JP2008094861A - Aqueous particle dispersion for forming three-dimensional particle crystal phase, method for producing the same and use of three-dimensional particle crystal phase - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous particle dispersion of an organic polymer spherical particle for drying and dehydrating/heat-fusing a coating green sheet phase containing a fine spherical particle to form a three-dimensional particle crystal phase and a three-dimensional particle crystal continuous phase exhibiting various functions including structural color visibility by using the aqueous particle dispersion as a coating member. <P>SOLUTION: The aqueous particle dispersion for forming a three-dimensional particle crystal phase of an organic polymer spherical particle to visualize a structural color under irradiation with a visible light is obtained by impregnating 5-18 parts by mass of a hydrophilic polymer having a Tg<SB>2</SB>of ≤40°C into the vicinity of the surface phase of the organic polymer spherical particle of the fine spherical particle based on 100 parts by mass of a hydrophobic polymer which forms the organic polymer spherical particle in the dispersion concentration of ≥25% and ≤45% based on the mass basis and has a Tg<SB>1</SB>of ≥50°C in an aqueous particle dispersion so as to unevenly distribute the hydrophilic polymer and drying and dehydrating/heat-fusing the aqueous green sheet phase applied to a base material to mutually fusion bond the fine spherical particle in the three axial directions of X, Y and Z. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous particle dispersion for forming a three-dimensional particle crystal phase, and more specifically, an aqueous green sheet phase coated on a base substrate is subjected to cracking, The present invention relates to an aqueous particle dispersion of organic polymer spherical particles that forms a three-dimensional particle crystal continuous phase of monodispersed fine spherical particles with little occurrence of peeling or the like.

  Further, the present invention uses a three-dimensional particle crystal phase formed on a base substrate as a printing phase, a writing phase, a transfer phase, or the like, using an aqueous particle dispersion exhibiting such characteristics for ink and paint. The present invention relates to an aqueous coating material of a three-dimensional particle crystal phase type in which a structural color is developed under visible light irradiation, and the structural hue gives a feeling of glossiness and / or metallic luster.

  In the present invention, the three-dimensional particle crystal phase of the organic polymer spherical particles formed on the base substrate in this way is, for example, conductive, semiconductive, insulating, The present invention also relates to a functional three-dimensional grain crystal thin film material that reflects functional properties such as ferroelectricity, organic EL luminous properties, and organic nonlinear photoelectronic properties.

  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 [Patent Document 1], a light-transmitting monodispersed solid is provided on the surface of a liquid-repellent underlayer such as a synthetic resin that is black or dark so that colored light due to interference can be clearly seen. It is described that the deposit, which is a regular periodic structure in which 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 2], 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 3] has a zeta potential (absolute value) of 10 mV in which fine particles such as AlN, InSb, ZnS and the like having a functional group such as a hydroxyl group, a silanol group, and a carboxyl group 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.

  [Patent Document 4] discloses that monodispersed spherical particles having a particle size in the range of 150 to 450 nm are about 10 to 50 nm in size in an aqueous suspension having a dispersion concentration of 20 to 55% by weight. A suspension containing a metal oxide or a colloidal species such as poly (methyl methacrylate), organic polymer such as poly (vinyl acetate) in the range of 5 to 25% by weight with respect to the monodispersed spherical particles is described. Has been. 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).

  [Patent Document 5] discloses a colloidal crystal having a three-dimensional periodic structure formed by drying and dewatering an aqueous fine particle dispersion in which core-shell type fine particles having a core particle diameter of 50 nm to 10 μm are dispersed. Is described. In addition, the shell layer is formed by emulsifying, for example, a polymer cross-linked product of an acrylamide monomer such as acrylamide, methacrylamide, N-methyl methacrylamide or the like solvated in an aqueous dispersion system of polymer core particles having a core particle size of 50 nm to 10 μm It is formed by a polymerization method. Moreover, when the aqueous dispersion of core-shell layer type fine particles is dried and concentrated, excessive aggregation between the fine particles is prevented by the solvated shell layer, so that a finely packed structure can be easily obtained, and the three-dimensional cycle is relatively easy. A structure is formed. Further, it is also described that the shell layer is solvated so that the aqueous fine particle dispersion can be prepared at a relatively high concentration and can be suitably used for colloidal crystal formation.

JP 2001-239661 A Japanese Patent Laid-Open No. 04-0213334 JP 2004-226891 A JP-T-2004-514558 JP 2004-109178 A

  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 an aqueous green sheet phase) in which such a suspension is applied and formed on a flat substrate is aggregated under dry dehydration. Thus, it is well known that monodispersed fine particles are formed in a three-dimensional particle matching body.

  However, as a technical problem that is difficult to solve conventionally, three-dimensional particles obtained by drying and agglomerating monodispersed spherical particles contained in an aqueous green sheet phase coated on a base substrate under dry dehydration In the matching body phase (or thin film-like crystal phase), it is difficult to form a uniform continuous phase in the two-dimensional direction of the coating phase by causing cracks and peeling as well known facts. It is in.

  That is, as can be understood from the above [Patent Document 3], 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 base material, innumerable cracks are generated and flaking is generated in a flake shape, and the aggregate of monodispersed spherical particles is uniform in the two-dimensional direction. The reality is that it is difficult to form and fix as a continuous phase of a dimensional regular array structure.

  In addition, the aqueous green sheet phase having a thickness corresponding to the three-dimensional particle matching body is usually formed by aggregating and suspending suspended particles by the capillary force of the dispersion medium water that evaporates as the drying and dehydration progresses. To form. As a result, the dispersion medium phase intervening 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. Generally remain as cracks (or cracks).

  Furthermore, when a binder resin component is conventionally interposed in such a green sheet phase, the ordered arrangement of the three-dimensional particle matched body phase formed with the progress of drying and dehydration, that is, three-dimensional particle crystallinity is significantly inhibited. Let As a result, there was a tendency to remarkably reduce the color developability of the structural hue that develops color under irradiation with visible light based on the three-dimensional grain crystal phase.

  In addition, as the coated green sheet phase surface provided on the base substrate further expands the coating occupation surface in the two-dimensional direction, the formation of the continuous phase is remarkably difficult due to more frequent cracks. It was general. Therefore, conventionally, a continuous phase of a three-dimensional particle matching body is stably formed as a three-dimensional particle crystalline phase in a two-dimensional direction without causing cracks (or cracks) or separation in the three-dimensional particle matching body phase. To fix it, the reality is that it has not yet been fully satisfied.

  Accordingly, an object of the present invention is to disperse and contain monodispersed fine spherical particles in a high concentration on various base materials that are non-flexible, flexible, or flexible, and to disperse aqueous particles excellent in castability. The aqueous green sheet phase formed by pouring or coating the body does not cause any cracks (or cracks), peeling, etc. under dry dehydration, and is also formed on a base substrate. By providing an aqueous particle dispersion excellent in castability and coatability for forming a continuous phase of a three-dimensional particle crystal phase, wherein the phase is spontaneously fixed as a uniform continuous phase in a two-dimensional direction. is there.

Another object of the present invention is to use a water-based particle dispersion excellent in castability for forming and fixing a three-dimensional particle crystal phase exhibiting such characteristics for printing or writing using water-based ink or water-based paint. Alternatively, the coating phase of printing / writing / transfer of a three-dimensional particle crystal phase composed of monodispersed spherical particles formed by transfer is as follows:
(1) It is fixed spontaneously as a continuous phase with no cracks (or cracks) and no peeling,
(2) Moreover, without containing a chromatic dye, it is reflected in the particle diameter specified by the monodisperse spherical particles, and develops a chromatic color under visible light irradiation,
(3) In addition, a sense of glossiness and / or metallic luster is made visible under irradiation with visible light,
It is to provide an aqueous coating material of a three-dimensional particle crystalline phase type characterized by being a coating phase.

