JP4804720B2 - Titanium oxide film-coated powder and method for producing the same - Google Patents
Titanium oxide film-coated powder and method for producing the same Download PDFInfo
- Publication number
- JP4804720B2 JP4804720B2 JP2004115087A JP2004115087A JP4804720B2 JP 4804720 B2 JP4804720 B2 JP 4804720B2 JP 2004115087 A JP2004115087 A JP 2004115087A JP 2004115087 A JP2004115087 A JP 2004115087A JP 4804720 B2 JP4804720 B2 JP 4804720B2
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- JP
- Japan
- Prior art keywords
- film
- powder
- titanium oxide
- coating
- oxide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000843 powder Substances 0.000 title claims description 94
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 70
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000758 substrate Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 150000002978 peroxides Chemical class 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 11
- 239000010953 base metal Substances 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 description 159
- 239000000243 solution Substances 0.000 description 68
- 239000002245 particle Substances 0.000 description 54
- 238000000034 method Methods 0.000 description 45
- 238000000576 coating method Methods 0.000 description 41
- 239000011248 coating agent Substances 0.000 description 40
- 239000002585 base Substances 0.000 description 24
- 239000011247 coating layer Substances 0.000 description 22
- 239000000049 pigment Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- 239000000976 ink Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000975 dye Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- -1 color toner Substances 0.000 description 11
- 239000007888 film coating Substances 0.000 description 10
- 238000009501 film coating Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000010363 phase shift Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
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- 238000013461 design Methods 0.000 description 5
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- 239000003960 organic solvent Substances 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
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- 239000004952 Polyamide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
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- 239000003921 oil Substances 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 241000692870 Inachis io Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000001055 blue pigment Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
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- 238000004040 coloring Methods 0.000 description 3
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- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は酸化チタン膜被覆粉体およびその製造方法に関するものである。本酸化チタン膜被覆粉体は、表面に被覆された酸化チタン膜による光学的干渉作用により、青色や赤紫色に着色されたものであり、カラーインキ、プラスチック、紙用カラーフィラー、カラートナー、インクジェットプリンター用カラーインク等多種の目的に用いられる粉体およびその製造方法に関するものである。 The present invention relates to a titanium oxide film-coated powder and a method for producing the same. This titanium oxide film-coated powder is colored blue or magenta due to the optical interference effect of the titanium oxide film coated on the surface. Color ink, plastic, color filler for paper, color toner, ink jet The present invention relates to powders used for various purposes such as color inks for printers and a method for producing the same.
これまでに発明者らは、金属アルコキシドを使用しての酸化チタン膜の被覆方法（特許文献１（特開平０６−２２８６０４号公報）など）や、硫酸チタニル溶液を使用しての酸化チタン膜の被覆方法（特許文献２（特開２０００-３４５０７２号公報）など）を開発してきた。さらに、これら酸化チタン膜被覆方法を利用し、黒色磁性粉体上にシリカ・酸化チタンによる干渉膜を被覆し、黒色の磁性粉体を着色する方法をも開発し、公開してきた（特許文献３（特開平１０−３３０６４４号公報）など）。 In the past, the inventors have applied a method of coating a titanium oxide film using a metal alkoxide (Patent Document 1 (Japanese Patent Laid-Open No. 06-228604) or the like) or a titanium oxide film using a titanyl sulfate solution. A coating method (Patent Document 2 (JP 2000-345072 A) and the like) has been developed. Furthermore, using these titanium oxide film coating methods, a method of coating an interference film made of silica / titanium oxide on black magnetic powder and coloring the black magnetic powder has been developed and disclosed (Patent Document 3). (Japanese Patent Laid-Open No. 10-330644).
一方、酸化チタン膜を被覆する方法としては、上記チタン原料のほかに塩化チタン（IV）溶液を使用したものが知られており、これらについては特許文献４（特開２０００−８６２９２号公報）や特許文献５（特開平５−２８６７３８号公報）など、多数の文献や特許が公開されている。
さらには、特許文献６（特開平０１−２２４２２０号公報）では、塩化チタン（IV）溶液からペルオキソチタン溶液を作成し、該ペルオキソチタン溶液を基材粉体共存下で加熱することにより該基材粉体表面上に酸化チタン膜を被覆させる方法が公開されている。
また、特許文献７（特開平０９−７１４１８号公報）、特許文献８（特開平１０−６７５１６号公報）などでは、塩化チタン（IV）溶液などのチタン含有液体にアンモニア水などの塩基性物質を添加して水酸化チタンゲルを沈殿させ、沈殿物を濾過洗浄後に分散液とし、そこに過酸化水素水を添加することによりペルオキソチタン溶液を生成させ、該ペルオキソチタン溶液により粉体の表面処理を施す方法が公開されている。
また、特許文献９（国際公開第０３／０３１６８３号パンフレット）では、塩化チタン（III）溶液を使用しての基材粉体上への酸化チタン膜被覆方法が公開されている。
On the other hand, as a method of coating a titanium oxide film, there is known a method using a titanium (IV) chloride solution in addition to the above titanium raw material, and these are disclosed in Patent Document 4 (Japanese Patent Laid-Open No. 2000-86292) and A large number of documents and patents such as Patent Document 5 (Japanese Patent Laid-Open No. 5-286738) are disclosed.
Furthermore, in Patent Document 6 (Japanese Patent Application Laid-Open No. 01-224220), a peroxotitanium solution is prepared from a titanium (IV) chloride solution, and the peroxotitanium solution is heated in the presence of a base material powder to thereby form the base material. A method of coating a titanium oxide film on the powder surface has been disclosed.
In Patent Document 7 (Japanese Patent Laid-Open No. 09-71418) and Patent Document 8 (Japanese Patent Laid-Open No. 10-67516), a basic substance such as aqueous ammonia is added to a titanium-containing liquid such as a titanium (IV) chloride solution. To precipitate titanium hydroxide gel, and the precipitate is filtered and washed to form a dispersion, and a hydrogen peroxide solution is added thereto to form a peroxotitanium solution, and the powder is surface-treated with the peroxotitanium solution. The method is public.
Patent Document 9 (International Publication No. 03/031683 pamphlet) discloses a method for coating a titanium oxide film on a substrate powder using a titanium (III) chloride solution.
しかし、上述したような、これまで知られていた酸化チタン膜の被覆方法にはいろいろな問題があることが解った。
まず、金属アルコキシドを酸化チタン膜被覆原料として使用した場合では、金属アルコキシドが不安定でありその加水分解反応が非常に早いため、反応系を恒温・恒湿度下で行わなければならないこと、さらに反応をアルコールなどの有機溶媒中で行わなければならず、反応装置が複雑になる。
However, it has been found that there are various problems with the titanium oxide film coating methods known so far.
First, when a metal alkoxide is used as a titanium oxide film coating raw material, the metal alkoxide is unstable and its hydrolysis reaction is very fast, so that the reaction system must be performed at constant temperature and humidity, and further the reaction Must be carried out in an organic solvent such as alcohol, which complicates the reaction apparatus.
また、硫酸チタニル溶液を酸化チタン膜被覆原料として使用した場合の問題点としては、硫酸チタニルの反応が遅いために製膜操作に時間がかかること、１回の製膜操作で被覆できる酸化チタン膜厚に限界のあること、そのために酸化チタン膜を厚くする必要がある場合には酸化チタン膜被覆操作を複数回に分ける必要があること、強酸性下条件で行う必要があり、易腐食性である基材には適用不可である。
そして、塩化チタン（IV）溶液を使用しての酸化チタン膜の被覆方法では、硫酸チタニル溶液を使用する場合よりも反応時間を大幅に短縮でき、しかも１回の酸化チタン膜被覆操作にてかなり厚く酸化チタン膜を被覆させることができるようになった。しかしながら、上記硫酸チタニル溶液や塩化チタン（IV）溶液を使用する従来の酸化チタン膜被覆方法は、反応液のｐＨが７以下の酸性であったり、塩化物イオンを含むため、鉄粉など耐酸性が弱いものや塩化物に対して腐食する基材粉体とした場合には、その基材粉体が変質されるなどの影響があり、適用することが難しい。
In addition, as a problem when a titanyl sulfate solution is used as a raw material for coating a titanium oxide film, it takes a long time for the film forming operation because the reaction of titanyl sulfate is slow, and the titanium oxide film that can be coated by one film forming operation When there is a limit to the thickness, and when it is necessary to increase the thickness of the titanium oxide film, it is necessary to divide the titanium oxide film coating operation into multiple times, and it must be performed under strongly acidic conditions. It is not applicable to certain substrates.
The titanium oxide film coating method using a titanium (IV) chloride solution can significantly reduce the reaction time compared with the case of using a titanyl sulfate solution, and can be considerably performed by a single titanium oxide film coating operation. A thick titanium oxide film can be coated. However, the conventional titanium oxide film coating method using the above titanyl sulfate solution or titanium (IV) chloride solution is acidic with a pH of 7 or less in the reaction solution or contains chloride ions. In the case of a weak base material or a base material powder that corrodes chloride, it is difficult to apply because the base material powder is affected.
