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
Aqueous particle dispersion for forming three-dimensional particle crystal phase, method for producing the same and use of three-dimensional particle crystal phase Download PDFInfo
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本発明は、3次元粒子結晶体相形成用の水性粒子分散体に関し、より詳細には、下地基材上に塗工させた水性グリーンシート相が、乾燥脱水・熱融着下に、クラック・剥離などを殆んど発生させずに、単分散微細球状粒子の3次元粒子結晶体連続相を形成させる有機ポリマー球状粒子の水性粒子分散体に関する。 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.
また、本発明は、このような特徴を発揮させる水性粒子分散体をインキ及び塗料に用いて、印刷相又は筆記相又は転写相等として下地基材上に形成される3次元粒子結晶体相が、可視光照射下に構造色を発色させ、その構造色相は艶やかさ感及び/又は金属光沢感を視感させる3次元粒子結晶体相型の水性塗工材に関する。 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.
また、本発明は、このように下地基材上に形成させた有機ポリマー球状粒子の3次元粒子結晶体相が、例えば、その微細球状粒子自体が有する導電体性、半導体性、絶縁体性、強誘電体性、有機EL発光体性及び有機非線形光電子体性等の機能特性を反映させる機能性3次元粒子結晶薄膜材にも関する。 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.
従来から、単分散球状微細粒子を分散質として分散する固−液分散型サスペンジョンを用いて平坦な下地部材上に流し込み、又は塗布させて、乾燥下に分散質の懸濁粒子を3次元方向に規則配列(又は整合)させて、分散質球状微細粒子を、縦・横方向に規則的に配列させた粒子状積層体が種々提案されている。このように球状微細粒子を規則的に配列させることで、その粒子状積層体は、その構成粒子素材が有する諸特性等に係わって発揮される各種の表面特性が期待される。特にその構成粒子サイズがサブミクロン、ナノサイズのような極微細領域になれば、それだけ超微細粒子の粒子表面に係わって発揮される表面特性もより明確になり、また、新しい表面機能を発揮させる機能素材としても期待される。 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.
そこで、[特許文献1]には、干渉による着色光が明瞭に視感させるために、黒色或いは暗色である合成樹脂等の撥液性の下地層表面上に、光透過性の単分散の固体微粒子を凝集配列させた規則的周期構造物なる付着物が、光干渉発色として明瞭な単色光を呈することが記載されている。この付着物を構成する無着色の固体微粒子は単分散粒子であって、このような固体微粒子としては、シリカ、アルミナ、チタニア、シリカ・アルミナ、チタニア・セレン等の無機酸化物微粒子や、(メタ)アクリル系樹脂、スチレン系樹脂、オレフィン系樹脂等の有機ポリマー微粒子を挙げることができ、その数平均粒子径が100nm〜1μmの範囲にあると記載されている。 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.
また、[特許文献2]には、乳化重合法等で調製される200〜700nmの球状単分散ポリマー粒子が分散する固−液サスペンジョンを、透析処理で電解質を実質的に除去させて分散質粒子に電気二重層を形成させてなるサスペンジョンを静置下に、乾燥(60℃温度下)させてなる有機高分子の球状単分散粒子からなる多層積層秩序配列構造体を形成させ、次いで、配列する相接触する粒子間を化学的に固定化させる多層積層秩序配列構造体の製造方法が記載されている。 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.
また、[特許文献3]には、表面にヒドロキシル基、シラノール基、カルボキシル基等の官能基を有する物質を付着させたAlN、InSb、ZnS等の微粒子が分散するゼータ電位(絶対値)が10mV以上、伝導度が300[μS/cm]以下で、その分散濃度が5wt%程度の希薄分散溶液をガラス板上に滴下・乾燥させてコロイド結晶化させたコロイド結晶体(微粒子が格子状に配列した3次元周期構造体)が記載されている。また、その希薄分散溶液中にメタクリル酸メチル、酢酸ビニル等の重合性ビニル系モノマー等を含有させ、コロイド結晶化させた後、重合させてコロイド結晶体を固定させてなる固定化コロイド結晶体が記載されている。 [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.
また、[特許文献4]には、粒子の大きさが150〜450nmの範囲にある単分散球体粒子が、分散濃度20〜55重量%水性懸濁液中に、大きさが約10〜50nmの金属酸化物又はポリ(メチルメタクリレート)、ポリ(ビニルアセテート)等の有機ポリマー等のコロイド種を、この単分散球体粒子に対して、5〜25重量%の範囲で含有させた懸濁液が記載されている。この懸濁液を平面基板上に塗布させたウエット状の結晶層を乾燥させて、基板上に薄片状に得られる単分散球体粒子の薄層薄片状結晶からなる乳白色効果を有する粒子(規則的に配列した三次元構造体としての着色顔料)が記載されている。 [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).
また、[特許文献5]には、コア粒径が50nm〜10μmのコア−シェル型微粒子が分散する水性微細粒子分散体を乾燥脱水させて形成させる三次元周期構造を有するコロイド結晶及びその製造方法が記載されている。また、そのシェル層は、コア粒径が50nm〜10μmのポリマーコア粒子の水性分散体系に溶媒和するアクリルアミド、メタクリルアミド、N−メチルメタクリルアミド等のアクリルアミド系モノマーのポリマー架橋体を、例えば、乳化重合法で形成させている。また、コア−シェル層型微粒子の水性分散体を乾燥・濃縮させると溶媒和されたシェル層によって、微粒子間の過度な凝集が防止されて細密充填構造を取りやすく、比較的容易に3次元周期構造が形成される。また、シェル層が溶媒和されていることにより、その微粒子水性分散体を比較的高濃度に調製でき、コロイド結晶形成に好適に用いられるとも記載されている。 [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.
以上から、上記する[特許文献1]〜[特許文献5]に記載されているようにコロイド結晶体(又は単分散微粒子の3次元規則配列構造体)を形成させる単分散球状微細粒子を5〜55%の希薄分散濃度から高分散濃度範囲に分散させた水性懸濁液が種々提案されている。従来から、このような懸濁液を平坦な基板上に塗布形成させたウエット状の粒子懸濁集合体相(以後、本発明においては水性グリーンシート相と記す。)を乾燥脱水下に凝集させて、単分散微細粒子が3次元粒子整合体に形成されることがよく知られている。 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.
しかしながら、従来から解決し難い技術的な課題として、乾燥脱水下に、下地基材上に塗工させた水性グリーンシート相中に、含有する単分散球状粒子を、乾燥凝集させてなる3次元粒子整合体相(又は薄膜状粒子結晶体相)には、従来から周知の事実としてクラックや、剥離等を発生させて、その塗工相の2次元方向に一様な連続相を形成させ難い傾向にある。 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.
すなわち、既に上記する[特許文献3]からも理解される如く、この3次元粒子整合体相を固定化させるために、予め固定化バインダー樹脂成分が含有されている。しかるに、基材上に得られる3次元粒子整合体相には、亀裂が無数に発生し又薄片状に剥離を発生させて、単分散球体粒子の集合体が、2次元方向に一様な3次元の規則配列構造体の連続相として形成固定され難いのが実状である。 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.
加えて、このようにそれ相応の厚みを有する水性グリーンシート相は、通常、乾燥脱水が進捗されるに伴い、蒸発する分散媒水の毛細管力でサスペンド粒子を凝集集合させて3次元粒子整合体を形成させる。その結果、微細粒子間に介在する分散媒相(又は予めバインダー樹脂分を含有する分散媒相においても同様である。)は、乾燥収縮して一様な表面を維持させ難く、その収縮相当分が亀裂(又はクラック)として残留するのが一般的である。 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).
更には、従来からこのようなグリーンシート相中にバインダー樹脂分を介在させると、乾燥脱水の進捗と共に形成される3次元粒子整合体相の規則配列性、すなわち、3次元粒子結晶性を著しく阻害させる。その結果、3次元粒子結晶体相に基づいて、可視光照射下に発色する構造色相の発色性を著しく低下させる傾向にあった。 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.
