JP2005060653A - New fluid colloidal crystalline material consisting of solid-liquid colloidal dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluid colloidal crystalline material which is a non-dried material-based fluid colloidal particle-conformed material formed by the spherical fine particles of colloidal particle-sized organic or inorganic polymer in a solid-liquid colloidal dispersion system, having characteristic of exhibiting an excellent reflection characteristic spectrum to irradiated visible light, ultraviolet light and infrared light. <P>SOLUTION: This fluid colloidal crystalline material is the solid-liquid dispersion under an electric charge of ≤2,000 μS/cm electric conductivity, of a dispersion medium solution of an aqueous or dissolvable water-containing non-aqueous system having <70 % dispersion concentration of dispersoid of the electric charging spherical colloidal particles of organic or inorganic polymer having less than several μm mean particle diameter (d). Around the dispersoid, an electric double layer having a thickness (Δe) is present. The distance between particles (L) expressed by a distance between the centers of particles opposing in central line direction each other satisfies a relationship: (d)<(L)≤(d)+2(Δe). The solid-liquid dispersion forms a 3-dimensional colloidal particle-conformed material exhibiting fluidity as a particle-arranged structural material conforming as a lattice state in vertical and horizontal directions. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fluid colloidal crystal comprising a solid-liquid colloidal dispersion, and more specifically, fluidity in which spherical fine particles having a colloidal particle size of an organic polymer or an inorganic polymer are formed in a solid-liquid colloidal dispersion system. In particular, the present invention relates to a novel colloidal crystal body having fluidity that exhibits excellent characteristic reflection spectra with respect to visible light, ultraviolet rays, and infrared rays to be irradiated.

  Conventionally, when we perceive color (or color), three kinds of fluorescent materials of R, G and B generated by irradiation of an electron beam emit light of the three primary colors of light, as in color television. In addition to the light source color for visualizing the chromatic light color, dyes or pigments as dyes or pigments as aggregates of fine particles or film-like aggregates thereof are irradiated with sunlight or white light to give a specific visible color. Absorbs the wavelength of light and makes the object color chromatic. The light source color or object color for visualizing such a color also absorbs, transmits, or reflects visible light in a specific wavelength region as the structural characteristics and surface characteristics of the material system irradiated with light, Either the transmitted color, the absorbed color or the reflected color is given priority, and we perceive it as a specific chromatic color. In addition, sunlight or white light is irradiated on the material system, and all of rainbow light refraction, liquid crystal light diffraction, blue sky, sunset light scattering, water surface oil film, soap bubble, opal interference color, etc. It can be said that this is a material property related to the aggregate system or dispersion system.

  Therefore, as the structural characteristics and surface characteristics of such a substance system, for example, relating to the visual color, [Patent Document 1] describes a coloring material such as a pigment which is not an object color or a light source color as a dye pigment substance. The monodispersed titanium oxide particles in which the monodispersed titanium oxide particles without using the base material are deposited on the base material have an appearance color tone that changes from red to blue interference color depending on the particle size of the particles. Single layer and multilayer thin films are described. Further, in [Patent Document 2], since colored light due to interference can be clearly seen, light-transmitting monodispersed light is formed on the surface of a liquid-repellent underlayer such as a synthetic resin having a black or dark color by a drying process. It is described that an adherent, which is a regular periodic structure in which solid fine particles having a number average particle diameter in the range of 100 to 1000 nm are aggregated and arranged, exhibits clear monochromatic light with light interference coloring. The non-colored monodispersed light-transmitting solid fine particles include inorganic oxide fine particles such as silica, alumina, titania, silica / alumina, titania / selenium, (meth) acrylic resin, styrene resin, olefin type. Organic polymer fine particles such as resins are mentioned.

  Therefore, in both [Patent Document 1] and [Patent Document 2], the colloidal particle-sized fine particles are visually perceived as the structural characteristics and surface characteristics of the material system in which the particles are regularly dispersed, assembled, and laminated. It has a color.

JP 2001-206719 A Japanese Patent Laid-Open No. 2001-239661

  Under the circumstances as described above, the present inventors have already made a black pigment such as gray to black with a dye / pigment in advance in connection with the structural characteristics of such a material system and the color developability as the surface characteristics. An aqueous dispersion is prepared by suspending organic or inorganic monodispersed spherical particles of a colloidal particle size of several hundreds of nanometers in achromatic color, and this aqueous dispersion (or suspension) is used to obtain a predetermined After a thick green sheet (or suspension layer) is formed, it is dried thoroughly and black-colored achromatic organic or inorganic monodisperse spherical particles are closely aligned in the vertical and horizontal directions to form a dry particulate laminate Formed. For example, the surface of the dry layered particulate laminate has a vertical reflected light color that is perceived by eyes under the irradiation of natural light (or white light) in the visible light wavelength region of 380 to 780 nm. It is proposed as a light-coloring member that exhibits a clear chromatic light color with a deep feeling such as red, green, and blue.

Therefore, the light-coloring member that emits a chromatic light color of this dried product is clearly distinguished from the conventional object color such as colored dyes and pigments or the light-emitting light source color such as color television, and the following (1) to (3 ), And a clear chromatic light color is visible under irradiation with visible light, and the present inventors refer to such a light-coloring member as a structural color-coloring member.
(1) As described above, the surface of the dried product-type laminate that the chromatic light color is observable is composed of at least organic or inorganic black-colored monodispersed spherical particles such as gray, black-brown, black, etc. It is a three-dimensional particulate laminate that matches the direction.
(2) The black achromatic organic or inorganic monodispersed spherical particles are spherical fine particles having a specific particle size of a colloidal particle size in which the average particle size (d) expressed on a volume basis is in the range of 130 to 350 nm. is there.
(3) In relation to monodispersed spherical particles having a specific particle size forming a dry matter-based particulate laminate, the surface of the particulate laminate has a specific particle size as a structural characteristic under irradiation with visible light. In connection with this, it exhibits spectral chromatic light colors such as purple, blue, green, yellow and red based on the spectral reflection spectrum.

