JP2007126646A - Aqueous suspension-type particle dispersion for formation of continuous phase of three-dimensionally ordered particle association - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous suspension-type particle dispersion for the formation of a continuous phase of a three-dimensionally ordered particle association, wherein the three-dimensionally ordered particle association phase formed under dehydration by drying is fixed as a continuous layer free from cracks and peelings and to provide a coated phase being a printed phase, a written phase, or a transferred phase utilizing e.g., the color development characteristics of the three-dimensionally ordered particle association by using the same in an ink or as a coating component. <P>SOLUTION: The aqueous suspension-type particle dispersion for the formation of a three-dimensionally ordered particle association continuous phase is one wherein monodisperse spherical particles (A), such as an organic polymer of a volume-mean particle diameter of 130 to 1,000 nm, are contained in an aqueous dispersion in a dispersion concentration of 20 to 60 vol.%, and a hydrosol-type aqueous resin solution (B) of an acrylic polymer of Tg≤60°C is contained in an amount of 1 to 30 pts.mass (in terms of a solids content) per 100 pts.mass monodisperse spherical particles (A) dispersed in the aqueous dispersion having an electrical conductivity of 3,500 [μS/cm] or lower. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aqueous suspension type particle dispersion for forming a continuous phase of a three-dimensional particle matching body, and more specifically, a three-dimensional particle matching body phase of monodispersed spherical particles formed on a base substrate under dry dehydration. Relates to an aqueous suspension type particle dispersion for forming a continuous phase of a three-dimensional particle matched body that is fixed as a continuous phase in the two-dimensional direction without generating cracks, peeling, and the like.

  The present invention also provides a three-dimensional particle that is fixed on an underlying substrate as a coating phase such as a printing phase, a writing phase, or a transfer phase, using an aqueous suspension type particle dispersion exhibiting such characteristics as an ink and a coating component. It also relates to an aqueous coating material in which the continuous phase of the matching body develops a structural color based on the continuous phase of the three-dimensional particle matching body and / or gives a metallic luster or glossiness under visible light irradiation.

  Conventionally, a solid-liquid dispersion type suspension that disperses monodispersed spherical fine particles as a dispersoid is poured or applied onto a flat base member, and the suspended particles of the dispersoid are dried in a three-dimensional direction under drying. Various particulate laminates in which dispersoid spherical fine particles are regularly arranged in the vertical and horizontal directions by regular arrangement (or matching) have been proposed. By arranging the spherical fine particles regularly in this way, the particulate laminate is expected to have various surface characteristics that are exhibited in connection with various characteristics of the constituent particle material. In particular, if the constituent particle size is an ultrafine region such as submicron or nanosize, the surface characteristics that are exhibited by the surface of ultrafine particles become clearer, and new surface functions are exhibited. It is also expected as a functional material.

  Therefore, in recent years, for example, [Patent Document 1] proposes, in addition to the object color by a dye or pigment material such as a dye or a light source color such as a color television, in order to make the color sense as a color material. As described above, in a thin film in which monodispersed titanium oxide particles are deposited on a base material using a coloring material such as a pigment, the appearance color tone varies from red to blue depending on the particle size of the particles. Monodispersed monolayer and multilayer thin films of monodispersed titanium oxide having an interference color of 2 are proposed. In addition, a monodispersed titanium oxide thinning material whose appearance interference light color tone can be freely adjusted from red to blue based on its size by controlling the particle size of the monodispersed titanium oxide is described Has been.

  [Patent Document 2] describes a liquid repellency of a synthetic resin or the like having a lightness of 6 or less and a saturation of 8 or less in black or dark color in a standard color solid so that colored light due to interference can be clearly seen. On the surface of a transparent base layer, it is described that an adherent consisting of a regular periodic structure in which light-transmitting monodispersed solid fine particles are aggregated and arranged exhibits clear monochromatic light as light interference coloring. The non-colored solid fine particles constituting the deposit are monodispersed particles. Examples of such solid fine particles include inorganic oxide fine particles such as silica, alumina, titania, silica / alumina, titania / selenium, ) Organic polymer fine particles such as acrylic resin, styrene resin and olefin resin can be mentioned, and the number average particle diameter is described as being in the range of 100 nm to 1 μm.

  In [Patent Document 3], a solid-liquid suspension in which spherical monodisperse polymer particles having a diameter of 200 to 700 nm prepared by an emulsion polymerization method or the like are dispersed is subjected to dialysis treatment to substantially remove the electrolyte and dispersoid particles. A suspension formed by forming an electric double layer on the substrate is allowed to stand still and dried (at a temperature of 60 ° C.) to form a multilayer stacked ordered array structure composed of spherical monodisperse particles of an organic polymer, and then arranged. A method for producing a multilayer stacked ordered array structure in which particles in phase contact are chemically fixed is described.

  [Patent Document 4] has a zeta potential (absolute value) of 10 mV in which fine particles such as AlN, InSb, ZnS, etc., on which a substance having a functional group such as a hydroxyl group, silanol group, or carboxyl group is attached to the surface are dispersed. As described above, a colloidal crystal obtained by colloidal crystallization by dropping and drying a dilute dispersion solution having a conductivity of 300 [μS / cm] or less and a dispersion concentration of about 5 wt% on a glass plate (fine particles are arranged in a lattice pattern) 3D periodic structures) are described. In addition, an immobilized colloidal crystal obtained by containing a polymerizable vinyl monomer such as methyl methacrylate and vinyl acetate in the dilute dispersion solution, followed by colloidal crystallization, and then polymerizing to fix the colloidal crystal. Are listed.

  In [Patent Document 5], monodispersed spherical particles having a particle size in the range of 150 to 450 nm are dispersed in a concentration of 5 to 65% by weight (preferably a dispersion concentration of 20 to 55% by weight). In an aqueous suspension, a metal oxide having a size of about 10 to 50 nm or a colloidal species such as an organic polymer such as poly (methyl methacrylate) or poly (vinyl acetate) is added to the monodisperse spherical particles. Suspensions contained in the range of ˜25% by weight are described. The wet crystal layer obtained by applying this suspension on a flat substrate is dried, and particles having a milky white effect (regularly formed of thin-layer flaky crystals of monodispersed spherical particles obtained on the substrate in the form of flaky particles are formed. (Color pigments as three-dimensional structures arranged in the above).

JP 2001-206719 A JP 2001-239661 A Japanese Patent Laid-Open No. 04-213334 JP 2004-226891 A JP-T-2004-514558

  As described above, monodispersed spherical fine particles for forming a colloidal crystal (or a three-dimensional ordered array of monodispersed fine particles) as described in [Patent Document 1] to [Patent Document 5] described above are 5 to 5. Various aqueous suspensions in which a dispersion concentration of 55% is dispersed in a high dispersion concentration range have been proposed. Conventionally, a wet particle suspension aggregate phase (hereinafter referred to as a green sheet phase in the present invention) obtained by coating and forming such a suspension on a flat substrate is aggregated under drying and dehydration. Thus, it is well known that monodisperse fine particles are formed in a three-dimensional particle matching body (or three-dimensional particle crystal).

