CN1833184A

CN1833184A - Fluid colloid crystal and process for producing three-dimensional aligned particle mass thereof

Info

Publication number: CN1833184A
Application number: CN 200480022254
Authority: CN
Inventors: 吉田哲也; 奥田有香; 滝沢容一; 渡边顺次
Original assignee: Soken Chemical and Engineering Co Ltd
Current assignee: Soken Kagaku KK; Soken Chemical and Engineering Co Ltd
Priority date: 2003-07-31
Filing date: 2004-07-30
Publication date: 2006-09-13
Anticipated expiration: 2024-07-30
Also published as: CN100456056C

Abstract

A solid-liquid dispersion electrostatically charged at 2000 muS/cm or below in terms of electric conductivity, comprised of an aqueous or soluble-water-containing nonaqueous dispersion medium solution wherein dispersoid electrostatically-charged spherical colloid particles of organic or inorganic polymer having an average particle diameter (d) of not exceeding 30 mum are dispersed in a concentration of not exceeding 70 %. In particular, there is provided a fluid colloid crystal constituting a fluid three-dimensional aligned colloid particle mass, comprised of a particle array structure consisting of particles aligned in latticed form in the longitudinal and lateral directions wherein around the dispersoid, there is electric double layer thickness (Deltae) and wherein interparticulate distance (L) defined as the distance between particle core centers arranged opposite to each other along the center line satisfies the relationship: (d) < (L) <= (d) + 2(Deltae). Further, there is provided a process for producing a three-dimensional aligned particle mass consisting of a uniform particle array structure of dispersoid organic or inorganic monodisperse spherical microparticles, comprising drying the above fluid colloid crystal.

Description

Mobile colloidal crystal and the method for using this crystal manufacturing three-dimensional order lattice

Technical field

The present invention relates to comprise the mobile colloidal crystal (fluid colloidalcrystal) of liquid-solid aqueous colloidal dispersion.More particularly, the present invention relates to comprise the mobile colloidal crystal of the novelty of solid-liquid aqueous colloidal dispersion system ordered structure, described ordered structure has flowability, this ordered structure is formed by the organic or inorganic polymer spherical particulate of colloid granularity, described crystal has the intrinsic character of various ordered structures, for example has fabulous feature reflectance spectrum under the irradiation of visible light, ultraviolet light and infrared light.

The invention still further relates to a kind of method that is used for preparing three-dimensional order lattice (three-dimension ordered lattice), this method comprises to be done above-mentioned colloidal crystal, make wherein as the organic or inorganic spherical particle of dispersed substance (dispersoid) vertically, laterally alignment regularly.

In addition, the invention still further relates to a kind of method that is used for preparing the three-dimensional order lattice of spherical particle, the The Nomenclature Composition and Structure of Complexes of described lattice all is a homogeneous, has various character based on its structural homogeneity, the invention still further relates to the three-dimensional order lattice that this method of use obtains.

In addition, the invention still further relates to a kind of method of using specific spherical particle to prepare the three-dimensional order lattice as dispersed substance, described spherical particle shows clean colour (chromatic color), has fabulous ultraviolet light and infrared light reflection character, also relate to the method for coated film of using the three-dimensional order lattice that this method makes and being used for preparing the three-dimensional order lattice of described specific spherical particle, wherein said particulate shows clean colour, has fabulous ultraviolet light and infrared light reflection character.

Background technology

When the human visual perception color, in colour television set, three kinds of fluorescent material R, G and B launch primitive color light when being subjected to electron beam irradiation, and the color of luminophor (illuminant color) is visually perceived with the form of colour.In addition, when the dyestuff of particle aggregate or strata collective form or pigment were subjected to sunlight or white light irradiation, dyestuff or pigment can absorb the visible light of specific wavelength, thereby can be by the colour of visually-perceptible object.When these colors of visually-perceptible or object color, according to structural property that is subjected to the photoirradiation material and surface nature, the visible light of particular range of wavelengths is absorbed, transmission or reflection, any in the color of transmitted light, light absorbing color and the catoptrical color with the form of colour mainly by the eyes perception.In addition, when using sunlight or white light irradiation material, can produce various phenomenons or colour developing (colordevelopment), the for example anaclasis of rainbow, the optical diffraction in liquid crystal, blue sky, the light scattering of sunset clouds, and the interference color on the water-surface oil film, soap bubble, opaline, we can say all these character all be assemble or the dispersed microparticles Substance Properties.

These structural properties and surface nature to material in various documents are described.For example, in about the Japanese Patent Application of visually-perceptible color No. 206719/2001 (patent documentation 1), described in a kind of film (the single or multiple lift film of monodisperse titanium dioxide), do not use the color material of any pigment and so on, with the monodisperse titanium dioxide particle packing on base material, the outward appearance tone becomes red to blue interference tone, this tone neither the object color of dyestuff or pigment neither be luminous color, decide according to the diameter of particle.In Japanese Patent Application No. 239661/2001 (patent documentation 2), the sediment of the monochromatic regular periodicity structure that can launch clean interference color has been described, this sediment is to obtain by (so that being clear that interference color by drying means) on the liquid-repellency substrate surface of the materials such as synthetic resin that single dispersing solid particles agglomerate are arranged in black or dead color, the number average particle size of wherein said single dispersing solid particulate is the 100-1000 nanometer, and this particulate has light transmission.Described in the document following material has been disperseed the colorless solid particulate as the list with light transmission: inorganic oxide particle, for example silicon dioxide, aluminium oxide, titania, silica-alumina and titania-selenium; And organic polymer particulate, for example (methyl) acrylic resin, styrene resin and olefine kind resin.Therefore, film described in No. the 239661/2001st, No. the 206719/2001st, Japanese Patent Application and the Japanese Patent Application and in the sediment any can both show appreciable color, and this is the structural property and the surface nature of regular-scattered or gathering or stacked colloid granularity particulate.

In addition, the various methods that prepare the particle duplexer have been proposed up to now, comprise use that solid-liquid dispersion or suspended matter (comprising the monodisperse spherical particulate that disperses as dispersed substance) are poured into a mould, spray, are coated with, migration etc., thereby to particle arrange, align, dry and fixing, thereby make dispersed substance spherical particle vertical and horizontal all be arranged in (base member) on the smooth substrate regularly.Be expected in the said method by the regularly arranged particle duplexer that makes to spherical particle, the various intrinsic properties based on forming particulate matter can have various surface naturies.Specifically, become more small particle (for example being of a size of submicron order or nanoscale) owing to form particle, the shown surface nature of fine surface becomes more obvious, and expection can be formed these particle as the functional materials with novel function of surface.

Except because the object color that dyestuff or pigment produce or the glow color of color TV for example, also there are the interference color that to see, as described in No. the 206719/2001st, top Japanese Patent Application, a kind of single or multiple lift film of monodisperse titanium dioxide has been proposed, do not use the colorant of any pigment and so in this film, with the monodisperse titanium dioxide particle packing on base material, this appearance of films tone become red to blue according to particle diameter and fixed interference tone.Also described to form the monodisperse titanium dioxide film,, to blue scope, freely controlled appearance of films interference tone according to granularity in redness by changing the diameter of monodisperse titanium dioxide particle.In No. the 239661/2001st, Japanese Patent Application, the sediment of the monochromatic regular periodicity structure that can launch clean interference color has been described, this sediment is to be arranged in by single dispersing solid particles agglomerate that will have light transmission that (so that being clear that interference color) obtains on black or the dark-coloured liquid-repellency base layer of resin surface, wherein black or the brightness of dead color in the standard colour solid are not more than 6, and saturation degree is not more than 8.The sedimentary not coloring solid of described composition particulate is a monodisperse particles, has described in the document following material is used as this solia particle: inorganic oxide particle, for example silicon dioxide, aluminium oxide, titania, silica-alumina and titania-selenium; And organic polymer particulate, for example (methyl) acrylic resin, styrene resin and olefine kind resin.The number average particle size of also having described solia particle is 100 nanometers to 1 micron.In No. the 213334/2004th, Japanese Patent Application, a kind of method that is used for preparing the multilayer laminated body structure of orderly arrangement has been described, this method comprises: to containing spherical monodisperse polymer particles (200-700 nanometer, pass through emulsion polymerization prepared) the solid-liquid suspension body carry out dialysis, thereby from this suspended matter, remove electrolyte substantially, the suspended matter that comprises spherical monodisperse polymer particles (being formed with electrostatic double layer on this particle) is carried out drying (temperature: 60 ℃), make suspended matter keep static simultaneously, the particle that will contact with each other arrangement is then fixed with chemical method.

Under above-mentioned situation, structural property and the surface nature of colour developing being regarded as material, the inventor has proposed a kind of method that is used for forming dried particle duplexer, this method comprises: prepare a kind of water-borne dispersions, (granularity: the hundreds of nanometer), this dispersion is colour killing (achromaticcolor) with dyestuff or pigment coloring grey to the black of black to the organic or inorganic monodisperse spherical particle of dispersoid granularity in this dispersion in advance; Use water-borne dispersions (or suspended matter) to form base sheet (or suspended matter layer) with specific thicknesses; Then the base sheet is carried out abundant drying, making black is inorganic or organic monodisperse spherical particle vertical and horizontal close alignment all of colour killing.When the natural light (being white light) in the visible wavelength range that uses the 380-780 nanometer carries out irradiation to the surface of dried particles duplexer, according to the concrete granularity of spheric grain, the color of the vertical reflection light of seeing is clean redness, clean green or clean blue dark colour.That is to say that this particle duplexer of doing becomes the optics colour development material.

Therefore can show colored dry type optics colour development material and satisfy following requirement (1) to (3).Use the glow color of object color that the shown color of these materials obviously causes with conventional dyestuff or pigment or color TV etc. different, under the irradiation of visible light, can see clean colour.The inventor is called " structure coloring material " with these optics colour development materials.

(1) the dried duplexer that can show appreciable colour is the three dimensional particles duplexer with surface, and the black of grey, dark-brown or black and so on is that the organic or inorganic monodisperse spherical particle of colour killing is arranged on the surface of described duplexer at vertical and horizontal as mentioned above at least in this duplexer.

(2) black be the organic or inorganic monodisperse spherical particle of colour killing be the colloid granularity specified particle size, be that the equal diameter of body (mean volume diameter) (d) is the spherical particle of 130-350 nanometer.

(3) owing to form the monodisperse spherical particle of the specified particle size of dried particle duplexer, the surface of particle duplexer has a kind of structural property, promptly can show the spectrum diffraction colour according to its specified particle size under the irradiation of visible light, for example purple, blueness, green, yellow and red

In addition, up to now after deliberation a kind of drying means, in the method, the solid-liquid suspension body that comprises dispersed microparticles (this particulate has the colloid granularity) is carried out drying, form the aggregation or the duplexer of this particulate.When to this solid-liquid dispersion (suspended matter layer) with quite big thickness when carrying out drying, the dispersed substance colloidal solid takes place to assemble and arrange in dry run, and from the teeth outwards usually can since dry contraction crack.Usually along with wanting dry suspended matter surface layer or suspended matter layer thickness to become big more, owing to the dry tendency that produces this crackle of shrinking increases.

That is to say, when the solid-liquid suspension body is carried out drying, along with the carrying out of drying, can produce a large amount of crackles usually from the teeth outwards, about 1 micron of almost not observing from naked eyes of the width of these crackles is easy to observed several millimeters to naked eyes and does not wait.On the surface of water-based that comprises particulate or oil dispersion, evaporation along with water or organic solvent, the particulate that suspends takes place to assemble and arrange by capillary force, dispersion medium between the particulate (can be the dispersion medium that comprises binder resin component) shrinks owing to dry, the surface that can not keep homogeneous like this, this contraction remains, and becomes crackle.

Under the situation of the structure coloring material of routine, even do not observe crackle from the teeth outwards, ordered structure also tend to comprise particle fully longitudinally with the layer of lateral alignment, perhaps form the ordered structure that particle is arranged along different directions.Therefore, under existing conditions, the purity of ordered structure is not met yet.

When the solid-liquid suspension body was dried, dispersed particles can be assembled the formation aggregation, but as a rule, can crack because of the drying contraction on the surface of this solid-liquid suspension body (or dispersion) layer.Along with wanting dry suspended matter surface layer or suspended matter thickness to become big more, owing to the dry tendency that produces this crackle of shrinking increases.

That is to say, when the solid-liquid suspension body is carried out drying, along with the carrying out of drying, can produce a large amount of crackles usually from the teeth outwards, about 1 micron of almost not observing from naked eyes of the width of these crackles is easy to observed several millimeters to naked eyes and does not wait.On the surface of water-based that comprises suspended particulates or oil dispersion, evaporation along with water or organic solvent, the particulate that suspends takes place to assemble and arrange by capillary force, dispersion medium between the particulate (can be the dispersion medium that comprises binder resin component) shrinks owing to dry, the surface that can not keep homogeneous like this, this contraction remains, and becomes crackle.

In patented claim before this---in the Japanese Patent Application No. 59210/2003 (patent documentation 4), the inventor has proposed a kind ofly to be used for making the non-dried spherical particle of making in the system to assemble and arrange, form with the spherical particle of the colloid granularity in the solid-liquid suspension body method of three-dimensional order lattice.This method comprises: the immersion of pair of electrodes plate comprised in the suspended matter of colloidal solid, and carries out electrophoretic process, and deposition (electro-deposition) particle duplexer on battery lead plate, the method can be avoided making particle alignment because dry the contraction cracks.

