JP5492373B2 - Oily gel composition containing organically modified clay mineral having plate-like particle structure, and W / O type emulsified composition using the same - Google Patents

Description

  The present invention relates to an oily gel composition containing an organically modified clay mineral having a plate-like particle structure, and a W / O type emulsion composition. It relates to the improvement of the stabilizing ability in the emulsion.

  Conventionally, W / O emulsification systems are used in various products. In particular, silicone oil has smooth characteristics and is excellent in volatility and water repellency, so it is an important oil component in the cosmetics field. Of course, it can also be added to W / O type cosmetics. It is desired. However, silicone oil is difficult to form a stable W / O emulsification system.

  In addition, from the viewpoint of usability, handling properties, etc., thickening in oil systems and gelation are performed not only in cosmetics and quasi drugs but also in various fields such as paints and resins. Agents or waxes are used, but silicone oil is particularly important in the cosmetics field.

  Until now, in order to gelate silicone oil and stabilize W / O emulsified system containing silicone oil, there is a method of solidifying silicone oil together with waxes, a method of using silica or silica that has been hydrophilized, etc. Has been.

However, the method of solidifying together with waxes has a problem in use feeling such as stickiness and stickiness, and the application range is limited because of poor fluidity. Further, the method using silica together has a problem that the stability over time is poor.
As a method for improving the problems of usability and stability over time, a method has been developed in which an organically modified clay mineral is treated with a polyether-modified silicone compound and blended into a gel composition or a W / O emulsion. (For example, see Patent Documents 1 and 2).

However, the gel-forming ability of the gel composition containing the organically modified clay mineral treated with the aforementioned polyether-modified silicone compound is low in sustainability, and the function as an emulsifier when blended in a W / O emulsion is It was not satisfactory enough.
Furthermore, when trying to ensure the stability of the emulsion using the organically modified clay mineral used conventionally, the gel properties brought about by the required amount of the component tend to have relatively high viscoelasticity, It was very difficult to obtain an emulsion having a low viscosity and excellent stability.
Japanese Patent Laid-Open No. 61-114721 JP-A-61-212321

The present invention has been made in view of the above-mentioned circumstances, and one of its purposes is an organically modified clay mineral-based thickening / gelling agent that exhibits excellent thickening / gelling ability with respect to oil. And providing an oily gel composition using the same.
In addition, for example, when used in a W / O emulsion, an organically modified clay mineral-based emulsifier that can exhibit an excellent temporal stabilization effect such as suppressing aggregation and coalescence of emulsified particles over time, And providing a W / O emulsion using the same.
Moreover, one is to provide an organically modified clay mineral-based emulsifier that can exhibit a W / O emulsion stabilization effect even at low viscosity, and a W / O emulsion using the same.

The gel-forming ability of the gel composition containing the organically modified clay mineral treated with the above-mentioned polyether-modified silicone compound has low durability, and the function as an emulsifier when blended in a W / O emulsion is insufficient. This point was considered as follows.
That is, the shape of the clay mineral is originally a layered (laminated) plate-like particle having a thickness of several nanometers. However, since a commercially available organically modified clay mineral is agglomerated during the production process, The clay mineral is further agglomerated, and the average thickness is usually 2 μm or more. Therefore, the treatment with the polyether-modified silicone compound alone does not make the aggregates of the clay mineral finer or plate-like, so that the organic-modified clay mineral is not sufficiently dispersed, resulting in a stable gel in oil. It was thought that the network structure was not sufficiently formed. And it was thought that this might be a cause of inferior functions as a gelling agent and an emulsifier.

  Based on such an idea, the present inventors have conducted an investigation, and the aggregate of the organically modified clay mineral is exfoliated in an oil component by mechanical shearing force and / or impact force to form fine plate-like particles. It was found that by controlling the shape, the thickening / gelling ability in the presence of a nonionic surfactant is remarkably increased. Moreover, the emulsion stabilization effect in a W / O emulsion becomes very high. For this reason, it becomes possible to provide a W / O emulsion having a relatively low viscosity and excellent stability by reducing the amount of the organically modified clay mineral plate-like particles and the nonionic surfactant used. As a result, the present invention has been completed.

That is, the oily gel composition according to the present invention is characterized by containing the following components (i) to (iii).
(i) an organically modified clay mineral having a plate-like particle structure having an average thickness of 0.1 μm or less and an average major axis of 0.5 to 50 μm,
(ii) Nonionic surfactant
(iii) Oil content In the present invention, each plate-like particle is not substantially aggregated.
In the oily gel composition of the present invention, it is preferable that the organically modified clay mineral having a plate-like particle structure is an organically modified hectorite.
In the oily gel composition of the present invention, it is preferable that the oil component contains silicone oil.

In the oily gel composition of the present invention, an aggregate of an organically modified clay mineral having a layered structure having an average thickness of 2 μm or more is subjected to mechanical shearing force and oil in an oil component in the presence of a nonionic surfactant. It is preferable to manufacture by a method of peeling treatment by impact force.
In the oily gel composition of the present invention, it is preferable that the nonionic surfactant is a polyether-modified silicone compound.

