JP2017214235A - Bright material and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bright material that has reduced influences on human bodies and is easily available, and a use therefor.SOLUTION: A bright material contains a film piece of a graphite-like carbon nitride film. The graphite-like carbon nitride film is a polymer of a compound represented by X+mYm- (X+ is a guanidinium ion, a melaminium ion, a melamium ion, a melemium ion, a guanidine derivative ion represented by formula (I), or a guanidine derivative ion represented by formula (II), Ym- is an anion, m is a valence of Y) (R-Rindependently represent an amino group, a nitro group, a C1-10 alkyl group, -(C2H4O) n-R, halogen, or a primary amide group; Ris a C1-4 alkyl group; n is an integer of 1-10).SELECTED DRAWING: None

Description

  The present invention relates to a novel glittering material, and a cosmetic and paint containing the glittering material, and more specifically, a glittering material that has little influence on a living body and can be easily manufactured, and the glittering material. It relates to cosmetics and paints.

  For example, a makeup material such as a foundation or a paint such as paint contains a glittering material in order to impart gloss. For example, a bright material used in cosmetics includes what is called a pearl pigment.

  In the glittering material, an interference color (also referred to as a structural color) is used in which color is developed by causing light to interfere using the refractive index difference of the transparent material. Interference colors also exist in nature, and examples include the morpho butterfly wings, the surface of saury and sardines, and the vivid colors of peacock wings. The interference color utilizes light reflection (Fresnel reflection) at the interface between materials having different refractive indexes, and the reflectance depends on the refractive index difference at the interface.

  Bright materials using such interference colors are less likely to cause discoloration than pigments, can achieve a metallic luster (color tone), and more vibrant color by strengthening to a specific wavelength due to interference There is an advantage that can be realized.

  Titanium oxide is one of inorganic materials having a high refractive index. Conventionally, it is known that the pearl pigment described above can be obtained by coating nano-sized titanium oxide on the surface of a plate-like powder such as mica.

Amir S. Yazdi et. Al., Nanoparticles activate the NLR pyrin domain containing 3 (Nlrp3) inflammasome and cause pulmonary inflammation through release of IL-1α and IL-1β, PNAS November 9, 2010 vol. 107 no. 45 19449-19454 Fine Chemical Series Cosmetic Development and Nanotechnology Supervision: Kunio Shimada CMC Publishing (Reference: https://books.google.co.jp/books?id=elsRKh9o2GkC&pg=PA18&lpg=PA18&dq=photocatalyst+cosmetics&source=bl&ots=luEtt8xA7L&sig=H ja & sa = X & ved = 0ahUKEwj72tu_3u_MAhVj4qYKHRG9AIg4ChDoAQg4MAU # v = onepage & q = photocatalyst% 20cosmetics & f = false)

  On the other hand, in recent years, it has been reported that nano-sized titanium oxide can adversely affect the human body (Non-patent Document 1). However, many materials that can replace titanium oxide as a material that has both a relatively high light-transmitting property (for example, transparency in visible light) and a refractive index, which are properties necessary for coloration based on interference light, are many. Absent.

  In addition, the oxidizing power of titanium oxide, zinc oxide and the like is high, and it takes time and effort to deactivate the photocatalytic activity by treatment such as coating in order to suppress decomposition of other components and adverse effects on the skin (Non-patent Document 2).

  In addition, in order to make the bright material using the interference color more intensely colored, for example, a method of increasing the reflectance as compared with a single layer film by forming the bright material itself with a multilayer film is also known. However, when the refractive index of the material forming the glittering material is not high, a large number of layers are required, and the manufacturing cost increases.

  Therefore, it has been desired to develop a new glittering material that has little influence on the living body, is excellent in coloration, and can be easily obtained.

  The present invention has been made in order to solve the above-described problems, and an object thereof is to provide a luster material that has little influence on a living body, is excellent in coloration, and can be easily obtained, and uses thereof. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a film piece obtained by pulverizing a graphite-like carbon nitride film can be used as a glittering material that solves the above problems. The headline and the present invention were completed.

  That is, the glittering material of the present invention includes a film piece of a graphite-like carbon nitride film.

In the glitter material of the present invention, the graphite-like carbon nitride film is a compound represented by X ⁺ _m Y ^m- (X ⁺ is a guanidinium ion, a melaminium ion, a melmium ion, a melium ion, ) Or a guanidine derivative ion represented by the following formula (II), Y ^m− is an anion, and m is a valence of Y).