さらに、特許文献６（特開平０１−２２４２２０号公報）で公開されている酸化チタン膜被覆粉体の製造方法は、生成したペルオキソチタン溶液を基材粉体共存下で９５℃以上に加温し、それを８時間以上保持させることにより該基材粉体表面上に酸化チタン膜を被覆させる方法であり、粉体表面上に短時間で簡単に酸化チタン膜を被覆させる方法とは言えないものであった。
また、特許文献６（特開平０１−２２４２２０号公報）、特許文献７(特開平０９−７１４１８号公報)などで公開されている酸化チタン膜被覆方法は、用途として粉体の表面処理が記載されているものの、被覆原料溶液であるペルオキソチタン溶液を得るためには、チタン含有液体に塩基性物質を添加した後の沈殿物を濾過洗浄し、その後に過酸化水素水を加えなければならないなど手間のかかること、一回の酸化チタン膜被覆操作により基材粉体上にどの程度の厚さの酸化チタン膜を被覆することができるのか、すなわち、本件が目的とする基材粉体上への酸化チタン膜を被覆する方法が紹介されていないので、光学的干渉作用を起こさせるような厚さの酸化チタン膜を被覆させうるかは難しい。
Furthermore, in the method for producing a titanium oxide film-coated powder disclosed in Patent Document 6 (Japanese Patent Laid-Open No. 01-224220), the produced peroxotitanium solution is heated to 95 ° C. or higher in the presence of a base material powder. This is a method of covering the surface of the substrate powder with the titanium oxide film by holding it for 8 hours or more, and cannot be said to be a method of easily covering the surface of the powder with the titanium oxide film in a short time. Met.
In addition, the titanium oxide film coating method disclosed in Patent Document 6 (Japanese Patent Laid-Open No. 01-224220), Patent Document 7 (Japanese Patent Laid-Open No. 09-71418), etc. describes surface treatment of powder as an application. However, in order to obtain a peroxotitanium solution that is a coating raw material solution, the precipitate after adding a basic substance to the titanium-containing liquid must be filtered and washed, and then hydrogen peroxide solution must be added. That is, how much thickness of the titanium oxide film can be coated on the base powder by one operation of coating the titanium oxide film, that is, on the target base powder Since a method for coating a titanium oxide film has not been introduced, it is difficult to coat a titanium oxide film having a thickness that causes an optical interference action.
また、特許文献９（国際公開第０３／０３１６８３号パンフレット）で公開されている方法においては、従来より極めて容易に酸化チタン膜被覆を製造できるようになった。しかしながら、この方法では、塩化チタン（III）溶液をペルオキソ化する過程のうちで塩化チタン（III）溶液に過酸化物を添加する段階で、発泡が頻繁に発生するため、ペルオキソチタン溶液を作製するのことがあまり容易ではなかったり、滴下液条件によっては液が騰沸する可能性があった。
上記従来の技術の欠点および不足点のため、より容易かつ迅速に高精度な酸化チタン被覆粉体を製造する方法が求められた。
In addition, in the method disclosed in Patent Document 9 (International Publication No. 03/031683 pamphlet), it has become possible to manufacture a titanium oxide film coating much more easily than before. However, in this method, foaming frequently occurs at the stage of adding peroxide to the titanium (III) chloride solution in the process of peroxolating the titanium (III) chloride solution, so a peroxotitanium solution is prepared. This is not so easy, and the liquid may boil depending on the conditions of the dropping liquid.
Due to the drawbacks and shortcomings of the conventional techniques described above, a method for producing a highly accurate titanium oxide-coated powder more easily and quickly has been demanded.
筆者らは鋭意努力した結果、テトライソプロポキシチタン（以下、ＴＰＴとも称する）溶液を使用し、ペルオキソチタン酸溶液を作製する工程等を経ることで上記問題点を解決でき、基材金属粉体を変質させることなく該基材金属粉体上に酸化チタン膜を被覆できることを見出した。 As a result of diligent efforts, the authors can solve the above problems by using a tetraisopropoxy titanium (hereinafter also referred to as TPT) solution and a process for preparing a peroxotitanic acid solution. It has been found that a titanium oxide film can be coated on the base metal powder without alteration.
すなわち、本発明は以下の通りである。
（１）テトライソプロポキシチタン溶液に過剰の塩基性物質を添加し、次いで過酸化物を加えて塩基性ペルオキソチタン酸溶液を生成させ、該ペルオキソチタン酸溶液を基材金属粉体懸濁液中に滴下する工程を含む、前記基材金属粉体上に酸化チタン膜を被覆して酸化チタン膜被覆粉体を製造する方法。
（２）上記基材金属粉体懸濁液がｐＨ８〜１２のアルカリ性緩衝液であることを特徴とする前記（１）記載の酸化チタン膜被覆粉体の製造方法。
That is, the present invention is as follows.
(1) adding an excess of basic substance tetraisopropoxytitanium solution and then added a peroxide to produce a basic peroxotitanic acid solution, the peroxotitanate solution base metal powder suspension method comprising the step of dropping, to produce a titanium oxide film-coated powder to coat the titanium oxide film to the substrate on the metal powder.
(2) Production how titanium oxide film-coated powder of the (1), wherein said base metal powder suspension is alkaline buffer PH8～12.
本発明によれば、ＴＰＴ溶液を使用しペルオキソチタン酸溶液を製作することで、安全でコストが小さく、また塩化物イオンを含まないので易腐食性である粉体を基材としても、基材を変質させること無く酸化チタン被覆粉体を製造する事が可能となった。
また、製膜反応を短時間に、効率よく、しかも低い温度で行うことが可能となった。
According to the present invention, by manufacturing a peroxotitanate solution using a TPT solution, a safe and low-cost powder that does not contain chloride ions and is easily corroded can be used as a substrate. It has become possible to produce titanium oxide-coated powders without altering the quality.
Further, it has become possible to perform the film forming reaction in a short time, efficiently and at a low temperature.
さらに、一回の酸化チタン膜の被覆操作で、光学的干渉作用を生じさせるに十分な厚さの酸化チタン膜を、その膜厚を容易に調節して被覆させることができ、酸化チタン膜を被覆させた基材粉体に高い光学的干渉作用を生じさせることが可能となった。そのため、青色や赤紫色の着色磁性粉体を製造することが可能となった。 Furthermore, it is possible to coat a titanium oxide film having a thickness sufficient to cause an optical interference effect by adjusting the film thickness by a single coating operation of the titanium oxide film. It became possible to produce a high optical interference effect on the coated substrate powder. For this reason, it has become possible to produce colored magnetic powders of blue or reddish purple.
本発明は、
（A）ＴＰＴ溶液に過剰の塩基性物質を添加し、
（B）次いで過酸化物を加えて塩基性ペルオキソチタン酸溶液を生成させ、
（C）該ペルオキソチタン酸溶液を基材金属粉体懸濁液中に滴下する
工程を含む、基材金属粉体上に酸化チタン膜を被覆して酸化チタン膜被覆粉体を製造する方法に関する。
本発明によれば、チタン源であるＴＰＴ溶液に対して、塩基性物質、過酸化物を順次添加し、その反応液を基体粒子分散液に滴下するだけで容易に基体粒子上に酸化チタン膜を製膜することができる。本発明では、沈殿物を濾過洗浄したり、加熱、長時間の放置等の時間がかかり煩雑な工程を経ずして容易に酸化チタン膜を製膜しうる。
以下に、本発明の製造方法について詳しく説明する。
The present invention
(A) adding excess basic material to the TPT solution;
(B) then the peroxide is added to produce a basic peroxotitanic acid solution,
(C) The present invention relates to a method for producing a titanium oxide film-coated powder by coating a titanium oxide film on a base metal powder, which comprises the step of dropping the peroxotitanic acid solution into the base metal powder suspension. .
According to the present invention, a titanium oxide film can be easily formed on a substrate particle by simply adding a basic substance and a peroxide sequentially to a TPT solution that is a titanium source and dropping the reaction solution onto the substrate particle dispersion. Can be formed. In the present invention, it is possible to easily form a titanium oxide film without going through complicated steps that require time for filtration, washing, heating, and standing for a long time.
Below, the manufacturing method of this invention is demonstrated in detail.
（A）ＴＰＴ溶液に過剰の塩基性物質を添加する工程
本発明において、ＴＰＴ溶液は、市販のものを使う事ができ、Ｔｉ濃度を１５．４５質量％含む原液をそのまま使う事ができる。
本発明において、ＴＰＴ溶液に添加する塩基性物質は、上記のＴＰＴ溶液に添加することで水酸化チタンゲルの沈殿物を形成させるものであれば特に限定されないが、例えばアンモニア水、水酸化ナトリウム水溶液等のアルカリ金属水酸化物水溶液などのものが挙げられる。これらの塩基性物質は、混合して用いることもできる。
ＴＰＴ溶液に添加する塩基性物質の量は、ＴＰＴ溶液に対して過剰量であり、水酸化チタンゲルの沈殿物を形成させることができれば特に制限されない。
(A) Step of adding excess basic substance to TPT solution In the present invention, a commercially available TPT solution can be used, and a stock solution containing Ti concentration of 15.45% by mass can be used as it is.
In the present invention, the basic substance to be added to the TPT solution is not particularly limited as long as it forms a precipitate of titanium hydroxide gel by adding to the above TPT solution. For example, ammonia water, sodium hydroxide aqueous solution, etc. And an aqueous alkali metal hydroxide solution. These basic substances can also be used as a mixture.
The amount of the basic substance to be added to the TPT solution is not particularly limited as long as it is excessive with respect to the TPT solution and can form a precipitate of titanium hydroxide gel.
（B）過酸化物を加えて塩基性ペルオキソチタン酸溶液を生成させる工程
ＴＰＴ溶液に塩基性物質を添加した後に加える過酸化物は、水酸化チタンゲルの沈殿物が溶解してペルオキソ錯体とすることができるものであれば特に制限されない。
過酸化物の添加量は、水酸化チタンゲルの沈殿物が溶解してペルオキソ錯体とすることができれば特に制限されないが、ＴＰＴ溶液中のチタンに対して好ましくは３〜１５倍モル数の過酸化物を添加することが望ましい。添加量が少ないと水酸化チタンゲルが十分に再溶解せず、水酸化チタンゲルの沈殿物となってしまう。また、添加する過酸化水素水の量が過剰に多すぎると、添加した過酸化物の過剰分が分解されて発生する泡により液が発泡してしまい、ペルオキソチタン水和物の沈殿物を生成する。
(B) Step of adding a peroxide to form a basic peroxotitanic acid solution The peroxide to be added after adding a basic substance to the TPT solution is to dissolve the precipitate of titanium hydroxide gel into a peroxo complex. If it can do, it will not be restrict | limited in particular.
