JP2010209325A - White fine particle, and method for producing the same fine particle - Google Patents
White fine particle, and method for producing the same fine particle Download PDFInfo
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- 239000010419 fine particle Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 112
- 239000010936 titanium Substances 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 38
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920000877 Melamine resin Polymers 0.000 claims description 21
- 239000004640 Melamine resin Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000012463 white pigment Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 9
- 239000007771 core particle Substances 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- 241000282994 Cervidae Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
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- 230000003247 decreasing effect Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229910018011 MK-II Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
本発明は、画像表示装置に用いる白色微粒子並びにその製造方法に関し、特に、電界を利用して複数種の着色粒子をセル内で飛翔移動させる事により、白黒又はフルカラー画像の表示及び消去が繰り返し可能な画像表示方法及び画像表示媒体に使用する白色微粒子並びにその製造方法に関する。 The present invention relates to white fine particles used in an image display device and a method for producing the same, and in particular, it is possible to repeatedly display and erase black and white or full-color images by moving a plurality of types of colored particles in a cell using an electric field. The present invention relates to an image display method, white fine particles used for an image display medium, and a method for producing the same.
近年、環境意識の高揚に伴い、省エネルギーや省資源の観点から、液晶表示装置（ＬＣＤ）の省電力化やペーパレス化などの課題に対して様々な技術開発の取り組みが進められている。上述の課題を解決する技術の一つとして電子ペーパー技術が期待されており、たとえば、電気泳動型、エレクトロクロミック型、サーマルリライタブル型など種々の電子ペーパー技術の提案がなされている。最近では応答速度の速さから溶液を使わない乾式の表示装置が着目されている（非特許文献１参照）。 In recent years, with the heightening of environmental awareness, various technological development efforts have been promoted with respect to problems such as power saving and paperless liquid crystal display (LCD) from the viewpoint of energy saving and resource saving. Electronic paper technology is expected as one of the technologies for solving the above-described problems. For example, various electronic paper technologies such as electrophoresis type, electrochromic type, and thermal rewritable type have been proposed. Recently, attention has been paid to a dry display device that does not use a solution because of its high response speed (see Non-Patent Document 1).
乾式の表示装置は、通常、粉体と流体の特性を合わせ持つ粉流体と呼ばれる性質を有し、且つ色と帯電極性が異なる２種類の粒子（白色粒子及び黒色粒子）を２枚の基板（電極）間に充填し、この基板間に静電界をかけて、互いに異なる方向の基板に飛翔付着させて表示する装置をさす。この両基板間に加える電界を切り替える事により、帯電した粒子が所定の電界に応じて気中を移動し表示を切り替える（特許文献１参照）。
しかし、白色を表示させる際、これまで使用してきた白色粒子では光の隠蔽性が十分でないために着色粒子の色を透過してしまい、コントラストの低下や反射率が制限されてしまうなどの問題があった。
A dry-type display device usually has a property called a powder fluid having the characteristics of a powder and a fluid, and has two types of particles (white particles and black particles) having different colors and charging polarities on two substrates ( This is a device that displays images by filling between the electrodes) and applying an electrostatic field between the substrates so as to fly and adhere to the substrates in different directions. By switching the electric field applied between the two substrates, the charged particles move in the air according to a predetermined electric field, and the display is switched (see Patent Document 1).
However, when displaying white, the white particles that have been used so far do not have sufficient light concealment properties, so that the color of the colored particles is transmitted, resulting in a decrease in contrast and a limitation in reflectance. there were.
上述の欠点を克服する方法として、アルミニウム粒子とダイアモンドスラリーを混合した後、又はポリカーボネート等の樹脂粒子とダイアモンドスラリーを混合した後に、アルミニウムをスパッタコーティングする事によって作製された、表面に微細な凹凸を有する白色粒子が提案されている（特許文献２参照）。この方法は、スパッタコーティングを用いているために高価であり、且つ煩雑な工程を必要とする。また、白色顔料と樹脂とを混練して樹脂を着色した後、粉砕・分級することによって粒子化し、さらに蛍光増白剤を配合させた白色粒子が提案されている（特許文献３参照）。同文献では、さらに表面に外添剤をコーティングする事によって粒子形状の制御を行っている。この方法においても工程数が多く白色粒子を得るまでに煩雑な操作が必要であるという問題点を有する。
一方、酸化チタンを多く含有する微粒子は優れた白色度や光の隠蔽性を示すものの、比重が高い（酸化チタン：３．８〜４．１）ため、沈降しやすく、分散状態の安定性維持が低いことなどが欠点とされていた。
As a method of overcoming the above-mentioned drawbacks, fine irregularities are formed on the surface produced by sputter coating aluminum after mixing aluminum particles and diamond slurry or after mixing resin particles such as polycarbonate and diamond slurry. White particles have been proposed (see Patent Document 2). This method is expensive and requires complicated steps because of the use of sputter coating. Further, white particles have been proposed in which a white pigment and a resin are kneaded to color the resin, and then pulverized and classified to form particles, and further a fluorescent whitening agent is blended (see Patent Document 3). In this document, the particle shape is controlled by coating the surface with an external additive. This method also has a problem that the number of steps is large and a complicated operation is required to obtain white particles.
On the other hand, fine particles containing a large amount of titanium oxide exhibit excellent whiteness and light hiding, but have a high specific gravity (titanium oxide: 3.8 to 4.1), so that they settle easily and maintain stability in the dispersed state. It was considered a drawback to be low.