Chen Ji particle duplexer is that this duplexer is a kind of optics colour development material that can show clean colour by the lattice of the three-dimensional order of electrophoresis formation like this, still the three-dimensional order lattice that forms with non-dry system.

In former patented claim---the Japanese Patent Application No. 73123/2003 (patent documentation 5), the inventor proposed a kind of can be as the particle duplexer of optics colour development material.This particle duplexer makes by the following method: (opening of this zanjon is the 50-170 micron having regularly arranged zanjon interval (division), depth-width ratio is 0.4-0.8), sheet (the smooth substrate of similar Web materials, be called " colour developing substrate ") go up and pour into a mould the solid-liquid suspension body that comprises colloidal solid, formation has the suspended matter layer of specific thicknesses, dry this suspended matter layer under 50-60 ℃ temperature, the stacked body of this particle can effectively prevent from can show clean colour owing to dry the contraction cracks.

That is to say that the optics colour development material (particle duplexer) that is proposed in the superincumbent description of the inventor is as follows.

(1) the described particle duplexer that can demonstrate the colour that can see, be a kind of in its surface black be that inorganic or organic monodisperse spherical particle of colour killing is at the regularly arranged particle duplexer of vertical and horizontal.

(2) the organic or inorganic spheric grain on described composition duplexer surface is that at least a black is the monodisperse spherical particle of colour killing (for example grey, dark-brown or black).

(3) described have black and be colour killing the single specified particle size (specific particle diameter) that disperses organic or inorganic spheric grain, be that the equal diameter of body (d) is the 130-350 nanometer.

(4) when the surface of the particle duplexer of the described optics colour development material that is made of for example organic polymer spherical is subjected to visible light irradiation, visual experience to the color of vertical reflection light be dark colour, for example purple, blueness, green, yellow or red.

(5) for (methyl) acrylic polymers monodisperse spherical particle, the color of the vertical reflection light that visual experience arrives and the equal diameter of particular volume (d) satisfy following relation:

(I) when d is the 160-170 nanometer, the colour that shows is purple (P),

(II) when d is the 180-195 nanometer, the colour that shows is blue (B),

(III) when d is the 200-230 nanometer, the colour that shows is green (G),

(IV) when d is the 240-260 nanometer, the colour that shows is yellow (Y),

(V) when d is the 270-290 nanometer, the colour that shows is red (R).

Yet, even passing through of proposing up to now the solid-liquid suspension body carried out thereby drying is arranged and the surface of the alignment formed particle duplexer of dispersed substance particle (or three-dimensional order lattice) on do not observe crackle, ordered structure also tend to comprise particle fully longitudinally with the layer of lateral alignment, perhaps form the ordered structure that particle is arranged along different directions, make this ordered structure lack structural homogeneity.Therefore, because the inhomogeneity and the defective structure of ordered structure, its character can't be satisfactory.

Under above-mentioned these situations, the inventor addresses the above problem to have carried out conscientious research, the result, they use the acrylic polymers colloidal solid to prepare aqueous suspension, described polymeric colloid particle is that black is the monodisperse spherical particle of colour killing, the equal diameter of its body is 200 nanometers, contains the carboxyl of high concentration.The inventor finds, the solid-liquid aqueous colloidal dispersion that makes by the following method can show appreciable clean redness: to the conductivity for preparing above is that the suspended matter of 4000 μ S/m carries out electrophoretic process, its conductivity is reduced to 400 μ S/m, and the volumetric concentration that the suspended matter of gained is concentrated into colloidal solid is about 42%.Finished the present invention based on this discovery.

Patent documentation 1: No. the 239661/2001st, Japanese Patent Application

Patent documentation 2: No. the 206719/2001st, Japanese Patent Application

Patent documentation 3: No. the 213334/1992nd, Japanese Patent Application

Patent documentation 1: No. the 59210/2003rd, Japanese Patent Application

Patent documentation 1: No. the 73123/2003rd, Japanese Patent Application Publication

Summary of the invention

The problem that invention will solve

The purpose of this invention is to provide a kind of novel mobile colloidal crystal that comprises the solid-liquid dispersion, this crystal is used to make the mobile ordered structure of the organic or inorganic polymer spherical particulate of colloid granularity, demonstrates fabulous feature reflectance spectrum under the irradiation of visible light, ultraviolet light and infrared light.

Another object of the present invention provides a kind of method that is used for preparing the mobile colloidal crystal of above-mentioned novelty.

Another purpose of the present invention is to use the very method of the three-dimensional order lattice coated film of the three-dimensional order lattice manufacturing spherical particle of homogeneous particle array structure (particle arraystructure).

The method of dealing with problems

Mobile colloidal crystal of the present invention is the mobile colloidal crystal that comprises the solid-liquid aqueous colloidal dispersion, and described aqueous colloidal dispersion comprises the monodisperse spherical colloidal solid as dispersed substance, wherein:

Described spherical colloidal particle is that the equal diameter of body (d) is not more than 30 microns organic or inorganic polymkeric substance list dispersion dispersed substance spherical colloidal particle,

Described solid-liquid aqueous colloidal dispersion comprises dispersed substance and as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving, the dispersion concentration of described dispersed substance is not less than 20 volume %, is not more than 70 volume %,

Under the temperature that is not less than the dispersion medium solution solidifying point, around being no more than dispersed substance spherical colloidal particle in the solid-liquid aqueous colloidal dispersion of 2000 little Siemens/cm (representing with conductivity), static electrification lotus degree (electrostaticcharging degree) forms electrostatic double layer with specific thicknesses (Δ e)

Described dispersed substance spherical colloidal particle has formed the lattice of three-dimensional order, this lattice has flowability, it is a kind of particle array structure, spherical colloidal particle aligns at vertical and horizontal with form crystal lattice in this structure, and the grain spacing (interparticledistance) that is defined as distance between the center of the particle of relatively arranging along center line (L) satisfies relational expression (d)＜(L)≤(d)+2 (Δ e).

Preferably described dispersed substance spherical colloidal particle is that to have a kind of black be colour killing (being selected from canescence, grey, grey black and black) and the equal diameter of body (d) for the organic or inorganic polymkeric substance list of 130-350 nanometer disperses specific (specific) spherical colloidal particle, and the three-dimensional order lattice that comprises these particles shows clean spectrum diffraction colour under the irradiation of natural light or white light.

In mobile colloidal crystal of the present invention, visual experience to the spectrum diffraction colour (this diffraction colour be on the three-dimensional order lattice right-angle view to diffraction colour) and grain spacing (L) preferably satisfy in the following relational expression (I) to (V) any:

(I) when L is the 160-170 nanometer, the colour that shows is clean purple (P),

(II) when L is the 180-195 nanometer, the colour that shows is clean blueness (B),

(III) when L is the 200-230 nanometer, the colour that shows is clean green (G),

(IV) when L is the 240-260 nanometer, the colour that shows is clean yellow (Y),

(V) when L is the 270-290 nanometer, the colour that shows is clean redness (R).

Preferably described dispersed substance colloidal solid is that the equal diameter of body (d) disperses specific spherical colloidal particle for the organic or inorganic polymkeric substance list of 10-130 nanometer, the described three-dimensional order lattice that comprises these particles has the ultraviolet light reflectivity properties when being subjected to wavelength and being no more than the ultraviolet irradiation of 400 nanometers.

Preferably described dispersed substance colloidal solid is that the equal diameter of body (d) disperses specific spherical colloidal particle for the organic or inorganic polymkeric substance list of 350-800 nanometer, the described three-dimensional order lattice that comprises these particles has infrared light reflection character when being subjected to wavelength and being the infrared light irradiation of 800-1500 nanometer.

In the present invention, described dispersed substance colloidal solid is preferably the organic polymer spherical of the polymkeric substance of (methyl) acrylic polymers of at least a being selected from (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replacement and (methyl) acrylic compounds-styrene polymer that fluorine replaces.

Described three-dimensional order lattice can prepare by the preparation method's (first method of the present invention) who may further comprise the steps:

Preparation comprises the mobile colloidal crystal (S-1) of following component: as the organic or inorganic polymkeric substance monodisperse spherical colloidal solid of dispersed substance, the equal diameter of the body of this particle (d) is not more than 30 microns; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; The dispersion concentration of wherein said colloidal solid is not less than 20 volume %, be not more than 70 volume %, under the temperature that is not less than the dispersion medium solution solidifying point, be no more than 2000 to form electrostatic double layer around the dispersed substance spherical colloidal particle in the solid-liquid aqueous colloidal dispersion of little Siemens/cm (representing) in static electrification lotus degree with specific thicknesses (Δ e) with conductivity, the dispersed substance spherical colloidal particle has formed the lattice of three-dimensional order, this lattice has flowability, it is a kind of particle array structure, spherical colloidal particle aligns at vertical and horizontal with form crystal lattice in this structure, the grain spacing (interparticle distance) that is defined as distance between the center of the particle of relatively arranging along center line (L) satisfies relational expression (d)＜(L)≤(d)+2 (Δ e)

The base sheet of the suspended matter of (S-1) above forming then, and this base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thus form longitudinally and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then,, then it is carried out polymerization or curing with the surface of filling the three-dimensional order lattice and the gap between particles of three-dimensional arrangement.

In addition, three-dimensional order lattice of the present invention also can prepare by the preparation method's (second method of the present invention) who may further comprise the steps:

Preparation comprises the mobile colloidal crystal (S-2) of following component: as the organic or inorganic polymkeric substance monodisperse spherical particulate of dispersed substance, it is colour killing that this particulate has a kind of black that is selected from canescence, grey, grey black and black, and the equal diameter of its body (d) is the 130-350 nanometer; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm,

The base sheet of the suspended matter of (S-2) above forming then, and this base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thus form longitudinally and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

Apply or spray in solution, organic polymer soln and the solution of inorganic binder of polymerizable organic monomer any then, fill the surface of three-dimensional order lattice and the gap between particles of three-dimensional arrangement, wherein the refractive index (nB) of polymkeric substance that is made by described solution or cured product is different with the refractive index (nP) of spherical particle, then it is carried out polymerization or curing.

In addition, three-dimensional order lattice of the present invention also can prepare by the preparation method's (third party's method of the present invention) who may further comprise the steps:

Preparation comprises the mobile colloidal crystal (S-3) of following component: as the organic or inorganic polymkeric substance monodisperse spherical particulate of dispersed substance, the equal diameter of its body (d) is the 10-130 nanometer; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm,

The base sheet of the suspended matter of (S-3) above forming then, and this base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thus form longitudinally and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

Apply or spray in solution, organic polymer soln and the solution of inorganic binder of polymerizable organic monomer any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, wherein the refractive index (nB) of polymkeric substance that is made by described solution or cured product is different with the refractive index (nP) of spherical particle, then it is carried out polymerization or curing.

In addition, three-dimensional order lattice of the present invention also can prepare by the preparation method's (cubic method of the present invention) who may further comprise the steps:

Preparation comprises the mobile colloidal crystal (S-4) of following component: as the organic or inorganic polymkeric substance monodisperse spherical particulate of dispersed substance, the equal diameter of its body (d) is the 350-800 nanometer; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume % and is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm,

The base sheet of the suspended matter of (S-4) above forming then, and this base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thus form longitudinally and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

In preparation method of the present invention, bonding agent is preferably and satisfies relational expression | the clear binder of nP-nB| 〉=0.05.

In preparation method of the present invention, described base sheet is preferably formed on the supporting member, and described supporting member is the Web materials of being made by stainless steel, fluororesin or nylon, and this Web materials has zanjon at interval, this zanjon has the opening of 1-10 millimeter at interval, and depth-width ratio is 0.4-0.8.

In preparation method of the present invention, the preferably at least a organic polymer spherical that is selected from the polymkeric substance of (methyl) acrylic polymers of (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replacement and (methyl) acrylic compounds-styrene polymer that fluorine replaces of described monodisperse spherical particulate.

The method that is used for preparing the coated film of spherical particle three-dimensional order lattice of the present invention comprises:

Preparation comprises the mobile colloidal crystal (S-5) of following component: as the organic or inorganic polymkeric substance monodisperse spherical particulate of dispersed substance, the equal diameter of its body (d) is the 0.01-30 micron; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm,

Mobile colloidal crystal (S-5) is applied on the plate that is selected from glass plate, plastic plate, steel plate, aluminium sheet, corrosion resistant plate, ceramic wafer, plank and piece of cloth,

The plate of this coating is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby form longitudinally onboard and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, then it is carried out polymerization or curing, the three-dimensional order lattice of spherical particle is fixed into coated film.

According to the present invention, can make the mobile colloidal crystal of the solid-liquid aqueous colloidal dispersion form that comprises monodisperse spherical colloidal solid (this particle disperses as dispersed substance).Monodisperse spherical colloidal solid contained in the described solid-liquid dispersion has formed the three-dimensional order lattice, and this lattice is a particle array structure, obviously has flowability.Described dispersed substance spherical colloidal particle is that the equal diameter of body (d) is no more than several microns organic or inorganic polymkeric substance monodisperse spherical colloidal solid.