The amount of peroxide added is not particularly limited as long as the precipitate of titanium hydroxide gel can be dissolved to form a peroxo complex, but preferably 3 to 15 times the number of moles of peroxide with respect to titanium in the TPT solution. It is desirable to add. If the amount added is small, the titanium hydroxide gel will not be sufficiently re-dissolved, resulting in a precipitate of titanium hydroxide gel. Also, if the amount of hydrogen peroxide added is too large, the excess of the added peroxide will be decomposed and bubbles will be generated due to the bubbles generated, producing a precipitate of peroxotitanium hydrate. To do.
過酸化物の添加方法は、添加する速度や温度は特に制限されないが、製造工程の簡便化の為に、加温や冷却を行わないことが好ましい。
過酸化物を添加してペルオキソ錯体溶液とした後で、ｐＨを調節するためにさらに塩基性物質を添加することもできる。ｐＨを調節する物質に特に制限は無いが、アンモニア水などの塩基性物質を添加することが好ましい。ここで塩基性物質を添加する場合、以上のように調整して得られた過酸化物添加後のペルオキソチタン酸溶液のｐＨを９〜１０までに上げるに十分な量加えることが好ましい。
In the method of adding the peroxide, the speed and temperature of addition are not particularly limited, but it is preferable not to perform heating or cooling in order to simplify the production process.
After the peroxide is added to form a peroxo complex solution, a basic substance can be further added to adjust the pH. Although there is no restriction | limiting in particular in the substance which adjusts pH, It is preferable to add basic substances, such as aqueous ammonia. When adding a basic substance here, it is preferable to add sufficient quantity to raise the pH of the peroxotitanic acid solution after the peroxide addition obtained by adjusting as mentioned above to 9-10.
（C）ペルオキソチタン酸溶液の基材粉体懸濁液中への滴下
ペルオキソチタン酸溶液を基材粉体懸濁液中に滴下していく際の滴下速度としては、ペルオキソチタン酸溶液の所定量を好ましくは２０〜６０分の間で終了させる速度、さらに好ましくは２０〜４０分程度で終了させる速度が好ましい。２０分より短い滴下速度では、酸化チタンの析出が急激に起きてしまい、平滑な酸化チタン膜を被覆させることが難しくなることがある。６０分より長い滴下速度では、被覆される酸化チタン膜の性状が２０〜６０分の滴下速度でされた場合とほとんど差がないために、被覆操作時間をいたずらに長くするのみである。
(C) The dropping rate at which the dropping peroxotitanate solution to peroxotitanic acid solution of the base powder suspension gradually added dropwise to the substrate a powder suspension, at the peroxotitanic acid solution The speed at which the quantification is preferably completed within 20 to 60 minutes, and more preferably the speed at which the determination is completed within about 20 to 40 minutes is preferable. When the dropping speed is shorter than 20 minutes, precipitation of titanium oxide occurs abruptly, and it may be difficult to coat a smooth titanium oxide film. When the dropping speed is longer than 60 minutes, the property of the titanium oxide film to be coated is almost the same as that when the dropping speed is 20 to 60 minutes. Therefore, the coating operation time is merely lengthened.
ペルオキソチタン酸溶液が滴下される基材粉体懸濁液は、特に限定されないが、具体的には、Ｔｒｉｓ系、ホウ酸系、ホウ酸塩系、リン酸系、リン酸塩系、グリシン系、炭酸塩系等が挙げられる。懸濁液のｐＨとしてはｐＨ８〜１２であることが好ましい。これより低いｐＨ条件では、滴下したペルオキソチタン酸溶液から酸化チタンの粒子が急激に析出してしまい、基材粉体上に酸化チタン膜を平滑に被覆することが難しくなることがある。滴下時において、反応系の反応温度としては１５〜６５℃の間が好ましい。反応系の反応温度があまり低いと、ペルオキソチタン酸溶液の反応速度が遅くなり、目的とする厚さの酸化チタン膜を被覆させることが難しくなることがある。反応温度があまり高い条件では、ペルオキソチタン酸溶液の反応が早くなりすぎ、平滑な酸化チタン膜を被覆させることが難しくなることがある。 The base powder suspension to which the peroxotitanic acid solution is dropped is not particularly limited, but specifically, it is a Tris type, boric acid type, borate type, phosphoric acid type, phosphate type, glycine type. And carbonate system. The pH of the suspension is preferably pH 8-12. Under lower pH conditions, titanium oxide particles may be rapidly precipitated from the dropped peroxotitanic acid solution, making it difficult to smoothly coat the titanium oxide film on the substrate powder. At the time of dropping, the reaction temperature of the reaction system is preferably between 15 and 65 ° C. If the reaction temperature of the reaction system is too low, the reaction rate of the peroxotitanic acid solution becomes slow, and it may be difficult to coat a titanium oxide film having a target thickness. If the reaction temperature is too high, the reaction of the peroxotitanic acid solution becomes too fast, and it may be difficult to coat a smooth titanium oxide film.
本発明においてチタン膜で被覆する対象となる基材粉体（以下、基体または基体粒子とも称する）としては、特に限定されないが、金属を含む無機物でも、有機物でもよく磁性体、誘電体、導電体および絶縁体等でもよい。基体が金属の場合、鉄、ニッケル、クロム、チタン、アルミニウム等、どのような金属でもよいが、その磁性を利用するものにおいては、鉄等磁性を帯びるものが好ましい。これらの金属は合金でも良く、前記の磁性を有するものであるときには、強磁性合金を使用することが好ましい。また、その粉体の基体が金属化合物の場合には、その代表的なものとして前記した金属の酸化物が挙げられるが、例えば、鉄、ニッケル、クロム、チタン、アルミニウム、ケイ素等の外、カルシウム、マグネシウム、バリウム等の酸化物、あるいはこれらの複合酸化物でも良い。さらに、金属酸化物以外の金属化合物としては、金属窒化物、金属炭化物、金属硫化物、金属フッ化物、金属炭酸塩、金属燐酸塩などを挙げることができる。 In the present invention, the base material powder (hereinafter also referred to as a substrate or substrate particles) to be coated with a titanium film is not particularly limited, and may be an inorganic material including a metal or an organic material, a magnetic material, a dielectric material, or a conductor. Also, an insulator or the like may be used. When the substrate is a metal, any metal such as iron, nickel, chromium, titanium, and aluminum may be used. However, in the case of utilizing the magnetism, a material having magnetism such as iron is preferable. These metals may be alloys, and when they have the above magnetism, it is preferable to use a ferromagnetic alloy. In addition, when the powder substrate is a metal compound, typical examples thereof include the above-mentioned metal oxides, such as iron, nickel, chromium, titanium, aluminum, silicon, etc., calcium Further, oxides such as magnesium and barium, or composite oxides thereof may be used. Furthermore, examples of metal compounds other than metal oxides include metal nitrides, metal carbides, metal sulfides, metal fluorides, metal carbonates, and metal phosphates.
さらに、基体粒子として、金属以外では、半金属、非金属の化合物、特に酸化物、炭化物、窒化物であり、シリカ、ガラスビーズ等を使用することができる。その他の無機物としてはシラスバルーン（中空ケイ酸粒子）などの無機中空粒子、微小炭素中空球（クレカスフェアー）、電融アルミナバブル、アエロジル、ホワイトカーボン、シリカ微小中空球、炭酸カルシウム微小中空球、炭酸カルシウム、パーライト、タルク、ベントナイト、合成雲母、白雲母など雲母類、カオリン等を用いることができる。 Further, as the base particles, other than metals, they are semi-metallic and non-metallic compounds, particularly oxides, carbides and nitrides, and silica, glass beads and the like can be used. Other inorganic substances include inorganic hollow particles such as shirasu balloon (hollow silicic acid particles), fine carbon hollow spheres (clecas spheres), fused alumina bubbles, aerosil, white carbon, silica fine hollow spheres, calcium carbonate fine hollow spheres, Mica such as calcium carbonate, pearlite, talc, bentonite, synthetic mica, muscovite, kaolin and the like can be used.
有機物としては、樹脂粒子が好ましい。樹脂粒子の具体例としては、セルロースパウダー、酢酸セルロースパウダー、ポリアミド、エポキシ樹脂、ポリエステル、メラミン樹脂、ポリウレタン、酢酸ビニル樹脂、ケイ素樹脂、アクリル酸エステル、メタアクリル酸エステル、スチレン、エチレン、プロピレン及びこれらの誘導体の重合または共重合により得られる球状または破砕の粒子などが挙げられる。特に好ましい樹脂粒子はアクリル酸またはメタアクリル酸エステルの重合により得られる球状のアクリル樹脂粒子である。
本発明の製膜方法は、従来技術と異なり酸に弱いものも用いることができるので、酸に弱い基体に対して本発明の製法を用いることが好ましい。酸に弱い基体としては、例えば金属粉末、特に鉄粉や鉄含有合金粉があげられる。
As the organic substance, resin particles are preferable. Specific examples of the resin particles include cellulose powder, cellulose acetate powder, polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate resin, silicon resin, acrylic ester, methacrylic ester, styrene, ethylene, propylene, and these. And spherical or crushed particles obtained by polymerization or copolymerization. Particularly preferred resin particles are spherical acrylic resin particles obtained by polymerization of acrylic acid or methacrylic acid ester.
Unlike the prior art, the film forming method of the present invention can be used which is weak against acid, and therefore, it is preferable to use the manufacturing method of the present invention for a substrate which is weak against acid. Examples of the substrate that is weak against acid include metal powder, particularly iron powder and iron-containing alloy powder.
