CN112533582B

CN112533582B - Gel particles and external preparation for skin containing the same

Info

Publication number: CN112533582B
Application number: CN201980052194.0A
Authority: CN
Inventors: 鸳渊孝太
Original assignee: Shiseido Co Ltd
Current assignee: Shiseido Co Ltd
Priority date: 2018-08-10
Filing date: 2019-08-06
Publication date: 2023-09-15
Anticipated expiration: 2039-08-06
Also published as: JP7221010B2; JP2020026404A; CN112533582A; WO2020032006A1

Abstract

The purpose of the present application is to provide gel particles which have flexibility, disintegration properties, and other use suitability, and manufacturing suitability, such as stirring durability. A gel particle comprising: a hydrophilic gelling agent having a structural skeleton with galactose; and a gellant dispersion medium comprising water and a C2-C5 polyol.

Description

Gel particles and external preparation for skin containing the same

RELATED APPLICATIONS

The present application claims priority from japanese patent application No. 2018-151700, filed on 8/10 in 2018, incorporated herein.

Technical Field

The present application relates to gel particles and an external preparation for skin containing the same, particularly to an improvement in the disintegrating property of the gel particles.

Background

Conventionally, a skin external preparation mainly containing a cosmetic has been blended with gel particles, and attention has been paid to improving the stability of components in the gel particles with time, the appearance of the cosmetic, and a unique feel accompanying the disintegration of particles when applied to the skin.

Prior art literature

Patent literature

Patent document 1: japanese patent No. 3756042

Patent document 2: japanese patent No. 4637991

Disclosure of Invention

Problems to be solved by the application

However, in particular, in gel particles to be blended in cosmetics, it is necessary to disintegrate the gel particles by fingers on the skin, and it is necessary to have proper softness and disintegrability, and on the other hand, it is necessary to withstand a strong stirring when blending into cosmetics, both of which are difficult, regardless of the release of the ingredients to be contained therein or the enjoyment of the appearance and touch.

The present application has been made in view of the problems of the prior art described above, and provides gel particles which achieve both use suitability such as flexibility and disintegration property and manufacturing suitability such as stirring durability.

Means for solving the problems

In order to achieve the above object, the present inventors have found that gel particles having excellent suitability for production and high flexibility and disintegration can be obtained by allowing a specific polyol to coexist when gel particles are formed from a polysaccharide having galactose as a structural skeleton, and have completed the present application.

That is, the gel particles according to the present application are characterized by comprising:

a hydrophilic gelling agent having a structural skeleton with galactose; and

a gellant dispersion medium comprising water and a C2 to C5 polyol.

The gel particles include:

0.1 to 5 mass percent of hydrophilic polymer gelatinizer with galactose as a structural framework; and

a gellant dispersion medium comprising water and a C2-C5 polyol, wherein the gellant dispersion medium comprises 80 mass% or more,

and the mass ratio of polyol/(water+polyol) is 0.13 to 0.71, the number average particle diameter of the gel particles is preferably 0.05 to 3mm.

In addition, it is preferable that the gel particles further contain a water-soluble polymer having an acrylamide-2-methylpropanesulfonic acid group.

Further, it is preferable that the gel particles further contain an internal oil phase dispersed in a gellant dispersion medium.

In addition, the polysaccharide of the gel particles is preferably agar or carrageenan.

The gel particles have a gel yield stress of 50 to 350g/mm ² Is suitable.

Further, it is preferable that the gel particles have a yield strain of 1.5 to 3.5 mm.

Furthermore, it is preferable that the gel particles have a yield energy of 500 to 600 g/mm.

The gel particles have a hardness of 50 to 200g/mm ³ Is suitable.

The external preparation for skin according to the present application is characterized by comprising the gel particles, and the external phase of the gel particles has a viscosity of 10000 to 100000mpa·s.

