JP2020097540A - Granular composition - Google Patents

Abstract

To provide a granular composition that has excellent vibration resistance, has excellent breakdown strength during application, and has excellent skin compatibility.SOLUTION: A granular composition contains following components (a)-(e): (a) agar, (b) phospholipids, (c) gellan gum, (d) polyethylene glycol with a number average molecular weight of 10000 or less, and (e) water.SELECTED DRAWING: None

Description

The present invention relates to particulate compositions.

As a cosmetic or an external preparation for the skin, a technique relating to a granular composition such as gel particles containing various cosmetic ingredients has been disclosed.
For example, in Patent Document 1, there is disclosed a technique relating to a skin cosmetic, which is prepared by mixing an aqueous solution of an alkali metal salt of alginic acid with an aqueous solution of a calcium salt of an inorganic acid or an organic acid to form a small spherical substance made of hydrous calcium alginate. It is disclosed.
For example, in Patent Document 2, the following components (A) to (E): (A) a gelling agent that causes gelation due to the thermoreversibility of the sol-gel, (B) a crosslinkable polyacrylate, and (C) a solid. A technique relating to hydrogel particles is disclosed, which comprises 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 a dispersant is cooled and solidified in a gas phase or a liquid phase by a dropping method. Particles having an average particle size 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 A technique relating to a skin cosmetic which is dispersed and suspended in a transparent or translucent aqueous base material having a pH of 0.0 is disclosed.

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 and the like under the condition that the granular composition is immersed in a solvent. , When it is not soaked in the solvent, the granular composition keeps its shape due to the vibration during transportation, the granular composition collapses without maintaining its shape against the vibration itself, or the granular compositions collide with each other. In some cases, it was inferior in vibration resistance, such as being impossible. That is, no granular composition excellent in vibration resistance has hitherto been known.

The present inventor tried to develop a granular composition having excellent vibration resistance in consideration of the above problems in the prior art, and depending on the type of polymer contained, the vibration resistance of the granular composition was improved. However, when the granular composition is applied to the skin or the like, the disintegration strength at the time of application is not preferable, and the granular composition is not crushed and cannot be applied, or even if the granular composition is crushed, it is familiar to the skin. There was still the problem that it was inferior to.
Therefore, as a result of further intensive studies, the present inventors have found that agar, phospholipids, gellan gum, polyethylene glycol having a number average molecular weight of 10,000 or less, and a water-containing granular composition are remarkably excellent in vibration resistance, and It was found that the disintegration strength at the time of application was excellent and that the skin familiarity was good.

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

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

The present invention provides the above granular composition having an average particle size of 1 to 20 mm.

The present invention provides the above-mentioned granular composition, which is spherical.

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

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

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

According to the present invention, it is possible to provide a granular composition having excellent vibration resistance, excellent disintegration strength when applied, and excellent in skin familiarity.

Hereinafter, the present invention will be described in detail. In addition, in this specification, "-" shall mean the range including the numerical value before and behind.

Component (a): Agar The component (a) used in the present invention is agar, and any one can be used regardless of its place of origin, origin or the like. As the agar, so-called low-strength agar (for example, disclosed in Japanese Patent Laid-Open No. 5-317008) may be used in which the molecule is cleaved by acid treatment to adjust the jelly strength. The jelly strength of this agar is not particularly limited, but is preferably ²⁰ to 2000 g/cm ² , and more preferably 30 to 1000 g/cm ² . Here, the jelly strength is 1.5% by mass (hereinafter, "% by mass" is simply referred to as "%"). Agar is heated and dissolved in water, and the gel is allowed to stand at 20°C for 15 hours to coagulate. Is the maximum mass that the surface can withstand for 20 seconds per cm ² . When agar having a jelly strength in this range is used, it is difficult for the agar to form a hard solid, and therefore a cosmetic having particularly good uniformity of the cosmetic film can be obtained. As such agar, commercially available products such as AX-100 and UP-37 (all manufactured by Ina Food Industry Co., Ltd.) can be used.

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

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 usually used in cosmetics and external preparations for skin. In addition, it is possible to use 1 type(s) or 2 or more types below.

The component (b) may be a natural product extracted/purified from an animal or plant, a chemically synthesized product, or a treatment such as hydrogenation, hydroxylation or enzyme treatment.
Examples of natural products include soybean-derived phospholipids and egg yolk-derived phospholipids. 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. Examples include added lysophospholipids and the like.
Of these, hydrogenated phospholipids are preferable, and soybean-derived hydrogenated phospholipids are more preferable. Hydrogenated phospholipids (preferably derived from soybean) are preferable in that when they are combined with the below-mentioned component (a) and component (c), the disintegration strength upon application and the skin familiarity are good.