  However, as a technical problem that is difficult to solve from the past, a three-dimensional particle matched body phase formed by agglomerating monodispersed spherical particles suspended and assembled in a green sheet phase on a flat substrate under drying ( As a well-known fact from the past, the thin-film particle crystal phase tends to be technically difficult to be stably fixed as a continuous phase uniform in the two-dimensional direction.

  That is, as can be understood from the above [Patent Document 5], an immobilizing binder resin component is contained in advance in order to immobilize the three-dimensional particle matching body phase. However, in the three-dimensional particle matched body phase obtained on the substrate, innumerable cracks are generated and flakes are peeled off, so that the aggregate of monodispersed spherical particles is uniform in two dimensions. The actual condition is that it is difficult to form and fix as a continuous phase of the ordered structure.

  In addition, the green sheet phase having an appropriate thickness as described above usually forms a three-dimensional particle matching body by aggregating and suspending suspended particles by the capillary force of the dispersion medium water that evaporates as the drying and dehydration progresses. The dispersion medium phase interposed between the fine particles (or the same in the dispersion medium phase containing the binder resin component in advance) is difficult to maintain a uniform surface by drying and shrinking, and the shrinkage equivalent is cracked ( Or, it is generally left as a crack).

  Furthermore, conventionally, when a binder resin component is interposed in such a green sheet phase, the ordered arrangement of the three-dimensional particle matching body phase formed along with the progress of drying and dehydration is significantly inhibited. There was a tendency to remarkably reduce the color of the structural color exhibited under visible light irradiation related to the dimensional particle matched body.

  In addition, as the green sheet phase surface provided on the substrate is expanded in the two-dimensional direction, it is common that the expanded occupation surface is usually more frequently cracked to significantly inhibit the formation of the continuous phase. It was. Therefore, it is still satisfactory enough to form and fix a continuous phase of a three-dimensional particle matching body in a two-dimensional direction without causing cracks (or cracks) and separation in the three-dimensional particle matching body phase. It has not been reached.

  Accordingly, an object of the present invention is to provide an aqueous suspension-type castable particle dispersion containing monodispersed fine spherical particles at a high concentration on various base materials that are non-flexible or flexible or flexible. The green sheet phase cast or applied is not cracked (or cracked) or peeled off when dried or dehydrated, and the three-dimensional particle matched body phase is two-dimensionally oriented on the underlying substrate. It is intended to provide an aqueous suspension-type castable particle dispersion for fixing and forming a continuous phase of a three-dimensional particle matched body characterized by being fixed as a uniform continuous phase.

  Another object of the present invention is to use an aqueous suspension type castable particle dispersion for forming and fixing a continuous phase of a three-dimensional particle matched body that exhibits such characteristics as a coating material such as aqueous ink or aqueous paint. A three-dimensional particle matching body type coating phase composed of monodispersed spherical particles such as a printing phase, a writing phase, or a transfer phase is spontaneously fixed as a continuous phase of a three-dimensional particle matching body with no cracks (or cracks) and peeling. Without the inclusion of chromatic dyes, the chromatic light color is developed under visible light irradiation and / or the metallic luster or glossiness is reflected, reflecting the specific particle size of the monodispersed spherical particles. Another object of the present invention is to provide a three-dimensional particle matched body type aqueous coating material characterized by being a coating phase.

  As a result of intensive studies on the above problems, the present inventors have found that the black achromatic MMA-based monodispersed spherical particles having an average particle diameter of 190 nm have a higher concentration (40% on a volume basis) than the conventional one. An aqueous suspension was prepared which was dispersed in Next, after adjusting the electrical conductivity of this aqueous dispersion to 450 [μS / cm], a commercially available acrylic polymer hydrosol-type water-soluble resin liquid having a Tg of 35 ° C. is added to the aqueous suspension-type flow. A ductile particle dispersion was prepared. Next, this dispersion liquid was applied onto a PET film to form a green sheet phase, and when exposed to indwelling in a temperature atmosphere of about 50 ° C., a bright blue color was irradiated on the PET film under visible light irradiation. The present invention has been completed by finding that the structural hue that develops a chromatic color is stably fixed as a uniform continuous phase in the two-dimensional direction without causing any cracks and peeling.

  According to the present invention, a three-dimensional particle matching body phase in which monodispersed spherical particles formed under drying and dehydration are regularly arranged in a three-dimensional direction is completely in a two-dimensional direction on a base substrate. Provided is an aqueous suspension type particle dispersion for forming a continuous phase of a three-dimensional particle matching body, which is spontaneously fixed as a continuous phase of the three-dimensional particle matching body that does not cause cracking and peeling.

That is, the aqueous suspension type particle dispersion (or fluid particle dispersion viscous body or cast particle suspension) for forming a continuous phase of the three-dimensional particle alignment body according to the present invention is represented by the following (1) to (3). An aqueous suspension-type particle dispersion characterized in that it is described.
(1) In the aqueous suspension, the monodispersed spherical particles (A) of the organic polymer or inorganic polymer having an average particle diameter expressed by volume of 130 nm or more and not exceeding 1000 nm are 25% or more by volume, and 60% It is contained at a high dispersion concentration not exceeding%.
(2) Moreover, the electric conductivity of the aqueous suspension type particle dispersion is adjusted to 3500 [μS / cm] or less.
(3) Further, an acrylic polymer hydrosol-type water-soluble resin liquid (B) having a Tg ≦ 60 ° C. per 100 parts by mass of the dispersed monodispersed spherical particles (A) in the aqueous suspension dispersion. In the range of 1 to 30 parts by mass in terms of solid content.

In addition, according to the present invention, the aqueous suspension-type cast particle dispersion for fixing a continuous phase of a three-dimensional particle matched body that exhibits such characteristics is as described in (1a) to (3a) below. Utilizing the structural requirements, for example, as a structural color water-based ink or a structural color water-based paint, it is applied onto various non-flexible, flexible or flexible base materials (in the present invention, as already explained) Defined as a coating phase consisting of a continuous phase of a three-dimensional particle matching body including a printing phase, a writing phase, a transfer phase, etc.) and chromatic under visible light irradiation without containing any chromatic coloring pigment. Provided is a three-dimensional particle matched body type aqueous coating material characterized by developing a structural color and making a “glossiness” and / or a “metallic luster” under visible light irradiation.
That is,
(1a) The coating phase which is a wet green sheet phase obtained by printing, writing or transferring using a castable particle suspension in which aqueous suspension-type monodispersed spherical particles are dispersed at a high concentration is 20 to 60. A three-dimensional particle matching body phase is formed under drying and dehydration in an atmosphere at a temperature of 0 ° C., and is stably and spontaneously fixed as a uniform continuous phase without causing cracks and separation in the two-dimensional direction.
(2a) As the particle size characteristics of the black achromatic monodispersed spherical particles (A) suspended and assembled in the coating phase, the average particle diameter expressed on a volume basis is specified in the range of 130 to 310 nm, and the vertical line-of-sight direction It is fixed as a continuous phase of a three-dimensional particle matching body that develops a chromatic structural color and that gives a “glossiness” and / or “metallic luster” under visible light irradiation.
(3a) The surface of the three-dimensional particle matching body to be spontaneously fixed has fine uneven surfaces regularly arranged in a two-dimensional direction.