Moreover, in the oily gel composition according to the present invention, the amount of the organically modified clay mineral having a plate-like particle structure is preferably 0.25 to 30% by mass in the oily gel composition, The blending amount of the organically modified clay mineral having the plate-like particle structure is preferably 0.25 to 10% by mass in the oily gel composition.
Moreover, the oil-based gel composition concerning this invention WHEREIN: It is suitable that the compounding quantity of the said nonionic surfactant is 0.1-10 mass% in an oil-based gel composition.
In particular, the blending amount of the organically modified clay mineral aggregate in the oil is 0.5 to 5.0% by mass in the mixture, and the blending amount of the nonionic surfactant is only 2.5 to 5.0% by mass in the mixture. However, it is preferable.
The W / O type emulsion composition or cosmetic according to the present invention is characterized by using any of the oily gel compositions described above.

  The organically modified clay mineral having a plate-like particle structure of the present invention exhibits an excellent thickening gelling effect on oils when used in combination with a nonionic surfactant. Moreover, since it is excellent also in the emulsion stabilization effect with respect to a W / O emulsion, by reducing the usage-amount of the organic modified clay mineral of a plate-like particle structure and a nonionic surfactant, it is low-viscosity and high in emulsion stability. It is possible to provide a W / O emulsion.

(1) Organically modified clay mineral plate-like particles The oily gel composition according to the present invention is an oily dispersion in which organically modified clay mineral particles are dispersed in an oil component, having an average thickness of 0.1 μm or less and an average major axis. Includes organically modified clay mineral particles having a plate-like particle structure having a particle size of 0.5 to 50 μm. Each plate-like particle is not substantially aggregated.
The organically modified clay mineral plate-like particles as described above exfoliate an aggregate of organically modified clay mineral having a layered structure having an average thickness of 2 μm or more in oil by mechanical shearing force and / or impact force. Can be obtained. For example, a sol composition having low viscosity and fluidity is usually obtained by the following treatment method.

(Processing method)
Add a glass bead (or zirconia bead, etc.) with the same volume to a mixture of a commercially available organically modified clay mineral (usually an aggregate having a layered structure with an average thickness of 2 μm or more) and oil, and paint. Thinning is performed by applying a mechanical shearing force and / or impact force using a shaker (Asada Iron Works Co., Ltd.), a bead mill (DISPERMAT, VMA-GETZMANN GMBH Verfahrenstechnik) or the like.

SEM photograph (FIG. 1) of a commercially available organically modified hectorite (Benton 38VCG, manufactured by Elementis Specialties (UK)) used as a raw material, and a plate-like particle structure obtained by treating this with the above treatment method FIG. 2 shows an SEM photograph (FIG. 2) of an organically modified hectorite having s.
(Decamethylcyclopentasiloxane: organically modified hectorite dispersed at a blending ratio of 95: 5, SEM
(S-4500 (manufactured by Hitachi High-Technologies Corporation))

In the present invention, the treatment method is carried out in the presence of a nonionic surfactant.
That is, the organically modified clay mineral aggregate (usually having an average thickness of 2 μm or more) is exfoliated by mechanical shearing force and / or impact force in oil in the presence of a nonionic surfactant. An organically modified clay mineral having a plate-like particle structure is formed in the oil phase.
By using the nonionic surfactant in combination, the viscosity is remarkably increased and the fluidity is lowered as compared with the sol composition. In the present invention, such a composition is referred to as a gel composition. Thus, it can be said that the gel composition of the present invention is an oily dispersion having a thicker viscosity than the sol composition (a dispersion obtained by removing a nonionic surfactant from the gel composition).

  The organically modified clay mineral according to the present invention has a plate-like shape having an average thickness of 0.1 μm or less by the above-described treatment method. In the conventional clay mineral, the plate-like particles are layered, and the commercially available organic modified clay mineral prepared by organic modification treatment of the clay mineral further forms an aggregate of the clay mineral having the layered structure, This aspect is shown in FIG.

In the present invention, a dispersion in which an organically modified clay mineral having a plate-like particle structure having an average thickness of 0.1 μm or less is independently present as a single particle can be obtained by subjecting the aggregate to a peeling treatment. . The dispersion once obtained can maintain a good dispersion state without agglomeration again in an oil phase such as silicone oil. If the aggregates are not sufficiently peeled and the thickness remains large, the thickening gelling ability and the W / O emulsification stabilizing ability as described later are not sufficiently exhibited.
Moreover, it is preferable that the organic modified clay mineral contained in the composition concerning this invention is 0.5-50 micrometers in average major axis. Each particle shape is not particularly limited as long as it has a sheet structure in the range of the above thickness and major axis, and may or may not be angular.

The average thickness and average major axis of the organically modified clay mineral contained in the oily gel composition according to the present invention can be determined, for example, by the following measuring method.
(Measuring method)
-Average thickness A sample obtained by sufficiently diluting the oily gel composition with silicone oil and drying the diluted solution is measured using a scanning electron microscope (S-4500, manufactured by Hitachi High-Technologies Corporation).
-Average major axis The oily gel composition is sufficiently diluted with silicone oil, and measured using a particle size distribution analyzer (Microtrac VSR, manufactured by Nikkiso Co., Ltd.).
For these measurements, the nonionic surfactant in the oily gel composition may be washed with silicone oil.
In the present invention, the average thickness and the average major axis can be measured using a sol composition obtained by dispersing and diluting an organically modified clay mineral in silicone oil as a measurement sample.
The shape of the organically modified clay mineral is determined by SEM photographs.