また、本発明の基体粒子を酸化チタン被膜で被覆する製膜方法は、更に他の基体への製膜方法と組み合わせて、複数の被膜をもつ粒子をつくることができる。
他の製膜方法と組み合わせて本発明の製膜方法を用いる場合、例えば他の製膜方法によって被覆した粉体の上に本発明の製膜方法を用いて酸化チタン膜を作る場合、他の製膜方法によって被覆した粉体を上述の基体粒子とみなして扱うことができる。同様に、本発明の方法で酸化チタン膜を被覆した粉体を基体粒子として、他の膜を被覆することもできる。
In addition, the film forming method for coating the substrate particles of the present invention with a titanium oxide film can be combined with a film forming method for another substrate to produce particles having a plurality of films.
When using the film forming method of the present invention in combination with other film forming methods, for example, when forming a titanium oxide film using the film forming method of the present invention on a powder coated by another film forming method, The powder coated by the film forming method can be treated as the above-mentioned substrate particles. Similarly, a powder coated with a titanium oxide film by the method of the present invention can be used as a base particle to coat another film.
基体の形状としては、球体、亜球状態、正多面体等の等方体、直方体、回転楕円体、菱面体、板状体、針状体（円柱、角柱）などの多面体、さらに粉砕物のような全く不定形な粉体も使用可能である。これらの基体は、粒径については特に限定するものでないが、０．０１μｍ〜数ｍｍの範囲のものが好ましい。 As the shape of the substrate, isotropic bodies such as spheres, subspheres, regular polyhedrons, rectangular parallelepipeds, spheroids, rhombohedrons, plate-like bodies, needle-like bodies (columns, prisms), and pulverized materials. A completely amorphous powder can also be used. These substrates are not particularly limited in terms of particle size, but those in the range of 0.01 μm to several mm are preferable.
（D）その他の工程
（C）の基材粉体懸濁液中への滴下後に、反応物を放置する熟成する工程をさらに設けることが好ましい。
熟成時の温度は、１５〜６５℃の間が好ましい。
熟成時間は、３０分〜６時間の間が好ましい。反応時間と熟成時間の合計があまり短い場合、滴下されたペルオキソチタン溶液の反応が不十分となり、目的とする厚さの酸化チタン膜が被覆されていないことがある。あまり長い場合、滴下されたペルオキソチタン溶液の反応が既に終了しているために、被覆操作時間をいたずらに長くするのみである。
(D) Other steps It is preferable to further provide an aging step in which the reaction product is allowed to stand after dropping into the substrate powder suspension in (C).
The aging temperature is preferably between 15 and 65 ° C.
The aging time is preferably between 30 minutes and 6 hours. When the total of the reaction time and the aging time is too short, the reaction of the dropped peroxotitanium solution becomes insufficient, and the titanium oxide film having the desired thickness may not be coated. If it is too long, the reaction of the dropped peroxotitanium solution has already been completed, so that the coating operation time is merely lengthened.
本発明の製膜方法において、基体粒子上に製膜する酸化チタン膜の厚さは、材料の量比を最適化することにより調節可能である。 In the film forming method of the present invention, the thickness of the titanium oxide film formed on the substrate particles can be adjusted by optimizing the material ratio.
本発明の製膜方法を他の製膜方法とともに用いて複数の膜で被覆された粉体を作製する場合、光干渉に関与する膜の層の各層の厚さを調整することによって、特別の機能を与えることができる。例えば、基体粒子の表面に、屈折率の異なる交互被覆膜を、次の式（１）を満たすように、被膜を形成する物質の屈折率ｎと可視光の波長の４分の１の整数ｍ倍に相当する厚さｄを有する交互膜を適当な厚さと膜数設けると、特定の波長λの光（フレネルの干渉反射を利用したもの）が反射または吸収される。 When producing a powder coated with a plurality of films using the film-forming method of the present invention together with other film-forming methods, by adjusting the thickness of each layer of the film involved in optical interference, Can give function. For example, an alternating coating film having a different refractive index on the surface of the base particle is an integer that is a quarter of the refractive index n of the substance forming the coating and the wavelength of visible light so as to satisfy the following formula (1): If an alternating film having a thickness d corresponding to m times is provided with an appropriate thickness and the number of films, light having a specific wavelength λ (using Fresnel interference reflection) is reflected or absorbed.
ｎｄ＝ｍλ／４ （１） nd = mλ / 4 (1)
この作用を利用して、基体粒子の表面に目標とする可視光の波長に対し、式（１）を満たすような膜の厚みと屈折率を有する被膜を製膜し、さらにその上に屈折率の異なる膜を被覆することを１度あるいはそれ以上交互に繰り返すことにより可視光域に反射ピークを有する膜が形成される。このとき製膜する物質の順序は次のように決める。まず核となる基体の屈折率が高いときには第１層目が屈折率の低い膜、逆の関係の場合には第１層目が屈折率の高い膜とすることが好ましい。 Using this action, a film having a film thickness and a refractive index satisfying the formula (1) is formed on the surface of the base particle with respect to the target visible light wavelength, and the refractive index is further formed thereon. A film having a reflection peak in the visible light region is formed by repeating coating of different films once or more alternately. At this time, the order of substances to be formed is determined as follows. First, when the refractive index of the substrate serving as the nucleus is high, the first layer is preferably a film having a low refractive index, and in the opposite case, the first layer is preferably a film having a high refractive index.
膜厚は、膜屈折率と膜厚の積である光学膜厚の変化を分光光度計などで反射波形として測定、制御するが、反射波形が最終的に必要な波形になるように各層の膜厚を設計する。例えば、多層膜を構成する各単位被膜の反射波形のピーク位置を特定の波長に精密に合わせると、染料や顔料を用いずとも青、緑、黄色などのの単色の着色粉体とすることができる。
ただし、実際の基体の場合、基体の粒径、形状、膜物質および基体粒子物質の相互の界面での位相ずれ及び屈折率の波長依存性によるピークシフトなどを考慮して設計する必要がある。例えば、基体粒子表面にある酸化物層のためのピークシフトや屈折率の波長依存性によるピークシフトも加味することが好ましい。
The film thickness is measured and controlled as a reflected waveform using a spectrophotometer, etc., as the change in the optical film thickness, which is the product of the film refractive index and the film thickness. Design the thickness. For example, if the peak position of the reflection waveform of each unit film constituting the multilayer film is precisely matched to a specific wavelength, it can be made into a single color powder such as blue, green, yellow, etc. without using a dye or pigment. it can.
However, in the case of an actual substrate, it is necessary to design in consideration of the particle size and shape of the substrate, the phase shift at the interface between the film material and the substrate particle material, and the peak shift due to the wavelength dependence of the refractive index. For example, it is preferable to take into account the peak shift for the oxide layer on the surface of the substrate particles and the peak shift due to the wavelength dependence of the refractive index.
また、金属や減衰係数の大きい核粒子あるいは膜を用いる場合についても、金属面減衰係数の大きい物質表面での反射光が楕円偏光する等、位相ずれが起こり、この干渉が核粒子と多層膜それぞれの粒子相互の位相に影響を及ぼすため、それを考慮する事が好ましい。
幾何学的な膜厚だけを合わせてもピーク位置がずれるため、特にシアン色系に着色する際に色が淡くなる。これを防ぐためには、すべての膜に対する位相ずれの影響を加味し、コンピュータシミュレーションであらかじめ膜厚の組合せが最適になるように設計する。
In addition, when using metal or a core particle or film having a large attenuation coefficient, a phase shift occurs, for example, the reflected light on the surface of the material having a large metal surface attenuation coefficient is elliptically polarized. It is preferable to take this into consideration because it affects the phase between particles.
Even if only the geometric film thickness is combined, the peak position is shifted, so that the color becomes light particularly when coloring in a cyan color system. In order to prevent this, the influence of the phase shift on all the films is taken into consideration, and the combination of film thicknesses is designed in advance by computer simulation so as to be optimized.
さらに、基体表面にある酸化物層のための位相ずれや、屈折率の波長依存性によるピークシフトがある。これらを補正するためには、分光光度計などで、反射ピークが最終目的膜数で目標波長になるよう最適の条件を見出すことが必要である。 Furthermore, there is a phase shift due to the oxide layer on the substrate surface and a peak shift due to the wavelength dependence of the refractive index. In order to correct these, it is necessary to find an optimal condition with a spectrophotometer or the like so that the reflection peak reaches the target wavelength by the final target film number.
球状粉体などの曲面に形成された膜の干渉は平板と同様に起こり、基本的にはフレネルの干渉原理に従う。したがって、着色方法も特定の色系に設計することができる。ただし曲面の場合には、粉体に入射し反射された光が複雑に干渉を起こす。これらの干渉波形は膜数が少ない場合には平板とほぼ同じである。しかし、膜数が増えると多層膜内部での干渉がより複雑になる。多層膜の場合もフレネル干渉に基づいて、反射分光曲線をコンピュータシミュレーションであらかじめ膜厚の組合せが最適になるよう設計することができる。特に基体粒子表面への被膜形成の場合、基体粒子表面とすべての膜に対する位相ずれの影響を加味し、コンピュータシミュレーションであらかじめ膜厚の組合せが最適になるよう設計する。さらに、基体粒子表面にある酸化物層のためのピークシフトや屈折率の波長依存性によるピークシフトも加味する。実際のサンプル製造では設計した分光曲線を参考にし、実際の膜においてこれらを補正するために、分光光度計などで反射ピークが最終目的膜数で目標波長になるよう膜厚を変えながら最適の条件を見出さねばならない。 Interference of a film formed on a curved surface such as a spherical powder occurs in the same manner as a flat plate, and basically follows the Fresnel interference principle. Therefore, the coloring method can also be designed to a specific color system. However, in the case of a curved surface, the light incident on and reflected by the powder causes complicated interference. These interference waveforms are almost the same as the flat plate when the number of films is small. However, as the number of films increases, the interference inside the multilayer film becomes more complicated. Also in the case of a multilayer film, based on Fresnel interference, the reflection spectral curve can be designed in advance by computer simulation so that the combination of film thicknesses is optimized. In particular, in the case of forming a film on the surface of the substrate particles, the influence of the phase shift on the surface of the substrate particles and all the films is taken into account, and the design is made so as to optimize the combination of film thicknesses in advance by computer simulation. Furthermore, the peak shift for the oxide layer on the surface of the substrate particles and the peak shift due to the wavelength dependence of the refractive index are taken into account. In actual sample production, in order to correct these in the actual film with reference to the designed spectroscopic curve, the optimum conditions are adjusted while changing the film thickness with a spectrophotometer etc. so that the reflection peak reaches the target wavelength with the final target film number. Must be found.