  In addition, a further object of the present invention is that the three-dimensional particle crystal phase of the organic polymer fine spherical particles formed on the base substrate is, for example, that the fine spherical particles themselves are conductive, semiconductive. By providing a functional three-dimensional grain crystal thin film material that exhibits any one of these functional characteristics when it has characteristic functions such as insulating properties, ferroelectric properties, organic EL light emitting properties, and organic nonlinear optoelectronic properties. is there.

As a result of intensive studies on the above problems, the present inventor used black achromatic MMA-based monodispersed spherical particles having an average particle diameter of 190 nm and a higher concentration (40% on a volume basis) than before. A dispersed aqueous suspension was prepared. Next, after preparing a water-dispersible aqueous particle dispersion having an electrical conductivity of 450 [μS / cm] for this aqueous dispersion system, this dispersion liquid was applied on a PET film to form a green sheet phase, As a result of being exposed to exposure in a temperature atmosphere of 100 ° C,
(1) The coated green sheet phase is a structural color body that develops a vivid blue chromatic color under visible light irradiation,
(2) The structural color body has almost no cracks or peeling,
(3) Furthermore, there is no feeling of powder falling off even when the coating phase is rubbed with a fingertip, that is, remarkably excellent in suspension.
(4) Moreover, the present invention has been completed by finding that it is stably fixed as a uniform continuous phase in the two-dimensional direction.

  According to the present invention, the aqueous green sheet phase applied and formed on the base substrate is dried, dehydrated and thermally fused, and the monodispersed fine spherical particles of the organic polymer contained in the green sheet phase are at least XYZ. Are fused (or fixed) to each other in the three-axis direction to form a three-dimensional grain crystal phase that is regularly arranged and fixed in the three-dimensional direction.

  Moreover, there is almost no cracking or peeling in the two-dimensional direction on the base substrate, and the coating phase is a continuous three-dimensional particle crystal with excellent “suspension” with no powder falling feeling. Provided is an aqueous particle dispersion excellent in casting and coating properties for forming a three-dimensional particle crystal phase characterized by being fixed as a phase.

That is, the aqueous particle dispersion for forming a three-dimensional particle crystal phase according to the present invention is as described in the following (1) and (2):
(1) In this aqueous fine particle dispersion, monodispersed organic polymer spherical particles (A) having a dispersion concentration of 25% or more and not exceeding 45% on a mass basis are the above-mentioned fixed fine spherical particles. The precursor particles are dispersed at a high concentration.
(2) The precursor particles have a hydrophilic polymer (P ₂ ) of Tg ₂ = 40 ° C. or less per 100 parts by mass of the hydrophobic polymer (P ₁ ) of Tg ₁ = 50 ° C. or more which is a resin component forming the precursor particles. ) Is “impregnated unevenly distributed” in the range of 5 to 18 parts by mass in the “surface phase vicinity of the precursor particles”.
This is an aqueous particle dispersion for forming a three-dimensional particle crystal phase.

  In addition, according to the present invention, the aqueous particle dispersion having such characteristics and excellent castability and coating property for forming a three-dimensional particle crystal phase is as described in the following (1a) to (3a). By making use of the structural requirements, for example, as a structural color water-based ink or a structural color water-based paint, it is applied on various non-flexible or flexible or flexible base materials (in the present invention, the printing phase or This means a coating consisting of a continuous phase of a three-dimensional particle crystal phase including the writing phase or the transfer phase.) The chromatic structure color is developed under irradiation of visible light without containing any chromatic dyes. Also provided is a three-dimensional crystalline particle phase type aqueous coating material characterized in that a “feeling of glossiness” and / or “feeling of metallic luster” can be observed under irradiation with visible light.

That is, as described in the following (1a) to (3a), the three-dimensional particle crystalline phase-type aqueous coating material according to the present invention,
(1a) The coating phase which is a wet green sheet phase formed by printing, writing or transferring using a castable particle suspension in which aqueous monodispersed spherical particles are dispersed at a high concentration is Tg ₂ + 50 ° C. or higher. dried dehydrated and heat-sealed under a temperature atmosphere below the melting point of ~ the hydrophilic polymer (P ₂₎ 3-dimensional particle-crystal of the continuous phase of an organic polymer spherical particles (a) is formed.
(2a) The continuous phase is hardly spontaneously cracked and peeled, and is stably and spontaneously fixed as a uniform continuous phase excellent in suspension.
(3a) Further, as the particle size characteristics of the black achromatic monodisperse organic polymer spherical particles (A) suspended and assembled in the coated green sheet phase, the average particle size expressed on a volume basis is in the range of 130 to 310 nm. As a continuous phase of a three-dimensional particle crystal that develops a chromatic structural color in the direction of the vertical line of sight, and gives a “glossiness” and / or “metallic luster” under visible light irradiation. Fixed spontaneously.

  Furthermore, according to the present invention, an aqueous particle dispersion excellent in castability for forming and fixing a continuous phase of a three-dimensional particle crystal phase that exhibits such characteristics is described in the following (1b) to (3b). The structural requirements of the above are utilized, and the structural color is not developed under visible light irradiation, but the “glossiness” and / or “metallic luster” that is also reflected in the three-dimensional particle crystal phase is visually observed. A three-dimensional grain crystalline phase-type aqueous coating material is provided.

That is, the aqueous coating material of the three-dimensional particle crystalline phase type according to the present invention, as described in the following (1b) to (3b),
(1b) A wet coated green sheet phase formed 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 Tg ₂ + 50 ° C. or higher. to an ambient temperature below the melting point of ~ the hydrophilic polymer (P ₂₎ and dried dehydrated and heat-sealing three-dimensional particle crystal phase in a continuous phase of an organic polymer spherical particles (a) is formed.
(2b) The continuous phase is stably and spontaneously fixed as a uniform continuous phase having excellent suspendability with little occurrence of cracking and peeling in the two-dimensional direction.
(3b) The monodisperse organic polymer spherical particles (A) suspended and assembled in the coating phase are transparent non-colored spherical particles that make white diffusely reflected color visible under irradiation with visible light, and the average particle size is By specifying a range exceeding 310 nm and not exceeding 800 nm, the chromatic structural color is not developed, but “glossiness” and / or “metallic luster” based on the three-dimensional particle crystal phase is visible. Is done.

Further, according to the present invention, an aqueous particle dispersion that exhibits such characteristics and forms a continuous phase of a three-dimensional particle crystal phase and that is excellent in castability is coated on a base substrate. The three-dimensional particle crystal phase of the thin fixed spherical particles obtained by drying, dehydrating and heat-sealing the green sheet phase is the organic polymer spherical particle (A) itself of the fixed fine spherical particles. In the case of such functional particles, a functional and functional three-dimensional grain crystal thin film material characterized by reflecting those functional characteristics is provided.
The functional characteristics of the fixed fine spherical particles are any one function selected from the group of, for example, electrical conductivity, semiconductivity, insulator properties, ferroelectric properties, organic EL luminescent properties, and organic nonlinear photoelectronic properties. It is functional organic polymer particle (A) which has a characteristic.

