JP3506755B2 - Photochromic composite, method for producing the same, and external preparation for skin - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composite, a method for producing the same, and a mechanism for imparting photochromic properties to a skin external preparation, particularly a composite suitable as an extender pigment.

[0002]

2. Description of the Related Art Photochromic or phototropic property is the property that a substance changes its color when it is irradiated with light and returns to its original color when the irradiation is stopped. It's being used. In addition, we have developed a color rendering property adjusting composition that utilizes photochromic properties to adjust the phenomenon that color appearance changes depending on the intensity of light, and a cosmetic composition that uses this to render a constant color appearance. (WO89 / 12084), the utilization of photochromic properties has become more widespread.

[0003]

However, all of the above-mentioned conventional photochromic substances have a relatively high light-hiding power, and therefore, when incorporated in a small amount in cosmetics, there is no problem, but a large amount. It has been pointed out that in the case of being blended in, the transparent feeling when applied to the skin is lacking, and further the spreadability is lacking and the usability is deteriorated.

On the other hand, for example, according to the above-mentioned WO89 / 12084, a method of coating photochromic titanium dioxide on mica or the like is disclosed. In this case, the hiding power and the like can be adjusted, but on the other hand It was revealed that there are problems such as photochromic properties, in particular, a reduction in restoration rate when light irradiation is stopped after discoloration. The present invention has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a photochromic composite having excellent photochromic properties and not having too strong hiding power, and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above object, as a result of coating titanium dioxide on the surface of a thin plate-like substrate and firing the titanium dioxide, It has been found that a composite exhibiting excellent usability and transparency and having excellent photochromic properties can be obtained by controlling the crystallite size within a specific range, and completed the present invention.

That is, the photochromic composite according to claim 1 of the present application includes a thin plate-shaped base material and a titanium dioxide layer coated on the surface of the thin plate-shaped base material. The titanium dioxide has a copper-cathode step angle of 0.00
Measure the (200) plane under the diffraction condition of 8 ° and time constant of 1 second,
According to the Scherrer 's equation, the crystallite size is 9.8 nm to 14.9 nm when the constant K is 0.9, and the titanium dioxide is characterized by having photochromic properties defined below.

Definition of photochromic property A sample left in a dark place at room temperature for about 10 hours is L
The color is measured using the ab color system, and the color is Lab ₁ . This sample is irradiated with ultraviolet rays for 30 minutes so that the intensity of ultraviolet rays becomes ² mW / cm ^2, and the color Lab ₂ when darkened is similarly measured. When the irradiated sample is left in the dark at room temperature for 24 hours, the color Lab ₃ is measured in the same manner. Then, the color difference ΔE between Lab ₂ and Lab ₁ is set to A, and La is
When the color difference ΔE between b ₃ and Lab ₁ is B and each ΔE is calculated by the following mathematical expression 2, 6 ≦ A B ≦ 3.

## EQU2 ## ΔE = {(ΔL) ² + (Δa) ² + (Δb) ² } ^1/2

Further, the manufacturing method according to claim 2 is characterized in that the surface of the thin plate-like base material is coated with titanium oxide and is baked at 400 to 600 ° C. The external preparation for skin according to claim 3 is characterized by containing 10% by weight or more of the photochromic complex.

The structure of the present invention will be described in more detail below. Examples of the titanium oxide used in the present invention include titanium dioxide, low-order titanium oxide, and the like. These may be a mixture, and either anatase type, rutile type, or amorphous type may be used, but especially the photochromic property is enhanced. Therefore, the anatase type is preferable. The shape of the particles may be irregular, plate-like, or spherical. The average particle size is generally about 0.005 to 10 μm.

Further, as the thin plate-like substrate, for example, thin plate-like minerals such as talc, kaolin, alumina, barium sulfate, muscovite, phlogopite, synthetic mica, sericite, biotite, lithia mica, vermiculite graphite and the like are preferable. Of these, muscovite and sericite are particularly preferable from the viewpoint of easy availability of raw materials, imparting of transparency, and the like. Although the coating amount of titanium oxide on the thin plate-shaped substrate depends on the surface area of the thin plate-shaped substrate, it is usually preferably about 10 to 50% as the amount of titanium dioxide with respect to the composite. If the amount of titanium dioxide is too large,
The hiding power may be too high and the transparency may be lost. Further, if the amount of titanium dioxide is too small, the photochromic properties may not be sufficiently exhibited.

Further, in producing the photochromic composite according to the present invention, a thin plate-shaped substrate is added to an aqueous solution of titanyl sulfate, and the mixture is heated to about 80 ° C. to the boiling point and stirred to hydrate the titanium dioxide on the surface of the mica. After coating, filtration,
Wash with water and dry to form a titanium dioxide coated composite. And it is preferable to bake this composite at 400-600 degreeC. It should be noted that an activator such as iron is not required for this firing and imparting photochromic properties.

