JP7183022B2 - granular composition - Google Patents

Description

The present invention relates to particulate compositions.

Techniques related to granular compositions such as gel particles containing various cosmetic ingredients and the like have been disclosed as cosmetics or external preparations for skin.
For example, Patent Document 1 discloses a technique relating to a skin cosmetic containing microspherical substances composed of hydrated calcium alginate, which is produced by mixing an aqueous solution of an alkali metal salt of alginic acid with an aqueous solution of a calcium salt of an inorganic or organic acid. disclosed.
For example, Patent Document 2 describes the following components (A) to (E): (A) a gelling agent that causes gelation due to the thermoreversibility of sol-gel, (B) a crosslinked polyacrylate, and (C) a solid Techniques are disclosed for hydrogel particles, including particles, (D) a gel-like component, and (E) water.
For example, in Patent Document 3, an O/W type dispersion containing a water-soluble polymer selected from agar and gelatin, an oily conditioning component, and an emulsifier or dispersant is cooled and solidified in a gas phase or liquid phase by a dropping method. Particles with an average particle diameter of 0.1 to 5 mm are obtained by uniformly dissolving a water-soluble thickener in water, have a viscosity at 25 ° C. of 300 to 5000 mPa · s, and have a specific gravity of 0.7 to 2 There is disclosed a technique relating to a skin cosmetic that is dispersed and suspended in a transparent or translucent aqueous base of 0.0.

JP-A-63-139108 JP 2010-131479 A Japanese Patent No. 3756043

However, all of the techniques of the small spherical substance in Patent Document 1, the hydrogel particles in Patent Document 2, and the particles in Patent Document 3 maintain the stability of the shape, etc. under the condition that the particulate composition is immersed in a solvent. , If you try to leave it in a state where it is not immersed in the solvent, the granular composition will not be able to maintain its shape against the vibration itself during transportation and will collapse, or the granular composition will collide with each other, etc., and the shape will not be maintained. In some cases, vibration resistance was poor, such that it was impossible to That is, a granular composition having excellent vibration resistance has not been known in the past.

In consideration of the problems in the prior art as described above, the present inventor attempted to develop a granular composition having excellent vibration resistance. However, when the granular composition is applied to the skin, etc., the disintegration strength at the time of application is not preferable, and if the granular composition is not crushed and cannot be applied, or even if the granular composition is crushed, the skin familiarity There was still the problem that it was sometimes inferior to
Therefore, as a result of further intensive studies, the present inventors have found that a granular composition containing agar, phospholipids, gellan gum, polyethylene glycol having a number average molecular weight of 10000 or less, and water has remarkably excellent vibration resistance, and It has been found that it has excellent disintegration strength when applied and has good skin compatibility.

That is, the present invention
the following components (a) to (e);
Provided is a granular composition containing (a) agar, (b) phospholipids, (c) gellan gum, (d) polyethylene glycol having a number average molecular weight of 10,000 or less, and (e) water.

The present invention provides the above granular composition, which is not immersed in a solvent.

The present invention provides the particulate composition characterized by having an average particle size of 1 to 20 mm.

The present invention provides the above granular composition, which is characterized by being spherical.

The present invention provides the granular composition, wherein the content ratio (a)/(d) of the component (a) and the component (d) is 0.05-2.

The present invention provides the granular composition, wherein the content ratio (b)/(d) of the component (b) and the component (d) is 0.1-3.

The present invention provides the above granular composition, which is a cosmetic or external preparation for skin.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a granular composition having excellent vibration resistance, excellent collapse strength upon application, and excellent skin compatibility.

The present invention will be described in detail below. In this specification, "-" shall mean a range including numerical values before and after it.