また、下地基材上に設ける塗工グリーンシート相面が、2次元方向への塗工占有面を一層拡張させるに伴い、一層、亀裂を多発させて連続相の形成を著しく困難にさせるのが一般的であった。従って、従来から、3次元粒子整合体相に、亀裂(又はクラック)、剥離を発生させずに2次元方向に3次元粒子整合体の連続相を、3次元粒子結晶体相として安定に形成・固定させるには、未だ十分満足させるに至っていないのが実状である。 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.
そこで、本発明の目的は、非屈曲性又は屈曲性又は可撓性の各種の下地基材上に、単分散の微細球状粒子を高濃度に分散含有させ、しかも、流延性に優れる水性粒子分散体を流し込み、又は塗工させてなす水性グリーンシート相を、乾燥脱水下に、全く亀裂(又はクラック)、剥離などの発生が無く、しかも、下地基材上に形成される3次元粒子結晶体相が2次元方向に一様な連続相として自発固定されることを特徴とする3次元粒子結晶体相の連続相形成用の流延性・塗工性に優れる水性粒子分散体を提供することである。 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.
また、本発明の他の目的は、このような特徴を発揮させる3次元粒子結晶体相を形成・固定させる流延性に優れる水性粒子分散体を、水性インキ又は水性塗料に用いて、印刷又は筆記又は転写させてなる単分散球状粒子からなる3次元粒子結晶体相の印刷・筆記・転写の塗工相が、
(1)全く亀裂(又はクラック)、剥離発生の無い連続相として自発固定され、
(2)しかも、有彩色染顔料を含有させることなく、その単分散球状粒子の特定する粒子径に反映されて、可視光照射下に有彩光色を発色させ、
(3)併せて、可視光照射下に艶やかさ感及び/又は金属光沢感を視感させ、
る塗工相であることを特徴とする3次元粒子結晶体相型の水性塗工材を提供することである。
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.
また、本発明の更なる目的は、このように下地基材上に形成させた有機ポリマー微細球状粒子の3次元粒子結晶体相が、例えば、その微細球状粒子自体が、導電体性、半導体性、絶縁体性、強誘電体性、有機EL発光体性、有機非線形光電子性等の特性機能を有する場合、これら何れかの機能特性を発揮させる機能性3次元粒子結晶薄膜材を提供することである。 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.
本発明者は、上記課題を鋭意検討した結果、平均粒子径が190nmの、黒色無彩色のMMA系単分散球状粒子を用いて、従来に比べて高濃度(体積基準で表して40%)に分散する水性サスペンジョンを調製した。次いで、この水性分散体系の電気伝導度を450[μS/cm]の流延性水性粒子分散体に調製した後、PETフィルム上に、この分散体液を塗工させてグリーンシート相を形成させ、約100℃の温度雰囲気下に靜置曝露させたとこら、
(1)その塗工グリーンシート相は、可視光照射下に鮮やかな青色の有彩色を発色させる
構造色体相であって、
(2)その構造色体相には、ほとんど亀裂や剥離発生がなく、
(3)更には、その塗布相を指先で擦っても全く粉落ち感がなく、すなわち、著しく懸垂性に優れ、
(4)しかも、2次元方向に一様な連続相として安定に固定されていることを見出して、本発明を完成させるに至った。
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.
本発明によれば、下地基材上に塗布・形成させた水性グリーンシート相を、乾燥脱水・熱融着させ、グリーンシート相中に含有する有機ポリマーの単分散微細球状粒子同士を、少なくともXYZの3軸方向に互いに融着(又は固着)させて、3次元方向に規則的に配列・固着されてなる3次元粒子結晶体相を形成させる。 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.
しかも、下地基材上の2次元方向に、ほとんど亀裂、剥離を発生させることがなく、更には、その塗工相は全く粉落ち感のない「懸垂性」に優れる3次元粒子結晶体の連続相として固定されることを特徴とする3次元粒子結晶体相形成用の流延・塗工性に優れる水性粒子分散体を提供する。 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.
すなわち、本発明による3次元粒子結晶体相形成用の水性粒子分散体は、下記(1)及び(2)に記載する如く、
(1)この水性微細粒子分散体中には、質量基準で表して25%以上で、45%を超えない分散濃度で、単分散性の有機ポリマー球状粒子(A)が、上記固着微細球状粒子の前駆体粒子として、高濃度で分散している。
(2)この前駆体粒子は、それを形成する樹脂成分であるTg1=50℃以上の疎水性ポリマー(P1)の100質量部当たり、Tg2=40℃以下の親水性ポリマー(P2)が、この「前駆体粒子の表相近傍部」に、5〜18質量部の範囲で「含侵偏在」している。
ことを特徴とする3次元粒子結晶体相形成用の水性粒子分散体である。
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.
また、本発明によれば、このような特徴を有する3次元粒子結晶体相形成用の流延性・塗工性に優れる水性粒子分散体は、下記(1a)〜(3a)に記載する如くの構成要件が活かされて、例えば、構造色水性インキ、構造色水性塗料として、非屈曲性又は屈曲性又は可撓性の各種下地基材上に塗工させて(本発明においては、印刷相又筆記相又は転写相等を含めて3次元粒子結晶体相の連続相からなる塗工を意味する。)、全く有彩色染顔料を含有させることなく、可視光照射下に有彩構造色を発色させ、且つ可視光照射下に「艶やかさ感」及び/又は「金属光沢感」を視感させることを特徴とする3次元粒子結晶体相型の水性塗工材を提供する。 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.
すなわち、本発明による3次元粒子結晶体相型の水性塗工材は、下記(1a)〜(3a)に記載する如く、
(1a)水性単分散球状粒子が高濃度で分散する流延性粒子懸濁液を用いて、印刷又は筆記又は転写させてなるウエット状のグリーンシート相である塗工相は、Tg2+50℃以上〜親水性ポリマー(P2)の融点未満の温度雰囲気下に乾燥脱水・熱融着されて有機ポリマー球状粒子(A)の3次元粒子結晶体の連続相が形成される。
(2a)その連続相は、クラック、剥離発生がほとんどなく、更には懸垂性に優れる一様な連続相として安定に自発固定される。
(3a)また、その塗工グリーンシート相中に懸濁集合する黒色系無彩色の単分散性の有機ポリマー球状粒子(A)の粒度特性として、体積基準で表す平均粒子径を130〜310nm範囲に特定させることで、垂直視線方向に有彩構造色を発色させ、且つ可視光照射下に「艶やかさ感」及び/又は「金属光沢感」を視感させる3次元粒子結晶体の連続相として自発固定される。
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.
更に、本発明によれば、このような特徴を発揮させる3次元粒子結晶体相の連続相形成固定用の流延性に優れる水性粒子分散体は、下記(1b)〜(3b)に記載する如くの構成要件が活かされて、可視光照射下に構造色を発色させないが、同じく3次元粒子結晶体相に反映されてなる「艶やかさ感」及び/又は「金属光沢感」を視感させることを特徴とする3次元粒子結晶体相型の水性塗工材を提供する。 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.
すなわち、本発明による3次元粒子結晶体相型の水性塗工材は、下記(1b)〜(3b)に記載する如く、
(1b)水性サスペンジョン型の単分散球状粒子が高濃度で分散する流延性粒子懸濁液を用いて、印刷又は筆記又は転写させてなるウエット状の塗工グリーンシート相は、Tg2+50℃以上〜親水性ポリマー(P2)の融点以下の温度雰囲気下に乾燥脱水・熱融着させて有機ポリマー球状粒子(A)の3次元粒子結晶体相の連続相が形成される。
(2b)その連続相は、2次元方向にクラック、剥離発生をほとんど起こすことなく、懸垂性に優れる一様な連続相として安定に自発固定される。
(3b)その塗工相中に懸濁集合する単分散性の有機ポリマー球状粒子(A)が、可視光照射下に白色乱反射色を視感させる透明無着色球状粒子で、その平均粒子径が310nmを超えて、800nmを超えない範囲に特定させることで、有彩色の構造色を発色させないが、3次元粒子結晶体相に基づく「艶やかさ感」及び/又は「金属光沢感」が視感される。
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.
