JP5491688B2 - Sol composition containing organically modified clay mineral having plate-like particle structure, oil-based gel composition containing the same, and W / O emulsion composition - Google Patents

Description

  The present invention relates to a sol composition containing an organically modified clay mineral having a plate-like particle structure, an oily gel composition containing the same, and a W / O emulsion composition. The present invention relates to improvement of gelling ability and stabilizing ability in W / O 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 sol composition according to the present invention includes 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 in the oil. . In the present invention, each plate-like particle is not substantially aggregated.
In the sol composition of the present invention, it is preferable that the organically modified clay mineral is an organically modified hectorite.
In the sol composition of the present invention, it is preferable that the oil contains a silicone oil.
In the sol 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 produced by a method of exfoliating in an oil component by mechanical shearing force and / or impact force. It is preferred that

The oily gel composition according to the present invention comprises any one of the sol compositions described above and a nonionic surfactant.
In the oily gel composition of the present invention, the aggregate of the organically modified clay mineral having a layered structure having an average thickness of 2 μm or more is subjected to a peeling treatment by mechanical shearing force and / or impact force in oil, It is suitable to manufacture by the method of adding a nonionic surfactant.
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.
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) Sol composition containing organically modified clay mineral The sol composition according to the present invention is an oily dispersion in which organically modified clay mineral particles are dispersed in an oil component, and has an average thickness of 0.1 μm or less, and Organic modified clay mineral particles having a plate-like particle structure with an average major axis of 0.5 to 50 μm are included. Each plate-like particle is not substantially aggregated.
The organically modified clay mineral can be obtained by subjecting an aggregate of organically modified clay mineral having a layered structure having an average thickness of 2 μm or more to exfoliation in an oil component by mechanical shearing force and / or impact force. . Specifically, it is usually obtained as a sol composition having low viscosity and fluidity 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 mixing ratio of 95: 5, then photographed with SEM S-4500 (manufactured by Hitachi High-Technologies Corporation))

  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 sol composition in which organic modified clay minerals having a plate-like particle structure having an average thickness of 0.1 μm or less are independently present as single particles can be obtained by subjecting the agglomerates to peeling treatment. it can. 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 sol 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 sol 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 sol 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 sol composition is sufficiently diluted with silicone oil and measured using a particle size distribution analyzer (Microtrac VSR, manufactured by Nikkiso Co., Ltd.).
The shape of the organically modified clay mineral is determined by an SEM photograph.

  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.

  In the sol composition according to the present invention, the amount of the organically modified clay mineral having the plate-like structure is not particularly limited, but is preferably 0.25 to 50% by mass. If the amount is too large, peeling treatment may be difficult.

  Moreover, the oil component 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.

(2) Gel composition containing organically modified clay mineral When a nonionic surfactant is used in combination with the sol composition as described above, 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 oily gel composition according to the present invention can be obtained by adding a nonionic surfactant to the sol composition.
That is, an aggregate of organically modified clay mineral having a layered structure having an average thickness of 2 μm or more is exfoliated by mechanical shearing force and / or impact force in oil, and then a nonionic surfactant is added. . When a nonionic surfactant is added after the release treatment of the organically modified clay mineral, the viscosity of the gel composition or the W / O emulsion using the gel composition is higher than when the release treatment is performed in the presence of the nonionic surfactant. Tend to be low.

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 contributes to the formation of a stable gel network. 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.

The sol composition or oily gel composition according to the present invention may contain any other oily component as long as there is no particular problem. Silicone oil and other oils may be added as necessary. May be.
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 silicone oil. It is also possible to add.
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%.

I. Sol composition containing an organic modified clay mineral First, show a process for preparing a sol composition of the organic modified clay mineral used in the following examples.
Sol compositions 1-4
Commercially available organically modified hectorite (Benton 38VCG, manufactured by Elementis Specialties (UK)) and 15% by mass of decamethylcyclopentasiloxane were mixed. In this state, a glass bead having a diameter of 1 mm is added to the mixture in the same volume as the mixture, and a thinning process is performed by applying high shearing force and / or impact force mechanically using a bead mill for 5 minutes, 10 minutes, 15 minutes. The sol compositions 1 to 3 were obtained by changing the minutes and the treatment time.
Moreover, as a comparative example, the glass composition was not added, and a sol composition 4 was obtained by treating with a disper for 10 minutes instead of the bead mill.