Furthermore, according to the present invention, the aqueous suspension type particle dispersion for forming a continuous phase of a three-dimensional particle matched body that exhibits such characteristics has the following structural requirements as described in (1b) and (2b) below. A three-dimensional particle characterized by having a “glossy feeling” and / or a “metallic luster feeling” reflected in the continuous phase of the three-dimensional particle matching body, although it does not make visible the structural color. Provided is a consistent-type aqueous coating material.
That is,
(1b) A coating phase which is a wet green sheet phase formed by printing, writing or transferring using a castable particle suspension in which aqueous dispersion type monodispersed spherical particles are dispersed at a high concentration is 20-60. The three-dimensional particle matched body phase formed under exposure drying / dehydration in a temperature atmosphere is stably fixed as a uniform continuous phase without causing cracks and peeling in the two-dimensional direction.
(2b) The monodispersed spherical particles (A) suspended and assembled in the coating phase are transparent non-colored spherical particles that make a white irregular reflection color visible under irradiation with visible light, and the average particle diameter exceeds 130 nm. By specifying in a range not exceeding 800 nm, the structural color is not developed, but “glossiness” and / or “metallic luster” based on the three-dimensional particle matched body phase is visually observed.
(3b) The surface of the three-dimensional particle matching body to be fixed has fine uneven surfaces arranged regularly in the two-dimensional direction.

  As described above, since the aqueous suspension type particle dispersion according to the present invention is a castable particle suspension, various non-flexible or flexible or flexible undercoats can be used as the aqueous ink member or the aqueous paint member. A coating phase that is a green sheet phase that is uniform in a two-dimensional direction can be formed by printing, writing, or transferring on the material.

Further, the aqueous suspension type particle dispersion according to the present invention is characterized by being constituted by the requirements described in the following (1c) to (3c), as already described above.
(1c) The monodispersed spherical particles (A) having an average particle size expressed by volume basis of 130 nm or more and not exceeding 1000 nm are contained at a high dispersion concentration not less than 25% and not exceeding 60% expressed by volume basis. Yes.
(2c) Moreover, the electric conductivity of the aqueous suspension dispersion is adjusted to 3500 [μS / cm] or less.
(3c) Further, in this aqueous suspension dispersion, an acrylic polymer hydrosol-type water-soluble resin liquid having a Tg ≦ 60 ° C. per 100 parts by mass of the monodispersed spherical particles (A) as the dispersed particles ( B) is contained in the range of 1 to 30 parts by mass in terms of solid content.

  The aqueous suspension-type particle dispersion according to the present invention is formed by applying a green sheet phase on various base materials according to the characteristic constituents described above, and the exposure phase is exposed to a temperature atmosphere of about 20 to 60 ° C. Under drying, monodispersed spherical particles (A) in a suspended and aggregated state are aggregated and aggregated, and a three-dimensional particle matching body is effectively formed without hindering regular self-arrangement in the three-dimensional direction.

  In addition, with the drying / dehydration progressing under such a drying heat history, a predetermined amount of the hydrosol-type water-soluble resin liquid (B) to be dispersed and contained as a gap material between the matching particles is the conventional method. Clearly, the green sheet phase exhibits a binder property without generating cracks and peeling, and the formed three-dimensional particle matching body phase is stably fixed as a uniform continuous phase in the two-dimensional direction.

In order to exert the above-described action, in the present invention, such a three-dimensional particle matched body is stably and spontaneously fixed as a uniform continuous phase without cracking and peeling in the two-dimensional direction. The monodispersed spherical particles exhibit visible light reflection characteristics in the continuous phase of the three-dimensional particle matched body, as described below, in relation to the particle characteristics.
(1d) When the particle characteristics of the monodispersed spherical particles (A) are black achromatic spherical particles, and the average particle diameter expressed by volume is 130 nm or more and does not exceed 310 nm, When the continuous phase is irradiated with natural light or white light in the visible light wavelength region of 380 to 780 nm, Bragg's reflection formula is applied to the face-centered cubic lattice (111) crystal plane of the three-dimensional particle matched body phase of this continuous phase. Colors the "primary light color" of vertical reflection that satisfies.
(2d) Further, this “primary light color” relates to the specified particle diameter of 130 to 310 nm, satisfies the angle dependence in Bragg's reflection formula, and, for example, red (R), green ( G), blue (B), and the like, a structural color having a spectral spectral coloration such as a monochromatic chromatic color is developed, and the surface of the continuous phase is “glossy” and / or “ A sense of “metallic luster”.
(3d) Further, in the present invention, the monodispersed spherical particles (A) have a particle characteristic of transparent non-colored spherical particles that make a white irregular reflection color visible under irradiation with visible light, and have an average particle diameter of 130 nm. If it is in the range not exceeding 800 nm, the particle characteristics and the structural characteristics of the three-dimensional particles are utilized, and the structural color is not perceived, but it is similarly based on the continuous phase of the three-dimensional particle matching body. “Glossy” and / or “Metal gloss”

  Hereinafter, embodiments of the aqueous suspension type particle dispersion for fixing a continuous phase of a three-dimensional particle matching body according to the present invention will be further described.

<Aqueous Suspension of Monodispersed Spherical Particles (A) Used in the Present Invention>
The monodisperse spherical particles (A) of the organic polymer or inorganic polymer having an average particle diameter expressed by volume of 130 nm or more and not exceeding 1000 nm used in the present invention have an electric conductivity of 3500 [μS as a solid-liquid dispersion. / Cm] or less aqueous suspension type particle dispersion. The dispersion concentration is suitably used as a high-concentration dispersion which is 20% or more expressed on a volume basis and does not exceed 60%. In addition, from the viewpoint of not reducing handling handling properties as a fluidity or casting property as a viscous high-concentration suspension, the dispersion concentration is preferably 30% or more and in a high concentration range not exceeding 50%. It can use suitably suitably.

