WO2002083296A1

WO2002083296A1 - Fine particles included in ultra-thin membrane in state of primary particles and cosmetic using the same

Info

Publication number: WO2002083296A1
Application number: PCT/JP2002/003400
Authority: WO
Inventors: Atsushi Takeda; Masuhiro Kogoma; Chihiro Kaito
Original assignee: Isi Corporation
Priority date: 2001-04-06
Filing date: 2002-04-04
Publication date: 2002-10-24
Also published as: JP2002308716A

Abstract

Fine particles included in an ultra-thin membrane in the state of primary particles, which is prepared by coating fine particles with a thin film forming material comprising an organic metal compound being less susceptible to hydrolysis and ultra-pure water and/or an organic solvent preventing hydrolysis, and disconnecting and removing the functional groups of the organic metal compound in the resulting coating, to thereby convert the coating to an ultra-thin oxide film; and a cosmetic using such fine particles.

Description

Specification

Fine particles encapsulated with a monodisperse ultrathin film and cosmetics using the same

The present invention relates to fine particles included in a monodispersed ultrathin film, a composite using the same, and a plasma film forming apparatus. Background art

Ultra-thin film formation technology has recently been developed mainly in the semiconductor field. However, the inventors have independently developed a technique for monodispersing fine particles or nanoparticles having a particle diameter of 1 ^ m or less on a trial basis. In addition, for particles of several tens or more, so-called plasma CVD methods are sometimes used to manufacture the particles because the contamination of the vacuum pump is small, (Bayer's paper).

However, from the industrial scale, mass productivity and material engineering material stability that can be used in actual industries have not yet been developed.

In addition, when applying the general plasma CVD method, the plasma destroys the bonding state of the particles that must be stably included, thermally evaporates, and the film forming material becomes a single particle, which is sufficient. It is known from the research of the present inventors that it is impossible to obtain a dense and highly adhesive ultrathin film in a completely monodispersed state.

Furthermore, there is no technology that can be used to freely design a heterogeneous film of several layers instead of a single layer as a film-forming substance. There is no technology that can be applied to substrates other than substrates having a certain area, such as semiconductor wafers. It is extremely difficult to completely form a film that is extremely chemically unstable. Disclosure of the invention In the case of particles that have formed a conventional thin film, the film contains the entire particle and cannot be monodispersed, and the shape and adhesion of the film are disturbed. It is almost impossible to do so, and the particles that can be handled are about 100 m, so it is easy to produce highly functional fine particles that can be used for various purposes. There was a problem that two or more layers had to be formed. Further, the development of a device for improving mass productivity was an important issue. The present invention is very stable, especially for particles that are difficult to process by the wet or dry method developed by one of the present inventors, and whose effects are attenuated, deteriorated, or decomposed by water absorption. To provide microparticles covered with a monodisperse ultrathin film, in which at least one layer of dense ultrathin film is deposited, and if necessary, several layers, and cosmetics using the obtained microparticles are provided. It is intended to be.

In order to achieve the above object, in the microparticles covered with the monodispersed ultrathin film of the present invention, an ultrathin film of 0.5 to 5 nm in which the interface with the group of fine particles is composed of high-purity silica, If necessary, a thin film coating of 30 to 40 nm is formed on a single particle, and the surface is treated with plasma to form a high-energy type siloxane bond, and a silanol group is partially added, and the A negative counter-potential is generated at, and a monodispersed state is obtained.

Further, in order to achieve the above object, in the fine particles encapsulated with the monodispersed ultrathin film of the present invention, another inorganic oxide thin film, for example, zirconia, titanium oxide, etc., is placed above the high purity silica ultrathin film. The plasma film is formed by overlapping.

The fine particles included in the monodisperse thin film of the present invention are agglomerated powder particles coated with a thin film-forming material comprising an organometallic compound that is difficult to hydrolyze and ultrapure water or an organic solvent that prevents hydrolysis. The group is completely monodispersed in each powder particle, and the powder particles are crystallized or broken by an ultra-thin oxide film obtained by cutting and removing the organometallic compound functional group. The coating is formed without crystal transition.

Here, in the present invention, the monodisperse thin film refers to a thin film that covers the thin film and disperses the fine particles without agglomeration and coagulation. In addition, “monodispersion” of particles in the present invention means that particles do not form secondary particles due to aggregation, coagulation, or the like, and each particle is in a dispersed state.

