long as the effects of the present invention are not impaired. And the like can be added. These components include lower alcohols such as ethanol and isopropyl alcohol, glycerin,
Propylene glycol, dipropylene glycol, 1,
3-butylene glycol, sorbitol, maltitol, polyhydric alcohols such as polyethylene glycol, humectants such as hyaluronic acid, talc, kaolin, titanium oxide, mica titanium, silicic anhydride, powders such as cellulose powder, polyvinylpyrrolidone, carboxy Methylcellulose, water-soluble polymers such as xanthan gum, anionic surfactants, amphoteric surfactants, nonionic surfactants, preservatives, bactericides, ultraviolet absorbers, chelating agents, antioxidants,
Coloring materials such as dyes and pigments;

Other layers of the multi-layer composition comprising an emulsified layer and other layers in the present invention include an aqueous layer, an oil layer, a powder layer, and the like, and those containing an aqueous layer are preferred. In particular, a two-layer composition comprising an emulsified layer and an aqueous layer is preferred from the viewpoint of ease of production. The emulsified layer may be either a water-in-oil type or an oil-in-water type.
In order to produce the multilayer composition of the present invention, a production method based on general emulsification means is used.For example, in an aqueous phase in which a water-soluble component is dissolved, Dissolving the salt of the phosphoric diester represented by Chemical Formula 2,
The oil phase is added to this water phase and emulsified. The multilayer composition of the present invention is characterized in that, by shaking, the cloudy emulsified layer that has been separated is uniformly dispersed throughout and becomes a whole cloudy state, and then left to stand, whereby the cloudy emulsified layer is separated again. To the original multilayer composition.

The multilayer composition of the present invention can be widely applied to pharmaceuticals, quasi-drugs, cosmetics, toiletries, miscellaneous goods and the like.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples. The compounding amount is% by weight. Prior to the description of the embodiment,
The evaluation method used in the present invention will be described.

[Emulsification stability test] A sample was kept at 45 ° C for one month.
Then, the turbidity of the emulsified layer, the state of separation of the oil component, and the like were observed, and evaluated according to the following criteria. ：: No change in the turbidity of the emulsified layer, and no separation of oil was observed. Δ: The emulsified layer was slightly transparent, but no separation of oil was observed. X: The emulsified layer is considerably transparent, but no separation of oil is observed. XX: Separation of oil is observed.

[Measurement of multilayer separation speed] Glass sedimentation tube (capacity 100 ml, outer diameter 30 mm, height 250 mm, 1
100 ml sample)
Put into a constant temperature bath at 30 ° C. and leave until the temperature reaches 30 ° C. When the temperature reached 30 ° C., the sedimentation tube was inverted about 25 times for 1 minute to disperse the content sample well, and then allowed to stand again in a thermostat at 30 ° C. Twenty-four hours after that, the volume of the other layer (the lower aqueous layer in the case of a two-layered aqueous layer) other than the emulsified layer in a state of being separated into multiple layers is measured. The evaluation of the multi-layer separation rate is different depending on the lower layer volume when the equilibrium state is reached, for example, in the case of a two-layer composed of an emulsified layer and an aqueous layer. When the value is half or more of 40 ml or more, it can be determined that the separation speed is sufficiently high, and when the value is about 0 to 10 ml, it is determined that the separation speed is low.

[Transparency Test of Transparent Layer] Glass sedimentation tube (capacity 100 ml, outer diameter 30 mm, height 250 mm, 1
100 ml sample)
And left in a 30 ° C. constant temperature bath for 24 hours to separate into multiple layers. The sedimentation tube was placed in front of a black plate, and the transparency of the transparent layer was observed with the naked eye, and judged based on the following criteria. ：: Complete or almost transparent. Δ: Transparent, but slightly cloudy. X: Cloudy and almost transparent.

[Usability test] About 1 ml of a sample was applied to the face of 10 female panels in their 20s and 30s, and a questionnaire on the feeling of use was taken, and evaluated according to the following criteria. ：: Two or less panelists answered "sticky". Δ: 3 or more and 5 or less panels answered “sticky”. ×: Six or more panels answered “sticky”.