ADVANTAGEOUS EFFECTS OF INVENTION

As described above, the gel particles according to the present application can obtain gel particles excellent in manufacturing suitability, flexibility, and feeling of use such as disintegrability by containing a polysaccharide having galactose as a structural skeleton and a polyol having 2 to 5 carbon atoms.

Detailed Description

The following describes the structure of the present application in detail based on examples.

First, the present inventors studied the physical properties of gel particles prepared from polysaccharides having galactose as a structural skeleton by using agar.

The gel particles of the present application can be obtained by preparing an aqueous phase containing a hydrophilic polymer gellant, dispersing and emulsifying the aqueous phase in an external oil phase to prepare a W/O emulsion, and solidifying the aqueous phase of the W/O emulsion to gel-granulate the aqueous phase.

The hydrophilic polymer gelling agent is a substance which is generally used in cosmetics, medicines, etc., and can be solidified to form a hydrophilic gel, and particularly, a substance which is solidified by heating and cooling to form a gel, such as agar or carrageenan, is preferable in that it is not easily affected by ions, and in that the preparation is simple and can be uniformly solidified. In the present application, it is preferable to use such a hydrophilic polymer gelling agent which solidifies by heating and cooling as a main component of the gel particles. Among them, agar and carrageenan are preferable, and agar is particularly preferable, in view of the properties, stability, feel in use, and the like of the gel. As the agar, for example, commercially available products such as Final agar PS-84, Z-10, AX-30, AX-100, AX-200, T-1, S-5, M-7, CS-110 (manufactured by Enafrican food industry Co., ltd.) and the like can be used.

The amount of the hydrophilic gelling agent to be added is preferably 1.2 to 3 mass% in the gel particles, and if it is less than 1.2 mass%, the stirring resistance of the gel particles is poor, and if it exceeds 3 mass%, intentional disintegration of the gel particles by a finger may be difficult to feel.

In the present application, the above-mentioned hydrophilic polymer gelling agent is dispersed in a gelling agent dispersion medium, and a C2 to C5 polyol is used together with water as the dispersion medium.

Examples of the C2-C5 polyol include glycerin, dipropylene glycol, and 1, 3-butanediol.

The gellant dispersion medium containing water and a C2 to C5 polyol is required to be 80 mass% or more in the gel particles, and the mass ratio of polyol/(water+polyol) is 0.13 to 0.71.

In the present application, the specific polyol reduces the hardness and yield stress of the gel, but hardly affects the yield energy.

Here, the ease of damage to the gel particles due to stirring during the production of cosmetics depends mainly on the yield energy, and the larger the yield energy is, the less damage the gel particles undergo during the production. On the other hand, when the gel particles are intentionally disintegrated by a finger, the hardness and yield stress of the gel particles have a large influence on the touch feeling to which the cosmetic user is exposed, and it is found that the smaller the hardness and yield stress, the more easily the gel particles disintegrate.

Therefore, it is recognized that if the concentration of the gelling agent is the same, the production suitability is substantially the same in the case where the polyhydric alcohol and water are used, and the disintegration property by the finger is greatly improved, compared to the case where only water is used as the gelling agent dispersion medium.

In the present application, a hydrophilic polymer gelling agent that is solidified by Ca plasma or other coagulants such as alginic acid, curdlan, hyaluronic acid or the like may be mixed with the hydrophilic gelling agent that is solidified by heating and cooling within a range that does not impair the effects of the present application.

As the aqueous phase, a component or a drug which can be dissolved or dispersed in water may be mixed in addition to water.

The external oil phase of the present application may be a polar oil to a nonpolar oil as a whole in the production as long as it is not mixed with the water phase, and is selected from a wide range of oils which can be generally used. Examples thereof include hydrocarbon oils, ester oils, higher alcohols, higher fatty acids, natural oils and fats, silicone oils, and the like. Further, a component or a drug which can be dissolved or dispersed in these oil components may be mixed.