(In the formula (I) and ^{(II), R 1, R} 2 and ^{R 3} independently of one another, an amino group, a nitro group, an alkyl group having 1 to 10 carbon _{atoms, - (C 2 H 4 O} ) n —R ⁴ (n = 1 to 10, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms), a halogen, or a primary amide group.
In the glitter material of the present invention, the film piece preferably has a film thickness of 50 nm to 2 μm.

  In the bright material of the present invention, the length of the film piece is preferably 1 μm to 2 mm.

  In the glitter material of the present invention, the film piece may be attached to a base material.

  In the glittering material of the present invention, it is preferable that the substrate has a negative charge on the surface or has π electrons on the surface.

  In the glitter material according to the present invention, the base material is preferably mica.

  Moreover, this invention provides the cosmetics and coating material with which the brilliant material which concerns on this invention was mix | blended.

  According to the present invention, a bright material including a film piece of a graphite-like carbon nitride film has little influence on a living body, is excellent in coloration, and can be easily obtained. For example, it is blended in cosmetics and paints. It is possible to provide a glittering material that can be made to occur.

It is a diagram based on a photograph showing the appearance of a dispersion of g-C ₃ N ₄ film piece after applying ultrasonic vibration to definitive Example 1. Is a diagram based on optical microscope photographs of the g-C ₃ N ₄ film piece before and after the grinding in Example 1, left before grinding, the right figure corresponds to after the grinding. Example is a diagram showing a photochemical properties of g-C ₃ N ₄ film in 2, a photo showing a g-C ₃ N ₄ film (left) and mica board (right) each appearance deposited on mica substrate is a diagram based on, b are views corresponding to a, is a diagram showing a g-C ₃ N ₄ film and mica substrate respectively diffuse reflectance spectra were deposited on mica substrate.

(Bright material)
The glitter material of the present invention includes a film piece of a graphite-like carbon nitride film (hereinafter sometimes referred to as “g-C ₃ N ₄ film”). In the present specification, the “brilliant material” means a material using coloration based on interference or scattering of light and the like and capable of giving gloss.

In the present invention, the g-C ₃ N ₄ film has a single-layer or multilayer sheet structure. Note that in the g-C ₃ N ₄ film having a single-layer sheet structure, the melem structural units are spread in a two-dimensional direction. In a g-C ₃ N ₄ film having a multilayer sheet structure, a plurality of sheets in which melem structural units spread in a two-dimensional direction are laminated. Further, in one g-C ₃ N ₄ film, there may be a portion where the number of layers is different. Further, when the g-C ₃ N ₄ film is attached to a substrate described in detail later, each layer (one or a plurality of phases) is laminated in parallel to the substrate.

The g-C ₃ N ₄ film in the present invention is preferably a polymer of a compound represented by X ⁺ _m Y ^m- (referred to as “compound X ⁺ _m Y ^m− ”). Incidentally, it details a method for manufacturing the _g-C 3 _{N 4} film will be described later.

In the compound X ⁺ _m Y ^m- , X ⁺ is a guanidinium ion (also referred to as “guanidinium ion”), a melaninium ion, a melmium ion, a melium ion, or a guanidine derivative ion represented by the following formula (1). Or a guanidine derivative ion represented by the following formula (II).

R ¹ in the above formula (I) is an amino group, a nitro group, an alkyl group having 1 to 10, preferably 1 to 5, more preferably 1 to 3 carbon atoms, — (C ₂ H ₄ O) _n —R ^4. , Halogen, or a primary amide group. _{- (C 2 H 4 O)} n is 1 to 10 in the n -R ^4, preferably 1 to 5, more preferably from 1 to 3, ^{R 4} is an alkyl group having 1 to 4 carbon atoms. _{Also, - (C 2 H 4 O} ) n moiety of are ethylene oxide groups, which C atoms are bonded to the N atom of the guanidine are contemplated. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Halogen includes fluorine, chlorine, bromine, and iodine. R ¹ is preferably an amino group or a nitro group.

R ² and R ³ in the formula (II) are independently of each other an amino group, a nitro group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, — (C ₂ H _{⁴ O)} n -R _4, halogen or a primary amide group. The description of — (C ₂ H ₄ O) _n —R ⁴ and halogen is the same as that in the above formula (I). R ² and R ³ are preferably independently of each other an amino group and a nitro group.

X ⁺ _m is preferably a guanidinium ion, a melaminium ion, a melaminium ion or a melemium ion, and more preferably a guanidinium ion.