In described solid-liquid aqueous colloidal dispersion, the dispersed substance spherical colloidal particle is dispersed in aqueous dispersion medium solution or contains in the non-aqueous dispersion medium solution of water of dissolving, and the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %.

Under the temperature that is not less than the dispersion medium solution solidifying point, around being no more than dispersed substance spherical colloidal particle in the solid-liquid aqueous colloidal dispersion of 2000 little Siemens/cm (representing with conductivity), static electrification lotus degree forms electrostatic double layer with specific thicknesses (Δ e).

In mobile colloidal crystal, the dispersed substance spherical colloidal particle has formed the three-dimensional order lattice, this lattice has flowability, it is a kind of particle array structure, spherical colloidal particle aligns at vertical and horizontal with form crystal lattice in this structure, is defined as along the grain spacing (L) of distance between the center of the relative particle of arranging of center line to satisfy relational expression (d)＜(L)≤(d)+2 (Δ e).

In being dispersed in mobile colloidal crystal as the monodisperse spherical particle alignment of dispersed substance on for example smooth substrate, and when using sem observation, find that spherical particle longitudinally and laterally regularly arranged, form the lattice of the three-dimensional order of spherical particle, this lattice is the particle array structure of homogeneous very, contains different array of particles hardly.

That is to say, in " first preparation method " of the present invention, prepared mobile colloidal crystal (S-1), described colloidal crystal comprises as the equal diameter of the body of dispersed substance (d) and is the organic or inorganic polymer spherical particulate of 0.01-30 micron, the base sheet of the suspended matter of (S-1) above forming then makes the base sheet be in the atmosphere that temperature is higher than the dispersion medium solidifying point then it is carried out drying.

Formed the lattice (SPL-1) of three-dimensional order like this in the base sheet, in this lattice, the monodisperse spherical particulate longitudinally and laterally regularly arranged.

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, then it is carried out polymerization or curing, thereby can make three-dimensional order lattice with the spherical particle of adhesive seal, this lattice is a kind of stable particle array structure, does not comprise the unordered homogeneous array of particles of three-dimensional order lattice (SPL-1).

When use has grey to the black of black is that the specific spherical particle of colour killing is as will be to be dispersed in the monodisperse spherical particulate in the solid-liquid suspension body as dispersed substance, and they are arranged on for example smooth substrate, when using sem observation again, find this black be colour killing specific spherical particle longitudinally and laterally regularly arranged and alignment, form the three-dimensional order lattice of spherical particle, this lattice comprises different array of particles hardly, can show clean colored diffraction colour when being subjected to natural light or white light irradiation.

That is to say; in " second preparation method " of the present invention; prepared mobile colloidal crystal (S-2); described colloidal crystal comprises as the equal diameter of the body of dispersed substance (d) for the organic or inorganic polymkeric substance list of 130-350 nanometer disperses specific spherical particle, and it is colour killing that this particulate also has a kind of black that is selected from canescence, grey, grey black and black.

The base sheet of the suspended matter of (S-2) above forming then, the base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby formed the lattice (SPL-2) of three-dimensional order, in this lattice, specific spherical particle longitudinally and laterally regularly arranged.

Apply or spray polymerizable organic monomer solution then, in organic polymer soln and the solution of inorganic binder any, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, wherein the refractive index (nB) of polymkeric substance that is made by described solution or cured product is different with the refractive index (nP) of spherical particle, then it is carried out polymerization or curing, thereby can make three-dimensional order lattice (SPL-2 with the spherical particle of organic binder resin or inorganic bond sealing, show colored three-dimensional order lattice), this lattice can show clean spectrum diffraction colour when being subjected to natural light or white light irradiation.

When the organic or inorganic polymkeric substance list that uses the equal diameter of body (d) as the 10-130 nanometer disperses specific spherical particle as will be to be dispersed in the monodisperse spherical particulate in the solid-liquid suspension body as dispersed substance, and they are arranged on for example smooth substrate, when using sem observation again, find that this specific spherical particle longitudinally and laterally regularly arranged and alignment, form the three-dimensional order lattice of spherical particle, this lattice comprises different array of particles hardly, has feature reflectance spectrum (property reflection spectrum) and fabulous ultraviolet light reflectivity properties when being subjected to being no more than the ultraviolet light irradiation of 400 nanometers.

That is to say, in " the 3rd preparation method " of the present invention, prepared mobile colloidal crystal (S-3), described colloidal crystal comprises as the equal diameter of the body of dispersed substance (d) and is the organic or inorganic polymer spherical particulate of 10-130 nanometer.

The suspended matter base sheet of (S-3) above forming then, the base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby formed the lattice of three-dimensional order, in this lattice, specific spherical particle longitudinally and laterally regularly arranged.

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, then it is carried out polymerization or curing, thereby can make the three-dimensional order lattice (ultraviolet light reflection three-dimensional order lattice) with the spherical particle of organic binder resin or inorganic bond sealing, this lattice is being subjected to having the ultraviolet light reflectivity properties when wavelength is no more than the ultraviolet light irradiation of 400 nanometers.

When use the equal diameter of body (d) as the specific spherical particle of the organic or inorganic polymkeric substance of 350-800 nanometer as to be dispersed in dispersed substance in the solid-liquid suspension body as the monodisperse spherical particulate, they are arranged on for example smooth substrate then, when using sem observation again, find that this specific spherical particle longitudinally and laterally regularly arranged, form the three-dimensional order lattice of spherical particle, this lattice comprises different array of particles hardly, has feature reflectance spectrum and fabulous infrared light reflection character when being subjected to the infrared light irradiation of 800-1500 nanometer.

That is to say, in " the 4th preparation method " of the present invention, prepared mobile colloidal crystal (S-4), described colloidal crystal comprises as the equal diameter of the body of dispersed substance (d) and is the organic or inorganic polymer spherical particulate of 350-800 nanometer.

The base sheet of the suspended matter of (S-4) above forming then makes the base sheet be in the atmosphere that temperature is higher than the dispersion medium solidifying point then it is carried out drying, thereby formed the lattice of three-dimensional order, and in this lattice, spherical particle longitudinally and laterally regularly arranged.

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, then it is carried out polymerization or curing, thereby can make the three-dimensional order lattice with the spherical particle of organic binder resin or inorganic bond sealing, this lattice has infrared light reflection character when being subjected to the infrared light irradiation of 800-1500 nanometer.

According to the present invention, the suspended matter that is used for making spherical particle three-dimensional order lattice (S-1) that " first preparation method " made applies onboard as coating fluid, thereby forms the coated film of the spherical particle three-dimensional order lattice with structure homogeneous surface nature.

That is to say that prepared suspended matter (S-1), this suspended matter comprises: be the organic or inorganic polymkeric substance monodisperse spherical particulate of 0.01-30 micron as the equal diameter of the body of dispersed substance (d); And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm.

Suspended matter (S-1) is applied in as coating fluid on the plate that is selected from glass plate, plastic plate, steel plate, aluminium sheet, corrosion resistant plate, ceramic wafer, plank and piece of cloth then, forms the base sheet of suspended matter (S-1).

This base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby form longitudinally onboard and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, then it is carried out polymerization or curing, thereby the three-dimensional order lattice of spherical particle is fixed into coated film with organic binder resin or inorganic bond.As a result, make the coated film of the three-dimensional order lattice of spherical particle.

In addition, according to the present invention, the suspended matter that is used for making spherical particle three-dimensional order lattice (S-2) that " second preparation method " made applies onboard as coating fluid, thereby make the homogeneous coated film of specific spherical particle three-dimensional order lattice, specifically, be the coated film that under natural light or white light irradiation, to show the apparent color three dimension ordered lattice of specific spherical particle of clean colour.

That is to say, prepared suspended matter (S-2), this suspended matter comprises: as the equal diameter of the body of dispersed substance (d) be the 130-350 nanometer, black with the canescence of being selected from, grey, grey black and black is that the organic or inorganic polymkeric substance list of colour killing disperses specific spherical particle; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm.

Then suspended matter (S-2) is applied in as coating fluid on the plate that is selected from glass plate, plastic plate, steel plate, aluminium sheet, corrosion resistant plate, ceramic wafer, plank and piece of cloth, forms the base sheet of suspended matter (S-2).

This base sheet is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby form longitudinally onboard and the horizontal three-dimensional order lattice of regularly arranged specific spherical particle.

Apply or spray in solution, organic polymer soln and the solution of inorganic binder of polymerizable organic monomer any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, wherein the refractive index (nB) of polymkeric substance that is made by described solution or cured product is different with the refractive index (nP) of spherical particle, then it is carried out polymerization or curing, thereby the three-dimensional order lattice that will can show the spherical particle of clean spectrum diffraction colour under the irradiation of natural light or white light is fixed as coated film.As a result, make the coated film of the apparent color three dimension ordered lattice of specific spherical particle.

In addition, according to the present invention, the suspended matter that is used for making spherical particle three-dimensional order lattice (S-3) that " the 3rd preparation method " made applies onboard as coating fluid, thereby make the homogeneous coated film of specific spherical particle three-dimensional order lattice, specifically, be to be no more than the coated film that shows the specific spherical particle three-dimensional order lattice of ultraviolet light reflectivity properties under the ultraviolet light irradiation of 400 nanometers at wavelength.

That is to say that prepared suspended matter (S-3), this suspended matter comprises: disperse specific spherical particle as the equal diameter of the body of dispersed substance (d) for the organic or inorganic polymkeric substance list of 10-130 nanometer; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm.

Then suspended matter (S-3) is applied in as coating fluid on the plate that is selected from glass plate, plastic plate, steel plate, aluminium sheet, corrosion resistant plate, ceramic wafer, plank and piece of cloth, forms the base sheet of suspended matter (S-3).

This base sheet is under the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby form longitudinally onboard and the horizontal three-dimensional order lattice of regularly arranged specific spherical particle.

Apply or spray in solution, organic polymer soln and the solution of inorganic binder of polymerizable organic monomer any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, wherein the refractive index (nB) of polymkeric substance that is made by described solution or cured product is different with the refractive index (nP) of spherical particle, then it is carried out polymerization or curing, being fixed is coated film, and the three-dimensional order lattice that will have the spherical particle of ultraviolet light reflectivity properties under wavelength is no more than the irradiation of ultraviolet light of 400 nanometers is fixed as coated film.As a result, make the ultraviolet light reflection coated film of the three-dimensional order lattice of spherical particle.

In addition, according to the present invention, the suspended matter that is used for making spherical particle three-dimensional order lattice (S-4) that " the 4th preparation method " made applies onboard as coating fluid, thereby make the homogeneous coated film of specific spherical particle three-dimensional order lattice, specifically, be to be not less than the coated film that shows the spherical particle three-dimensional order lattice of infrared light reflection character under the infrared light irradiation of 800 nanometers at wavelength.

That is to say that prepared suspended matter (S-4), this suspended matter comprises: be the organic or inorganic polymkeric substance monodisperse spherical particulate of 350-800 nanometer as the equal diameter of the body of dispersed substance (d); And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm.

Then suspended matter (S-4) is applied in as coating fluid on the plate that is selected from glass plate, plastic plate, steel plate, aluminium sheet, corrosion resistant plate, ceramic wafer, plank and piece of cloth, forms the base sheet of suspended matter (S-4).

Apply or spray in solution, organic polymer soln and the solution of inorganic binder of polymerizable organic monomer any then, with the surface of filling three-dimensional order lattice and the gap between particles of three-dimensional arrangement, wherein the refractive index (nB) of polymkeric substance that is made by described solution or cured product is different with the refractive index (nP) of spherical particle, then it is carried out polymerization or curing, to be fixed is coated film, and the three-dimensional order lattice that will have the spherical particle of infrared light reflection character under wavelength is the irradiation of infrared light of 800-1800 nanometer is fixed as coated film.As a result, make the infrared light reflection coated film of the three-dimensional order lattice of specific spherical particle.

As mentioned above, the invention provides following preparation method: be used for preparing " first preparation method " of the three-dimensional order lattice of spherical particle, wherein the particle array structure that is made of the three-dimensional arrangement spherical particle stably is fixed into the structure of special homogeneous; Be used for preparing " second preparation method " that show the color three dimension ordered lattice, spherical particle is that the equal diameter of body is that the specific black of 130-350 nanometer is the colour killing spherical particle in this lattice; Be used for preparing " the 3rd preparation method " of ultraviolet light reflection three-dimensional order lattice, spheric grain is that the equal diameter of body is the specific spherical particle of 10-130 nanometer in this lattice; Be used for preparing " the 4th preparation method " of infrared light reflection three-dimensional order lattice, spherical particle is that the equal diameter of body is the specific spherical particle of 350-800 nanometer in this lattice.Research according to the inventor, the solid-liquid suspension body and function for preparing in above-mentioned arbitrary method is made coating fluid, coating fluid is applied on the plate that is selected from various plates then, form the base sheet, thereby this base sheet is carried out the three-dimensional order lattice that drying forms spherical particle, and this lattice has the particle array structure of homogeneous, and has even curface onboard, then not hurtful simultaneously with this three-dimensional order lattice of adhesive seal, thereby form the homogeneous coated film to particle array structure.

