JP7153028B2 - Vesicle-containing composition - Google Patents

Description

The present invention relates to vesicle-containing compositions.

Amphipathic compounds having both hydrophilic and hydrophobic properties include, for example, compounds such as phospholipids that form spherical vesicles consisting of bilayer membranes such as lamellar layers in an aqueous phase. be. Such bilayer vesicles are called liposomes or vesicles, and they can retain aqueous components inside their vesicle and/or can retain oily components within the vesicle membrane. For this reason, for example, such vesicles are used as microcapsules in the fields of pharmaceuticals, cosmetics, foods, etc., because of their advantages such as the ability to retain drugs and administer them into the body and maintain their efficacy over a long period of time. By forming liposomes or vesicles, a composition having excellent appearance such as transparency can be obtained, and thus such vesicles are also expected to be used as bases for cosmetics.

Patent Document 1 describes one or more anionic surfactants selected from (a) silicone-based surfactants, (b) polyoxyethylene alkyl (12-15) ether phosphates, acylmethyl taurate salts, and acylglutamate salts. 0.001 to 0.2% by weight of an active agent, (c) a polar oil and/or silicone oil having an IOB of 0.05 to 0.80, and (d) 0.5 to 5% by weight of the composition. A vesicle-containing composition containing water containing a water-soluble drug, wherein (a) a silicone-based surfactant forms a vesicle, (b) an anionic surfactant adheres to the surface of the vesicle, ( c) A vesicle-containing composition is disclosed wherein a polar oil and/or silicone oil is present within the bilayer of the vesicle.

WO2011/122477

For example, conventional cosmetics containing vesicles generally exhibit a smooth feel like water, a smooth feel like a thick consistency, or a feel like high-viscosity mayonnaise. On the other hand, there has been a demand for a cosmetic or the like that presents a novel feel in use that is different from the conventional one.

It is therefore a subject of the present invention to provide vesicle-containing compositions exhibiting a novel feel in use.

式１中、
Ｒ¹は、水素又は炭素原子数１～６のアルキル基であり、
Ａのうちの少なくとも一方は、式－（ＣＨ₂）_a－（Ｃ₂Ｈ₄Ｏ）_b－（Ｃ₃Ｈ₆Ｏ）_c－Ｒ²で示されるポリオキシアルキレン基であり、ここで、Ｒ²は、水素又は炭素原子数１～６のアルキル基であり、ａは１～６、ｂは０～５０、ｃは０～５０の整数であり、ｂ＋ｃは少なくとも５以上であり、かつその他のＡは、水素又は炭素原子数１～６のアルキル基であり、かつ
ｍは１～２００、ｎは０～５０の整数である。
〈態様４〉
前記ベシクルが、ブロック型アルキレンオキシド誘導体から形成され、かつ
前記ブロック型アルキレンオキシド誘導体が、下記式２又は３で示される、
態様２に記載の組成物：
Ｒ^３Ｏ－［（ＥＯ）_e－（ＡＯ）_f－（ＥＯ）_g］－Ｒ^４ …式２
式２中、
ＥＯは、オキシエチレン基、ＡＯは、炭素原子数３～４のオキシアルキレン基であり、これらの付加形態はブロック状であり、
ｅ及びｇは、前記オキシエチレン基の平均付加モル数、ｆは、前記オキシアルキレン基の平均付加モル数で、１≦ｅ＋ｇ≦７０、１≦ｆ≦７０であり、
前記オキシエチレン基と前記オキシアルキレン基との合計に対する前記オキシエチレン基の割合は、２０～８０質量％であり、
Ｒ^３及びＲ^４は、同一又は異なっていてもよい炭素原子数１～４の炭化水素基である；
Ｒ^３Ｏ－［（ＥＯ）_ｓ ^１－（ＡＯ）_ｒ ^１］－Ｂ－［Ｏ（ＡＯ）_ｒ ^２－（ＥＯ）_ｓ ^２］－Ｒ^４
…式３
式３中、
ＥＯは、オキシエチレン基、ＡＯは、炭素原子数３～４のオキシアルキレン基、Ｂは、ダイマージオールから水酸基を除いた残基であり、これらの付加形態はブロック状であり、
ｓ^１及びｓ^２は、前記オキシエチレン基の平均付加モル数、ｒ^１及びｒ^２は、前記オキシアルキレン基の平均付加モル数で、１≦ｓ^１＋ｓ^２≦１５０、１≦ｒ^１＋ｒ^２≦１５０であり、
前記オキシエチレン基と前記オキシアルキレン基との合計に対する前記オキシエチレン基の割合は、１０～９９質量％であり、
Ｒ^３及びＲ^４は、同一又は異なっていてもよい炭素原子数１～４の炭化水素基である。
〈態様５〉
前記疎水変性ポリエーテルウレタンが、下記式４で表される、態様１～４のいずれか一項に記載の組成物：
Ｒⁱ－｛（Ｏ－Ｒⁱⁱ）_k－ＯＣＯＮＨ－Ｒⁱⁱⁱ［－ＮＨＣＯＯ－（Ｒ^iv－Ｏ）_p－Ｒ^v］_h｝_q …式４
式４中、
Ｒⁱ、Ｒⁱⁱ及びＲ^ivは、それぞれ独立に、炭素原子数２～４の炭化水素基を示し、
Ｒⁱⁱⁱは、ウレタン結合を有していてもよい炭素原子数１～１０の炭化水素基を示し、
Ｒ^vは、炭素原子数８～３６の炭化水素基を示し、
ｋは、１～５００の整数であり、
ｐは、１～２００の整数であり、
ｈは、１以上の整数であり、かつ
ｑは、２以上の整数である。
〈態様６〉
前記疎水変性ポリエーテルウレタンが、ポリエチレングリコール－デシルテトラデセス－ヘキサメチレンジイソシアネートコポリマーである、態様５に記載の組成物。
〈態様７〉
前記両親媒性物質と前記疎水変性ポリエーテルウレタンとの重量比が、４：１～１：２である、態様１～６のいずれか一項に記載の組成物。
〈態様８〉
前記ベシクルの平均粒径が２００ｎｍ以下である、態様１～７のいずれか一項に記載の組成物。
〈態様９〉
前記ベシクルが油分を保持している、態様１～８のいずれか一項に記載の組成物。
〈態様１０〉
波長６００ｎｍにおける光透過率が４０％以上である、態様１～９のいずれか一項に記載の組成物。
〈態様１１〉
とろみ状の形態であって、濃縮したときにジェル状の形態に変化する、態様１～１０のいずれか一項に記載の組成物。
〈態様１２〉
態様１～１１のいずれか一項に記載の組成物を含む、化粧料基剤。<Aspect 1>
(a) vesicles formed by amphiphilic substances;
(b) a hydrophobically modified polyether urethane; and (c) water.
<Aspect 2>
Aspect 1, wherein the amphiphilic substance is selected from the group consisting of silicone surfactants, block-type alkylene oxide derivatives, sugar fatty acid esters, polyoxyethylene hydrogenated castor oil derivatives, acylamino acid metal salts, and phospholipids. The described composition.
<Aspect 3>
The vesicle is formed from a silicone-based surfactant, and the silicone-based surfactant is a polyoxyalkylene-modified silicone represented by the following formula 1.
The composition according to aspect 2:

In formula 1,
R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
At least one of A is a polyoxyalkylene group of the _formula -( _CH2 ) _{a- ( C2H4O} ) _b- ( _{C3H6O)c -} ^R2 , wherein R ² is hydrogen or an alkyl group having 1 to 6 carbon atoms, a is 1 to 6, b is 0 to 50, c is an integer of 0 to 50, b+c is at least 5, and other A is hydrogen or an alkyl group having 1-6 carbon atoms, m is an integer of 1-200, and n is an integer of 0-50.
<Aspect 4>
The vesicle is formed from a block-type alkylene oxide derivative, and the block-type alkylene oxide derivative is represented by the following formula 2 or 3,
The composition according to aspect 2:
R ³ O-[(EO) _e -(AO) _f -(EO) _g ]-R ⁴ Formula 2
In formula 2,
EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and these addition forms are block-like,
e and g are the average number of added moles of the oxyethylene group, f is the average number of added moles of the oxyalkylene group, 1 ≤ e + g ≤ 70, 1 ≤ f ≤ 70,
The ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 20 to 80% by mass,
R ³ and R ⁴ are hydrocarbon groups having 1 to 4 carbon atoms which may be the same or different;
R ³ O-[(EO) _s ¹ -(AO) _r ¹ ]-B-[O(AO) _r ² -(EO) _s ² ]-R ⁴
…equation 3
In formula 3,
EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, B is a residue obtained by removing a hydroxyl group from dimer diol, and these addition forms are block-like,
s ¹ and s ² are the average number of added moles of the oxyethylene group, r ¹ and r ² are the average number of added moles of the oxyalkylene group, 1 ≤ s ¹ + s ² ≤ 150, 1 ≤ r ¹ + r ² ≤ 150,
The ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 10 to 99% by mass,
R ³ and R ⁴ are hydrocarbon groups of 1 to 4 carbon atoms which may be the same or different.
<Aspect 5>
The composition of any one of aspects 1-4, wherein the hydrophobically modified polyether urethane is represented by Formula 4 below:
R ⁱ -{(O-R ⁱⁱ ) _k -OCONH-R ⁱⁱⁱ [-NHCOO-(R ^iv -O) _p -R ^v ] _h } _q ... Formula 4
In formula 4,
R ⁱ , R ⁱⁱ and R ^iv each independently represent a hydrocarbon group having 2 to 4 carbon atoms,
R ⁱⁱⁱ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond,
R ^v represents a hydrocarbon group having 8 to 36 carbon atoms,
k is an integer from 1 to 500,
p is an integer from 1 to 200,
h is an integer of 1 or greater; and q is an integer of 2 or greater.
<Aspect 6>
6. The composition of aspect 5, wherein said hydrophobically modified polyether urethane is a polyethylene glycol-decyltetradeceth-hexamethylene diisocyanate copolymer.
<Aspect 7>
The composition according to any one of aspects 1-6, wherein the weight ratio of said amphiphile to said hydrophobically modified polyether urethane is from 4:1 to 1:2.
<Aspect 8>
8. The composition according to any one of aspects 1 to 7, wherein the vesicle has an average particle size of 200 nm or less.
<Aspect 9>
9. The composition of any one of aspects 1-8, wherein said vesicle retains oil.
<Aspect 10>
The composition according to any one of aspects 1 to 9, which has a light transmittance of 40% or more at a wavelength of 600 nm.
<Aspect 11>
11. A composition according to any one of aspects 1-10, wherein the composition is in a thickened form and transforms into a gel-like form when concentrated.
<Aspect 12>
A cosmetic base comprising the composition according to any one of aspects 1-11.

INDUSTRIAL APPLICABILITY According to the present invention, a vesicle-containing composition exhibiting a novel feel in use can be provided. In particular, the vesicle-containing composition of the present invention provides a novel feel in use, such as an elastic and plump feel in use, or a low-viscosity, thick and smooth feel immediately after application of a cosmetic containing such a composition to the skin. However, as the cosmetic is dried and concentrated, it can provide a feel of use that changes into a gel-like, elastic and plump feel.

(a) is a schematic diagram before concentration of a vesicle-containing composition of one embodiment of the present invention, and (b) is a schematic diagram after concentration of a vesicle-containing composition of one embodiment of the present invention. 1 is a graph of shear rate and shear viscosity of a vesicle-containing composition of one embodiment of the present invention. FIG. 2 is a graph of shear rate and shear viscosity of vesicle-free compositions. Fig. 3 is a graph of shear rate and shear viscosity of vesicle-containing compositions of another embodiment of the present invention; FIG. 2 is a graph of shear rate and shear viscosity of vesicle-free compositions.

Embodiments of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the spirit of the invention.

The vesicle-containing composition of the present invention is a vesicle-containing composition comprising (a) vesicles formed by an amphipathic substance, (b) hydrophobically modified polyether urethane, and (c) water.

While not limited by any principle, it is believed that the working principle of the present invention is as follows.

In the vesicle-containing composition of the present invention, vesicles and hydrophobically modified polyetherurethane are dispersed in water so that at least part of the hydrophobically modified polyetherurethane blended is interposed between adjacent vesicles. thinking.

As a result, the vesicle-containing composition of the present invention, for example, when the amount of water blended in the composition is increased to form a thick vesicle-containing composition, as the composition is concentrated, the vesicles A cross-linking point is formed between the vesicles and the hydrophobically modified polyether urethane to form a connected network structure, which easily retains moisture and forms a gel. Play. Thus, the vesicle-containing composition of the present invention has both a thickening effect due to the hydrophobically modified polyetherurethane itself and a thickening effect due to the development of a network structure due to the formation of cross-linking points between the vesicle and the hydrophobically modified polyetherurethane. can be synergistically exerted, it is possible to change from a thick and smooth feeling in use to a gel-like elastic and plump feel in use.

More specifically, for example, in the case of a vesicle-containing composition formed by increasing the amount of water to be blended, the amount of moisture is large immediately after application of such a composition to the skin, and is shown in (a) of FIG. As described above, the formation of a network structure is insufficient, so it has a low viscosity and a thick, smooth feel. However, as the composition is dried and concentrated, the distance between the vesicles and the hydrophobically modified polyether urethane located between the vesicles gradually approaches, as shown in FIG. 1(b). , the formation of cross-linking points in vesicles becomes easier, and the network structure in which vesicles and hydrophobically modified polyether urethane are linked becomes easier to develop. As a result, in addition to the increase in viscosity and water retention capacity, elasticity due to the network structure is also exhibited, so it is believed that the composition changes to a gel-like form that exhibits an elastic and bouncy feeling when used.

Alternatively, when the vesicle-containing composition of the present invention is brought into a state in which the network structure can be expressed from the beginning by reducing the amount of water blended in the composition, such a composition is gel-like from the initial stage. It is possible to exhibit an elastic and plump feeling in use.

As a technology capable of emulsifying oil, for example, nanoemulsion is also known. However, even if such a nanoemulsion and a hydrophobically modified polyether urethane are used in combination, the novel feeling in use of the present invention could not be achieved. The reason for this is that the nanoemulsion is in a thermodynamically non-equilibrium and unstable state, and the hydrophobically modified polyether urethane, which has a hydrophobic portion and a hydrophilic portion, functions like a surfactant. It is thought that this is because it is difficult to form a stable cross-linking point between the polyether urethane and the hydrophobic modified polyether urethane, and the balance of emulsification is also disturbed and the emulsified state is destroyed. On the other hand, since vesicles are generally in a thermodynamic equilibrium and stable state, even if the hydrophobic moieties of hydrophobically modified polyether urethane form cross-linking points with respect to the vesicle bilayer membrane, the vesicle bilayer membrane It is believed that the new feeling of use of the present invention was achieved because the foam did not collapse.