また、本発明によれば、このような特徴を発揮させて3次元粒子結晶体相の連続相を形成させる流延性に優れる水性粒子分散体を用いて、下地基材上に塗工させた水性グリーンシート相を、乾燥脱水・熱融着させて得られる薄膜状の固着微細球状粒子の3次元粒子結晶体相は、その固着微細球状粒子の有機ポリマー球状粒子(A)自体が、下記に挙げるような機能性粒子である場合には、それらの機能特性が反映されてなることを特徴とする能機能性3次元粒子結晶薄膜材を提供する。
その固着微細球状粒子が有する機能特性が、例えば、導電体性、半導体性、絶縁体性、強誘電体性、有機EL発光体性、有機非線形光電子性の群から選ばれる何れか1種の機能特性を有する機能性有機ポリマー粒子(A)である。
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.
また、本発明によれば、このような水性粒子分散体を下地基材上に塗工させた水性グリーンシート相を、乾燥脱水・熱融着させ、グリーンシート相中に含有する有機ポリマー球状粒子(A)を、少なくともXYZの3軸方向に相互に固着させた微細球状粒子からなる3次元粒子結晶体相を形成させることを特徴とする有機ポリマー球状粒子(A)からなる3次元粒子結晶体相の製造方法を提供する。 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.
すなわち、本発明による3次元粒子結晶体相の製造方法は、下記(1C−工程)〜(5C−工程)に記載する如く、
(1C−工程);所定量の水相に、重合ポリマー化後のTg1=50℃以上である疎水性モノマー(m1)と、その100質量部当たり、同様に重合ポリマー化後のTg2=40℃以下である親水性モノマー(m2)の5〜18質量部と、重合開始剤及び乳化剤とを加えて乳化懸濁させる。
(2C−工程);次いで、予め調製した有機ポリマーをシード粒子とする水性シード粒子分散体の所定量を注加させた後、温度65〜80℃に昇温させながらシード乳化重合させる。
(3C−工程);得られる有機ポリマー球状粒子(A)は、上記する少なくともXYZの3軸方向に互いに融着(又は固着)される微細球状粒子の前駆体粒子である。その形成樹脂成分のTg1=50℃以上の疎水性ポリマー(P1)の100質量部当たり、その前駆体粒子の表相近傍部には、Tg2=40℃以下の親水性ポリマー(P2)を、5〜18質量部の範囲で含侵偏在させる。
(4C−工程);次いで、例えば、クロスフロー洗浄装置を用いて洗浄・濃縮させて、重量基準で表す分散濃度25〜45%で、且つその水性粒子分散体系の電気伝導度を3500[μS/cm]以下である有機ポリマー微細球状粒子の水性粒子分散体(AS)を調製させる。
(5C−工程);次いで、この水性粒子分散体(AS)を用いて、下地基材上に塗工させた水性グリーンシート相を、Tg2+50℃以上〜親水性ポリマー(P2)の融点未満の温度下に乾燥脱水・熱融着させて、有機ポリマー球状粒子(A)の固着微細球状粒子からなる3次元粒子結晶体相を形成させる。
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).
以上から、本発明が提供する有機ポリマー球状粒子(A)の3次元粒子結晶体相を形成させる水性粒子分散体の特徴は、
(1c)固着微細球状粒子の前駆体粒子である単分散性の有機ポリマー球状粒子(A)が、質量基準で表して25〜45%の高分散濃度で含有している。
(2c)その前駆体粒子を形成する樹脂成分は、Tg1=50℃以上の疎水性ポリマー(P1)で、その樹脂成分の100質量部当たり、この「前駆体粒子の表相近傍部」には、Tg2=40℃以下の親水性ポリマー(P2)が、5〜18質量部の範囲で「含侵偏在」している有機ポリマー球状粒子(A)の水性粒子分散体である。
(3c)このような特徴からなる水性粒子分散体を、下地基材上に塗布させてなる水性グリーンシート相は、Tg2+50℃以上〜親水性ポリマーの融点未満の所定温度下に、乾燥脱水・熱融着させることで、3次元的に規則配列する前駆体粒子の表相近傍部に、含侵偏在するTg2=40℃以下の親水性ポリマー(P2)を介して、少なくともXYZの3軸方向に相互に固着されて、3次元粒子結晶体相を効果的に形成させる。
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
(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.
また、本発明による3次元粒子結晶体相は、2次元方向にクラック、剥離発生がほとんどなく、3次元粒子結晶体相の連続相は、それを形成する単分散球状粒子の粒子特性に係わって、可視光線波長領域380〜780nmの自然光又は白色光が照射されて、以下の如の可視光反射特性を発揮させる。
(1d)有機ポリマー球状粒子(A)の粒子特性が、黒色系無彩色球状粒子で、体積基準で表す平均粒子径が130〜310nmの範囲にあって、この3次元粒子粒子結晶体相の面心立方格子(111)結晶面に対してブラッグの反射式を満足させる垂直反射の「一次光色」を発色させる。
(2d)更に、この「一次光色」は、特定粒子径130〜310nmに係わって、ブラッグの反射式における角度依存を満足させてスペクトル分光発色として、例えば、赤色(R)、緑色(G)、青色(B)等の鮮明な単色系有彩色のスペクトル分光発色の構造色を発色させ、しかも、この連続相は、この可視光照射下に「艶やかさ感」及び/又は「金属光沢感」を視感させる。
(3d)また、この有機ポリマー球状粒子(A)の粒子特性が、可視光照射下に白色乱反射色を視感させる透明無着色球状粒子で、その特定粒子径が310〜800nmに係わって、有彩光色の構造色を視感させないが、この連続相は、この可視光照射下に「艶やかさ感」及び/又は「金属光沢感」を視感させる。
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.
また、上記する如くの特徴ある水性粒子分散体は、流延性粒子懸濁液として、水性インキ部材又は水性塗料部材として、各種の非屈曲性又は屈曲性又は可撓性の下地基材上に塗工グリーンシート相の構造色相からなる印刷又は筆記又は転写像を視感させることができる。 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.
また、更には、本発明による有機ポリマー球状粒子(A)の3次元粒子結晶体相は、この有機ポリマー球状粒子(A)の微細球状粒子の薄膜状3次元粒子結晶体相として、この有機ポリマー球状粒子(A)が有する導電体性、半導体性、絶縁体性、強誘電体性、有機EL発光体性、非線形光電子性の群から選ばれる何れかの機能特性を有する有機ポリマー球状粒子からなる機能性3次元粒子結晶薄膜材を提供することができる。 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.
以下に、本発明による3次元粒子結晶体相形成用の水性粒子分散体の実施形態について更に説明する。 Hereinafter, embodiments of the aqueous particle dispersion for forming a three-dimensional particle crystal phase according to the present invention will be further described.
<本発明に用いる有機ポリマー球状粒子(A)の水性粒子分散体>
(1e)本発明に用いられる体積基準で表す平均粒子径が、少なくとも130nm以上で、数μmを超えない単分散性の有機ポリマー球状粒子(A)は、本発明者の従来からの知見として、好ましくは、乾燥凝集下に3次元的に規則配列させる観点から、固−液分散体としての電気伝導度が3500[μS/cm]以下の水性粒子分散体として用いられる。
(2e)また、その分散濃度は、好ましくは、体積基準で表して25%以上で、45%を超えない高濃度分散体として適宜好適に用いられる。
(3e)また、粘稠性高濃度懸濁液としての流動性又は流延性として、水性粒子分散体としての分散安定性や取り扱いハンドリング性を低下させない観点から、好ましくは、その分散濃度は、30%以上で、40%以下の高濃度範囲で適宜好適に用いることができる。
(4e)この上限値45%を超える分散濃度では水性サスペンジョン中の分散質粒子は、ランダムに部分凝集する粒子群を生じさせ易くなって、本発明が求める3次元粒子結晶体相を形成させる粒子の規則的な整合を著しく阻害させる傾向にあって好ましくない。
(5e)また、その下限値は、その水性グリーンシート中に、例えば、乾燥下に粒子整合体を形成させる速度や、また、その水性粒子分散体の取り扱いハンドリング性から、その下限値は25%以上であることが適宜好適である。
<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.