上述したように、画像表示装置に用いる白色粒子として、光の隠蔽性や白色度、また経時的な分散性といった性能面を満足し、且つ、製造コストや製造操作・製造工程といった粒子製造の観点からも満足できるものはこれまで提案されていなかった。 As described above, the white particles used in the image display device satisfy the performance aspects such as light concealment, whiteness, and dispersibility over time, and the viewpoint of particle production such as production cost, production operation and production process. Until now, no one has been satisfied.
本発明は、上記の事情に鑑みなされたものであって、白色度が高く充分な光の隠蔽性を有し、且つ優れた粉流体特性を有し、且つ、比較的平易な製造方法にて製造できる画像表示素子用の白色微粒子とその製造方法の提供を目的とする。 The present invention has been made in view of the above circumstances, has a high whiteness, has sufficient light hiding properties, has excellent powder fluid characteristics, and is a relatively simple manufacturing method. An object of the present invention is to provide white fine particles for an image display element that can be produced and a method for producing the same.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、熱硬化性樹脂からなる粒子核の表面をチタンアルコキシドの重縮合物で覆った白色微粒子という構成を採用した。そして該微粒子を製造するにあたり、熱硬化性樹脂からなる粒子核をアルコール中に分散した分散液に、チタンアルコキシドと微量のアンモニア水などのアルカリを添加することによって、チタンアルコキシドがアルカリによって加水分解され、この加水分解されたチタンアルコキシドが熱硬化性樹脂からなる粒子核表面で選択的に重縮合反応することにより、熱硬化性樹脂からなる粒子核表面にチタンアルコキシドの重縮合物からなる白色皮膜を形成できることを見出し、そして該製造方法によって得られた微粒子が、従来の球状樹脂粒子や酸化チタンからなる球状粒子の課題を克服し、上記目的の白色微粒子となることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have adopted a configuration of white fine particles in which the surface of particle nuclei made of a thermosetting resin is covered with a polycondensate of titanium alkoxide. In producing the fine particles, titanium alkoxide is hydrolyzed by alkali by adding titanium alkoxide and a small amount of alkali such as ammonia water to a dispersion in which particle nuclei made of thermosetting resin are dispersed in alcohol. The hydrolyzed titanium alkoxide selectively undergoes a polycondensation reaction on the surface of the particle core made of thermosetting resin, so that a white film made of a polycondensate of titanium alkoxide is formed on the surface of the particle core made of thermosetting resin. The present inventors have found that the fine particles obtained by the production method can overcome the problems of conventional spherical resin particles and spherical particles made of titanium oxide, and become the above-mentioned white fine particles. .
すなわち、本発明は第１観点として、熱硬化性樹脂からなる粒子核と、前記粒子核の表面を覆うチタンアルコキシドの重縮合物からなる白色皮膜を含むことを特徴とする白色微粒子に関する。
第２観点として、前記熱硬化性樹脂からなる粒子核がメラミン樹脂である、第１観点記載の白色微粒子に関する。
第３観点として、前記熱硬化性樹脂からなる粒子核の形状が球状である、第１観点又は第２観点記載の白色微粒子に関する。
第４観点として、前記白色微粒子の粒径が０．０１μｍ〜１００μｍの範囲にある、第１観点乃至第３観点のうちいずれか一項に記載の白色微粒子に関する。
第５観点として、前記白色微粒子の白色皮膜の厚さが１ｎｍ〜１μｍの範囲にある、第１観点乃至第４観点のうちいずれか一項に記載の白色微粒子に関する。
第６観点として、熱硬化性樹脂からなる粒子核をアルコール系溶媒に添加し、分散液を製造する工程、及び該分散液にアルカリ及びチタンアルコキシドを添加し、チタンアルコキシドの加水分解を進行させて、熱硬化性樹脂からなる粒子核表面にチタンアルコキシドの重縮合物からなる白色皮膜を形成する工程を含む、白色微粒子の製造方法に関する。
第７観点として、第１観点乃至第５観点のうちいずれか一項に記載の白色微粒子又は第６観点に記載の製造方法によって得られた白色微粒子を含む白色顔料に関する。
第８観点として、第１観点乃至第５観点のうちいずれか一項に記載の白色微粒子又は第６観点に記載の製造方法によって得られた白色微粒子からなる電子ペーパー表示装置用表示粒子に関する。
That is, as a first aspect, the present invention relates to a white fine particle comprising a particle core made of a thermosetting resin and a white film made of a polycondensate of titanium alkoxide covering the surface of the particle nucleus.
As a 2nd viewpoint, the particle nucleus which consists of the said thermosetting resin is related with the white fine particle of a 1st viewpoint description which is a melamine resin.
As a third aspect, the present invention relates to the white fine particles according to the first aspect or the second aspect, wherein the shape of the particle nucleus made of the thermosetting resin is spherical.
As a fourth aspect, the present invention relates to the white fine particles according to any one of the first to third aspects, wherein the white fine particles have a particle size in the range of 0.01 μm to 100 μm.
As a fifth aspect, the present invention relates to the white fine particles according to any one of the first to fourth aspects, wherein the thickness of the white coating of the white fine particles is in the range of 1 nm to 1 μm.
As a sixth aspect, the step of adding a particle nucleus made of a thermosetting resin to an alcohol solvent to produce a dispersion, and adding an alkali and titanium alkoxide to the dispersion to advance hydrolysis of the titanium alkoxide. The present invention also relates to a method for producing white fine particles, including a step of forming a white film made of a polycondensate of titanium alkoxide on a particle core surface made of a thermosetting resin.
As a seventh aspect, the present invention relates to a white pigment containing the white fine particles according to any one of the first aspect to the fifth aspect or the white fine particles obtained by the production method according to the sixth aspect.