In addition, if an attempt is made to develop such an elastic gel-like form using only the hydrophobically-modified polyetherurethane, the hydrophobically-modified polyetherurethane must be used in a larger amount than the vesicle-containing composition system of the present invention. As a result, it is believed that the cost increases and the stickiness derived from the hydrophobically modified polyether urethane increases. On the other hand, the vesicle-containing composition of the present invention can further reduce the cost compared to a system containing only hydrophobically modified polyether urethane, and exhibits a moist feeling while reducing the sticky feeling derived from the hydrophobically modified polyether urethane. can also

Definitions of terms used in the present invention are as follows.

In the present invention, the term "thickened" is used, for example, as a thickened cosmetic, and in this case, the characteristic of the thickened cosmetic of the present invention is that it exhibits properties as a Newtonian fluid in a wide range of shear rates. It is intended to exhibit a state of high viscosity compared to the water contained in the composition. Such a viscosity is, for example, using MCR-302 (manufactured by Anton-Paar) as a rheometer, and the viscosity in the linear region of the measurement object when measured at 25 ° C. and 1 atm is 0.01 Pa s or more. , 0.1 Pa·s or more, or 1 Pa·s or more, 100 Pa·s or less, 90 Pa·s or less, or 80 Pa·s or less.

In the present invention, the term “gel-like” means a state having flexibility like a liquid and elasticity to return to its original shape when stress is applied, and a state of higher viscosity than a thick state. The viscosity is not limited to the following, but specifically, the viscosity at which the shear rate is infinitely close to 0 s ⁻¹ , that is, the static viscosity, “thick” is 100 Pa・While the static viscosity is less than s, the “gel-like” static viscosity can be defined as a range of 300 Pa s or more, 500 Pa s or more, 700 Pa s or more, or 1000 Pa s or more. can.

"Vesicles" in the present invention also include liposomes and polymersomes.

In the present invention, the term "crosslinking point" means, unlike a crosslinking point based on polymerization, at least one of the hydrophobic moieties of at least one hydrophobically modified polyether urethane is incorporated into the vesicle bilayer membrane. Sites adsorbed near the bilayer membrane are intended.

<<(a) a vesicle formed by an amphipathic substance>>
The vesicle of the present invention can be formed from an amphiphilic substance capable of forming a vesicle (hereinafter sometimes referred to as a "vesicle-forming amphiphilic substance"). The average particle size of the vesicles is not particularly limited, and is usually about 500 nm or less. preferably less than or equal to about 100 nm. The lower limit of the average particle size of the vesicle is also not particularly limited, but can be about 20 nm or more or about 50 nm or more. By controlling the average particle size of the vesicles, the vesicle-containing composition can be adjusted from translucent to transparent. The vesicle-containing composition of the present invention can, for example, have a light transmittance of 40% or more, 45% or more, or 50% or more at a wavelength of 600 nm. Here, the average particle size of the vesicles can be measured by, for example, a dynamic light scattering method using a particle size distribution meter FPAR-1000 (BX51: manufactured by Otsuka Electronics Co., Ltd.), or using a freeze replica method. , can be measured from a photograph taken by a transmission electron microscope (TEM, H-7000: manufactured by Hitachi, Ltd.). The light transmittance can be obtained from the light transmittance of the composition at a wavelength of 600 nm at 25° C. using an absorption photometer (V550: manufactured by JASCO Corporation).

The amount of the vesicle-forming amphiphilic substance can be 0.1% by mass or more or 0.2% by mass or more, based on the total amount of the composition, in consideration of vesicle-forming properties, stability, etc. It can be 10% by mass or less or 5% by mass or less.

<Amphiphilic substance>
The vesicle-forming amphiphilic substance is not particularly limited, but examples thereof include silicone surfactants, block-type alkylene oxide derivatives, sugar fatty acid esters, polyoxyethylene hydrogenated castor oil derivatives, acylamino acid metal salts, phospholipids, and the like. mentioned.

(Silicone-based surfactant)
The silicone-based surfactant is not particularly limited, and examples thereof include polyoxyalkylene-modified silicones. As the vesicle-forming amphiphilic substance of the present invention, it is preferable to use a polyoxyalkylene-modified silicone represented by the following formula 1 from the viewpoints of feeling in use such as moist feeling and vesicle-forming properties. The HLB of such silicone is preferably in the range of 4-12, more preferably in the range of 6-9.

In Formula 1, R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms, and at least one of A is represented by the formula --(CH ₂ ) _a --(C ₂ H ₄ O) _b --(C ₃ H ₆ O) A polyoxyalkylene group represented by _c —R ² , wherein R ² is hydrogen or an alkyl group having 1 to 6 carbon atoms, a is 1 to 6, b is 0 ~ 50, c is an integer of 0 to 50, b + c is at least 5 or more, and other A is hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is 1 to 200, n is an integer from 0 to 50;

In Formula 1 above, R ¹ is a side chain in the polysiloxane structure of the main chain and is hydrogen or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. For example, when all R ¹ are methyl groups, it has a dimethylpolysiloxane structure, and when it is a methyl group and a phenyl group, it has a methylphenylpolysiloxane structure. A is a site where a polyoxyalkylene group can be introduced in the polysiloxane structure of the main chain, and at least one of them has the formula —(CH ₂ ) _a —(C ₂ H ₄ O) _b —(C ₃ H ₆ O ) is a polyoxyalkylene group represented by _c -R ² . In the formula, R ² is hydrogen or an alkyl group having 1 to 6 carbon atoms, a is 1 to 6, b is 0 to 50, c is an integer of 0 to 50, and b+c is at least 5 or more.

In the above formula 1, when part of A is the above polyoxyalkylene group, the other A may be hydrogen or an alkyl group having 1 to 6 carbon atoms. The silicone represented by Formula 1 is, for example, when two terminal A's are polyoxyalkylene groups, it becomes a polyoxyalkylene-modified silicone represented by ABA type, while only non-terminal A's are polyoxyalkylene groups. When it is an alkylene group, it becomes a pendant-type polyoxyalkylene-modified silicone. The polyoxyalkylene group may be a polyoxyethylene group, a polyoxypropylene group, or a polyoxyethylene/polyoxypropylene group. m representing the number of moles of the unsubstituted polysiloxane structure is an integer of 1-200, and n representing the number of moles of the polyoxyalkylene-substituted polysiloxane structure is an integer of 0-50. When n is 0, either or both of the two terminal A's must be polyoxyalkylene groups.

Examples of such polyoxyalkylene-modified silicone include, for example, polyoxyethylene ( 12 mol)-modified dimethylpolysiloxane, polyoxyethylene (8 mol)-modified dimethylpolysiloxane, and polyoxyethylene (20 mol)-modified dimethylpolysiloxane are preferably used. In addition, ABA type polyoxyethylene -methylsiloxane-polyoxyethylene block copolymer and the like. When polyoxyethylene-modified silicone is used, the molecular weight of ethylene oxide in the total molecular weight is preferably 20 to 60%.

The silicone-based surfactant may be produced by a known production method, or a commercially available product may be used. Examples of commercial products include SH3772M with an HLB of 6, SH3773M with an HLB of 8, SH3775M with an HLB of 5, and the like, manufactured by Dow Corning Toray Co., Ltd.

(Block type alkylene oxide derivative)
As the block-type alkylene oxide derivative, a block-type alkylene oxide derivative represented by Formula 2 or 3 below can be used. Vesicles composed of such derivatives are also called polymersomes.