<本発明による水性粒子分散体の電気伝導度>
また、このような高濃度分散体である水性粒子分散体系の電気伝導度を3500[μS/cm]以下であることに係わって、このような水性サスペンジョン粒子(又は水性懸濁粒子)を調製する製造方法にもよるが、分散媒溶液中に含有する有機及び/又は無機の酸・塩基官能基等に係わるサスペンジョン中の電解質濃度(体積濃度で表して)を電気伝導度で表して本発明においては、水性懸濁粒子の3次元粒子結晶体相を形成させる観点から、3500[μS/cm]以下であって、好ましくは2500[μS/cm]以下で、更に好ましくは1500[μS/cm]以下で、200[μS/cm]以上の範囲に適宜好適に調整することができる。
<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.
<水性粒子分散体の「3次元粒子結晶性」とその「水性懸濁粒子状態図」>
更には、本発明においては、このような流延性の水性粒子分散体に係わって、水性媒体中に懸濁分散する単分散球状粒子の状態を、「ランダム分散粒子」状態領域と、「3次元規則配列粒子」状態領域と、「ランダム凝集粒子」状態領域の何れかの状態を形成させるとして、このような状態領域にある「水性懸濁粒子」の「3次元粒子整合性」を明確に関連付けすることができる。本発明において、添付[図1]に図示するように、本発明による水性サスペンジョン型流延性粒子分散体の「サスペンジョン特性」との関係下に「水性懸濁粒子」状態を以下のようにして評価することができる。
<“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.
すなわち、この水性単分散球状粒子の「水性懸濁粒子」の「3次元粒子整合性」を、「サスペンジョン特性」値としての「その懸濁濃度」と「その電気伝導度(又はイオン濃度又は帯電濃度)」との関係下に、添付[図1]に図示する如く、下記(a)〜(d)なるそれぞれの粒子集合領域及び粒子分散領域を示す懸濁粒子状態図として適宜に関連付けすることができる。
(a)結晶域;水性サスペンジョン相中の懸濁粒子が、構造色を視感させる3次元粒子整合体として規則配列懸濁相を形成している。
(b)共存域;水性サスペンジョン相が、(a)なる粒子規則配列懸濁相と、懸濁粒子がランダムに分散する粒子ランダム分散相とが共存している。
(c)分散域;全懸濁粒子がランダム分散状態にある。
(d)凝集域;全懸濁粒子がランダムに凝集群を形成している。
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.
その結果、本発明においては、この「結晶域」にある水性サスペンジョン型粒子分散体は、上記段落[0035]〜[0038]に記載するサスペンジョン特性とする「その懸濁濃度」及び「その電気伝導度」の関係下に、水性懸濁粒子体として構造色を視感させる有用な水性サスペンジョン発色部材として、各種の産業分野に適宜好適に用いることができるものである。 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.
しかるに、本発明のように、水性サスペンジョン型の流延性粒子分散体として用いて、下地基材上に塗布形成させたグリーンシート相中の懸濁集合粒子を、乾燥雰囲気下に曝露させて、3次元粒子整合体なる粒子規則配列を2次元方向に連続相として形成させる場合には、その詳細な理由は不明ではあるが、水性サスペンジョンとして既に3次元粒子整合状態にある上記する「結晶域」にある水性サスペンジョン型粒子分散体よりも、好ましくは、上記する「共存域」にあるより水性サスペンジョン型の流延性粒子分散体であることが、優れた「3次元粒子整合性=3次元粒子結晶性」を発揮させる水性サスペンジョン型の流延性・塗工性を有する水性粒子分散体として適宜好適に用いられる。 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 “
すなわち、「共存域」状態にある水性サスペンジョン型粒子分散体の場合には、下地基材上に塗布させた塗布相に形成される3次元粒子整合体(又は3次元粒子結晶体)は、その塗布相の2次元方向面に沿って、例えば、略単一の結晶面を呈する多結晶体相を形成させる。一方、「結晶域」状態にある水性サスペンジョン型粒子分散体を塗布させた場合には、複数の結晶面を呈する多結晶体相となる傾向にある。 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.
<形成結晶面及びその反映特性>
そこで、前者のような「共存域」状態にある水性サスペンジョン型流延性粒子分散体を塗布させた場合には、下地基材上に形成固定される3次元粒子結晶体相から視感される構造色相は、照射可視光の干渉反射面が略同一の結晶面からとなって反射光色が強まり、しかも、2次元方向に色ムラのない鮮やかな構造色を発色させる。
<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.
一方、後者のような「結晶域」状態にある水性サスペンジョン型粒子分散体を塗布させた場合には、下地基材上に形成固定される3次元粒子結晶体連続相から視感される構造色相は、その干渉反射光は異なる複数の結晶面からとなって、視感させる構造色相には色ムラを生じさせる。また、2次元方向面に沿って、形成される結晶面が、複数の結晶面を有していることから、その3次元粒子整合体連続相は、その単分散性の有機ポリマー球状粒子(A)が有する機能を2次元方向に均等に発揮させ難くなる。 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.
<本発明に用いる単分散球状粒子(A)の粒子径>
本発明においては、可視光照射下に3次元粒子整合体相が発色させる有彩色構造色と、且つ可視光照射下に艶やかさ感及び/又は金属光沢感を視感させる3次元粒子整合体を形成する有機ポリマーの単分散球状粒子(A)の粒子径との係わりが、既に上述する如く、その体積基準で表す平均粒子径130〜1000nmの範囲において、以下に記載するような粒子構成要件を満たす有機ポリマー質の単分散球状粒子(A)[既に説明済みの有機ポリマー球状粒子(A)である。]を適宜好適に用いることができる。
(1f)特に、本発明においては、この単分散球状粒子(A)が、色みの無い灰黒色、黒色から選ばれる何れか1種の黒色系無彩色球状粒子で、体積基準で表す平均粒子径が130〜310nmの範囲にある。
(2f)また、本発明においては、可視光照射下に白色乱反射色を視感させる透明無着色の白色系無彩色粒子で、その体積基準で表す平均粒子径が130〜1000nmの範囲で、好ましくは、310nm以上で、800nm以下にある。
<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.
<本発明に用いる単分散球状粒子(A)の反射色について>
また、本発明における上記する白色系又は黒色系の無彩色について更に説明すると、
(1g)白色系無彩色とは、マンセル色票に表す彩度=0(零)であって、明度が限りなく≧10である。
(2g)また、黒色系無彩色とは、彩度=0であって、明度が限りなく≦0である。
(3g)また、本発明においては、上記する彩度=0で、0<明度<10にある灰色、好ましくは、灰黒色等の色相は、何れも黒色系無彩色として扱うことができる。
(4g)更に、本発明においける透明無着色粒子に係わる白色系無彩色とは、平均粒子径が100nm〜1μmサイズにある透明無着色球状粒子においては、通常、その粒子の分散系に対して、可視光照射下に視感される乱反射色は、例えば、透明ガラスの微粉砕物体から視感される反射色は、白色として視感されることからよく理解することができる。
<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.
<本発明による有機ポリマー球状粒子(A)及びその製造方法>
以上から、本発明による下地基材上に塗工させた水性グリーンシート相中に含有する有機ポリマー球状粒子(A)を、乾燥脱水・熱融着させて、微細球状粒子の3次元粒子結晶体相を形成させることを特徴とするものである。その有機ポリマー球状粒子(A)は、乾燥脱水・熱融着下に3次元粒子結晶化される微細球状粒子の前駆体粒子である単分散性の有機ポリマー球状粒子(A)は、既に説明する如く、重量基準で表して25〜45%範囲にある高濃度水性粒子分散体として適宜好適に調製することができる。
<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.
<本発明による有機ポリマー球状粒子(A)>
その水性乳化懸濁系で形成され有機ポリマー球状粒子(A)は、既に詳細に説明済みである重合ポリマー化後のTg1=50℃以上で、好ましくはTg1=60℃以上で、更に好ましくはTg1=80℃以上である疎水性モノマー(m1)からなる疎水性ポリマー(P1)として形成されている。このような本発明による有機ポリマー球状粒子(A)は、熱融着3次元粒子結晶体相中に固定する微細球状粒子の前駆体粒子であって、その前駆体粒子100質量部当たり、同様に重合ポリマー化後のTg2=40℃以下で、好ましくはTg2=20℃以下で、更に好ましくはTg2=10℃以下である親水性モノマー(m2)からなる親水性ポリマー(P2)が、5〜18質量部の範囲で、この前駆体粒子の有機ポリマー球状粒子(A)の表相近傍部に含侵偏在していることを特徴とするものである。しかも、本発明においては、所定の温度下に熱融着3次元粒子結晶体相を形成させるに、その熱特性であるガラス転移温度(Tg)は、常にTg1>Tg2の関係にあることが重要な特徴である。
<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.