Examples of commercially available products of component (b) include Recinol S-PIE, Nikkor Recinol S-10, Nikkor Recinol S-10E (above, Nikko Chemicals), Basis LS-60HR (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.

Further, the content of the component (b) is not particularly limited, but is preferably 2 to 8%, more preferably 4 to 7% from the viewpoint of excellent vibration resistance, disintegration strength at application, and excellent skin familiarity. ..

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

As the component (c), a native type and a deacyl type in which acetyl group and glyceryl group existing in 1-3-bonded glucose are removed are known, and any of them can be used. The component (c) has a property of further thickening by the addition of a metal cation such as calcium ion or sodium ion, has high salt resistance, and can maintain the viscosity even in the presence of a high concentration of electrolyte. preferable. As commercially available products, KELCOGEL CC (manufactured by Sansho Co., Ltd.), Gelcogel (manufactured by Sumitomo Dainippon Pharma Co., Ltd.), Kercogel F (manufactured by Sumitomo Dainippon Pharma Co., Ltd.), Kercogel HM (manufactured by Sumitomo Dainippon Pharma Co., Ltd.), Kelcogel HT (manufactured by Dai Nippon Sumitomo Pharma Co., Ltd.) Sumitomo Nippon Pharma Co., Ltd.), Kelcogel LT100 (manufactured by Dainippon Sumitomo Pharma Co., Ltd.), and the like, and one or more kinds can be used.

The content of the component (c) is not particularly limited, but is preferably 0.01 to 0.1%, more preferably 0.03 to 0.08% from the viewpoint of excellent disintegration strength when applied.

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 the component (d) is preferably 300 to 10,000, more preferably 300 to 5,000, from the viewpoint of excellent vibration resistance. Further, it is particularly preferable that polyethylene glycol having a number average molecular weight of 300 and a polyethylene glycol having a number average molecular weight of 1540 are contained together in terms of excellent vibration resistance.

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

Component (e): Water The component (e) used in the present invention is water. As the component (e), those usually used for cosmetics and external preparations for skin can be used, and there is no particular limitation. As the component (e) water, tap water may be used, or purified water purified by distillation or the like, hot spring water, deep water, or the like may be used. In addition, plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose water may be used.

Since the granular composition of the present invention contains the components (a) to (e) in combination, vibration resistance, disintegration strength upon application, and skin familiarity are improved. Even if the strength required for forming granules is maintained by the components (a) and (c), if the components (b) and (d) are not contained, vibration resistance, collapse strength at the time of application, It may not be familiar to 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 good is not clear in some parts, but the components (a) and (c) ) Exists in the system of the composition, the component (b) acts as a binder to the polymer, and the component (d) also exists in the system of the composition, so that the vibration resistance is improved. It is thought that while it has good properties, it also has excellent disintegration strength when applied. Furthermore, it is considered that the component (b) can have good affinity with an application site such as the skin, and the granular composition containing the components (a) to (e) is excellent in skin familiarity.

The content mass ratio (a)/(d) of the component (a) and the component (d) in the present invention is not particularly limited, but is preferably 0.05 to 2 in terms of excellent disintegration strength upon application, and 0.0. 1 to 0.4 is more preferable, and 0.2 to 0.3 is even more preferable.

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

In the granular composition of the present invention, in addition to the above-mentioned components, components usually used in cosmetics and external preparations for the skin, for example, components (a) to (e), as long as the effects of the present invention are not impaired. Other than the above, surfactants, lower alcohols, oils, moisturizers, thickeners, sequestering agents, cooling agents, antioxidants, antiseptic/bactericidal agents, pH adjusters, colorants, various fragrances, etc. depending on the purpose. It can be contained as appropriate.

The method for producing the granular composition of the present invention is not particularly limited. For example, water, agar, and gellan gum are heated and dissolved at about 90° C., phospholipids are added at about 70° C., and solidification by cooling and defoaming are performed. It is preferred to produce the agar gel from which the granular composition of the present invention is based. It is preferable that 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 close to spherical and has a beautiful appearance. .. The obtained granular composition can be washed with purified water to remove oil on the surface before use.

The shape of the granular composition of the present invention is not particularly limited, but it is preferably spherical. In the present invention, the term “spherical” includes spherical particles, spherical particles, spheroids, and spherical particles having irregularities on the surface. The ratio of the minor axis/major axis of the spherical powder, that is, the ellipticity, is preferably 1.5 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

The average particle size of the granular composition of the present invention is not particularly limited, but from the viewpoint of collapse strength at the time of application and vibration resistance, 1 to 20 mm is preferable, 5 to 20 mm is more preferable, and 8 to 20 mm is even more preferable. , 8 to 13 mm is particularly preferable. Further, the average particle size of the granular composition of the present invention, after preparing 100 particles of the granular composition, select any 20 particles, measure the particle size using a caliper, etc., the average value It is possible to obtain it by calculating. Further, when there is a difference between the short diameter and the long diameter of the granular composition, the average value of the short diameter and the long diameter is taken as the particle diameter of the granular composition.