R ³ O-[(EO) _e -(AO) _f -(EO) _g ]-R ⁴ Formula 2

In Formula 2, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and these addition forms are block-like. AO specifically includes an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group, an oxytetramethylene group, etc. Among them, an oxypropylene group and an oxybutylene group are preferable, and an oxybutylene group Especially preferred.

In Formula 2, e and g represent the average number of added moles of oxyethylene groups, and f represents the average number of added moles of oxyalkylene groups. From the viewpoint of vesicle stability, feel in use, etc., e and g are preferably in the range of 1 ≤ e + g ≤ 70, more preferably 5 ≤ e + g ≤ 60, and f is preferably in the range of 1 ≤ f ≤ 70. , 5≦f≦55.

In formula 2, the ratio of the oxyethylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is preferably 20 to 80% by mass from the viewpoint of vesicle formation and the like. It is more preferably ~70% by mass.

The molecular weight of the alkylene oxide derivative represented by Formula 2 is preferably 1,000 to 5,000 from the viewpoint of obtaining a sufficient amount of vesicles.

In Formula 2, R ³ and R ⁴ are hydrocarbon groups having 1 to 4 carbon atoms and may be the same or different. Hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, N-propyl group, isopropyl group, N-butyl group, sec-butyl group, tert-butyl group and the like, among which methyl group. , ethyl groups are preferred. One or a combination of two or more block type alkylene oxide derivatives in which R ³ and R ⁴ are the same or different may form a vesicle.

In the alkylene oxide derivative represented by Formula 2, either or both of R ³ and R ⁴ may be a hydrogen atom derivative, as long as the effect of the present invention is not adversely affected.

The block-type alkylene oxide derivative of the invention can be produced by a known method. For example, after addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms to a compound having a hydroxyl group, the alkyl halide is subjected to an ether reaction in the presence of an alkali catalyst to obtain a block type alkylene oxide derivative. be able to.

The block-type alkylene oxide derivative represented by Formula 2 is not limited to the following, but examples include POE(9)POP(2)dimethylether, POE(14)POP(7)dimethylether, POE(10)POP( 10) dimethyl ether, POE (6) POP (14) dimethyl ether, POE (15) POP (5) dimethyl ether, POE (25) POP (25) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (22) POP ( 40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether, POE (55) POP (30) dimethyl ether, POE (30) POP (34) dimethyl ether, POE (25) POP ( 30) dimethyl ether, POE (27) POP (14) dimethyl ether, POE (55) POP (28) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (17) POP ( 4) dimethyl ether, POE (9) POB (2) dimethyl ether, POE (14) POB (7) dimethyl ether, POE (15) POB (14) dimethyl ether, POE (18) POB (17) dimethyl ether, POE (23) POB ( 21) dimethyl ether, POE (27) POB (25) dimethyl ether, POE (32) POB (29) dimethyl ether, POE (35) POB (32) dimethyl ether, POE (10) POB (15) dimethyl ether, POE (20) POB ( 28) dimethyl ether, POE (17) POB (10) dimethyl ether, POE (28) POB (17) dimethyl ether, POE (45) POB (27) dimethyl ether, POE (34) POB (14) dimethyl ether, POE (55) POB ( 22) dimethyl ether, POE (44) POB (12) dimethyl ether, POE (10) POP (10) diethyl ether, POE (10) POP (10) dipropyl ether, POE (10) POP (10) dibutyl ether, POE ( 35) POP (30) glycol, POE (35) POB (32) glycol, and the like. Here, POE, POP, and POB are abbreviations of polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively, and the numbers in parentheses after POE, POP, and POB represent the number of added moles of each. Hereinafter, it may be abbreviated as follows.

R ³ O-[(EO) _s ¹ -(AO) _r ¹ ]-B-[O(AO) _r ² -(EO) _s ² ]-R ⁴
…equation 3

In Formula 3, B is a residue obtained by removing a hydroxyl group from dimer diol, and EO is an oxyethylene group. AO is an oxyalkylene group having 3 to 4 carbon atoms, examples thereof include oxypropylene group, oxybutylene group, oxyisobutylene group, oxy t-butylene group and the like, among which oxypropylene group and oxybutylene group are An oxybutylene group is preferred, and an oxybutylene group is more preferred. The addition forms of B, EO and AO are blocky from the standpoint of vesicle formation. As for the order of addition, it is preferable that AO and EO are bonded to the dimer diol in that order.

In Formula ³ , s1 and s2 represent the ^average number of added moles of oxyethylene groups, and r1 and r2 represent the ^{average number} of added moles of oxyalkylene groups. From the viewpoint of stability of vesicles, feeling in use, etc., these preferably satisfy the relationships of 1≦s ¹ +s ² ≦150 and 1≦r ¹ +r ² ≦150, and 5≦s ¹ +s ² ≦120. , and 2≦r ¹ +r ² ≦70, and particularly preferably 10≦s ¹ +s ² ≦100 and 2≦r ¹ +r ² ≦50.

In Formula 3, the ratio of oxyethylene groups to the total of oxyethylene groups and oxyalkylene groups is preferably 10 to 99% by mass, more preferably 20 to 70% by mass, from the viewpoint of vesicle-forming properties.

The molecular weight of the alkylene oxide derivative represented by Formula 3 is preferably 1,000 to 6,000 from the viewpoint of vesicle formation.

R ³ and R ⁴ are hydrocarbon groups having 1 to 4 carbon atoms. Since the terminal hydroxyl group that causes stickiness can be etherified, R ³ and R ⁴ can improve compatibility with the skin and provide a good feel during use. Hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and mixed groups thereof. groups are preferred. R ³ and R ⁴ may be the same or different, and one or more block type alkylene oxide derivatives having the same or different R ³ and R ⁴ may be combined to form a vesicle.

In the alkylene oxide derivative represented by Formula 3, B is a residue obtained by removing a hydroxyl group from dimer diol. Here, the dimer diol is a diol obtained by reducing a dimer acid. When B is a diol other than dimer diol, vesicles may not be formed, or even if vesicles are formed, the stability may be insufficient.

Dimer acid, which is a raw material for dimer diol, is a dimer obtained by polymerizing an unsaturated fatty acid or a lower alcohol ester thereof, and specifically unsaturated fatty acids such as oleic acid, linoleic acid, and linoleic acid. Alternatively, it can be synthesized by a method of reacting esters of these lower alcohols by thermal polymerization such as the Diels-Alder reaction or other reaction methods. An unreacted fatty acid may remain in the produced dimer acid as long as it does not impair the effects of the present invention.

The dimer acid is preferably a dimerized unsaturated fatty acid having 12 to 24 carbon atoms or a lower alcohol ester thereof. In this case, B is a dimer diol residue having 24 to 48 carbon atoms. Examples of such unsaturated fatty acids include myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linoleic acid, and lower fatty acids having 1 to 3 carbon atoms. Among them, unsaturated fatty acids having 18 carbon atoms are preferred, and oleic acid or linoleic acid or lower alcohol esters thereof are more preferred. As the dimer acid, a dimer acid obtained by hydrogenating the remaining unsaturated double bonds after dimerization may be used.

Dimer diols derived from animal fats and oils and those derived from vegetable fats and oils are commercially available, and although both can be used in the present invention, dimer diols derived from vegetable fats and oils are more preferable. Examples of such dimer diol include Sovermol 908 (manufactured by Cognis Japan), PRIPOL (registered trademark) 2033 (manufactured by Uniqema), and Pespol HP-1000 (manufactured by Toagosei Co., Ltd.).