<本発明による有機ポリマー球状粒子(A)が分散する3次元粒子結晶体相形成用の水性粒子分散体の調製>
<下地基材上に形成される有機ポリマー球状粒子(A)の3次元粒子結晶体相の製造>
(1C−工程1);所定量の水相に、重合ポリマー化後のTg1=50℃以上である疎水性モノマー(m1)と、その100質量部当たり、同様に重合ポリマー化後のTg2=40℃以下である親水性モノマー(m2)の5〜18質量部と、重合開始剤及び乳化剤とを加えて乳化懸濁させる。
(1C−工程2);また、本発明においては、本発明に用いる黒色系無彩色の有機ポリマー球状粒子(A)を調製するには、例えば、重合性単量体、乳化剤及び水との混合水相系に着色剤である黒色系の油溶性染料又はカーボンブラックを含む黒色系の染顔料を適宜分散混合又は懸濁混合させる。
すなわち、上記する重合性モノマー(m1)及び(m2)から適宜選んだ単量体100質量部当たり、水200〜350質量部の範囲にある水を含む系に、例えば、C.Iソルベントブラック27のような黒色系染料の5〜10質量部を、攪拌下に加温し、次いで、乳化剤の0.05〜0.7質量部を加えて乳化懸濁させる。
(2C−工程);次いで、予め調製した有機ポリマーをシード粒子とする水性シード粒子分散体の所定量を注加させた後、温度65〜80℃に昇温させてシード乳化重合させる。すなわち、有機ポリマーの球状単分散微細粒子は 通常、一般的に用いられているソープフリー乳化重合、懸濁重合等の乳化重合系で適宜調製させる。
(3C−工程);得られる有機ポリマー球状粒子(A)は、上記する少なくともXYZの3軸方向に互いに融着(又は固着)される微細球状粒子の前駆体粒子であり、その形成樹脂成分のTg1=50℃以上の疎水性ポリマー(P1)の100質量部当たり、この前駆体粒子の表相近傍部には、Tg2=40℃以下の親水性ポリマー(P2)が、5〜18質量部範囲で含侵偏在するように形成されている。
(4C−工程);次いで、例えば、クロスフロー洗浄装置を用いて洗浄・濃縮させて、重量基準で表す分散濃度25の〜45%で、且つその水性粒子分散体系の電気伝導度を3500[μS/cm]以下である有機ポリマー微細球状粒子の水性粒子分散体(AS)を調製させる。
(5C−工程);次いで、この水性粒子分散体を用いて、下地基材上に塗工させた水性グリーンシート相を、Tg2+50℃以上〜親水性ポリマー(P2)の融点未満の温度下に乾燥脱水・熱融着させて、上記固着微細球状粒子からなる3次元粒子結晶体相が形成される。また、本発明においては、このような乾燥脱水を、大気圧以下の減圧下においても適宜好適に実施することもできる。
<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.
以上から、下地基材上に塗工させてなす水性グリーンシート相を、乾燥脱水・熱融着させ、含有する有機ポリマー球状粒子を、少なくともXYZの3軸方向に相互に固着されてなる有機ポリマー球状粒子(A)の3次元粒子結晶体相を形成させる水性粒子分散体の特徴は、
(1)固着微細球状粒子の前駆体粒子である単分散性の有機ポリマー球状粒子(A)が、重量基準で表して25〜45%の高分散濃度で含有されている。
(2)その前駆体粒子を形成する樹脂成分は、Tg1=50℃以上の疎水性ポリマー(P1)で、その樹脂成分の100質量部当たり、この「前駆体粒子の表相近傍部」には、Tg2=40℃以下の親水性ポリマー(P2)が、5〜18質量部の範囲で「含侵偏在」されている。
(3)この前駆体粒子が高濃度で分散する水性粒子分散体系の電気伝導度が、3500[μS/cm]以下に調整されている。
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
(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.
このような特徴を有する水性粒子分散体を、各種の下地基材上に塗工させた水性グリー
ンシート相を、Tg2+50℃以上〜親水性ポリマー(P2)の融点未満の温度下に、乾燥脱水・熱融着させて、3次元的に規則自己配列する前駆体粒子の表相近傍部に、含侵偏在させたTg2=40℃以下の親水性ポリマー(P2)を介して、少なくともXYZの3軸方向に相互に固着されて、3次元粒子結晶体相を効果的に形成させることが特徴である。
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.
また、本発明においては、既に説明する如くTg1=50℃以上の疎水性ポリマー(P1)である疎水性モノマー(m1)に組合せ使用する親水性ポリマー(P2)となる親水性モノマー(m2)は、そのポリマーのTg2=40℃以下であれば適宜好適に用いられるが、本発明においては、その融着(又は固着)がより瞬時に進捗させる観点から、好ましくは、そのTg2=20℃以下で、更に好ましくはTg2=10℃以下の親水性ポリマー(P2)となる親水性モノマー(m2)を用いることがより好適である。 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.
例えば、ソープフリー乳化重合では、通常、用いる重合開始剤として、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩が重合時に水性媒体に可溶であればよい。通常、重合単量体100質量部に対して、重合開始剤を0.1〜10質量部、好ましくは0.2〜2質量部の範囲で添加すればよい。また、乳化重合法の場合では、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ポリエチレングリコールノニルフェニルエーテル等のポリエチレングリコールアルキルエーテル等の乳化剤を重合単量体100質量部に対して、通常、0.01〜5質量部、好ましくは0.1〜2質量部で水性媒体に混合させて乳化状態にし、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩の重合開始剤を、重合単量体100質量部に対して、0.1〜10質量部、好ましくは0.2〜2質量部で添加すればよい。 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.
また、懸濁重合を含め、上記する乳化剤も特に特定する必要がなく、通常に使用されているアニオン系界面活性剤、カチオン系界面活性剤又は必要に応じてノニオン系界面活性剤等から選んで、その単独又は組み合わせて使用することができる。例えば、アニオン系界面活性剤としてはドデシルベンゼンスルホネート、ドデシルベンゼンスルホネート、ウンデシルベンゼンスルホネート、トリデシルベンゼンスルホネート、ノニルベンゼンスルホネート、これらのナトリウム、カリウム塩等が挙げられ、また、カチオン系界面活性剤としてはセチルトリメチルアンモニウムプロミド、塩化ヘキサデシルピリジニウム、塩化ヘキサデシルトリメチルアンモニウム等が挙げられ、また、ノニオン系界面活性剤としては、リピリジニウム等が挙げられる。 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.
<本発明に用いる疎水性モノマー(m1)>
また、本発明において、疎水性モノマー(m1)としては、例えば、メタクリル系モノマー;メタクリル酸メチル,メタクリル酸エチル,メタクリル酸プロピル,メタクリル酸イソプロピル,メタクリル酸ブチル,メタクリル酸イソブチル,メタクリル酸ペンチル,メタクリル酸ヘキシル,メタクリル酸2−エチルヘキシル等のアクリル酸アルキルエステル;ジエチルアミノエチルメタクリレート等のジアルキルアミノアルキルメタクリレート;メタクリルアミド;N-メチロールメタクリルアミド及びジアセトンアクリルアミド等のメタクリルアミド類並びにグリシジルメタクリレート;エチレングリコールのジメタクリル酸エステル,ジエチレングリコールのジメタクリル酸エステル,トリエチレングリコールのジメタクリル酸エステル,プロピレングリコールのジメタクリル酸エステル,ジプロピレングリコールのジメタクリル酸エステル,トリプロピレングリコールのジメタクリル酸エステル等の(ポリ)アルキレングリコールのジメタクリル酸エステル類等を挙げることができる
<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.