  When preparing an organically modified clay mineral having a plate-like particle structure according to the present invention, the organically modified clay mineral as a raw material thereof is not particularly limited as long as it is generally used in cosmetics. Can also be used. Specifically, it is obtained by ion exchange of an interlayer cation of a water-swellable clay mineral with a cationic surfactant such as an alkyl quaternary ammonium salt, which is exchanged with benzyldimethylstearyl ammonium ion, Examples include those exchanged with stearyl ammonium ions. Specific examples of the water-swellable clay mineral include montmorillonite, smectite, and hectorite. In the present invention, the organically modified clay mineral preferably used is the aforementioned organically modified hectorite. Examples of commercially available organically modified clay minerals include Benton 27 and Benton 38 (manufactured by Elementis Specialties (UK)). Etc.

(2) Oil content Moreover, the oil content used in the above-mentioned processing method is not specifically limited. It is possible to use one or two or more oils that are usually blended in cosmetics, pharmaceuticals, etc., but it is preferable that the oil is a liquid oil at room temperature (20 ° C.) as a whole. Particularly in the present invention, silicone oil is preferably used.

The silicone oil is not particularly limited as long as it is generally used in cosmetics. Specifically, for example, chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and other problems Unless otherwise, silicone resins forming a three-dimensional network structure, various silicone rubber polysiloxanes (amino-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) and the like can be mentioned.
In the present invention, one or more silicone oils can be selected and used.

  The organically modified clay mineral having a plate-like structure of the present invention can be well dispersed particularly in an oil component mainly composed of silicone oil, and is thickened together with a nonionic surfactant such as a polyether-modified silicone compound. It is possible to perform gelation effectively. In addition, an excellent emulsion stabilizing effect can be exhibited even in a W / O emulsion composition containing silicone oil as a main component.

Examples of the oil other than silicone oil include hydrocarbon oil, ester oil, vegetable oil, animal oil, higher alcohol, higher fatty acid and the like.
Examples of the hydrocarbon oil include liquid paraffin, paraffin, squalane, squalene, ozokerite, pristane, ceresin, petrolatum, and microcrystalline wax.

  Ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearic acid N-alkyl glycol, dicapric acid neopentyl glycol, malic acid diacid Isostearyl, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, triisostearate Methylolpropane, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, 2-ethylhexyl palmitate Glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamate-2-octyl Dodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, palmiti 2-hexyl decyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

Examples of vegetable oils include avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, peanut oil, almond oil, soybean oil, tea seed oil, jojoba oil, germ oil, etc. .
Animal fats and oils include turtle oil, egg yolk oil, mink oil and the like.
Examples of higher alcohols include oleyl alcohol, isostearyl alcohol, octyldodecanol, decyltetradecanol, jojoba alcohol, cetyl alcohol, and myristyl alcohol, and examples of higher fatty acids include oleic acid, isostearic acid, linoleic acid, linolenic acid, and ethanol. Examples include icosapentaenoic acid, docosahexaenoic acid, palmitic acid, and stearic acid.

(3) Nonionic surfactant In the oily gel composition according to the present invention, the nonionic surfactant is adsorbed on the surface of the plate-like particle of the organically modified clay mineral having the plate-like structure, and is a stable gel. Contributes to network formation. Nonionic surfactant is adsorbed on the surface of fine plate-like particles, so the adsorption rate is improved and less nonionic surfactant than gel composition using organically modified clay mineral of conventional aggregates The blending effect is demonstrated by the amount.
In addition, when a W / O emulsion composition is prepared using the oily gel composition according to the present invention, finely dispersed particles of an organically modified clay mineral whose surface is improved by a nonionic surfactant are used as the membrane wall of the emulsion particles. Forming an emulsified composition having excellent stability.

Examples of the nonionic surfactant used in the present invention include those usually used for pharmaceuticals, cosmetics and the like.
Specifically, for example, POE (2-50) oleyl ether, POE (2-40) stearyl ether, POE (2-50) lauryl ether, POE (1-50) alkylphenyl ether, POE (5-30) Ether type activators such as behenyl ether, POE (5-25) 2-decyl pentadecyl ether, POE (3-20) 2-decyl tetradecyl ether, POE (5-25) 2-octyldodecyl ether, and POE ( 4-100) Hardened castor oil, POE (3-60) castor oil, POE (2-150) fatty acid monoester, POE (2-150) fatty acid diester, POE (5-20) sorbitan fatty acid ester, etc. Agent, POE (2-60) glyceryl monoisostearate, POE (3-60) Ethylene oxide addition type surfactants such as ether ester type activator such as seryl triisostearate, POE (5-60) hydrogenated castor oil triisostearate, and decaglyceryl tetraoleate, diglyceryl diisostearate, decaglyceryl Polyglycerin fatty acid esters such as tetraisostearate, decaglyceryl tetrastearate, decaglyceryl heptaoleate, decaglyceryl dekaorate, decaglyceryl decaisostearate, glyceryl monostearate, glyceryl monoisostearate, glyceryl monooleate Examples include polyhydric alcohol fatty acid ester type surfactants such as glycerin fatty acid esters. One or more nonionic surfactants can be selected and used.