A two-layer composition having the composition shown in Tables 1 and 2 was prepared. That is, in Table 1, glycerin and sodium alginate were added and dissolved in purified water. Next, α-tocopherol-2-L-ethanol was added to ethanol.
Dipotassium ascorbic acid diester phosphate or polyoxyethylene sorbite oleate (polyoxyethylene 40 mol adduct) and a solution in which a preservative was dissolved were mixed. Next, liquid paraffin, pentaerythyl tetraoctanoate, and decamethylcyclopentasiloxane were added and emulsified by vigorous stirring. In addition, about Table 2,
It was prepared according to Table 1. These compositions were subjected to an emulsion stability test, a two-layer separation speed measurement, a transparency test of a lower layer (aqueous layer) after separation, and a usability test. In addition, the prescription was adjusted so that the lower layer volume when the equilibrium state was reached in each experiment was almost the same. In Table 1, the POE of POE40 represents polyoxyethylene, and the numeral 40 represents the number of moles of POE added.

[0029]

[Table 1]

As is evident from Table 1, the two-layer composition of Example 1 emulsified with α-tocopherol-2-L-ascorbic acid dipotassium phosphate diester has good emulsion stability and two-layer separation. It can be seen that the speed is high and the transparency and usability of the aqueous layer are excellent.

On the other hand, the multilayer composition of Comparative Example 1 emulsified using polyoxyethylene sorbite oleate (POE40), which is a general emulsifier, has emulsion stability, two-layer separation speed, transparency of an aqueous layer, It can be seen that all of them are inferior in sex.

[0032]

[Table 2]

As is clear from Table 2, when the amount of disodium α-tocopherol-2-L-ascorbic acid disodium phosphate is 3% by weight, the two-layer separation speed is slightly lowered, and the transparency and use of the aqueous layer are reduced. Sex becomes slightly worse.

(Example 6) An oil-in-water type two-layer cosmetic having the following composition was prepared. [Formulation] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.2 dipotassium diphosphate phosphate (2) squalane 2 (3) glyceryl tri-2-ethylhexanoate 10 (4) octa Methylcyclotetrasiloxane 5 (5) dimethylpolysiloxane 5 (6) citric acid 0.1 (7) sodium citrate 0.3 (8) L-ascorbic acid-2-glucoside 1 (9) methylcellulose 0.1 (10 ) Sodium carboxymethylcellulose 0.3 (11) Ethanol 10 (12) Preservative appropriate amount (13) Caustic potassium appropriate amount (14) Flavor appropriate amount (15) Purified water residue

[Production method] After (9) and (10) are dissolved in (15) with stirring, (6), (7), (8) and (13) are added and dissolved. Next, (1), (12) and (14) dissolved in (11) are mixed. Next, (2), (3), (4), and (5) are added, and emulsification is performed by vigorous stirring. Good emulsion stability,
An oil-in-water two-layer cosmetic having an emulsified layer having a high two-layer separation speed, good usability and excellent transparency of the aqueous layer was obtained.

Hereinafter, according to the manufacturing method of the sixth embodiment, the seventh embodiment
-A multilayer composition comprising the composition of Example 16 was prepared.
Both have good emulsion stability, high multilayer separation speed, good usability, and transparency of the transparent layer is a good multilayer composition.
Application to cosmetics, etc. was possible.