  Therefore, conventionally, a drying method has been studied in which fine particles are formed into a dried product aggregate or laminate through a solid-liquid suspension in which fine particles of colloidal particle size are dispersed. However, when a solid-liquid dispersion (or suspension layer) having such a considerable thickness is dried, the dispersoid colloidal particles are usually aggregated and matched (arranged) as the drying progresses. Tends to cause cracks due to drying shrinkage. Moreover, the tendency to generate such dry cracks generally tends to generate cracks if the surface of the suspension layer, which is a dry occupying surface, is large and if the thickness of the suspension layer is large. .

  That is, under the drying of such a solid-liquid suspension, the cracks with a width of about 1 mm, which are usually difficult to see with the naked eye, and cracks with a width of about mm, which are easily visible, are innumerable with the progress of drying. Occur. On the surface of an aqueous or oil dispersion where such fine particles are suspended, as the water or organic solvent evaporates, the suspended fine particles are aggregated and arranged by capillary force, and the dispersion medium (or binder resin component previously interposed between the fine particles is previously removed). The contained dispersion medium may be dried and shrunk to maintain a uniform surface, and a portion corresponding to the shrinkage remains as a crack.

  Accordingly, the inventors of the present application, in Japanese Patent Application No. 2003-59210, applied non-drying when making spherical fine particles of colloidal particle size in such a solid-liquid suspension into a three-dimensional particle matching body. A method of coagulating and aligning in physical systems is proposed. A pair of opposing electrode plates are immersed in a suspension in which such colloidal particles are dispersed, and a particulate laminate is electrophoretically deposited (or electrodeposited) on the electrode plate under electrophoresis, and shrinkage cracks due to drying are observed. This is a method that enables particle matching without fear. The electrophoretic deposit is a three-dimensional particle alignment body that is aligned under the electrophoresis, and the electrophoretic deposit is a light-coloring member that produces a clear chromatic light color, and is formed in a non-drying system to the last. 3D particle matching body.

  Moreover, in the conventional structural color light-coloring member, even if no cracking is observed on the color-developing surface, it is sufficiently aligned within the particle alignment body, particularly along the vertical and horizontal directions of the particle arrangement. Due to the presence of unmatched layers and the presence of particle alignment bodies that are aligned in different directions, the particle alignment bodies are mixed with different particle structures, and the purity of the particle alignment bodies is still sufficient. The reality is that they have not been satisfied.

  Therefore, the object of the present invention is that when aligning colloidal particle-sized spherical fine particles dispersed in such a suspension in the three-dimensional direction, the system of the alignment body is remarkably limited as in the electrophoresis method. In addition, the formed photochromic particulate laminate does not have the possibility of drying / shrinking cracks as in the conventional drying method. Different particle arrangements do not coexist on the surface of the object and / or the particulate laminate, and the structure is highly pure as a particle matching body, and various properties including optical properties are clearly exhibited in relation to the purity. To provide a three-dimensional particle matching body of a new matching system composed of spherical fine particles of colloidal particle size.

  In the situation as described above, the present inventors diligently studied the above problems, and as a result, the average particle diameter is 200 nm, black achromatic monodispersed spherical particles, and the particles contain a high concentration of carboxyl groups. An aqueous suspension was prepared using acrylic polymer colloidal particles. The electrical conductivity of this suspension was 4000 μS / cm, but when the electrical conductivity was reduced to 400 μS / cm by dialysis treatment, the volume concentration as colloidal particles was concentrated to about 42%. The present inventors have found that the solid-liquid colloidal dispersion in which the suspending colloidal particles are dispersed has a vivid red chromatic light color, and completed the present invention.

  According to the present invention, a particle arrangement structure comprising a solid-liquid colloidal dispersion in which monodispersed spherical colloidal particles are dispersed as a dispersoid, and the three-dimensional particle matching has clearly fluidity as a solid-liquid colloidal dispersion. Provided is a fluid colloidal crystal composed of monodispersed spherical colloidal particles.

That is, the dispersoid spherical colloidal particles are monodisperse spherical colloidal particles of an organic polymer or an inorganic polymer whose average particle diameter (d) expressed on a volume basis does not exceed several μm.
In this solid-liquid colloidal dispersion, the dispersoid spherical colloidal particles contain a water-based or dissolved water-free dispersion medium solution at a concentration not less than 20% and not exceeding 70% as a dispersion concentration expressed by volume. Are distributed.
In addition, the electric double layer thickness (Δe) formed above the freezing point of the dispersion medium solution around the dispersoid spherical colloidal particles in the solid-liquid colloidal dispersion having a charge of 2000 μS / cm or less in terms of electrical conductivity. Is formed.
The dispersoid spherical colloidal particles in the solid-liquid colloidal dispersion as the non-dried material system have an interparticle distance (L) expressed between the centers of the particles facing each other in the direction of the centerline, and (d) <(L) ≦ (d) +2 (Δe) satisfying the relationship, a flowable colloidal crystal that forms a three-dimensional colloidal particle matching body that exhibits fluidity as a particle arrangement structure that matches in a lattice shape in the vertical and horizontal directions Is the body.

  From the above, the solid-liquid colloidal dispersion composed of monodisperse dispersoid spherical colloidal particles according to the present invention can be obtained by observing the SEM photographic image of the dried particle-based particle matched body as a solid-form precursor before drying. The liquid colloidal dispersion clearly forms a new three-dimensional particle matching body in which dispersoid spherical colloidal particles are regularly arranged in a lattice pattern. In addition, this dispersion easily flows in the vertical and horizontal directions due to external stress as a solid-liquid dispersion, and again forms a uniform lattice-like three-dimensional particle alignment body as a particle array structure under placement. A solid-liquid colloidal dispersion. In addition, while the dispersoid colloidal particles are stably formed as a solid-liquid matching body in a lattice shape, the spherical colloidal particles as the dispersoids face each other in the center line direction in the solid-liquid colloid dispersion system. The inter-particle distance (L) expressed between the centers of the particles to be satisfied is regularly aligned in the vertical and horizontal directions satisfying the relationship of (d) <(L) ≦ (d) +2 (Δe).