  Further, according to the present invention, the organic polymer spherical particles contained in the green sheet phase are obtained by drying and dewatering and heat-sealing the aqueous green sheet phase in which such an aqueous particle dispersion is coated on the base substrate. A three-dimensional particle crystal composed of organic polymer spherical particles (A), characterized in that a three-dimensional particle crystal phase composed of fine spherical particles in which (A) is fixed to each other in at least three XYZ directions. A method for producing a phase is provided.

That is, the method for producing a three-dimensional grain crystal phase according to the present invention includes the following (1C-step) to (5C-step):
(1C-step): To a predetermined amount of the aqueous phase, Tg ₁ after polymerization polymerization is equal to or higher than 50 ° C., and the hydrophobic monomer (m ₁ ) having a Tg _{2 of} 100 g by mass is similarly converted to Tg ₂ after polymerization polymerization = 5-18 parts by mass of hydrophilic monomer (m ₂ ) having a temperature of 40 ° C. or less, a polymerization initiator and an emulsifier are added and emulsified and suspended.
(2C-step); Next, after a predetermined amount of an aqueous seed particle dispersion using an organic polymer prepared in advance as seed particles is added, seed emulsion polymerization is performed while raising the temperature to 65 to 80 ° C.
(3C-step): The obtained organic polymer spherical particles (A) are precursor particles of fine spherical particles that are fused (or fixed) to each other in at least three XYZ directions. 100 parts by weight per _Tg 1 = 50 ° C. or more hydrophobic polymers that form the resin component _{(P 1),} Table phase vicinity of the precursor particles, _Tg 2 = 40 ℃ or less of the hydrophilic polymer _{(P 2} ) In a range of 5 to 18 parts by mass.
(4C-step); Next, for example, it is washed and concentrated using a cross-flow washing apparatus, and the dispersion concentration is 25 to 45% expressed on a weight basis, and the electric conductivity of the aqueous particle dispersion system is 3500 [μS / cm] or less, an aqueous particle dispersion (AS) of organic polymer fine spherical particles is prepared.
(5C-step); Next, using this aqueous particle dispersion (AS), the aqueous green sheet phase coated on the base substrate was converted to Tg ₂ + 50 ° C. or higher to the melting point of the hydrophilic polymer (P ₂ ). Dry dehydration and heat fusion are performed at a temperature lower than that to form a three-dimensional particle crystal phase composed of fixed fine spherical particles of organic polymer spherical particles (A).

From the above, the characteristics of the aqueous particle dispersion that forms the three-dimensional particle crystal phase of the organic polymer spherical particles (A) provided by the present invention are:
(1c) Monodispersed organic polymer spherical particles (A), which are precursor particles of fixed fine spherical particles, are contained at a high dispersion concentration of 25 to 45% on a mass basis.
(2c) The resin component forming the precursor particles is a hydrophobic polymer (P ₁ ) having a Tg _{1 of} 50 ° C. or higher, and this “near surface phase portion of the precursor particles” per 100 parts by mass of the resin component. Is an aqueous particle dispersion of organic polymer spherical particles (A) in which the hydrophilic polymer (P ₂ ) having a Tg _{2 of} 40 ° C. or less is “impregnated unevenly distributed” in the range of 5 to 18 parts by mass.
(3c) The aqueous green sheet phase obtained by applying the aqueous particle dispersion having the above characteristics onto the base substrate is dried and dehydrated at a predetermined temperature of Tg ₂ + 50 ° C. or higher and lower than the melting point of the hydrophilic polymer. -By heat-sealing, in the vicinity of the surface phase of the precursor particles regularly arranged three-dimensionally, impregnated unevenly distributed Tg ₂ = 40 ° C. or less hydrophilic polymer (P ₂ ), at least XYZ The three-dimensional grain crystal phases are effectively formed by being fixed to each other in the three axial directions.

In addition, the three-dimensional particle crystal phase according to the present invention is almost free from cracks and exfoliation in the two-dimensional direction, and the continuous phase of the three-dimensional particle crystal phase is related to the particle characteristics of the monodisperse spherical particles forming the three-dimensional particle crystal phase. Irradiation with natural light or white light in the visible light wavelength region of 380 to 780 nm causes the following visible light reflection characteristics.
(1d) The particle characteristics of the organic polymer spherical particles (A) are black achromatic spherical particles, and the average particle diameter expressed on a volume basis is in the range of 130 to 310 nm. A “primary light color” of vertical reflection that satisfies Bragg's reflection formula is developed on the crystal plane of the center cubic lattice (111).
(2d) Furthermore, this “primary light color” relates to a specific particle diameter of 130 to 310 nm, satisfies the angle dependence in Bragg's reflection formula, and as spectral spectral color development, for example, red (R), green (G) In addition, a continuous monochromatic chromatic color spectral color such as blue (B) is developed, and this continuous phase is "glossy" and / or "metallic luster" under visible light irradiation. Make you feel.
(3d) The organic polymer spherical particles (A) are transparent and non-colored spherical particles that give a white diffuse reflection color under visible light irradiation. The specific particle diameter is 310 to 800 nm. Although the structural color of the chromatic color is not made visible, this continuous phase gives a “glossiness” and / or a “metallic luster” under the visible light irradiation.

  Further, the characteristic aqueous particle dispersion as described above is applied as a castable particle suspension, as a water-based ink member or a water-based paint member, onto various non-flexible or flexible or flexible base materials. Printing, writing, or a transfer image having the structural hue of the engineered green sheet phase can be made visible.

  Furthermore, the three-dimensional particle crystal phase of the organic polymer spherical particle (A) according to the present invention is used as the thin film-like three-dimensional particle crystal phase of the fine spherical particle of the organic polymer spherical particle (A). The spherical particles (A) are composed of organic polymer spherical particles having any one of the functional properties selected from the group consisting of electrical conductivity, semiconductivity, insulator properties, ferroelectric properties, organic EL luminous properties, and nonlinear photoelectron properties. A functional three-dimensional grain crystal thin film material can be provided.

  Hereinafter, embodiments of the aqueous particle dispersion for forming a three-dimensional particle crystal phase according to the present invention will be further described.

<Aqueous particle dispersion of organic polymer spherical particles (A) used in the present invention>
(1e) The monodisperse organic polymer spherical particles (A) having an average particle diameter represented by volume used in the present invention of at least 130 nm and not exceeding a few μm are as the inventor's conventional knowledge, Preferably, it is used as an aqueous particle dispersion having an electric conductivity of 3500 [μS / cm] or less as a solid-liquid dispersion from the viewpoint of three-dimensional regular arrangement under dry aggregation.
(2e) Further, the dispersion concentration is preferably suitably used as a high concentration dispersion which is 25% or more on a volume basis and does not exceed 45%.
(3e) Further, from the viewpoint of not reducing the dispersion stability and handling properties as an aqueous particle dispersion as the fluidity or castability as a viscous high-concentration suspension, the dispersion concentration is preferably 30. % Can be suitably used in a high concentration range of 40% or less.
(4e) At a dispersion concentration exceeding the upper limit of 45%, the dispersoid particles in the aqueous suspension are likely to form a group of particles that are randomly partially aggregated, and particles that form the three-dimensional particle crystal phase required by the present invention. This is not preferable because it tends to significantly hinder the regular alignment of the above.
(5e) Further, the lower limit value is 25% from the speed at which a particle matched body is formed in the aqueous green sheet, for example, and the handling property of the aqueous particle dispersion. The above is suitably suitable.