The particle shape of the organically modified clay mineral contained in the obtained sol composition is shown in Table 1 below. The average thickness and the 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.).

  In the sol composition 4 obtained by a normal dispersion treatment with a disper, the organically modified clay mineral remained relatively large particles (aggregates) as shown in the SEM photograph of FIG. On the other hand, in the sol compositions 1 to 3 obtained by the high dispersion treatment using the bead mill, the organically modified clay mineral was peeled into fine plate-like particles as shown in FIG.

II. Oily Gel Compositions Containing Organic Modified Clay Minerals Further, oily gel compositions 1 to 4 were prepared using the organic modified clay mineral sol compositions 1 to 4 prepared as described above. A production example is shown below.

Oily gel compositions 1-4
33.33 parts by weight of each of the sol compositions 1 to 4 of the organically modified clay mineral, a polyoxyethylene / methylpolysiloxane copolymer (general formula (I) type, polyoxyethylene content 20%, viscosity 400 to 800 cs) , HLB4.5, R ′ = H, p = 3, y = 0) 2.5 parts by weight, 64.17 parts by weight of decamethylcyclopentasiloxane (3.5 to 4.5 cs) was dispersed with a disper for 10 minutes. It processed and obtained the oily gel compositions 1-4 (the organic modified clay mineral density | concentration in each oily gel composition was 5 mass%).

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 clear from the results in Table 2 above, the oily gel composition 4 obtained using the oily sol composition 4 obtained by the disper treatment and the nonionic surfactant has poor swelling properties. It was.
On the other hand, in the oily gel compositions 1 to 3 obtained using the sol compositions 1 to 3 obtained by the treatment with the bead mill and the nonionic surfactant, the swelling is higher than that of the oily gel composition 4. The swellability of the oily gel composition was improved as the treatment time of the sol composition was extended from 10 minutes to 15 minutes. This is considered to be because fine exfoliation of the organically modified clay mineral proceeds with the treatment time as shown in Table 1. In particular, the organically modified clay mineral contained in the oily gel composition 3 had a plate-like particle structure with good dispersibility having an average thickness of 0.1 μm or less and an average major axis of about 5 μm.

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.

  Further, the organically modified clay minerals contained in the sol compositions 1 to 3 have different average major diameters and dispersibility depending on the treatment time, but are sliced in about 15 minutes or more. Thus, it is clear from the above results that excellent swelling properties can be obtained.

In the production process of the oily gel compositions 3 and 4, the dispersion state of the organically modified clay mineral before and after the addition of the polyether-modified silicone, which is a nonionic surfactant, was photographed with SEM photographs (FIGS. 4 and 4). 5).
From this photograph, when an oily gel composition was prepared using an organically modified clay mineral having a plate-like particle structure contained in the sol composition according to the present invention (FIG. 4), before and after addition of the polyether-modified silicone compound In both cases, it is clear that the clay mineral particles are dispersed in a refined state.
On the other hand, in the case of using a granular (aggregate) organically modified clay mineral that has been subjected to a normal dispersion treatment (FIG. 5), the addition of a 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.

Furthermore, the stability of the gel structure of the oily gel composition was evaluated from the measurement of 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. 6 shows the relationship between the storage elastic modulus (G ′) and the shear stress of the oily gel composition 3 (organically modified clay mineral: plate-like particles) according to the present invention, and FIG. 6 shows the oily gel composition 4 (organically modified clay mineral: FIG. 7 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. 6).
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 such as the oily gel 4 is used, the gel elasticity is smaller than in the case of FIG. Also, the stable region where the gel elastic state is constant was poor.
It was a thing.

  From the above results, the organically modified clay mineral having a plate-like particle structure contained in the sol composition according to the present invention was excellent in the formation of 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 that exhibits the effect and has a conventional aggregate structure.

III. W / O emulsion composition Next, in the W / O emulsion composition, the organically modified clay mineral plate-like particles according to the present invention were compared with the conventional organically modified clay mineral aggregate.