  In the present invention, in order to constitute such an interparticle distance (L), the floating ion species and electrolyte diffusing in the dispersion medium solution of the solid-liquid colloidal dispersion system are reduced by dialysis or the like. The counter ion species of the chargeable colloidal particles dispersed in the solid-liquid colloidal dispersion system are fixed to form an electric double layer (Δe) with a predetermined layer thickness (Δe) on the surface of the chargeable colloidal particles. Therefore, in the present invention, for example, the remaining colloid ions and counterelectrolytes that tend to diffuse and float in addition to the fixed counterions on the particle surface are reduced and removed by dialysis or the like. The particles maintain the above-described interparticle distance (L) and effectively prevent randomization of the particle arrangement in the vertical and horizontal directions.

  In the present invention, by desalting by dialysis or the like, the thickness of the electric double layer that tends to diffuse in the vicinity of the electric double layer (Δe) including the floating electrolyte is reduced / removed. The surface charge strength of colloidal particles and spherical fine particles of a dispersed system is relatively increased. Due to this increase in surface charge intensity, the electric double layer thickness (Δe) formed on the particle surface as a counter ion is attracted by the colloidal particles and the charge density is further increased, and the interparticle distance between the dispersoid colloidal particles is increased. (L) is made more stable. That is, it is balanced as a repulsive force that cancels the direction of particle aggregation caused by vanden-Walls attraction acting between particles, and a constant distance between particles is formed in the vertical and horizontal directions to stabilize the particle.

  Further, in the present invention, the distance (L) between the particles facing each other in the center line direction in the vertical and horizontal directions on the particle matching surface is (d) <(L). Although it is difficult to actually measure the electric double layer thickness (Δe) when the relationship of ≦ (d) +2 (Δe) is satisfied and stabilized, it is shown after dialysis treatment as shown in the examples described later. As a fact seen when the electric conductivity of the solid-liquid colloidal dispersion system is made constant, the higher the surface chargeability of the dispersoid colloidal particles, the more (d) <(L) ≦ (d) +2 The particle arrangement structure in which the relationship (Δe) is more smoothly satisfied, regularly aligned in the vertical and horizontal directions, and aligned in a lattice shape in the three-dimensional direction is formed as a solid-liquid dispersion. It can be said that it is a crystal of colloidal particles.

  Further, as described above, the solid-liquid dispersion of colloidal particles regularly aligned in the three-dimensional direction as the crystal body can be easily maintained while maintaining the lattice-like particle shape in the three-dimensional direction by a slight external stress. It flows and forms a recrystallized body easily as a lattice-like particle form of colloidal particles under placement.

  Hereinafter, the best mode for carrying out the flowable colloidal crystal as the solid-liquid colloidal dispersion according to the present invention will be further described.

  According to the present invention, as already described above, the flowable colloidal crystal according to the present invention has a chargeable colloidal spherical particle exhibiting a degree of charge of 2000 μS / cm or less in terms of electrical conductivity, and 20 in terms of volume. It is a solid-liquid colloidal dispersion at a dispersion concentration of not less than 70% and not exceeding 70%. This dispersoid-charged colloidal particle is a solid material formed in a non-dry matter system using a water-based solution containing a counter-ion species and counter-electrolyte corresponding to the surface charge or a non-aqueous solution containing soluble water as a dispersion medium. -A liquid colloidal dispersion, which is a novel colloidal crystal characterized by exhibiting fluidity as a lattice-like particle structure aligned in the three-dimensional direction.

  That is, the colloidal crystal as a solid-liquid dispersion comprising the chargeable colloidal particles according to the present invention has an average particle diameter (d) as a dispersoid in the range of at least several 1000 nm or less as an organic polymer or inorganic. Solid-liquid colloidal dispersion having a charged spherical colloidal particle of polymer and a nonaqueous dispersion medium solution containing an aqueous system or soluble water containing a counterion species and a counterelectrolyte of charged ion of colloidal spherical particle as a dispersoid It is formed as a body.

  In addition, around the dispersoid spherical colloidal particles arranged in the solid-liquid colloid dispersion, there is an electric double layer thickness (Δe) formed above the freezing point of the dispersion medium solution. The spherical spherical colloidal particles satisfy the relationship (d) <(L) ≦ (d) +2 (Δe) in which the interparticle distance (L) expressed between the centers of the particles facing each other in the center line direction satisfies the relationship of (d) <(L) ≦ (d) +2 (Δe). Regularly aligned with the direction.

  In addition, the charged colloidal particles observed from the scanning electron micrograph image have a completely different arrangement in both the vertical and horizontal directions, and the charged colloidal particles are homogeneous in the vertical and horizontal directions. It is characterized by being aligned in a grid pattern.

  In the present invention, the colloidal particles for forming the fluid colloidal crystal body, which is a homogeneous lattice-like three-dimensional particle matching body, are specific spherical colloidal particles having an average particle diameter (d) expressed on a volume basis of 130 to 350 nm, Moreover, in the case of any one kind of black achromatic organic polymer or inorganic polymer selected from grayish white, gray, grayish black and black, preferably monodisperse specific spherical colloidal particles, natural light or white light As a structural characteristic of a flowable colloidal crystal under irradiation of visible light, a chromatic light coloring property characterized by exhibiting a clear light spectral coloration in relation to the inter-particle distance (L) of the lattice-like three-dimensional particle matched body It is a colloidal crystal. Also, based on such a spectral reflection spectrum, the remarkably clear optical properties are exhibited. This is because the arrangement of the charged colloidal particles in the solid-liquid colloidal dispersion is correctly arranged in a homogeneous lattice as a crystal. It is consistent. In addition, it is a three-dimensional matching body of black achromatic colloidal particles in which particle groups randomly arranged in the vertical and horizontal directions are not mixed.

  For example, a colloidal crystal that exhibits chromatic color development as a light characteristic according to the present invention has light characteristics similar to those of a conventional structural color light coloring member in terms of its light colorability. However, the particle matching body is a material that is significantly different as a particle structure in that it is a colloidal particle matching body formed as a solid-liquid colloidal dispersion. Moreover, as already mentioned above, the particles in which the colloidal particles are arranged in a homogeneous lattice so that it can be called a colloidal single crystal in relation to the distance (L) between the particles arranged in the solid-liquid colloidal dispersion system. The matching body is characterized by being a colloidal particle matching body with high purity as a particle structure, which makes it difficult to mix different matching body surfaces.