Component (a): Agar Component (a) used in the present invention is agar, and any one can be used regardless of the place of production or origin. For this agar, so-called low-strength agar (disclosed, for example, in JP-A-5-317008), which is acid-treated to cut molecules, may be used in order to adjust the jelly strength. Although the jelly strength of this agar is not particularly limited, it is preferably 20 to 2000 g/cm ² , more preferably 30 to 1000 g/cm ² . Here, the jelly strength is a gel obtained by heating and dissolving agar in water so as to give a jelly strength of 1.5% by mass (hereinafter, "mass%" is simply referred to as "%"), leaving it at 20°C for 15 hours, and solidifying it. , refers to the maximum mass that the surface can withstand for 20 seconds per 1 cm ² . When agar with a jelly strength within this range is used, it is difficult to form a hard solid, so a cosmetic having a particularly good uniformity of the cosmetic film can be obtained. Commercially available products such as AX-100 and UP-37 (manufactured by Ina Food Industry Co., Ltd.) can be used as such agar.

The content of component (a) is not particularly limited, but is preferably 0.8 to 2%, more preferably 1 to 1.5%, from the standpoint of good disintegration strength and skin compatibility when applied.

Component (b): Phospholipid The component (b) used in the present invention is a phospholipid, and is not particularly limited as long as it is a phospholipid commonly used in cosmetics and external preparations for skin. One or more of the following examples can be used.

Component (b) may be a natural product extracted and purified from animals and plants, or may be chemically synthesized, and may be processed by hydrogenation, hydroxylation, enzyme treatment, or the like.
Examples of natural products include soybean-derived phospholipids and egg yolk-derived phospholipids, and examples of processed products include hydrogenated phospholipids and lysophospholipids. More specifically, soybean-derived phospholipids, soybean-derived hydrogenated phospholipids, soybean-derived lysophospholipids, soybean-derived hydrogenated lysophospholipids, egg yolk-derived phospholipids, egg yolk-derived hydrogenated phospholipids, egg yolk-derived lysophospholipids, egg yolk-derived hydrogen Additional lysophospholipids and the like are included.
Among these, hydrogenated phospholipids are preferred, and soybean-derived hydrogenated phospholipids are more preferred. Hydrogenated phospholipids (preferably derived from soybeans) are preferable in terms of good collapse strength and skin compatibility when applied when combined with components (a) and (c) described below.

Commercially available products of component (b) include Resinol S-PIE, Nikkol Resinol S-10, Nikkol Resinol S-10E (manufactured by Nikko Chemicals), Basis LS-60HR (manufactured by Nisshin Oillio Group), HSL- 70 (manufactured by YMC), lecithin CLO (manufactured by J-Oil Mills), egg yolk lecithin PL-100P (manufactured by Kewpie) and the like.

In addition, the content of component (b) is not particularly limited, but is preferably 2 to 8%, more preferably 4 to 7%, in terms of excellent vibration resistance, collapse strength when applied, and excellent skin compatibility. .

Component (c): Gellan Gum Component (c) used in the present invention is gellan gum. Gellan gum is a polymer, also known as a polysaccharide, extracellularly produced by a microorganism called Sphingomonas elodea. In particular, it is preferably an aqueous gelling agent that forms an elastic gel by swelling with water.

As component (c), a native type and a deacylated type obtained by removing the acetyl group and glyceryl group present in the 1-3-bonded glucose are known, and either can be used. Component (c) has the property of further thickening with the addition of metal cations such as calcium ions and sodium ions, has high salt resistance, and can maintain viscosity even in the presence of high-concentration electrolytes. preferable. Commercially available products include KELCOGEL CC (manufactured by Sansho), GELCOGEL (manufactured by Sumitomo Dainippon Pharma), KELCOGEL F (manufactured by Sumitomo Dainippon Pharma), KELCOGEL HM (manufactured by Sumitomo Dainippon Pharma), and KELCOGEL HT (manufactured by Dainippon Sumitomo). Sumitomo Dainippon Pharma Co., Ltd.), Kelcogel LT100 (manufactured by Dainippon Sumitomo Pharma Co., Ltd.), and the like, and one or more of them can be used.

The content of component (c) is not particularly limited, but is preferably 0.01 to 0.1%, more preferably 0.03 to 0.08%, from the standpoint of excellent collapse strength upon application.