  That is, in the present invention, the dispersion concentration of the spherical fine particles of the dispersoid particles that are monodisperse dispersed in the suspension thus adjusted is adjusted so as not to exceed 60% on a volume basis. It is preferable to do. When the dispersion concentration exceeds the upper limit of 60%, the dispersoid particles in the suspension are likely to form a group of particles that are randomly partially aggregated, and the regular alignment of particles that forms the three-dimensional particle matching body required by the present invention. In the tendency to significantly inhibit

  As a result, from the viewpoint of dispersion stability as a solid-liquid suspension and handling properties for handling the suspension, it is preferable to adjust the dispersion concentration to about 50% as the upper limit value. Further, the lower limit value is, for example, from the speed at which a particle matched body is formed by a drying method in the green sheet, and from the handling handling property of the suspension, the lower limit value is 20 to 25% or more, The three-dimensional particle matching body according to the present invention can be suitably and suitably prepared within a high concentration range of 30% or more and not exceeding 50%. As described in Japanese Patent Application Laid-Open No. 2005-60653, which has already been filed by the applicant of the present application, particularly when the concentration is low and does not satisfy the lower limit of 20%, the three-dimensional particles The ordered arrangement of the matching body is significantly lowered, and as a result, the structural color related to the three-dimensional particle matching body becomes difficult to be visually perceived (colored).

<Electrical conductivity of monodispersed spherical particles (A) aqueous suspension>
Further, since the electric conductivity of the aqueous suspension solid-liquid dispersion which is such a high-concentration dispersion is 3500 [μS / cm] or less, such aqueous suspension particles (or aqueous suspensions) are used. Depending on the manufacturing method for preparing the particles, the electrolyte concentration (expressed in volume concentration) in the suspension related to the organic and / or inorganic acid / base functional groups contained in the dispersion medium solution In the present invention, from the viewpoint of the three-dimensional particle consistency of the aqueous suspension particles, it is 3500 [μS / cm] or less, preferably 2500 [μS / cm] or less, more preferably 1500 [μS / cm]. cm] or less and can be suitably adjusted within a range of 300 [μS / cm] or more. In the present invention, in particular, even if the lower limit of 300 [μS / cm] is adjusted, the cost is simply increased, and in the present invention, from the viewpoint of three-dimensional particle consistency. There is no need. Further, in connection with this electric conductivity, in a particle suspension having an electric conductivity exceeding 3500-4000 [μS / cm], the regular arrangement of the three-dimensional particle matching body is remarkably deteriorated, so that it cannot be used in the present invention. .

<Aqueous Suspension Type Monodispersed Spherical Particles (A) Used in the Present Invention>
From the above, in the present invention, such an aqueous suspension-type organic polymer monodispersed spherical particle (A) is not necessarily limited to the organic polymers listed below. , Styrene, (meth) acryl-styrene, fluorine-substituted (meth) acryl, fluorine-substituted (meth) acryl-styrene, styrene-diene, acryl-imide, styrene-imide The organic polymer monodispersed spherical particles (A) can be suitably used as appropriate.

  Specific examples of the polymerizable organic monomer include, for example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate as acrylic monomers. , Butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid Nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid alkyl esters such as lauryl acrylate; (meth) acrylic acid phenyl; (meth) acrylic acid methoxyethyl, (meth) Ethoxyethyl acrylate, propoxyethyl (meth) acrylate, (meta (Meth) acrylic acid alkoxyesters such as butoxyethyl acrylate and ethoxypropyl (meth) acrylate; dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate; (meth) acrylamide; N-methylol (meth) acrylamide And (meth) acrylamides such as diacetone acrylamide and glycidyl (meth) acrylate; di (meth) acrylic acid ester of ethylene glycol, di (meth) acrylic acid ester of diethyl glycol, diacrylic acid (meth) ester of triethylene glycol , Polyethylene glycol di (meth) acrylic acid ester, dipropylene glycol di (meth) acrylic acid ester, tripropylene glycol di (meth) acrylic acid ester, etc. (Poly) di (meth) acrylate of alkylene glycol, may be mentioned (meth) (meth) acrylates of alicyclic alcohols cyclohexyl acrylate and the like.

  Examples of the fluorine-substituted acrylic monomer include trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-methacrylic acid-2-perfluoromethylethyl, ( (Meth) acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid-2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid dipar Fluorine-substituted (meth) acrylic acid monomers such as fluoromethylmethyl can be mentioned.

  Examples of the styrene monomer include alkyl styrene such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; Halogenated styrene such as styrene, chlorostyrene, bromostyrene, dibromostyrene, chloromethylstyrene; nitrostyrene, acetylstyrene, methoxystyrene, α-methylstyrene, vinyltoluene, and the like.

  Fluorine-containing vinyl monomers such as vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, capron Vinyl esters such as vinyl acrylate, vinyl persuccinate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl tert-butyl benzoate, vinyl salicylate; vinylidene chloride, vinyl chlorohexanecarboxylate, acrylic acid-2 -Chloroethyl, 2-chloroethyl methacrylate and the like.

  If necessary, examples of the monomer having a functional group include tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene- Examples thereof include unsaturated carboxylic acids such as 5,6-dicarboxylic acid, and derivatives thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept- 2-ene-5,6-dicarboxylic anhydride, and also vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methacrylamine, N-methylacrylamine, N, N-dimethyl Allyla such as acrylamide, N, N-dimethylaminopropyl acrylamide Amino group-containing ethylenic unsaturation such as 6-aminohexyl succinimide, 2-aminoethyl succinimide, etc. A monomer having a bond can be suitably used as appropriate.

  Examples of other polymerizable monomers in consideration of the heat resistance of the polymer material include, for example, acrylamide derivatives such as acrylamide and N-methylacrylamide, aminostyrenes such as p-aminostyrene, maleimide, and N-methylmaleimide. , N-phenylmaleimide, N-cyclohexylmaleimide, 6-aminohexyl succinimide, 2-aminoethyl succinimide, and the like, and butadiene having two polymerizable double bonds, isoprene, cyclopentadiene, Examples include dienes such as 1,3-pentadiene and dicyclopentadiene.

  In the present invention, it is not always necessary to form a cross-linked structure, but a cross-linked structure can be appropriately introduced from the viewpoint of increasing the mechanical strength of the formed polymer, if necessary. In order to form such a crosslinked structure, a polyfunctional monomer having two or more functionalities can be suitably used. As the polyfunctional monomer, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethanetri Examples thereof include acrylate, 1,1,1-trishydroxymethylpropane triacrylate, N-methylol acrylate, and the like.

  Therefore, spherical monodisperse fine particles of organic polymer dispersed in a solid-liquid dispersion suspension having the above-mentioned characteristics are generally used in soap-free emulsion polymerization, suspension polymerization, and emulsion polymerization system. Can be appropriately prepared.

  For example, in soap-free emulsion polymerization, a persulfate such as potassium persulfate or ammonium persulfate is usually soluble in an aqueous medium during polymerization as a polymerization initiator to be used. Usually, the polymerization initiator may be added in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the polymerization monomer.

  In the case of the emulsion polymerization method, an emulsifier such as an alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate or a polyethylene glycol alkyl ether such as polyethylene glycol nonylphenyl ether is usually added to 100 parts by mass of the polymerization monomer. .01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, mixed with an aqueous medium to give an emulsified state, and a polymerization initiator of a persulfate such as potassium persulfate or ammonium persulfate is used as a polymerization monomer of 100 parts by mass. 0.1 to 10 parts by mass, preferably 0.2 to 2 parts by mass with respect to parts.