  A preferred nonionic surfactant in the present invention is a polyether-modified silicone compound. Examples of the polyether-modified silicone compound include polyoxyalkylene-modified organopolysiloxanes represented by the following general formulas (I) to (VII).

(In the general formulas (I) to (VII), R is an alkyl group having 1 to 3 carbon atoms or a phenyl group, R ′ is hydrogen or an alkyl group having 1 to 12 carbon atoms, p is an integer of 1 to 50, m and a is an integer of 1 to 100, n, q, x, and z are integers of 1 to 50, and t and y are integers of 0 to 50.)

Use of the polyether-modified silicone compounds represented by the general formulas (I) to (VII) is particularly suitable when the oil contained in the oily gel composition according to the present invention is a silicone oil. In the present invention, it is preferable that one or more or two or more of the polyether-modified silicone compounds represented above are arbitrarily selected and used.
Commercially available compounds can be used as the compounds represented by the general formulas (I) to (VII), and examples thereof include polyoxyethylene / methylpolysiloxane copolymers.
In addition, the oil-based gel composition concerning this invention WHEREIN: The suitable compounding quantity of a silicone oil is 20-90 mass% in the gel composition whole quantity.

In the oily gel composition according to the present invention, a suitable amount of the nonionic surfactant is 0.1 to 10% by mass based on the total amount of the oily gel composition.
In the oily gel composition, the mass ratio of the nonionic surfactant to the organically modified clay mineral having a plate-like structure is as follows: plate-like organically modified clay mineral: nonionic surfactant = 1: 1 to 10: 1 is preferred.
If the amount of nonionic surfactant is too small, the effect will not be fully exerted. On the other hand, if excessive amount of nonionic surfactant is used, a significant improvement in the effect cannot be expected, which may adversely affect the feeling of use. is there.

  In the oily gel composition according to the present invention, the preferred blending amount of the organically modified clay mineral having a plate-like particle structure is 0.25 to 30% by mass, more preferably 0.25 to 25% by weight based on the total amount of the oily gel composition. 10% by mass. Most preferably, it is 0.5-5 mass%. If it is less than 0.25% by mass, no blending effect is observed, and if it exceeds 30% by mass, a solid gel tends to be formed in combination with a nonionic surfactant. There is no improvement.

In the present invention, the oily gel composition may contain other arbitrary oily components as long as there is no particular problem, and silicone oil and other oils may be added as necessary.
For example, suitable oily gel compositions according to the present invention include those containing, as a main component, an organically modified clay mineral having a plate-like particle structure, a polyether-modified silicone compound, and a silicone oil. Is also possible.
Examples of other oils include hydrocarbon oils, ester oils, vegetable oils, animal oils, higher alcohols, and higher fatty acids. In addition, it is preferable that these oil components melt | dissolve in silicone oil and become a uniform liquid state at normal temperature (20 degreeC) as a whole.
Moreover, the oil-based gel composition concerning this invention WHEREIN: The suitable compounding quantity of an oil component is 70 mass% or more in the oil-based gel composition whole quantity.

(3) W / O emulsion composition Next, the W / O emulsion composition concerning this invention is demonstrated.
As the water phase constituting the W / O type emulsion composition, water and a water-soluble component are blended.
On the other hand, the oily gel composition is used as a main component in the oil phase.

The W / O emulsion composition according to the present invention is produced by a conventional method for producing a W / O emulsion composition. For example, it can be obtained by adding a water phase to an oil phase containing the oily gel composition and emulsifying it.
In the total amount of the W / O emulsion composition, the water phase: oil phase is preferably in a ratio of 80:20 to 5:95.

The oily gel composition or the W / O emulsion composition according to the present invention can be appropriately mixed with other components generally used in cosmetics.
Examples include drugs, various surfactants, inorganic powders, organic powders, pigments, dyes, humectants, thickeners, metal sequestering agents, various water-soluble polymers, pH adjusters, antioxidants, preservatives, and the like. .
The oily gel composition or W / O emulsion composition according to the present invention can be used as a base for conventional oily gel cosmetics or W / O emulsion cosmetics. For example, skin care cosmetics such as emulsions, creams, cleaning products, packs, massage cosmetics; makeup cosmetics such as foundations, lipsticks, blushers, eyeliners, eye shadows; sunscreen cosmetics; hair treatments and hair stylings, etc. However, the present invention is not limited to these.

  Hereinafter, the present invention will be described in more detail with specific examples. The present invention is not limited to these examples. Unless otherwise specified, the blending amount is expressed in mass%.