また、フッ素置換アクリル系モノマーとしては、例えば、(メタ)アクリル酸トリフルオロメチルメチル,(メタ)アクリル酸−2−トリフルオロメチルエチル,(メタ)アクリル酸−2−パ−フルオロメチルエチル,(メタ)アクリル酸−2−パ−フルオロエチル−2−パ−フルオロブチルエチル,(メタ)アクリル酸−2−パ−フルオロエチル,(メタ)アクリル酸パ−フルオロメチル,(メタ)アクリル酸ジパ−フルオロメチルメチル等のフッ素置換(メタ)アクリル酸系モノマー等を挙げることができる。 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.
また、スチレン系モノマーとしては、例えば、スチレン,メチルスチレン,ジメチルスチレン,トリメチルスチレン,エチルスチレン,ジエチルスチレン,トリエチルスチレン,プロピルスチレン,ブチルスチレン,ヘキシルスチレン,ヘプチルスチレン及びオクチルスチレン等のアルキルスチレン;フロロスチレン,クロルスチレン,ブロモスチレン,ジブロモスチレン,クロルメチルスチレン等のハロゲン化スチレン;ニトロスチレン,アセチルスチレン,メトキシスチレン、α−メチルスチレン,ビニルトルエン等を挙げることができる。 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.
また、フッ化ビニリデン等のフッ素含有ビニルモノマー;ビニルトリメトキシシラン、ビニルトリエトキシシラン等のケイ素含有ビニル系モノマー;酢酸ビニル,プロピオン酸ビニル,n−酪酸ビニル,イソ酪酸ビニル,ピバリン酸ビニル,カプロン酸ビニル,パーサティック酸ビニル,ラウリル酸ビニル,ステアリン酸ビニル,安息香酸ビニル,p−t−ブチル安息香酸ビニル、サリチル酸ビニル等のビニルエステル類;塩化ビニリデン、クロロヘキサンカルボン酸ビニル、アクリル酸−2−クロロエチル、メタクリル酸−2−クロロエチル等が挙げられる。また、アクリル酸シクロヘキシル等の脂環式アルコールのアクリル酸エステルや、メタクリル酸シクロエキシル等の脂環式アルコールのメタクリル酸エステル等が挙げられる。 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.
<本発明に用いる親水性モノマー(m2)>
本発明において、親水性モノマー(m2)としては、特に好ましくは、例えば、MA(アクリル酸メチル)、MEA(アクリル酸メトキシエチル)、4HBA(アクリル酸4ヒドロキシブチル)、3HPA(アクリル酸ヒドロキシプロピル)、2HEA(アクリル酸2ヒドロキシエチル)の群から選ばれる親水性モノマーを挙げることができる。
<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).
<本発明に用いる機能性有機ポリマー及び機能性有機化合物>
また、本発明においては、上記する有機ポリマーに限定されることなく、水相系で単分散球状微細粒子を形成可能な有機化合物として、例えば、以下の(A1)〜(A5)に記載するような機能を有する有機ポリマー及びその有機モノマー化合物を用いて、その有機ポリマーの機能性有機ポリマー球状粒子(A)として適宜好適に用いられる。又は、例えば、PMMAなどの有機ポリマー球状粒子(A)のホスト粒子を調製させるに際して、予めこれらの機能性有機ポリマー及びそのモノマー化合物を機能性ゲストとして含有させて、PMMAホスト粒子を機能性有機ポリマー球状粒子(A)として適宜好適に用いられる。
<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.
(A1)有機ELポリマー及びそのモノマー化合物;ポリビニルカルバゾール(PVK)系、ポリフェニレン系、ポリフェニレンビニレン(PPV)系、Cyano−PPV系、MEH−PPV系、ポリ[2−メトキシ,5−(2’−エチルヘキソキシ)−1,4−フェニレンビニレン]、ポリ(3−アルキリチオフェン)等を挙げることができる。
(A2)強誘電性ポリマー及びそのモノマー化合物;フッ化ビニリデン(VDF)と3フッ化エチレンの共重合体のP(VDF−TrFE)、P(VDF−TeFE)、3フッ化エチレン及び/又は4フッ化エチレンの共重合体のポリフッ化ビニリデン(PVDF)、フッ化ビニリデン(VDF)と4フッ化エチレン共重合体、フッ化ビニリデン(VDF)とフッ化ビニル共重合体、フッ化ビニリデン(VDF)と4フッ化エチレンと6フッ化プロピレン共重合体、ポリシアン化ビニリデン、シアン化ビニリデンと酢酸ビニル共重合体等を挙げることができる。半導体性ポリマー;ポリピロール、ポリチオフェン、ポリパラフェニレン、ポリアルキルピロール、ポリアルキチオフェン、オリゴピロール、オリゴチオフェン等を挙げることができる。
(A3)導電性ポリマー及びそのモノマー化合物;ポリアニリン、ポリピロール、ポリチオフェン系[3,4−ポリエチレンジオキシチオフェン、ポリ(3−ヘキシル)チオフェン、ポリ(3−オクチル)チオフェン、ポリ(3−ドデシル)チオフェン等やおれらの誘導体の重合体]、ポリチオフェンビニレン、ポリアセチレン、ポリパラフェニレン、ポリフェニレンビニレン、ポリメトキシフェニレン、ポリフェニレンスルファイド、ポリフェニレンオキシド、ポリアントラセン、ポリナフタレン等を挙げることができる。特にLi、Na、K等のアルカリ金属、Ca等のアルカリ土類金属のドナー型ドーパンターでドーピングする。
(A4)半導性ポリマーおよびそのモノマー化合物;π共役系化合物として、チオフェン、ビニレン、チェニレンビニレン、フェニレンビニレン、p−フェニレン、これらの置換体又はこれらの2種以上を用いてなる繰り返し単位のn数が4〜10のオリゴマー、又はn数20以上のポリマー、ペンタセン等の縮合多環芳香族化合物、縮合環テトラカルボン酸ジイミド等を挙げることができる。
(A5)有機非線形化合物;p−ニトロアニリン、2−メチル−4−ニトロアニリン、メロシアニン色素、アントラキノン系化合物、p−ニトロアニリド、ベンゾイミダゾール誘導体、ヒドラジン誘導体、ヒドラゾン誘導体、オキサジアゾール誘導体、含N複素環化合物、含N五員環化合物、スチルベン誘導体、ジアミノベンゼン誘導体、N,N’−ビス−(4−ニトロフェニル)−メタンジアミン等を挙げることができる。
(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.
また、本発明においては、必ずしも架橋構造を形成させる必要はないが、必要に応じて、形成されるポリマーの機械的強度を高める観点から、架橋構造を適宜導入させることができる。このような架橋構造を形成させるに、2官能性以上の多官能性モノマーを適宜好適に使用することができる。その多官能性モノマーとして、例えば、エチレングリコールジ(メタ)アクリレート,トリエチレングリコールジ(メタ)アクリレート,テトラエチレングリコールジ(メタ)アクリレート,ジエチレングリコールジ(メタ)アクリレート,ポリプロピレングリコールジ(メタ)アクリレート,ネオペンチルグリコールジ(メタ)アクリレート,トリメチロールプロパントリ(メタ)アクリレート,ペンタエリスリトールトリ(メタ)アクリレート,1,1,1−トリスヒドロキシメチルエタンジアクリレート,1,1,1−トリスヒドロキシメチルエタントリアクリレート,1,1,1−トリスヒドロキシメチルプロパントリアクリレート,N−メチロールアクリルアマイド等を挙げることができる。 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.
また、本発明に用いる単分散性の有機ポリマー球状粒子(A)として、上述する如く、例えば、黒色系の無彩色に着色さる染顔料を含め、単分散性を阻害させるとか又は熱融着性を阻害させる等がない限りにおいて、必要に応じて予め他の添加剤として、例えば、紫外線吸収剤、近赤外線吸収剤、酸化防止剤、蛍光増白剤、染料、顔料、帯電付与剤、帯電防止剤、垂れ止め防止剤、消泡剤等を有機ポリマー球状粒子(A)中に適宜添加させることができる。 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).
また、本発明においては、各種の下地基材上に塗工させる水性グリーンシート相なる塗工相は、その塗工相を形成させる目的によって、従来から公知である例えば、流し込み法、刷毛塗り法、ブレードコーター、エアナイフコーター等の各種のコーター法、噴霧法(又はエアロジル法)、スピンコート法、スクリーン印刷及びインクジェット法等を適宜選んで好適に用いることができる。 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.