As an eighth aspect, the present invention relates to display particles for an electronic paper display device comprising the white fine particles according to any one of the first aspect to the fifth aspect or the white fine particles obtained by the production method according to the sixth aspect.
本発明の白色微粒子は、酸化チタンなどの無機物を主体とする微粒子よりも低い比重を有すると共に、白色度や光の隠蔽性に優れ、さらに優れた粉流体特性を有するものである。
また本発明の白色微粒子は、平易な製造によって製造することが可能である。
The white fine particles of the present invention have a specific gravity lower than fine particles mainly composed of inorganic substances such as titanium oxide, are excellent in whiteness and light concealing properties, and have excellent powder fluid characteristics.
The white fine particles of the present invention can be produced by simple production.
さらに、本発明の製造方法によれば、上述の優れた粉流体特性を有し、白色度、光の隠
蔽性に優れる白色微粒子を簡便に製造することができる。
Furthermore, according to the production method of the present invention, white fine particles having the above-described excellent powder fluid characteristics and excellent in whiteness and light concealability can be easily produced.
しかも本発明の白色微粒子は、上述の優れた粉流体特性、白色度を有し、且つ光の隠蔽性に優れることから、たとえば、少なくとも一方が透明な対向する基板間に色と帯電特性の異なる少なくとも二種以上の粒子を封入し、粒子へ電界を与えて粒子を移動させて画像を表示する画像表示用パネル（いわゆる電子ペーパー表示装置）に好適に使用できる、表示粒子を提供できる。 Moreover, since the white fine particles of the present invention have the above-described excellent powder fluid characteristics, whiteness, and excellent light concealing properties, for example, at least one of the transparent and opposite substrates has different colors and charging characteristics. It is possible to provide display particles that can be suitably used for an image display panel (so-called electronic paper display device) that encloses at least two kinds of particles and moves the particles by applying an electric field to the particles to display an image.
以下に、本発明の実施形態を詳しく説明する。
本発明の白色微粒子は、熱硬化性樹脂からなる粒子核の表面をチタンアルコキシドの重縮合物からなる白色皮膜で覆った微粒子であり、該微粒子は、熱硬化性樹脂からなる粒子核を分散させたアルコール系溶媒中にアルカリ及びチタンアルコキシドを添加し、チタンアルコキシドの加水分解を進行させ、それにより、熱硬化性樹脂からなる粒子核の表面に選択的にチタンアルコキシドの重縮合物からなる白色皮膜を形成させることを特徴とする製造方法から得られる。
まず、本発明において使用する熱硬化性樹脂からなる粒子核について説明する。
Hereinafter, embodiments of the present invention will be described in detail.
The white fine particles of the present invention are fine particles in which the surface of particle nuclei made of a thermosetting resin is covered with a white film made of a polycondensate of titanium alkoxide, and the fine particles disperse particle nuclei made of a thermosetting resin. Alkaline and titanium alkoxide are added to the alcoholic solvent, and the hydrolysis of titanium alkoxide is allowed to proceed, whereby a white film made of a polycondensate of titanium alkoxide selectively on the surface of the particle core made of thermosetting resin. It is obtained from the manufacturing method characterized by forming.
First, the particle nucleus made of the thermosetting resin used in the present invention will be described.
［熱硬化性樹脂からなる粒子核］
本発明において用いられる熱硬化性樹脂からなる粒子核としては、例えばフェノール樹脂、尿素樹脂、ベンゾグアナミン樹脂、エポキシ樹脂、ポリウレタン樹脂、メラミン樹脂等からなる熱硬化性樹脂からなる粒子核が挙げられ、好ましくはメラミン樹脂からなる。これらの粒子は一種単独で、又は二種以上を組み合わせて用いる事ができる。これらの熱硬化性樹脂からなる粒子核は、好ましくは球状であることが好ましく、その平均粒子径は特に制限されるものではないが一般に０．０１〜１００μｍ、より好ましくは０．１〜２０μｍの範囲の粒径を有する事が好ましい。ここで平均粒子径とは、Ｍｉｅ理論に基づくレーザー回折式粒度分布測定装置［例えば、マルバーン社製、マスターサイザー２０００
］にて体積粒度分布を測定した際の、累積体積５０％通過径（Ｄ50）を指す。
[Particle core made of thermosetting resin]
Examples of the particle core made of a thermosetting resin used in the present invention include a particle core made of a thermosetting resin made of a phenol resin, urea resin, benzoguanamine resin, epoxy resin, polyurethane resin, melamine resin, etc. Consists of melamine resin. These particles can be used alone or in combination of two or more. The particle nuclei composed of these thermosetting resins are preferably spherical, and the average particle diameter is not particularly limited, but is generally 0.01 to 100 μm, more preferably 0.1 to 20 μm. It is preferable to have a particle size in the range. Here, the average particle diameter is a laser diffraction particle size distribution measuring apparatus based on the Mie theory [for example, Mastersizer 2000 manufactured by Malvern, Inc.
] Indicates the 50% cumulative volume passage diameter (D 50 ) when the volume particle size distribution is measured.
［白色皮膜］
上記熱硬化性樹脂からなる粒子核を覆うように形成されるチタンアルコキシドの重縮合物からなる白色皮膜について説明する。
上記白色皮膜の厚さは特に限定されず、通常１ｎｍ〜１０００ｎｍの範囲であるが、好ましくは１０ｎｍ〜５００ｎｍの範囲である。白色皮膜の厚さが１ｎｍ未満である場合には、白色皮膜を構成するチタンアルコキシドの重縮合物が持つ白色度及び光の隠蔽性効果が発揮できない。また、白色皮膜の厚さが１０００ｎｍを超えると白色皮膜の剥離や割れが生じる虞が高くなる。
[White film]
A white film made of a polycondensate of titanium alkoxide formed so as to cover the particle core made of the thermosetting resin will be described.