Component (d): Polyethylene glycol having a number average molecular weight of 10,000 or less Component (d) used in the present invention is polyethylene glycol having a number average molecular weight of 10,000 or less. The number average molecular weight can be measured by the GPC method using polystyrene as a standard. The number average molecular weight of component (d) is preferably 300 to 10,000, more preferably 300 to 5,000, from the viewpoint of excellent vibration resistance. Furthermore, from the viewpoint of excellent vibration resistance, it is particularly preferable to contain polyethylene glycols having a number average molecular weight of 300 and a number average molecular weight of 1540 in combination.

The content of component (d) is not particularly limited, but is preferably 1 to 15%, more preferably 3 to 10%, more preferably 4 to 6%, from the standpoint of excellent disintegration strength and skin familiarity when applied. more preferred.

Component (e): Water Component (e) used in the present invention is water. As the component (e), those commonly used in cosmetics and external skin preparations can be used, and are not particularly limited. Component (e) water may be tap water, purified water purified by distillation or the like, hot spring water, deep-sea water, or the like. Plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose water may also be used.

By containing the components (a) to (e) in combination, the granular composition of the present invention has good vibration resistance, collapse strength upon application, and skin compatibility. Even if the strength required to form granules can be maintained by the components (a) and (c), if the components (b) and (d) are not contained, vibration resistance, collapse strength during application, It may not fit well on the skin. When the components (a) to (e) are contained as a combination, the mechanism that the vibration resistance, the collapse strength at the time of application, and the skin familiarity are improved is not clear, but the components (a) and (c) ) is present in the system of the composition, while the component (b) acts as a binder for these polymers, and the component (d) is also present in the composition system together, vibration resistance It is considered to have excellent collapse strength at the time of application while having good properties. Furthermore, it is thought that the component (b) can have good affinity with the application site such as the skin, and the granular composition containing the components (a) to (e) has excellent skin compatibility.

The content ratio (a)/(d) of component (a) and component (d) in the present invention is not particularly limited, but is preferably 0.05 to 2, and 0.05 to 2 in terms of excellent collapse strength when applied. 1 to 0.4 is more preferred, and 0.2 to 0.3 is even more preferred.

The content mass ratio (b)/(d) of the component (b) and the component (d) in the present invention is not particularly limited, but from the viewpoint of excellent vibration resistance, it is preferably 0.1 to 3, and 0.5 to 1 is more preferred.

The granular composition of the present invention may contain, in addition to the aforementioned components, components commonly used in cosmetics and external preparations for skin, such as components (a) to (e), as long as they do not impair the effects of the present invention. Surfactants, lower alcohols, oils, moisturizers, thickeners, sequestering agents, cooling agents, antioxidants, preservatives/bactericides, pH adjusters, coloring agents, various fragrances, etc. It can be contained as appropriate.

The method for producing the granular composition of the present invention is not particularly limited, but for example, water, agar, and gellan gum are heated and dissolved at about 90°C, phospholipids are added at about 70°C, solidified by cooling, and defoamed. It is preferred to produce an agar gel from which the granular composition of the invention is based. The agar gel is heated again to about 70° C. and dropped into an oily component such as silicone oil or hydrocarbon oil at about 25° C. to obtain a granular composition, which is preferable because it approaches a spherical shape and has a beautiful appearance. . The obtained granular composition can be used after washing with purified water to remove surface oil.

Although the shape of the granular composition of the present invention is not particularly limited, it is preferably spherical. In the present invention, the term "spherical" includes a true sphere, a substantially spherical shape, and a spheroid, and may be a spherical powder having an uneven surface. The ratio of the minor axis to the major axis of the spherical powder, that is, the ellipticity is preferably 1.5 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.

The average particle diameter of the granular composition of the present invention is not particularly limited, but is preferably 1 to 20 mm, more preferably 5 to 20 mm, and even more preferably 8 to 20 mm in terms of collapse strength and vibration resistance when applied. , 8 to 13 mm are more particularly preferred. In addition, the average particle size of the granular composition of the present invention is determined by selecting 20 arbitrarily selected grains after preparing 100 grains of the granular composition, measuring their particle diameters using a vernier caliper, etc., and calculating the average value. It is possible to obtain by calculating. Moreover, when there is a difference between the minor axis and the major axis of the granular composition, the average value of the minor axis and the major axis is taken as the particle size of the granular composition.