The granular composition of the present invention may be immersed in a solvent, or may not be immersed in a solvent, and is not particularly limited, but in view of disintegration strength at the time of application, vibration resistance, and skin familiarity, in a solvent. It is preferably not dipped 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 examples thereof include liquid compositions. Further, specific examples of the liquid composition include water, ethanol, a liquid oil agent, an emulsified composition and the like. In addition, the liquid in the present invention has fluidity at normal temperature (25° C.) and normal pressure.
The granular composition is not particularly limited as being not immersed in the solvent, but the granular composition of the present invention can be filled in an airtight container, a hermetically sealed container, a hermetically sealed container or the like without particularly adding a solvent. .. 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 in a container without particular limitation. At that time, the filling state is not particularly limited, the granular composition in the container, even if the closest packed state, there is a lot of excess space, whether the granular composition is not in contact with each other Is 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.

Further, in particular, problems such as disintegration strength during application and vibration resistance can be a problem in a granular composition which is not immersed in a solvent. That is, it can be said that the state of being immersed in the solvent and the state of not being immersed in the solvent are scientifically and technically different. Therefore, in the granular composition immersed in the solvent, the collapse strength and vibration resistance at the time of application, even if excellent, even in the granular composition in the state of not being immersed in the solvent, the collapse strength at the time of application It is difficult to imagine whether or not the vibration resistance is excellent.

The granular composition of the present invention is not particularly limited, in a state of being immersed in a solvent, it can be used as a cosmetic or a skin external preparation, etc., in a state of not being immersed in a solvent, a cosmetic or the like. It can also be used as a skin external preparation. Examples of the cosmetics include solid preparations for external use, liquid preparations for external use, sprays, ointments, creams, gels, patches and the like, emulsions, lotions, pack cosmetics, facial cleansers, cosmetics for massage, and hair. Cosmetics, sunscreen, body cream and other body cosmetics, eye cream and other eye area cosmetics, lip essence, lip cream and other lip care cosmetics, foundation, foundation, concealer, white powder, eye shadow, Makeup preparations such as blusher, lipstick, mascara and eyebrow can be mentioned. Examples of the external preparation for skin include liniment agents, lotions, ointments and the like. Among them, the granular composition of the present invention is preferably used as a cosmetic composition for massage in a state of not being immersed in a solvent, from the viewpoint of disintegration strength at the time of application.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

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

(Production method)
According to the formulations shown in Tables 1 to 3, components 1, 3 to 7 were heated and dissolved at about 90° C., components 2 and 8 to 15 were added at about 70° C., and the mixture was cooled and solidified to once produce a gel. .. The gel is heated again to about 70° C., dropped into silicone oil (100 cs) at about 25° C. by using Terumo syringe ss-50ESz (manufactured by Terumo Corp.), solidified, and then washed with purified water. Thus, a granular composition (cosmetic composition for spherical massage) was obtained. In addition, Examples 1 to 10 and Comparative Examples 1 to 6 were all spherical and had an average particle diameter of 10 mm.

(Evaluation item 1: Collapse strength when applied)
After each of the samples of Examples 1 to 10 and Comparative Examples 1 to 6 was manufactured and stored at room temperature for 2 hours, 10 grains were randomly taken out from 100 grains of each sample, and 1 grain was compared with 1 grain of the sample. At room temperature (25° C.), the texture analyzer TA. Using XTplus (manufactured by Stable Micro Systems), the maximum load under the following conditions (probe: cylindrical polyacetal resin with a diameter of 10 mm (Delrin (registered trademark) DuPont), speed: 0.1 mm/sec, compression: at 3 mm) The value (g) was measured. After that, the average value of 10 grains was calculated and judged according to the following judgment standard 1.

<Criteria 1>
(Average of maximum load values): (Judgment)
Over 30g: × (too hard to be used)
More than 20g and less than 30g: ○ (A little hard, but there is no problem in usability)
More than 10 g and 20 g or less: ◎ (suitable hardness, no problem in usability, and feel good in collapse)
10 g or less: × (too soft and poor in usability)

(Evaluation method 2: Vibration resistance)
After each of the samples of Examples 1 to 10 and Comparative Examples 1 to 6 was manufactured and stored at room temperature for 2 hours, about 20 grains (initial mass: about 10 g) of each sample were stored in a glass bottle at room temperature (25°C). (No. 3 standard bottle (manufactured by Kawaguchi Chemical Co., Ltd.)), set it on the multi-mixer MIX-101 (manufactured by Synics Co., Ltd.), and vibrate for 5 hours under the condition that the scale of the swivel knob faces upward. , Vibrated. Then, the sample disintegrated by vibration was removed, washed with purified water, the residual mass was measured, divided by the initial mass, and 100 times the value was taken as the vibration resistance, and the judgment criteria 2 below were used.