  In addition, it is not necessary to particularly specify the above-mentioned emulsifiers including suspension polymerization, and it is selected from commonly used anionic surfactants, cationic surfactants or nonionic surfactants as necessary. These can be used alone or in combination. Examples of anionic surfactants include dodecyl benzene sulfonate, dodecyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, nonyl benzene sulfonate, sodium and potassium salts thereof, and cationic surfactants. Cetyltrimethylammonium promide, hexadecylpyridinium chloride, hexadecyltrimethylammonium chloride and the like, and nonionic surfactants include lipidinium and the like. Further, in order to obtain black resin particles for use in the present invention, for example, a black pigment containing a black oil-soluble dye or carbon black as a colorant in a mixed system of a polymerizable monomer, an emulsifier and water. Can be dispersed and mixed as appropriate.

  Therefore, a system containing water in the range of 200 to 350 parts by mass of water per 100 parts by mass of the monomer appropriately selected from the polymerizable monomers described above is exemplified by C.I. 5 to 10 parts by weight of a black dye such as I Solvent Black 27 is heated with stirring, then 0.05 to 0.7 of an emulsifier is added, and after sufficient stirring and mixing, a nitrogen purge is performed. The temperature is raised to 60-80 ° C. with stirring underneath. Next, a polymerization initiator such as potassium persulfate is added in the range of 0.3 to 0.6 parts by mass, and a polymerization reaction is performed at 70 to 90 ° C. for 4 to 8 hours. In the reaction dispersion liquid obtained by such soap-free emulsion polymerization, monodispersed spherical polymer particles having an average particle diameter expressed by volume in the range of 130 to 800 nm, or monodispersed spherical polymer particles in the range of 800 nm to 20 μm are contained. The solid concentration is 10 to 35% by weight.

  Further, among the monodispersed spherical particles used in the present invention, as described above, for example, spherical monodispersed particles colored in a black achromatic color are used as other additives in advance, for example, ultraviolet rays. Absorbers, near-infrared absorbers, antioxidants, fluorescent agents, dyes, pigments, charge imparting agents, antistatic agents, anti-sagging agents, antifoaming agents, various medicinal components, etc. may be added as appropriate to the particles. it can.

  In addition, these additives include the sphericalness, monodispersity of the dispersoid particles to be generated, the dispersibility in the suspension, or the three-dimensional particle consistency at the time of forming the three-dimensional particle matching body after forming the green sheet. As long as the above-mentioned additives are not inhibited, various functional agents or functional groups such as magnetic properties, conductivity, semiconductivity, and dielectric properties can be modified on the encapsulated or particle surface as necessary. .

  In the present invention, the water-dispersion-type inorganic polymer monodispersed spherical particles (A) are not necessarily limited to the following inorganic polymers. For example, silica, alumina, silica-alumina Any one kind of inorganic polymer particles selected from the group consisting of zirconia, titania, zirconia-silica, titania-silica, and titania-selenium can be suitably used.

  In particular, as inorganic polymer particles such as aluminum, zirconium, and titanium, inorganic polymer particles prepared by a metal alkoxide sol-gel method are suitably suitable because they are relatively easily colored in a black achromatic color using a dye / pigment. Used for. Examples of the metal alkoxide include aluminum ethoxide, aluminum triethoxide, isobutyl aluminum methoxide, isobutyl aluminum ethoxide, aluminum isopropoxide, isobutyl aluminum isopropoxide, aluminum butoxide, aluminum t-butoxide, and aluminum tri-n. Al alkoxide such as propoxide, aluminum tri-n-butoxide, tin t-butoxide, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-i-propoxy titanium, titanium methoxide, titanium Ti alkoxides such as ethoxide, titanium-n-propoxide, titanium isopropoxide, titanium-n-butoxide, titanium isobutoxide It may be mentioned zirconium ethoxide, zirconium -n- propoxide, zirconium isopropoxide, zirconium -n- butoxide, a Zr alkoxide such ethoxide tetra -n- propoxy zirconium. In the present invention, although not a metal element, similarly, as inorganic polymer particles, a sol-gel method of Si alkoxide such as methyltrimethoxysilane, vinyltrimethoxysilane, tetraethylsilicate, tetraisopropylsilicate, tetrabutylsilicate, etc. Prepared Si inorganic polymer particles are also used.

<Regarding the particle size of the monodispersed spherical particles (A) used in the present invention>
In the present invention, there is provided a chromatic structural color that the three-dimensional particle matching body phase develops under visible light irradiation, and a three-dimensional particle matching body that gives a feeling of glossiness and / or metallic luster under visible light irradiation. In relation to the particle diameter of the monodispersed spherical particles (A) of the organic polymer or inorganic polymer to be formed, as already described above, the following (1-a) And organic polymer or inorganic polymer monodisperse spherical particles (A) satisfying the particle constituent requirements as described in (2-b) can be suitably used.
(1-a) In particular, in the present invention, the monodispersed spherical particles (A) are any one type of black achromatic spherical particles selected from colorless black and black, and are expressed on a volume basis. The average particle size is in the range of 130 to 310 nm.
(2-b) Further, in the present invention, transparent non-colored spherical particles that give a white diffuse reflection color under visible light irradiation, and an average particle diameter expressed by volume thereof is in the range of 130 to 1000 nm, preferably, 800 nm or less.

<About the reflection color of the monodisperse spherical particles (A) used in the present invention>
Further, the white or black achromatic color described above in the present invention will be further described.
(1a) The white achromatic color is saturation = 0 (zero) expressed in the Munsell color chart, and the brightness is ≧ 10.
(2b) The black achromatic color is saturation = 0 and lightness is ≦ 0.
(3c) Further, in the present invention, the above-described saturation of 0, 0 <brightness <10, gray, preferably gray black or the like, can be treated as a black achromatic color.
(4d) Furthermore, the white achromatic color relating to the transparent non-colored particles in the present invention means that, in the case of transparent non-colored spherical particles having an average particle diameter of 100 nm to 1 μm, the dispersion system of the particles is usually used. Thus, the diffusely reflected color that is perceived under irradiation with visible light can be well understood because, for example, the reflected color that is perceived from a finely pulverized object of transparent glass is perceived as white.

<About the hydrosol-type water-soluble resin liquid (B) used in the present invention>
In the present invention, as already described, the three-dimensional particle matching body phase formed under drying / dehydration is formed and fixed stably as a continuous phase in the two-dimensional direction. In the aqueous suspension type particle dispersion of Tg ≦ 60 ° C., preferably Tg ≦ 35 ° C. per 100 parts by mass of the dispersed particles contained, and from the “stickiness” of the stationary continuous phase, the lower limit of Tg is The acrylic polymer hydrosol-type water-soluble resin liquid (B) having a Tg of 0 ° C. or higher and particularly preferably a lower limit of Tg of 10 ° C. or higher is in the range of 1 to 30 parts by mass, preferably 5 to 25 in terms of solid content. It is an aqueous suspension type particle dispersion contained in the range of parts by mass.