The granular composition of the present invention may or may not be immersed in a solvent, and is not particularly limited. preferably not immersed in Here, the solvent in the present invention is not particularly limited as long as it is used in cosmetics, external preparations for skin, and the like, and includes liquid compositions and the like. Furthermore, specific examples of liquid compositions include water, ethanol, liquid oils, emulsion compositions, and the like. In addition, the term “liquid” in the present invention means fluidity at normal temperature (25° C.) and normal pressure.
The state in which the granular composition is not immersed in a solvent is not particularly limited, but the granular composition of the present invention can be filled in an airtight container, a sealed container, a sealed container, or the like without adding a solvent. . Moreover, the gas filled in the container is not particularly limited, but air, nitrogen, carbon dioxide, or the like can be used.

The granular composition of the present invention can be filled into a container without any particular limitation. At that time, the state of packing is not particularly limited, and the granular composition may be in the closest packed state in the container, or may be in a state where there is a lot of excess space and the granular compositions are not in contact with each other. Also good. From the viewpoint of vibration resistance, the packing density is preferably 0.5 to 0.8, more preferably 0.55 to 0.75.

In particular, problems such as collapse strength and vibration resistance during application can be problematic for granular compositions that have not been immersed in a solvent. That is, the state of being immersed in a solvent and the state of not being immersed in a solvent are scientifically and technically different. Therefore, even if the granular composition immersed in the solvent has excellent collapse strength and vibration resistance at the time of application, the granular composition not immersed in the solvent has the collapse strength at the time of application. It is thought that it is difficult to imagine whether or not the vibration resistance is excellent.

Although the granular composition of the present invention is not particularly limited, it can be used as a cosmetic, an external skin preparation, or the like in a state of being immersed in a solvent, and can be used in a cosmetic or skin preparation without being immersed in a solvent. It can also be used as a skin external preparation. Cosmetics include, for example, external solid agents, external liquid agents, sprays, ointments, creams, gels, patches, emulsions, lotions, pack cosmetics, facial cleansers, cosmetics for massage, and hair products. Cosmetics, sunscreens, body cosmetics such as body cream, cosmetics around the eyes such as eye cream, lip care cosmetics such as lip essence, lip balm, foundation, primer, concealer, powder, eye shadow, Makeup formulations such as blush, lipstick, mascara, and eyebrow are included. Examples of external preparations for skin include liniments, lotions, ointments and the like. Among these, the granular composition of the present invention is preferably used as a cosmetic for massage without being immersed in a solvent, from the standpoint of disintegration strength upon application.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

Examples 1 to 10 and Comparative Examples 1 to 6: Granular composition (spherical massage cosmetic)
Granular compositions (spherical massaging cosmetics) having the formulations shown in Examples 1 to 10 and Comparative Examples 1 to 6 were prepared, and the collapse strength, vibration resistance, and familiarity with the skin during application were evaluated by the following evaluation methods. did. The results are also shown in Tables 1-3.

(Production method)
According to each formulation shown in Tables 1 to 3, components 1, 3 to 7 were heated and dissolved at about 90°C, components 2, 8 to 15 were added at about 70°C, and solidified by cooling to produce a gel. . The gel is heated again to about 70° C., dropped into silicone oil (100 cs) at about 25° C. using Terumo Syringe ss-50ESz (manufactured by Terumo Corporation), solidified, and then washed with purified water. , to obtain a granular composition (spherical massage cosmetic). Moreover, Examples 1 to 10 and Comparative Examples 1 to 6 were all spherical and had an average particle size of 10 mm.

(Evaluation item 1: collapse strength at the time of application)
After manufacturing each sample of Examples 1 to 10 and Comparative Examples 1 to 6, after storing for 2 hours at room temperature, out of 100 grains of each sample, 10 grains were randomly taken out, and for 1 grain of sample, At room temperature (25°C), texture analyzer TA. Using XTplus (manufactured by StableMicroSystems), the maximum load under the following conditions (probe: cylindrical polyacetal resin with a diameter of 10 mm (Delrin (registered trademark) manufactured by DuPont), speed: 0.1 mm / sec, compression: 3 mm) Value (g) was measured. After that, the average value of 10 grains was determined and judged according to the following judgment criteria 1.