^{Y m-is} the X ^{+ _m} Y ^m- is an anion, m is the valence of Y. Examples of the anion include CO ₃ ²⁻ , SO ₄ ²⁻ , Cl ⁻ , HPO ₄ ²⁻ , NO ₃ ⁻ , SCN ⁻ , SO ₃ NH ₃ ⁻ , CrO ₄ ²⁻ , p-toluenesulfonate, and ReO _4. ^- and the like. Y ^m− is preferably CO ₃ ²⁻ , SO ₄ ²⁻ or Cl ⁻ , and particularly preferably CO ₃ ²⁻ . If Y ^m-is _CO ³ is ^2, since the compound ^X ₊ ^{m Y m-} in the absence of the melting point, the _CO ^{3 2-} is a system before the compound ^X ₊ ^{m Y m-,} or the reaction product thereof is vaporized It is thought that it is hard to escape. ^Therefore, when ^{Y m-is} _CO ³ is ^2, as compared with the case ^{Y m-is} another, the number amount of compound ^X ₊ ^{m Y m-,} or reaction product thereof to vaporize, more efficient film It is thought that can be manufactured.

The film piece constituting the glitter material of the present invention refers to a small piece of g-C ₃ N ₄ film that maintains the single-layer or multi-layer sheet structure of the g-C ₃ N ₄ film described above. This film piece has various characteristics of g-C ₃ N ₄ film (for example, excellent light transmittance in the visible light region, high refractive index (depending on the wavelength of incident light, the refractive index in the in-plane direction is 2) to 4), for example, about 3.0 to 2.0) and low photocatalytic activity, etc.), and is excellent in coloration and has an influence on the environment and the living body (particularly the human body). It can be used as a low brightness material.

  Although the shape of the film piece which comprises the brilliant material of this invention is not specifically limited, For example, a substantially disc shape, a substantially elliptic disc shape, a substantially polygon disc shape (substantially rectangular disc shape), a wavy shape etc. are mentioned. Moreover, the film piece may be a shape rounded into a cylindrical shape, for example.

  The film thickness of the film piece constituting the glittering material of the present invention is not particularly limited, but is, for example, in the range of 50 nm to 2 μm, preferably in the range of 100 nm to 1.5 μm, and more preferably in the range of 100 nm to 1 μm. Within range. However, what is necessary is just to set the film thickness of a film piece suitably according to the use of the brilliant material of this invention.

  When the glitter material of the present invention is blended in cosmetics such as a foundation, the film thickness of the film piece is 50 nm to 2 μm, preferably 100 nm to 1.5 μm, more preferably 100 nm to 1 μm.

  Moreover, when mix | blending the optical base material of this invention with coating materials, such as a paint, the film thickness of a film piece is 50 nm-2 micrometers, Preferably it is 50 nm-1 micrometer, More preferably, it is 100 nm-500 nm.

  In the present invention, the length of the film piece can be appropriately set according to the pulverization method and use of the available film, and is not particularly limited. For example, it is in the range of 1 μm to 2 mm, preferably 1 μm to 800 μm. More preferably, it is in the range of 1 μm to 500 μm, and more preferably in the range of 1 μm to 300 μm. Although the width of the film piece is not particularly limited, for example, it is in the range of 1 μm to 800 μm, preferably in the range of 1 μm to 500 μm, more preferably in the range of 1 μm to 300 μm (however, the same film piece) The width is less than or equal to the length). However, the length and width of the film piece may be appropriately set according to the use of the glitter material of the present invention. In the present specification, the “length of the film piece” refers to the size in the longitudinal direction of the flat portion (film surface) of the film piece (corresponding to the diameter when the longitudinal direction cannot be defined as in a disk shape). ). The “width of the film piece” refers to the size in the direction perpendicular to the longitudinal direction in the plane portion of the film piece. Even when the film piece is rounded, for example, in a cylindrical shape, the length and width of the film piece are defined in the plane portion of the film piece before rounding.

  When blending the glitter material of the present invention in a cosmetic, the length of the film piece is 1 μm to 800 μm, preferably 1 μm to 300 μm, more preferably 1 μm to 200 μm.

  Moreover, when mix | blending the glittering material of this invention with a coating material, the length of a film piece is 1 micrometer-2 mm, Preferably it is 1 micrometer-200 micrometers, More preferably, it is 1 micrometer-100 micrometers.

The coloration of the g-C ₃ N ₄ film is low angle dependent. Therefore, the glitter material of the present invention has an advantage that uniform gloss can be easily obtained even when applied to a target surface having irregularities on the surface.

  In the present invention, the film piece may be attached to a substrate. In the present invention, the substrate is preferably a substrate having a negatively charged surface or having π electrons on the surface.