Emulsions 1-4
A W / O emulsion having the composition shown in Table 3 was prepared. The preparation method is as follows.
(Emulsion 1-2)
Commercially available organically modified hectorite and half amount of silicone oil were mixed and dispersed with a disper for 15 minutes to obtain an oily sol composition. A polyether-modified silicone compound and the remaining silicone oil were added thereto, and further dispersed with a disper for 10 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 and a half amount of silicone 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 sol composition. A polyether-modified silicone compound and the remaining silicone oil were added thereto, and further dispersed with a disper for 10 minutes to obtain an oily gel composition. 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.

The evaluation method and evaluation criteria for the emulsion stability of the W / O emulsion composition are shown below.
(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 3 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), 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, when an organically modified clay mineral having a plate-like particle structure is used, when the blending amount is 0.5 mass% (emulsion 3), although it has a low viscosity, an aggregate clay mineral of the same blending amount The stability was better than that of Emulsion 1 using 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, it is clear that by making the organic modified clay mineral of the aggregate into a plate shape, it is possible to obtain a W / O type emulsion composition with improved viscosity and excellent stability with a smaller amount of blending. became.

Further, the emulsifying action of the organically modified clay mineral itself was examined without adding a polyether-modified silicone compound to the W / O emulsion composition.
Emulsions 5-9
A W / O emulsion having the composition shown in Table 4 was prepared. Emulsions 5-6 were prepared according to the method of emulsions 1-2 (organic modified clay mineral: aggregate). Emulsions 7 to 9 were prepared according to the methods of the above emulsions 3 to 4 (organic modified clay mineral: plate-like particles). The measuring method of a viscosity and an emulsified particle diameter is 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).

As is clear from the results of Table 4 above, when the organically modified clay mineral plate-like particles according to the present invention are used, even if the polyether-modified silicone compound is not blended as in the emulsions 7 to 9. A certain degree of viscosity adjustment is possible only with clay minerals, and an emulsifying function can also be exhibited.
On the other hand, when a commercially available aggregate organically modified clay mineral is used as an aggregate, it cannot produce an appropriate viscosity by itself as in the case of the emulsions 5 to 6, and the emulsion stability. Was inferior.
From the above results, it was confirmed that the organically modified clay mineral having a plate-like structure according to the present invention can exhibit thickening and emulsifying functions by itself without blending other activators. However, it is preferable to blend a polyether-modified silicone compound in order to maintain good stability.

Emulsions 10-13
Furthermore, the nonionic surfactant mix | blended with an oil-based gel composition and the kind of oil component were changed, and it examined. The results are shown in Table 5 below. The method for preparing the W / O emulsion shown in Table 5 is as follows.
(Emulsions 10-13)
Commercially available organically modified hectorite and a half amount of 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 sol composition. A nonionic surfactant and the remaining oil were added thereto, and further dispersed with a disper for 10 minutes to obtain an oily gel composition. 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.

  As is clear from the results of Table 5 above, in the emulsion 11 in which the nonionic surfactant is changed, and in the emulsions 12 to 13 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) Sol composition of dimethyl distearyl ammonium hectorite / decamethylcyclopentasiloxane (1/20) 21
(2) Trimethylsiloxysilicic acid 1
(3) Polyoxyethylene / methylpolysiloxane copolymer (formula (I) type, HLB 4.5, POE content of about 20%,
400 to 800 cs, R ′ = H, p = 3, y = 0) 0.5
(4) Squalane 5
(5) Silicone-coated fine particle titanium oxide (20 nm) 10
(6) Talc (hydrophobized product) 6
(7) 2-Ethylhexyl paramethoxycinnamate 7
(8) Diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl 0.5
(9) Spherical polyethylene powder 5
(10) Dipropylene glycol 4
(11) Trisodium edetate 0.02
(12) Paraben appropriate amount (13) Phenoxyethanol Appropriate amount (14) Purified water Residual (15) Fragrance Appropriate amount (Manufacturing method)
(2) to (9) were added to the sol composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and stirred. The aqueous phase parts (10) to (14) were added and emulsified, and then (15) was added to obtain the target sunscreen.