The thickness of the white film is not particularly limited, and is usually in the range of 1 nm to 1000 nm, preferably in the range of 10 nm to 500 nm. When the thickness of the white film is less than 1 nm, the whiteness and light concealing effect of the titanium alkoxide polycondensate constituting the white film cannot be exhibited. On the other hand, when the thickness of the white film exceeds 1000 nm, there is a high possibility that the white film is peeled off or cracked.
［白色微粒子の製造方法］
次に、白色皮膜を形成する工程、すなわち本発明の白色微粒子の製造方法について説明する。
まず、上記熱硬化性樹脂からなる粒子核をアルコール系溶媒へ分散させて該粒子核の分散液を得る。ここで用いられるアルコール系溶媒として、例えば、メタノール、エタノール、プロパノールなどの低級アルコール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノールなどの中級アルコール等が挙げられる。これら低級及び中級アルコールは直鎖状アルコール又は分岐状アルコールのいずれでも良く、これらアルコールを単独のみならず二種以上を混合して使用しても良い。さらに、上記アルコール系溶媒に加えて、親水性の有機溶媒、例えばアセトニトリル、ＴＨＦ（テトラヒドロフラン）、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）、ＤＭＳＯ（ジメチルスルホキシド）等を全アルコールに対して少量（例えば２０ｖｏｌ％未満）添加することもできる。
[Method for producing white fine particles]
Next, the process for forming a white film, that is, the method for producing white fine particles of the present invention will be described.
First, particle nuclei made of the thermosetting resin are dispersed in an alcohol solvent to obtain a dispersion of the particle nuclei. Examples of the alcohol solvent used here include lower alcohols such as methanol, ethanol and propanol, intermediate alcohols such as butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol. These lower and intermediate alcohols may be either linear alcohols or branched alcohols, and these alcohols may be used alone or in admixture of two or more. Further, in addition to the above alcohol solvents, hydrophilic organic solvents such as acetonitrile, THF (tetrahydrofuran), DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide) and the like are added in small amounts (for example, 20 vol). %)) Can also be added.
次に、前記工程で得られた熱硬化性樹脂からなる粒子核の分散液に、アルカリ及びチタンアルコキシドを添加する。ここでアルカリとチタンアルコキシドは一緒に添加してもよいし、先にアルカリを添加した後にチタンアルコキシドを添加してもよく、あるいは、先にチタンアルコキシドを添加した後にアルカリを添加してもよい。好ましくは、先にアルカリを添加した後、チタンアルコキシドを添加することが望ましい。
チタンアルコキシドは通常５分以上かけて反応溶液（熱硬化性樹脂からなる粒子核の分散液）に滴下することが好ましく、より好ましくは２０分以上かけて滴下することが望ましい。
チタンアルコキシドの滴下時の反応溶液の温度としては、通常５℃乃至分散液の溶媒の沸点以下の温度であり、好ましくは１０℃乃至６０℃、より好ましくは２０℃乃至４０℃である。
また、チタンアルコキシドの添加量は、滴下後の反応溶液中の濃度として通常０．００１乃至１ｍｏｌ／Ｌであり、より好ましくは０．０１乃至０．３ｍｏｌ／Ｌである。
Next, alkali and titanium alkoxide are added to the dispersion of particle nuclei made of the thermosetting resin obtained in the above step. Here, alkali and titanium alkoxide may be added together, titanium alkoxide may be added after adding alkali first, or alkali may be added after adding titanium alkoxide first. Preferably, it is desirable to add titanium alkoxide after adding alkali first.
The titanium alkoxide is preferably added dropwise to the reaction solution (a dispersion of particle nuclei made of a thermosetting resin) usually over 5 minutes or more, more preferably over 20 minutes.
The temperature of the reaction solution at the time of dropping the titanium alkoxide is usually 5 ° C. to a temperature not higher than the boiling point of the solvent of the dispersion, preferably 10 ° C. to 60 ° C., more preferably 20 ° C. to 40 ° C.
The addition amount of titanium alkoxide is usually 0.001 to 1 mol / L, more preferably 0.01 to 0.3 mol / L as the concentration in the reaction solution after dropping.
熱硬化性樹脂からなる粒子核の分散液にアルカリ水溶液を添加することにより、熱硬化性樹脂からなる粒子核の表面が活性化処理される。ここでいう活性化処理とは、熱硬化性樹脂からなる粒子核表面へアルカリが吸着することを意味し、これにより、該粒子核表面において、周囲に存在するチタンアルコキシドの加水分解が促進される。すなわち、周囲に存在するチタンアルコキシドの少なくとも一つのアルコキシ基が加水分解されてチタノール基が生成され、さらにアルカリによってチタノール基からのプロトン脱離が促進され、チタンと酸素が謂わばネットワークを構築して、皮膜が形成される。
この活性化処理を行うことにより、熱硬化性樹脂からなる粒子核の表面において選択的に白色皮膜が生成し、ひいては熱硬化性樹脂からなる粒子核との密着性が向上し、被覆層の剥離や割れが防止される。
By adding an alkaline aqueous solution to the dispersion of particle nuclei made of thermosetting resin, the surface of the particle nuclei made of thermosetting resin is activated. The activation treatment here means that alkali is adsorbed on the surface of the particle core made of a thermosetting resin, and this promotes hydrolysis of titanium alkoxide existing around the surface of the particle core. . That is, at least one alkoxy group of the titanium alkoxide present in the surroundings is hydrolyzed to produce a titanol group, and further, proton elimination from the titanol group is promoted by alkali, so that titanium and oxygen form a so-called network. A film is formed.