By the SEM photo of dry type ordered structure (the present invention comprises single colloidal crystal desciccate that disperses the dispersed substance spheric grain) is observed, proved in colloidal crystal (solid-liquid aqueous colloidal dispersion) as the precursor before dry, spherical colloidal particle (dispersed substance) is arranged with the formal rule of lattice, has obviously formed the three-dimensional order lattice of novel novelty.This dispersion is can be easy to by the effect of external stress at the mobile solid-liquid aqueous colloidal dispersion of vertical and horizontal, and when making this dispersion transfixion, colloidal solid forms the particle array structure of homogeneous three-dimensional order lattice.When forming stable lattice-like solid-liquid ordered structure by the dispersed substance colloidal solid, longitudinally and laterally regularly arranged, the grain spacing (L) that is defined as distance between the center of the particle of arranging relatively along center line simultaneously satisfies relational expression (d)＜(L)≤(d)+2 (Δ e) to the dispersed substance spherical colloidal particle in solid-liquid aqueous colloidal dispersion system.

In the present invention, in order to obtain such grain spacing (L), reduce ionic species and the electrolyte that in the dispersion medium solution of solid-liquid aqueous colloidal dispersion, disperses or float by methods such as dialysis, the result, but be dispersed in the solid-liquid aqueous colloidal dispersion can static electrification the counter ion counterionsl gegenions material of colloidal solid be fixed on the surface of charged colloidal particle particle, form electrostatic double layer (Δ e) with specific thicknesses (Δ e).Therefore, in the present invention, the counter ion counterionsl gegenions on being fixed on particle surface, also reduce or removed easy dispersion or unsteady counter ion counterionsl gegenions material and the electrolyte that contends with, thereby make the charged colloidal solid of energy of dispersed substance keep grain spacing (L), thereby prevent the random arrangement of particle effectively at vertical and horizontal.

In the present invention, carry out desalination, reduce or remove near the electrostatic double layer and the unsteady electrolyte of the easy dispersion of electrostatic double layer (Δ e) by methods such as dialysis, the result, the density of the spherical particle surface charge of colloid granularity also improves relatively in the solid-liquid dispersion.By improving surface charge density, the electrostatic double layer with specific thicknesses (Δ e) that is formed at particle surface as counter ion counterionsl gegenions is subjected to the attraction of colloidal solid, further increased electric density, thereby made that the grain spacing (L) between the dispersed substance colloidal solid is further stable.That is to say, make the repulsion balance of the opposing particle aggregation direction that the Van der Waals force between the particle causes, make the grain spacing of vertical and horizontal of regulation stable.

In the present invention, the grain spacing (L) of distance satisfies under the situation of relational expression (d)＜(L)≤(d)+2 (Δ e) between the center of the particle that upper edge, the ordered structure plane center line that is defined as the solid-liquid aqueous colloidal dispersion is arranged relatively, be difficult to the thickness (Δ e) of the formed electrostatic double layer of actual measurement, but work embodiment as described below is described, when the conductivity of solid-liquid aqueous colloidal dispersion keeps constant after dialysis is handled, can see the following fact.That is to say, because the dispersed substance colloidal solid has higher surperficial static electrification lotus degree, can more successfully satisfy relational expression (d)＜(L)≤(d)+2 (Δ e), particle can be longitudinally and is laterally arranged more regularly and form particle array structure, in this structure, particle becomes the form of lattice with three-dimensional arrangement.We can say that such particle array structure has constituted the colloidal solid crystal that forms with solid-liquid dispersion form.

As mentioned above, the solid-liquid dispersion that comprises the colloidal solid that three-dimensional regular arranges is easy under the situation that keeps the three-dimensional lattice form basically in the effect current downflow of slight external stress, is easy to form colloidal crystal with the three-dimensional lattice form of colloidal solid when transfixion again.

Be used to form among first to fourth kind of preparation method of the three-dimensional order lattice (wherein being arranged with the particle array structure of monodisperse spherical particulate) of homogeneous extremely in the present invention, very important requirement be the preparation conductivity be no more than 2000 μ S/cm, dispersed substance concentration be 20-70 volume % the solid-liquid suspension body as comprise with dispersed substance disperse the solid-liquid dispersion of spherical particle, to form the three-dimensional order lattice of utmost point homogeneous.SEM photo shown in observation accompanying drawing 1 and the accompanying drawing 2 can be understood " homogeneity " as the particle array structure of the three-dimensional order lattice of spherical particle better.

(1) the SEM photo of Fig. 1 has shown the surface of the three-dimensional order lattice of the monodisperse spherical particulate that the present invention makes.Explain from crystallography, shown the array of particles figure of ordered structure in the photo on [001] plane of c direction of principal axis [001] (lattice plane of particle array structure, Miller indices (hkl) face).From this SEM photo as can be seen, formed the very array of particles of homogeneous rule.

(2) the SEM photo of Fig. 2 has shown the vertical cross-section (perpendicular to the surface) of the three-dimensional order lattice of the monodisperse spherical particulate that the present invention makes.Similarly, shown at [100] face ([hkl] face) of a direction of principal axis [100] or b direction of principal axis [010] or the array of particles image of [010] face ([hkl] face).From the SEM photo as can be seen, obviously form the very particle duplexer of homogeneous rule.

In [001] of described ordered structure c direction of principal axis [001] face stacked, the monodisperse spherical particulate in a direction of principal axis [100] and b direction of principal axis [010] phase shift [1/2 (d)] (being the radius of spherical particle) thus form [001] face of ordered structure, and [001] face is stacked continuously.The result, we can say that the three-dimensional order lattice that the present invention makes often is the three-dimensional order lattice of simple orthorhombic crystallographic system, this orthorhombic system is equivalent to by making ordered structure [001] face that oblique migration in a direction of principal axis and b direction of principal axis migration [1/2 (d)] forms, but [001] face is stacked at the c direction of principal axis on crystallography.

Therefore, in the three-dimensional order lattice of the spherical particle that the present invention makes, [001] face shown in Figure 1 is stacked in [001] the direction rule that is vertical direction, and this three-dimensional order lattice is the particle array structure of homogeneous very.

That is to say, in preparation method of the present invention, make under the static situation of suspended matter maintenance, be not higher than under the low temperature that is about room temperature of dispersion medium boiling point, solid-liquid suspension body by the preparation of " to the electrostatic charge optimization of solid-liquid dispersion " and " to the dispersion concentration optimization of dispersed substance monodisperse spherical particle " step is carried out drying, thereby form the very three-dimensional order lattice of the particle array structure of homogeneous.Above preparation the solid-liquid dispersion in make the dispersion medium that fixedly has the static charge of contending with around its static electrification spherical fine grain as dispersed substance and under alap conductivity, thereby the formation electrostatic double layer.As a result, needn't worry that be not more than 30 microns particulate, particularly granularity by granularity be dry check crack to occur in the three-dimensional order lattice that forms of the colloidal solid of 10 nanometers-3 micron, this and conventional drying method are very different; There is not any different array of particles in addition on the surface of particle duplexer and/or in the particle duplexer.Therefore, can pass through comparatively easy and easy method, effectively prevent to form the three-dimensional order lattice that preparation has high homogeneity and high structural purity under the ordered structure situation of non-homogeneous.

In addition, because the described three-dimensional order lattice particle array structure that is homogeneous, and wherein [001] face of ordered structure surface is stacked in c direction of principal axis (vertical direction) [001] direction rule, so this lattice has fabulous surface nature.For example, because aforementioned specific spheric grain, under the irradiation of visible light and ultraviolet light, the homogeneity of particle array structure reduces or has stoped because the uncertain light direction that scattering causes, effectively strengthen interference effect, thereby obtain the extremely obviously reflectivity properties (seeing Fig. 3 to Fig. 6) of (definite).Therefore, except the character of above-mentioned specific particle, as the structural property of the particle array structure of homogeneous very, this three-dimensional order lattice is clearly shown that and comprises various sense reagent or functional group's (these sense reagent or functional group have magnetization character, charging quantity, adsorption property, ion-exchange character, chemical reactivity etc.) or with the character of the spherical particle of these sense reagent or functional group modification.

Preferred forms of the present invention

With reference to preferred forms colloidal crystal of the present invention and the method for using this colloidal crystal to prepare the three-dimensional order lattice of monodisperse spherical particulate are further described.

Mobile colloidal crystal of the present invention makes with the form of solid-aqueous colloidal dispersion, in this dispersion, comprise and disperse concentration to be not less than 20 volume %, the static electrification lotus degree that is not more than 70 volume % be no more than 2000 milli Siemens/cm (representing) with conductivity but the charged colloidal particle spheric grain.

Described solid-liquid aqueous colloidal dispersion is formed by following component: the electrifiable colloidal solid of dispersed substance, and comprising the counter ion counterionsl gegenions material of particle surface electric charge and the electrolytical water-based or contain the non-aqueous solution of the water of dissolving of contending with as dispersion medium; This dispersion comprises and has mobile novel colloidal crystal as the lattice-like grain pattern of being made up of the three-dimensional arrangement particle.Conductivity is no more than 2000 μ S/cm usually, preferably is no more than 1000 μ S/cm, and more preferably no more than 500 μ S/cm, the lower limit of conductivity is generally 100 μ S/cm.Even lower limit is lower than 100 μ S/cm, also only can increase industrial cost usually.

That is to say that colloidal crystal of the present invention forms with the solid-liquid aqueous colloidal dispersion form that comprises following component: by as the equal diameter of the body of dispersed substance (d) but be no more than the spherical colloidal particle of the static electrification of making by the organic or inorganic polymkeric substance of several thousand nanometers; And as the water-based of dispersion medium or contain the non-aqueous solution of the water of dissolving, this solution comprise the electrifiable colloid spheric grain of dispersed substance with the counter ion counterionsl gegenions material of ion and the electrolyte that contends with.

In described solid-liquid aqueous colloidal dispersion, under the temperature that is not less than the dispersion medium solution solidifying point, around the dispersed substance spherical colloidal particle of arranging, form electrostatic double layer with specific thicknesses (Δ e), the electrifiable spherical colloidal particle of dispersed substance longitudinally and laterally regularly arranged, the grain spacing (L) that is defined as distance between the center of the particle of arranging relatively along center line simultaneously satisfies relational expression (d)＜(L)≤(d)+2 (Δ e).

Can see from the scanning electron micrograph of colloidal solid, but the colloidal solid of static electrification with the form of homogeneous lattice longitudinally with transversely arranged, and can not form any different array of particles in the either direction of vertical and horizontal.

In the present invention, the colloidal solid that constitutes mobile colloidal crystal (this colloidal crystal is used to form homogeneous three-dimensional order lattice) is that the equal diameter of body (d) is the specific spherical colloidal particle of 130-350 nanometer, and the organic or inorganic polymkeric substance that these particles are colour killing by a kind of black that is selected from canescence, grey, grey black and black is made.Particularly in the present invention, described colloidal solid is preferably single specific spherical colloidal particle that disperses, in the case, colloidal solid forms and shows colored colloidal crystal, structural property as mobile colloidal crystal, according to the grain spacing (L) of described three-dimensional order lattice, this crystal can show clean spectral color under natural light or white light irradiation.Demonstration means the formal rule arrangement with the homogeneous lattice in the solid-liquid aqueous colloidal dispersion of electrifiable colloidal solid based on these very pure optical properties of reflectance spectrum, and perhaps having formed the black that is not contained in the groups of grains of vertical and horizontal random arrangement is achromatism three-dimensional order lattice.

According to the present invention, have can show colored optical property colloidal crystal from optics colour developing character, identical with the optical property of the structure coloring material of routine.

Yet, be that as the significant difference of the ordered structure of grain pattern it is the ordered structure that forms with at the solid-liquid aqueous colloidal dispersion.In addition, in ordered structure, colloidal solid is arranged with the homogeneous form crystal lattice, therefore can be referred to as mentioned above with the solid-liquid aqueous colloidal dispersion in the colloid monocrystalline of grain spacing (L), this ordered structure is highly purified ordered structure, and this structure seldom comprises the different particle faces of arranging.

Mobile colloidal crystal of the present invention forms with the form of solid-liquid aqueous colloidal dispersion, so its notion has different significantly with the notion of conventional crystal growth.In addition, the scope of the crystalline density of solid-liquid aqueous colloidal dispersion is very wide, not only can be at an easy rate at the thickness that vertically increases crystal layer, and can laterally form crystal (or crystal growth) at an easy rate.

From the optics colour rendering and the conventional structure colour development material similar angle of crystal, disperse and be arranged in the solid-liquid aqueous colloidal dispersion to be preferably the colloidal solid that the black that is selected from canescence, grey, grey black and black is colour killing with the colloidal solid that forms the colloid monocrystalline as dispersed substance.That is to say, the present invention does not have any different lattice plane as the colloid monocrystalline of solid-liquid aqueous colloidal dispersion in array of particles, therefore the surface of ordered structure suitably and effectively absorbs or reduces diffused light and do not absorb or reduces the reflected light of launching around the particle, and described diffused light is owing to the part generation scattering of the visible light that applies or transmission generation.In the present invention, colloidal solid preferably has saturation degree and is no more than 5, preferably is no more than 3 colourless colour killing, and this is owing to can make as the reflected light color of optical property distinct more like this.Therefore, in the present invention, it is the organic or inorganic polymer spherical particle of colour killing that the saturation degree that colloidal solid more preferably is selected from canescence, grey, grey black, black is almost 0 black.