(Example 7) [Formulation] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.05 disodium phosphate diester phosphate (2) Liquid paraffin 3 (3) Tetraoctane Acid pentaerythritol 7 (4) decamethylcyclopentasiloxane 2 (5) methylphenylpolysiloxane 5 (6) tocopherol acetate 0.1 (7) sodium carboxymethylcellulose 0.2 (8) sodium hyaluronate 0.1 (9) ) Ethanol 15 (10) Dipropylene glycol 5 (11) Preservative proper amount (12) Chelating agent proper amount (13) Antioxidant proper amount (14) Purified water residue

(Example 8) [Prescription] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.01 dipotassium phosphate diester dipotassium (2) squalane 5 (3) tri-2- Trimethylolpropane ethylhexanoate 4 (4) Dimethylpolysiloxane 5 (5) Sodium alginate 0.1 (6) Arbutin 5 (7) Ethanol 15 (8) Glycerin 5 (9) Preservative proper amount (10) Chelating agent proper amount ( 11) Antioxidant appropriate amount (12) Purified water residue

(Example 9) [Formulation] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.2 calcium phosphate diester phosphate (2) squalane 8 (3) sebacic acid 2 -Hexyldecyl 6 (4) methylphenylpolysiloxane 4 (5) hydroxypropylcellulose 0.2 (6) arbutin 5 (7) ethanol 15 (8) dipropylene glycol 5 (9) preservative appropriate amount (10) chelating agent appropriate amount (11) Antioxidant appropriate amount (12) Purified water residue

Example 10 [Prescription] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.05 dipotassium phosphate diester dipotassium (2) squalane 2 (3) diisomalate Stearyl 10 (4) Octamethylcyclotetrasiloxane 10 (5) Dimethylpolysiloxane 5 (6) Citric acid 0.1 (7) Sodium citrate 0.3 (8) L-Ascorbic acid-2-glucoside 1 (9) Methylcellulose 0.1 (10) Sodium carboxymethylcellulose 0.3 (11) Ethanol 10 (12) Preservative appropriate amount (13) Caustic potassium appropriate amount (14) Dye appropriate amount (15) Purified water residue

Example 11 [Prescription] Amount (% by weight) (1) β-tocopherol-2-L-ascor 0.2 dipotassium phosphate diester dipotassium (2) squalane 2 (3) tri-2-ethyl Glyceryl hexanoate 8 (4) Trimethylolpropane triisostearate 2 (5) Octamethylcyclotetrasiloxane 5 (6) Methylphenylpolysiloxane 5 (7) Citric acid 0.1 (8) Sodium citrate 0.3 (9) ) Methylcellulose 0.1 (10) Sodium carboxymethylcellulose 0.3 (11) Ethanol 10 (12) Preservative appropriate amount (13) Caustic potassium appropriate amount (14) Flavor appropriate amount (15) Purified water residue

(Example 12) [Formulation] Compounding amount (% by weight) (1) γ-tocopherol-2-L-ascor 0.05 dipotassium diphosphate phosphate dibasic (2) γ-tocopherol-2-L-ascor 0.15 Disodium disodium phosphate diphosphate (3) Squalane 2 (4) Neopentyl glycol dioctanoate 10 (5) Octamethylcyclotetrasiloxane 5 (6) Dimethylpolysiloxane 5 (7) Citric acid 0.1 (8 ) Sodium citrate 0.3 (9) Methylcellulose 0.1 (10) Sodium carboxymethylcellulose 0.3 (11) Ethanol 10 (12) Preservative proper amount (13) Caustic potassium proper amount (14) Flavor proper amount (15) Purified water residue

(Example 13) [Prescription] Compounding amount (% by weight) (1) δ-tocopherol-2-L-ascor 0.1 dipotassium phosphate diester dipotassium (2) liquid paraffin 2 (3) tri-2- Glyceryl ethylhexanoate 10 (4) Octamethylcyclotetrasiloxane 5 (5) Dimethylpolysiloxane 5 (6) Citric acid 0.1 (7) Sodium citrate 0.3 (8) L-ascorbic acid-2-glucoside 1 (9) Methylcellulose 0.1 (10) Sodium carboxymethylcellulose 0.3 (11) Glycerin 5 (12) Ethanol 10 (13) Preservative appropriate amount (14) Caustic potassium appropriate amount (15) Perfume appropriate amount (16) Purified water residue