  In addition, since the fluid colloidal crystal according to the present invention is formed as a solid-liquid colloidal dispersion as described above, it is significantly different from the conventional concept of crystal growth, and as a solid-liquid colloidal dispersion, The degree of crystal packaging is also dealt with extensively as appropriate, not to mention the thickness of the crystal layer in the vertical direction, but the remarkable feature is that crystals can be easily formed (or grown) in the horizontal direction. .

  In this way, the colloidal particles of dispersoids that form a colloidal single crystal by dispersion-matching as a dispersoid in a solid-liquid colloidal dispersion system, as in the conventional structural color light-coloring member, have the optical properties of the crystals. In view of the photochromic property, it is preferably any one kind of black achromatic colloidal particles selected from grayish white, gray, grayish black and black. That is, as already mentioned above, the colloidal single crystal as the solid-liquid colloidal dispersion of the present invention does not have a different lattice plane as a so-called colloidal crystal, so A part of the surface of the particulate matching body effectively absorbs stray light due to scattering, transmission, etc. generated in addition to the reflected light generated around the particle, and exhibits an effect of reducing it appropriately. In the present invention, since the color of the reflected light color as the light characteristic is made clearer, the color saturation of the colloidal particles is preferably 5 or less, more preferably 3 or less, achromatic color having no color. Is good. Accordingly, in the present invention, as such achromatic particles, gray particles of organic polymer or inorganic polymer that are gray-white, gray, gray-black, and black-colored achromatic that has a saturation of substantially zero. Is more preferred.

  In the present invention, the dispersoid organic polymer or inorganic polymer particles that form the solid-liquid colloidal dispersion are present as colloidal particles in the solid-liquid colloidal dispersion system, and the particle diameter is usually at least several thousand nm. In general, a fine particle size of a micron size or less is a suitable particle size as a colloidal particle. In the present invention, for example, from the viewpoint of clearly exhibiting optical characteristics such as reflection, absorption, and transmission of light in relation to visible light wavelength region light (380 to 780 nm), the particle diameter is an average particle diameter expressed on a volume basis ( It is suitably suitable that d) is an organic polymer or an inorganic polymer in the range of 350 nm or less, preferably 330 nm or less, particularly preferably 300 nm or less. Further, from the viewpoint of dispersibility in a solid-liquid colloidal dispersion system, chargeability on the surface of spherical colloidal particles, consistency, etc., the lower limit is 120 nm or more, the upper limit is 380 nm or less, and the average particle diameter (d) is preferably 130. It is suitable to be in the range of ˜350 nm, more preferably in the range of 150 to 300 nm. In addition, for example, in the ultraviolet wavelength region (380 nm or less), for example, reflection, the average particle diameter (d) expressed on a volume basis is 130 nm or less, preferably 10 to 120 nm. . In addition, for example, in the infrared wavelength region (800 to 1500 nm), the particle diameter is 340 nm or more, preferably 350 nm or more, and more preferably 380 to 800 nm. Preferably it is.

  For the reasons already described above, the solid-liquid colloid dispersion according to the present invention has a volume-based concentration of at least 70% in relation to the interparticle distance (L) of the dispersoid spherical colloid particles in this dispersion. It is formed with a dispersion concentration not exceeding. That is, when the dispersion concentration of the dispersoid in the dispersion system is low, for example, less than 10%, it becomes extremely difficult to align the particles in a fixed arrangement and stabilize the arrangement. On the other hand, a concentration exceeding the upper limit is not preferable because a group of particles that aggregate randomly is likely to occur, and the regular arrangement of particles tends to be significantly inhibited. Further, from the viewpoint of the degree of package, stability, or purity of the solid-liquid colloidal dispersion according to the present invention, it is preferably 20% or more, not exceeding 60%, and more preferably 25% or more. The solidity according to the present invention is excellent in fluidity from the viewpoint of purity, stability, clarity of various characteristics to be exhibited, handling properties, etc. at a concentration not exceeding 55%, particularly preferably 35% or more and not exceeding 50%. -A colloidal crystal as a liquid colloidal dispersion can be provided.

  In order to form a homogeneous lattice-like three-dimensional particle matching body in such a solid-liquid colloid dispersion system, in the present invention, the solid-liquid of the dispersoid spherical colloid particles in the solid-liquid colloid dispersion system is used. It is preferable that the existence environment as a system is appropriately present in the pH dispersion region of the non-isoelectric point. The details are not clear, but in the case of [isoelectric point−pH], the electric colloidal particles at the isoelectric point, that is, the neutralization point of pH, have a predetermined electric double layer thickness with a counter ion. It seems that it tends to be difficult to maintain (Δe) and form the interparticle distance (L) specified in the present invention.

In the present invention, as already described above, the surface charge amount of the dispersoid colloid particles in the solid-liquid colloidal dispersion system, that is, the chargeability in the solid-liquid colloidal dispersion system is important. As the surface chargeability of the particles, in the organic polymer or inorganic polymer particles, a carboxyl group (—COOH), a sulfone group (—SO ₃ H), a hydroxyl group (—OH), an amino group (—NH ₂ ), Acid / base functional groups such as amide group (—CONH ₂ ), and alkenes (—CH═CH—), alkynes (—C≡C—), vinyl ethers (—CH═CH—O) -), a nitrile group (-C≡N), isocyanate group (-N = C = O), nitro group, a thiol group (-SH), - adsorbing ions the functional sites of the CF ₃ group such as an adsorption active sites It is preferable that the absolute value of the (+) or (−) surface charge value charged by, for example, is 50 to 500 (μC / g) as measured by the blow-off method.

  Further, in the solid-liquid colloidal dispersion system in the present invention, in order to form a highly pure particle matched body, the particle shape of the colloidal particles is preferably spherical, and the organic polymer or inorganic polymer is spherical. The average particle size of the colloidal particles is preferably 5% or less, more preferably 3% monodisperse particles, expressed as a Cv value indicating the degree of uniformity. Also, from the viewpoint of optical characteristics, the visible light irradiated on the surface of the colloidal single crystal surface is reflected and reflected by diffraction interference. Preferably, the organic or inorganic monodisperse spherical particles are suitably monodisperse particles. The Cv value, which is the degree of uniformity of the particle diameter representing the monodispersity, is 5% or less, and the monodisperse particles are more preferably 3% or less from the darkness and vividness of the reflected light color. More preferred.