また、金属や減衰係数の大きい核粒子あるいは膜を用いる場合についても、金属面減衰係数の大きい物質表面での反射光が楕円偏光する等、位相ずれが起こり、この干渉が核粒子と多層膜それぞれの粒子相互の位相に影響を及ぼすため、それぞれを最適化し、目標波形を得ることは非常に複雑であり、最適干渉反射波形を得るために、前記のように核粒子および多層膜各膜の物質の光学物性値を求め、それを基にコンピュータシミュレーションであらかじめ目標波形が得られる膜厚および膜の組合せを求めておかなければならない。
不定形状の粉末に着色する場合も多層膜による干渉が起こり、球状粉体の干渉多層膜の条件を参考にし基本的な膜設計を行う。上記の多層膜を構成する各単位被膜のピーク位置は各層の膜厚により調整することができ、膜厚は基体粒子の表面に金属酸化物等の固相成分を形成させる被覆形成条件中、原料組成、固相析出速度および基体量などを制御することにより、精度良く膜厚を制御でき、均一な厚さの被膜を形成することができ、所望の色系に着色することができる。
In addition, when using metal or a core particle or film having a large attenuation coefficient, a phase shift occurs, for example, the reflected light on the surface of the material having a large metal surface attenuation coefficient is elliptically polarized. It is very complicated to obtain the target waveform by optimizing each of the particles in order to obtain the optimum interference reflection waveform, as described above. It is necessary to obtain the optical property values of the film thickness and to obtain the film thickness and the combination of the films from which the target waveform can be obtained in advance by computer simulation.
Interference with the multilayer film also occurs when the powder of irregular shape is colored, and the basic film design is performed with reference to the condition of the interference multilayer film of spherical powder. The peak position of each unit film constituting the multilayer film can be adjusted by the film thickness of each layer, and the film thickness is the raw material in the coating forming conditions for forming a solid phase component such as a metal oxide on the surface of the base particle. By controlling the composition, the solid phase deposition rate, the amount of the substrate, and the like, the film thickness can be controlled with high accuracy, a film having a uniform thickness can be formed, and a desired color system can be colored.
以上のように、反射スペクトルのピーク、バレー波長が最終目的膜数で目標波長になるよう膜形成溶液などの製膜条件を変えながら最適の条件を見出すことにより、特定の色系の粉体を得ることができる。また、多層膜を構成する物質の組合せおよび各単位被膜の膜厚を制御することにより多層膜干渉による発色を調整することができる。これにより、染料や顔料を用いなくても粉体を所望の色系に鮮やかに着色することができる。
また、カラーシフトを最大にするためには鋭い反射ピーク波長およびピークの数を最適化することが必要であり、各層の膜厚制御の最適化を行う。特に反射ピークが可視域外から、見る角度を変えることにより、可視域内に現れる場合、あるいは逆に、見る角度を変えることにより、可視域の反射ピークが現れる場合、鋭い反射ピークであれば、わずかに見る角度が変わることにより、色も同時に変化させることができ、有効である。
As described above, by finding the optimum conditions while changing the film forming conditions such as the film forming solution so that the peak and valley wavelengths of the reflection spectrum become the target wavelength by the final target film number, Obtainable. Further, the color development due to multilayer film interference can be adjusted by controlling the combination of substances constituting the multilayer film and the thickness of each unit film. Thereby, the powder can be vividly colored in a desired color system without using a dye or a pigment.
Further, in order to maximize the color shift, it is necessary to optimize the sharp reflection peak wavelength and the number of peaks, and the film thickness control of each layer is optimized. In particular, when the reflection peak appears in the visible range by changing the viewing angle from the outside of the visible range, or conversely, when the reflection peak in the visible range appears by changing the viewing angle, the sharp reflection peak is slightly By changing the viewing angle, the color can be changed at the same time, which is effective.
また、カラーシフトによる色変化は、前記式１または前記式１と下記式２の組合わせにおいて、入射角を変えた場合のピーク位置の計算値から予測することができる。
膜被覆粉体を製造するにあたり、予め、基体粒子の材質、基体粒子の粒径、被覆層の数、各被覆層の被覆順序、各被覆層の材質、所望の反射光波長を選定する必要がある。特に、基体粒子および各被覆層の材質を選定するということは、それらの屈折率を自ずと特定することとなる。基体粒子および各被覆層の屈折率の特定は、各層間のフレネル反射係数、振幅反射強度の算出に関与する。
Further, the color change due to the color shift can be predicted from the calculated value of the peak position when the incident angle is changed in the formula 1 or the combination of the formula 1 and the formula 2 below.
In manufacturing the film-coated powder, it is necessary to select in advance the material of the base particles, the particle size of the base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer, and the desired reflected light wavelength. is there. In particular, selecting the material of the base particles and the respective coating layers naturally identifies their refractive index. The specification of the refractive index of the base particle and each coating layer is involved in the calculation of the Fresnel reflection coefficient and the amplitude reflection intensity between the respective layers.
基体粒子の粒径を選定することにより、基体粒子および多層膜の曲率を特定する。曲率が特定されなければ、後述する膜厚監視用分光光度特性の補正が困難になる。
被覆層の数を選定することにより、後述するＲflat値の特定に関与する。
基体粒子が平板体の場合の多層膜反射強度Ｒflatは、予め選定された基体粒子の材質（屈折率）、被覆層数、各被覆層の被覆順序、各被覆層の材質（屈折率）、所望の反射光波長を、下記漸化式２に当てはめて解くことにより求められる。
By selecting the particle size of the substrate particles, the curvature of the substrate particles and the multilayer film is specified. If the curvature is not specified, it becomes difficult to correct the spectrophotometric characteristic for film thickness monitoring described later.
By selecting the number of coating layers, it is involved in specifying the R flat value described later.
The multilayer film reflection strength R flat in the case where the substrate particle is a flat body is a previously selected substrate particle material (refractive index), number of coating layers, coating order of each coating layer, material of each coating layer (refractive index), The desired reflected light wavelength is obtained by applying the following recurrence formula 2 and solving it.
（式中、Ｒj+1,j：下から第ｊ番目の層とその直上の層との間の振幅反射強度、
ｊ：１以上の整数（Ｊ−１＝０は基盤を示す）、
ｉ：虚数単位、
ｒj+1,j：下から第ｊ番目の層とその直上の層との間の界面のフレネル反射係数、
Ｒj,j-1：下から第ｊ−１番目の層とその直上の層との間の振幅反射強度、
２δj：下から第ｊ番目の層における位相差、
λ：所望の反射光波長、
ｎj：下から第ｊ番目の層の屈折率、
ｄj：下から第ｊ番目の層の膜厚、
φj：下から第ｊ番目の層への光の入射角。）
(Wherein R j + 1, j : amplitude reflection intensity between the j-th layer from the bottom and the layer immediately above it,
j: an integer greater than or equal to 1 (J-1 = 0 indicates a base),
i: imaginary unit,
r j + 1, j : Fresnel reflection coefficient of the interface between the j-th layer from the bottom and the layer immediately above it,
R j, j−1 : Amplitude reflection intensity between the j−1th layer from the bottom and the layer immediately above it,
2δ j : phase difference in the j-th layer from the bottom,
λ: desired reflected light wavelength,
n j : refractive index of the j-th layer from the bottom,
d j : film thickness of the j-th layer from the bottom,
φ j : the incident angle of light from the bottom to the j-th layer. )
上記の様にして得られた多層膜反射強度Ｒflatを基体粒子の形状により補正する手法としては特に限定されないが、該Ｒflat値をさらに下記式３ The method of correcting the multilayer film reflection intensity R flat obtained as described above according to the shape of the base particles is not particularly limited, but the R flat value is further expressed by the following formula 3
（式中、θ：最外層への入射角を示す）
に適用させ、Ｒ（λ）値が所望の波長で最大値または最小値になるように各被覆層の膜厚を求めることにより行う手法が好ましい。
Ｒflat値を上記式３に適用させるということは、多層膜被覆粉体への光入射角の角度分布を１個の被覆半球への光入射角度分布に近似することにより上記式２の解を補正することを意味する。
この各被覆膜の膜厚を求める場合には、コンピュータによるシミュレーションで行うことが効率的である。
(Where θ represents the angle of incidence on the outermost layer)
It is preferable to apply this method to obtain the film thickness of each coating layer so that the R (λ) value becomes the maximum value or the minimum value at a desired wavelength.
Applying the R flat value to the above equation 3 means that the solution of the above equation 2 is solved by approximating the angle distribution of the light incident angle to the multilayer coated powder to the light incident angle distribution to one coated hemisphere. It means to correct.
When determining the film thickness of each coating film, it is efficient to carry out by computer simulation.