Examples of the block-type alkylene oxide derivative represented by Formula 3 include, but are not limited to, POB(25) POE(34) dimethyl dimer diol ether, POB(25) POE(35) dimethyl dimer diol ether, POB (4) POE (13) dimethyl dimer diol ether, POB (5) POE (15) dimethyl dimer diol ether, POB (6) POE (18) dimethyl dimer diol ether, POB (7) POE (20) dimethyl dimer diol ether , POB(10) POE(24) dimethyl dimer diol ether, POB(10) POE(30) dimethyl dimer diol ether, POB(25) POE(52) dimethyl dimer diol ether, POB(18) POE(41) dimethyl dimer Diol ether, POB(18) POE(41) diethyl dimer diol ether, POB(18) POE(41) dipropyl dimer diol ether, POB(18) POE(41) dibutyl dimer diol ether, POB(11) POE(30) ) dimethyl dimer diol ether, POB(15) POE(45) dimethyl dimer diol ether, POB(18) POE(50) dimethyl dimer diol ether, POB(21) POE(56) dimethyl dimer diol ether, POB(12) POE (50) dimethyl dimer diol ether, POB (18) POE (61) dimethyl dimer diol ether, POB (3) POE (40) dimethyl dimer diol ether, POB (6) POE (82) dimethyl dimer diol ether, POB (40) ) POE (120) dimethyl dimer diol ether, POB (100) POE (40) dimethyl dimer diol ether, POE (35) POP (30) dimethyl dimer diol ether, POE (52) POP (30) dimethyl dimer diol ether, etc. mentioned. Here, the added mole numbers of POE, POP, and POB are respectively expressed as the total added mole numbers in the molecule, that is, the values of r ¹ +r ² and s ¹ +s ² .

Such block-type alkylene oxide derivatives can be produced by known methods. For example, after addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms to a compound having a hydroxyl group, the alkyl halide is subjected to an ether reaction in the presence of an alkali catalyst to obtain a block type alkylene oxide derivative. be able to.

(sugar fatty acid ester)
Sugar fatty acid esters include, for example, sucrose fatty acid esters, maltitol fatty acid esters, trehalose fatty acid esters, and the like.

Although the number of hydroxyl groups substituted by fatty acids is not particularly limited, monoesters, diesters and triesters are preferred, monoesters and diesters are more preferred, and monoesters are more preferred.

The constituent fatty acid in the sugar fatty acid ester is preferably a saturated or unsaturated fatty acid having 12 to 22 carbon atoms and having a straight or branched chain. These fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, octadecadienoic acid, eicosenoic acid, eicosatetraenoic acid, Docosenoic acid, octadecatrienoic acid and the like can be mentioned, among which stearic acid is preferred. In the case of diesters, the two fatty acids may be different.

(Polyoxyethylene hydrogenated castor oil derivative)
As the polyoxyethylene hydrogenated castor oil derivative, it is preferable to use a compound represented by the following formula 5.

In Formula 5, L+M+N+X+Y+Z represents the average added mole number E of ethylene oxide, and 10≦E≦20.

(acyl amino acid metal salt)
As the acylamino acid metal salt, an acylamino acid metal salt having 12 to 22 carbon atoms is preferred. Examples of such acyl amino acid metal salts include sodium N-lauroyl-L glutamate, sodium N-stearoyl-L glutamate, and sodium di(N-lauroylglutamyl)lysine.

(Phospholipid)
Phospholipids include, for example, egg yolk phospholipids, soybean phospholipids, hydrogenated products thereof, sphingophospholipids such as sphingomyelin, and glycerophospholipids such as lecithin.

(Other amphiphilic substances)
The vesicle-containing composition of the present invention may contain other amphiphilic substances in addition to the amphiphilic substances described above, as long as the effects of the present invention are not impaired.

<<(b) Hydrophobic modified polyether urethane>>
The hydrophobically modified polyether urethane of the present invention is a material that is also called associative thickener, associative polymer, etc., and is not limited to the following formula 4
R ⁱ -{(O-R ⁱⁱ ) _k -OCONH-R ⁱⁱⁱ [-NHCOO-(R ^iv -O) _p -R ^v ] _h } _q ... Formula 4
and preferred examples of hydrophobically modified polyether urethanes include polyethylene glycol-decyltetradeceth-hexamethylene diisocyanate copolymer. A particularly preferred example is a hydrophobically modified polyether urethane with the INCI designation "(PEG-240/Decyltradeceth-20/HDI) Copolymer (PEG-240/HDI COPOLYMER BISDECYLTETRADECETH-20 ETHER)". The copolymer is commercially available from ADEKA Corporation under the trade name “ADEKA NOL GT-700”.

In Formula 4, R ⁱ , R ⁱⁱ and R ^iv are each independently a hydrocarbon group having 2 to 4 carbon atoms, preferably an alkyl group or alkylene group having 2 to 4 carbon atoms. R ⁱⁱⁱ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond. R ^v represents a hydrocarbon group having 8 to 36 carbon atoms, preferably 12 to 24 carbon atoms. k is an integer of 1-500, preferably an integer of 100-300. p is an integer of 1-200, preferably an integer of 10-100. h is an integer of 1 or more, preferably 1; q is an integer of 2 or more, preferably 2;

The hydrophobically modified polyether urethane represented by Formula 4 is, for example, one or more polyether polyols represented by R ⁱ —[(O—R ⁱⁱ ) _k —OH] _q , R ⁱⁱⁱ —(NCO ) reacting one or more polyisocyanates represented by _h+1 and one or more polyether monoalcohols represented by HO—(R ^iv —O) _p —R ^v can be obtained by wherein R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv , R ^v , k, p, h, and q are as defined above.

In this production method, R ⁱ to R ^v in formula 4 are raw materials R ⁱ —[(O—R ⁱⁱ ) _k —OH] _q , R ⁱⁱⁱ —(NCO) _h+1 , HO—(R ^iv -O) determined by _p - ^Rv . The compounding ratio of these three is not particularly limited, but the ratio of the hydroxyl group derived from the polyether polyol and polyether monoalcohol and the isocyanate group derived from the polyisocyanate is NCO/OH = 0.8: 1 ~ 1.4:1 is preferred.

<Polyether Polyol Represented by R ⁱ —[(O—R ⁱⁱ ) _k —OH] _q >
A polyether polyol represented by R ⁱ -[(OR ⁱⁱ ) _k -OH] _q is obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide, alkylene oxide such as epichlorohydrin, styrene oxide, etc. to q-valent polyol. can be obtained by

Here, the polyol is preferably dihydric to octahydric, for example, dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol; glycerin, trioxyisobutane, 1,2,3- Butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol , 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin , pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trihydric alcohols such as trimethylolpropane; pentaerythritol, 1,2,3,4-pentanetetrol, Tetrahydric alcohols such as 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol and 1,3,4,5-hexanetetrol; hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol and idite; and octahydric alcohols such as sucrose.

R ⁱⁱ is determined by the alkylene oxide, styrene oxide, etc. to be added. Alkylene oxides having 2 to 4 carbon atoms or styrene oxides are particularly preferred because they are readily available and can exhibit excellent effects. The alkylene oxide, styrene oxide, etc. to be added may be homopolymerized, random polymerized with two or more kinds, or block polymerized. The method of addition may be any conventional method. The degree of polymerization k is an integer of 1-500. The proportion of ethylene groups in R ⁱⁱ is preferably 50 to 100% by mass of the total R ⁱⁱ .