In addition, as a solid-liquid colloidal dispersion having such characteristics, the Koroit crystal is a blackish achromatic monodisperse spherical particle which is a dispersoid particle dispersed as a matching body in this colloidal dispersion. In a solid-liquid colloidal dispersion system arranged in a single lattice, the inter-particle distance (L) expressed between the centers of particles opposed to each other in the center line direction is clear under natural light or white light. It is a colloidal crystal body having a light characteristic exhibiting a chromatic light coloring of a simple monochromatic system. That is, as shown in the following (A) to (E), for example, light spectral colors such as purple, blue, green, yellow and red are developed. The perceived chromatic light color is the vertical light color of the colloidal crystal surface.
(A) (L) = 160-170 nm-The chromatic light color is purple (P),
(B) In the range of (L) = 180-195 nm-the chromatic light color is blue (B),
(C) In the range of (L) = 200-230 nm-the chromatic light color is green (G),
(D) In the range of (L) = 240-260 nm-the chromatic light color is yellow (Y),
(E) In the range of (L) = 270-290 nm-the chromatic light color is red (R),
It is a flowable colloidal crystal that can exhibit light spectral color development related to a certain inter-particle distance (L), that is, spectral light color development.

  In the present invention, the characteristics of the solid-liquid colloidal dispersion already described above are utilized, and the crystal layer thickness of the fluid colloidal crystal is 200 nm or more, preferably 400 nm or more. It can be formed appropriately.

  Therefore, in the present invention, such monodispersed spherical colloidal particles of an organic polymer are not necessarily limited, but are preferably (meth) acrylic, (meth) acrylic-styrene, fluorine-substituted ( Suitable examples include at least one organic polymer spherical particle selected from (meth) acrylic and fluorine-substituted (meth) acryl-styrene. Similarly, although not necessarily limited, at least one inorganic polymer spherical particle selected from silica, alumina, silica-alumina, titania and titania-silica is suitably used as the monodisperse spherical colloidal particle of inorganic polymer. Can be mentioned. Further, in the present invention, it is important and characteristic that all of these are black achromatic colloidal particles which are gray to black depending on a dye and a pigment, and monodispersed spherical particles. That is, it is important that colloidal particles having such characteristics can be appropriately prepared as chargeable colloidal particles in a solid-liquid colloidal dispersion system.

  In connection with the crystal as a solid-liquid colloidal dispersion having the above characteristics, the monodispersed spherical particles of the organic polymer are not necessarily specified by the polymer species described below. For example, poly (meth) acrylic acid Methyl, tetrafluoroethylene, poly-4-methylpentene-1, polybenzyl (meth) acrylate, polyphenylene methacrylate, polycyclohexyl (meth) acrylate, polyethylene terephthalate, polystyrene, styrene / acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride , Polyvinyl acetate, polyvinyl alcohol, polyurethane and the like. In the present invention, as already described above, the reflected light color as the light-coloring member can be visually perceived in relation to the light in the visible wavelength region under the irradiation of natural light such as sunlight or white light as the light characteristics. The polymer resin is preferably a (meth) acrylic, (meth) acrylic-styrene-based, fluorine-substituted (meth) acrylic and fluorine-substituted (meth) excellent in weather resistance from the viewpoint of excellent light resistance. Any acrylic organic polymer fine particles selected from acrylic-styrene are suitably used as appropriate.

  Therefore, specific examples of the chargeable acrylic resin represented by the monomer species include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Butyl acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, (Meth) acrylic acid alkyl ester such as (meth) acrylic acid butoxysilane Ter; dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate, (meth) acrylamides, (meth) acrylamides such as N-methylol (meth) acrylamide and diacetone acrylamide, and glycidyl (meth) acrylates; ethylene glycol Of dimethacrylic acid ester, diethylene glycol dimethacrylic acid ester, triethylene glycol dimethacrylic acid ester, polyethylene glycol diacrylic acid ester, propylene glycol dimethacrylic acid ester, dipropylene glycol dimethacrylic acid ester, tripropylene glycol A dimethacrylic acid ester etc. can be mentioned. Examples of other monomers other than the (meth) acrylic monomer described above include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptyl. Alkyl styrenes such as styrene and octyl styrene; Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, chloromethylstyrene; Styrenes such as nitrostyrene, acetylstyrene, methoxystyrene, α-methylstyrene, vinyltoluene Mention may be made of monomers. Further, as monomers other than styrene monomers, for example, silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, pivalic acid Vinyl esters such as vinyl, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl salicylate; vinylidene chloride, vinyl chlorohexanecarboxylate, etc. Can be mentioned. Furthermore, if necessary, as other monomers having a functional group, for example, acrylic acid, methacrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo Examples include unsaturated carboxylic acids such as [2,2,1] hept-2-ene-5,6-dicarboxylic acid, and derivatives thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydroanhydride Examples of the polymerization reactive monomer having a phthalic acid and a hydroxyl group (OH; hydroxyl group) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1,1,1- Trihydroxymethylethane triacrylate, 1,1,1-trishydroxymethyl Tyrethane triacrylate, 1,1,1-trishydroxymethylpropane triacrylate; hydroxyalkyl vinyl ethers such as hydroxy vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, diethylene glycol Examples thereof include hydroxyalkyl (meth) acrylates such as mono (meth) acrylate, and these single or two or more complex monomers can be suitably used. Furthermore, as a (meth) acrylic acid moiety or a completely fluorine-substituted monomer, for example, (meth) acrylic acid trifluoromethylmethyl, (meth) acrylic acid-2-trifluoromethylethyl, (meth) acrylic acid- 2-perfluoromethylethyl, (meth) acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid-2-perfluoroethyl, (meth) acrylic acid perfluoro Fluorine-substituted (meth) acrylic acid monomer (or fluoro (meth) alkyl acrylate) such as methyl, (meth) acrylic acid diperfluoromethylmethyl, etc., and fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoro Ethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3- Fluoroolefins such as dioxoles are listed. In the present invention, these homopolymers or copolymers with other polymerizable monomers may be used.

  Further, the monodispersed spherical particles used in the present invention, as described above, in addition to being colored in a black achromatic color, other additives as necessary in advance, for example, an ultraviolet absorber, an antioxidant, A charge imparting agent, a dispersion stabilizer, an antifoaming agent, a stabilizer and the like can be appropriately added.