In the present application, it is preferable to add a hydrophilic thickener containing an acrylamide-2-methylpropanesulfonic Acid Monomer (AMPS) to the gelling agent dispersion medium in order to improve the manufacturing suitability without increasing the hardness and yield stress of the gel particles. The mixing amount of the hydrophilic thickener to the gel particles is preferably 0.05 to 0.3 mass%. If the content is less than 0.05 mass%, the effect of the hydrophilic thickener may not be sufficiently exhibited, and if the content exceeds 0.3 mass%, the yield stress may be increased.

In addition, in the present application, it is also suitable to form an internal oil phase within the gel particles.

When an internal oil phase is formed in the gel particles, an O/W emulsion is prepared from the internal oil phase which becomes oil droplets and a gellant dispersion medium containing a hydrophilic gellant, and the O/W emulsion is prepared by dispersing and emulsifying the O/W emulsion in an external oil phase, and an aqueous phase of the O/W/O emulsion is solidified to form gel particles.

In addition, from the viewpoint of preventing the oil droplets in the inner oil from infiltrating into the outer oil phase, it is preferable that the polarities of the inner oil phase and the outer oil phase are different.

In the preparation of the O/W emulsion in the 1 st stage of the production of the gel particles of the present application, it is necessary to prepare an extremely fine and stable emulsion having an average particle diameter of 0.01 to 30. Mu.m, preferably 0.1 to 5. Mu.m. If the particle size is too large, the subsequent O/W/O emulsification tends to cause fusion of the inner oil phase and the outer oil phase, and the inner oil phase and the outer oil phase cannot be sufficiently emulsified. Further, there is a tendency that the loss of the internal oil phase becomes large.

As a method for easily obtaining such an O/W emulsion, for example, an emulsion method using a hydrophilic nonionic surfactant and a water-soluble solvent (Japanese patent publication No. 57-29213) is effective. That is, an oil-in-water type emulsion is produced by adding an internal oil phase to a water-soluble solvent containing a hydrophilic nonionic surfactant, and an aqueous solution of a hydrophilic polymer gelling agent is added to the emulsion to obtain an O/W emulsion. The hydrophilic polymer gellant may be added by adding water to the oil-in-water type water-soluble solvent emulsion to prepare an O/W emulsion, and then diluting the emulsion with an aqueous solution of the hydrophilic polymer gellant. In addition, as long as no particular problem occurs, a hydrophilic polymer gelling agent may be added to the water-soluble solvent in advance.

The water-soluble solvent is a substance having an effect of dissolving a hydrophilic nonionic surfactant and efficiently orienting the surfactant at the interface with an internal oil phase to be added later, and is a lower polyol, specifically, a lower monohydric alcohol such as ethanol or propanol, a lower polyol such as 1, 3-butanediol or diethylene glycol. The water-soluble solvent may contain a small amount of water, for example, 15% by weight or less of water relative to the water-soluble solvent.

The hydrophilic nonionic surfactant is preferably a POE addition type or POE/POP addition type nonionic surfactant, and specifically, japanese patent publication No. 57-29213 discloses an example.

The O/W/O emulsion of stage 2 is prepared by dispersing and emulsifying the O/W emulsion in the external oil phase. The emulsifying machine used in this case is not particularly limited as long as a stirring device used for general emulsification is appropriately used.

In addition, in the outer oil phase, a lipophilic surfactant is preferably blended as an emulsifier. As the lipophilic surfactant, both ionic surfactants and nonionic surfactants may be used, and they may be appropriately selected from known ones depending on the kind of the external oil phase component and the like.

By solidifying the aqueous phase of such an O/W/O emulsion, gel particles containing a large number of fine oil droplets can be produced.