  The negative charge carried by the base material may be one that the base material originally has, or may be artificially applied. Examples of the substrate having a negatively charged surface include metal materials and mineral materials (for example, mica).

  Examples of the substrate having π electrons on the surface include graphite, fullerene, and carbon nanotube.

Further, when the g-C ₃ N ₄ film is a polymer of a compound represented by X ⁺ _m Y ^m- as described above, heating is required in the polymerization reaction of g-C ₃ N _4. The substrate is preferably heat resistant. The degree of heat resistance may be determined according to the heating temperature and time. For example, the substrate is preferably one that can withstand 700 ° C. heat, and more preferably one that can withstand 1000 ° C. heat. In addition, the base material which has desired heat resistance is easily selected by those skilled in the art.

  The size and shape of the substrate are not particularly limited. Moreover, the film piece of this invention may adhere to the whole surface of a base material, and may adhere to a part of base material.

  For example, when the glitter material of the present invention is blended in cosmetics, the base material is preferably made of mica or fullerene from the viewpoint of little influence on living bodies.

The glitter material of the present invention has an extremely high refractive index as an organic substance. Therefore, the reflectance can be effectively increased without requiring a large number of layers as in the case of a bright material using an interference color caused by an organic material. Therefore, according to the glittering material of the present invention, it is possible to reduce the manufacturing cost. In addition, for example, it is known in the literature that the valence band of titanium oxide is very noble and has high oxidizing power (literature Landong Liet al. Nat. Commun. 6: 5881 doi: 10.1038 / ncomms6881 (2015) ). On the other hand, the valence band of g-C ₃ N ₄ is lower than that of titanium oxide, and its oxidizing power is lower than that of titanium oxide (documents Yanjuan Cui et al. Phys. Chem. Chem. Phys, 2012, 14, 1455). -1462.) Therefore, it is considered that the glittering material of the present invention has much less adverse effects on the skin and decomposition of other components than titanium oxide.

  Next, a method for preparing the glitter material of the present invention will be described.

(Preparation of glitter material)
The method of preparing the glitter material of the present invention is not particularly limited as long as it is a film piece of a g-C ₃ N ₄ film. For example, the glitter material of the present invention is a g-C ₃ N ₄ film. For example, it can be easily obtained by pulverizing by a method such as pulverization while maintaining a single-layer or multilayer sheet structure of the g-C ₃ N ₄ film.

As production method of _g-C 3 _{N 4} film, for example, a method developed by the inventors (the method is described in WO WO2014 / 098251.) Can be used. Hereinafter, specific description will be given of a manufacturing method of _g-C 3 _{N 4} film.

[Production Method of g-C ₃ N ₄ Film]
The g-C ₃ N ₄ film is, for example, a compound represented by X ⁺ _m Y ^m- (X ⁺ is represented by the following formula (I): guanidinium ion, melaminium ion, melaminium ion, melemium ion, A guanidine derivative ion or a guanidine derivative ion represented by the following formula (II), wherein Y ^m− is an anion and m is a valence of Y), and the compound or a reaction product thereof is heated. It is obtained by vaporizing and adhering to the surface of a heated substrate, and polymerizing the compound or its reaction product on the substrate to produce graphite-like carbon nitride. Note that the substrate is preferably a substrate having a negatively charged surface or having π electrons on the surface.

(material)
The compound used as a raw material is a compound represented by X ⁺ _m Y ^m- (referred to as “compound X ⁺ _m Y ^m− ”). ^{X +} _m Y X ⁺ in ^m- is guanidinium ion, melamine ions, main Ramiumu ions, Meremiumuion above formula guanidine derivative ions represented by the general formula (I) or a guanidine derivative ion represented by above-mentioned formula (II), It is.

R ¹ in the above formula (I) is an amino group, a nitro group, an alkyl group having 1 to 10, preferably 1 to 5, more preferably 1 to 3 carbon atoms, — (C ₂ H ₄ O) _n —R ^4. , Halogen, or a primary amide group. _{- (C 2 H 4 O)} n is 1 to 10 in the n -R ^4, preferably 1 to 5, more preferably from 1 to 3, ^{R 4} is an alkyl group having 1 to 4 carbon atoms. _{Also, - (C 2 H 4 O} ) n moiety of are ethylene oxide groups, which C atoms are bonded to the N atom of the guanidine are contemplated. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Halogen includes fluorine, chlorine, bromine, and iodine. R ¹ is preferably an amino group or a nitro group.

R ² and R ³ in the formula (II) are independently of each other an amino group, a nitro group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, — (C ₂ H _{⁴ O)} n -R _4, halogen or a primary amide group. The description of — (C ₂ H ₄ O) _n —R ⁴ and halogen is the same as that in the above formula (I). R ² and R ³ are preferably independently of each other an amino group and a nitro group.