Oily gel compositions 1-4
5 parts by weight of a commercially available organically modified hectorite (Benton 38VCG, manufactured by Elementis Specialties (UK)), a polyoxyethylene / methylpolysiloxane copolymer (general formula (I) type, polyoxyethylene content approximately Glass beads (or zirconia) with respect to 20%, viscosity 400 to 800 cs, HLB4.5, R ′ = H, p = 3, y = 0) 2.5 parts by weight and decamethylcyclopentasiloxane 92.5 parts by weight Oil gel compositions 1 to 3 were obtained by adding the same volume of beads, etc., and using a bead mill with stirring and uniform mixing by mechanical shearing force and / or impact force for 5 minutes, 10 minutes, and 15 minutes.
In addition, as a comparative example, an oily gel composition 4 was obtained by performing a normal dispersion treatment with a disper for 10 minutes instead of a bead mill without using beads.

SEM observation of the particle shape of the organically modified clay mineral contained in the oily gel compositions 1 to 4 showed that the organically modified clay mineral in the oily gel composition 4 remained a relatively large granular aggregate. The organically modified clay mineral in the oily gel compositions 1 to 3 had a fine plate-like particle structure.
The particle shape of the organically modified clay mineral contained in the oily gel compositions 1 to 4 is shown in Table 1 below. This particle shape characteristic is a result obtained by collecting and measuring a sol composition obtained by dispersing an organically modified clay mineral in advance with decamethylcyclopentasiloxane as a sample. The average thickness and average major axis were measured as follows.

(Measuring method)
-Average thickness A sample obtained by sufficiently diluting the sol composition with decamethylcyclopentasiloxane and drying the diluted solution was measured using a scanning electron microscope (S-4500, manufactured by Hitachi High-Technologies Corporation).
-Average major axis The sol composition was sufficiently diluted with decamethylcyclopentasiloxane and measured using a particle size distribution analyzer (Microtrac VSR, manufactured by Nikkiso Co., Ltd.).

The oily gel compositions 1 to 4 were examined for swellability. The results are shown in Table 2 below. Swellability evaluation methods and evaluation criteria are as follows.
(Swellability of oily gel composition)
A sample was put in a transparent glass bottle, and each oily gel composition was evaluated visually under the following criteria.
○: No change such as liquid phase separation is observed.
Δ: 1/5 or less of the entire gel composition is separated.
X: 1/5 or more of the entire gel composition is separated.

As is apparent from the results in Table 2 above, the oily gel composition 4 obtained by the disper treatment was inferior in swelling property.
On the other hand, the oily gel compositions 1 to 3 treated by the bead mill have improved swellability as the treatment time is extended to 10 minutes and 15 minutes. In particular, the organically modified clay mineral contained in the oily gel composition 3 has an average thickness. Was a plate-like structure with good dispersibility, having an average major axis of about 5 μm or less.

The shape of the organically modified clay mineral particles contained in the oily gel composition 4 is granular and is different from the shape of the organically modified clay mineral having the plate-like particle structure.
In the organically modified clay mineral having a plate-like particle structure, the plate-like particle surface (flat surface) tends to be hydrophobic and the end surface tends to be hydrophilic. Therefore, exposure of the end surface of the hydrophilic portion in silicone oil is reduced. Be placed. When schematically expressed, it is considered that a gel network as shown in FIG. 3 is formed and high swelling property is exhibited.
On the other hand, in the case of granular organically modified clay mineral particles, it is difficult to form a gel network due to the contribution of the hydrophilic / hydrophobic part.

  In addition, the organically modified clay minerals contained in the oily gel compositions 1 to 3 have different average major diameters and dispersibility depending on the treatment time, but they are exfoliated in a treatment time of about 15 minutes or more. It is clear from the above results that an excellent swelling property can be obtained.

Furthermore, the stability of the gel structure of the oily gel composition was evaluated from dynamic viscoelasticity. The measurement method is as follows.
(Dynamic viscoelasticity measurement)
Measuring device: Rheometer AR1000-N (TA Instruments)
Measurement method: Dynamic viscoelasticity measurement was performed using a cone-type plate. The storage elastic modulus G ′ [Pa] of the gel with respect to shear stress (0.01-50 [Pa]) was measured at a measurement frequency of 1 Hz.
FIG. 4 shows the relationship between the storage elastic modulus (G ′) and shear stress of the oily gel composition 3 (organically modified clay mineral: plate-like particles) according to the present invention, and FIG. 4 shows the oily gel composition 4 (organically modified clay mineral: FIG. 5 shows a relationship diagram of (aggregates). Each figure also shows the case where the concentration of the polyether-modified silicone compound contained in each oily gel composition is changed (the increase or decrease is adjusted with decamethylcyclopentasiloxane).

When the organically modified clay mineral is a plate-like particle as in the oily gel composition 3 according to the present invention, the elasticity of the gel is high in a certain shear stress range, a constant state is maintained, and a stable gel structure is achieved. It was confirmed that it was taken (FIG. 4).
On the other hand, when a granular (aggregate) organically modified clay mineral obtained by normal dispersion treatment of a commercially available organically modified clay mineral like the oily gel composition 4 is used, the gel elasticity is higher than that in the case of FIG. And the stable region where the gel elastic state is constant was also poor (FIG. 5).

  From the above results, the organically modified clay mineral having a plate-like particle structure according to the present invention exhibits an excellent effect in forming a stable gel structure in the presence of a nonionic surfactant in oil, It is very clear that the thickening gelling effect is improved as compared with the organically modified clay mineral having an aggregate structure of

Oily dispersions 1-8
Furthermore, the swellability of organically modified clay minerals in oil was investigated by changing the amount of nonionic surfactant added. The results are shown in Table 3 below. FIG. 6 shows the swelling. The manufacturing method is as follows.