Cosmetic 2: Sunscreen
(mass%)
(1) Sol composition of dimethyl distearyl ammonium hectorite / decamethylcyclopentasiloxane (1/20) 21
(2) Trimethylsiloxysilicic acid 1
(3) Polyoxyethylene / methylpolysiloxane copolymer (formula (V) type, HLB 3-4, POE content of about 19%,
200 to 700 cs, R ′ = H, p = 3, y = 0) 0.3
(4) Cetyl 2-ethylhexanoate 3
(5) Methyl polysiloxane 5
(6) Silicone-coated fine particle titanium oxide (20 nm) 5
(7) Silicone-coated fine particle zinc oxide (20 nm) 10
(8) 2-Ethylhexyl paramethoxycinnamate 5
(9) 4-tert-butyl-4′-methoxybenzoylmethane 0.5
(10) Spherical silicone resin powder 5
(11) 1,3-butylene glycol 4
(12) Edetate trisodium 0.02
(13) Paraben appropriate amount (14) Phenoxyethanol appropriate amount (15) Purified water Residual (16) Fragrance Appropriate amount (production method)
(2) to (10) were added to the sol composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and stirred. The aqueous phase parts (11) to (15) were added and emulsified, and then (16) was added to obtain the target sunscreen.

Cosmetic 3: Moisturizing cream
(mass%)
(1) Dimethyl distearyl ammonium hectorite / decamethylcyclopentasiloxane (2/18) sol composition 20
(2) Petrolatum 2
(3) Microcrystalline wax 3
(4) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 5
(5) Squalane 3
(6) Polyoxyethylene / methylpolysiloxane copolymer (formula (I) type, HLB 4.5, POE content of about 20%,
400-800 cs, R ′ = H, p = 3, y = 0) 1.5
(7) Isostearic acid 1
(8) Cetyl 2-ethylhexanoate 3
(9) Glycerin 10
(10) 1,3-butylene glycol 4
(11) Xylitol 2
(12) Sodium chloride 0.5
(13) Sodium hexametaphosphate 0.05
(14) Stearyl glycyrrhetinate 0.05
(15) DL-pyrrolidone carboxylate sodium 1
(16) Turmeric extract 0.1
(17) Trisodium edetate 0.1
(18) Paraben appropriate amount (19) Purified water Residue (20) Fragrance appropriate amount (Manufacturing method)
(2) to (7) were added to the sol composition (1) dispersed in fine particles in advance using a bead mill or the like, and mixed and stirred. The aqueous phase parts (8) to (19) were added and emulsified there, and then (20) was added to obtain the desired moisturizing cream.

Cosmetic 4: Emulsion foundation
(mass%)
(1) Sol composition of dimethyl distearyl ammonium hectorite / decamethylcyclopentasiloxane (1/20) 21
(2) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 15
(3) Polyoxyethylene / methylpolysiloxane copolymer (formula (I) type, HLB 4.5, POE content of about 20%,
400-800 cs, R ′ = H, p = 3, y = 0) 5
(4) Palmitic acid 0.5
(5) Cetyl 2-ethylhexanoate 5
(6) Silicone-coated yellow iron oxide 2
(7) Silicone coated bengara 1
(8) Silicone-coated black iron oxide 0.3
(9) Silicone-coated titanium oxide 10
(10) Silicone-coated talc 1.5
(11) Silicone-coated spindle-shaped titanium oxide 3
(12) Spherical nylon powder 1
(13) Macadamia nut oil fatty acid cholesteryl 0.1
(14) DL-α-tocopherol acetate 0.1
(15) Glycerin 5
(16) 1,3-butylene glycol 10
(17) paraoxybenzoic acid ester appropriate amount (18) purified water residue (19) perfume appropriate amount (production method)
(2) to (14) were added and mixed and dispersed in the sol composition (1) previously dispersed in fine particles using a bead mill or the like. The aqueous phase parts (15) to (18) were added and emulsified, and then (19) was added to obtain the desired emulsified foundation.