  The structures of the above-described guanidinium ion, melaminium ion, melaminium ion and melemium ion are as shown below.

X ⁺ _m is preferably a guanidinium ion, a melaminium ion, a melaminium ion or a melemium ion, and more preferably a guanidinium ion.

^{Y m-is} the X ^{+ _m} Y ^m- is an anion, m is the valence of Y. Examples of the anion include CO ₃ ²⁻ , SO ₄ ²⁻ , Cl ⁻ , HPO ₄ ²⁻ , NO ₃ ⁻ , SCN ⁻ , SO ₃ NH ₃ ⁻ , CrO ₄ ²⁻ , p-toluenesulfonate, and ReO _4. ^- and the like. Y ^m− is preferably CO ₃ ²⁻ , SO ₄ ²⁻ or Cl ⁻ , and particularly preferably CO ₃ ²⁻ . If Y ^m-is _CO ³ is ^2, since the compound ^X ₊ ^{m Y m-} in the absence of the melting point, the _CO ^{3 2-} is a system before the compound ^X ₊ ^{m Y m-,} or the reaction product thereof is vaporized It is thought that it is hard to escape. ^Therefore, when ^{Y m-is} _CO ³ is ^2, as compared with the case ^{Y m-is} another, the number amount of compound ^X ₊ ^{m Y m-,} or reaction product thereof to vaporize, more efficient film It is thought that can be manufactured.

As the compound represented by X ⁺ _m Y ^m- , an acid salt of guanidine may be preferable from the viewpoint of availability, and from the viewpoint of production efficiency of the g-C ₃ N ₄ film, guanidine carbonate, Guanidine sulfate and guanidine hydrochloride are more preferable, and guanidine carbonate is more preferable.

The compound represented by X ⁺ _m Y ^m- may be commercially available or may be synthesized by a known method. It is also possible to mixing a plurality of kinds of compounds may be mixed with other compounds capable of forming a g-C ₃ N _4.

(Base material)
The substrate used in the above-described method for producing a g-C ₃ N ₄ film is preferably a substrate having a negatively charged surface or having π electrons on the surface, and as these substrates, Specifically, the base material illustrated in description of the luster material of this invention is mentioned.

(Details of g-C ₃ N ₄ film production method)
The g-C ₃ N ₄ film manufacturing method, by heating the compound comprising the above-described raw material, to vaporize the compound or the reaction. The “reactant” refers to a raw material compound that has been reacted with each other by heating and changed to a compound having another structure. For example, when guanidine carbonate is used as a raw material, it is expected to change according to the following scheme by heating.

Further, in the above scheme, vaporization (sublimation) is expected when it is changed to melemium ions. Therefore, when X ⁺ is a guanidinium ion, a melaminium ion, a melaminium ion, a guanidine derivative ion represented by the above formula (I), or a guanidine derivative ion represented by the above formula (II), it is vaporized to form a group. It is thought that it is the melium ion (salt form) produced by heating that adheres to the material.

  “Vaporization” includes both the change of a liquid into a gas and the change of a solid directly into a gas (sublimation).

The amount of the raw materials used in the manufacturing method of the g-C ₃ N ₄ film is desired thickness of the film strip, it may be suitably determined according to the length and width. The heating temperature may be appropriately determined according to the type of raw material to be used, and is, for example, 300 to 700 ° C, preferably 380 to 550 ° C. Heating time is be appropriately set depending on the thickness of the g-C ₃ N ₄ film to be produced, for example, it is a 1 minute to 4 hours.

  The above-mentioned vaporized raw material or a reaction product thereof (referred to as “vaporized material”) is attached to the surface of the substrate having a negatively charged surface or having π electrons on the surface. Since the vaporized substance has a positive charge as described above, the vaporized substance interacts with the substrate having a negative charge on the surface. Therefore, the surface adheres to the surface of the base material having a negative charge. Further, since the vaporized raw material or the reaction product thereof has π electrons, it interacts with the base material having π electrons on the surface. Therefore, it adheres to the surface of the substrate having π electrons on the surface.