(Example 14) [Prescription] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.03 disodium phosphate diester phosphate (2) glycerin 2 (3) tri-2- Glyceryl ethylhexanoate 10 (4) Octamethylcyclotetrasiloxane 5 (5) Dimethylpolysiloxane 5 (6) Citric acid 0.1 (7) Sodium citrate 0.3 (8) L-ascorbic acid-2-glucoside 1 (9) Methylcellulose 0.1 (10) Sodium carboxymethylcellulose 0.3 (11) Ethanol 10 (12) Preservative appropriate amount (13) Caustic potassium appropriate amount (14) Perfume appropriate amount (15) Purified water residue

(Example 15) [Prescription] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.005 dipotassium diphosphate phosphate dibasic acid (2) squalane 2 (3) tri-2-ethyl Glyceryl hexanoate 10 (4) Jojoba oil 3 (5) Octamethylcyclotetrasiloxane 3 (6) Dimethylpolysiloxane 5 (7) Methylphenylpolysiloxane 2 (8) Citric acid 0.1 (9) Sodium citrate 0. 3 (10) Sodium hyaluronate 0.1 (11) Sodium carboxymethyl cellulose 0.3 (12) Polyethylene glycol 2 (13) Ethanol 10 (14) 1,3-butylene glycol 3 (15) Preservative proper amount (16) Caustic potash Appropriate amount (17) Fragrance Appropriate amount (18) Purified water residue

(Example 16) [Prescription] Compounding amount (% by weight) (1) α-tocopherol-2-L-ascor 0.05 disodium phosphate diester phosphate (2) β-tocopherol-2-L- Ascor 0.05 Disodium phosphate diphosphate disodium (3) Liquid paraffin 2 (4) Glyceryl tri-2-ethylhexanoate 8 (5) Ethylene glycol di-2-ethylhexanoate 2 (6) Octamethylcyclotetrasiloxane 5 (7) Methylphenylpolysiloxane 5 (8) Octyl paramethoxycinnamate 5 (9) Citric acid 0.1 (10) Sodium citrate 0.3 (11) L-Ascorbic acid-2-glucoside 1 (12) Methylcellulose 0.5 (13) Ethanol 10 (14) Kaolin 2.0 (15) Preservative appropriate amount (16) Caustic Appropriate amount of potash (17) Appropriate amount of fragrance (18) Purified water residue

[0047]

As described in detail above, according to the present invention,
A stable emulsified layer is formed, and a multilayer composition having good appearance is obtained. Further, when the composition is shaken, the separated emulsified layer is uniformly dispersed throughout and becomes a whole cloudy state,
Thereafter, the emulsion layer is allowed to stand still, whereby the cloudy emulsified layer is immediately separated again, and is restored to a multilayer composition comprising an emulsified layer having good appearance before shaking and other layers.

Continued on front page F-term (reference) 4C083 AA122 AB032 AB051 AB052 AC022 AC102 AC122 AC302 AC342 AC352 AC372 AC392 AC422 AC442 AC901 AC902 AD042 AD152 AD172 AD262 AD272 AD282 AD302 AD332 AD392 AD621 AD622 AD641 AD642 BB11 DD05 DD31 EE01 FF04 AB11A02A AC03 DC02X DC04X DC07X DC13X DC15X DC19X DC32X DC67X 4G065 AA01 AB01X AB02X AB03X AB05X AB09X AB11X AB25X AB33X BA07 CA03 CA04 DA02 EA01

Claims (4)

[Claims] 1. A multilayer composition comprising an emulsifying layer and another layer, comprising the following formula (1): (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group.) A multilayer composition comprising a phosphate diester salt, an oily component and water. . 2. The multilayer composition according to claim 1, wherein the other layer is at least an aqueous layer. 3. The composition according to claim 1, wherein the content of the phosphate diester salt is 0.001 to 1% by weight based on the total weight of the composition.
A multilayer composition as described. 4. The multilayer composition according to claim 1, wherein the phosphate diester salt is α-tocopherol-2-L-ascorbic acid phosphate diester salt.