By performing this activation treatment, a white film is selectively formed on the surface of the particle core made of the thermosetting resin, thereby improving the adhesion with the particle core made of the thermosetting resin, and peeling of the coating layer. And cracking is prevented.
ここで添加されるアルカリ水溶液としては、アンモニア、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属塩、アルカリ土類金属塩などの水溶液の他、アルコール系溶媒に溶解する第一級アミン、例えばメチルアミン、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、ｎ−ブチルアミン、イソブチルアミン、ｓｅｃ−ブチルアミン、ｔｅｒｔ−ブチルアミン、また、第二級アミンとして、Ｎ，Ｎ−ジメチルアミン、Ｎ，Ｎ−ジエチルアミン、Ｎ，Ｎ−ジ−ｎ−プロピルアミン、Ｎ，Ｎ−ジイソプロピルアミン、Ｎ，Ｎ−ジ−ｎ−ブチルアミン、Ｎ，Ｎ−ジイソブチルアミン、Ｎ，Ｎ−ジ−ｓｅｃ−ブチルアミン、また第三級アミンとしてトリメチルアミン、トリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミンが用いられるが、特にアンモニア水溶液を用いるのが好ましい。
またアルカリの添加量は、添加後の反応溶液中の濃度として０．００１乃至１ｍｏｌ／Ｌ、より好ましくは０．０１乃至０．１ｍｏｌ／Ｌである。
As the aqueous alkali solution added here, in addition to aqueous solutions of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal salts, alkaline earth metal salts, etc., primary solutions that are soluble in alcoholic solvents. Amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, and secondary amines such as N, N-dimethylamine, N, N- Diethylamine, N, N-di-n-propylamine, N, N-diisopropylamine, N, N-di-n-butylamine, N, N-diisobutylamine, N, N-di-sec-butylamine, and third As the tertiary amine, trimethylamine, triethylamine, tri-n-propylamine, tri- - butylamine is used but is preferably in particular to use aqueous ammonia.
The addition amount of the alkali is 0.001 to 1 mol / L, more preferably 0.01 to 0.1 mol / L as the concentration in the reaction solution after the addition.
前記熱硬化性樹脂からなる粒子核の表面を覆うように形成される白色皮膜に用いられるチタン化合物としては、一般式：Ｔｉ（ＯＲ）4又はＴｉ（Ｒ’）n（ＯＲ）4-n（式中、
Ｒ及びＲ’は炭素原子数１〜５のアルキル基又は炭素原子数２〜６のアシル基を表し、ｎは１〜３の整数である）で示されるチタンアルコキシド、又はこれらの部分加水分解物が挙げられる。
Ｒ及びＲ’の具体例としては、メチル基、エチル基、直鎖又は分岐プロピル基、直鎖又は分岐ブチル基、直鎖又は分岐ペンチル基、アセチル基、プロピオニル基等が挙げられる。分散液中に添加されたこれらのチタン化合物（チタンアルコキシド）は、加水分解されて所謂チタニアゾルとなりこれが球状粒子表面を覆うことにより皮膜が形成される。
As the titanium compound used for the white film formed so as to cover the surface of the particle core made of the thermosetting resin, a general formula: Ti (OR) 4 or Ti (R ′) n (OR) 4-n ( Where
R and R ′ represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 2 to 6 carbon atoms, and n is an integer of 1 to 3), or a partial hydrolyzate thereof Is mentioned.
Specific examples of R and R ′ include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, an acetyl group, and a propionyl group. These titanium compounds (titanium alkoxide) added to the dispersion are hydrolyzed to form a so-called titania sol, which forms a film by covering the surface of the spherical particles.
このようにして得られた白色微粒子は、白色皮膜が未焼成であるため表面にチタノール基が多く残存したものとなっている。そこで表面のチタノール基を利用してビニルトリエトキシシラン、メタクロキシプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン等のシランカップリング剤等によって容易に表面修飾できる。
こうした表面修飾を施すことにより、本発明の白色微粒子は粒子表面の帯電特性や粉流体特性を制御することが可能である。なおここでいう粉流体特性とは、粒子と液体の両特性を兼ね備える特性、すなわち、粒子でありながらその特徴である重力の影響を極めて受けずに高流動性を示すような特性を指す。
The white fine particles thus obtained have many titanol groups remaining on the surface because the white film has not been fired. Therefore, surface modification can be easily performed using silane coupling agents such as vinyltriethoxysilane, methaxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane using the surface titanol group. it can.
By applying such surface modification, the white fine particles of the present invention can control the charging characteristics and powder fluid characteristics of the particle surface. In addition, the pulverized fluid characteristic here refers to a characteristic that has both characteristics of a particle and a liquid, that is, a characteristic that exhibits high fluidity without being significantly affected by gravity, which is a characteristic of the particle.