At this time, the substrate is heated. Thus, when the vaporization material adhering to the surface of the substrate to polymerization one after another vapors on the substrate, g-C ₃ N ₄ is produced. to construct a _g-C 3 _{N 4} ^is a moiety derived from _X + ^{m Y m-} for ^{X +.} The anion (Y ^m− ) is considered to be eliminated by reacting with the proton (H ⁺ ) of the vaporized substance simultaneously with the polymerization reaction to g-C ₃ N ₄ on the substrate. For example, when Y ^m− is CO ₃ ²⁻ , protons and CO ₃ ²⁻ react to desorb as CO ₂ and H ₂ O. Furthermore, when a layer of g-C ₃ N ₄ is formed on the base material, the vaporized material that has been vaporized thereafter is interacted with the π electrons of g-C ₃ N ₄ that has already been formed. It adheres (adsorbs) to the surface of C ₃ N ₄ . Then, the polymerization reaction for further _g-C 3 _{N 4} on _g-C 3 _{N 4} proceeds. In this way, a g-C ₃ N ₄ film can be produced on the substrate.

Although the temperature which heats a base material should just be determined suitably according to the kind of raw material to be used, it is 300-700 degreeC, for example, and it is preferable that it is 380-550 degreeC. Heating time is be appropriately set depending on the thickness of the g-C ₃ N ₄ film to be produced, for example, it is a 1 minute to 4 hours.

The raw material and the substrate may be heated separately or may be heated together. From the viewpoint of simplicity, it is preferable to heat the raw material and the substrate together in one heating means (for example, a heating furnace). In addition, by integrally heating the raw material and the base material and the space between the raw material and the base material, a polymerization reaction from the raw material to g-C ₃ N ₄ (reaction from raw material to vaporized substance, vaporization, and vaporization) Since the polymerization from the substance to g-C ₃ N ₄ occurs sequentially, a better quality g-C ₃ N ₄ film can be produced.

For example, a large-area g-C ₃ N ₄ film can be produced by diverting an existing organic EL vapor deposition apparatus.

The film thickness of the g-C ₃ N ₄ film affects the properties as the luminous material, the thickness, g-C ₃ N ₄ change in the manufacturing conditions of the films, for example, changing the type of the above-mentioned substrate Can be easily adjusted.

[Grushing of g-C ₃ N ₄ film]
The film piece according to the glittering material of the present invention can be obtained, for example, by pulverizing the g-C ₃ N ₄ film obtained as described above. The crushing of the g-C ₃ N ₄ film is performed, for example, by a method of applying ultrasonic vibration to a medium containing the g-C ₃ N ₄ film (hereinafter, this method may be referred to as “ultrasonic crushing method”). be able to. Hereinafter, the ultrasonic grinding method will be specifically described.

(Ultrasonic grinding method)
In the ultrasonic pulverization method, the film piece of the present invention is obtained by applying ultrasonic vibration to a medium containing a g-C ₃ N ₄ film.

  In the ultrasonic grinding method, examples of the medium include one or more media selected from the group consisting of polar organic solvents such as water and alcohol, nonpolar solvents such as hexane, and the like.

  The temperature of the medium in the ultrasonic pulverization method is not particularly limited, but is 5 ° C to 80 ° C, preferably 15 ° C to 50 ° C, more preferably 20 ° C to 35 ° C.

The amount of the g-C ₃ N ₄ film used in the ultrasonic pulverization method is not particularly limited. For example, the amount of the g-C ₃ N ₄ film used for 100 g of the medium described above is 70 g to 0 g. 0.1 g, preferably 60 g to 0.1 g, more preferably 50 g to 0.1 g.

Further, the frequency of ultrasonic vibration applied to the g-C ₃ N ₄ film in the ultrasonic pulverization method may be appropriately set depending on the size of the desired film piece, but is usually 20 kHz to 1 MHz, preferably 28 kHz to 400 kHz. More preferably, it is 38 kHz to 42 kHz.

In the ultrasonic pulverization method, the g-C ₃ N ₄ film adhered to the base material in the production of the g-C ₃ N ₄ film is once peeled off from the base material, and then the g-C ₃ N ₄ film is pulverized. Alternatively, the g-C ₃ N ₄ film attached to the base material may be pulverized while the g-C ₃ N ₄ film remains attached to the base material.

As a method for peeling the g-C ₃ N ₄ film from the substrate in the ultrasonic pulverization method, for example, the g-C ₃ N ₄ film attached to the substrate is 40 ° C. to 80 ° C., preferably 50 ° C. to 80 ° C. More preferably, by immersing in hot water of 70 ° C. to 80 ° C. for half a day to 3 days, preferably half a day to 2 days, more preferably 1 day to 2 days without damaging the g-C ₃ N ₄ film. It can be efficiently peeled from the material.

  The method of pulverizing the film pieces is not limited to the ultrasonic pulverization method described above, but if the ultrasonic pulverization method is used, it is effective while suppressing aggregation of the film pieces constituting the glittering material of the present invention. Can be prepared.