<Electrical conductivity of aqueous particle dispersion according to the present invention>
Further, such aqueous suspension particles (or aqueous suspension particles) are prepared in connection with the electric conductivity of the aqueous particle dispersion system which is such a high-concentration dispersion being 3500 [μS / cm] or less. Depending on the production method, 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 is expressed in terms of electric conductivity in the present invention. Is 3500 [μS / cm] or less, preferably 2500 [μS / cm] or less, more preferably 1500 [μS / cm] from the viewpoint of forming a three-dimensional particle crystal phase of aqueous suspension particles. Below, it can adjust suitably suitably in the range of 200 [microS / cm] or more.

<“3-dimensional particle crystallinity” of aqueous particle dispersion and its “aqueous suspension particle phase diagram”>
Furthermore, in the present invention, in relation to such a castable aqueous particle dispersion, the state of monodispersed spherical particles suspended and dispersed in an aqueous medium is changed to a “random dispersed particle” state region and “three-dimensional”. Clearly associating the “three-dimensional particle consistency” of the “aqueous suspension particles” in such a state region with the formation of any state of the “regularly arranged particles” state region and the “random aggregated particle” state region can do. In the present invention, as shown in the attached [FIG. 1], the “aqueous suspension particle” state is evaluated as follows in relation to the “suspension characteristics” of the aqueous suspension type cast particle dispersion according to the present invention. can do.

That is, the “three-dimensional particle consistency” of the “aqueous suspension particle” of this aqueous monodispersed spherical particle is expressed by “the suspension concentration” as the “suspension characteristic” value and “the electric conductivity (or ion concentration or charge). As shown in the attached [FIG. 1], as shown in the attached [FIG. 1], the following (a) to (d) are appropriately associated as suspended particle phase diagrams showing the respective particle aggregation regions and particle dispersion regions. Can do.
(A) Crystalline region: Suspended particles in the aqueous suspension phase form a regularly arranged suspended phase as a three-dimensional particle matching body for visualizing the structural color.
(B) Coexistence region: The aqueous suspension phase coexists with the particle ordered array suspension phase (a) and the particle random dispersion phase in which the suspended particles are randomly dispersed.
(C) Dispersion zone: all suspended particles are in a random dispersion state.
(D) Aggregation zone: all suspended particles randomly form aggregated groups.

  As a result, in the present invention, the aqueous suspension-type particle dispersion in the “crystal region” has the “suspension concentration” and “the electric conductivity” having the suspension characteristics described in the above paragraphs [0035] to [0038]. As a useful aqueous suspension color developing member for visualizing the structural color as an aqueous suspension particle, it can be suitably used in various industrial fields.

  However, as in the present invention, the suspended aggregate particles in the green sheet phase formed by coating on the base substrate using the aqueous suspension type cast particle dispersion are exposed in a dry atmosphere, and 3 In the case of forming a particle ordered array as a two-dimensional particle matching body as a continuous phase in the two-dimensional direction, the detailed reason is unknown, but in the above-mentioned “crystal region” already in a three-dimensional particle matching state as an aqueous suspension. It is preferable that the aqueous suspension type cast particle dispersion in the above-mentioned “coexistence region” is superior to a certain aqueous suspension type particle dispersion. It is suitably used as an aqueous particle dispersion having an aqueous suspension type casting property and coating property that exhibits “

  That is, in the case of an aqueous suspension type particle dispersion in the “coexistence zone” state, the three-dimensional particle matching body (or three-dimensional particle crystal) formed in the coating phase coated on the base substrate is For example, a polycrystalline phase exhibiting a substantially single crystal plane is formed along the two-dimensional plane of the coating phase. On the other hand, when the aqueous suspension type particle dispersion in the “crystal region” state is applied, it tends to be a polycrystalline phase exhibiting a plurality of crystal faces.

<Formation crystal plane and its reflection characteristics>
Therefore, when an aqueous suspension-type castable particle dispersion in the “coexistence zone” state as in the former is applied, a structure that can be seen from the three-dimensional particle crystal phase formed and fixed on the base substrate As for the hue, the interference reflection surface of irradiated visible light is formed from substantially the same crystal plane, and the reflected light color is strengthened, and a vivid structural color without color unevenness is developed in the two-dimensional direction.

  On the other hand, when the aqueous suspension type particle dispersion in the “crystal region” state as described above is applied, the structural hue perceived from the three-dimensional particle crystal continuous phase formed and fixed on the base substrate The interference reflection light consists of a plurality of different crystal planes, and causes a color unevenness in the structural hue to be perceived. Further, since the crystal plane formed along the two-dimensional direction plane has a plurality of crystal planes, the three-dimensional particle matched body continuous phase has monodisperse organic polymer spherical particles (A ) Is difficult to exert evenly in the two-dimensional direction.

<Particle size of 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 size of the monodispersed spherical particles (A) of the organic polymer to be formed, as already described above, in the range of the average particle size of 130 to 1000 nm expressed on the volume basis, the particle constituent requirements as described below are satisfied. Filled organic polymer monodisperse spherical particles (A) [Organic polymer spherical particles (A) already described. ] Can be suitably used as appropriate.
(1f) In particular, in the present invention, the monodispersed spherical particles (A) are any one kind of black achromatic spherical particles selected from gray-black and black without color, and are average particles expressed on a volume basis. The diameter is in the range of 130-310 nm.
(2f) Further, in the present invention, transparent non-colored white achromatic particles for visualizing white irregularly reflected color under visible light irradiation, preferably having an average particle size in a range of 130 to 1000 nm on a volume basis. Is 310 nm or more and 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.
(1g) The white achromatic color is saturation = 0 (zero) expressed in the Munsell color chart, and the brightness is ≧ 10.
(2g) Further, the black achromatic color is saturation = 0 and lightness is ≦ 0.
(3g) Further, in the present invention, the above-mentioned saturation of 0, 0 <brightness <10, gray, preferably gray-black, etc., can be treated as black achromatic colors.
(4g) Furthermore, in the present invention, the white achromatic color relating to the transparent non-colored particles 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.

<Organic polymer spherical particles (A) and production method thereof according to the present invention>
From the above, the organic polymer spherical particles (A) contained in the aqueous green sheet phase coated on the base substrate according to the present invention are dried, dehydrated and heat-sealed to obtain three-dimensional particle crystals of fine spherical particles. It is characterized by forming a phase. The organic polymer spherical particles (A) are monodisperse organic polymer spherical particles (A) that are precursor particles of fine spherical particles that are crystallized three-dimensionally under dry dehydration and heat fusion. Thus, it can be suitably suitably prepared as a high-concentration aqueous particle dispersion in the range of 25 to 45% expressed on a weight basis.

<Organic polymer spherical particles (A) according to the present invention>
The organic polymer spherical particles (A) formed in the aqueous emulsified suspension system have Tg ₁ = 50 ° C. or higher, preferably Tg ₁ = 60 ° C. or higher, after polymerization polymerization, which has already been described in detail, and more preferably Is formed as a hydrophobic polymer (P ₁ ) composed of a hydrophobic monomer (m ₁ ) with Tg ₁ = 80 ° C. or higher. Such organic polymer spherical particles (A) according to the present invention are precursor particles of fine spherical particles fixed in the heat-sealed three-dimensional particle crystal phase, and are similarly applied to 100 parts by mass of the precursor particles. Hydrophilic polymer (P ₂ ) composed of a hydrophilic monomer (m ₂ ) with Tg ₂ = 40 ° C. or less after polymerization, preferably Tg ₂ = 20 ° C. or less, more preferably Tg ₂ = 10 ° C. or less However, in the range of 5 to 18 parts by mass, the precursor particles are characterized by being impregnated unevenly in the vicinity of the surface phase of the organic polymer spherical particles (A). Moreover, in the present invention, the glass transition temperature (Tg), which is the thermal characteristic, is always in a relationship of Tg ₁ > Tg ₂ in order to form the heat-fused three-dimensional particle crystal phase at a predetermined temperature. Is an important feature.