以上の工程からなる方法を実施することにより得られた本発明の白色微粒子は、酸化チタン膜により形成された高屈折率な膜を表面に有し、該膜は厚さを用途に応じて調節でき、しかも白色化度が高く、且つ亀裂、剥離しにくいことから、本発明の白色微粒子は十分な光の隠蔽性を有する特長を有する。また前述したように、微粒子の表面修飾によって表面特性を容易に改変できることから、本発明の白色微粒子は、たとえば、少なくとも一方が透明な対向する基板間に色と帯電特性の異なる少なくとも二種以上の粒子を封入し、粒子へ電界を与えて粒子を移動させて画像を表示する画像表示用パネル（いわゆる電子ペーパー表示装置）に用いる表示粒子として、好適に使用できる。
上述の用途のほか、本発明の白色微粒子は白色顔料として光拡散素子、インク、塗料、プラスチック・紙用フィラー、自動車用粉体顔料、筆記用具、スタンプ用インキ、修正用インキ等に好適に使用される。
The white fine particles of the present invention obtained by carrying out the method comprising the above steps have a high refractive index film formed of a titanium oxide film on the surface, and the thickness of the film is adjusted according to the application. In addition, since the degree of whitening is high and cracking and peeling are difficult, the white fine particles of the present invention have a feature of having sufficient light concealment. In addition, as described above, since the surface characteristics can be easily modified by surface modification of the fine particles, the white fine particles of the present invention include, for example, at least two or more kinds having different colors and charging characteristics between opposing substrates at least one of which is transparent. It can be suitably used as display particles used in an image display panel (so-called electronic paper display device) that encloses the particles, applies an electric field to the particles, and moves the particles to display an image.
In addition to the applications described above, the white fine particles of the present invention are suitably used as white pigments in light diffusing elements, inks, paints, plastic / paper fillers, automotive powder pigments, writing instruments, stamp inks, correction inks, etc. Is done.
以下に実施例を掲げて本発明をさらに詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
＜実施例１：白色微粒子の調製＞
熱硬化性樹脂からなる粒子核として、粒子径約３．５μｍのメラミン樹脂粒子（日産化学工業（株）製、オプトビーズ（登録商標）３５００Ｍ）、アルコール系溶媒として無水エタノール、加水分解により酸化チタンを形成し得るチタン化合物としてチタンテトラブトキシド、水として脱イオン後にメンブランフィルターでろ過した純水を使用した。
まず無水エタノール１００ｍＬにメラミン樹脂粒子１．６６ｇを、別の無水エタノール５０ｍＬにチタンテトラブトキシド０．８５ｇを、さらに別の無水エタノール５０ｍＬに水１．８０ｇを添加した。メラミン樹脂粒子を含む溶液を１５分間超音波照射し、メラミン樹脂粒子の分散液を得た。分散液を反応器に移して２５％アンモニア水０．３０ｍＬを添加し、乾燥窒素雰囲気下１５分間３０℃の恒温槽内で攪拌した。チタンテトラブトキシドを含むエタノール溶液を反応器に加えてさらに１０分間攪拌した。その後、水を含むエタノール溶液をマイクロチューブポンプにより６０分かけて滴下し、滴下後９０分間さらに攪拌を続けた。
得られた懸濁液を遠心分離により沈降させ、デカンテーションにより上澄み液を取り除いた。これにエタノールを加えてデカンテーションを繰り返した後、６０℃で２４時間以上真空乾燥させて酸化チタン（含水物）でコーティングされたメラミン樹脂粒子を得た。
<Example 1: Preparation of white fine particles>
Melamine resin particles having a particle diameter of about 3.5 μm (manufactured by Nissan Chemical Industries, Ltd., Opt Beads (registered trademark) 3500M) as particle nuclei made of thermosetting resin, anhydrous ethanol as alcohol solvent, titanium oxide by hydrolysis Titanium tetrabutoxide was used as a titanium compound capable of forming, and pure water filtered through a membrane filter after deionization was used as water.
First, 1.66 g of melamine resin particles were added to 100 mL of absolute ethanol, 0.85 g of titanium tetrabutoxide was added to 50 mL of another absolute ethanol, and 1.80 g of water was added to 50 mL of another absolute ethanol. The solution containing melamine resin particles was irradiated with ultrasonic waves for 15 minutes to obtain a dispersion of melamine resin particles. The dispersion was transferred to a reactor, 0.30 mL of 25% aqueous ammonia was added, and the mixture was stirred in a constant temperature bath at 30 ° C. for 15 minutes under a dry nitrogen atmosphere. An ethanol solution containing titanium tetrabutoxide was added to the reactor and stirred for an additional 10 minutes. Then, the ethanol solution containing water was dripped over 60 minutes with the microtube pump, and stirring was further continued for 90 minutes after dripping.
The resulting suspension was sedimented by centrifugation, and the supernatant was removed by decantation. Ethanol was added thereto and decantation was repeated, followed by vacuum drying at 60 ° C. for 24 hours or more to obtain melamine resin particles coated with titanium oxide (hydrous material).
＜実施例２：白色微粒子の調製＞
実施例１においてチタンテトラブトキシドの量を１．７０ｇに変更した以外は、実施例１と同様の操作を行い、酸化チタン（含水物）でコーティングされたメラミン樹脂粒子を得た。
<Example 2: Preparation of white fine particles>
Except that the amount of titanium tetrabutoxide was changed to 1.70 g in Example 1, the same operation as in Example 1 was performed to obtain melamine resin particles coated with titanium oxide (hydrous material).
＜実施例３：白色微粒子の調製＞
実施例１においてチタンテトラブトキシドの量を２．５５ｇに、溶媒を無水エタノールからエタノール［関東化学(株)製、鹿１級］にそれぞれ変更した以外は、実施例１と同様の操作を行い、酸化チタン（含水物）でコーティングされたメラミン樹脂粒子を得た。
<Example 3: Preparation of white fine particles>
In Example 1, the same operation as in Example 1 was performed except that the amount of titanium tetrabutoxide was changed to 2.55 g and the solvent was changed from absolute ethanol to ethanol (Kanto Chemical Co., Ltd., deer grade 1), respectively. Melamine resin particles coated with titanium oxide (hydrous material) were obtained.