  Therefore, black achromatic monodispersed spherical fine particles, which are organic polymers for preparing the fluid colloidal crystal according to the present invention as a solid-liquid colloidal dispersion having the above-described characteristics, are generally used generally. Can be appropriately prepared in the soap-free emulsion polymerization, suspension polymerization, emulsion polymerization system.

  For example, in soap-free emulsion polymerization, a persulfate such as potassium persulfate or ammonium persulfate is usually soluble in an aqueous medium during polymerization as a polymerization initiator to be used. Usually, the polymerization initiator may be added in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight, per 100 parts by weight of the polymerization monomer. In the case of the emulsion polymerization method, an emulsifier such as an alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate or a polyethylene glycol alkyl ether such as polyethylene glycol nonylphenyl ether is usually added to 100 parts by weight of the polymerization monomer. 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, mixed with an aqueous medium to make an emulsified state, and a polymerization initiator of a persulfate such as potassium persulfate or ammonium persulfate is added to 100 parts by weight of a polymerization monomer. 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight, based on parts. In addition, it is not necessary to particularly specify the above-mentioned emulsifiers including suspension polymerization, and it is selected from commonly used anionic surfactants, cationic surfactants or nonionic surfactants as necessary. These can be used alone or in combination. Examples of anionic surfactants include dodecyl benzene sulfonate, dodecyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, nonyl benzene sulfonate, sodium and potassium salts thereof, and cationic surfactants. Cetyltrimethylammonium promide, hexadecylpyridinium chloride, hexadecyltrimethylammonium chloride and the like, and nonionic surfactants include lipidinium and the like. Examples of reactive emulsifiers (for example, emulsifiers having a polymerizable group such as acryloyl group, methacryloyl group) include anionic, cationic or nonionic reactive emulsifiers, and are used without particular limitation. The In order to obtain black resin particles for use in the present invention, for example, a black pigment containing a black oil-soluble dye or carbon black as a colorant in a mixed system of a polymerization monomer, an emulsifier and water is used. Appropriately dispersed or suspended and mixed.

  Therefore, a system containing water in the range of 200 to 350 parts by weight of water per 100 parts by weight of the monomer appropriately selected from the above-described polymerizable monomers is exemplified by C.I. 5-10 parts by weight of a black dye such as I Solvent Black 27 is heated with stirring, then 0.05 to 0.7 of an emulsifier is added, and after thoroughly stirring and mixing, a nitrogen purge is performed. The temperature is raised to 60-80 ° C. with stirring underneath. Next, a polymerization initiator such as potassium persulfate is added in the range of 0.3 to 0.6 parts by weight, and a polymerization reaction is performed at 70 to 90 ° C. for 4 to 8 hours. In the reaction dispersion obtained by such soap-free emulsion polymerization, monodisperse black spherical polymer particles having an average particle diameter (d) in the range of 50 to 900 nm on a volume basis are 10 as solid content concentration. Prepared at ~ 35 wt%.

  Further, in the present invention, monodisperse spherical particles made of a black-colored achromatic inorganic polymer for forming a particle matching body as a solid-liquid colloidal dispersion are appropriately used instead of the above-described organic polymer colloidal particles. Can do. The inorganic polymer is not necessarily limited to the following inorganic polymers. In the present invention, examples include inorganic polymers such as silica, alumina, silica-alumina, zirconia, titania and titania-silica, silicon carbide, and silicon nitride. it can. In particular, inorganic polymer particles prepared by a sol-gel method of metal alkoxides such as silica, aluminum, and titanium are suitably used because they are relatively easy to be colored in a black achromatic color using a dye / pigment. Examples of the metal alkoxide include methyltrimethoxysilane, vinyltrimethoxysilane, tetraethylsilicate, tetraisopropylsilicate, tetrabutylsilicate; aluminum ethoxide, aluminum triethoxide, isobutylaluminum methoxide, isobutylaluminum ethoxide, aluminum iso Propoxide, isobutylaluminum isopropoxide, aluminum butoxide, aluminum t-butoxide, tin t-butoxide; aluminum tri-n-propoxide, aluminum tri-n-butoxide; tetraethoxytitanium, tetra-n-propoxytitanium, tetra- n-butoxy titanium, tetra-i-propoxy titanium, titanium methoxide, titanium ethoxide, titanium-n- Roxoxide, titanium isopropoxide, titanium-n-butoxide, titanium isobutoxide; zirconium ethoxide, zirconium-n-propoxide, zirconium isopropoxide, zirconium-n-butoxide, ethoxide tetra-n-propoxyzirconium, etc. Can be mentioned.

  In the present invention, the suspension in which the black achromatic colloidal particles of the organic polymer or inorganic polymer prepared as described above are dispersed is filtered as necessary, and then subjected to dialysis treatment with a usual known formulation. Then, the electrolyte concentration in the suspension is expressed by electric conductivity (μS / cm) and is adjusted to 600 (μS / cm) or less, preferably 50 to 500 (μS / cm). The slurry can then be concentrated to a concentration not exceeding 70%, preferably not exceeding 60%, expressed as a volume concentration of dispersoid colloidal particles, as already described above.

  From the above, the colloidal crystal according to the present invention thus provided as a solid-liquid colloidal dispersion of colloidal particles is, for example, opposed so that the facing gap is 400 nm or more and the gap, that is, the crystal layer thickness is constant. If sandwiched, the occupied surface in the planar direction is not particularly limited and can be formed by being enclosed between the opposing transparent members. As the opposing transparent encapsulant, a colloidal crystal is formed by encapsulating between members such as a soft (flexible) plastic film, a hard plastic sheet, a glass plate, or a combination thereof. In addition, the characteristics of such a solid-liquid colloid dispersion are utilized, and between the same transparent members, the shape of the members is not limited to the planar shape as described above, but is also a double cylinder, double polygon. A colloidal crystal is similarly formed by enclosing it in a shape, a double spherical body, a flexible fine cylinder, an optical fiber cylinder, or the like.

