JP4038572B2 - Method for producing phthalocyanine-based near-infrared absorbing dye - Google Patents
Method for producing phthalocyanine-based near-infrared absorbing dye Download PDFInfo
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- JP4038572B2 JP4038572B2 JP2003293801A JP2003293801A JP4038572B2 JP 4038572 B2 JP4038572 B2 JP 4038572B2 JP 2003293801 A JP2003293801 A JP 2003293801A JP 2003293801 A JP2003293801 A JP 2003293801A JP 4038572 B2 JP4038572 B2 JP 4038572B2
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- phthalocyanine
- infrared absorbing
- absorbing dye
- antimony
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- 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 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000000975 dye Substances 0.000 claims description 38
- 239000007800 oxidant agent Substances 0.000 claims description 20
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 4
- 229920006391 phthalonitrile polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000001462 antimony Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006464 oxidative addition reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical class I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 methoxy, ethoxy Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910020314 ClBr Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
この出願の発明は、フタロシアニン系近赤外線吸収色素の製造方法に関するものである。さらに詳しくはこの出願の発明は、フタロシアニン系近赤外線吸収色素を収率高く製造するための簡便で汎用性の高い製造方法に関するものである。 The invention of this application relates to a method for producing a phthalocyanine-based near-infrared absorbing dye. More specifically, the invention of this application relates to a simple and versatile production method for producing a phthalocyanine-based near infrared absorbing dye with high yield.
カメラの自動露出部に使用されているシリコンフォトダイオード（SPD）や電荷結合素
子（CCD）は光信号を電気信号に変換する素子であるが、これらは必要とされる視感領域
よりも近赤外線（700〜1000 nm）を含む広い波長領域に応答してしまうため、正確な露出やカラーバランスの調整が出来ないという問題がある。そこで、近赤外線をカットするフィルターを使用することにより、素子の応答波長領域を視感領域のみに限定することが行われている。また、近赤外線吸収フィルターは、プラズマディスプレイパネル（PDP）が
放つ無用の近赤外域の雑音の悪影響からSPDを用いた機器（リモコン付き家電など）を保
護する目的でも使用されている。
Silicon photodiodes (SPDs) and charge-coupled devices (CCDs) used in the camera's automatic exposure parts are devices that convert optical signals into electrical signals, but these are near-infrared light than the required visual area. Since it responds to a wide wavelength region including (700 to 1000 nm), there is a problem that accurate exposure and color balance cannot be adjusted. Therefore, by using a filter that cuts off near-infrared rays, the response wavelength region of the element is limited to the luminous region only. Near-infrared absorption filters are also used to protect devices using SPD (such as home appliances with remote controls) from the adverse effects of unwanted near-infrared noise emitted by plasma display panels (PDPs).
一方で、光コピー、レーザープリンター、または光ディスク（CD-R）等、半導体レーザーを使用する産業においては、近赤外光を積極的に利用するために、レーザー光の波長に応じた感度をもつ安定な感光色素が求められている。 On the other hand, in industries that use semiconductor lasers such as optical copying, laser printers, or optical discs (CD-R), in order to actively use near infrared light, it has sensitivity corresponding to the wavelength of the laser light. There is a need for stable photosensitive dyes.
これらの波長域に感度を持つ色素としては、フタロシアニン系化合物が知られている。しかし、一般にフタロシアニンの光吸収極大波長は可視域（典型的には600〜690 nm）に
存在し、近赤外線の波長域とは一致しない。
As dyes having sensitivity in these wavelength ranges, phthalocyanine compounds are known. However, in general, the light absorption maximum wavelength of phthalocyanine exists in the visible region (typically 600 to 690 nm) and does not coincide with the near infrared wavelength region.
この差を克服するための方法として、従来、フタロシアニンの結晶を制御して吸収を広幅化させる方法、分子骨格に特殊な置換基を導入して吸収極大を長波長シフトさせる方法、フタロシアニンのπ電子系を拡張したナフタロシアニンの誘導体により近赤外に吸収を持たせる方法などが採用されてきた。しかし、これらの方法は高価な試薬を用いて数段階の反応経路を必要とし多大な労力を要する、薄膜化が困難である、薄膜化した場合でも会合の影響により短波長シフトしやすく十分な吸収強度を発揮できない等の問題があった。 As a method for overcoming this difference, conventionally, a method of broadening absorption by controlling the crystals of phthalocyanine, a method of introducing a special substituent into the molecular skeleton to shift the absorption maximum by a long wavelength, and a π electron of phthalocyanine A method of making the near infrared absorption by a naphthalocyanine derivative having an expanded system has been adopted. However, these methods require several steps of reaction pathways using expensive reagents and require a lot of labor. There were problems such as inability to exhibit strength.