In addition, in the present invention, be present in the solid-liquid aqueous colloidal dispersion with the form of colloidal solid in order to make dispersed substance organic or inorganic polymer beads, granularity is generally the 0.01-30 micron, is preferably the 0.01-3 micron.From display optical character brightly, for example to the angle of reflection of light, absorption and transmission in the visible wavelength range (380-780 nanometer), described colloidal solid be preferably the equal diameter of body (d) be no more than 350 nanometers, preferably be no more than 330 nanometers, especially preferably be no more than the organic or inorganic polymer beads of 300 nanometers.From the dispersiveness of solid-liquid aqueous colloidal dispersion, the charged character and the orientation angle on spherical colloidal particle surface, preferably be limited to the particle that is limited to 380 nanometers on 120 nanometers, the granularity under the granularity, more preferably the equal diameter of body (d) is the 130-350 nanometer, is preferably the particle of 150-300 nanometer.Consider the reflection that (is no more than 380 nanometers) in the ultraviolet wavelength zone, the equal diameter of body (d) preferably is no more than 130 nanometers, more preferably the 10-120 nanometer.For the reflection of (800-1500 nanometer) in the infrared wavelength zone, the equal diameter of body (d) preferably is not less than 340 nanometers, more preferably is not less than 350 nanometers, more preferably the 380-800 nanometer.

For above-mentioned reasons, relevant with the grain spacing (L) of dispersed substance spherical colloidal particle in the dispersion, the dispersion concentration of solid-liquid aqueous colloidal dispersion of the present invention is no more than 70 volume %.If the dispersion concentration of dispersed substance is less than 10% in the dispersion, can become is difficult to particle be alignd in constant array and make array stable.If concentration surpasses the upper limit of above-mentioned scope, random gathering takes place in groups of grains easily, and the regularly arranged meeting of particle is subjected to significant inhibition, does not therefore wish to adopt such concentration.The angle that comprises package quality (packaging degree), stability and the purity of the colloidal crystal of solid-liquid aqueous colloidal dispersion from the present invention, concentration preferably is not less than 20%, is not more than 60%, more preferably be not less than 25%, be not more than 55%, especially preferably be not less than 35%, be not more than 50%.When concentration is in this scope, sharpness, working properties and the flowability of the various character that colloidal crystal of the present invention (being the solid-liquid aqueous colloidal dispersion) has fabulous purity, stability, showed.

In order to form the three-dimensional order lattice of homogeneous in the solid-liquid aqueous colloidal dispersion, preferably the dispersed substance spherical colloidal particle is in the pH of non-isoelectric point dispersion scope.When explaining " isoelectric pH value ", suppose in isoelectric point, be the pH neutral point, the electrostatic double layer that the electrifiable colloidal solid with counter ion counterionsl gegenions is difficult to form grain spacing of the present invention (L) and keeps specific thicknesses (Δ e), but details it be unclear that.

In the present invention, as mentioned above, the surface charging lotus degree of the dispersed substance colloidal solid in the solid-liquid aqueous colloidal dispersion, be that the electrically charged character of solid-liquid aqueous colloidal dispersion is very important.Surface charging lotus degree for the organic or inorganic polymer beads, the absolute value of particle surface (+) or (-) electric charge (measuring by electric discharge (blow-off method)) is preferably 50-500 microcoulomb/gram, described particle be to have static by adion with functional group position contained in the polymkeric substance (as the adsorption activity position).The example of these functional groups comprises acid or basic functionality, for example carboxyl (COOH), sulfonic group (SO ₃H), hydroxyl (OH), amino (NH ₂) and amide group (CONH ₂), thiazolinyl (CH=CH-), alkynyl (C ≡ C-), vinyl ether (CH=CH-O-), cyano group (C ≡ N), isocyanate group (N=C=O), nitro, sulfydryl (SH) and-CF ₃Base.

In order to form the high-purity ordered structure in the solid-liquid aqueous colloidal dispersion of the present invention, the spherical colloidal particle of organic or inorganic polymkeric substance preferably Cv value (equalization of the equal diameter of this numeric representation body) preferably is no more than 5%, more preferably 3% monodisperse particles.Same angle from optical property, described organic or inorganic spheric grain is preferably monodisperse particles, this be since when the visible light that apply by diffraction interference reflex time on the colloidal crystal face, specific reflection efficiency is influential to the color that the optics colour development material shows.Be used to represent that the Cv value of epigranular ratio and monodispersity matter preferably is no more than 5%, from the density and the sharpness angle of reflected light color, the Cv value preferably is no more than 3%.

As mentioned above, colloidal crystal as the solid-liquid aqueous colloidal dispersion with above-mentioned feature has certain optical property, make in dispersion and to disperse and the black that is arranged in ordered structure is that colour killing monodisperse spherical particle shows clean monochromatic color under the irradiation of natural light or white light with form crystal lattice, this monochromatic color be defined as dispersion in along center line relatively between the center of the particle of arrangement the grain spacing (L) of distance relevant.That is to say that to shown in (V), they show purple, blueness, green, yellow and red and so on spectral color as following (I).Visual experience to spectral color (this spectral color is the color of right-angle view on the colloid crystal face) as follows:

(I) when (L) is the 160-170 nanometer, the colour that shows is purple (P),

(II) when (L) is the 180-195 nanometer, the colour that shows is blue (B),

(III) when (L) is the 200-230 nanometer, the colour that shows is green (G),

(IV) when (L) is the 240-260 nanometer, the colour that shows is yellow (Y),

(V) when (L) is the 270-290 nanometer, the colour that shows is red (R).

That is to say that described mobile colloidal crystal can carry out the spectral color colour developing according to grain spacing (L).

In the present invention, described mobile colloidal crystal can suitably form thickness and be not less than 200 nanometers, preferably is not less than the crystal layer of 400 nanometers, utilizes the above-mentioned characteristic of solid-liquid aqueous colloidal dispersion best.

In the present invention, needn't limit organic polymer monodisperse spherical colloidal solid, but these particles are preferably at least a spheric grain that is selected from the organic polymer of following polymkeric substance: (methyl) acrylic compounds-styrene polymer that (methyl) acrylic polymers that (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replace and fluorine replace.Equally, to inorganic polymer monodisperse spherical particle and unrestricted, but they are preferably at least a spheric grain that is selected from the inorganic polymer of silicon dioxide, aluminium oxide, silica-alumina, titania and titania-silica.In the present invention, very important feature is that any organic or inorganic polymer beads is with dyestuff or pigment coloring, to have grey to the black of black be the colloidal solid of colour killing, and they are monodisperse spherical particles.Also have the colloidal solid that a bit importantly has this specific character, but can suitably make with the form of the charged colloidal particle particle in the solid-liquid aqueous colloidal dispersion.

The example of organic polymer that is used for preparing the organic polymer monodisperse spherical particle of the solid-liquid aqueous colloidal dispersion with above-mentioned feature comprises poly-(methyl) methyl acrylate, tetrafluoroethene, poly--4-methyl-1-pentene, poly-(methyl) benzyl acrylate, polymethyl acid phenenyl ester, poly-(methyl) cyclohexyl acrylate, polyethylene terephthalate, polystyrene, styrene/acrylonitrile copolymer, Polyvinylchloride, Vingon, polyvinyl acetate, polyvinyl alcohol (PVA) and polyurethane, but available polymkeric substance is not limited to these examples.As mentioned above, under the irradiation of the natural light of daylight or white light and so on, according to the reflected light color of wavelength of visible light scope visual experience to the optics colour development material, therefore from fabulous photostability angle, the fluoropolymer resin that the present invention preferably uses is to be selected from the following acrylic compounds organic polymer with fabulous weatherability: (methyl) acrylic compounds-styrene polymer that (methyl) acrylic polymers that (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replace and fluorine replace.

But the example of the monomer of the acrylic resin of static electrification electric charge comprises (methyl) alkyl acrylate, for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) 2-ethyl hexyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid dodecane ester, (methyl) phenyl acrylate, (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid ethoxy ethyl ester, (methyl) acrylic acid propoxyl group ethyl ester and (methyl) acrylic acid butoxy ethyl ester; (methyl) propenoic acid dialkyl aminoalkyl ester of (methyl) acrylic acid diethylamino ethyl ester and so on, (methyl) acrylamide of (methyl) acrylamide, N-methylol (methyl) acrylamide and diacetone acrylamide and so on, and (methyl) glycidyl acrylate; And the dimethylacrylate of ethylene glycol, the dimethylacrylate of diglycol, the dimethylacrylate of triethylene glycol, the diacrylate of polyglycol, the dimethylacrylate of propylene glycol, the dimethylacrylate of dipropylene glycol and the dimethylacrylate of 3 third glycol.The example of other monomer except above-mentioned (methyl) acrylic monomer comprises styrene; Ring-alkylated styrenes, for example methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene and octyl group styrene; Halogenated styrenes, for example fluorostyrene, chlorostyrene, bromostyrene, dibromo-benzene ethene and chloro methyl styrene; Styrene monomer, for example nitrostyrolene, acetylbenzene ethene, methoxy styrene, α-Jia Jibenyixi and vinyltoluene.The example of the monomer except styrene monomer comprises siliceous vinyl monomer, for example vinyltrimethoxy silane and vinyltriethoxysilane; Vinyl esters, for example vinyl acetate, propionate, vinyl propionate, isobutyric acid vinyl acetate, new vinyl acetate acid, vinyl caproate, tertiary ethylene carbonate (vinylversatate), vinyl laurate, stearic acid vinyl ester, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate and vinyl salicylate; Vinylidene chloride and chloro-hexane vinyl formate.Also can use following monomer when needing in addition.Example with monomer of functional group comprises unsaturated carboxylic acid, for example acrylic acid, methacrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, methacrylate, nornenedicarboxylic acid and dicyclo [2,2,1] hept-2-ene"-5, the 6-dicarboxylic acid, the example of their derivant comprises maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride.Example with polymerisable activated monomer of hydroxyl (OH) comprises 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, acrylic acid-2-hydroxy propyl ester, 1,1,1-trihydroxy methyl ethane three acrylic acid esters, 1,1,1-trihydroxy methyl propane three acrylic acid esters; Hydroxy alkyl vinyl ether, for example hydroxyl vinyl ether, hydroxypropyl vinyl ether and hydroxybutyl vinyl ether; And (methyl) acrylic acid hydroxyalkyl acrylate, for example (methyl) 2-Hydroxy ethyl acrylate, acrylic acid-2-hydroxy propyl ester and diglycol monotertiary (methyl) acrylate.These monomers can use separately or two or more is used in combination.Example with part or all of (methyl) acrylic monomers that replaces of fluorine comprises (methyl) acrylic monomers (or (methyl) fluoroalkyl acrylate) that fluorine replaces, for example (methyl) acrylic acid trifluoromethyl methyl esters, (methyl) acrylic acid-2-trifluoromethyl ethyl ester, (methyl) acrylic acid-2-perfluoro-methyl ethyl ester, (methyl) acrylic acid-2-perfluor ethyl-2-perfluoro butyl ethyl ester, (methyl) acrylic acid-2-perfluor ethyl ester, (methyl) acrylic acid perfluor methyl esters and (methyl) acrylic acid two perfluoro-methyl methyl esters.The example of fluoroolefin comprises fluorothene, vinylidene, tetrafluoroethene, hexafluoroethylene, hexafluoropropylene and perfluor-2,2-dimethyl-1,3-dioxole.In the present invention, can use the homopolymer of these monomers or the multipolymer of these monomers and other polymerisable monomer.

When needing, can in the used monodisperse spherical particle of the present invention (comprising that black is the spherical monodisperse particles of colour killing), suitably add adjuvant, for example ultraviolet absorber, antioxidant, fluorescer, charging agent, antistatic agent, dispersion stabilizer and defoamer.They also can comprise other adjuvant, functional agent or functional group in particle or on the surface of particle, as long as can not damage sphere, monodispersity matter and the dispersiveness in suspended matter of gained dispersed substance particle with various character (for example magnetizing character, charging quantity, adsorption property, ion-exchange character, chemical reactivity).

The black that is used for preparing the mobile colloidal crystal of the present invention (the solid-liquid aqueous colloidal dispersion with above-mentioned characteristic) is the organic polymer monodisperse spherical particulate of colour killing, usually can use method commonly used to make, for example emulsifier-free emulsion polymerization, emulsion polymerization, seeding polymerization, swollen-state polymerization and dispersin polymerization.