<本発明による水性粒子分散体及び3次元粒子結晶体相の用途>
以上から、本発明による水性サスペンジョン型流延性粒子分散体を用いて得られる各種の下地基材上に設けられる3次元粒子整合体の固定化連続相は、単分散球状粒子の粒子整合体面である(001)粒子整合体面が、垂直方向であるc軸方向の[001]方向に規則的に数層〜数十層を積層する3次元粒子整合体相の2次元方向に連続相として提供される。
<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. .
従って、本発明による水性サスペンジョン型流延性粒子分散体を用いて形成させた3次元粒子整合体の2次元方向への固定化連続相部材は、その連続相を形成する黒色系無彩色の単分散球状粒子の粒度特性として、既に詳細に説明する如く、体積基準で表す平均粒子径を130〜310nmの範囲に特定することで、粒子配列構造体としての均質さによって効率よく光干渉効果として強められて、著しく明確な反射特性を発揮させて構造色を発色させる構造色型の水性塗工材を提供することができる。 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.
<3次元粒子整合体型の水性塗工材>
すなわち、構造色を発色させる水性サスペンジョン型流延性粒子分散体は、既に説明済みであるように、水性インキ又は水性塗料の主成分として、印刷又は筆記又は転写させてなる塗布相が、3次元粒子整合体の連続相であって、その連続相が可視光照射下に有彩色の構造色を発色させる。また、その連続相は艶やかさ感及び/又は金属光沢感を視感させるものである。よって、本発明においては、このような水性インキ(又は水性発色材)及び水性塗料として、被印刷体又は被転写体であるガラス板、モルタル板、セラミックス板、磁器板、プラスチックス板、シリコン・ウエハー、鋼板、銅板、アルミニュウム板、アルミニュウム合金板、ステンレス板、木質板、毛皮シート、布地シート、厚紙シート、プラスチックフィルム群から選ばれる何れかの下地基材上に、塗布することで所望する構造色図柄及び/又は構造色文字を印刷又は転写させて、印刷相又は印字相又は転写相なる塗布相を提供することができる。また、本発明においては、これらの下地基材は、その下地材の使用目的によって、透明体であっても、白色系又は黒色系無彩色体であっても、又は有彩着色体であっても適時用いることができる。
<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.
<構造色相型の水性塗工材;水性インキ、水性塗料>
また、本発明においては、有機ポリマー球状粒子(A)が、体積基準で表す平均粒子径が130〜310nmの範囲にあって、しかも、灰黒色、黒色から選ばれる何れか1種の黒色系無彩色の有機ポリマー又は無機ポリマーの単分散球状粒子(A)であると、既に詳細に説明する如く、その印刷相又は筆記相又は転写相は、可視光照射下に3次元粒子整合体の構造色連続相として有彩光色を発色させ、その発色相は、同時に艶やかさ感及び/又は金属光沢感を視感させる構造色相型の水性塗工材を提供することができる。
<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.
<金属光沢感を賦与させる3次元粒子結晶体相型の水性塗工材>
本発明においては、有機ポリマー球状粒子(A)が、可視光照射下に白色乱反射色を視感させる透明無着色の白色系無彩色粒子で、しかも、平均粒子径が体積基準で表して130〜800nmの範囲にある3次元粒子整合体連続相形成固定用の水性サスペンジョン型流延性粒子分散体を、水性塗布材として印刷又は又は筆記又は相転させてなる印刷相又筆記相又は転写相なる塗布相は、可視光照射下に「艶やかさ感」及び/又は「金属光沢感」を視感(又は賦与)させる3次元粒子整合体相型の水性塗工材を提供することができる。
<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.
<機能性3次元粒子結晶体相型の機能性水生塗工材>
本発明においては、有機ポリマー球状粒子(A)が、有機ELポリマー、強誘電体性ポリマー、半導体性ポリマー、導電体性ポリマー及び有機非線形光学化合物を含有するPMMA等の透明性ポリマーの機能性粒子である水性粒子分散体を用いることで、各種の下地基材上にキャリヤー移動性に優れえる有機EL、特にフレキシブル性に優れる強誘電性(圧電性、焦電性)、半導体性及び導電性及び特にレーザー光に係わっての非線形光電子特性を発揮させる機能性3次元粒子結晶薄膜材を提供することができる。
<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.
以下に、本発明を実施例により説明するが、本発明はこれらの実施例にいささかも限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
(実施例1)
<Tg2;親水性モノマー(m2)=4HBA>
MMA100gをフラスコに入れ、乳化剤ドデシルベンゼンスルホン酸ナトリウムの0.1g、水567gを加え72℃に昇温させた。窒素雰囲気下で重合開始剤として過硫酸アンモニウム0.5gを加え乳化重合を行って体積基準で表す平均粒子径123nmの単分散球状粒子が、体積基準で表す分散濃度15%のサスペンジョン(S−1)を調製した。
次いで、MMA30g、エチレングリコールジメタクリレート30g、4−ヒドロキシブチルアクリレート(4HBA)10g、メタクリル酸5g、ベンゾイルパーオキサイド(BPO)1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水259gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を166g加えた。
これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了した。
これを、クロスフロー洗浄装置で濃縮と洗浄を行い、分散濃度29.9%、電気伝導度280[μS/cm]である本発明による水性粒子分散体(C−1)を調製した。得られたこの分散粒子である本発明による有機ポリマー球状粒子(A)の粒子径は198nmで、単分散性の非常に高い粒子であった。
(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.
(実施例2)
<Tg2;親水性モノマー(m2)=MA>
MMA32.5g、エチレングリコールジメタクリレート30g、メチルアクリレート(MA)20g、メタクリル酸5g、BPO1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水329gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を83g加えた。これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了した。
これを、クロスフロー洗浄装置で濃縮と洗浄を行い、分散濃度29.8%、電気伝導度225[μS/cm]である本発明による水性粒子分散体(C−2)を調製した。得られた本発明による有機ポリマー球状粒子(A)の粒子径は244nmで、単分散性の非常に高い粒子であった。
(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.
(実施例3)
<Tg2;親水性モノマー(m2)=MEA>
MMA37.2g、エチレングリコールジメタクリレート30g、メトキシエチルアクリレート(MEA)10g、メタクリル酸5g、BPO1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水300gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を118g加えた。これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了した。
これを、クロスフロー洗浄装置で濃縮と洗浄を行い、分散濃度30.4%、電気伝導度257[μS/cm]である本発明による水性粒子分散体(C−3)を調製した。この得られた有機ポリマー球状粒子(A)の粒子径は220nmで、単分散性の非常に高い粒子であった。
(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.
(比較例1)
<Tg2;親水性ポリマー(P2)無し>
MMA40g、エチレングリコールジメタクリレート30g、メタクリル酸5g、ベンゾイルパーオキサイド(BPO)1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水259gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を166g加えた。これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了した。
これを、クロスフロー洗浄装置で濃縮と洗浄を行い、分散濃度29.6%、電気伝導度275[μS/cm]で、Tg2に相当する親水性モノマー(m2)を用いないで調製した水性粒子分散体(H−1)を調製した。このサスペンジョンの粒子径は202nmであり、単分散性の非常に高い粒子であった。
(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.
(比較例2)
<Tg2;親水性ポリマー(P2)が疎水性ポリマー>
MMA30g、エチレングリコールジメタクリレート30g、ラウリルメタクリレート10g、メタクリル酸5g、ベンゾイルパーオキサイド(BPO)1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水259gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を166g加えた。これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了した。
これを、クロスフロー洗浄装置で濃縮と洗浄を行い、分散濃度31.0%、電気伝導度323[μS/cm]で、Tg2に相当するポリマー(P2)が疎水性ポリマーである水性粒子分散体(H−2)を調製した。この分散粒子の粒子径は199nmで、単分散性の非常に高い粒子であった。
(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.