次いで、各被覆膜を、上記のようにして求められた膜厚になるように、基体粒子上に製膜する。
但し、先にも述べたが、多層膜被覆粉体における実際の製膜作業においては、設計値通りの膜厚になるまで実膜厚を直接監視しながら行うことは不可能であり、そのため、製膜作業中の膜厚の監視は、各被覆層を被覆した被覆物体の反射強度が最大値または最小値になる波長を分光光度計にて測定し、該膜厚に相対する最大または最小反射波長値に達した時点で製膜作業を終了させることが考えられる。
しかしながら基材が粉体の場合においては、その粒子形状および粒子径に依存する各被覆層の曲率によって、最大または最小反射波長測定値と膜厚との関係に狂いが生じ、分光光度計にて測定される最大または最小反射波長が所望の値になるように製膜すると、最終的に得られる多層膜被覆粉体が、所望の波長で所望の反射強度とならないという問題が生じる。
Next, each coating film is formed on the base particles so as to have the film thickness obtained as described above.
However, as described above, in the actual film-forming operation in the multilayer-coated powder, it is impossible to directly monitor the actual film thickness until the film thickness reaches the designed value. The film thickness is monitored during film formation by measuring the wavelength at which the reflection intensity of the coated object covering each coating layer reaches the maximum or minimum value with a spectrophotometer, and measuring the maximum or minimum reflection relative to the film thickness. It can be considered that the film forming operation is terminated when the wavelength value is reached.
However, when the substrate is a powder, the curvature of each coating layer depending on the particle shape and particle diameter causes a deviation in the relationship between the measured maximum or minimum reflected wavelength and the film thickness. When the film is formed so that the maximum or minimum reflection wavelength to be measured becomes a desired value, there arises a problem that the finally obtained multilayer film-coated powder does not have a desired reflection intensity at a desired wavelength.
そのため、基体粒子の形状および粒子径に依存する各被覆層の曲率による補正が必要になる。
この補正手法としては、特に限定されないが、選定した基体粒子上に選定した各被覆層を段階的に数種類に膜厚を変えて被覆して粒径補正用膜被覆粉体とし、該粒径補正用膜被覆粉体の各被覆層の実膜厚値（ｄM）を測定し、また、該膜被覆粉体のそれぞれを分光光度計にて測定しそれぞれの粒径補正用膜被覆粉体の各被覆層の光学膜厚（ｎｄ）を求め、各粒径補正用膜被覆粉体の各被覆層の実膜厚値と屈折率（ｎ）との積（ｎｄM）に対する各被覆層の光学膜厚（ｎｄ）の比（ｎｄ／ｎｄM）を求め、多層膜反射強度を求める上記漸化式２の２δjに上記比（ｎｄ／ｎｄM）値を乗じて各被覆層を有する粉体の分光光度特性を補正し、該補正分光光度特性になるように各被覆層を製膜することにより行わうことが好ましい。
Therefore, it is necessary to correct the curvature of each coating layer depending on the shape and particle diameter of the base particles.
The correction method is not particularly limited, but the coating layer selected on the selected substrate particles is coated with various thicknesses in stages to form a coating powder for particle size correction. The actual film thickness value (d M ) of each coating layer of the membrane-coated powder is measured, and each of the membrane-coated powders is measured with a spectrophotometer, The optical film thickness (nd) of each coating layer is obtained, and the optical value of each coating layer with respect to the product (nd M ) of the actual film thickness value of each coating layer and the refractive index (n) of each particle size correcting film-coated powder. obtains the film thickness (nd) ratio (nd / nd M), the ratio 2.delta. j of the recurrence formula 2 to obtain a multilayer film reflection intensity (nd / nd M) powder having a respective coating layers multiplied by the value It is preferable to carry out by correcting the spectrophotometric characteristics of the film and forming each coating layer so as to obtain the corrected spectrophotometric characteristics.
なお、上記粒径補正用膜被覆粉体の各被覆層の実膜厚値（ｄM）を測定する際の手法としては、特に限定されないが、該粒径補正用膜被覆粉体のそれぞれを切断しその切断面から測定することにより行うことが好ましい。また、前記粒径補正用膜被覆粉体を切断する際には、集束イオンビーム（ＦＩＢ）加工により行うことが、その切断面が明瞭になり、各被覆層の実膜厚値（ｄM）を測定に好適である。 The method for measuring the actual film thickness value (d M ) of each coating layer of the particle size correcting film-coated powder is not particularly limited. It is preferable to carry out by cutting and measuring from the cut surface. Further, when cutting the particle-correcting film-coated powder, it is performed by focused ion beam (FIB) processing, the cut surface becomes clear, and the actual film thickness value (d M ) of each coating layer Is suitable for measurement.
本発明の方法で得られる酸化チタン膜被覆粉体は、表面に被覆された酸化チタン膜による光学的干渉作用により、青色や赤紫色を呈するものであり、カラーインキ、プラスチック、紙用カラーフィラー、カラートナー、インクジェットプリンター用カラーインク等多種の目的に用いることができる。 The titanium oxide film-coated powder obtained by the method of the present invention exhibits a blue or reddish purple color due to optical interference caused by the titanium oxide film coated on the surface, and is a color ink, plastic, color filler for paper, It can be used for various purposes such as color toners and color inks for inkjet printers.
本発明の方法で得られる酸化チタン膜被覆粉体を含有する塗料組成物を調製する場合のうち、（１）各特定色系インキあるいは塗料様組成物（流体）および（２）各特定色系トナー、各特定色系乾式インキ様組成物（粉体）について詳しく説明する。 Among the cases where a coating composition containing a titanium oxide film-coated powder obtained by the method of the present invention is prepared, (1) each specific color ink or paint-like composition (fluid) and (2) each specific color system The toner and each specific color dry ink-like composition (powder) will be described in detail.
（１）本発明において特定の色系インキあるいは塗料様組成物（流体）の媒質（ビヒクル）としては、カラー印刷用、カラー磁気印刷用、カラー磁気塗料用に用いられる、従来公知のワニスを用いることができ、例えば液状ポリマー、有機溶媒に溶解したポリマーやモノマーなどを粉体の種類やインキの適用方法、用途に応じて適宜に選択して使用することができる。
上記液状ポリマーとしては、ポリペンタジエン、ポリブタジエン等のジエン類、ポリエチレングリコール類、ポリアミド類、ポリプロピレン類、ワックス類あるいはこれらの共重合体編成体等を挙げることができる。
(1) In the present invention, a conventionally known varnish used for color printing, color magnetic printing, and color magnetic paint is used as a medium (vehicle) for a specific color ink or paint-like composition (fluid) in the present invention. For example, a liquid polymer, a polymer or a monomer dissolved in an organic solvent, and the like can be appropriately selected and used depending on the kind of powder, the ink application method, and the use.
Examples of the liquid polymer include dienes such as polypentadiene and polybutadiene, polyethylene glycols, polyamides, polypropylenes, waxes, and copolymer knitted bodies thereof.
有機溶媒に溶解するポリマーとしては、オレフィン系ポリマー類、オリゴエステルアクリレート等のアクリル系樹脂類、ポリエステル類、ポリアミド類、ポリイソシアネート類、アミノ樹脂類、キシレン樹脂類、ケトン樹脂類、ジエン系樹脂類、ロジン変性フェノール樹脂、ジエン系ゴム類、クロロプレン樹脂類、ワックス類あるいはこれらの変性体や共重合体などを挙げることができる。
有機溶媒に溶解するモノマーとしては、スチレン、エチレン、ブタジエン、プロピレンなどを挙げることができる。
有機溶媒としては、エタノール、イソプロパノール、ノルマルプロパノール等のアルコール類、アセトン等のケトン類、ベンゼン、トルエン、キシレン、ケロシン、ベンジン炭化水素類、エステル類、エーテル類あるいはこれらの変性体や共重合体などを挙げることができる。
Polymers that are soluble in organic solvents include olefin polymers, acrylic resins such as oligoester acrylates, polyesters, polyamides, polyisocyanates, amino resins, xylene resins, ketone resins, and diene resins. Rosin-modified phenolic resins, diene rubbers, chloroprene resins, waxes, modified products and copolymers thereof, and the like.
Examples of the monomer that can be dissolved in the organic solvent include styrene, ethylene, butadiene, and propylene.
Examples of organic solvents include alcohols such as ethanol, isopropanol, and normal propanol, ketones such as acetone, benzene, toluene, xylene, kerosene, benzine hydrocarbons, esters, ethers, and modified products and copolymers thereof. Can be mentioned.
（２）特定色系トナー、特定色系乾式インキ、特定色系乾式塗料様組成物（粉体）は、上記特定色系多層膜被覆粉体を、樹脂とあるいは必要に応じて調色材とを、スクリュー型押出機、ロールミル、ニーダなどで直接混練し、ハンマミル、カッターミルで粗粉砕したあと、ジェットミルなどで微粉砕し、エルボージェットなどで必要な粒度に分級することにより粉体状シアン色色材組成物を得ることができる。また、乳化重合法や懸濁重合法などの重合法を用いて、特定色系多層膜被覆粉体を粉体状特定色系塗料組成物とすることもできる。
さらに、特定色系多層膜被覆粉体と樹脂、調色剤などの添加剤および溶剤をコロイドミルや３本ロールで液状化しインキ塗料などの液状特定色系塗料組成物とすることもできる。
(2) The specific color toner, the specific color dry ink, and the specific color dry paint-like composition (powder) include the specific color multilayer coating powder, a resin, or a toning material as necessary. Is directly kneaded with a screw type extruder, roll mill, kneader, etc., coarsely pulverized with a hammer mill or cutter mill, then finely pulverized with a jet mill, etc., and classified to the required particle size with an elbow jet etc. A color material composition can be obtained. Further, the specific color multilayer coating powder can be made into a powder specific color coating composition by using a polymerization method such as an emulsion polymerization method or a suspension polymerization method.
Further, the specific color multilayer coating powder, resin, additives such as toning agents, and solvent can be liquefied with a colloid mill or three rolls to obtain a liquid specific color coating composition such as an ink coating.