<Preparation of aqueous particle dispersion for forming three-dimensional particle crystal phase in which organic polymer spherical particles (A) according to the present invention are dispersed>
<Production of three-dimensional particle crystal phase of organic polymer spherical particles (A) formed on base substrate>
(1C-Step 1): To a predetermined amount of aqueous phase, Tg ₁ after polymerization and polymerization is a hydrophobic monomer (m ₁ ) having a temperature of 50 ° C. or higher, and the Tg after polymerization is similarly converted per 100 parts by mass. ₂ = 5-18 parts by mass of a hydrophilic monomer (m ₂ ) of 40 ° C. or less, a polymerization initiator and an emulsifier are added and emulsified and suspended.
(1C-Step 2); Further, in the present invention, for preparing the black achromatic organic polymer spherical particles (A) used in the present invention, for example, mixing with a polymerizable monomer, an emulsifier and water. A black dye / pigment containing a black oil-soluble dye or carbon black as a colorant in a water phase is dispersed or mixed as appropriate.
That is, 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 (m ₁ ) and (m ₂ ) described above is exemplified by C.I. 5 to 10 parts by mass of a black dye such as I Solvent Black 27 is heated with stirring, and then 0.05 to 0.7 parts by mass of an emulsifier is added and emulsified and suspended.
(2C-step); Then, after adding a predetermined amount of an aqueous seed particle dispersion using a pre-prepared organic polymer as a seed particle, the temperature is raised to 65 to 80 ° C. to carry out seed emulsion polymerization. That is, the spherical monodisperse fine particles of the organic polymer are appropriately prepared by a commonly used emulsion polymerization system such as soap-free emulsion polymerization or suspension polymerization.
(3C-step): The obtained organic polymer spherical particles (A) are precursor particles of fine spherical particles that are fused (or fixed) to each other in at least the three axial directions of XYZ described above. The hydrophilic polymer (P ₂ ) of Tg ₂ = 40 ° C. or lower contains 5 to 5 parts per 100 parts by mass of the hydrophobic polymer (P ₁ ) of Tg ₁ = 50 ° C. or higher in the vicinity of the surface phase of this precursor particle. It is formed so as to be unevenly distributed in the range of 18 parts by mass.
(4C-step); Next, for example, by washing and concentrating using a cross-flow washing apparatus, the electric conductivity of the aqueous particle dispersion system is 3500 [μS at a dispersion concentration of 25 to 45% expressed on a weight basis. / Cm] or less, an aqueous particle dispersion (AS) of organic polymer fine spherical particles is prepared.
(5C-step); Next, using this aqueous particle dispersion, the aqueous green sheet phase coated on the base substrate is subjected to a temperature of Tg ₂ + 50 ° C. or higher to the melting point of the hydrophilic polymer (P ₂ ). A three-dimensional particle crystal phase composed of the above-mentioned fixed fine spherical particles is formed by drying and dehydrating and heat-sealing. In the present invention, such dry dehydration can also be suitably performed even under a reduced pressure below atmospheric pressure.

From the above, the organic polymer formed by drying and dewatering and heat-sealing the aqueous green sheet phase formed on the base substrate and fixing the organic polymer spherical particles contained in each other at least in the three-axis directions of XYZ The characteristics of the aqueous particle dispersion that forms the three-dimensional particle crystalline phase of the spherical particles (A) are:
(1) Monodispersed organic polymer spherical particles (A), which are precursor particles of fixed fine spherical particles, are contained at a high dispersion concentration of 25 to 45% on a weight basis.
(2) The resin component that forms the precursor particles is a hydrophobic polymer (P ₁ ) having a Tg _{1 of} 50 ° C. or higher, and this “near surface phase portion of the precursor particles” per 100 parts by mass of the resin component. The hydrophilic polymer (P ₂ ) having a Tg _{2 of} 40 ° C. or less is “impregnated unevenly” in the range of 5 to 18 parts by mass.
(3) The electric conductivity of the aqueous particle dispersion system in which the precursor particles are dispersed at a high concentration is adjusted to 3500 [μS / cm] or less.

An aqueous green sheet phase obtained by coating the aqueous particle dispersion having such characteristics on various base substrates is at a temperature below Tg ₂ + 50 ° C. to less than the melting point of the hydrophilic polymer (P ₂ ). Through the hydrophilic polymer (P ₂ ) of Tg ₂ = 40 ° C. or less that is impregnated unevenly in the vicinity of the surface phase of the precursor particles that are dry-dehydrated and heat-sealed and are three-dimensionally regularly self-aligned, It is characterized in that it is fixed to each other at least in the XYZ triaxial directions to effectively form a three-dimensional grain crystal phase.

Further, in the present invention, as already described, the hydrophilic monomer that becomes the hydrophilic polymer (P ₂ ) used in combination with the hydrophobic monomer (m ₁ ) that is the hydrophobic polymer (P ₁ ) of Tg ₁ = 50 ° C. or higher. (M ₂ ) is suitably used as long as Tg ₂ = 40 ° C. or less of the polymer. In the present invention, from the viewpoint of making the fusion (or fixing) progress more instantaneously, It is more preferable to use a hydrophilic monomer (m ₂ ) that becomes a hydrophilic polymer (P ₂ ) with Tg ₂ = 20 ° C. or lower, more preferably Tg ₂ = 10 ° C. or lower.

  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. 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, mixed with an aqueous medium to make an emulsified state, and a polymerization initiator of a persulfate such as potassium persulfate or ammonium persulfate is added to 100 parts by weight of a polymerization monomer. 0.1 to 10 parts by 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.

<Hydrophobic monomer (m ₁ ) used in the present invention>
In the present invention, examples of the hydrophobic monomer (m ₁ ) include methacrylic monomers; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, Acrylic acid alkyl esters such as hexyl methacrylate and 2-ethylhexyl methacrylate; dialkylaminoalkyl methacrylates such as diethylaminoethyl methacrylate; methacrylamide; methacrylamides such as N-methylolmethacrylamide and diacetoneacrylamide; and glycidyl methacrylate; Dimethacrylic acid ester, diethylene glycol dimethacrylic acid ester, triethylene glycol dimethacrylic acid ester, Examples include (poly) alkylene glycol dimethacrylates such as propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, and tripropylene glycol dimethacrylate.

  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. Further, acrylic acid esters of alicyclic alcohols such as cyclohexyl acrylate, methacrylic acid esters of alicyclic alcohols such as cyclohexyl methacrylate, and the like can be given.

<Hydrophilic monomer (m ₂ ) used in the present invention>
In the present invention, the hydrophilic monomer (m ₂ ) is particularly preferably MA (methyl acrylate), MEA (methoxyethyl acrylate), 4HBA (4-hydroxybutyl acrylate), 3HPA (hydroxypropyl acrylate), for example. ) And a hydrophilic monomer selected from the group of 2HEA (2-hydroxyethyl acrylate).