  In the present invention, the monodispersed spherical particles are added to an aqueous suspension having a high dispersion concentration of 25 to 60% on a volume basis, and an acrylic polymer hydrosol-type water-soluble resin (B) having a Tg ≦ 60 ° C. Is preferably from the viewpoint of not inhibiting fluidity and castability as a high-concentration suspension of an aqueous suspension type particle dispersion, and the resin solid content concentration is in the range of 25 to 30%, and the viscosity is 0.1 to It is a hydrosol-type resin viscous liquid that is 2 [Pa · s] / 25 ° C.

  Therefore, as the acrylic polymer hydrosol-type water-soluble resin (B) having the above-described characteristics used in the present invention, for example, an acrylic monomer having a Tg ≦ 60 ° C. is obtained by polymerizing or copolymerizing the acrylic monomers listed above. It can be suitably suitably prepared as a sol-type water-soluble resin which is an aqueous sol-type water-sol type water-soluble resin of a polymer and hardly contains a dispersion stabilizer such as a surfactant.

<Preparation of aqueous suspension-type castable particle dispersion according to the present invention> and <Continuous phase formation immobilization of three-dimensional particle matched body>
In the present invention, the hydrosol-type water-soluble resin liquid (B) having the characteristics as described above is dispersed and mixed in the aqueous suspension of the monodispersed spherical particles (A) having the characteristics as described above. An aqueous suspension type castable particle dispersion according to the present invention is prepared.
First, as already described above, monodispersed spherical particles (A) having the following characteristics (1) and (2), high-dispersion aqueous suspension-type particle dispersions (S- 1) and a particle dispersion (S-2) are prepared.
(1) The average particle diameter expressed on a volume basis is in the range of 130 to 310 nm, and the visible color of the particles is gray, gray-black, or black, and more preferably from the viewpoint of color development as a structural color. Among these, monodisperse spherical particles (A) of any one type of black achromatic organic polymer or inorganic polymer selected from gray black and black are particularly preferable.
(2) Or an organic polymer of white achromatic particles which is in a range where the average particle size expressed on a volume basis does not exceed 130 to 1000 nm, and is transparent and non-colored to make white diffuse reflection color visible under irradiation with visible light. Or it is the monodisperse spherical particle (A) of an inorganic polymer.

Next, the aqueous suspensions of the particle dispersion (S-1) and the particle dispersion (S-2) are each subjected to dialysis treatment, so that the aqueous conductivity is in the range of 3500 [μS / cm] to 300 [μS / cm]. Adjust to dispersion.
Subsequently, Tg ≦ 60 ° C. per 100 parts by mass of the monodispersed spherical particles (A) dispersed in these aqueous suspensions in the aqueous suspension type particle dispersion (S-1) and particle dispersion (S-2). The hydrosol-type water-soluble resin (B) of the acrylic polymer is 1 to 30 parts by mass in terms of solid content, preferably from 5 to 20 parts by mass from the viewpoint of fixability of the continuous phase and color development of the structural hue. The aqueous suspension-type particle dispersion according to the present invention is prepared by adding in a range.

  Next, using the aqueous suspension type particle dispersion according to the present invention thus prepared, in the present invention, a glass plate, a mortar plate, a ceramic plate, a plastic plate, a silicon wafer, a steel plate, a copper plate, an aluminum plate, an aluminum plate A predetermined amount of the castable particle dispersion is poured or applied (sprayed) onto any base material selected from an alloy plate, stainless steel plate, wood plate, fur sheet, fabric sheet, cardboard sheet, and plastic film group. Alternatively, printing (transfer) is performed to form a continuous phase green sheet phase having a predetermined thickness in a two-dimensional direction on these base substrates.

  Subsequently, these green sheet phases are exposed to a temperature atmosphere (20 to 60 ° C.) exceeding the freezing point of the dispersion medium in the green sheet phase and dried, and then the vertical and horizontal directions (three-dimensional directions) are formed on these base substrates. The three-dimensional particle matching body phase of the monodispersed spherical particles regularly arranged in () is fixedly formed as a continuous phase in the two-dimensional direction. In the present invention, such exposure and drying can be suitably performed even under a reduced pressure below atmospheric pressure.

  In the present invention, in the aqueous suspension type particle dispersion (S-1) and particle dispersion (S-2), the obtained three-dimensional particle matched body phase continuous phase is related to the structural color continuous phase. Therefore, the optical refractive index (nB) of the hydrosol-type water-soluble resin liquid (B) serving as an immobilizing resin component in the three-dimensional particle matched body phase continuous phase is the refractive index (nP) of monodispersed spherical particles. Unlikely, preferably, it is important to satisfy the relationship | nP−nB | ≧ 0.05 between the refractive indexes of the two. Deviating from this relational expression is not preferable because the color tone of the structural color is lowered and the structural color is hardly visible.

  In the present invention, a three-dimensional particle is provided by providing a topcoat phase, which is a transparent resin phase having an optical refractive index (nA), as necessary, on the three-dimensional particle matched body phase continuous phase thus obtained. For example, scratch resistance can be appropriately imparted to the matched body phase continuous phase. In the present invention, similarly, the optical refractive index (nA) is different from the refractive index (nP) of monodispersed spherical particles, and preferably, | nP−nA | ≧ 0. It is preferable to satisfy the relationship of 05.

  In the present invention, the green sheet phase coating phase formed on various base materials is conventionally known depending on the purpose of forming the coating phase, for example, a casting method, a brush coating method, a blade coater, Various coater methods such as an air knife coater, spraying method (or aerosil method), spin coating method, screen printing, ink jet method and the like can be appropriately selected and used suitably. Moreover, also in this invention, a transparent topcoat phase can be formed as needed.

<Use of aqueous suspension type particle dispersion according to the present invention>
From the above, the fixed continuous phase of the three-dimensional particle matching body provided on various base materials obtained using the aqueous suspension-type cast particle dispersion according to the present invention is the particle matching body surface of monodispersed spherical particles. The (001) particle matching body surface is provided as a continuous phase in the two-dimensional direction of the three-dimensional particle matching body phase in which several layers to several tens of layers are regularly stacked in the [001] direction of the c-axis direction that is the vertical direction. .

  Therefore, the fixed continuous phase member in the two-dimensional direction of the three-dimensional particle matched body formed using the aqueous suspension type particle dispersion according to the present invention is a black achromatic monodispersed spherical particle forming the continuous phase. As described above in detail, by specifying the average particle diameter on a volume basis in the range of 130 to 310 nm as described in detail, the homogeneity as a particle array structure can be effectively enhanced as a light interference effect, It is possible to provide a structural color type aqueous coating material that develops a remarkably clear reflection characteristic to develop a structural color.