明度を上げるための調色材としては、白色顔料（展色材）である、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化珪素、酸化アンチモン、酸化鉛等あるいはこれらの複合酸化物類、また炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等の炭酸塩、あるいは硫酸バリウム、硫酸カルシウムのような硫酸塩類、硫酸亜鉛のような硫化物あるいは前記酸化物や炭酸塩および硫酸塩を焼結した複合酸化物、複合含水酸化物類が挙げられる。 As the color-adjusting material for increasing the brightness, it is a white pigment (color developing material), for example, titanium oxide, zinc oxide, tin oxide, silicon oxide, antimony oxide, lead oxide or the like, or complex oxides thereof, Carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, sulfates such as barium sulfate and calcium sulfate, sulfides such as zinc sulfate, or composite oxides obtained by sintering the oxides, carbonates and sulfates, A composite hydrous oxide is mentioned.
彩度、色相を調整するため、特にフルカラー用混色で色再現用に使用する場合の調色材としては、青色顔料である（有機染料・顔料）アルカリブルーレーキ、ピーコックレーキ、ピーコックレーキブルー等のレーキ染料およびレーキ顔料、オイルブルー等、オイル染料顔料、アルコールブルー等のアルコール染料、フタロシアニン、銅フタロシアニン等のフタロシアニン系顔料等、（無機顔料）ウルトラマリン等の酸化物硫化物複合顔料、鉄青、ミロリーブルー等の銅系群青紺青顔料類、コバルトブルー、セルリアンブルー等の酸化コバルト系複合酸化物類青色顔料、青色系有機染料および顔料および青色無機顔料アルカリブルーレーキ、ピーコックブルーレーキ等のレーキ染料、レーキ系顔料無金属フタロシアニン、銅フタロシアニン等のフタロシアニン系染顔料および緑色顔料であるクロームグリーン、ジンクグリーン、酸化クロム、含水クロム（ビリジアン）等のクロム系酸化物および含水酸化物、エメラルドグリーン等の銅系酸化物、コバルトグリーン等のコバルト系酸化物等の無機顔料あるいは、ピグメントグリーン、ナフトールグリーンなどのニトロソ顔料、グリーンゴールド等のアゾ系顔料、フタロシアニングリーン、ポリクロム銅フタロシアニン等のフタロシアニン系顔料、マラカイトグリーンレーキ、アシッドグリーンレーキなどのレーキ系、オイルグリーン等、オイル染料顔料アルコールブルー等のアルコール染料顔料等有機染顔料が挙げられる。しかし本発明はこれらのみに限定されるものではない。 In order to adjust the saturation and hue, especially as a toning material for color reproduction with full color mixing, blue pigments (organic dyes / pigments) such as alkali blue lake, peacock lake, peacock lake blue, etc. Lake dyes and lake pigments, oil blue, oil dye pigments, alcohol dyes such as alcohol blue, phthalocyanine pigments such as phthalocyanine and copper phthalocyanine, (inorganic pigments) oxide sulfide composite pigments such as ultramarine, iron blue, Copper group blue and blue pigments such as milory blue, cobalt oxide complex oxides such as cobalt blue and cerulean blue, blue pigments, blue organic dyes and pigments, and blue inorganic pigments rake dyes such as alkali blue lakes and peacock blue lakes, lakes Pigments such as metal-free phthalocyanine and copper phthalocyanine Chromium oxides and hydrated oxides such as chromium green, zinc green, chromium oxide, hydrous chromium (viridian), and green oxides such as talocyanine dyes and green pigments, copper oxides such as emerald green, and cobalt oxides such as cobalt green Inorganic pigments such as pigments, nitroso pigments such as pigment green and naphthol green, azo pigments such as green gold, phthalocyanine pigments such as phthalocyanine green and polychrome copper phthalocyanine, lake systems such as malachite green lake and acid green lake, oil Examples include organic dyes such as green, oil dye pigments, alcohol dyes such as alcohol blue, and the like. However, the present invention is not limited to these.
さらに、微妙な色調制御においては青色、黄色、赤紫色などの顔料や染料を用いて調色することが必要な場合は、これらの顔料を添加することにより最適の特定色とすることが好ましい。
この粉体状特定色系塗料組成物の場合、（ａ）上記粉砕法で製造する場合の樹脂としては、特に限定されるものではないが、ポリアミド、エポキシ樹脂、ポリエステル、メラミン樹脂、ポリウレタン、酢酸ビニル樹脂、ケイ素樹脂、アクリル酸エステル、メタアクリル酸エステル、スチレン、エチレン、ブタジエン、プロピレン及びこれらの誘導体の重合体または共重合体などが挙げられる。
（ｂ）重合法の場合、エステル、ウレタン、酢酸ビニル、有機ケイ素、アクリル酸、メタアクリル酸、スチレン、エチレン、ブタジエン、プロピレン等のうち１種あるいは複数の混合物から重合を開始させ、重合体あるいはこれらの共重合体などが形成される。
Furthermore, when it is necessary to adjust colors using pigments or dyes such as blue, yellow, and reddish purple in delicate color tone control, it is preferable to add these pigments to obtain an optimum specific color.
In the case of this powdery specific color coating composition, (a) the resin for production by the above pulverization method is not particularly limited, but polyamide, epoxy resin, polyester, melamine resin, polyurethane, acetic acid Examples thereof include vinyl resins, silicon resins, acrylic acid esters, methacrylic acid esters, styrene, ethylene, butadiene, propylene, and polymers or copolymers of these derivatives.
(B) In the case of a polymerization method, polymerization is started from one or a mixture of esters, urethane, vinyl acetate, organic silicon, acrylic acid, methacrylic acid, styrene, ethylene, butadiene, propylene, etc. These copolymers are formed.
本発明の膜被覆粉体を含有する塗料組成物は上記のように、（１）各特定色系インキあるいは塗料様組成物（流体）および（２）各特定色系トナー、各特定色系乾式インキ様組成物（粉体）の形をとることができる。
また、流体状の場合には、特定色系インキ、塗料等であり、前記調色材、乾燥の遅い樹脂には固化促進剤、粘度を上げるために増粘剤、粘性を下げるための流動化剤、粒子同志の分散のために分散剤などの成分を含ませることができる。
As described above, the coating composition containing the film-coated powder of the present invention comprises (1) each specific color ink or paint-like composition (fluid) and (2) each specific color toner, each specific color dry type. It can take the form of an ink-like composition (powder).
In the case of fluid, it is a specific color ink, paint, etc., the toning material, a slow-drying resin, a solidification accelerator, a thickener to increase the viscosity, and a fluidization to decrease the viscosity In order to disperse the agent and particles, a component such as a dispersant can be included.
一方、粉体の場合には、（ａ）粉砕法で粉体を製造する場合には、前記調色材、乾燥の遅い樹脂には固化促進剤、混練の際の粘性を下げるためには流動化剤、粒子同志の分散のためには分散剤、紙等への定着のための電荷調整剤、ワックスなどの成分を含ませることができる。
（ｂ）重合法を用いる場合には、前記調色材、重合開始剤、重合促進剤、粘度を上げるためには増粘剤、粒子同志の分散のためには分散剤、紙等への定着のための電荷調整剤、ワックスなどの成分を含ませることができる。
On the other hand, in the case of powder, (a) when powder is produced by a pulverization method, the toning material, a slow-drying resin, a solidification accelerator, and a fluid to reduce the viscosity during kneading. In order to disperse the agent and the particles, a component such as a dispersant, a charge adjusting agent for fixing on paper or the like, and a wax can be included.
(B) When a polymerization method is used, the toning material, the polymerization initiator, the polymerization accelerator, a thickener for increasing the viscosity, and a dispersing agent for fixing particles, fixing to paper, etc. Ingredients such as a charge control agent and wax may be included.
本発明の多層膜被覆粉体は、単一の粉体ないしは分光特性の異なる複数の粉体の組み合せにより、湿式および乾式カラー印刷や湿式および乾式カラー磁気印刷に適用できるほか、３原色の粉体を用いて、可視光、非可視光（紫外域およびシアン外域）、蛍光発色および磁気、さらに電気（電場の変化）の６種の組合せの識別機能を持ち、印刷物の偽造防止用カラー磁性インキなどセキュリティ機能を必要とする他の用途に適用することができる。 The multilayer coated powder of the present invention can be applied to wet and dry color printing and wet and dry color magnetic printing by combining a single powder or a plurality of powders having different spectral characteristics. Has a distinguishing function of six types of combination of visible light, invisible light (ultraviolet and cyan outside), fluorescent color and magnetism, and electricity (change in electric field), and color magnetic ink for preventing counterfeiting of printed matter, etc. It can be applied to other uses requiring a security function.
前記本発明の被覆粉体を各特定色系インキあるいは塗料様組成物または各特定色系トナー、各特定色系乾式インキ様組成物、各特定色系乾式塗料組成物として、基材に印刷、溶融転写または被塗装体に塗布する場合、塗料組成物中の各特定色系多層膜被覆粉体と樹脂の含有量の関係は、体積比で１：０．５〜１：１５である。媒質の含有量が少な過ぎると塗布した膜が被塗装体に固着しない。また、多過ぎると顔料の色が薄くなりすぎ良いインキまたは塗料といえない。
また、各色系インキあるいは塗料組成物中の各色系色材および樹脂を合わせた量と溶剤の量との関係は、体積比で１：０．５〜１：１０であり、溶剤の量が少な過ぎると塗料の粘度が高く、均一に塗布できない。また、溶剤の量が多過ぎると塗膜の乾燥に時間を要し塗布作業の能率が極端に低下する。
The coating powder of the present invention is printed on a substrate as each specific color ink or paint-like composition or each specific color toner, each specific color dry ink-like composition, each specific color dry paint composition, In the case of melt transfer or application to an object to be coated, the relationship between the specific color multilayer coating powder and the resin content in the coating composition is 1: 0.5 to 1:15 in volume ratio. When the content of the medium is too small, the applied film does not adhere to the object to be coated. On the other hand, if the amount is too large, the color of the pigment becomes too thin to be a good ink or paint.