A preferred method for producing the gel particles of the present application is a method in which a hydrophilic polymer gelling agent which is solidified by heating and cooling is dissolved in water (other aqueous components may be contained as long as there is no problem) in advance to prepare an aqueous gelling agent solution, and the aqueous gelling agent solution is added to the oil-in-water type water-soluble solvent emulsion at a temperature equal to or higher than the solidification temperature of the gelling agent to prepare an O/W emulsion, and the O/W emulsion is prepared while maintaining the temperature of the system at a temperature equal to or higher than the solidification temperature, and then cooled to a temperature equal to or lower than the solidification temperature to solidify the aqueous phase, thereby producing the gel particles. For example, in the case of agar or carrageenan, a setting temperature of about 30℃and a preparation temperature of an aqueous solution of a gelling agent of 90 to 100℃are suitable, and a preparation temperature of an emulsion of about 50 to 90 ℃.

In the case of using a substance that solidifies by the addition of ions or the like in combination, the metal salt containing the ions or an aqueous solution thereof may be added to the O/W/O emulsion before cooling, and then cooled.

Since the gel particles of the present application have the internal oil phase finely and stably dispersed in the O/W emulsion as described above, the emulsification conditions at the time of preparing the O/W/O emulsion can be freely set, and the control of the gel particle diameter is easy. For example, the temperature at the time of O/W/O emulsification may be in the range of room temperature to about 90℃and the stirring speed may be in the wide range of about 100 to 10,000rpm, and in such a case, there is no loss of the inner oil phase, and there is little increase in the diameter of the oil-in-packet droplets due to fusion of the inner oil phase. The higher the temperature and stirring speed at the time of O/W/O emulsification, the smaller the gel particle diameter, and the higher the hydrophilic gellant concentration and viscosity of the external oil phase, the larger the gel particle diameter tends to be. According to the method of the present application, the number average gel particle size can be controlled in a wide range of 5 to 5000. Mu.m, preferably 50 to 3,000. Mu.m.

In the conventional gel particles, if added to an emulsification step or the like, the gel particles may be broken, and in the case of mixing the gel particles into an emulsion system, it is necessary to prepare an emulsion in advance, and then mix the gel particles while stirring slowly, which is complicated in the step.

The gel particles of the present application have excellent manufacturing suitability in that even when they are added to an emulsification step involving high-speed stirring, breakage of the gel particles hardly occurs. Therefore, in the case of mixing in an emulsifying system, the gel particles may be added as a solid component or in the state of an oily dispersion together with other components, and then emulsified. In addition, the polymer may be blended with other various base materials.

In addition, in the gel particles of the present application, there are few cases where the oil droplets in the inner oil phase infiltrate into the outer oil phase or the gel particles break up, as the oil droplets in the inner oil phase infiltrate into the gel particles over time during storage. Therefore, if an oily agent having poor stability is blended into the oil-in-oil droplets, the stability of the agent can be improved. Examples thereof include easily oxidizable agents such as retinol and vitamin E, easily crystalline oily agents such as cyclosporine, vitamin C palmitate and 4-tert-butyl-4' -methoxybenzoyl methane.

In particular, if higher fatty acid glycerides, dextrin fatty acid esters, or the like are blended in the oil phase as an oily gelling agent at the time of O/W emulsion preparation, the infiltration of oil-in-oil droplets can be significantly suppressed. The amount of the oily gelling agent to be blended is 0.05 to 5% by weight, preferably 0.2 to 1% by weight, in the internal oil phase. If the amount is too small, the effect of preventing the oil-based gelling agent from being impregnated cannot be sufficiently exhibited, and if the amount is too large, other components may be affected.

The cosmetic to be mixed with the gel particles is not particularly limited, and examples thereof include basic cosmetics such as lotions, creams, lotions, massage products, and frostings, cleansing products such as shower gels and cleansing products, color cosmetics such as foundations, powder, blush, lipsticks, eye shadows, eyebrows, mascaras, and powder, hair cosmetics such as hair creams, hair tonic, hair cream, hair care products, and hair conditioner. Examples of the properties include emulsion, solubilized, liquid, solid, gel, wire, and spray. They are not particularly limited as long as they do not impair the effects of the present application. In addition, the cosmetic of the present application may be blended with components commonly used in cosmetics.