At this time, even if the firing temperature is lower than 400 ° C. or higher than 600 ° C., the development of photochromic properties is adversely affected. The photochromic composite in the present invention was further subjected to surface treatment such as silicon treatment, surfactant treatment, surface alkoxylation, metal soap treatment, fatty acid treatment, fluorine resin treatment, wax treatment, or the like, or using two or more of these. You may use what performed the compound process. When the dispersibility is improved by the surface treatment, the photochromic property can be further improved.

When the photochromic composite according to the present invention is used in, for example, cosmetics, other components usually used in compositions such as cosmetics can be appropriately blended if necessary. For example, talc, kaolin, muscovite,
Phlogopite, synthetic mica, sericite, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, Inorganic powder such as metal tungstate, silica, magnesium oxide, calcium oxide, zeolite, boron nitride, ceramic powder, nylon powder, polyethylene powder, benzoguanamine powder, tetrafluoroethylene powder, organic powder such as microcrystalline cellulose, squalane. , Liquid paraffin, petrolatum,
Microcrystalline wax, ozokerite, ceresin, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, cetyl-2-ethylhexanoate,
2-ethylhexyl palmitate, 2-octyldodecyl myristate, 2-octyldodecyl gum ester,
Neopentyl glycol-2-ethylhexanoate,
Isooctylic acid triglyceride, 2-octyldodecyl oleate, isopropyl myristate, isostearic acid triglyceride, coconut oil fatty acid triglyceride, olive oil, avocado oil, beeswax, myristyl myristate, mink oil, lanolin, various hydrocarbons such as dimethylpolysiloxane, oils and fats , Esters, higher alcohols, waxes, oils such as silicone oils and silicone resins, UV absorbers, antioxidants, preservatives, surfactants, humectants, fragrances, water, alcohols, thickeners, etc. You can

When the complex according to the present invention is blended with an external preparation for skin, 10% by weight based on the total amount of the external preparation.
By the above, usability, transparency, and photochromic properties are exhibited well. Further, when the photochromic composite according to the present invention is used in, for example, a cosmetic, the form of the cosmetic is powder, cake, pencil, stick, ointment, liquid, emulsion, cream. And so on.

[0015]

The preferred embodiments of the present invention will be described below. The present invention is not limited to these examples.

Measurement of photochromic property 2 g of the powder is uniformly dispersed in 8 g of nitrocellulose lacquer with a disperser, and a coating film is formed on art paper with an applicator of 76 μm. This coating film is dried and used as a sample for measuring photochromic properties. As the light irradiation conditions, a FL20S / BLB lamp manufactured by Toshiba and a FL20S / E lamp manufactured by Toshiba are fixed at a distance of 11 cm, one by one, and an ultraviolet intensity integrating meter (SUV-T manufactured by Toray Techno Co., Ltd.) is used. The distance is adjusted so that the intensity of ultraviolet light irradiated on the sample is ² mW / cm ² . Then, the sample is allowed to stand in a dark place at room temperature for about 10 hours, and the spectrophotometer (Minolta CM-1000) is used for measurement. This sample is irradiated with the ultraviolet ray for 30 minutes, and the color when darkened is measured in the same manner. The color of the irradiated sample when left in the dark for 24 hours at room temperature is measured in the same manner.

When the color difference ΔE with and is A (color change degree) and the color difference ΔE with is B (restoration degree), “having photochromic property” in the present invention is 6 ≦ A B ≦ 3. Means there is. It should be noted that the color difference is calculated based on the equation 2.

Measurement of Crystallite Diameter Titanium on mica forms a titanium dioxide crystallite on mica by being fired while being coated on the mica. The diameter of this crystallite is closely related to the fired state, and the fired state is also closely related to the photochromic property. Therefore, by measuring the crystallite size of titanium dioxide on mica, it is possible to identify the firing state and evaluate the photochromic property.

In the present invention, the Scherrer equation is used to measure the diameter of this crystallite. That is, when the crystallites become finer, the Debye ring becomes broad. Therefore, when the diffraction line is measured with a diffractometer, the spread of the profile is shown by the following Scherrer's equation, assuming that the crystallites have a uniform size.

[Equation 3] D = (K · λ) / (β cos θ) here, D: Crystallite size (Å) λ: measured X-ray wavelength (Å) β: Diffraction line spread (radian) due to crystallite size θ: Bragg angle of diffraction line K: constant

This K is 1 / the maximum peak value.
Using the X-ray wavelength width at the height of 2,
It becomes 0.9. Therefore, in the present invention, 0.9 was used as K, the size of the crystallite of the titanium dioxide-coated powder to be each sample was measured, and the crystallite diameter of titanium dioxide in the titanium dioxide-coated powder was calculated.