<Functional organic polymer and functional organic compound used in the present invention>
In the present invention, without being limited to the organic polymer described above, as the organic compound capable of forming monodisperse spherical fine particles in an aqueous phase system, for example, the following (A ₁₎ according to _~ (A ₅₎ The organic polymer having such a function and the organic monomer compound thereof are suitably used as functional organic polymer spherical particles (A) of the organic polymer. Alternatively, for example, when preparing host particles of organic polymer spherical particles (A) such as PMMA, these functional organic polymers and monomer compounds thereof are previously contained as functional guests, and the PMMA host particles are then functional organic polymers. The spherical particles (A) are suitably used as appropriate.

(A ₁ ) Organic EL polymer and monomer compound thereof: polyvinylcarbazole (PVK), polyphenylene, polyphenylene vinylene (PPV), Cyano-PPV, MEH-PPV, poly [2-methoxy, 5- (2 ′) -Ethylhexoxy) -1,4-phenylenevinylene], poly (3-alkylthiophene) and the like.
(A ₂ ) Ferroelectric polymer and monomer compound thereof; P (VDF-TrFE), P (VDF-TeFE), trifluoride ethylene and / or a copolymer of vinylidene fluoride (VDF) and ethylene trifluoride Polyethylene vinylidene copolymer (PVDF), vinylidene fluoride (VDF) and tetrafluoroethylene copolymer, vinylidene fluoride (VDF) and vinyl fluoride copolymer, vinylidene fluoride (VDF) ), Tetrafluoroethylene and hexafluoropropylene copolymer, polyvinylidene cyanide, vinylidene cyanide and vinyl acetate copolymer, and the like. Semiconducting polymer; polypyrrole, polythiophene, polyparaphenylene, polyalkylpyrrole, polyalkthiophene, oligopyrrole, oligothiophene, etc. can be mentioned.
(A ₃ ) conductive polymer and monomer compound thereof; polyaniline, polypyrrole, polythiophene-based [3,4-polyethylenedioxythiophene, poly (3-hexyl) thiophene, poly (3-octyl) thiophene, poly (3-dodecyl) And polymers of thiophene and their derivatives], polythiophene vinylene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene and the like. In particular, doping is performed with a donor type dopant of an alkali metal such as Li, Na, or K, or an alkaline earth metal such as Ca.
(A ₄ ) Semiconductive polymer and monomer compound thereof; as π-conjugated compound, thiophene, vinylene, chelenylene vinylene, phenylene vinylene, p-phenylene, a substituted unit thereof, or a repeating unit of two or more of these And an oligomer having an n number of 4 to 10, a polymer having an n number of 20 or more, a condensed polycyclic aromatic compound such as pentacene, and a condensed ring tetracarboxylic acid diimide.
_{(A 5)} organic nonlinear compound; p-nitroaniline, 2-methyl-4-nitroaniline, merocyanine dyes, anthraquinone compounds, p- nitroanilide, benzimidazole derivatives, hydrazine derivatives, hydrazone derivatives, oxadiazole derivatives, including N heterocyclic compounds, N-containing five-membered ring compounds, stilbene derivatives, diaminobenzene derivatives, N, N′-bis- (4-nitrophenyl) -methanediamine and the like can be mentioned.

  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.

  In addition, as described above, the monodispersed organic polymer spherical particles (A) used in the present invention include, for example, black pigments that are colored in an achromatic color, and inhibit monodispersity or heat-fusibility. As long as there is no such thing as inhibiting other additives, for example, UV absorbers, near-infrared absorbers, antioxidants, fluorescent brighteners, dyes, pigments, charge-imparting agents, antistatic agents are used as necessary in advance. An agent, an anti-sagging agent, an antifoaming agent, and the like can be appropriately added to the organic polymer spherical particles (A).

  Further, in the present invention, the coating phase that is an aqueous green sheet phase to be coated on various base materials is conventionally known depending on the purpose of forming the coating phase, for example, a pouring method, a brush coating method, etc. Various coater methods such as blade coater and air knife coater, spray method (or aerosil method), spin coat method, screen printing and ink jet method can be appropriately selected and used suitably.

<Use of aqueous particle dispersion and three-dimensional particle crystal phase 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 three-dimensional particle alignment body formed by using the aqueous suspension-type cast particle dispersion according to the present invention has a fixed continuous phase member in the two-dimensional direction. The black achromatic monodisperse that forms the continuous phase. As already explained in detail, as the particle size characteristics of the spherical particles, by specifying the average particle diameter expressed on a volume basis within the range of 130 to 310 nm, it can be efficiently enhanced as the light interference effect by the homogeneity as the particle array structure. Thus, 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 water-based coating material>
That is, the aqueous suspension type castable particle dispersion that develops a structural color is a three-dimensional particle having a coating phase that is printed, written, or transferred as a main component of a water-based ink or water-based paint, as already described. A continuous phase of the matching body, which 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 ceramic plate, a plastic plate, Desired structure by coating on any base substrate selected from wafer, steel plate, copper plate, aluminum plate, aluminum alloy plate, stainless steel plate, wood board, fur sheet, fabric sheet, cardboard sheet, plastic film group Color designs and / or structural color letters 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 organic polymer spherical particles (A) have an average particle diameter in a range of 130 to 310 nm on a volume basis, and any one kind selected from grayish black and black 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. A chromatic light color is developed as a continuous phase, and the colored phase can provide a structural hue type water-based coating material that gives a sense of glossiness and / or metallic luster at the same time.

<Three-dimensional particle crystalline phase-type aqueous coating material imparting metallic luster>
In the present invention, the organic polymer 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 expressed on a volume basis from 130 to 300. A coating phase or a writing phase or a transfer phase obtained by printing, or writing, or inverting the aqueous suspension type castable particle dispersion for fixing and forming a three-dimensional particle matching body continuous phase in the range of 800 nm as an aqueous coating material. The phase can provide an aqueous coating material of a three-dimensional particle matching body phase type that visually (or imparts) “feeling of glossiness” and / or “feeling of metallic luster” under visible light irradiation.

<Functional three-dimensional particle crystalline phase type functional aquatic coating material>
In the present invention, the organic polymer spherical particles (A) are functional particles of a transparent polymer such as PMMA containing an organic EL polymer, a ferroelectric polymer, a semiconductive polymer, a conductive polymer and an organic nonlinear optical compound. By using the aqueous particle dispersion, the organic EL can be excellent in carrier mobility on various base materials, in particular, ferroelectricity (piezoelectricity, pyroelectricity) excellent in flexibility, semiconductivity and conductivity and In particular, it is possible to provide a functional three-dimensional particle crystal thin film material that exhibits non-linear optoelectronic properties related to laser light.

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

(Example 1)
<Tg ₂ ; hydrophilic monomer (m ₂ ) = 4HBA>
MMA100g was put into the flask, 0.1g of emulsifier sodium dodecylbenzenesulfonate and 567g of water were added, and it heated up at 72 degreeC. Suspension (S-1) having a dispersion concentration of 15% expressed on a volume basis, with monodisperse spherical particles having an average particle size of 123 nm expressed on a volume basis by adding 0.5 g of ammonium persulfate as a polymerization initiator under a nitrogen atmosphere and performing emulsion polymerization Was prepared.
Next, 30 g of MMA, 30 g of ethylene glycol dimethacrylate, 10 g of 4-hydroxybutyl acrylate (4HBA), 5 g of methacrylic acid, 1.5 g of benzoyl peroxide (BPO), 3.3 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.), sodium nitrite 0.05 g and 259 g of water were put in a flask and emulsified with a homomixer at 9000 rpm for 10 minutes, and then 166 g of S-1 was added.
The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. The temperature was further raised to 85 ° C. to complete the polymerization reaction.
This was concentrated and washed with a cross flow washing apparatus to prepare an aqueous particle dispersion (C-1) according to the present invention having a dispersion concentration of 29.9% and an electric conductivity of 280 [μS / cm]. The obtained dispersed particles, ie, the organic polymer spherical particles (A) according to the present invention had a particle diameter of 198 nm and were very highly monodispersed.