The gel particles of the present application may be blended with other base materials after removing a part or all of the external oil phase in the state of an oily dispersion or by a conventional method such as centrifugation or filtration. In addition, the composition can be blended with an aqueous base such as a solid cosmetic such as foundation, lipstick, or the like, and a astringent. In addition, since shrinkage may occur when the gel particles of the present application are left in a solid state for a long period of time, the gel particles are preferably stored in an aqueous base or an oily base.

The present application will be described below with reference to specific examples. The blending amount is expressed as weight% unless otherwise specified.

(yield test)

The aqueous phase was heated to 90℃to dissolve, and cooled to prepare a gel having a thickness of 32 mm. For this gel, a cylindrical probe was press-fitted using a TEXTURE ANALYSER TA XT plus (manufactured by english finisher, ltd.) and the maximum stress value was set as a yield value, the inclination until the maximum stress was generated was set as a hardness, and the energy value until the maximum stress was generated was set as a yield energy.

The range is as follows: 350g

Test speed: 10mm/s

Probe diameter: 10mm of

(stirring resistance)

The stability (stirring resistance) in the case of adding the gel particles to the emulsification step was examined as follows. Specifically, a W/O cream containing gel particles was prepared according to the following formulation. The W/O emulsification was carried out with a homomixer at 70℃X 9000 rpm.

The presence or absence of breakage of the gel particles in the obtained cream was observed by a microscope, and when breakage of the gel particles was confirmed, the resistance to stirring was set to C; if the breakage was slightly confirmed, but the range was not practically problematic, the stirring resistance B was set; if no damage is confirmed, the stirring resistance is set to a value of stirring resistance A.

Manufacturing an adaptive inspected cream:

(test of finger disintegrability)

0.1g of the oily dispersion of gel particles was placed inside the left and right wrists with a spatula, respectively. The gel particle remaining rate was evaluated by the following criteria before (before) and immediately after (after) spreading the gel particles with the fingertips.

Evaluation criterion

S: the gel particles remained completely undetected.

A: fragments of a small amount of gel particles were confirmed.

B: fragments of gel particles were confirmed, and the gel particles were uncomfortable to apply.

C: the gel particles remained were confirmed.

TABLE 1

(preparation of gel particles)

An internal oil phase (liquid paraffin) was slowly added to a mixture of polyol and POE (60) hydrogenated castor oil (part of water without polyol addition) to obtain a water-soluble oil-in-solvent emulsion. Agar was dissolved in ion-exchanged water by heating at 90℃to prepare an aqueous agar solution, and cooled to 50 ℃. The agar aqueous solution was added to the water-soluble oil-in-solvent emulsion heated to 50℃while stirring, to obtain an O/W emulsion.

The O/W emulsion was added to an external oil phase (49 parts by weight of octamethyltetrasiloxane, 1 part by weight of POE methylpolysiloxane copolymer) and emulsified at 50℃X 500rpm to prepare an O/W/O emulsion. It was cooled slowly to room temperature, and the agar in the aqueous phase solidified, thereby obtaining an oily dispersion of gel particles.

In test example 1-1, if 1.8 mass% of agar is compounded without adding a polyol, the gel particles formed have stirring durability but are not easily crushed by fingers. On the other hand, if agar is reduced to 0.9 mass% as in test examples 1-2, the gel particles formed have improved finger disintegrability but deteriorated stirring durability.

On the other hand, in test examples 1 to 3, the mixing of agar 1.8 mass% with polyol improved the finger disintegrability while maintaining the stirring durability.

Further, in test examples 1 to 4, the finger disintegrability was further improved by adding AMPS/ACRYLAMIDE (N, N '-dimethylacrylamide-2-acrylamido-2-methylpropanesulfonic acid sodium-N, N' -methylenebisacrylamide copolymer).

Next, the present inventors studied the kind and the amount of the polyol to be added. The results are shown in table 2.

TABLE 2

In test example 2-1, ethanol was used as a monohydric alcohol, and in test example 2-2, polyglycerol (polyol) having 6 or more carbon atoms was used, but the method was not applicable in terms of manufacturing suitability.