In emulsifier-free emulsion polymerization, the persulfate that uses potassium persulfate or ammonium persulfate and so on usually is as polymerization initiator, and only polymerization initiator just must be dissolved in aqueous medium when carrying out polyreaction.In the monomer of wanting polymerization is 100 weight portions, and the consumption of polymerization initiator is generally the 0.1-10 weight portion, is preferably the 0.2-2 weight portion.In emulsion polymerization, use emulsifying agent.The example of emulsifying agent comprises the polyethylene glycol alkyl ether of the alkyl benzene sulfonate of neopelex and so on and polyethylene glycol nonylphenyl ether and so on.In the monomer that is used for polymerization is 100 weight portions, and the consumption of emulsifying agent is generally the 0.01-5 weight portion, is preferably the 0.1-2 weight portion.Emulsifying agent is mixed the formation emulsion with aqueous medium, in this emulsion, add the 0.1-10 weight portion, be preferably the polymerization initiator of 0.2-2 weight portion (is 100 weight portions in the monomer that is used for polymerization), for example the persulfate of potassium persulfate or ammonium persulfate and so on.In any polyreaction in seeding polymerization, swollen-state polymerization, dispersin polymerization and suspension polymerization, used emulsifying agent be there is no concrete restriction, and use surfactant usually, for example anionic surfactant, cationic surfactant and non-ionics, these surfactants can be used singly or in combination.Examples of anionic surfactants comprises dodecylbensenesulfonate, dodecyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, nonylbenzene sulfonates, their sodium salt and sylvite.The example of cationic surfactant comprises cetyl trimethyl ammonium bromide, cetylpyridinium chloride and hexadecyltrimethylammonium chloride.Non-ionic surfactant is for example pyridine.The example of active emulsifier (emulsifying agent that for example has the polymerizable groups of acryloyl group or methacryl and so on) comprises anionic, cationic or non-ionic activity emulsifying agent, and the use of these active emulsifiers is not subjected to any restriction.For making the used resin particle of the present invention have black is color, and oil-soluble black based dye or the black series pigments that contains carbon black suitably are dispersed or suspended in the potpourri of polymerisable monomer, emulsifying agent and water as colored materials.

More particularly, to comprising the black based dye (for example C.I.Solvent Black 27) that system that 100 weight portions are selected from the monomer of aforementioned polymerisable monomer and 200-350 weight parts water adds the 5-10 weight portion, when stirring, it is heated then, add the emulsifying agent of 0.05-0.7 weight portion then, it is fully mixed.Then, this system is blasted nitrogen, when stirring with this mixture heated to 60-80 ℃.Add the polymerization initiator of the potassium persulfate and so on of 0.3-0.6 weight portion then, polyreaction was carried out under 70-90 ℃ 4-8 hour.In the reaction dispersion that the emulsifier-free emulsion polymerization reaction makes, making solid concentration is that 10-35 weight % and the equal diameter of body (d) are single black spherical polymer particles of disperseing of 50-900 nanometer.

In the present invention, can suitably use black is the inorganic polymer monodisperse spherical particle replacement organic polymer colloidal solid formation colloidal crystal of colour killing.The example of inorganic polymer comprises silicon dioxide, aluminium oxide, silica-alumina, zirconia, titania, titania-silica, silit and silicon nitride, but can be used for inorganic polymer of the present invention is not limited to these examples.Specifically, preferred use is by the inorganic polymer particle of the sol-gel process preparation of the alkoxide of the metal of silicon, aluminium or titanium and so on, and this is owing to dyestuff or pigment they are caught the colour of black system than being easier to.The example of metal alkoxide comprises methyltrimethoxy silane, vinyltrimethoxy silane, tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four butyl esters, aluminum ethoxide, aluminium ethoxide, the methoxyl aluminium isobutyl, the ethoxy aluminium isobutyl, aluminum isopropoxide, the isopropoxy aluminium isobutyl, butoxy aluminium, tert-butoxy aluminium, tert-butoxy tin, three positive propoxy aluminium, three n-butoxy aluminium, purity titanium tetraethoxide, four positive propoxy titaniums, four titanium n-butoxide, tetraisopropoxy titanium, the methoxyl titanium, ethanolato-titanium, the positive propoxy titanium, titanium isopropoxide, titanium n-butoxide, the isobutoxy titanium, the ethoxy zirconium, n-propoxyzirconium, the isopropoxy zirconium, n-butoxy zirconium and ethoxy four n-pro-pyl zirconiums.

In the present invention, when needing, the suspended matter (form with dispersed substance in this suspended matter is dispersed with the organic or inorganic polymeric colloid particle that black is colour killing) for preparing is above filtered, with the method for routine suspended matter is carried out dialysis then and handle, the electrolyte concentration of representing with conductivity (μ S/cm) in the suspended matter is adjusted to is no more than 600 μ S/cm, preferred 50-500 μ S/cm.As mentioned above the slurries that make are concentrated into then and disperse concentration (volumetric concentration with the dispersed substance colloidal solid is represented) to be not more than 70%, preferably be not more than 60%.

The colloidal crystal that the present invention provides with the form of the solid-liquid aqueous colloidal dispersion that contains colloidal solid, can make in the following manner: top suspended matter is encapsulated between two relative transparent components (member), being spaced apart between the transparent component for example is not less than 400 nanometers, the mode of encapsulation makes at interval that (crystal layer thickness) keeps constant, to parts at the shared area of in-plane without limits.The example of transparent component comprises flexible plastic film, rigidity plastics film and glass plate.By suspended matter is encapsulated between the transparent component, formed colloidal crystal.By utilizing the characteristic of solid-liquid aqueous colloidal dispersion best, suspended matter can be encapsulated in transparent component with the shape that is different from above-mentioned plane (for example bicylindrical parts, two polygon parts, two spherical member, flexible thin tube-like parts or be used for fibre-optic hollow tubular parts), thereby form colloidal crystal.

In the present invention, conventional have flexible organic polymer sheet and can use without restriction, as long as these sheet materials have water tolerance or solvent resistance (owing to will encapsulate suspended matter).Particularly when the needs clear sheet, can use for example polyester, for example polyethylene terephthalate and Polyethylene Naphthalate; Acrylic resin, for example poly-(methyl) methyl acrylate and poly-(methyl) ethyl acrylate; Polycarbonate; Polystyrene and polystyrene.Flexible if not special needs, can use plastic plate and glass plate etc., when needing, also other surface elements, the non-transparent parts of itself and plastic foil or plastic sheet, aluminium sheet, ceramic wafer and corrosion resistant plate and so on can be used in combination.

As mentioned above, the present invention's method of being used for preparing the three-dimensional order lattice of monodisperse spherical particulate may further comprise the steps: " preparation solid-liquid suspension body "-" reducing the conductivity of solid-liquid suspension body best "-" making dispersion concentration the best of dispersed substance spherical particle "-" carrying out particle alignment under the low temperature that is not higher than the dispersion medium boiling point "-" using the adhesive seal ordered structure ".In the method, make as dispersed substance by dialysis etc. to be dispersed in the conductivity that monodisperse spherical particulate in the solid-liquid suspension body has regulation, and granularity to be no more than 30 microns or even granularity be that the spherical particle of 0.01-30 micron forms the three-dimensional order lattice.This method is very different with the drying means of routine, needn't worry that dry check crack appears in the three-dimensional order lattice that makes, and different array of particles seldom occurs on the surface of particle duplexer and/or in the particle duplexer.In addition, can be when preventing that effectively non-uniform and ordered structure from forming, prepare efficiently with simpler method and to have the highly purified three-dimensional order lattice of structure.

As mentioned above, in the present invention, from the optics colour developing character of three-dimensional order lattice, spherical particle is preferably the monodisperse spherical colloidal solid that the black that is selected from canescence, grey, grey black and black is colour killing.That is to say, similarly, as described above, the three-dimensional order lattice of the spherical particle that the present invention makes is the particle array structure that does not contain the very homogeneous of different ordered structures, the surface of ordered structure can suitably and effectively absorb or reduce diffused light and do not absorb or reduce the reflected light of emission around the particle like this, described diffused light is because the part generation scattering of the visible light that applies or transmission produce, because the optical interference effect that the high homogeneity of particle array structure causes has obtained enhancing, make catoptrical color distinct more.In addition, the preferred brightness of colloidal solid is not more than 5, preferably is not more than 3 colourless colour.Therefore, in the present invention, the black that colloidal solid more preferably is selected from canescence, grey, grey black and black is the specific organic or inorganic polymer spherical particulate of colour killing, and according to the Mang Saier colour system, the brightness of described color and saturation degree all are almost 0.

Preferably will be dispersed in the dispersion concentration adjustment of the monodisperse spherical particulate in the suspended matter to being not more than 70 volume % as dispersed substance.If disperse concentration to surpass this upper limit, random gathering takes place in groups of grains easily, and regular particles is arranged the process that forms the three-dimensional order lattice can be subjected to significant inhibition, does not therefore wish to adopt this concentration.From the angle of the processability of the dispersion stabilization of solid-liquid suspension body and suspended matter, should disperse the upper limit of concentration to be adjusted to about 40-60%.From forming the speed of ordered structure or the processability of suspended matter by drying means the base sheet, lower limit preferably is not less than 20%, more preferably is not less than 30%, especially preferably is not less than 40%, with this understanding, can prepare three-dimensional order lattice of the present invention.

In the present invention, the specific dispersion concentration of dispersed substance spherical particle and the solid-liquid suspension body of certain electric conductance have been adjusted to by using, can make the three-dimensional order lattice, this lattice does not need to worry to occur dry check crack as the particle duplexer of conventional drying method preparation is viewed, a kind of particle duplexer is provided, on this duplexer surface and/or do not have different array of particles in the duplexer, this lattice has structural homogeneity, and because homogeneity clearly shows the various character that comprise as the optical property of surface nature.

In order will to seal by the three-dimensional order lattice (particle array structure) of dry specific suspended matter preparation with resin binder or organic bond, apply or spray in solution (the polymerizable organic monomer solution that for example comprises polymerization initiator), organic polymer soln and the solution of inorganic binder of polymerizable organic monomer any, thereby fill the surface of three-dimensional order lattice and the gap between particles of three-dimensional arrangement, thereby can be under the situation of not damaging particle array structure that the three-dimensional order lattice is stably fixing, but details it be unclear that.

After in the solution, organic polymer soln and the solution of inorganic binder that have applied or sprayed the polymerizable organic monomer any, carry out polymerization or curing.In the present invention, the particle of arrangement and bonding agent are not necessarily fastened to each other with chemical method, and they are can physical method fastened to each other.

Be applicable to the sealing and fixedly the organic or inorganic bonding agent of three-dimensional order lattice be preferably transparent adhesives, the angle that can optically clearly be discerned from the particle of during showing the color three dimension ordered lattice, arranging, it is important, described bonding agent is a kind of transparent adhesives, this bonding agent has following character: the refractive index (nB) of resin binder or inorganic bond (being the product of polymkeric substance or curing) is different with the refractive index (nP) of spherical particle, and refractive index (nB) and refractive index (nP) satisfy relational expression | nP-nB| 〉=0.05.If | nP-nB|＜0.05, then the brightness meeting reduces, thereby makes tone deepening and reduction, does not therefore wish to adopt such numerical value.

The suspended matter for preparing above is cast on the smooth substrate, sprays or apply above-mentioned solution then, form quite thick suspended matter layer (or base sheet).In the present invention, the temperature that the suspended matter layer is in be not less than the solidifying point of dispersion medium in the solid-liquid suspension body, preferably be generally under the low temperature as 20 ℃ ± 5 ℃ and so on room temperature, thereby on substrate, form gradually by longitudinally and the three-dimensional order lattice formed of the spherical particle of laterally rule alignment.In order to accelerate to form the speed of three-dimensional order lattice, the static residing temperature of suspended matter layer suitably can be increased to and preferably be not less than 40 ℃, be more preferably 50 ℃.In the present invention, the suspended matter layer suitably is under quiescent conditions is not higher than under the atmospheric decompression.

In the present invention, to the smooth substrate that is used for forming base sheet (or suspended matter layer) thereon and without particular limitation, any in transparent component, semi-opaque feature and the non-transparent parts all can use.These examples of members comprise plastic foil, rigidity plastics sheet, glass plate, ceramic wafer, various steel plate, corrosion resistant plate, aluminium alloy plate, copper coin, plank and fabric.Conventional organic polymer all can be used as plastic components and without any restriction, needs only them and have water tolerance or solvent resistance---and this is owing to will pour into a mould suspended matter thereon.The example of transparent component comprises polyester, for example polyethylene terephthalate and Polyethylene Naphthalate; Acrylic resin, for example poly-(methyl) methyl acrylate and poly-(methyl) ethyl acrylate; Polycarbonate; Polystyrene and polystyrene.Substrate can be an adhesive plate, and in the case, the base plate of adhesive plate can be at least a material that is selected from steel plate, corrosion resistant plate, aluminium sheet, aluminium alloy plate, ceramic wafer, fat board, glass plate, plastic plate, plank and ground paper.

Can provide smooth substrate with support unit, a large amount of rules on in-plane or compact arranged brokenly zanjon are arranged at interval in this support unit, in the present invention, preferably on this substrate, form the suspended matter layer.Support unit is the Web materials of being made by stainless steel, fluororesin or nylon.It is that 50-200 micron, depth-width ratio are the zanjon interval of 0.4-0.8 that Web materials has opening, can preferably this Web materials be used as support unit.Another embodiment of support unit is negativity or positive photoresist sheet, a large amount of furrow width 1-10 microns, depth-width ratio are the zanjon regular or closely arrangement brokenly at in-plane at interval of 0.5-2 in this sheet, can preferably this photoetching film be used as support unit.Although reason is not clear, the present invention can prevent crackle by support unit is provided.When to being formed at the base sheet with specific thicknesses (suspended matter layer) on the support unit when carrying out drying, the particle that is suspended in the base sheet takes place down to assemble and arrangement in dry convergent force (or dry cohesion) effect.In the present invention, suspended particle consequently is inhaled in the zanjon interval in upward gathering and arrangement of zanjons interval (this zanjon interval is evenly distributed at in-plane) in a large number.Therefore, the dry convergent force that produces in the base sheet is assigned with and is dispersed on the zanjon interval, thereby can alleviate or eliminate dry convergent force.