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

(Evaluation method 3: familiar with the skin)
After manufacturing the samples of Examples 1 to 10 and Comparative Examples 1 to 6 and storing them at room temperature for 2 hours, 20 panelists specialized in cosmetic evaluation evaluated 1 grain of each sample on the cheek with the index finger and the middle finger. The skin familiarity felt after applying for 30 seconds so as to roll was evaluated by the following five-level absolute evaluation, and a score was given. After that, the average value of the scores was calculated and judged according to the following judgment standard 3.

<5-level absolute evaluation>
(Score): (Evaluation)
5 points: There is no residue of the granular composition, and the skin feels plump strongly. 4 points: No residue of the granular composition exists, but the skin feels slightly plump. 3 points: The residue of granular composition exists. However, there is no fluffy feeling on the skin. 2 points: Remnants of the granular composition having a diameter of less than 1 mm are present, and the skin is not familiar. 1 point: Remnants of the granular composition having a diameter of 1 mm or more are present, and the skin is very familiar. Bad

<Criteria 3>
(Judgment): (Average score)
A: More than 4 points (very good)
◯: More than 3 points and 4 points or less (good)
Δ: More than 2 points and 3 points or less (somewhat bad)
X: 2 points or less (defective)

<Results>
As is clear from Tables 1 to 3, the granular compositions of Examples 1 to 10 (cosmetics for spherical massage) are superior in disintegration strength upon application, vibration resistance, and skin familiarity as compared with Comparative Examples 1 to 6. It was
On the other hand, Comparative Example 1 containing no component (a) was inferior in collapse strength at the time of application, vibration resistance, and skin familiarity.
Comparative Example 2 which did not contain the component (b) was inferior in disintegration strength at application and skin familiarity.
Comparative Example 3 containing no component (c) was inferior in vibration resistance and skin familiarity.
Comparative Example 4 containing no component (d) was inferior in disintegration strength at the time of application, vibration resistance, and skin familiarity.
Comparative Example 5, which did not contain the component (d) but contained PEG-400, was inferior in disintegration strength upon application, vibration resistance, and skin familiarity.
Comparative Example 6, which did not contain the component (d) but contained polyvinyl alcohol, was inferior in collapse strength at the time of application, vibration resistance, and skin familiarity.

Example 11: Spherical hand care cosmetic (component) (%)
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. Purified water Remaining amount 9. Phenoxyethanol 0.05
10. PEG-1508
11. PEG-60 hydrogenated castor oil 0.5
12. Na hydroxide 0.018
*10: Inagarten UP-37CS (manufactured by Ina Food Industry Co., Ltd.)
*11: COMPOSITE-PC (Nippon Seika)

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

Example 11: The spherical hand care cosmetics had good disintegration strength, vibration resistance and skin familiarity when applied.

Example 12: Spherical whitening cosmetic composition (component) (%)
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. Purified water Remaining amount 8. Phenoxyethanol 0.3
9. PEG-8 5
10. Ascorbyl glucoside 2

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

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

Example 13: Spherical white cosmetic (component) (%)
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. Purified water Remaining amount 7. Titanium oxide 0.2
8. Triceteareth-4-phosphate 0.01
9. Phenoxyethanol 0.2
10. PEG-8 6
11. Sodium hydroxide 0.012

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

Example 13: The spherical whitening cosmetic composition had good disintegration strength when applied, vibration resistance, and good skin familiarity.

Claims (7)

The following components (a) to (e);
A granular composition containing (a) agar (b) phospholipid (c) gellan gum (d) polyethylene glycol (e) water having a number average molecular weight of 10,000 or less. The granular composition according to claim 1, which is not immersed in the solvent. The granular composition according to claim 1 or 2, wherein the average particle size is 1 to 20 mm. The granular composition according to any one of claims 1 to 3, which has a spherical shape. The granular composition according to any one of claims 1 to 4, wherein the content mass ratio (a)/(d) of the component (a) and the component (d) is 0.05-2. Stuff. The granular composition according to any one of claims 1 to 5, wherein a content mass ratio (b)/(d) of the component (b) and the component (d) is 0.1 to 3. Stuff. The granular composition according to any one of claims 1 to 6, which is a cosmetic or a skin external preparation.