[Use of bright materials]
The glittering material of the present invention can be used as it is or after being subjected to treatments such as filtration, washing and drying by a conventional method. Further, if necessary, it can be used after being surface-treated by polymer coating, adhesion of inorganic fine particles or the like.

  The glittering material of the present invention can be used as a novel pearl pigment that gives glossiness to the skin, for example, by blending it in cosmetics such as a foundation. The glitter material can also be used by blending with paint such as paint. Hereinafter, cosmetics and paints will be specifically described as an example of a composition containing the glittering material of the present invention. In addition, it cannot be overemphasized that the brilliant material of this invention can be mix | blended other than the cosmetics and coating material which are demonstrated below.

(Cosmetics)
The cosmetics containing the glitter material of the present invention can be prepared by combining conventional cosmetic ingredients with the glitter material of the present invention according to a conventional method.

  Therefore, for example, the bright material of the present invention and components usually used in cosmetics include, for example, oily components, surfactants, lower alcohols, preservatives, bactericides, colorants, powders, perfumes, water-soluble polymers, buffering agents. Etc. can be appropriately mixed to prepare a cosmetic containing the glitter material of the present invention.

  The amount of the glittering material in the cosmetic is arbitrarily selected as long as the effect of the present invention is not impaired, but is usually 30% by weight to 0.1% by weight, preferably 20% by weight to 0.00%. 5% by weight, more preferably 15% by weight to 1% by weight.

  The cosmetic dosage form in which the glittering material of the present invention is blended may be any of powder, solid, cream, emulsion, gel, spray, etc., in particular, foundation, eye shadow, lipstick, Makeup cosmetics such as blusher, skin care cosmetics such as sunscreen emulsions, and hair care cosmetics.

The glitter material of the present invention is made from a g-C ₃ N ₄ film, which has little influence on the human body, particularly the skin. Therefore, the bright material of the present invention can be used as a novel pearl pigment with reduced influence on the human body, particularly the skin, instead of the conventional pearl pigment using titanium oxide, for example. Further, according to the light absorption / reflection characteristics of the g-C ₃ N ₄ film, it is assumed that the effects of UV cut and blue light cut can also be obtained (see also FIG. 3 in the Examples).

(paint)
The paint containing the glitter material of the present invention can be prepared by combining conventional paint components with the glitter material of the present invention according to a conventional method.

  Therefore, for example, the glittering material of the present invention is blended by appropriately mixing, for example, a binder, a pigment, a preservative, a stabilizer, a desiccant, a solvent, and the like as the components used in the coating material with the glittering material of the present invention. Paints can be prepared.

  The blending amount of the glittering material in the coating is arbitrarily selected as long as the effect of the present invention is not impaired, but is usually 60% by weight to 1% by weight, preferably 50% by weight to 1% by weight, Preferably, it may be blended in the range of 50 wt% to 10 wt%.

  The dosage form of the paint blended with the glitter material of the present invention may be any of liquid, gel, spray and the like.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

[Example 1]
<Preparation of _g-C 3 _{N 4} film in a nitrogen atmosphere>
A g-C ₃ N ₄ film was produced by the following method. Guanidine carbonate (3.0 g, 16.7 mmol) was spread on the bottom of a glass test tube (18 mm diameter), a substrate was placed in the middle of the test tube, and sealed with aluminum foil with holes. An Eagle XG (registered trademark) glass substrate was used as the substrate. Place the test tube in a quartz tube, raise the temperature to 430 ° C. at 10 ° C./min using a tube furnace while flowing nitrogen gas, and increase the temperature to 2 ° C./max until the maximum temperature becomes 530 ° C. to 560 ° C. The temperature rose in minutes. Note that the maximum temperature differs because the optimum temperature differs depending on the furnace. After heating at the maximum temperature for 30 minutes and then naturally cooling to room temperature, a g-C ₃ N ₄ film adhered on the glass substrate was obtained.