<Judgment Criteria 1>
(Average value of maximum load value): (judgment)
Over 30 g: × (too hard and poor usability)
More than 20 g and less than 30 g: 〇 (slightly hard, but there is no problem with usability)
More than 10 g and 20 g or less: ◎ (preferable hardness, no problem in usability, and good crumbling feeling)
10 g or less: × (too soft and poor usability)

(Evaluation method 2: vibration resistance)
After producing each sample of Examples 1 to 10 and Comparative Examples 1 to 6, after storing for 2 hours at room temperature, about 20 grains of each sample (initial mass: about 10 g) was placed in a glass bottle at room temperature (25 ° C.). (No. 3 standard bottle (manufactured by Kawaguchi Yakuhin Kagaku Co., Ltd.)), set it on the multi-mixer MIX-101 (manufactured by Synix Co., Ltd.), and set it on the vibration condition with the scale of the turning knob facing upward for 5 hours. , oscillated. Then, after removing the sample that collapsed due to vibration and washing with purified water, the remaining mass was measured, divided by the initial mass, and the value multiplied by 100 was defined as vibration resistance, and was judged according to the following judgment standard 2.

<Judgment Criteria 2>
(Vibration resistance): (judgment)
60% or less: × (defective)
Over 60% and 80% or less: ○ (good)
Over 80%: ◎ (very good)

(Evaluation method 3: familiarity with the skin)
After each sample of Examples 1 to 10 and Comparative Examples 1 to 6 was produced and stored at room temperature for 2 hours, 20 cosmetic evaluation specialist panels placed one grain of each sample on their cheeks with their index and middle fingers. After application for 30 seconds in a rolling motion, the familiarity with the skin felt was evaluated according to the following 5-grade absolute evaluation, and a score was given. After that, the average value of the scores was calculated and judged according to the following judgment criteria 3.

<5-step absolute evaluation>
(Rating): (Evaluation)
5 points: No remnants of the granular composition are present, and the skin feels strongly plump. 4 points: There are no remnants of the granular composition, and the skin feels slightly plump. 3 points: Remains of the granular composition are present. 2 points: Remains of the granular composition with a diameter of less than 1 mm are present, and skin compatibility is poor. defective

<Judgment Criteria 3>
(Judgment): (Average score)
◎: more than 4 points (very good)
○: More than 3 points and 4 points or less (good)
△: More than 2 points and 3 points or less (slightly poor)
×: 2 points or less (defective)

<Results>
As is clear from Tables 1 to 3, the granular compositions (spherical massaging cosmetics) of Examples 1 to 10 are superior to Comparative Examples 1 to 6 in terms of collapse strength, vibration resistance, and skin familiarity when applied. rice field.
On the other hand, Comparative Example 1, which does not contain component (a), was inferior in collapse strength, vibration resistance, and skin compatibility when applied.
Comparative Example 2, which does not contain the component (b), was inferior in terms of disintegration strength and skin compatibility when applied.
Comparative Example 3, which does not contain component (c), was inferior in vibration resistance and skin compatibility.
Comparative Example 4, which does not contain component (d), was inferior in collapse strength, vibration resistance, and skin compatibility when applied.
Comparative Example 5, which did not contain component (d) but contained PEG-400, was inferior in disintegration strength, vibration resistance, and skin compatibility when applied.
Comparative Example 6, which did not contain component (d) but contained polyvinyl alcohol, was inferior in collapse strength, vibration resistance, and skin compatibility when applied.

Example 11: Spherical hand care cosmetic (ingredient) (%)
1. Agar *10 2.0
2. Phospholipid *11 3.0
3. Gellan gum *3 0.05
4. Carbomer 0.06
5. Vaseline 5
6. Glycerin 10
7. BG 10
8. Remaining amount of purified water 9 . Phenoxyethanol 0.05
10. PEG-150 8
11. PEG-60 hydrogenated castor oil 0.5
12. Na hydroxide 0.018
* 10: Ina agar UP-37CS (manufactured by Ina Food Industry Co., Ltd.)
*11: COMPOSITE-PC (manufactured by Nippon Fine Chemical Co., Ltd.)