  Moreover, in this invention, if it has water resistance or solvent resistance in connection with the said suspension, the organic polymer sheet which has normal flexibility will be used without limitation. If a transparent sheet is particularly suitable if necessary, examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate, acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate, polycarbonate, polystyrene, and polystyrene. It is done. In addition, if flexibility is not particularly required, a plastic plate, a glass plate, etc. can be mentioned, and if necessary, one side can be combined with an opaque member such as a plastic film sheet, an aluminum plate, a ceramic plate, a stainless steel plate, etc. Can do.

  Such a fluid colloidal crystal encapsulating member according to the present invention exhibits vivid chromatic color development ranging from red to blue under the irradiation of natural light, white light or fluorescence, so that various interiors, decorations, designs It is possible to provide a novel color material that can be used in the field of display materials and the like. In addition, since the light characteristics of the fluid colloidal crystal encapsulating member are related to the inter-particle distance (L), it exhibits visible light spectral coloration, that is, spectral light coloration. An adjustment filter, a color filter, an indoor fluoroscopic prevention film (sheet), and the like can be provided. Furthermore, the fluid colloidal crystal encapsulating member according to the present invention is made into a matrix system by turning on-off of natural light or white light irradiation into an electric field type such as LCD, PDA, PLD, LED, PDP, etc. A novel non-electric field type color display device that replaces the display device can be provided.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Reference Example 1)
Black achromatic monodispersed spherical particles used in the present invention are prepared. In a 1-liter four-necked flask, 100 parts by weight of monomeric methyl methacrylate (MMA) and black dye C.I. 7.5 parts by weight of I solvent black 27, 0.6 parts by weight of sodium dodecylbenzenesulfonate, and 290 parts by weight of water were stirred and mixed, and then heated to 80 ° C. while stirring under a nitrogen purge. Next, 0.5 part by weight of potassium persulfate was added, and a polymerization reaction was performed at 80 ° C. for about 7 hours. In the suspension (S-1) obtained by this soap-free emulsion polymerization, black monocopolymer particles having almost monodispersed spherical particles having an average particle diameter of 180 nm expressed on a volume basis measured by an electron microscope were prepared. The volume concentration of the dispersoid particles in the suspension (S-1) was 29%.

(Example 1)
Impurities such as unreacted monomers and emulsifier in the suspension (S-1) were removed and dialysis was performed to reduce the initial electrical conductivity from 4000 μS / cm to 400 μS / cm. When the dialyzed suspension was gradually concentrated to a volume concentration of 36%, the visual color in the vertical direction of the solid-liquid colloidal dispersion, which was the suspension, was green light spectral color development.

(Example 2)
Next, after 80 parts by weight of MMA and 1.0 part by weight of benzoyl peroxide were dissolved in a four-liter flask having a capacity of 1 liter, 200 parts by weight of water and polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier were added. 3.3 parts by weight of an ester salt, C.I. 6.5 parts by weight of I Solvent Black 27 was added and mixed under strong stirring. Next, 28.6 parts by weight of the suspension (S-1) obtained in Reference Example 1 was added, stirred gently at 50 ° C. for 0.5 hour, and then reacted at 75 ° C. for 1.5 hour to obtain polymer particles. Suspension (S-2) was obtained. In the obtained suspension (S-2), black polymer particles of monodispersed spherical particles having an average particle diameter of 200 nm expressed on a volume basis measured by electron microscopy were prepared. The solid content was 21% in terms of volume concentration. Impurities such as unreacted monomer and emulsifier in the resulting suspension were removed and dialyzed, and the suspension whose initial electrical conductivity was reduced from 4000 μS / cm to 400 μS / cm was gradually concentrated to a volume concentration of 42%. The visual color in the vertical direction of the solid-liquid colloidal dispersion, which was a suspension at that time, was red light spectral color development.

(Example 3)
The suspension obtained by performing the same operation as in Example 2 except that the electric conductivity after the dialysis treatment was set to 100 μS / cm was gradually concentrated to the suspension when the volume concentration reached 38%. The visual color in the vertical direction of the solid-liquid colloidal dispersion was red light spectral color development.

Example 4
In Example 2, except for using MMA and MAA (90:10 monomer weight ratio), the suspension obtained in the same manner as in Example 2 was similarly dialyzed to remove impurities, and the electrical conductivity was 3900 μS / When the suspension from cm to 400 μS / cm was gradually concentrated to a volume concentration of 37%, the vertical visual color of the solid-liquid colloidal dispersion, which was the suspension, was red light spectral color development. It was.

(Example 5)
In Example 3, the suspension obtained in the same manner as in Example 3 except that the electric conductivity after dialysis was set to 100 μS / cm was gradually concentrated to a volume concentration of 31%. The visual color in the vertical direction of the solid-liquid colloidal dispersion was red light spectral color development. Further, although this suspension was further concentrated to a volume concentration of 54%, the red light spectral color development was stably exhibited.

(Example 6)
To a 1 liter four-necked flask was added 78 parts by weight of MMA, 2 parts by weight of ethylene glycol dimethacrylate, and 15 parts by weight of 2-hydroxyethyl methacrylate, followed by 0.5 parts by weight of benzoyl peroxide. 1.0 part by weight of dimethyl-2,2′-azobis-2-methylpropionate; I. After 8 parts by weight of Solvent Black 27 was added and dissolved, 250 parts by weight of water, 10 parts by weight of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier and 0.1 parts by weight of UNA-Na were added to increase the strength. Mix under agitation. Next, 40 parts by weight of the suspension (S-1) obtained in Reference Example 1 was added, gently stirred at 50 ° C. for 0.5 hour, reacted at 78 ° C. for 1.5 hours, and then 90 ° C. × In the suspension obtained by aging for 1.5 hours, black polymer particles of monodisperse spherical particles having an average particle diameter of 270 nm expressed on a volume basis measured by an electron microscope are dispersed, and the dispersoid in the suspension is dispersed. The volume concentration of the particles was 31%. Similarly, when the suspension in which the electrical conductivity after dialysis treatment is reduced from 3900 μS / cm to 400 μS / cm is gradually concentrated to a volume concentration of 37%, the suspension of the solid-liquid colloidal dispersion is vertically The visual color of the direction was blue light spectral color development.

(Comparative Example 1)
When the suspension was concentrated in the same manner as in Example 1 except that dialysis was not performed in Example 2, the suspension aggregated at 38%, and color development could not be confirmed.