The molecular weight of R ⁱ —[(OR ⁱⁱ ) _k —OH] _q is preferably 500 to 100,000, more preferably 1,000 to 50,000.

<Polyisocyanate Represented by R ⁱⁱⁱ −(NCO) _h+1 >
The polyisocyanate represented by R ⁱⁱⁱ -(NCO) _h+1 is not particularly limited as long as it has two or more isocyanate groups in the molecule. Diisocyanates, biphenyl diisocyanates, di-, tri- or tetra-isocyanates of phenylmethane, and the like can be used.

Examples of aliphatic diisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, meta-xylylene diisocyanate, para-xylyl diisocyanate, tetramethylxylylene diisocyanate, and the like.

Examples of aromatic diisocyanates include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, and the like.

Examples of alicyclic diisocyanates include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

Examples of biphenyl diisocyanate include biphenyl diisocyanate, 3,3'-dimethylbiphenyl diisocyanate, 3,3'-dimethoxybiphenyl diisocyanate and the like.

Diisocyanates of phenylmethane include, for example, diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2′ ,5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis(4-isocyantophenyl)methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane- 3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2,2'-dimethyl-5,5'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'- dichlorodiphenyldimethylmethane-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate and the like.

Examples of triisocyanates of phenylmethane include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate, isocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4', 4″-triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenyl) thiophosphate and the like.

These polyisocyanate compounds may be used in the form of trimers based on dimers, isocyanurate linkages, etc., or may be reacted with amines and used as biurets.

These polyisocyanate compounds and polyisocyanates having urethane bonds reacted with polyols can also be used. As the polyol, those having 2 to 8 valences are preferable, and the aforementioned polyols are preferable. When a polyisocyanate having a valence of 3 or more is used as R ⁱⁱⁱ -(NCO) _h+1 , the polyisocyanate having this urethane bond is preferred.

<Polyether monoalcohol represented by HO—(R ^iv —O) _p —R ^v >
The polyether monoalcohol represented by HO--(R ^iv --O) _p --R ^v is not particularly limited as long as it is a polyether of monohydric alcohol. Such compounds can be obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide, alkylene oxides such as epichlorohydrin, styrene oxide, and the like to monohydric alcohols.

The monohydric alcohols referred to here are represented by the following formulas I to III.
R ^vi —OH Formula I

That is, R ^v is a group obtained by removing the hydroxyl group from the monohydric alcohols of formulas I to III. In Formulas I to III above, R ^vi , R ^vii , R ^viii , R ^x and R ^xi are hydrocarbon groups such as alkyl groups, alkenyl groups, alkylaryl groups, cycloalkyl groups, cycloalkenyl groups, and the like. be.

Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, and dodecyl. , tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl and the like.

Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

Alkylaryl groups include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl. Examples include phenyl, α-naphthyl, β-naphthyl groups and the like.

Cycloalkyl groups and cycloalkenyl groups include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, and methylcycloheptenyl groups. etc.

In Formula II above, R ^ix is a hydrocarbon group, such as an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, a cycloalkenylene group, and the like.

R ^v is a hydrocarbon group, preferably an alkyl group, and preferably has a total number of carbon atoms of 8 to 36, particularly preferably 12 to 24.

The alkylene oxide, styrene oxide, etc. to be added may be homopolymerized, random polymerized with two or more kinds, or block polymerized. The method of addition may be any conventional method. The degree of polymerization p is an integer of 0-1000, preferably an integer of 1-200, more preferably an integer of 10-200. The proportion of ethylene groups in R ^iv is preferably in the range of 50 to 100% by mass, more preferably in the range of 65 to 100% by mass of the total R ^iv .

(Method for producing copolymer represented by Formula 4)
The copolymer represented by Formula 4 above can be produced by heating and reacting, for example, at 80 to 90° C. for 1 to 3 hours, similar to the reaction of general polyether and isocyanate.

A polyether polyol D represented by R ⁱ -[(OR ⁱⁱ ) _k -OH] _q , a polyisocyanate E represented by R ⁱⁱⁱ -(NCO) _h+1 , and HO-(R ^iv -O ) When reacting with a polyether monoalcohol F represented by _p - ^Rv , other than the copolymer having the structure of Formula 4 may be produced as a by-product. For example, when a diisocyanate is used, the main product is a FEDEF type copolymer represented by the formula 4, but there are also FEF type and FE A copolymer such as -(DE) _x -DEF type may be produced as a by-product. In this case, the copolymer of formula 4 type can be used in the present invention in the form of a mixture containing the copolymer of formula 4 type without separating it.

(Amount of hydrophobically modified polyether urethane compounded)
The amount of the hydrophobically modified polyether urethane in the vesicle-containing composition of the present invention is 0.1% by mass or more, 0.2% by mass or more, or 0.2% by mass or more, based on the total amount of the composition, from the viewpoint of obtaining a novel feeling in use. .3% by weight or more, and may be 3% by weight or less, 2% by weight or less, or 1% by weight or less.

In the vesicle-containing composition of the present invention, the weight ratio of the vesicle-forming amphiphilic substance to the hydrophobically modified polyether urethane is preferably 4:1 to 1:2, more preferably 3:1 to 4:5. A composition containing both components within this range synergistically combines the thickening effect of the hydrophobically-modified polyetherurethane and the thickening effect associated with the development of a network structure due to the formation of cross-linking points between the vesicles and the hydrophobically-modified polyetherurethane. Therefore, it is possible to further develop a new feeling of use that is different from the past.

《(c) Water》
The amount of water to be blended is not particularly limited, but from the viewpoint of vesicle formation, it is preferably 70 to 95% by mass, more preferably 80 to 90% by mass, based on the total amount of the composition. preferable.

《Oil》
Vesicles formed by the amphiphiles of the invention can optionally retain oil within the bilayer membrane of the vesicle. The oil that can be retained is not limited to the following, but at least one selected from the group of polar oils and silicone oils can be used. The oil content that can be retained in the vesicle can be appropriately selected based on the IOB value and the like. For example, when employing a vesicle formed of a silicone-based surfactant, it is selected from the group of polar oils having an IOB value of 0.05 to 0.80 and silicone oils from the viewpoint of vesicle stability. It is preferable to employ at least one type. Here, the IOB value of oil can be calculated by a known calculation method based on its structure.

The total oil content can be blended in the range of 0.001 to 0.3% by mass with respect to the total amount of the composition. The vesicle-containing composition of the present invention can be used in combination with a polar oil having an IOB value other than 0.05 to 0.80, or a non-polar oil such as mineral oil, as long as the stability of the vesicle is not impaired. be.

<Polar oil>
Polar oils include, for example, isostearic acid, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, isononane isononyl acid, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cetyl ethylhexanoate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearic acid N-alkyl glycol, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythyl tetra-2-ethylhexanoate Slit, glyceryl tri-2-ethylhexanoate (triethylhexanoin), trimethylolpropane triisostearate, cetyl isooctanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, benzoic acid (C12- 15) Alkyl, cetearyl isononanoate, tri (caprylic/capric) glycerin, (dicaprylic/capric) butylene glycol, glyceryl trimyristate, tri-2-heptyl undecanoic acid glyceride, castor oil fatty acid methyl ester, olein Oleyl acid, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid 2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, sebatin Di-2-ethylhexyl acid, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, di-2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate , 2-ethylhexyl paramethoxycinnamate, tripropylene glycol dipivalate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Polar oils can be used in combination of one or more arbitrarily selected.