<Peeling and crushing of g-C ₃ N ₄ film>
The g-C ₃ N ₄ film adhering to the glass substrate is immersed in hot water maintained at about 70 ° C. to 80 ° C. for several days, and the g-C ₃ N ₄ film is shaken by hand shaking or ultrasonic vibration (ultrasonic wave) The g-C ₃ N ₄ film was peeled from the glass substrate while applying a vibration frequency of 42 kHz or 38 kHz. Against exfoliated _g-C 3 _{N 4} film, by further applying ultrasonic vibration (frequency 42kHz or 38kHz ultrasonic vibration), grinding the _g-C 3 _{N 4} film in water, _{g-C 3} It was obtained N ₄ film piece. The resulting average size of _g-C 3 _{N 4} film pieces has a thickness of 100 nm to 300 nm, a length of 10 m to 500 m, a width of 10 m to 500 m, the shape is a substantially polygonal plate shape. The state of the obtained g-C ₃ N ₄ film piece is shown in FIG. FIG. 1 is a view based on a photograph showing the appearance of a dispersion of g-C ₃ N ₄ film pieces after application of ultrasonic vibration. As shown in FIG. 1, the obtained g-C ₃ N ₄ film piece has an interference color, and reflected light of various colors can be observed from the dispersion liquid of the g-C ₃ N ₄ film piece. It was.

Further, the g-C ₃ N ₄ film piece obtained by the above-described method was filtered and dried, and then the g-C ₃ N ₄ film piece was further crushed by a bead crusher (TAITEC μT-12). However, in order to obtain g-C ₃ N ₄ film pieces as possible large size, sonication during peeling in this experiment it was minimized. Filtered what was then dispersed in water to obtain a powdery g-C ₃ N _4. The result is shown in FIG. FIG. 2 is a view based on optical micrographs of g-C ₃ N ₄ film pieces before and after grinding, the left figure corresponds to before grinding, and the right figure corresponds to after grinding. As shown in FIG. 2, the g-C ₃ N ₄ film piece before pulverization shows gloss due to reflection, whereas after pulverization, the gloss decreases with scattering. Looking at the enlarged image with an optical microscope, it can be seen that the pulverized location has a very small size of the film and shows a mud texture compared to a large piece of film.

[Example 2]
<Preparation of _g-C 3 _{N 4} film on mica substrate>
A g-C ₃ N ₄ film was produced by the following method. Guanidine carbonate (6.0 g, 33.4 mmol) was spread on the bottom of a glass test tube (30 mm diameter), sealed with absorbent cotton, and a substrate was placed in the middle of the test tube. A mica substrate was used as the substrate. Using a tube furnace (KOYO KTF035N1), the temperature was raised at 10 ° C./min and heated in air at 550 ° C. for 30 minutes. After the heating, the mixture was naturally cooled to room temperature, and a g-C ₃ N ₄ film adhered on the mica substrate was obtained.

<Diffuse reflectance spectra of the _g-C 3 _{N 4} film deposited on mica substrate>
In order to examine the photochemical properties of the g-C ₃ N ₄ film deposited on the mica substrate obtained as described above, a diffuse reflection spectrum (JASCO V-670, JASCO ISN-723) was measured. The result is shown in FIG. In Figure 3, a is a diagram based on a photograph showing the respective appearance of g-C ₃ N ₄ film deposited on mica substrate (left) and mica board (right), b is a graph corresponding to a there are shows g-C ₃ N ₄ film and mica substrate, respectively diffuse reflectance spectra were deposited on mica substrate.

The reflection intensity of light depends on the refractive index of the substance. Since the g-C ₃ N ₄ film has a high refractive index as shown in FIG. 3, it can be used as a bright material with high luminance.

  The glitter material of the present invention can be suitably used, for example, as a material excellent in coloration imparting glossiness, for example, in a cosmetic or paint.

Claims (9)

  A bright material comprising a film piece of graphite-like carbon nitride film. The graphite-like carbon nitride film is a compound represented by X ⁺ _m Y ^m- (X ⁺ is a guanidinium ion, a melaminium ion, a melmium ion, a melium ion, or a guanidine derivative ion represented by the following formula (I). Or a guanidine derivative ion represented by the following formula (II), Y ^m− is an anion, and m is a valence of Y).
(In the formula (I) and ^{(II), R 1, R} 2 and ^{R 3} independently of one another, an amino group, a nitro group, an alkyl group having 1 to 10 carbon _{atoms, - (C 2 H 4 O} ) n —R ⁴ (n = 1 to 10, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms), a halogen, or a primary amide group.   The glitter material according to claim 1 or 2, wherein the film piece has a thickness of 50 nm to 2 µm.   The luster material of any one of Claims 1-3 whose length of the said film piece is 1 micrometer-2 mm.   The glitter material according to any one of claims 1 to 4, wherein the film piece is attached to a substrate.   The bright material according to claim 5, wherein the substrate has a negative charge on the surface or has π electrons on the surface.   The bright material according to claim 6, wherein the base material is mica.   A cosmetic comprising the glitter material according to any one of claims 1 to 7. A paint in which the bright material according to any one of claims 1 to 7 is blended.