＜実施例４：白色微粒子の調製＞
実施例１においてチタンテトラブトキシドの量を３．４０ｇに、溶媒を無水エタノールからエタノール［関東化学(株)製、鹿１級］にそれぞれ変更した以外は、実施例１と同様の操作を行い、酸化チタン（含水物）でコーティングされたメラミン樹脂粒子を得た。
<Example 4: Preparation of white fine particles>
Except that the amount of titanium tetrabutoxide in Example 1 was changed to 3.40 g and the solvent was changed from absolute ethanol to ethanol (manufactured by Kanto Chemical Co., Inc., deer grade 1), the same operation as in Example 1 was performed, Melamine resin particles coated with titanium oxide (hydrous material) were obtained.
＜酸化チタン含有量の算出＞
各実施例で調製した白色微粒子を、それぞれ硝酸、フッ化水素酸により分解した後、高周波誘導結合プラズマ／発光分光分析（ＩＣＰ−ＡＥＳ）［セイコーインスツル（株）製、Ｖｉｓｔａ−ＰＲＯ］によりチタン含有量を測定した。得られたチタン含有量から白色微粒子の酸化チタンの含有量を算出した。結果を表１に示す。
表１に示すように実施例１乃至実施例４で得られた白色微粒子からはそれぞれチタンが検出され、酸化チタンにより皮膜が形成されていることがわかった。
<Calculation of titanium oxide content>
The white fine particles prepared in each example were decomposed with nitric acid and hydrofluoric acid, respectively, and then subjected to high frequency inductively coupled plasma / emission spectroscopic analysis (ICP-AES) [manufactured by Seiko Instruments Inc., Vista-PRO] with titanium. The content was measured. The content of titanium oxide in the white fine particles was calculated from the obtained titanium content. The results are shown in Table 1.
As shown in Table 1, titanium was detected from the white fine particles obtained in Examples 1 to 4, and it was found that a film was formed of titanium oxide.
＜白色度（光隠蔽性）測定＞
各実施例で調製した白色微粒子、及び各実施例において粒子核として用いたオプトビーズ（登録商標）３５００Ｍ（メラミン微粒子）並びに市販の白色粒子（シリコーン樹脂粒子、シリカ粒子）を、それぞれガラス基板上に単粒子層となるように固定し、分光式測色色差計［（有）東京電色製、オートマチックカラーアナライザー ＴＣ−１８００ ＭＫ−ＩＩ］により、各粒子の明度を測定し、白色度（光隠蔽性）の指標とした。結果を表１に示す。
表１に示すように、実施例１及び実施例２で得られた白色微粒子は市販の白色粒子よりも白色度に優れ、また、白色皮膜処理前のメラミン樹脂粒子と比べて６％程度白色度が向上しているという結果が得られた。さらに、よりチタンアルコキシドの添加量が多い実施例４で得られた白色微粒子に至っては、白色皮膜処理前のメラミン樹脂粒子と比べて２４
％も白色度が向上しているという結果が得られた。
<Whiteness (light hiding) measurement>
White fine particles prepared in each example, Optobead (registered trademark) 3500M (melamine fine particles) used as particle nuclei in each example, and commercially available white particles (silicone resin particles, silica particles) on a glass substrate, respectively. The lightness of each particle was measured with a spectroscopic colorimetric colorimeter [manufactured by Tokyo Denshoku Co., Ltd., automatic color analyzer TC-1800 MK-II], and whiteness (light hiding) Index). The results are shown in Table 1.
As shown in Table 1, the white fine particles obtained in Example 1 and Example 2 are superior in whiteness to commercially available white particles, and are about 6% whiteness compared to melamine resin particles before white film treatment. The result was improved. Furthermore, the white fine particles obtained in Example 4 with a larger addition amount of titanium alkoxide reach 24 compared with the melamine resin particles before the white film treatment.
%, The result that the whiteness was improved was obtained.
＜表面観察＞
各実施例で調製した白色微粒子、及び各実施例において粒子核として用いたオプトビーズ（登録商標）３５００Ｍ（メラミン微粒子）のそれぞれについて、走査型電子顕微鏡（ＳＥＭ）［日本電子（株）製、ＪＳＭ−７４００Ｆ］によりその表面観察を行った。オプトビーズ（登録商標）３５００ＭのＳＥＭ画像を図１に、実施例１及び実施例２で調製した白色微粒子のＳＥＭ画像をそれぞれ図２、図３に示す。また、実施例３及び実施例４で調製した白色微粒子のＳＥＭ画像をそれぞれ図７、図８に示す。
図１乃至図３、図７及び図８に示す走査型電子顕微鏡写真を参照すると、実施例１（図２）、実施例２（図３）、実施例３（図７）及び実施例４（図８）で得られた白色微粒子は、白色皮膜処理前のメラミン樹脂粒子（図１）と比べて滑らかな表面形状を有しているという結果が得られた。
また、実施例１（図２）と実施例２（図３）を比較すると、チタンアルコキシドの添加量（処理濃度）が多い実施例２（図３）の白色微粒子の方が、表面の凹凸が減少しているという結果が得られた。同様に、実施例２（図３）と対比して実施例３（図７）、実施例３（図７）と対比して実施例４（図８）の結果から判るように、チタンアルコキシドの添加量（処理濃度）の増加に伴い、得られた白色微粒子の表面の凹凸が減少するという結果が得られた。
<Surface observation>
For each of the white fine particles prepared in each example and OPTOBEADS (registered trademark) 3500M (melamine fine particles) used as particle nuclei in each example, a scanning electron microscope (SEM) [manufactured by JEOL Ltd., JSM The surface was observed by -7400F]. FIG. 1 shows an SEM image of OPTOBEADS (registered trademark) 3500M, and FIGS. 2 and 3 show SEM images of white fine particles prepared in Example 1 and Example 2, respectively. Further, SEM images of the white fine particles prepared in Example 3 and Example 4 are shown in FIGS. 7 and 8, respectively.