<Silicone oil>
The silicone oil is not particularly limited as long as it is an oily component having a polysiloxane structure, and may be either linear or cyclic, or volatile or nonvolatile. Examples of silicone oils include linear silicones such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, and cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. , these can be used in combination by arbitrarily selecting one or two or more.

Among these silicone oils, volatile cyclic silicone oils, particularly octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, can be preferably used. By using such a volatile cyclic silicone oil, it becomes possible to incorporate more perfume components into the vesicle bilayer membrane. Excellent usability is obtained. Diphenylsiloxyphenyltrimethicone, methylphenylpolysiloxane and the like are particularly preferred as the non-volatile silicone oil.

《Other Ingredients》
The vesicle-containing composition of the present invention can contain various components as appropriate depending on the intended use of the composition, as long as the vesicle-forming properties, stability and the like are not affected. Examples of various components include additive components that can be usually blended in cosmetics, such as lower alcohols, polyhydric alcohols, various extracts, moisturizers, antioxidants, buffers, preservatives, pigments, fragrances, chelating agents, A pH adjuster, an ultraviolet absorber, and the like can be mentioned. Various components can be blended into the aqueous phase as the continuous phase in the vesicle-containing composition, the aqueous phase as the dispersed phase inherent in the vesicles, or the oil phase as the dispersed phase in the vesicle bilayer membrane, depending on their properties. .

In addition to water-soluble drugs that can be applied to pharmaceuticals, quasi-drugs, cosmetics, etc., the aqueous phase contains any aqueous ingredients that are usually used in pharmaceuticals or cosmetics, etc., as long as they do not affect the stability of the vesicles. You may mix|blend with a compounding quantity. In particular, as the aqueous component, one or more selected from ethanol and polyols are preferably blended from the viewpoint of stabilization of vesicles and feeling during use.

Examples of polyols include ethylene glycol, propylene glycol, 1,3-butylene glycol, tetramethylene glycol, glycerin, sorbitol, diethylene glycol, dipropylene glycol, tetramethylene glycol, diglycerin, polyethylene glycol, polypropylene glycol, etc. Propylene glycol, dipropylene glycol and 1,3-butylene glycol are particularly preferred. One or two or more aqueous components selected from ethanol and polyol can be blended in the range of 1 to 20% by mass, or 3 to 10% by mass, relative to the total amount of the composition.

<<Use of vesicle-containing composition>>
The vesicle-containing composition of the present invention can be used in, for example, a gel-like form exhibiting an elastic and plump feel, or a thickening-like form, by adjusting the amount of water to be blended. In the case of such a thick form, as it dries and concentrates, the feel of use can change from the thick form to an elastic gel form. The elastic gel-like vesicle-containing composition can exhibit a refreshing feeling as if the gel state is broken at once when a load exceeding the limit value is applied, and water is repelled. The vesicle-containing compositions of the invention can also be transparent or translucent depending on the application. Therefore, the vesicle-containing composition of the present invention exhibiting such properties can be used, for example, as a base for cosmetics applied to the skin or the like.

Cosmetics include, for example, moisturizing gels, massage gels, serums, lotions, skin care cosmetics such as milky lotions, makeup cosmetics, sun care products, hair cosmetics such as hair setting agents or hair gels, or hair dyes. can be mentioned.

<<Method for producing vesicle-containing composition>>
The vesicle-containing composition of the present invention can be produced using known methods. For example, a vesicle-forming amphiphilic substance such as a silicone-based surfactant is mixed with water optionally containing a water-soluble drug, an aqueous component, etc. to form a vesicle solution. The vesicle-containing composition of the present invention can be obtained by adding ether urethane and stirring and mixing. Here, when an oil such as a polar oil or silicone oil is blended, the oil may be mixed with the vesicle-forming amphiphilic substance.

In such a production method, vesicles composed of the vesicle-forming amphiphilic substance are spontaneously formed in the aqueous phase by mixing water and the vesicle-forming amphiphilic substance. When oil is contained together with the vesicle-forming amphiphile, the oil is solubilized and incorporated into the bilayer membrane of the formed vesicle.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, the compounding amount is indicated by mass %.

<<Example 1 and Comparative Examples 1 to 4>>
The vesicle-containing composition of the present invention and a nanoemulsion-containing composition for comparison obtained by the formulation and manufacturing method shown in Table 1 below were evaluated for their appearance stability. Appearance stability was evaluated by visually observing the vesicle-containing composition or nanoemulsion-containing composition in each example, and classified into "no problem", "aggregation", "phase separation", and "aggregation separation". Here, "aggregation separation" intends to be a state in which an aggregated state and a phase-separated state coexist.

<Method for producing vesicle-containing composition>
(Example 1)
A mixture A was prepared by stirring and dissolving polyether-modified silicone, which is a vesicle-forming amphiphilic substance, and methylphenylpolysiloxane in ethanol. Then, some ion-exchanged water, glycerin, 1,3-butylene glycol, polyoxyethylene (14) polyoxypropylene (7) random copolymer dimethyl ether, phenoxyethanol, citric acid, sodium citrate, EDTA-2Na.2H Mixture B was prepared by stirring and mixing ₂ O. The obtained mixture A and mixture B were stirred and mixed to prepare a vesicle solution C. Separately, an aqueous solution D was prepared by stirring and dissolving the hydrophobic modified polyether urethane in the remaining ion-exchanged water heated to 70°C. Vesicle solution C and aqueous solution D were stirred and mixed to prepare a vesicle-containing composition.

(Comparative Examples 1 to 4)
Various components listed in Table 1 other than the components used in the aqueous solution D were stirred and mixed to prepare nanoemulsion-containing solutions. The nanoemulsion-containing solution and aqueous solution D were stirred and mixed to prepare nanoemulsion-containing compositions of Comparative Examples 1 to 4, respectively.

<result>
As is clear from Table 1, in all of the nanoemulsion-containing compositions in Comparative Examples 1 to 4, aggregation, phase separation, or both occurred with the addition of the hydrophobically modified polyether urethane. It was not possible to evaluate the feel. On the other hand, in the case of the vesicle-containing composition of Example 1, even when the hydrophobically modified polyether urethane was added, it was possible to maintain the composition as a transparent solution without problems such as aggregation and phase separation. When this vesicle-containing composition was applied to the skin, it had a thick and smooth feel immediately after application, but as it dried and concentrated, it gradually changed to a gel-like form, giving a bouncy and elastic feel. and changed. Such a vesicle-containing composition did not have a sticky feeling that occurs when the hydrophobic modified polyether urethane was blended at a high concentration, and after drying and concentrating, a moist feeling was obtained.

<<Examples 2 to 11 and Comparative Examples 5 to 11>>
Rheological measurements were performed on the vesicle-containing composition and the vesicle-free composition of the present invention obtained by the formulation and production method shown in Table 2 below. Here, the rheology measurement was performed by flow curve measurement using a rheometer MCR302 manufactured by Anton Paar, and the shear viscosity was measured under the shear rate conditions and 25° C. shown in FIGS.

<Method for producing vesicle-containing composition>
(Examples 2 to 11)
A vesicle-containing composition was prepared in the same manner as in Example 1 using various components listed in Table 2. Here, the vesicles in Examples 2 to 8 obtained by employing polyether-modified silicone as the vesicle-forming amphiphilic substance are referred to as "silicone vesicles", polyoxybutylene (21) and polyoxyethylene (23) blocks. The vesicles in Examples 9 to 11 obtained by employing copolymer dimethyl ether are sometimes referred to as "polymer vesicles".