(Example 2)
<Tg ₂ ; hydrophilic monomer (m ₂ ) = MA>
32.5 g of MMA, 30 g of ethylene glycol dimethacrylate, 20 g of methyl acrylate (MA), 5 g of methacrylic acid, 1.5 g of BPO, 3.3 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.), 0.05 g of sodium nitrite and 329 g of water are added to the flask. The mixture was emulsified with a homomixer at 9000 rpm × 10 minutes, and 83 g of S-1 was added. The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. The temperature was further raised to 85 ° C. to complete the polymerization reaction.
This was concentrated and washed with a cross flow washing apparatus to prepare an aqueous particle dispersion (C-2) according to the present invention having a dispersion concentration of 29.8% and an electric conductivity of 225 [μS / cm]. The obtained organic polymer spherical particles (A) according to the present invention had a particle size of 244 nm and were very highly monodispersed particles.

(Example 3)
<Tg ₂ ; hydrophilic monomer (m ₂ ) = MEA>
Flask containing 37.2 g of MMA, 30 g of ethylene glycol dimethacrylate, 10 g of methoxyethyl acrylate (MEA), 5 g of methacrylic acid, 1.5 g of BPO, 3.3 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.), 0.05 g of sodium nitrite, and 300 g of water And emulsified with a homomixer at 9000 rpm for 10 minutes, and 118 g of S-1 was added. The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. The temperature was further raised to 85 ° C. to complete the polymerization reaction.
This was concentrated and washed with a cross flow washing apparatus to prepare an aqueous particle dispersion (C-3) according to the present invention having a dispersion concentration of 30.4% and an electric conductivity of 257 [μS / cm]. The obtained organic polymer spherical particles (A) had a particle size of 220 nm and were very highly monodispersed.

(Comparative Example 1)
<Tg ₂ ; No hydrophilic polymer (P ₂ )>
40 g of MMA, 30 g of ethylene glycol dimethacrylate, 5 g of methacrylic acid, 1.5 g of benzoyl peroxide (BPO), 3.3 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.), 0.05 g of sodium nitrite and 259 g of water are placed in a flask. After emulsification at 9000 rpm × 10 minutes with a mixer, 166 g of S-1 was added. The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. The temperature was further raised to 85 ° C. to complete the polymerization reaction.
This was concentrated and washed with a cross-flow washing apparatus, prepared with a dispersion concentration of 29.6% and an electric conductivity of 275 [μS / cm] without using a hydrophilic monomer (m ₂ ) corresponding to Tg ₂ . An aqueous particle dispersion (H-1) was prepared. This suspension had a particle diameter of 202 nm and was very highly monodispersed.

(Comparative Example 2)
<Tg ₂ ; hydrophilic polymer (P ₂ ) is hydrophobic polymer>
Flask containing 30 g of MMA, 30 g of ethylene glycol dimethacrylate, 10 g of lauryl methacrylate, 5 g of methacrylic acid, 1.5 g of benzoyl peroxide (BPO), 3.3 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.), 0.05 g of sodium nitrite, and 259 g of water And emulsified with a homomixer at 9000 rpm for 10 minutes, and then 166 g of S-1 was added. The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. The temperature was further raised to 85 ° C. to complete the polymerization reaction.
This is concentrated and washed with a cross-flow washing apparatus, and a water-based particle having a dispersion concentration of 31.0%, an electric conductivity of 323 [μS / cm], and a polymer (P ₂ ) corresponding to Tg ₂ is a hydrophobic polymer A dispersion (H-2) was prepared. The dispersed particles had a particle size of 199 nm and were very highly monodispersed.

(Comparative Example 3)
<Tg ₂ ; equivalent hydrophilic monomer (m2) is 4 parts of HBA>
MMA 37 g, ethylene glycol dimethacrylate 30 g, 4-hydroxybutyl acrylate (4HBA) 3 g, methacrylic acid 5 g, benzoyl peroxide (BPO) 1.5 g, New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.) 3.3 g, sodium nitrite 05 g and 259 g of water were put in a flask and emulsified with a homomixer at 9000 rpm for 10 minutes, and then 166 g of S-1 was added. The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. The temperature was further raised to 85 ° C. to complete the polymerization reaction.
This was concentrated and washed with a cross flow washing device to prepare an aqueous suspension (H-3) having 29.5% and electric conductivity of 276 [μS / cm]. The particle diameter of this suspension was 192 nm, and the particles were very highly monodispersed.

(Comparative Example 4)
<Tg ₂ ; equivalent hydrophilic monomer (m2) is 4 parts of HBA>
20 g of MMA, 30 g of ethylene glycol dimethacrylate, 20 g of 4-hydroxybutyl acrylate (4HBA), 5 g of methacrylic acid, 1.5 g of benzoyl peroxide (BPO), 3.3 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.), sodium nitrite 05 g and 259 g of water were put in a flask and emulsified with a homomixer at 9000 rpm for 10 minutes, and then 166 g of S-1 was added. The mixture was heated to 50 ° C. while stirring, and after 20 minutes, further heated to 75 ° C. and polymerized for 1 hour. Further, the temperature was raised to 85 ° C. to complete the polymerization reaction, but no organic polymer spherical particles were obtained.

The base material on which the aqueous particle dispersion in which the organic polymer spherical particles prepared in Examples 1 to 3 and Comparative Examples 1 to 3 are dispersed is previously applied with 3 μmdry of adhesive SK Dyne 2094 manufactured by Soken Chemical Co., Ltd. On a black PET film having a thickness of 50 μm, an aqueous green sheet phase having a layer thickness of 10 μmdry was formed.
Next, the coated aqueous green sheet phase on the PET substrate was dried in an atmosphere at 25 ° C. At this time, the color development as a structural color perceived under the vertical line of sight, that is, the three-dimensional crystallinity of the coating phase formed under dry dehydration is observed, and the surface of the coating phase is observed with a finger. Suspension (= powder removal property) when rubbed was evaluated.
Subsequently, the heat sealing | fusion process was performed on the heating conditions of 120 degreeC x 10 minutes. Similarly, the color development as a structural color perceived under the vertical line of sight, that is, the three-dimensional particle crystallinity of the coating phase formed under heat fusion, is observed, and the surface of the coating phase is similarly observed. Each of the suspension properties (= powder removal properties) was evaluated by the following evaluation method, and the results are shown in [Table 1] below.
<Suspension of coating phase (= powder of surface)>
・ Particles do not fall off when rubbed with fingers ... ○
・ Slightly drops particles when rubbed with fingers ... △
・ Particles fall off when rubbed with fingers ... ×
<Structural color coloring of coating phase [= three-dimensional particle crystallinity]>
・ Same color as when dried at 25 ℃… ○
・ Slightly inferior to the color when dried at 25 ℃… △
・ Don't keep the color when dried at 25 ℃… ×

As a result, as apparent from [Table 1], the aqueous particle dispersion according to the present invention in which the organic polymer spherical particles (A) according to the present invention are dispersed is obtained by subjecting the monodispersed fine spherical particles to dry dehydration and heat melting. , 3-dimensional particles adjuster phase low temperature thermal adhesion properties is formed harnessed the hydrophilic polymer Tg ₂ was allowed to localize in the vicinity of the surface of the particles (P2) are seen the structural color under visible light irradiation Therefore, the three-dimensional particle matching body phase is a three-dimensional particle crystal body phase formed by the organic polymer spherical particles (A) being regularly self-fixed in the three-dimensional direction, and the self-adhesion. It is well understood that the formed three-dimensional grain crystal phase has an excellent suspension.