Referring to the scanning electron micrographs shown in FIGS. 1 to 3, 7 and 8, Example 1 (FIG. 2), Example 2 (FIG. 3), Example 3 (FIG. 7) and Example 4 ( The result that the white fine particle obtained by FIG. 8) has a smooth surface shape compared with the melamine resin particle (FIG. 1) before a white film process was obtained.
Further, when Example 1 (FIG. 2) and Example 2 (FIG. 3) are compared, the white fine particles of Example 2 (FIG. 3) with a larger amount of titanium alkoxide added (treatment concentration) have surface irregularities. The result was decreased. Similarly, as can be seen from the results of Example 3 (FIG. 7) in contrast to Example 2 (FIG. 3) and Example 4 (FIG. 8) in contrast to Example 3 (FIG. 7), the titanium alkoxide The result that the unevenness | corrugation of the surface of the obtained white fine particle decreased with the increase in addition amount (process density | concentration) was obtained.
＜断面観察＞
各実施例で調製した白色微粒子、及び各実施例において粒子核として用いたオプトビーズ（登録商標）３５００Ｍ（メラミン微粒子）のそれぞれについて、各微粒子を樹脂へ埋包させた後、スライス片を作成し、透過型電子顕微鏡（ＴＥＭ）［（株）日立製作所製、Ｈ−８０００］によりその断面観察を行った。オプトビーズ（登録商標）３５００ＭのＴＥＭ画像を図４に、実施例１及び実施例２で調製した白色微粒子のＴＥＭ画像をそれぞれ図５、図６に示す。また、実施例３及び実施例４で調製した白色微粒子のＴＥＭ画像をそれぞれ図９、図１０に示す。
なお、図４乃至図６、図９及び図１０は粒子の表面部分を拡大して示したものであり、図４は画面右側が粒子内部を示し、その隣りの濃淡のある粒団の画像（画面中央を上から下に亘る）は粒子の表面層を示す。また図５、図６、図９及び図１０は画面左下側が粒子内部を示し、画面上側左寄りから画面右側（或いは画面下側）に向かって粒子の表面層を示す。
<Cross-section observation>
For each of the white fine particles prepared in each example and the Optobead (registered trademark) 3500M (melamine fine particles) used as the particle core in each example, each fine particle was embedded in a resin, and then a slice piece was prepared. The cross section was observed with a transmission electron microscope (TEM) [H-8000, manufactured by Hitachi, Ltd.]. FIG. 4 shows a TEM image of OPTOBEADS (registered trademark) 3500M, and FIGS. 5 and 6 show TEM images of white fine particles prepared in Example 1 and Example 2, respectively. Further, TEM images of the white fine particles prepared in Example 3 and Example 4 are shown in FIGS. 9 and 10, respectively.
4 to 6, FIG. 9 and FIG. 10 are enlarged views of the surface portion of the particle, and FIG. 4 shows the inside of the particle on the right side of the screen, and an image of a particle aggregate having a light and shade adjacent to it ( The center of the screen (from top to bottom) shows the surface layer of the particles. In FIGS. 5, 6, 9 and 10, the lower left side of the screen shows the inside of the particle, and the surface layer of the particle is shown from the upper left side of the screen toward the right side (or the lower side of the screen).
図４乃至図６、図９及び図１０に示す透過型電子顕微鏡写真を参照すると、実施例１（図５）、実施例２（図６）、実施例３（図９）及び実施例４（図１０）で得られた白色微粒子は、白色皮膜処理前のメラミン樹脂粒子（図４）と比べると粒子表面にはっきりとした黒色のコントラストが見え、すなわち、酸化チタン皮膜が形成しているという結果が得られた。
また、実施例１（図５）と実施例２（図６）を比較すると、チタンアルコキシドの添加量（処理濃度）が多い実施例２（図６）の白色微粒子の方が、粒子表面の酸化チタン皮膜の厚さが厚くなるという結果が得られた。同様に、実施例２（図６）と対比して実施例３（図９）、実施例３（図９）と対比して実施例４（図１０）の結果から判るように、チタンアルコキシドの添加量（処理濃度）の増加に伴い、得られた白色微粒子の粒子表面の酸化チタン皮膜の厚さが厚くなるという結果が得られた。
Referring to the transmission electron micrographs shown in FIGS. 4 to 6, 9 and 10, Example 1 (FIG. 5), Example 2 (FIG. 6), Example 3 (FIG. 9) and Example 4 ( The white fine particles obtained in FIG. 10) show a clear black contrast on the particle surface as compared with the melamine resin particles before the white film treatment (FIG. 4), that is, a titanium oxide film is formed. was gotten.
Further, when Example 1 (FIG. 5) and Example 2 (FIG. 6) are compared, the white fine particles of Example 2 (FIG. 6) with a larger amount of titanium alkoxide added (treatment concentration) are oxidized on the particle surface. As a result, the thickness of the titanium film was increased. Similarly, as can be seen from the results of Example 3 (FIG. 9) compared to Example 2 (FIG. 6) and Example 4 (FIG. 10) compared to Example 3 (FIG. 9), the titanium alkoxide As the addition amount (treatment concentration) increased, the result was that the thickness of the titanium oxide film on the surface of the obtained white fine particles increased.
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| US10414173B2 (en) | 2012-07-26 | 2019-09-17 | Ceraloc Innovation Ab | Digital binder printing |
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| WO2014109700A1 (en) * | 2013-01-11 | 2014-07-17 | Floor Iptech Ab | Dry ink for digital printing |
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