(Oil dispersion 1 to 4)
A commercially available organic modified hectorite (Benton 38VCG, manufactured by Elementis Specialties (UK)) was used as the organic modified clay mineral, and it was prepared with a disper in the same manner as the method for producing the oily gel composition 4 (usually dispersion treatment). The organically modified clay mineral in the obtained oily dispersion was a granular aggregate.
(Oil dispersion 5-8)
A commercially available organic modified hectorite (Benton 38VCG, manufactured by Elementis Specialties (UK)) was used as the organic modified clay mineral, and was prepared by a bead mill in the same manner as the method for producing the oily gel composition 3 (high dispersion treatment). The organically modified clay mineral in the obtained oil dispersion was fine plate-like particles.

As is apparent from Table 3 above, when the organically modified hectorite of the aggregate that has been subjected to the dispersion treatment is used, it hardly swells unless a polyether-modified silicone compound that is a nonionic surfactant is added (dispersion) 1) Although gradually changing as the amount added was increased, the amount reached 5% by mass, and only moderate swelling was observed (dispersion 4).
On the other hand, when an organically modified hectorite having a plate-like particle structure that has been highly dispersed using a bead mill is used, even when no polyether-modified silicone compound is added, it is somewhat higher than when using an aggregate. It is clear from FIG. 6 that the swelling property is exhibited. When the amount of the polyether-modified silicone compound added exceeds 1% by mass, a sufficiently satisfactory swelling property was observed.
From the above results, it is clear that the oily gel composition containing the organically modified clay mineral having a plate-like structure is extremely swellable compared to the oily gel composition containing the organically modified clay mineral in the aggregate. .

In the production process of the oily gel compositions 3 and 4, after mixing and dispersing components other than the polyether-modified silicone which is a nonionic surfactant, the organics before and after the addition of the polyether-modified silicone The dispersion state of the modified clay mineral was photographed with SEM photographs (see FIGS. 7 and 8).
From this photograph, when the oily gel composition according to the present invention is prepared (FIG. 7), the clay mineral particles are dispersed in a finely divided state both before and after the addition of the polyether-modified silicone compound. It is clear that
On the other hand, when using a granular (aggregate) organically modified clay mineral that has been subjected to normal dispersion treatment (FIG. 8), the addition of the polyether-modified silicone compound slightly advances the refinement of the organically modified clay mineral aggregate. However, a large aggregate is still confirmed and it is not recognized that the dispersed state is good.

Next, in the W / O emulsion composition, the organically modified clay mineral plate-like particle according to the present invention was compared with the conventional organically modified clay mineral aggregate.
Emulsions 1-4
W / O emulsion compositions having the compositions shown in Table 4 were prepared. The preparation method is as follows.
(Emulsion 1-2)
Commercially available organically modified hectorite, polyether-modified silicone compound and silicone oil were mixed and dispersed with a disper for 15 minutes to obtain an oily gel composition. The organically modified clay mineral in the oily gel composition was an aggregate similar to the oily gel composition 4.
The resulting oily gel composition was emulsified with a disper while gradually adding ion-exchanged water to obtain a W / O type emulsion composition.

(Emulsions 3-4)
Commercially available organically modified hectorite, polyether-modified silicone compound and silicone oil are mixed, glass beads having the same volume as this mixture (diameter 1 mm) are added, and dispersion treatment is performed for 15 minutes by a bead mill to obtain an oily gel composition. It was. The organically modified clay mineral in the oily gel composition was fine plate-like particles similar to the oily gel composition 3.
The resulting oily gel composition was emulsified with a disper while gradually adding ion-exchanged water to obtain a W / O type emulsion composition.

Evaluation methods and evaluation criteria for viscosity, emulsion particle size and emulsion stability are as follows.
(viscosity)
After leaving still in a 30 degreeC thermostat for 1 hour, it measured on the conditions of 12 rpm using a single cylindrical rotational viscometer (Shibaura System Co., Ltd.) (rotor No. 3 or No. 4).
(Emulsified particle size)
The emulsified particle size of the sample after storage under each condition was measured using an optical microscope (OLYMPUS BM60).
(Stability)
The sample was preserve | saved on each condition, and the external appearance change was visually evaluated according to the following evaluation criteria.
A: No change such as separation or aggregation of the liquid phase is observed.
B: Some separation is observed on the surface layer.
C: 1/5 or less of the whole emulsified composition is separated.
D: 1/5 or more of the whole emulsion composition is separated.

As is clear from the results in Table 4 above, emulsions 1 and 2 prepared using commercially available organically modified clay minerals in the form of aggregates were inferior in stability over time. In particular, when the content of the organically modified clay mineral is 0.5% by mass (emulsion 1), it is found that the viscosity is extremely low and it is difficult to maintain a stable emulsion. When the content is increased to 1% by mass (emulsion 2), although the viscosity is improved, the temporal stability is not satisfactory.
On the other hand, in the W / O emulsion composition using the organically modified clay mineral having a plate-like particle structure, when the blending amount is 0.5% by mass (emulsion 3), although the viscosity is low, Compared with the emulsion 1 using an aggregate clay mineral, stability was good. Furthermore, when the content was increased to 1% by mass (emulsion 4), the viscosity became extremely high and the stability over time became excellent.