  As described above, according to the present invention, various types including a chromatic color developing property related to a structural color, mainly composed of an aqueous suspension type aqueous particle dispersion for forming a three-dimensional particle matched body continuous phase in which monodispersed fine spherical particles are dispersed. It was possible to provide an aqueous particle dispersion that forms a functional three-dimensional particle crystal phase that exhibits the above functional characteristics.

  That is, using the aqueous dispersion of organic polymer spherical particles according to the present invention, glass plate, mortar plate, ceramic plate, porcelain plate, plastic plate, steel plate, copper plate, aluminum plate, aluminum alloy plate, stainless steel plate, wood plate Various interiors that display structural color chromatic light as an optical property, metallic luster, etc. by printing, transferring and applying to various base materials such as fur sheets, fabric sheets, cardboard sheets, plastic films, etc. As a decoration, design and display material, it was possible to provide a coating-type color-developing three-dimensional grain crystal thin film material useful in various industrial fields.

  Further, according to the present invention, as a functional three-dimensional particle crystal thin film material, a conductive crystal thin film material; a member for a solar cell (separator, electrode, electrolyte film), a solid electrolytic capacitor, a photoelectric conversion element, an organic nonlinear optoelectronic material Optical disc, optical modulation, optical switch, optical memory, stimulated light emission, semiconducting crystal thin film material; TFT thin film element, ozone gas detecting element, ammonia gas sensor, ferroelectric crystalline thin film material; coating type useful in various industrial fields It was possible to provide a functional three-dimensional grain crystal thin film material.

FIG. 4 is a phase diagram of aqueous suspension particles showing the state of the crystal region, the dispersion region, the coexistence region, and the aggregation region formed under the relationship between the dispersion concentration of the aqueous suspension particles and the electric conductivity of the aqueous suspension type particle dispersion according to the present invention. Show.

Claims (7)

Three-dimensional particle crystals of fine spherical particles formed by drying, dewatering and heat-sealing the coated aqueous green sheet phase on the base substrate and fixing the organic polymer spherical particles contained in each other at least in the three axial directions of XYZ An aqueous particle dispersion for forming a body phase,
The organic polymer spherical particles (A) contained in the aqueous particle dispersion in a dispersion concentration of 25% or more expressed by mass basis and not exceeding 45% are precursor particles of the fixed fine spherical particles,
A hydrophilic component having a Tg _{2 of} 40 ° C. or less is present in the vicinity of the surface phase of the precursor particle per 100 parts by mass of the hydrophobic polymer (P ₁ ) having a Tg _{1 of} 50 ° C. or more as a resin component forming the precursor particles. An aqueous particle dispersion for forming a three-dimensional particle crystal phase, wherein the conductive polymer (P ₂ ) is impregnated unevenly in a range of 5 to 18 parts by mass.   The aqueous particle dispersion for forming a three-dimensional particle crystalline phase according to claim 1, wherein the electric conductivity of the aqueous particle dispersion system is 3500 [µS / cm] or less.   The precursor particles are black achromatic particles of an organic polymer having an average particle diameter expressed by volume basis of 130 nm or more and not exceeding 310 nm, and the three-dimensional particle crystal phase has a monochromatic system under visible light irradiation. 3. The three-dimensional particle crystal phase according to claim 1 or 2, wherein the structural hue is a structural hue that develops a chromatic color, and the structural hue gives a feeling of glossiness and / or metallic luster to visible light irradiation. Aqueous particle dispersion for forming.   The precursor particles are transparent non-colored particles having an average particle size expressed by volume basis of 310 nm or more and visualizing white irregular reflection color under visible light irradiation of an organic polymer not exceeding 800 nm, and the three-dimensional particle crystal 3. The aqueous particle dispersion for forming a three-dimensional particle crystal phase according to claim 1, wherein the phase gives a feeling of glossiness and / or metallic luster under visible light irradiation.   Using the aqueous particle dispersion for forming a three-dimensional particle crystal phase according to claim 3, printing, writing or transfer is performed on a base substrate which is a printing phase, a writing phase or a transferring phase. The coating phase of the printing phase, writing phase or transfer phase develops a chromatic structural color under visible light irradiation, and gives a sense of glossiness and / or metallic luster under visible light irradiation. A three-dimensional particle crystalline phase type aqueous coating material. Using the aqueous particle dispersion for forming a three-dimensional particle crystal phase according to any one of claims 1, 2, and 4, an aqueous green sheet phase coated on a base substrate is dried, dehydrated and heat-melted. The three-dimensional particle crystal phase of the thin film-like fixed fine spherical particles obtained is a functional three-dimensional particle crystal thin film material,
The organic polymer spherical particles (A) of the fixed fine spherical particles are any one selected from the group consisting of electrical conductivity, semiconductivity, insulation properties, ferroelectric properties, organic EL light emission properties, and nonlinear photoelectron properties. A functional three-dimensional grain crystal thin film material having the following functional characteristics: The aqueous green sheet phase coated on the base substrate is dried, dehydrated and heat-sealed, and the organic polymer spherical particles (A) of the fine spherical particles contained are fixed to each other at least in the three axial directions of XYZ. In the method for producing a three-dimensional particle crystal phase of fine spherical particles formed,
The hydrophobic monomer (m ₁ ) having a polymerized polymer Tg ₂ = 50 ° C. or higher, and 100 parts by mass of the polymerized polymer Tg ₂ = 40 ° C. or lower in the same manner. 5-18 parts by weight of a hydrophilic monomer (m ₂ ), a polymerization initiator and an emulsifier are added and emulsified and suspended.
Then, a predetermined amount of a pre-prepared organic polymer seed particle aqueous dispersion is added to cause seed emulsion polymerization,
The obtained organic polymer spherical particles (A) are precursor particles of the above-mentioned fixed fine spherical particles, and the precursor per 100 parts by mass of the hydrophobic resin (P ₁ ) having a resin component Tg ₁ = 50 ° C. or higher. In the vicinity of the surface phase of the particles, the hydrophilic polymer (P ₂ ) having a Tg _{2 of} 40 ° C. or less is impregnated unevenly in a range of 5 to 18 parts by mass,
Next, it is washed and concentrated to a dispersion concentration of 25 to 45% expressed on a mass basis, and the electric conductivity of the aqueous particle dispersion system is adjusted to 3500 [μS / cm] or less,
Next, using this aqueous particle dispersion, the aqueous green sheet phase coated on the base substrate is dried and dehydrated at a temperature below Tg ₂ + 50 ° C. to below the melting point of the hydrophilic polymer (P ₂ ). Heat fusing,
A method for producing a three-dimensional particle crystal phase of organic polymer spherical particles, wherein a three-dimensional particle crystal phase of the fixed fine spherical particles is formed.

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