On the other hand, as shown in test examples 1-4, 2-4 and 2-5, when glycerin, dipropylene glycol and 1, 3-butanediol were used as the polyhydric alcohols of C3 to 5, they exhibited excellent stirring durability and finger disintegration property.

Further, as shown in test examples 2 to 3, if the polyol/(water+polyol) was 11%, sufficient finger disintegrability was not obtained, but if it was 13%, both effects of stirring durability and finger disintegrability were exhibited, and the two effects were confirmed to be exhibited up to 71% (test examples 2 to 5). However, if it is 77% (test examples 2 to 6), the finger disintegrability is reduced, and therefore the proportion of the polyol is preferably 13 to 71%.

The present inventors have also studied the amount of a gelling agent (agar) to be added. The results are shown in table 3.

TABLE 3

As shown in the table, the addition amount of the gelling agent was 1.2 to 3 mass% relative to the gel particles, and both of the finger disintegrability and the stirring durability were satisfied.

Further, the inventors have studied on a thickener. The results are shown in tables 4 and 5.

TABLE 4

TABLE 5

As is clear from Table 4, AMPS/ACRYLAMIDE (manufactured by SU-GEL Tong Chemicals), AMPS/POE-methacrylic acid addition behenyl ether/VP (manufactured by Aristoflex-HMB) and acryl-dimethyl taurine/VP (manufactured by Aristoflex-AVD) each show excellent effects. On the other hand, (PEG-240/decyl tetradecyl polyether-20/HDI) copolymer without AMPS monomer(s), xanthate gum (GT-700), carboxyvinyl polymer (carbomer), do not exert the desired effect, and a thickener suitable for use in the present application is a thickener comprising AMPS monomer.

As shown in table 5, the mixing amount of the thickener is considered to exert a remarkable effect in 0.05 to 0.3 mass%.

The inventors of the present application have studied next, and as a result, have considered that the finger disintegrability of the gel particles is closely related to the viscosity of the composition in which the gel particles are blended. That is, when the gel particles are crushed by fingers, they may run aside and are not easily crushed. This "run-aside" has a close relationship with the viscosity of the composition to which the gel particles are added.

Regarding the gel particles according to the present application, the relationship between the gel particles and the viscosity of the composition in which they are blended was examined, and as a result, it was found that the viscosity of the composition is preferably 10000 to 100000mpa·s or more.

Claims

1. A gel particle comprising:

1.2 to 3 mass percent of agar;

a gellant dispersing medium comprising water and a C2 to C5 polyol; and

0.05 to 0.3 mass% of a water-soluble polymer having an acrylamide group-2-methylpropanesulfonic acid group,

the C2-C5 polyalcohol is glycerin and 1, 3-butanediol,

the mass ratio of polyol/(water+polyol) is 0.13 to 0.71.

2. The gel particles of claim 1, wherein the gel particles are,

the gelling agent dispersion medium containing water and a C2-C5 polyol is 80 mass% or more, and the number average particle diameter of the gel particles is 0.05-3 mm.

3. The gel particles of claim 1 or 2, further comprising an internal oil phase dispersed in the gellant dispersion medium.

4. Gel particle according to claim 1 or 2, characterized in that the gel constituting the gel particle has a yield stress of 50-350 in g/mm ² 。

5. Gel particle according to claim 1 or 2, characterized in that the gel constituting the gel particle has a yield strain in mm of 1.5-3.5.

6. Gel particle according to claim 1 or 2, characterized in that the gel constituting the gel particle has a yield energy of 35 to 600 in g/mm.

7. According to claimThe gel particles according to claim 1 or 2, wherein the gel particles have a gel hardness of 50 to 200 in g/mm ³ 。

8. A skin external agent comprising the gel particles according to any one of claims 1 to 7, and the external phase of the gel particles has a viscosity of 10000 to 100000 mPa-s.