  From the above results, by using an oily gel composition containing an organically modified clay mineral obtained by forming a plate of an organically modified clay mineral of an aggregate, it is possible to improve the viscosity with a smaller blending amount and to have excellent stability. It was revealed that a mold emulsion composition can be obtained.

Furthermore, the nonionic surfactant mix | blended with an oil-based gel composition and the kind of oil component were changed, and it examined.
Emulsions 5-8
The method for preparing the W / O emulsion shown in Table 5 below is as follows.
(Emulsions 5-8)
Organic modified hectorite, nonionic surfactant and oil were mixed, glass beads having the same volume as this mixture (diameter 1 mm) were added, and dispersion treatment was performed for 15 minutes by a bead mill to obtain an oily gel composition. . Similar to the oily gel composition 3, the organically modified clay mineral in the oily gel composition was fine plate-like particles.
The resulting oily gel composition was emulsified with a disper while gradually adding ion-exchanged water to obtain a W / O type emulsion composition.

  As is clear from the results in Table 5 above, in the emulsion 6 in which the nonionic surfactant is changed, and in the emulsions 7 to 8 in which the oil content is changed to hydrocarbon oil or ester oil, the W / O type emulsion composition The stability of was maintained to some extent. When the organically modified clay mineral having a plate-like structure according to the present invention is used, it is possible to maintain the best stability in silicone oil. Therefore, it is expected to be applied to a wide variety of W / O type emulsion compositions, especially cosmetics in which silicone oil is a mainstream.

  Hereinafter, examples in which a W / O type emulsion composition using an oily gel composition containing an organically modified clay mineral having a plate-like structure of the present invention is used in cosmetics will be shown. The present invention is not limited to these.

Cosmetic 1: Sunscreen
(mass%)
(1) Dimethyl distearyl ammonium hectorite /
Polyoxyethylene / methylpolysiloxane copolymer (general formula (I) type,
HLB 4.5, POE content 20%, 400-800cs,
R ′ = H, p = 3, y = 0) / decamethylcyclopentasiloxane (0.8 / 0.4 / 19.8)
21
(2) Trimethylsiloxysilicic acid 1
(3) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 5
(4) Cetyl 2-ethylhexanoate 5
(5) Silicone-coated fine particle zinc oxide (20 nm) 15
(6) 2-Ethylhexyl paramethoxycinnamate 7
(7) Diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl 0.5
(8) Spherical polyethylene powder 3
(9) Dipropylene glycol 4
(10) Trisodium edetate 0.02
(11) Paraben appropriate amount (12) Phenoxyethanol appropriate amount (13) Purified water Residue (14) Fragrance Appropriate amount (production method)
(2) to (8) were added to the gel composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and dispersed. The aqueous phase parts (9) to (13) were added and emulsified, and then (14) was added to obtain the desired sunscreen.

Cosmetic 2: Moisturizing cream
(mass%)
(1) Dimethyl distearyl ammonium hectorite /
Polyoxyethylene / methylpolysiloxane copolymer (general formula (VI) type,
HLB 3-4, 200-800cs) / decamethylcyclopentasiloxane (2/1/17)
20
(2) Petrolatum 2
(3) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 5
(4) Squalane 1
(5) Isostearic acid 1
(6) Cetyl 2-ethylhexanoate 5
(7) Glycerin 12
(8) 1,3-butylene glycol 4
(9) Erythritol 2
(10) Sodium chloride 0.5
(11) Sodium hexametaphosphate 0.05
(12) L-ascorbyl magnesium phosphate 2
(13) Thiotaurine 0.1
(14) Turmeric extract 0.1
(15) Trisodium edetate 0.1
(16) Paraben appropriate amount (17) Purified water Residue (18) Fragrance appropriate amount (Manufacturing method)
(2) to (6) were added to the gel composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and stirred. After adding the water phase parts of (7)-(17) and emulsifying there, (18) was added and the target moisturizing cream was obtained.

Cosmetic 3: Emulsion foundation
(mass%)
(1) Dimethyl distearyl ammonium hectorite /
Polyoxyethylene / methylpolysiloxane copolymer (general formula (I) type,
HLB 4.5, POE content 20%, 400-800 cs, R ′ = H,
p = 3, y = 0) / decamethylcyclopentasiloxane (1 / 0.5 / 19.5)
21
(2) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 5
(3) Palmitic acid 0.5
(4) Squalane 5
(5) Dextrin fatty acid-treated titanium dioxide 15
(6) Dextrin fatty acid-treated yellow iron oxide 3
(7) Dextrin fatty acid treatment Bengala 1.5
(8) Dextrin fatty acid-treated black iron oxide 0.5
(9) Metal soap treated talc 3
(10) Silicone coated spindle-shaped titanium oxide 3
(11) Cross-linked silicone powder (Trefil E-506) 0.1
(12) Bengala-coated mica titanium 0.5
(13) N-lauroyl-L-lysine 2
(14) DL-α-tocopherol acetate 0.1
(15) Glycerin 3
(16) 1,3-butylene glycol 5
(17) paraoxybenzoic acid ester appropriate amount (18) purified water residue (19) perfume appropriate amount (production method)
(2) to (13) were added and mixed and dispersed in the gel composition (1) previously dispersed in fine particles using a bead mill or the like. The aqueous phase parts (14) to (18) were added and emulsified, and then (19) was added to obtain the desired emulsified foundation.