The firing temperature, crystallite size and photochromic property
Relationship 250 mg of 2 molar titanyl sulfate aqueous solution with 40 kg of sericite
1 and 550 l of tap water were further added, and the mixture was heated with sufficient stirring. After boiling, the mixture was aged for 5 hours, allowed to cool, filtered, washed with water, and dried at 150 ° C. for 12 hours to obtain 60 kg of hydrous titanium dioxide-coated sericite. Each of the generated water-containing titanium dioxide-coated sericite was filled in a square-shaped ingot in an amount of 1 kg.
After baking at 000 ° C. for 2 hours and allowing to cool, the photochromic property of the produced powder was measured. The photochromic properties measured as described above are shown in Table 1 below and FIGS.

[0022]

[Table 1] ──────────────────────────────── Firing temperature (℃) A B Crystallite size ────────────────────────────────   200 2.00 0.22 9.94   300 4.90 0.53 9.66 ────────────────────────────────   400 10.00 0.84 9.77   450 11.32 0.52 10.44   500 9.36 0.22 11.83   550 7.28 0.26 12.83   600 6.07 0.57 14.86 ────────────────────────────────   700 2.12 0.18 22.73   800 1.45 0.42 29.47   900 0.69 0.32 32.20 1000 4.03 0.11 35.13 ────────────────────────────────

As is apparent from Table 1, it is understood that the crystallite size has a close relationship with the firing temperature. Then, as compared with the case of firing by adding an activator metal to titanium dioxide, the photochromic property is suitably exhibited in a low firing temperature range, and firing at 400 to 600 ° C. is preferable,
The crystallite size at this time is 9.8 to 14.9 nm. Also,
FIG. 2 shows the time-dependent change in the color restoration rate when the composite baked at 500 ° C. is irradiated with light to change its color and then placed in a dark place. The photochromic composite according to the present invention is shown in FIG. It is understood that is restored to 90% in about 20 minutes.
The extremely short restoration time is extremely advantageous in using the photochromic property for color rendering adjustment of cosmetics and the like.

Relationship between transparency, usability and titanium dioxide coating amount
In the same manner as above, 5 μm of mica was coated with various amounts of titanium dioxide, and the transparency and usability were evaluated. In addition,
In the test, the following components (1) to (3) were mixed to prepare a powder foundation and then evaluated. (1) Photochromic composite 90.0 (2) Polydimethylsiloxane 5.0 (3) 2-Ethylhexyl palmitate 5.0 The results are shown in Table 2.

[0025]

[Table 2] ──────────────────────────────────── Coating amount (%) 5 10 15 20 30 40 50 60 ──────────────────────────────────── Transparency ○ ○ ○ ○ ○ ○ ○ △ Use Properties ○ ○ ○ ○ ○ ○ ○ △ Photochromic properties × ○ ○ ○ ○ ○ ○ ○ ─────────────────────────────── As is clear from Table 2 above, when the coating amount of titanium dioxide is less than 10%, the degree of discoloration is small and the photochromic properties may not be sufficiently exhibited. Further, if the coating amount exceeds 50%, the transparency is lacked and the spreadability tends to be lowered.

Compounding amount of the composite in the composition A composition obtained by coating 5 μm of mica with 40% of titanium dioxide in the same manner as described above to impart photochromic properties, and then compounding the composite in a predetermined amount. The transparency and usability of (powder foundation) were evaluated. In addition, in the test, the following components (1) to (4) were mixed to prepare a foundation and then evaluated. (1) Photochromic complex X (2) Sericite 90-X (3) Polydimethylsiloxane 5.0 (4) 2-Ethylhexyl palmitate 5.0 Further, as a comparative example, the same amount of photo as the complex was used. An example in which chromic titanium dioxide was blended was evaluated. The results are shown in Table 3.

[0027]

[Table 3] ──────────────────────────────────── Compounding amount (X%) Complex titanium dioxide               Transparency Usability Photochromic Property Transparency Usability Photochromic Property ────────────────────────────────────   10 ○ ○ × ○ ○ ○   20 ○ ○ △ △ △ ○   30 ○ ○ ○ × × ○   40 ○ ○ ○ × × ○   50 ○ ○ ○ × × ○   60 ○ ○ ○ × × ○   70 ○ ○ ○ × × ○   80 ○ ○ ○ × × ○   90 ○ ○ ○ × × ○ ────────────────────────────────────

As a result, when photochromic titanium dioxide is used as a skin external preparation, the range that does not affect its usability is up to about 20%, but when it is used as a complex, it is 30% or more. However, it becomes possible to exhibit photochromic properties while maintaining good transparency and usability. Hereinafter, suitable compounding examples of the external preparation for skin according to the present invention will be shown. In addition, it is possible to exhibit good photochromic properties while maintaining excellent transparency and usability.