In the present invention, to organic polymer monodisperse spherical colloidal solid without limits, but the preferably at least a spheric grain that is selected from following organic polymer: (methyl) acrylic compounds styrene polymer that (methyl) acrylic polymers that (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replace and fluorine replace.Equally, to inorganic polymer particle monodisperse spherical colloidal solid without limits, still preferably be selected from the spheric grain of at least a inorganic polymer of silicon dioxide, aluminium oxide, silica-alumina, titania and titania-silica.In the present invention, very important feature be arbitrarily the organic or inorganic polymer beads be with dyestuff or pigment coloring, grey to the black of black is the colloidal solid of colour killing, and they are monodisperse spherical particles.That is to say, but importantly can suitably prepare colloidal solid with the form of the charged colloidal particle particle in the solid-liquid aqueous colloidal dispersion with this specific character.

As mentioned above, the three-dimensional order lattice of the monodisperse spherical particulate that makes by preparation method of the present invention is that base sheet by the solid-liquid suspension body is in the form that forms film, sheet or model product on the various substrates or in various containers.For example, show the color three dimension ordered lattice and show under the irradiation of natural light, white light or fluorescence from the extremely blue clean colour of redness, therefore, this lattice can provide novel color material for the various fields of upholstery, decoration, design and demonstration and so on.

Ultraviolet or infrared light reflection three-dimensional order lattice can provide the ultraviolet light or the infrared light shielding material of various forms of novelties.

Specifically, show the color three dimension ordered lattice and under the irradiation of visible light, show spectral color according to the size of granularity (d), therefore, this lattice can provide various forms of optical modulation materials, light quantity to regulate optical filter, color filter, be used for preventing to indoor film of spying on or sheet etc.

The method that is used to prepare three-dimensional order lattice of the present invention by use, novel various function coating materials can be provided, these materials comprise various sheet materials or sheet material, for example glass plate, plastic plate, steel plate, corrosion resistant plate, ceramic wafer, plank, fur sheet and piece of cloth, and the three-dimensional order lattice that is applied in the spherical particle on these sheet materials or the sheet material with various functions.

Industrial applicability

The of the present invention mobile colloidal crystal that provides with the solid-liquid aqueous colloidal dispersion form of colloidal solid, can make by being encapsulated between two relative transparent components, the width at the interval between the described transparent component (being the gained crystal layer thickness) is not less than 400 nanometers, and be constant, described transparent component is not specifically limited on the shared surface of in-plane.The form that mobile colloidal crystal can be encapsulated between the various transparent components is used, and these transparent components are for example flexible plastic films, rigidity plastics sheet, glass plate and their combination.

According to the present invention, mobile colloidal crystal can be encapsulated in the form use in other transparent component except above-mentioned flat piece, and these other transparent components are for for example bicylindrical parts, two polygon parts, two spherical member, flexible thin tube-like parts or be used for fibre-optic hollow tubular parts.

The of the present invention mobile colloidal crystal that is encapsulated in these parts can show under the irradiation of natural light, white light or fluorescence from redness to blue clean colour, therefore, the color material of the novelty in the various fields that can be used for interior decoration, decoration, design and demonstration field and so on can be provided.

By effectively utilizing these optical properties, except utilizing mobile colloidal crystal to show the color material of spectral color, also can provide various forms of optical modulation materials, light quantity to regulate optical filter, color filter, be used for preventing to indoor film of spying on or sheet etc. according to grain spacing (L).

The non-electric field type color monitor of the novelty of the electric field type display by with the form of matrix (matrix) on-off of photoirradiation being carried out systematization, can provide being used for replacing LCD, PDA, PLD, LED and PDP and so on.

The three-dimensional order lattice of the monodisperse spherical particulate that makes by preparation method of the present invention is on the various substrates or form the form of film, plate or layered product in various containers.Show the color three dimension ordered lattice and under the irradiation of natural light, white light or fluorescence, show clean colour as spectrum diffraction color according to its granularity (d).Therefore, not only can be provided for the novel color material in the various fields of interior decoration, decoration, design and demonstration and so on, also can provide various forms of optical modulation materials, light quantity to regulate optical filter, color filter, be used for preventing to indoor film of spying on or sheet etc.

Ultraviolet light or infrared light reflection can take place in the three-dimensional order lattice of the spherical particle with specified particle size that makes by preparation method of the present invention under the irradiation of ultraviolet light or infrared light, therefore, the ultraviolet light or the infrared light shielding material of various forms of novelties can be provided.

Be used for preparing the method for three-dimensional order lattice of the present invention by use, formed the coated film of the three-dimensional order lattice of spherical particle with various functions, therefore, various function coating materials can be provided, these materials comprise various sheet materials or sheet material, for example glass plate, plastic plate, steel plate, corrosion resistant plate, ceramic wafer, plank, fur sheet and piece of cloth, and the three-dimensional order lattice that is applied in the spherical particle on these sheet materials or the sheet material with various functions.

Embodiment

With reference to following examples the present invention has been carried out further description, but be to be understood that the present invention is not limited to these embodiment.

Reference example 1

Prepared and be used for the monodisperse spherical particle that black is colour killing that has of the present invention.The water of the sodium dodecylsulphonate of 100 parts by weight of methylmethacrylate (MMA) monomer, 7.5 weight portion C.I Solvent Black, 27 black dyess, 0.6 weight portion and 290 weight portions added in 1 liter the four neck flasks, then it is mixed, while under situation, stir mixture heated to 80 ℃ with the nitrogen purge flask.The potassium persulfate that adds 0.5 weight portion then, polyreaction was carried out about 7 hours at 80 ℃.Comprise the black polymer particle in the suspended matter (S1) by this emulsifier-free emulsion polymerization preparation, this polymer beads almost is monodispersed spheric grain, records by electron microscope method, and the equal diameter of the body of these spheric grain is 180 nanometers.The volumetric concentration of the dispersed substance particle in the suspended matter (S1) is 29%.

Embodiment 1

From suspended matter (S1), remove the impurity of unreacted monomer and emulsifying agent and so on, then suspended matter (S1) is carried out dialysis and handle, make its conductivity reduce to 400 μ S/cm by 4000 initial μ S/cm.It is 36% that the suspended matter that dialysis was handled is concentrated into volumetric concentration gradually.At this moment, the vertical direction visual experience to the color of solid-liquid aqueous colloidal dispersion (suspended matter) be green spectrum diffraction color.

Embodiment 2

The benzoyl peroxide of the MMA of 80 weight portions and 1.0 weight portions added in 1 liter the four neck flasks and form solution, encircle C.I Sclvent Black 27 black dyess of phenyl ether sodium sulfovinate emulsifier and 6.5 weight portions then to the polyoxyethylene of the water that wherein adds 200 weight portions, 3.3 weight portions, vigorous stirring is mixed them more.In this potpourri, add the suspended matter (S1) that the reference example 1 of 28.6 weight portions makes then.The potpourri that makes then 75 ℃ of reactions 1.5 hours, makes the suspended matter (S2) of polymer beads 50 ℃ of following gentle agitation 0.5 hour.Formed the polymer beads of black in the suspended matter that makes (S2), recorded according to electron microscope method, this particle is that the equal diameter of body is the monodisperse spherical particle of 200 nanometers.The volumetric concentration of solid is 21%.From this suspended matter, remove the impurity of unreacted monomer and emulsifying agent and so on, then suspended matter (S1) is carried out dialysis and handle, make its conductivity reduce to 400 μ S/cm by 4000 initial μ S/cm.It is 42% that the suspended matter that dialysis was handled is concentrated into volumetric concentration gradually.At this moment, the vertical direction visual experience to the color of solid-liquid aqueous colloidal dispersion (suspended matter) be red spectrum diffraction color.

Embodiment 3

Prepare suspended matter by the method identical, just conductivity is reduced to 100 μ S/cm by dialysis with embodiment 2.It is 38% that suspended matter is concentrated into volumetric concentration gradually.At this moment, the vertical direction visual experience to the color of solid-liquid aqueous colloidal dispersion (suspended matter) be red spectrum diffraction color.

Embodiment 4

Prepare suspended matter by the method identical with embodiment 2, just with MMA and MAA (weight ratio=90: 10) as monomer.The same impurity of removing from suspended matter carries out dialysis to suspended matter and handles, and makes its conductivity reduce to 400 μ S/cm by 3900 μ S/cm.It is 37% that suspended matter is concentrated into volumetric concentration gradually.At this moment, the vertical direction visual experience to the color of solid-liquid aqueous colloidal dispersion (suspended matter) be red spectrum diffraction color.

Embodiment 5

Prepare suspended matter by the method identical, just conductivity is reduced to 100 μ S/cm by dialysis with embodiment 3.It is 31% that suspended matter is concentrated into volumetric concentration gradually.At this moment, the vertical direction visual experience to the color of solid-liquid aqueous colloidal dispersion (suspended matter) be red spectrum diffraction color.Although it is 54% that suspended matter further is concentrated into volumetric concentration, red spectrum diffraction color still keeps stable.

Embodiment 6

The Ethylene glycol dimethacrylate of the MMA of 78 weight portions, 2 weight portions and the methacrylic acid of 15 weight portions-2-hydroxy methacrylate added in 1 liter the four neck flasks.Then to the dimethyl-2 of the benzoyl peroxide that wherein adds 0.5 weight portion, 1.0 weight portions, 2 '-azo is two-the C.I SolventBlack 27 of 2 Methylpropionic acid ester and 8 weight portions, form solution.Encircle the UNA-Na of phenyl ether sodium sulfovinate emulsifier and 0.1 weight portion then to the polyoxyethylene of the water that wherein adds 250 weight portions, 10 weight portions, vigorous stirring is mixed them more.In this potpourri, add the suspended matter (S1) that the reference example 1 of 40 weight portions makes then.The potpourri that makes is 50 ℃ of following gentle agitation 0.5 hour, then 78 ℃ of reactions 1.5 hours, and then 90 ℃ of ageings 1.5 hours, thereby make suspended matter.Be scattered here and there in the suspended matter that the makes polymer beads of black records according to electron microscope method, and this particle is that the equal diameter of body is the monodisperse spherical particle of 270 nanometers.The volumetric concentration of dispersed substance particle is 31% in the suspended matter.Suspended matter is carried out dialysis handle, make its conductivity reduce to 400 μ S/cm by 3900 μ S/cm, then, it is 37% that suspended matter is concentrated into volumetric concentration gradually.At this moment, the vertical direction visual experience to the color of solid-liquid aqueous colloidal dispersion (suspended matter) be blue spectrum diffraction color.

Comparative Examples 1

Prepare suspended matter by the method identical, just do not carry out dialysis and handle with embodiment 2.By the mode identical suspended matter is concentrated with embodiment 1.When the result reaches 38% when concentration, produce and assemble, therefore can not confirm colour developing.

Comparative Examples 2

The suspended matter that carried out colour developing among the embodiment 2 is carried out further concentrating, when the result reaches 50% when concentration, produce and assemble, be difficult to confirm colour developing.

Comparative Examples 3

Prepare suspended matter by the method identical, just do not carry out dialysis and handle with embodiment 4.Suspended matter is concentrated.Even the result does not still develop the color when concentration reaches 37 volume %.When concentration reaches 43%, produce and assemble, therefore can not confirm colour developing.

Comparative Examples 4

The suspended matter that carried out colour developing among the embodiment 4 is carried out further concentrating, when the result reaches 54% when concentration, produce and assemble, be difficult to confirm colour developing.

Reference example 2

The benzoyl peroxide of the MMA of 80 weight portions and 1.0 weight portions added in 1 liter the four neck flasks and form solution, encircle C.I Sclvent Black 27 black dyess of phenyl ether sodium sulfovinate emulsifier and 6.5 weight portions then to the polyoxyethylene of the water that wherein adds 200 weight portions, 3.3 weight portions, vigorous stirring is mixed them more.In this potpourri, add the dispersion (S1) that the reference example 1 of 28.6 weight portions makes then.The potpourri that makes 75 ℃ of reactions 1.5 hours, makes dispersion of polymer particles (S2) then 50 ℃ of following gentle agitation 0.5 hour.Comprise the polymer beads of black in the dispersion that makes (S2), record according to electron microscope method, this particle is that the equal diameter of body is the monodisperse spherical particle of 210 nanometers.The content of solid is 29.8%.

Reference example 3

The Ethylene glycol dimethacrylate of the MMA of 78 weight portions, 2 weight portions and the methacrylic acid of 15 weight portions-2-hydroxy methacrylate added in 1 liter the four neck flasks.Then to the dimethyl-2 of the benzoyl peroxide that wherein adds 0.5 weight portion, 1.0 weight portions, 2 '-azo is two-the C.I SolventBlack 27 of 2 Methylpropionic acid ester and 8 weight portions, form solution.Then to the water that wherein adds 250 weight portions, 10 weight portions polyoxyethylene encircle the UNA-Na of phenyl ether sodium sulfovinate emulsifier and 0.1 weight portion more, vigorous stirring is mixed them.In this potpourri, add the dispersion (S1) that the reference example 1 of 40 weight portions makes then.The potpourri that makes is 50 ℃ of following gentle agitation 0.5 hour, then 78 ℃ of reactions 1.5 hours, and then 90 ℃ of ageings 1.5 hours, thereby make dispersion of polymer particles.Comprise the polymer beads of black in the dispersion that makes, record according to electron microscope method, this particle is that the equal diameter of body is the monodisperse spherical particle of 270 nanometers.The content of solid is 31%.