<Three-dimensional particle-matched aqueous coating material>
That is, as already described, the aqueous suspension type particle dispersion that develops a structural color has a coating phase formed by printing, writing, or transferring as a main component of an aqueous ink or aqueous coating, and a three-dimensional particle matching body. The continuous phase develops a chromatic structural color under visible light irradiation. Further, the continuous phase gives a feeling of glossiness and / or metallic luster. Therefore, in the present invention, as such water-based ink (or water-based color developing material) and water-based paint, a glass plate, a mortar plate, a ceramic plate, a plastics plate, a silicon wafer, a steel plate, which is a printed or transferred material. , Copper plate, aluminum plate, aluminum alloy plate, stainless steel plate, wood board, fur sheet, fabric sheet, cardboard sheet, plastic film group, and any desired structural color pattern by applying on the base substrate The structural color characters can be printed or transferred to provide a printing phase or a coating phase that is a printing phase or a transfer phase. In the present invention, these base materials may be transparent, white or black achromatic, or chromatic colored, depending on the intended use of the base. Can also be used in a timely manner.

<Structural hue type water-based coating material; water-based ink, water-based paint>
Further, in the present invention, the monodispersed spherical particles (A) have an average particle diameter in the range of 130 to 310 nm expressed on a volume basis, and any one kind selected from gray black and black is not used. As already described in detail, when the colored organic polymer or inorganic polymer is monodispersed spherical particles (A), the printed phase, writing phase or transfer phase is a structural color of the three-dimensional particle matching body under visible light irradiation. It is possible to provide a structural hue type aqueous coating material that develops a chromatic light color as a continuous phase, and at the same time the glossy phase and / or metallic luster.

<A three-dimensional particle-matched phase-type aqueous coating material that imparts a metallic luster>
In the present invention, the monodispersed spherical particles (A) are transparent and non-colored white achromatic particles that make a white diffuse reflection color visible under irradiation with visible light, and the average particle diameter is 130 to 300 on a volume basis. A coating phase or a writing phase or a transfer phase obtained by printing, or writing, or inverting an aqueous suspension type castable particle dispersion for forming and fixing a three-dimensional particle matching body continuous phase in the range of 1000 nm as an aqueous coating material. The phase can provide an aqueous coating material of a three-dimensional particle-matched body phase type that gives a “feel of glossiness” and / or a “metallic luster” feeling under visible light irradiation.

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

Example 1
In this example, the monodispersed spherical particles (A) of the organic polymer dispersed in the aqueous suspension are black achromatic organic polymers having an average particle diameter expressed by volume of 250 nm.
90 g of MMA and 10 g of MAA were put in a flask and black dye C.I. 7.5 g of I Solvent Black 27, 0.8 g of sodium dodecylbenzenesulfonate emulsifier and 567 g of water were added and the temperature was raised to 72 ° C. Suspension in which black achromatic monodispersed spherical particles having an average particle diameter of 250 nm expressed on a volume basis having a negative charge are subjected to emulsion polymerization by adding 0.5 g of initiator KPS in a nitrogen atmosphere and having a dispersion concentration of 15% expressed on a volume basis Was prepared. Next, an aqueous suspension (S-1) having 40% by dialysis and concentration and an electric conductivity of 500 [μS / cm] was prepared. In this suspension (S-1), a commercially available hydrosol emulsion HD-3 (manufactured by Toa Gosei Co., Ltd.) (which is a hydrosol-type water-soluble resin (B) of acrylic polymer of Tg = 30 ° C.) is dispersed in the suspension. An aqueous suspension type particle dispersion (SS-1) for forming a three-dimensional particle matched body continuous phase according to the present invention by adding 10 parts by mass in terms of solid content per 100 parts by mass of the monodispersed spherical particles (A) Was prepared.
Next, this aqueous suspension type particle dispersion (SS-1) was applied at a phase thickness of 10 μmdry on a 50 μm thick transparent PET film previously coated with 3 μmdry of adhesive SK Dyne 2094 manufactured by Soken Chemical Co., Ltd. . Next, the green sheet phase applied on the base substrate of this PET film was dried in an atmosphere of 25 ° C. As a result, it was stably fixed on the base substrate as a continuous phase free from cracks and delamination in the two-dimensional direction of the three-dimensional particle matched body phase. Moreover, this continuous phase was able to perceive a clear chromatic structural hue.

(Example 2)
In this example, the monodisperse spherical particles (A) of the organic polymer dispersed in the aqueous suspension are a black achromatic organic polymer having an average particle diameter of 450 nm on a volume basis or a white organic polymer having a 650 nm.
In the same manner as in Example 1, a black achromatic organic polymer having an average particle diameter of 450 nm and a white organic polymer having an average particle diameter of 650 nm were dispersed at a concentration of 30% and 45%, respectively, and the electric conductivity was 1000 μS / cm. Aqueous suspensions (S-2) and (S-3) were prepared. Next, in the same manner as in Example 1, in the aqueous suspensions (S-2) and (S-3), a hydrosol emulsion HD-3 which is a hydrosol-type water-soluble resin (B) of an acrylic polymer having a Tg = 30 ° C. In the same manner as in Example 1, 10 parts by mass and 15 parts by mass were added in terms of solid content, respectively, to thereby form an aqueous suspension type cast particle dispersion (SS) for forming a three-dimensional particle matched body continuous phase according to the present invention. -2) and (SS-3) were prepared.
Subsequently, using this aqueous suspension type castable particle dispersion (SS-2) and (SS-3), the green sheet phase applied on the PET film base substrate was treated at 35 ° C. in the same manner as in Example 1. It dried under atmosphere and was stably fixed as a continuous phase in the two-dimensional direction of the three-dimensional particle matching body phase on the base substrate. As a result, these continuous phases are different from the first embodiment in that the structural colors that are perceived are not perceived at all in the vertical gaze direction, but a clear structural color reflected color is perceived in the tilted gaze direction.

(Example 3)
In this example, the organic polymer monodispersed spherical particles (A) dispersed in the aqueous suspension are transparent and non-colored so that a white irregular reflection color can be seen under irradiation with visible light having an average particle size expressed by volume of 290 nm or 580 nm. It is an organic polymer of spherical particles.
C. of black dye Except that I Solvent Black 27 was not used, the organic polymer of white achromatic particles having an average particle diameter of 290 nm and 580 nm, which were transparent and colorless, was dispersed at 26% and 50%, respectively, as in Example 1. Aqueous suspensions (S-4) and (S-5) having electrical conductivities of 1000 [μS / cm] and 450 [μS / cm], respectively, were prepared.
Subsequently, 10 parts by weight and 25 parts by weight of the hydrosol emulsion HD-3 are added in terms of solid content, respectively, and the aqueous suspension type particle dispersion (SS-4) for forming a three-dimensional particle matched body continuous phase according to the present invention and (SS-5) was prepared.
Next, in the same manner as in Example 1 using the aqueous suspension type particle dispersions (SS-4) and (SS-5), the green sheet phase applied on the PET film base substrate was subjected to a 40 ° C. atmosphere. It was made to dry and it was made to fix stably as a continuous phase without a crack and peeling generation | occurrence | production in the two-dimensional direction of a three-dimensional particle matching body phase, respectively on a base substrate. As a result, any of these continuous phases gives a vivid glossiness or metallic luster.