The fine particles encapsulated with the monodispersed thin film according to the present invention are obtained by mixing a thin film-forming material comprising an organic metal compound which is unlikely to be hydrolyzed and ultrapure water or / and an organic solvent which protects against hydrolysis with a dry mixer. After at least 0.1 part by weight of the target powder is uniformly jetted onto the target powder, the precursor is dried and formed without damaging the organometallic compound. Ultra-thin oxide film obtained by irradiating high-energy ultraviolet rays and / or plasma while completely dispersing monodispersely with an ultrasonic horn having a longitudinal amplitude of 40 m or more to cut and remove the organometallic compound functional groups. Characterized by being coated with We also propose a method for producing fine particles encapsulated with the monodisperse thin film thus produced. The fine particles according to claim 1 or 2 are preferably a pigment, an ultraviolet shielding inorganic material, an organic compound, or a lake pigment.

The thin film according to claim 1, 2 or 3, is MeinxOy (where Me is a metal element, n is the number of metal elements (n = integer), l≤x, y≤9, and X and y are A transparent film with a thickness of 4 O nm or more, preferably 3 nm or less, which is not eroded and dissolved by the medium. It preferably has all the functional properties such as oxidation resistance, color development, fluidity and mechanical strength.

The thin film according to claim 4 is preferably composed of a plurality of different laminated films.

The cosmetic according to the present invention preferably contains fine particles encapsulated with the monodispersed thin film according to claims 1, 2, 3, 4 or 5. If the compound constituting the core of the present invention shows a very sensitive degradation reaction to humidity, water cannot act on the film-forming material, so that anhydrous ethanol or a hydrocarbon-based organic solvent that prevents hydrolysis is used. After the film-forming materials were diluted and dissolved, they were quickly mixed in a dry-gas-balanced glove box--a vacuum chamber--by a method such as jet injection to form a film-forming precursor. After that, it is dried and irradiated with plasma introduced into a plasma device or high-speed mixer with loop-shaped piping to cut and remove the functional group of the organometallic compound.At the same time, the vertical amplitude is 40 m or more in the same space. The particles during the film formation process are collided with the ultrasonic horn to explode the agglomerates to obtain fine particles that are completely encapsulated with a monodisperse ultrathin film.

Further, in order to mix and disperse the fine particles included in the monodispersed ultrathin film obtained in the present invention into an intermediate or a finished composition used for various purposes, unnecessary additives are removed as much as possible. If necessary, it is desirable to produce the multifunctional liquid monodispersion by using an ultrasonic homogenizer having a longitudinal amplitude of 30 m or more, and to introduce it into the final product production process.

Further, the fine particles encapsulated with the dried monodispersed ultrathin film of the present invention can be mixed with various powders to obtain the above-mentioned multifunctional cosmetics such as foundations.

Since the present invention is configured as described above, the following effects can be obtained.

By forming an oxide thin film using plasma, the degree of polymerization of the film is increased, and the bonding property with the core fine particles is enhanced.

Ultra-thin oxide films can be produced multiple times from extremely unstable compounds without operating in a vacuum, and materials that are susceptible to deterioration and structural destruction by conventional plasma can be easily handled, and even organic pigments can be processed. It is possible.

Silica, a thin film forming material that dissolves in alkali, is processed by the plasma method. As well as monodispersed, and the upper layer is coated with a film of insoluble alkali, such as zirconia and titania, to protect multiple layers and to raise the light scattering and reflection effect to an extremely high level. I can.

By removing the pinholes to the smallest unit of the ultra-thin film to about 1 nm and removing pinholes, fine particles with the same mechanical strength, abrasion resistance, flow characteristics, color development, oxidation resistance, and heat resistance, Highly functional particles in the micron range can be obtained.

The ultrafine particles included in the monodisperse thin film according to the present invention can be used as an electromagnetic wave shielding material or a material of a display device, particularly as an electronic material such as a phosphor (luminescent pigment). BRIEF DESCRIPTION OF THE FIGURES

1, F e ₃ 0 ₄ (Black iron oxide: Magunetai g) coated with shea Li Ca ultra thin film formed by the plasma shows a high-resolution electron micrograph of. Amorphous silica layers are continuously formed without pinholes on the iron oxide surface with a clear crystal lattice. This material is 1 0 0 ° C shall be crystal transition, since the change to red Qt F e ₂ 0 ₃ (red iron oxide), Me enough attention for damaged due to the plasma is required low temperature treatment is determined Can be Furthermore, since this material is a magnetic material, it has strong magnetic aggregation. At the film thickness (silica weight% 8.0) in this photograph, it has been found that the magnetic cohesion is released by the surface potential of the silica force. (A) is an overall view of black iron oxide encapsulated by an ultra-thin Si-force ultra-thin film, and (b) is a phase diagram of a crystal near the interface between an ultra-thin Si force and an iron oxide (high-resolution transmission type). Electron microscope; by Ritsumeikan University). BEST MODE FOR CARRYING OUT THE INVENTION

Next, examples of the present invention will be described.