Embodiment 7

Use suspended matter on the substrate of forming by smooth nylon substrates and bonding thereon nylon Web materials, to form the three-dimensional order lattice, wherein said suspended matter prepares by following steps: dispersion (S1) the preparation concentration of suspended particles that makes in the use reference example 1 is 30% emulsion, and spent ion exchange resin carries out desalination to this emulsion then; Has opening on the described nylon Web materials and is 60 microns, depth-width ratio and be 0.67 zanjon at interval.The vertical direction visual experience to the color of three-dimensional order lattice be clean purple.In addition, on sheet, do not observe with the naked eye any crackle.

Embodiment 8

Use suspended matter on the substrate of forming by glass substrate and bonding thereon the netted material of stainless steel, to form the three-dimensional order lattice, wherein said suspended matter prepares by following steps: using the equal diameter of body that makes in reference example 2 or the reference example 3 is that the black that has of 210 nanometers or 270 nanometers is that the monodisperse spherical preparation of granules concentration of suspended particles of colour killing is 38% emulsion, and spent ion exchange resin carries out desalination to this emulsion then; Has opening on the netted material of described stainless steel and is 150 microns, depth-width ratio and be 0.67 zanjon sept.The vertical direction visual experience to the color of three-dimensional order lattice be clean green or clean red.In addition, on sheet, do not observe with the naked eye any crackle.

Embodiment 9

Positive photoresist is applied on the glass substrate, and it is carried out prebake conditions, form the photoresist layer of 3 micron thickness.Make the photoresist layer exposure by mask pattern then, make the zanjon of 2 microns of 4 microns of furrow widths, depth-width ratio 0.75, bank wide (bank width) regularly arranged on in-plane at interval like this, then it is developed and the back baking, to form the colour developing substrate with photoresist.Then, using the equal diameter of body that makes in the reference example 3 is that the black of 270 nanometers is that the monodisperse spherical preparation of granules concentration of suspended particles of colour killing is 35% emulsion, and spent ion exchange resin carries out desalination to this emulsion then, makes suspended matter.Use this suspended matter to form the three-dimensional order lattice.The vertical direction visual experience to the color of three-dimensional order lattice be clean redness.In addition, on sheet, do not observe with the naked eye any crackle.

Embodiment 10

Add the emulsifying agent SDS of 0.02 weight portion and the polymerization initiator KP of 0.95 weight portion in the monomer solution of the MMA of 90 parts by weight of styrene and 10 weight portions, carrying out emulsion polymerization, to prepare the equal diameter of body be that 240 nanometers the single suspended matter that disperses white spheric grain (disperses concentration: 25%).Add acetone, black dyes (5), active emulsifier (1) and water then spheric grain is dyed black.Make the suspended matter that makes by semi-permeable diaphragm then, obtain representing to be about the static electrification lotus degree of 300 μ S/cm with conductivity.Then the solid-liquid suspension body is concentrated and make suspended matter (S4), the black spherical particle disperses with the concentration of about 40 volume % as dispersed substance in this suspended matter (S4).Then, use scraper (No. 2) on the glass plate of handling, to be coated with suspended matter (S4) with water wettability cementing agent SK Dyne 2094, form the base sheet of suspended matter (S4), at room temperature the base sheet is carried out drying, use the 100 weight portion fluorine monomers (acrylic acid perfluoro capryl ethyl ester) and the binder solution of 5 weight portion Photoepolymerizationinitiater initiaters that it is coated with then, carry out UV irradiation then and carry out polymerization and curing, thus the three-dimensional lattice of sealing and fixed black spherical particle.The three-dimensional order lattice that makes shows very clean green optical color under the irradiation of visible light.

Reflectance spectrum that obtains under the irradiation of ultraviolet light, visible light and infrared light and transmitted spectrum by Fig. 3-6 are readily appreciated that and can prepare the three-dimensional order lattice that can show clean colour and have the spherical particle of ultraviolet light reflection, infrared light reflection by " first preparation method " of the present invention.

(1) Fig. 3 shows when the three-dimensional order lattice of being made up of the specific spherical particle of organic polymer (adhesive seal product) that uses natural light or white light to " second preparation method " of the present invention preparation and carries out irradiation and the visible light feature reflectance spectrum that obtains, described spherical particle has the colour killing of black system, and the equal diameter of its body is 330 nanometers.Visual experience to colour be clean purple.

(2) Fig. 4 show when the ultraviolet light that uses wavelength to be no more than 400 nanometers be that the three-dimensional order lattice (adhesive seal product) that the specific spherical particle of organic polymer of 110 nanometers is formed carries out the ultraviolet light reflectance spectrum that irradiation obtains to " the 3rd preparation method " of the present invention preparation by the equal diameter of body.Described three-dimensional order lattice shows the ultraviolet light reflectivity properties brightly.

(3) Fig. 5 shows when what use that wavelength prepares " the 4th preparation method " of the present invention as the infrared light of 800-1500 nanometer to be that the three-dimensional order lattice (adhesive seal product) that the specific spherical particle of organic polymer of 350 nanometers is formed carries out the infrared light reflection spectrum that irradiation obtains by the equal diameter of body.It is that the infrared light of 800-1500 nanometer pair carries out the infrared transmission spectrum that irradiation obtains with top identical three-dimensional order lattice (adhesive seal product, sheet thickness: 20 microns) that Fig. 6 shows with wavelength.Can see that from these spectrum the three-dimensional order lattice has fabulous infrared light reflection character.

The accompanying drawing summary

Fig. 1 is the SEM photo of the three-dimensional order lattice surface particles array structure of the spherical particle for preparing of the present invention.

Fig. 2 is the SEM photo of particle array structure in the three-dimensional order patterned perpendicular cross section (with Surface Vertical) of the spherical particle for preparing of the present invention.

Fig. 3 has shown that the black of the present invention's preparation is the visible reflectance spectrum of the three-dimensional order lattice of colour killing spherical particle.

Fig. 4 has shown the ultraviolet light reflectance spectrum of the three-dimensional order lattice of the specific spherical particle that the present invention prepares.

Fig. 5 has shown the infrared light reflection spectrum of the three-dimensional order lattice of the specific shape particulate that the present invention prepares.

Fig. 6 has shown the infrared transmission spectrum of the three-dimensional order lattice of specific spherical particle shown in Figure 5 at region of ultra-red.

Claims

1. the mobile colloidal crystal that comprises the solid-liquid aqueous colloidal dispersion, described aqueous colloidal dispersion comprise the monodisperse spherical colloidal solid as dispersed substance, wherein:

Described spherical colloidal particle is that the equal diameter of body (d) is no more than 30 microns organic or inorganic polymkeric substance list dispersion dispersed substance spherical colloidal particle,

Described solid-liquid aqueous colloidal dispersion comprises and disperses concentration to be not less than 20 volume %, is not more than the dispersed substance of 70 volume %, and as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving,

Under the temperature that is not less than the dispersion medium solution solidifying point, representing to be no more than dispersed substance spherical colloidal particle in the solid-liquid aqueous colloidal dispersion of 2000 little Siemens/cm with conductivity around, static electrification lotus degree forms electrostatic double layer with specific thicknesses (Δ e),

Described dispersed substance spherical colloidal particle has formed the lattice of three-dimensional order, this lattice has flowability, it is a kind of particle array structure, spherical colloidal particle aligns at vertical and horizontal with form crystal lattice in this structure, is defined as along the grain spacing (L) of distance between the center of the relative particle of arranging of center line to satisfy relational expression (d)＜(L)≤(d)+2 (Δ e).

2. mobile colloidal crystal as claimed in claim 1, it is characterized in that, described dispersed substance spherical colloidal particle be have a kind of black that is selected from canescence, grey, grey black and black be the equal diameter of colour killing and body (d) for the organic or inorganic polymkeric substance list of 130-350 nanometer disperses specific spherical colloidal particle, the three-dimensional order lattice that comprises these particles shows clean spectrum diffraction colour under natural light or white light irradiation.

3. mobile colloidal crystal as claimed in claim 2 is characterized in that, the spectrum diffraction colour that visual experience arrives, and any below promptly color that right-angle view arrives on the surface of three-dimensional order lattice and grain spacing (L) satisfy in the relation (I) to (V):

(I) when L is the 160-170 nanometer, the colour that shows is clean purple (P),

4. mobile colloidal crystal as claimed in claim 1, it is characterized in that, described dispersed substance colloidal solid is that the equal diameter of body (d) disperses specific spherical colloidal particle for the organic or inorganic polymkeric substance list of 10-130 nanometer, the described three-dimensional order lattice that comprises these particles has the ultraviolet light reflectivity properties when being subjected to wavelength and being no more than the ultraviolet irradiation of 400 nanometers.

5. mobile colloidal crystal as claimed in claim 1, it is characterized in that, described dispersed substance colloidal solid is that the equal diameter of body (d) disperses specific spherical colloidal particle for the organic or inorganic polymkeric substance list of 350-800 nanometer, the described three-dimensional order lattice that comprises these particles has infrared light reflection character when being subjected to wavelength and being the infrared light irradiation of 800-1500 nanometer.

6. as each described mobile colloidal crystal in the claim 1 to 5, it is characterized in that described dispersed substance colloidal solid is the organic polymer spherical that at least a being selected from (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replace the polymkeric substance of (methyl) acrylic compounds-styrene polymer that (methyl) acrylic polymers and fluorine replace.

7. method for preparing the three-dimensional order lattice of spherical particle, this method comprises:

Preparation comprises the mobile colloidal crystal (S-1) of following component: as the organic or inorganic polymkeric substance monodisperse spherical colloidal solid of dispersed substance, the equal diameter of the body of particle (d) is not more than 30 microns; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; The dispersion concentration of wherein said colloidal solid is not less than 20 volume %, be not more than 70 volume %, under the temperature that is not less than the dispersion medium solution solidifying point, representing to be no more than dispersed substance spherical colloidal particle in the solid-liquid aqueous colloidal dispersion of 2000 little Siemens/cm with conductivity around, static electrification lotus degree forms electrostatic double layer with specific thicknesses (Δ e), described dispersed substance spherical colloidal particle forms the lattice of three-dimensional order, this lattice has flowability, it is a kind of particle array structure, spherical colloidal particle aligns at vertical and horizontal with form crystal lattice in this structure, be defined as along the grain spacing (L) of distance between the center of the relative particle of arranging of center line and satisfy relational expression (d)＜(L)≤(d)+2 (Δ e)

8. method for preparing the three-dimensional order lattice of spherical particle, this method comprises:

The base sheet of the suspended matter of (S-2) above forming then, and this base sheet is in the atmosphere that temperature is higher than the dispersion medium freezing point it is carried out drying, thus form longitudinally and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

9. method for preparing the three-dimensional order lattice of spherical particle, this method comprises:

10. method for preparing the three-dimensional order lattice of spherical particle, this method comprises:

Preparation comprises the mobile colloidal crystal (S-4) of following component: as the organic or inorganic polymkeric substance monodisperse spherical particulate of dispersed substance, the equal diameter of its body (d) is the 350-800 nanometer; And as the aqueous solution of dispersion medium or contain the non-aqueous solution of the water of dissolving; Wherein the dispersion concentration of dispersed substance is not less than 20 volume %, is not more than 70 volume %, and the conductivity of solid-liquid dispersion is not more than 2000 little Siemens/cm,

11. the method as the three-dimensional order lattice of each described preparation spherical particle in the claim 7 to 10 is characterized in that, bonding agent is for satisfying relational expression | the clear binder of nP-nB| 〉=0.05.

12. method as the three-dimensional order lattice of each described preparation spherical particle in the claim 7 to 11, it is characterized in that, the base sheet is formed on the supporting member, described supporting member is the Web materials of being made by stainless steel, fluororesin or nylon, this Web materials has zanjon at interval, this zanjon has the opening of 1-10 millimeter at interval, and depth-width ratio is 0.4-0.8.

13. method as the three-dimensional order lattice of each described preparation spherical particle in the claim 7 to 12, it is characterized in that described monodisperse spherical particulate is the organic polymer spherical that is selected from the polymkeric substance of (methyl) acrylic polymers of (methyl) acrylic polymers, (methyl) acrylic compounds-styrene polymer, fluorine replacement and (methyl) acrylic compounds-styrene polymer that fluorine replaces.

14. the method for the coated film of a three-dimensional order lattice for preparing spherical particle, this method comprises:

The plate that was coated with is in the atmosphere that temperature is higher than the dispersion medium solidifying point it is carried out drying, thereby form longitudinally onboard and the horizontal three-dimensional order lattice of regularly arranged spherical particle,

Apply or spray in polymerizable organic monomer solution, organic polymer soln and the solution of inorganic binder any then, fill the surface of three-dimensional order lattice and the gap between particles of three-dimensional arrangement, then it is carried out polymerization or curing, the three-dimensional order lattice of spherical particle is fixed as coated film.