Example 1 Powder foundation (1) Photochromic composite 40.0 (2) Talc 10.0 (3) Sericite 29.5 (4) Spherical nylon powder 8.0 (5) Polydimethylsiloxane 5 0.0 (6) 2-Ethylhexyl palmitate 5.0 (7) Sorbitan sesquioleate 1.5 (8) Preservative 0.9 (9) Perfume 0.1 (Production method) (1) to (6) in Henschel After mixing with a mixer and adding (7) to (9) to the mixture by heating and melting and mixing, the mixture was pulverized with a pulverizer (Hosokawa Micron) and molded into an intermediate dish to obtain a powder foundation. .

Example 2 Dual-use foundation (1) Photochromic complex 31.0% (2) Silicone-treated mica 36.25% (3) Silicone-treated talc 20.0% (4) Trimethylolpropane triisostearate 5.0% (5) Squalane 3.0% (6) Beeswax 2.0% (7) Sorbitan trioleate 1.0% (8) Preservative 0.5% (9) Vitamin E 0.05% ( 10) Butylmethoxybenzoylmethane 1.0% (11) Perfume 0.2% (Production method) (1) to (3) are mixed, and (4) to (1
What was heated and dissolved in 1) was mixed and crushed. This was molded into a medium plate to obtain a dual-purpose foundation.

Example 3 Compact emulsion foundation (1) Decamethylcyclopentasiloxane 10.0% (2) Dimethylpolysiloxane (6cs) 5.0% (3) Jojoba oil 1.0% (4) Paraffin wax 6 0.0% (5) Microcrystalline wax 4.0% (6) Polyoxyalkylene-modified organopolysiloxane 3.0% (7) Hydrophobized photochromic composite 36.0% (8) Hydrophobized iron oxide Pigment 4.0% (9) Ion-exchanged water 10.0% (10) Glycerin 8.0% (11) 1,3 Butylene glycol 2.0% (12) Preservative proper amount (13) Perfume proper amount (production method ) After heating (1) to (6) and (13) to 80 ° C, (7) and (8) are added and dispersed. Next 8
The mixture of (9) to (12) heated to 0 ° C. is added and emulsified and dispersed. Then, it was filled in a medium state in a fluid state, cooled to room temperature and mounted in a compact container to obtain a target compact emulsion foundation.

[0032]

As described above, according to the photochromic composite of the present invention, since titanium dioxide is coated on the plate-like substrate as a specific crystallite size, usability and transparency are impaired. Can exhibit excellent photochromic properties.

[Brief description of drawings]

FIG. 1 is an explanatory view of the degree of color change of a photochromic composite according to the present invention.

FIG. 2 is an explanatory view of the restitution degree of the photochromic composite according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI // G03C 1/725 503 G03C 1/725 503 (58) Fields surveyed (Int.Cl. ⁷ , DB name) A61K 7/00 -7/50

Claims (4)

(57) [Claims] 1. A composite comprising a thin plate-shaped substrate and a titanium dioxide layer coated on the surface of the thin plate-shaped substrate, wherein a copper-cathode step angle is 0.008 ° and a time constant is 1 second. The surface is measured under the condition, and the constant K is set to 0 in Scherrer 's formula.
When the number is 9, the size of the crystallite of the titanium dioxide is 9.8 nm to 14.9 nm , and the photochromic composite. Definition of photochromic property (1) A sample left to stand at room temperature in a dark place for about 10 hours is measured with a Lab colorimetric system to obtain a color Lab ₁ . (2) Color Lab when this sample was irradiated with UV light for 30 minutes so that the UV intensity was ² mW / cm ² and was darkened.
₂ is measured similarly. (3) In the same manner, the color Lab ₃ of the irradiated sample left at room temperature in the dark for 24 hours is measured. And L
Let A be the color difference ΔE between ab ₂ and Lab ₁ , and let Lab ₃ and La 1
Let B be the color difference ΔE from b ₁ , and let each ΔE be the following equation 1
When calculated with, 6 ≦ A B ≦ 3. ## EQU1 ## ΔE = {(ΔL) ² + (Δa) ² + (Δb) ² }
^1/2 2. The surface of a thin plate-shaped substrate is coated with titanium oxide,
By firing at 400-600 ° C, copper anticathode step angle 0.008 °, time constant 1 second diffraction
The surface is measured under the condition, and the constant K is set to 0 in Scherrer 's formula.
When set to 9, the binding of titanium dioxide on the surface of the thin plate-shaped substrate is performed.
Characterized by the crystallite size being 9.8 nm to 14.9 nm
And a photochromic complex . 3. The surface of a thin plate-shaped substrate is coated with titanium oxide,
Claim 1, characterized by firing at 400 to 600 ° C.
Or the method for producing the photochromic composite powder according to item 2 . 4. An external preparation for skin comprising the complex according to claim 1 or 2 in an amount of 10% by weight or more.