(比較例3)
<Tg2;相当親水性モノマー(m2)が4HBA3部>
MMA37g、エチレングリコールジメタクリレート30g、4−ヒドロキシブチルアクリレート(4HBA)3g、メタクリル酸5g、ベンゾイルパーオキサイド(BPO)1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水259gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を166g加えた。これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了した。
これを、クロスフロー洗浄装置で濃縮と洗浄を行い、29.5%、電気伝導度276[μS/cm]である水性サスペンジョン(H−3)を調製した。このサスペンジョンの粒子径は192nmであり、単分散性の非常に高い粒子であった。
(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.
(比較例4)
<Tg2;相当親水性モノマー(m2)が4HBA20部>
MMA20g、エチレングリコールジメタクリレート30g、4−ヒドロキシブチルアクリレート(4HBA)20g、メタクリル酸5g、ベンゾイルパーオキサイド(BPO)1.5g、ニューコール707SF(日本乳化剤社製)3.3g、亜硝酸ナトリウム0.05g、水259gをフラスコに入れ、ホモミキサーにて9000rpm×10分乳化させたのち、S−1を166g加えた。これを攪拌しながら50℃まで昇温し、20分後にさらに75℃まで昇温し1時間重合させた。さらに85℃に昇温させて重合反応を終了したが、有機ポリマー球状粒子は得られなかった。
(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.
上記実施例1〜3、比較例1〜3にて調製した有機ポリマー球状粒子が分散する水性粒子分散体を、綜研化学(株)製の粘着剤SKダイン2094を予め3μmdryで塗布した下地基材の50μm厚の黒色PETフィルム上に、塗工させて層厚10μmdryの水性グリーンシート相を形成させた。
次いで、このPET基材上の塗工水性グリーンシート相を、25℃雰囲気下で乾燥させた。この時、垂直視線下に視感される構造色としての発色性、すなわち、乾燥脱水下に形成される塗工相の3次元粒子結晶性を観察し、また、その塗工相表面を指で擦った時の懸垂性(=粉落ち性)をそれぞれ評価した。
次いで、120℃×10分の加熱条件下に熱融着処理を行った。同様にして垂直視線下に視感される構造色としての発色性、すなわち、熱融着下に形成される塗工相の3次元粒子結晶性を観察し、また、その塗工相表面を同様にして懸垂性(=粉落ち性)のそれぞれを下記する評価法で評価して、その結果を下記[表1]に示した。
<塗工相の懸垂性(=表面の粉落ち性)>
・指で擦っても粒子の脱落がない…○
・指で擦るとやや粒子が脱落する…△
・指で擦ると粒子が脱落する…×
<塗工相の構造色発色性[=3次元粒子結晶性]>
・25℃乾燥時と同じ色…○
・25℃乾燥時の色と比べてやや劣る…△
・25℃乾燥時の色を維持していない…×
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 ℃… ×
その結果、[表1]から明らかなように、本発明による有機ポリマー球状粒子(A)を分散させた本発明による水性粒子分散体は、その単分散微細球状粒子が乾燥脱水・熱溶融下に、その粒子の表層近傍に偏在させたTg2の親水性ポリマー(P2)の低温度熱融着特性が活かされて形成される3次元粒子整合体相は、可視光照射下に構造色を視感させることから、その3次元粒子整合体相は、その有機ポリマー球状粒子(A)が、3次元方向に規則的に自己固着されて形成された3次元粒子結晶体相で、しかも、自己固着形成された3次元粒子結晶体相面は、極めて懸垂性に優れていることが良く理解される。 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.
以上から、本発明によって、単分散微細球状粒子が分散する3次元粒子整合体連続相形成用の水性サスペンジョン型の水性粒子分散体を主成分に、構造色に係わる有彩色の発色性を含む各種の機能特性を発揮させる機能性3次元粒子結晶体相を形成させる水性粒子分散体を提供することができた。 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.
すなわち、本発明による有機ポリマー球状粒子の水性粒子分散体を用いて、ガラス板、モルタル板、セラミックス板、磁器板、プラスチックス板、鋼板、銅板、アルミニュウム板、アルミニュウム合金板、ステンレス板、木質板、毛皮シート、布地シート、厚紙シート、プラスチックフィルム等の各種下地基材に印刷、転写及び塗布させて、光学特性としての構造色有彩光発色や、金属光沢感等を発揮する各種の内装、装飾、意匠、ディスプレイ材として、各種の産業分野に有用な塗工型の発色性3次元粒子結晶薄膜材を提供することができた。 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.
また、本発明によれば、機能性3次元粒子結晶薄膜材として、導電性結晶薄膜材;太陽電池用部材(セパレーター、電極、電解質膜)、固体電解型コンデンサー、光電変換素子、有機非線形光電子材料;光ディスク、光変調、光スイッチ、光メモリ、誘導発光、半導体性結晶薄膜材;TFT薄膜素子、オゾンガス検知素子、アンモニアガスセンサー、強誘電体性結晶薄膜材;各種の産業分野に有用な塗工型の機能性3次元粒子結晶薄膜材を提供することができた。 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.
Claims (7)
水性粒子分散体中に質量基準で表して25%以上で、45%を超えない分散濃度で含有する有機ポリマー球状粒子(A)が、前記固着微細球状粒子の前駆体粒子で、
この前駆体粒子を形成する樹脂成分であるTg1=50℃以上の疎水性ポリマー(P1)の100質量部当たり、その前駆体粒子の表相近傍部に、Tg2=40℃以下の親水性ポリマー(P2)が、5〜18質量部の範囲で含侵偏在していることを特徴とする3次元粒子結晶体相形成用の水性粒子分散体。 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.
前記固着微細球状粒子の有機ポリマー球状粒子(A)が、導電体性、半導体性、絶縁体性、強誘電体性、有機EL発光体性、非線形光電子体性の群から選ばれる何れか1種の機能特性を有していることを特徴とする機能性3次元粒子結晶薄膜材。 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:
所定量の水相に、重合ポリマー化後のTg2=50℃以上である疎水性モノマー(m1)と、その100質量部当たり、同様に重合ポリマー化後のTg2=40℃以下である親水性モノマー(m2)の5〜18質量部と、重合開始剤及び乳化剤とを加えて乳化懸濁させ、
次いで、予め調製した有機ポリマーのシード粒子水性分散体の所定量を注加させてシード乳化重合させ、
得られる有機ポリマー球状粒子(A)は、前記固着微細球状粒子の前駆体粒子で、その形成樹脂成分のTg1=50℃以上の疎水性ポリマー(P1)の100質量部当たり、この前駆体粒子の表相近傍部に、Tg2=40℃以下の親水性ポリマー(P2)を、5〜18質量部の範囲で含侵偏在させ、
次いで、洗浄・濃縮させて質量基準で表す分散濃度25〜45%で、且つその水性粒子分散体系の電気伝導度を3500[μS/cm]以下に調整させ、
次いで、この水性粒子分散体を用いて、下地基材上に塗工させた水性グリーンシート相を、Tg2+50℃以上〜前記親水性ポリマー(P2)の融点未満の温度下に乾燥脱水・熱融着させ、
て前記固着微細球状粒子の3次元粒子結晶体相を形成させることを特徴とする有機ポリマー球状粒子の3次元粒子結晶体相の製造方法。 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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JP2021028379A (en) * | 2019-08-09 | 2021-02-25 | 東洋インキScホールディングス株式会社 | Resin composition for overcoat |
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JP2011038001A (en) * | 2009-08-12 | 2011-02-24 | Fujifilm Corp | Aqueous ink composition, manufacturing method for composite particle, ink set, and image forming method |
CN107406699A (en) * | 2014-12-17 | 2017-11-28 | 汉高股份有限及两合公司 | Printable ferroelectricity ink |
JP2016186608A (en) * | 2015-03-27 | 2016-10-27 | 東洋インキScホールディングス株式会社 | Production method of colored film exhibiting structural color |
JP2021028379A (en) * | 2019-08-09 | 2021-02-25 | 東洋インキScホールディングス株式会社 | Resin composition for overcoat |
JP2021028378A (en) * | 2019-08-09 | 2021-02-25 | 東洋インキScホールディングス株式会社 | Primer |
JP7226293B2 (en) | 2019-08-09 | 2023-02-21 | 東洋インキScホールディングス株式会社 | Primer |
JP7226294B2 (en) | 2019-08-09 | 2023-02-21 | 東洋インキScホールディングス株式会社 | Overcoat resin composition |
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