Example 4
In Example 3, 1% by mass of black carbon particles was dispersed in the aqueous suspension (S-4). Next, 10 parts by mass of the hydrosol emulsion HD-3 in terms of solid content was added to prepare an aqueous suspension type particle dispersion (SS-6) for forming a three-dimensional particle matched body continuous phase according to the present invention.
Next, in the same manner as in Example 1 using this aqueous suspension type particle dispersion (SS-6), the green sheet phase applied on the PET film substrate was dried in an atmosphere of 30 ° C. The material was stably fixed as a continuous phase free from cracks and delamination in the two-dimensional direction of the three-dimensional particle matched body phase. As a result, this continuous phase gave a vivid chromatic structural color.

(Example 5)
In this example, the monodispersed spherical particles (A) of the organic polymer dispersed in the aqueous suspension are transparent and uncolored organic polymers having an average particle size expressed by volume of 2.5 nm.
In the same manner as in Example 1, a transparent uncolored organic polymer having an average particle size of 2.5 nm was dispersed at a concentration of 30%, and a commercially available Bengala pigment was dispersed at a concentration of 5%, and the electric conductivity was 900 [μS / cm]] of aqueous suspension (S-6).
Next, in the same manner as in Example 1, 10 parts by mass of hydrosol emulsion HD-3 in terms of solid content was added, and the aqueous suspension type particle dispersion (SS-) for forming a three-dimensional particle matched body continuous phase according to the present invention was added. 7) was prepared.
Next, using this aqueous suspension type particle dispersion (SS-7), on the transparent glass base substrate on which the adhesive SK Dyne 2094 made by Soken Chemical Co., Ltd. was applied in advance at 3 μmdry in the same manner as in Example 1. The applied green sheet phase was dried in an atmosphere of 30 ° C., and stably fixed on the base substrate as a continuous phase free from cracking and peeling in the two-dimensional direction of the three-dimensional particle matching body phase. As a result, this continuous phase did not make the structural color visually perceived, but this continuous phase exhibited a bengara color with a metallic luster.

(Example 6)
In each of the aqueous suspension type particle dispersion (SS-1) prepared in Example 1 and the aqueous suspension type particle dispersion (SS-7) prepared in Example 5, commercially available aerosil silica was used as an anti-sagging agent. After adding 0.5 mass%, each was formed by spray coating (or aerosil coating) on a stainless steel base substrate previously coated with 3 μmdry of adhesive SK Dyne 2094 manufactured by Soken Chemical Co., Ltd. The sheet phase was dried in an atmosphere of 30 ° C. and stably fixed as a continuous phase in the two-dimensional direction of the three-dimensional particle matching body phase on the base substrate.
As a result, the same structural color and metallic luster as those of the continuous phases obtained in Example 1 and Example 5 were exhibited.

  As described above, according to the present invention, water-based color development that exhibits chromatic color related to structural color based on the aqueous suspension type cast particle dispersion for forming a three-dimensional particle matched body continuous phase in which monodispersed spherical particles are dispersed. It was possible to provide an aqueous coating material that imparts a metallic luster feeling related to the material and the three-dimensional particle matching body.

  That is, using the aqueous suspension according to the present invention, glass plate, mortar plate, ceramic plate, plastic plate, steel plate, copper plate, aluminum plate, aluminum alloy plate, stainless steel plate, wood board, fur sheet, fabric sheet, cardboard sheet, Various interiors, decorations, designs, and display materials that exhibit structural color, chromatic light, and metallic luster as optical characteristics by printing, transferring, and applying to various base materials such as plastic films It was possible to provide a coating-type three-dimensional particle matching body thin film material useful in the industrial field.

Claims (5)

An aqueous suspension type particle dispersion for forming a continuous phase of a three-dimensional particle matching body phase in which the three-dimensional particle matching body phase formed under dry dehydration is fixed as a continuous phase in a two-dimensional direction,
In the aqueous suspension, the monodisperse spherical particles (A) of the organic polymer or inorganic polymer having an average particle diameter expressed by volume of 130 nm or more and not exceeding 1000 nm are expressed by 20% or more and 60% by volume. Contained at a dispersion concentration not exceeding,
And per 100 parts by mass of the monodispersed spherical particles (A) dispersed in the aqueous suspension having an electric conductivity of 3500 [μS / cm] or less,
The hydrosol-type water-soluble resin liquid (B) of acrylic polymer having Tg ≦ 60 ° C. contains 1 to 30 parts by mass in terms of solid content, for forming a three-dimensional particle matched body continuous phase. Aqueous suspension type particle dispersion.   The monodispersed spherical particles (A) are gray or black black achromatic particles of an organic polymer or inorganic polymer having an average particle size expressed by volume basis of 130 nm or more and not exceeding 310 nm, and are formed in a two-dimensional direction. The continuous phase to be fixed is a structural hue that develops a monochromatic chromatic color under visible light irradiation, and the structural hue causes a sense of glossiness and / or metallic luster under visible light irradiation. The aqueous suspension type particle dispersion for forming a three-dimensional particle matched body continuous phase according to claim 1.   A transparent, non-colored white system in which the monodispersed spherical particles (A) have a mean particle diameter of 310 nm or more expressed by volume and have a white diffuse reflection color under visible light irradiation of an organic polymer or inorganic polymer not exceeding 800 nm. 2. The three-dimensional particle matched body continuous phase formation and fixation according to claim 1, wherein the continuous phase is an achromatic color particle and makes the glossy and / or metallic luster feel under visible light irradiation. An aqueous suspension type particle dispersion.   Using the aqueous suspension type particle dispersion for forming a three-dimensional particle matching body continuous phase according to claim 2, printing is performed on a base substrate that is a coating phase that is a printing phase, a writing phase, or a transferred phase. Or, the printed phase or the coated phase that is written or transferred, develops a chromatic structural color under irradiation with visible light, and gives a glossy feeling and / or metallic luster under visible light irradiation. A three-dimensional particle-aligned water-based coating material characterized by being visually sensed.   Using the aqueous suspension type castable particle dispersion for fixing and forming a three-dimensional particle matched body continuous phase according to claim 3, on a base substrate which is a coated phase as a printing phase, a writing phase or a transferred phase In addition, a three-dimensional particle matching characterized in that a printing phase or a writing phase or a coating phase that is a writing phase or a transfer phase that is printed or written or transferred causes a glossy feeling and / or a metallic luster feeling to be sensed under irradiation with visible light. Body-shaped aqueous coating material.