[Surface of organic pigment (red 202) covered with monodispersed ultra-thin silica film Example]

It has been pointed out by the pigment manufacturer that this pigment begins to deteriorate due to water absorption development immediately after its production, causing color change. However, usually, since the rosin (rosin) is converted to a rosin to develop color, the surface treatment as in the present invention cannot be practically hindered by rosin. Therefore, in the present invention, red pure No. 202 (Dainichi Seika Kogyo Co., Ltd.) immediately after production, which is produced without passing through the rosinization process, is used to express high-purity tetraethoxysilane (hereinafter referred to as “ethyl silicate”). They were combined as in 1.

【table 1】

Formula _ _ _Actual blending amount Isoform weight%

A, Red color just after production No. 202 5 kg 9 40 B, ethyl silicate 0 7 kg 60 C, ultrapure water 0 0 kg 0 0

1 0 0 .0

After mixing B with C and vibrating vigorously, it is uniformly processed with a high-speed mixer for 5 minutes to create a homogeneous emulsion, and the above pigment is poured into a small hen-shell mixer to generate high-speed swirling turbulence. The above emulsion was jet-jetted using an airless gun to completely leak the pigment.

This was put into a thick large bur bag and hydrolyzed without a catalyst.

Furthermore, it was gently dried at 52 ° C to obtain a dry powdery film-forming pigment. It is injected into an inverted triangular Pyrex glass chamber at a rate of 500 L / time, and power is applied to it while passing helium oxygen gas into an atmospheric pressure glow discharge plasma device installed in the chamber. 0 W is applied to generate plasma, and the dry powder The pigment for film formation was transported by gas and circulated through the system.

At this time, the powder was exploded and monodispersed while driving four ultrasonic horns with a diameter of 50 mm or more and a vertical amplitude of 40 m or more installed at the bottom of the chamber for 15 minutes. did.

As a result, a monodispersed hydrophilic red No. 202 pigment excellent in color was obtained. The pigment was mixed 1.0% in pure water and dispersed with an ultrasonic homogenizer without mixing any dispersing aid. The dispersion was stable for one month for one month.

In addition, when the heat resistance was measured by a thermal analysis method, the starting point of the thermal decomposition was increased by 30 to 40 ° C. The thickness of the silica film was 1 to 2 nm in the analysis with a high-resolution transmission electron microscope (TEM). In addition, Si was clearly detected by X-ray analysis of the membrane using an EDX apparatus. Furthermore, in the XPS analysis using the ESC A apparatus, the ethyl silicate was completely decomposed from the Si 2 p data of the silica film, and it was concluded that the bonding state was high-energy silica.

Table 2 shows the evaluation results of Red No. 202 to which the above silica monodispersed ultrathin film was applied.

[Table 2]

Test item-Red No. 202 with silica monodispersed ultra-thin film Fluidity and peelability High flowability and suitable peelability were confirmed in a grinding test in a mortar.

TEM analysis results No mechanical breakage of pigment, particles covered entirely with silica film (l to 2 nm) (mechanical breakage status), particles dispersed in flakes, no damage.

Oxidation resistance · K weatherability 25 3, 365 5 η ηι UV resistance was strong. No visible abnormality in visible and ultraviolet absorption.

Lipstick coloring Bright and very high coloring. Good fluidity and high skin-to-adhesion.

Table 3 shows the results of the evaluation of untreated Red No. 202. [Table 3]

Test item Red No. 2-0-2 with a monodispersed silica ultra-thin film Flowability and peelability Easy to stick in a pulverization test with agate milk. Peelability from agate is extremely poor.

TEM analysis results Focus is difficult to determine and evaporation of the pigment by electron beam is accelerated.

Oxidation resistance * Weather resistance 25 3, 365 nm The UV resistance was weak. Visible and UV absorption waveforms are distorted, discolored, dull and poor in fluidity. Lipstick coloring Skin poor adhesion. Color missing. Very light color when stretched.

[Example of ultraviolet shielding type zinc oxide ultrafine particles]

Since these particles exhibit high alkalinity due to water and sweat, they are not normally used in skin care products and are applied to inexpensive sunscreen preparations, but have been applied to various cosmetics after FDA approval. However, the manufacturer does not require the integrity of the photochemical hazard. At present, the present inventors fully understand that there is a demand for an inexpensive treatment by a simple method, and in particular, a sunscreen formulation containing as much as 20% of this is associated with considerable danger. . In addition, due to this strength, mutual dissolution occurs in a monodispersed oxide ultrathin film by a wet method or a semi-dry method, which is not successful.

Therefore, in the present invention, an oxide ultrathin film was formed without using water. First, zinc oxide (manufactured by Sumitomo Osaka Cement Co., Ltd.) was used, and high-purity tetraethoxysilane (hereinafter referred to as “ethyl siligate”) was blended as shown in Table 4.