(Comparative Examples 5-11)
Each vesicle-free composition was prepared in the same manner as in Example 1, except that the various components listed in Table 2 were used and vesicles were not formed.

<result>
From FIG. 3, it can be seen that in the vesicle-free composition as well, the shear viscosity tends to increase as the amount of hydrophobically modified polyether urethane (hereinafter sometimes referred to as "ADK") added increases. On the other hand, in the case of the vesicle-containing composition of the present invention, the silicone vesicle-containing composition in FIG. 2 and the vesicle-free composition in FIG. 3, and the polymer vesicle-containing composition in FIG. As is clear from the comparison of the results of the containing compositions, the system containing vesicles showed an increase in shear viscosity regardless of the type of vesicle, even if the amount of ADK added was the same. I understand.

In the case of the vesicle-containing composition, this is thought to be due to the formation of cross-linking points between the vesicles and the hydrophobically modified polyether urethane, resulting in the development of a network structure. Therefore, the vesicle-containing composition of the present invention has a thickening effect due to the hydrophobically modified polyetherurethane, which is also a thickening agent, and a thickening effect due to the network structure due to the formation of cross-linking points between the vesicles and the hydrophobically modified polyetherurethane. Synergistic expression was confirmed. As a result, the vesicle-containing composition of the present invention, in addition to providing the above-described unprecedented new feeling in use, is superior to the vesicle-free system in achieving the same viscosity. It has been found that since the ether urethane can be used in a lower amount, the sticky feeling derived from the hydrophobically modified polyether urethane can be reduced, and at the same time, the moist feeling can be exhibited.

<<Prescription example of vesicle-containing composition>>
Examples of formulations of cosmetics based on the vesicle-containing composition of the present invention are given below, but are not limited to these examples. The cosmetic preparations described in the formulation examples below have varying feel in use based on the vesicle-containing composition of the present invention, that is, a thick and smooth feel, a plump and elastic feel, and a moist feeling after concentration. was

<Prescription example 1 Lotion>
(Component) (% by mass)
Purified water Appropriate amount Glycerin 5
1,3-butylene glycol 5
Phenoxyethanol 0.5
Citric acid 0.02
Sodium citrate 0.08
EDTA _- 2Na.2H2O 0.03
Ethanol 5
Polyether-modified silicone 0.8
Polyoxyethylene (14) Polyoxypropylene (7)
Random copolymer dimethyl ether 0.5
Methylphenylpolysiloxane 0.1
(PEG-240/decyltetradeceth-20/HDI) copolymer 0.3
Perfume Appropriate amount

(Manufacturing method of lotion)
A mixture M was prepared by stirring and dissolving the polyether-modified silicone, methylphenylpolysiloxane, and fragrance in ethanol. Then some purified water, glycerin, 1,3-butylene glycol, polyoxyethylene (14) polyoxypropylene (7) random copolymer dimethyl ether, phenoxyethanol, citric acid, sodium citrate and EDTA-2Na.2H ₂ Mixture N was prepared by stirring and mixing O. The obtained mixture M and mixture N were stirred and mixed to prepare a vesicle solution O. Separately, a hydrophobically modified polyether urethane (PEG-240/decyltetradeceth-20/HDI) copolymer was stirred and dissolved in the remaining deionized water heated to 70° C. to prepare an aqueous solution D. Vesicle solution O and aqueous solution D were stirred and mixed to prepare a lotion.

Claims (9)

(a) vesicles formed by amphiphilic substances;
(b) a hydrophobically modified polyether urethane; and (c) water, comprising :
The hydrophobically modified polyether urethane is represented by the following formula 4,
The content of the hydrophobic polyether urethane is 0.2% by mass or more with respect to the total amount of the composition,
The weight ratio of the amphiphilic substance and the hydrophobic polyether urethane is 4:1 to 1:2, and
It is a thick form with a static viscosity of less than 100 Pa s, and when concentrated, changes to a gel-like form with a static viscosity of 300 Pa s or more.
Composition:
R ⁱ -{(O-R ⁱⁱ ) _k -OCONH-R ⁱⁱⁱ [-NHCOO-(R ^iv -O) _p -R ^v ] _h } _q ... Formula 4
In formula 4,
R ⁱ , R ⁱⁱ and R ^iv each independently represent a hydrocarbon group having 2 to 4 carbon atoms,
R ⁱⁱⁱ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond,
R ^v represents a hydrocarbon group having 8 to 36 carbon atoms,
k is an integer from 1 to 500,
p is an integer from 1 to 200,
h is an integer of 1 or more, and
q is an integer of 2 or more. the amphiphilic substance is selected from the group consisting of silicone surfactants, block-type alkylene oxide derivatives, sugar fatty acid esters, polyoxyethylene hydrogenated castor oil derivatives, acylamino acid metal salts, and phospholipids ;
The block-type alkylene oxide derivative is represented by the following formula 2 or 3,
The polyoxyethylene hydrogenated castor oil derivative is represented by the following formula 5,
The composition of claim 1 :
R ³ O-[(EO) _e -(AO) _f -(EO) _g ]-R ⁴ Formula 2
In formula 2,
EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and these addition forms are block-like,
e and g are the average number of added moles of the oxyethylene group, f is the average number of added moles of the oxyalkylene group, 1 ≤ e + g ≤ 70, 1 ≤ f ≤ 70,
The ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 20 to 80% by mass,
R ³ and R ⁴ are hydrocarbon groups having 1 to 4 carbon atoms which may be the same or different;
R ³ O-[(EO) _s ¹ -(AO) _r ¹ ]-B-[O(AO) _r ² -(EO) _s ² ]-R ⁴
…equation 3
In formula 3,
EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, B is a residue obtained by removing a hydroxyl group from dimer diol, and these addition forms are block-like,
s ¹ and s ² are the average number of added moles of the oxyethylene group, r ¹ and r ² are the average number of added moles of the oxyalkylene group, 1 ≤ s ¹ + s ² ≤ 150, 1 ≤ r ¹ + r ² ≤ 150,
The ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 10 to 99% by mass,
R ³ and R ⁴ are hydrocarbon groups of 1 to 4 carbon atoms which may be the same or different.

In Formula 5, L+M+N+X+Y+Z represents the average added mole number E of ethylene oxide, and 10≦E≦20. The vesicle is formed from the silicone surfactant, and the silicone surfactant is a polyoxyalkylene-modified silicone represented by the following formula 1.
The composition of claim 2:

In formula 1,
R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
At least one of A is a polyoxyalkylene group of the _formula -( _CH2 ) _{a- ( C2H4O} ) _b- ( _{C3H6O)c -} ^R2 , wherein R ² is hydrogen or an alkyl group having 1 to 6 carbon atoms, a is 1 to 6, b is 0 to 50, c is an integer of 0 to 50, b+c is at least 5, and other A is hydrogen or an alkyl group having 1-6 carbon atoms, m is an integer of 1-200, and n is an integer of 0-50. wherein the vesicle is formed from the block-type alkylene oxide derivative;
3. The composition of claim 2 . A composition according to any preceding claim, wherein the hydrophobically modified polyether urethane is a polyethylene glycol-decyltetradeceth-hexamethylene diisocyanate copolymer. The composition according to any one of claims 1 to 5 , wherein the vesicle has an average particle size of 200 nm or less. The composition according to any one of claims 1 to 6 , wherein said vesicle retains oil. The composition according to any one of claims 1 to 7 , which has a light transmittance of 40% or more at a wavelength of 600 nm. A cosmetic base comprising the composition according to any one of claims 1 to 8 .

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