(Comparative Example 2)
When the suspension colored in Example 2 was further concentrated, aggregation occurred at 50%, and almost no color development could be confirmed.

(Comparative Example 3)
When the suspension was concentrated in the same manner as in Example 4 except that dialysis was not performed, the color did not develop even after 37 vol%, and the suspension finally aggregated at 43%, and the coloration could not be confirmed.

(Comparative Example 4)
When the suspension colored in Example 4 was further concentrated, aggregation occurred at 54%, and color development could hardly be confirmed.

  From the above, the flowable colloidal crystal according to the present invention provided as a solid-liquid colloidal dispersion of colloidal particles is, for example, in the plane direction if the opposing gap is 400 nm or more and the gap, that is, the crystal layer thickness is constant. The occupied surface can be formed by being enclosed between opposed transparent members that are not particularly limited. As the opposing transparent encapsulant, it can be used as a crystal encapsulated between members such as a soft (flexible) plastic film, a hard plastic sheet, a glass plate, or a combination thereof.

  Further, according to the present invention, between the same transparent members, the shape of the members is not limited to the planar shape as described above, but is also a double cylindrical body, a double polygonal body, a double spherical body, a flexible fine space. It can be used as a crystal body sealed in a cylindrical body and an optical fiber hollow cylinder material.

  Such a fluid colloidal crystal encapsulating member according to the present invention exhibits vivid chromatic color development ranging from red to blue under the irradiation of natural light, white light or fluorescence, so that various interiors, decorations, designs It is possible to provide a novel color material that can be used in the field of display materials and the like.

  Further, by effectively utilizing such optical characteristics, the above-described colorant which is a fluid colloidal crystal that can exhibit optical spectral color development related to the inter-particle distance (L), that is, spectral optical color development. In addition to practical use, for example, various shapes of light modulation members, light amount adjustment filters, color filters, and indoor see-through prevention films (sheets) can be provided.

Further, by forming the light irradiation on-0ff in a matrix, a novel non-electric field type color display device can be provided that replaces the electric field type display device such as LCD, PDA, PLD, LED, and PDP.

Claims (9)

In a colloidal particle matching body having fluidity composed of a solid-liquid colloidal dispersion having a monodispersed spherical colloidal particle as a dispersoid,
The spherical colloidal particles are monodisperse dispersoid spherical colloidal particles of an organic polymer or an inorganic polymer whose average particle diameter (d) expressed on a volume basis does not exceed several μm,
The solid-liquid colloidal dispersion includes a dispersoid having a dispersion concentration expressed on a volume basis of 20% or more and not exceeding 70%, and a non-aqueous solution containing an aqueous or dissolved water as a dispersion medium,
The electric double layer thickness formed above the freezing point of the dispersion medium solution around the dispersoid spherical colloidal particles in the solid-liquid colloidal dispersion having an electric conductivity of 2000 μS / cm or less in electrical conductivity. (Δe)
The dispersoid spherical colloidal particles satisfy the relationship (d) <(L) ≦ (d) +2 (Δe) in the interparticle distance (L) expressed between the centers of the particles opposed to each other in the center line direction. A flowable colloidal crystal, characterized in that a three-dimensional colloidal particle alignment body exhibiting fluidity is formed as a particle arrangement structure aligned in a lattice shape in the vertical and horizontal directions.   The dispersoid spherical colloidal particles are any one of black achromatic organic polymer or inorganic polymer selected from grayish white, gray, grayish black, and black whose average particle diameter (d) expressed on a volume basis is 130 to 350 nm. The three-dimensional colloidal particle matched body composed of specific monodispersed spherical colloidal particles exhibits a clear chromatic spectral coloration based on a characteristic reflection spectrum under irradiation of natural light or white light. Item 2. The fluid colloidal crystal according to Item 1. The chromatic light spectral color to be perceived is related to the inter-particle distance (L) as the vertical light color of the surface of the three-dimensional colloidal particle matching body, and any of the relationships described in (a) to (e) below: ,
(A) (L) = 160-170 nm-The chromatic color development is a vivid purple system (P),
(B) In the range of (L) = 180 to 195 nm-the chromatic light coloring is a clear blue system (B),
(C) In the range of (L) = 200 to 230 nm-the chromatic light coloring is a clear green system (G),
(D) In the range of (L) = 240-260 nm-the chromatic light coloration is a clear yellow system (Y),
(E) In the range of (L) = 270 to 290 nm-the chromatic light coloring is a clear red system (R),
The fluid colloidal crystal according to claim 2, wherein the fluidic colloidal crystal is present.   The three-dimensional colloidal particle matching body comprising monodisperse specific spherical colloidal particles of an organic polymer or inorganic polymer having an average particle diameter (d) expressed on a volume basis of 10 to 130 nm is a wavelength of 400 nm. The fluid colloidal crystal according to claim 1, which exhibits ultraviolet reflectivity based on a characteristic reflection spectrum under the following ultraviolet irradiation.   The three-dimensional colloidal particle matched body comprising the monodisperse specific spherical colloidal particles of an organic polymer or an inorganic polymer having an average particle diameter (d) expressed on a volume basis of 350 to 800 nm. The flowable colloidal crystal according to claim 1, which exhibits infrared reflectivity based on a characteristic reflection spectrum under irradiation of infrared rays of ˜1500 nm.   The flowable colloidal crystal according to any one of claims 1 to 5, wherein the dispersoid spherical colloidal particles in the solid-liquid colloidal dispersion are present in a pH dispersion region having a non-isoelectric point. .   The surface charge amount of the dispersoid spherical colloidal particles in the solid-liquid colloidal dispersion is characterized by exhibiting (+) or (−) surface charge in relation to functional groups and adsorbed ions that are modified on the particle surface in advance. The fluid colloidal crystal according to any one of claims 1 to 6.   The dispersoid spherical colloidal particles of the organic polymer are at least one organic polymer selected from (meth) acrylic, (meth) acrylic-styrene, fluorine-substituted (meth) acrylic and fluorine-substituted (meth) acrylic-styrene. The fluid colloidal crystal according to claim 1, which is a spherical particle. 7. The dispersoid spherical colloidal particle of an inorganic polymer is at least one inorganic polymer spherical particle selected from silica, alumina, silica-alumina, titania and titania-silica. The fluid colloidal crystal described.