Further, the relationship between the amount of each color-based color material and resin in each color-based ink or coating composition and the amount of solvent is 1: 0.5 to 1:10 in volume ratio, and the amount of solvent is small. If it is too high, the viscosity of the paint is so high that it cannot be applied uniformly. Moreover, when there is too much quantity of a solvent, time will be required for drying of a coating film, and the efficiency of an application | coating operation will fall extremely.
また、基材に印刷、溶融転写または被塗装体に塗料を塗布した際の塗膜の色の濃度は、被塗装体の単位面積当たりに載った顔料の量によって決まる。塗料が乾燥した後の被塗装体上の本発明の膜被覆粉体の量は、均一に塗布した場合の面積密度で１平方メートルあたり０．１〜３００ｇであり、好ましくは０．１〜１００ｇであれば良好な塗装色が得られる。面積密度が前記の値より小さければ被塗装体の地の色が現れ、前記の値より大きくても塗装色の色濃度は変わらないので不経済である。すなわち、ある厚さ以上に顔料を被塗装体上に載せても、塗膜の下側の顔料にまでは光りが届かない。かかる厚さ以上に塗膜を厚くすることは、塗料の隠蔽力を越えた厚さであるので塗装の効果がなく不経済である。ただし、塗膜の磨耗を考慮し、塗膜の厚さが摩り減るため厚塗りする場合はこの限りではない。また特定の意匠等を部分的に形成する場合にもこの限りではない。 In addition, the color density of the coating film when printing, melt transfer, or coating on the substrate is determined by the amount of pigment placed per unit area of the substrate. The amount of the film-coated powder of the present invention on the object to be coated after the paint is dried is 0.1 to 300 g per square meter in area density when uniformly coated, preferably 0.1 to 100 g. If it is, a good paint color can be obtained. If the area density is smaller than the above value, the ground color of the object to be coated appears, and if it is larger than the above value, the color density of the painted color does not change, which is uneconomical. That is, even if the pigment is placed on the object to be coated more than a certain thickness, the light does not reach the pigment below the coating film. Making the coating film thicker than this thickness is uneconomical because it has a coating thickness that exceeds the hiding power of the coating material and has no coating effect. However, in consideration of wear of the coating film, the thickness of the coating film is worn down. This is not the case when a specific design or the like is partially formed.
以下、本発明を実施例によりさらに具体的に説明するが、本発明の範囲はこれらに限定されるものではない。
実施例１
（１）緩衝液の調整
イオン交換水３００ミリリットルに塩化カリウム（関東化学社製試薬特級）の２９．８２ｇ（０．４モル量）とホウ酸（関東化学社製試薬特級）の２４．２３ｇ（０．４モル量）を溶解し、イオン交換水で１０００ミリリットルにメスアップしてＡ溶液とした。
イオン交換水３００ミリリットルに水酸化ナトリウム（関東化学社製鹿１級試薬）の１６．０ｇ（０．４モル量）を溶解し、イオン交換水で１０００ミリリットルにメスアツプしてＢ溶液とした。
上記Ａ溶液２００ｇおよびＢ溶液８０ｇを混合し、緩衝液Ｃとした。この緩衝液ＣのｐＨは９．１であった。
Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited thereto.
Example 1
(1) Preparation of buffer solution In 300 ml of ion-exchanged water, 29.82 g (0.4 mol) of potassium chloride (Kanto Chemical Co., Ltd. reagent special grade) and boric acid (Kanto Chemical Co., Ltd. reagent special grade) 24.23 g ( 0.4 mol amount) was dissolved, and the solution was made up to 1000 ml with ion-exchanged water to obtain a solution A.
13.0 g (0.4 mole amount) of sodium hydroxide (Kanto Chemical Co., Ltd., first grade reagent) was dissolved in 300 ml of ion-exchanged water, and made up to 1000 ml with ion-exchanged water to obtain a solution B.
200 g of the A solution and 80 g of the B solution were mixed to obtain a buffer solution C. The pH of this buffer C was 9.1.
（２）ペルオキソチタン酸溶液の調整
ＴＰＴ溶液（日本曹達社製）３．６９グラム（ＴｉＯ2量 １．０３８グラム）をＴＰＴ溶液量に対して５倍のイオン交換水で希釈した。次にこのＴＰＴ溶液にアンモニア水（関東化学社製鹿１級試薬）１６グラムを添加し水酸化チタンスラリー液を作る。
次にこの酸化チタンスラリー液に過酸化水素水（関東化学社製試薬特級）１０．０グラムをゆっくりと添加し、十分に攪拌して水酸化チタンを溶解させ、黄色透明のペルオキソチタン酸溶液を得る。
最後に、ｐＨ調整としてアンモニア水（関東化学社製鹿１級試薬）４．５０グラムを添加し、ペルオキソチタン酸溶液を得る。
(2) it was diluted with peroxo adjustment TPT solution of titanium acid solution (manufactured by Nippon Soda Co., Ltd.) 3.69 g 5 times the ion-exchanged water (TiO 2 weight 1.038 g) to the TPT solution volume. Next, 16 g of ammonia water (Kanto Chemical Co., Ltd., first grade reagent) is added to the TPT solution to make a titanium hydroxide slurry.
Then added slowly aqueous hydrogen peroxide (manufactured by Kanto Chemical Co., Inc. reagent grade) 10.0 g of this titanium oxide slurry, thoroughly stirred to dissolve the titanium hydroxide, peroxotitanic acid solution clear yellow obtain.
Finally, 4.50 g of ammonia water (Kanto Chemical Co., Ltd. deer grade 1 reagent) is added as a pH adjustment to obtain a peroxotitanic acid solution.
（３）酸化チタン膜被覆
基材粉体として１５０グラムの板状鉄粉（平均粒径３７μｍ）を、予め用意しておいた上記緩衝液Ｃの２８０グラムに懸濁させた。この懸濁液の入った容器を５０℃に保温した恒温槽に浸け６００ｒｐｍにて攪拌しながら上記ペルオキソチタン酸溶液５３グラムを２．２ミリリットル／分の滴下速度で滴下する。滴下終了後、さらに１２０分攪拌を続け、基材粉体上に酸化チタン膜被覆を行う。所定時間経過後、酸化チタン膜被覆された粉体を含むスラリーを静置沈降させ、上澄みを除去した。さらに、脱イオン水による洗浄を行った上で、１２０℃で１時間乾燥し、チタニア被覆粉体を得た。
得られた酸化チタン膜被覆粉体の７９６ｋＡ／ｍ（≒１０ｋＯｅ）での磁 化を振動試料型磁力計（玉川製作社製、ＴＭ ＶＳＭ１０１４ ＭＲＯ−Ｎ型）により測定した結果、１９２Ａ・ｍ2／ｋｇ（ｅｍｕ／ｇ）であった。
膜厚値は、紫外／可視／近赤外域分光光度計（日本分光社製、ＩＬＮ−４７２型積分分球付Ｖ−５７０型）で測定して得られた分光反射曲線ピーク、ボトム波長より算出される値であり、算出される膜厚は４３ｎｍである。
(3) Titanium oxide film coating 150 g of plate-like iron powder (average particle size 37 μm) was suspended in 280 g of the buffer solution C prepared in advance as the base powder. The container containing the suspension is immersed in a thermostatic bath kept at 50 ° C., and 53 g of the peroxotitanic acid solution is dropped at a dropping rate of 2.2 ml / min while stirring at 600 rpm. After completion of the dropping, stirring is further continued for 120 minutes, and the base material powder is coated with a titanium oxide film. After a predetermined period of time, the slurry containing the powder coated with the titanium oxide film was allowed to settle and the supernatant was removed. Furthermore, after washing with deionized water, it was dried at 120 ° C. for 1 hour to obtain a titania-coated powder.
The resulting titanium oxide film-coated powder was magnetized at 796 kA / m (≈10 kOe) with a vibrating sample magnetometer (TM VSM1014 MRO-N type, manufactured by Tamagawa Manufacturing Co., Ltd.). As a result, 192 A · m 2 / kg (emu / g).
The film thickness value is calculated from the spectral reflection curve peak and the bottom wavelength obtained by measuring with an ultraviolet / visible / near infrared spectrophotometer (manufactured by JASCO Corporation, ILN-472 type V-570 with integral dividing ball). The calculated film thickness is 43 nm.
本発明は酸化チタン膜被覆粉体の製造方法およびそれにより得られた粉体は、表面に被覆された酸化チタン膜による光学的干渉作用により、青色や赤紫色に着色されたものとすることができ、カラーインキ、プラスチック、紙用カラーフィラー、カラートナー、インクジェットプリンター用カラーインク等多種の目的に用いることができる。 The present invention relates to a method for producing a titanium oxide film-coated powder and the powder obtained thereby is colored blue or magenta due to the optical interference effect of the titanium oxide film coated on the surface. It can be used for various purposes such as color ink, plastic, color filler for paper, color toner, and color ink for inkjet printer.
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| JP2549691B2 (en) * | 1988-03-02 | 1996-10-30 | 触媒化成工業株式会社 | Method for producing titanium oxide coated body |
| JP2938376B2 (en) * | 1995-08-31 | 1999-08-23 | 佐賀県 | Liquid for forming titania film, titania film and method for producing the same |
| JP3640566B2 (en) * | 1999-04-12 | 2005-04-20 | 株式会社資生堂 | Titanium oxide coated powder and cosmetics |
| CA2462487C (en) * | 2001-10-04 | 2010-02-02 | Nittetsu Mining Co., Ltd. | Titania film-coated powder and process for producing the same |
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2004
- 2004-04-09 JP JP2004115087A patent/JP4804720B2/en not_active Expired - Lifetime
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