(Production method)
Components 1, 3, 4, 6 to 9, and 12 were heated and dissolved at about 90°C, components 2, 5, 10, and 11 were added at about 70°C, solidified by cooling, and defoamed to produce a gel. . The gel is heated again to about 65° C., dropped into silicone oil (6 cs) at about 25° C. using Terumo Syringe ss-50ESz (manufactured by Terumo Corporation), solidified, and then washed with purified water. , to obtain a granular composition (spherical hand care cosmetic). The obtained granular composition was spherical and had an average particle size of 15 mm.

Example 11: The spherical cosmetic for hand care had good collapse strength, vibration resistance, and familiarity with the skin when applied.

Example 12: Spherical whitening cosmetic (ingredient) (%)
1. Agar *1 1.0
2. Phospholipid *2 2.0
3. Gellan gum *3 0.04
4. Sodium hyaluronate 0.001
5. Glycerin 8
6. BG 5
7. Remaining amount of purified water 8 . Phenoxyethanol 0.3
9. PEG-8 5
10. ascorbyl glucoside 2

(Production method)
Components 1, 3, 5 to 8 were heated and dissolved at about 90°C, components 2, 4, 9, and 10 were added at about 70°C, solidified by cooling, and defoamed to produce a gel. The gel is heated again to about 70° C., dropped into silicone oil (100 cs) at about 25° C. using Terumo Syringe ss-50ESz (manufactured by Terumo Corporation), solidified, and then washed with purified water. , to obtain a granular composition (spherical whitening cosmetic). The obtained granular composition was spherical and had an average particle size of 8 mm.

Example 12: The spherical whitening cosmetic had good collapse strength, vibration resistance, and skin familiarity when applied.

Example 13: Spherical powder cosmetic (ingredient) (%)
1. Agar 1.2
2. Phospholipid 5
3. Gellan gum 0.05
4. (Acrylates/alkyl acrylate (C10-C30) crosspolymer) 0.04
5. DPG 12
6. Remaining amount of purified water 7. Titanium oxide 0.2
8. Triceteareth-4-phosphate 0.01
9. Phenoxyethanol 0.2
10. PEG-8 6
11. Na hydroxide 0.012

(Production method)
Components 1, 3 to 6, and 9 were heated and dissolved at about 90°C, components 2, 7, 8, 10, and 11 were added at about 70°C, solidified by cooling, and defoamed to produce a gel. The gel is heated again to about 70° C., dropped into silicone oil (6 cs) at about 25° C. using Terumo Syringe ss-50ESz (manufactured by Terumo Corporation), solidified, and then washed with purified water. , to obtain a granular composition (spherical face powder cosmetic). The obtained granular composition was spherical and had an average particle size of 13 mm.

Example 13: The spherical face powder cosmetic had good collapse strength, vibration resistance, and skin familiarity when applied.

Claims (7)

the following components (a) to (e);
(a) 0.8 to 2% by mass of agar with a jelly strength of 20 to 2000 g/cm ²
(b) Phospholipid 2-8% by mass
(c) 0.01 to 0.1% by mass of gellan gum
(d) 1 to 15% by mass of polyethylene glycol having a number average molecular weight of 10,000 or less
(e) a granular composition containing water; 2. The particulate composition of claim 1, which is not immersed in a solvent. A granular composition according to any one of claims 1 or 2, characterized in that the average particle size is between 1 and 20 mm. 4. A particulate composition according to any one of claims 1 to 3, characterized in that it is spherical. The granular composition according to any one of claims 1 to 4, wherein the content ratio (a)/(d) of the component (a) and the component (d) is 0.05 to 2. thing. The granular composition according to any one of claims 1 to 5, wherein the content ratio (b)/(d) of the component (b) and the component (d) is 0.1 to 3. thing. 7. The granular composition according to any one of claims 1 to 6, which is a cosmetic or an external preparation for skin.