[Table 4]

Blended formula Actual blended amount Solid content% by weight

A, zinc oxide ultrafine particles 50 kg 95.2 B, ethyl silicate 9 kg 4.8

0 0. 0 This is mixed at high speed in the same mixer, and a plasma gas tail whose temperature is reduced to 30 DC plasma jet is injected into the same mixer to completely eliminate the ethoxy group of the ethyl silicate. I let it.

Next, a very stable neoalkoxy zirconate coupling agent (NZ-44: Genrich Petrochemical Co., USA) is used to form a zirconium film, an alkali-resistant material, on the surface of the silicon film. ) Was surface-coupled as shown in Table 5.

[Table 5]

Blended formula Actual blended amount Solid content% by weight

A, Ultrafine zinc oxide particles forming silica film 52.5 kg 9 8.0

B, NZ—44 Zirconate 5.4 kg 2.0

10.0 While this was mixed at high speed in the same mixer, a plasma gas tail whose DC plasma jet was lowered to 300 ° C was injected into the same mixer, and the coupling agent function was applied. The entire group was completely annihilated, and an ultra-thin zirconia thin film was formed on the silica film surface. As a result, the zirconium film showed an interference color.

Next, 5% of the zinc oxide formed with the laminated film was poured into physiological saline and mixed and stirred for 2 hours with a mixer to perform a forced elution test of zinc ions. After filtering this solution through No. 5C Toyo filter paper, ICP plasma emission analysis was performed to compare ion elution. Table 6 shows the results. [Table 6]

Type Zn ion concentration (ppm) Untreated zinc oxide 4 5

Zirconium oxide film forming zinc oxide 2 Laminated film forming zinc oxide Out of detection limit Furthermore, after forming an ultra-thin zirconia thin film, a silica thin film was formed on the outermost layer to improve the dispersibility, and a three-layer structure was formed. At this time, the treatment was carried out under the same conditions as those for the red organic pigment No. 202. As a result, the zinc oxide ultrafine particles were able to absorb the entire ultraviolet shielding area of 38 Onm or less, but the prototype powder foundation, which is considered to be the safest, was manufactured and its performance was confirmed.

That is, after irradiating powder foundation with an ultraviolet lamp generating the above-mentioned wavelength, 50 mg was immediately poured into 5 g of high-purity squalene, and the radical reactivity was confirmed. Table 7 shows the results.

[Table 7]

Type Coloring of zinc oxide due to oxygen radicals _ Zinc oxide forming laminated film Little coloration.

Thin film forming zinc oxide Thin pink color

Untreated zinc oxide Colors dark orange for a long time

Industrial applicability

As described above, the fine particles included in the monodispersed ultrathin film of the present invention can be mixed with various powders to obtain the above-mentioned multifunctional foundation and other cosmetics.

Claims

The scope of the claims

1. Aggregated powder particles, which are previously coated with a thin film-forming material consisting of an organic metal compound that is difficult to hydrolyze and ultrapure water or / and an organic solvent that prevents hydrolysis, are completely monodispersed in each powder particle. A monodisperse thin film characterized in that the powder particles are coated with an ultra-thin oxide film obtained by cutting and removing the organometallic compound functional group without crystal destruction and / or crystal transition. Microparticles included in.

2. At least 0.1 parts by weight of a thin film-forming material consisting of an organic metal compound that is unlikely to be hydrolyzed and ultrapure water or / and an organic solvent that protects from hydrolysis is used as a target powder in a dry mixer. The precursor, which is formed by dry jetting without damaging the organometallic compound after jetting the jet uniformly, is completely produced in space by an ultrasonic horn having a longitudinal amplitude of 40 m or more. While being monodispersed, irradiated with high-energy ultraviolet rays or Z and plasma, the organometallic compound functional group is cut and removed. Fine particles.

3. The fine particles enclosed with a monodisperse thin film, wherein the fine particles according to claim 1 are pigments, ultraviolet shielding inorganic materials, organic compounds, and lake pigments.

4. The thin film according to claim 1, 2 or 3, wherein Mei ^ DxOy (where Me is a metal element, n is the number of metal elements (n = integer), l≤x, y≤9 Where x and y are integers). A strong film that is not eroded and dissolved by the medium. A transparent film with a thickness of 40 nm or more, preferably a transparent film of 3 nm or less. Preferably all functional properties such as heat resistance, oxidation resistance, color development, fluidity and mechanical strength Characterized in that the fine particles are enclosed by a monodisperse thin film.

5. The fine particles enclosed by a monodisperse thin film, wherein the thin film according to claim 4 comprises a plurality of laminated films different from each other.

6. A cosmetic comprising fine particles included in the monodispersed thin film according to claim 1, 2, 3, 4 or 5.