Cosmetic 5: Sunscreen
(mass%)
(1) Sol composition of dimethyl distearyl ammonium hectorite / decamethylcyclopentasiloxane (1/20) 21
(2) Trimethylsiloxysilicic acid 1
(3) Polyoxyethylene / methylpolysiloxane copolymer (general formula (VI) type, HLB 3-4, 200-800 cs) 0.5
(4) Squalane 5
(5) Silicone-coated fine particle titanium oxide (20 nm) 10
(6) Talc (hydrophobized product) 6
(7) 2-Ethylhexyl paramethoxycinnamate 7
(8) Diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl 0.5
(9) Spherical polyethylene powder 5
(10) Dipropylene glycol 4
(11) Trisodium edetate 0.02
(12) Paraben appropriate amount (13) Phenoxyethanol Appropriate amount (14) Purified water Residual (15) Fragrance Appropriate amount (Manufacturing method)
(2) to (9) were added to the sol composition (1) dispersed in fine particles in advance using a bead mill or the like and mixed and stirred. The aqueous phase parts (10) to (14) were added and emulsified, and then (15) was added to obtain the target sunscreen.

Cosmetic 6: Emulsion foundation
(mass%)
(1) Sol composition of dimethyl distearyl ammonium hectorite / decamethylcyclopentasiloxane (1/20) 21
(2) Dimethylpolysiloxane (5.6 cs / 25 ° C.) 15
(3) Polyoxyethylene / methylpolysiloxane copolymer (general formula (VII) type, HLB 3-4, 200-700cs,
R ′ = H, p = 3, y = 0) 5
(4) Palmitic acid 0.5
(5) Cetyl 2-ethylhexanoate 5
(6) Silicone-coated yellow iron oxide 2
(7) Silicone coated bengara 1
(8) Silicone-coated black iron oxide 0.3
(9) Silicone-coated titanium oxide 10
(10) Silicone-coated talc 1.5
(11) Silicone-coated spindle-shaped titanium oxide 3
(12) Spherical nylon powder 1
(13) Macadamia nut oil fatty acid cholesteryl 0.1
(14) DL-α-tocopherol acetate 0.1
(15) Glycerin 5
(16) 1,3-butylene glycol 10
(17) paraoxybenzoic acid ester appropriate amount (18) purified water residue (19) perfume appropriate amount (production method)
(2) to (14) were added and mixed and dispersed in the sol composition (1) previously dispersed in fine particles using a bead mill or the like. The aqueous phase parts (15) to (18) were added and emulsified, and then (19) was added to obtain the desired emulsified foundation.

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 a photograph figure which shows the dispersion state before and after addition of a polyether modified silicone compound when an oily gel composition is prepared by highly dispersing treatment of a commercially available organically modified clay mineral (gel composition 3). It is a photograph figure which shows the dispersion state before and after polyether-modified silicone compound addition at the time of preparing an oily gel composition by the normal dispersion process of a commercially available organic modified clay mineral (gel composition 4).

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.

Claims (9)

An average thickness obtained by subjecting a mixture composed only of an organically modified clay mineral aggregate having a layered structure and silicone oil to a peeling treatment by applying mechanical shearing force and / or impact force to the aggregate in the silicone oil. An oil-based sol composition, wherein plate-like particles having a length of 0.1 μm or less and an average major axis of 0.5 to 50 μm are dispersed in the silicone oil .   The sol composition according to claim 1, wherein the organically modified clay mineral is an organically modified hectorite. The oily sol composition according to claim 1 or 2 , wherein the aggregate of the organically modified clay mineral has a layered structure having an average thickness of 2 µm or more. In a mixture composed only of an organically modified clay mineral aggregate having a layered structure and a silicone oil other than a polyether-modified silicone compound , the aggregate is subjected to mechanical shearing force and / or impact force in silicone oil to which glass beads are added. In addition, after obtaining an oily sol composition in which plate-like particles having an average thickness of 0.1 μm or less and an average major axis of 0.5 to 50 μm obtained by performing a release treatment are dispersed in the silicone oil ,
Furthermore, an oily gel composition obtained by adding a polyether-modified silicone compound . The oily gel composition according to claim 4 , wherein the amount of the organically modified clay mineral having a plate-like particle structure is 0.25 to 30% by mass in the oily gel composition. . 6. The oily gel composition according to claim 5 , wherein the amount of the organically modified clay mineral having the plate-like particle structure is 0.25 to 10% by mass in the oily gel composition. . The oily gel composition according to any one of claims 4 to 6 , wherein the amount of the polyether-modified silicone compound is 0.1 to 10% by mass in the oily gel composition. . W / O type emulsified composition using the oil-based gel composition according to any one of claims 4-7. Cosmetics with oily gel composition according to any one of claims 4-7.