Cosmetic 4: Emulsion foundation
(mass%)
(1) Dimethyl distearyl ammonium hectorite /
Polyoxyethylene methylpolysiloxane copolymer (general formula (VII) type,
HLB 3-4, 200-700cs, R '= H, p = 3, y = 0) /
Decamethylcyclopentasiloxane (1 / 0.5 / 19.5)
21
(2) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 5
(3) Squalane 5
(4) Silicone-treated titanium dioxide 12
(5) Silicone-treated yellow iron oxide 3
(6) Silicone-treated Bengala 1.5
(7) Silicone-treated black iron oxide 0.5
(8) Silicone-treated sericite 5
(9) Silicone coated spindle-shaped titanium oxide 3
(10) Cross-linked silicone powder (Trefil E-506) 0.1
(11) Bengala-coated mica titanium 0.5
(12) Spherical silica 3
(13) Dipropylene glycol 3
(14) 1,3-butylene glycol 5
(15) paraoxybenzoic acid ester appropriate amount (16) purified water remaining (17) alcohol 5
(18) Perfume appropriate amount (production method)
(2) to (12) were added to the gel composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and dispersed. After adding (13)-(16) water phase parts and emulsifying there, (17)-(18) was added and the target emulsification foundation was obtained.

Cosmetic 5: Sunscreen
(mass%)
(1) Dimethyl distearyl ammonium hectorite /
Polyoxyethylene / methylpolysiloxane copolymer (general formula (V) type,
HLB 3-4, POE content 19%, 200-700 cs, R ′ = H,
p = 3, y = 0) / decamethylcyclopentasiloxane (0.8 / 0.4 / 19.8)
21
(2) Trimethylsiloxysilicic acid 1
(3) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 5
(4) Cetyl 2-ethylhexanoate 5
(5) Silicone-coated fine particle zinc oxide (20 nm) 15
(6) 2-Ethylhexyl paramethoxycinnamate 7
(7) Diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl 0.5
(8) Spherical polyethylene powder 3
(9) Dipropylene glycol 4
(10) Trisodium edetate 0.02
(11) Paraben appropriate amount (12) Phenoxyethanol appropriate amount (13) Purified water Residue (14) Fragrance Appropriate amount (production method)
(2) to (8) were added to the gel composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and dispersed. The aqueous phase parts (9) to (13) were added and emulsified, and then (14) was added to obtain the desired sunscreen.

It is a SEM photograph figure of a commercially available organic modified clay mineral. It is a SEM photograph figure of the organic modified clay mineral which has a plate-like particle structure. It is the figure which showed typically formation of the gel network in the silicone oil of the organic modified clay mineral which has an aggregate or a plate-like particle structure. It is the figure which showed the relationship between the storage elastic modulus (G ') and shear stress of the oil-based gel composition using the organic modified clay mineral which has a plate-shaped particle structure concerning this invention. It is the figure which showed the relationship between the storage elastic modulus (G ') and the shear stress of the oil-based gel composition using the normal dispersion processing goods of a commercially available organic modified clay mineral.

It is the figure which showed the swelling property of the oil-based gel compositions 3 and 4 by changing the addition amount of a polyether modified silicone compound. It is a photograph figure which shows the dispersion state before and after polyether-modified silicone compound addition at the time of preparing an oil-based gel composition by the high dispersion process of a commercially available organic modified clay mineral. It is a photograph figure which shows the dispersion | distribution state before and after addition of a polyether modified silicone compound at the time of preparing an oil-based gel composition by the normal dispersion process of a commercially available organic modified clay mineral.

Claims (4)

In the silicone oil other than the polyether-modified silicone compound, only 0.5 to 5.0% by mass of the organically modified clay mineral aggregate in the mixture and 2.5 to 5.0% by mass of the polyether-modified silicone compound in the mixture are blended. To make a mixture
In the mixture were added glass beads, by peeling process by adding mechanical shearing force and / or impact force to the aggregates, the average thickness before Kiko Atsumaritai zero. 1μm or less, an average major diameter of 0. And 5~50μm of plate-like particles, to obtain an oily gel composition by dispersing the obtained plate-like particles in said mixture,
A W / O type emulsion composition obtained by gradually adding water to the oily gel composition.   The W / O type emulsion composition according to claim 1, wherein the organically modified clay mineral having a plate-like particle structure is an organically modified hectorite. The W / O type emulsion composition according to claim 1 or 2 , wherein the organically modified clay mineral aggregate has a layered structure having an average thickness of 2 µm or more. The W / O type emulsified composition according to any one of claims 1 to 3, wherein the volume of the glass beads is equal to the volume of the mixture.