このような問題を解決するものとして、本願の発明者らは、フタロシアニンとアンチモン（Ｖ）との相互作用により吸収極大波長が近赤外にまで達する新規な非会合性色素（[Sb(Pc)X2]+）を合成し、報告している（例えば、特許文献１、非特許文献１）。このよう
な非会合性色素の吸収極大波長は、置換基Ｘを換えることにより調節でき、有用性が高い。しかし、非会合性色素（[Sb(Pc)X2]+）は、フタロシアニンの前駆体であるフタロニト
リルとアンチモン塩（SbX3）との直接反応によって合成されるものであったため、合成し得る非会合性色素（[Sb(Pc)X2]+）の種類が原料のアンチモン塩によって限定されてしま
うという問題があった。また、全てのアンチモン塩がフタロニトリルとの直接反応によって目的のフタロシアニン錯体を生成するわけではなく、例えば含臭素色素は従来の方法では合成できなかったのが実情である。
そこで、この出願の発明は、以上のとおりの事情に鑑みてなされたものであり、従来技術の問題点を解消し、様々なフタロシアニン系近赤外線吸収色素を安価に収率高く製造するための簡便な方法を提供することを課題としている。 Therefore, the invention of this application has been made in view of the circumstances as described above, and is a simple method for solving various problems of the prior art and producing various phthalocyanine-based near-infrared absorbing dyes at low cost and in high yield. To provide a simple method.
この出願の発明は、上記の課題を解決するものとして、次式（Ｉ） In order to solve the above-described problems, the invention of this application has
（ただし、Ｒは各々のベンゼン環に結合する１以上の置換基であって、同一または別異であってよく、異種原子を有していてもよい炭化水素基であり、ＸおよびＹは同一または別異に、アンチモンに配位しうる基であり、Ｗ’は対陰イオンである）
で表されるフタロシアニン系近赤外線吸収色素の製造方法であって、次式（II）
(However, R is one or more substituents bonded to each benzene ring, which may be the same or different, and may be a hydrocarbon group which may have different atoms, and X and Y are the same. Or, alternatively, a group capable of coordinating with antimony, and W ′ is a counter anion)
A phthalocyanine-based near-infrared absorbing dye represented by the following formula (II)
（ただし、Ｒは前記と同じ置換基であり、Ｗは対陰イオンである）
で表される三価アンチモンフタロシアニン錯体を、ＸおよびＹを含有する酸化剤にて酸化し、前記式ＩのＸ、Ｙの置換基を生成することを特徴とする五価アンチモンフタロシアニン錯体よりなるフタロシアニン系近赤外線吸収色素の製造方法を提供する。
(Wherein R is the same substituent as above, and W is a counter anion)
The in trivalent antimony phthalocyanine complex represented, phthalocyanine oxidized by oxidizing agents containing X and Y, consisting of pentavalent antimony phthalocyanine complex and generating an X, Y substituents of formula I A method for producing a near-infrared absorbing dye is provided.
この出願の発明は、第２には、式（Ｉ）および（II）において、Ｒが分枝鎖状アルキル基である前記のフタロシアニン系近赤外線吸収色素の製造方法を提供する。
The invention of this application, in the second, in formula (I) and (II), the production method of the phthalocyanine near infrared absorbing dye R is a branched chain alkyl group provides.
そして、第３には、この出願の発明は、酸化剤がハロゲン、有機過酸化物、過酸または酸ハロゲン化物のいずれかである前記いずれかのフタロシアニン系近赤外線吸収色素の製造方法をも提供する。 Third , the invention of this application also provides a method for producing any one of the above phthalocyanine-based near-infrared absorbing dyes, wherein the oxidizing agent is any one of halogen, an organic peroxide, a peracid or an acid halide. To do.
この出願の発明のフタロシアニン系近赤外線吸収色素の製造方法では、三価アンチモンのフタロシアニン錯体を原料とし、酸化的付加反応により五価アンチモンのフタロシアニン錯体を製造する。このとき、得られるフタロシアニン系近赤外線吸収色素の配位子ＸおよびＹは酸化剤から供給されるものであるため、製造し得る色素の選択肢が既存の方法よりも広がる。また、出発物質の三価アンチモンフタロシアニン錯体は、安価な置換フタロニトリルとヨウ化アンチモンから容易に収率高く合成されることから、近赤外線吸収色素の製造コストを削減することが可能となる。さらに、このような方法によって得られるフタロシアニン系近赤外色素は、一般の有機溶媒に対して高い溶解性を示すことから、精製も容易であり、スピンコート法や溶媒キャスト法による成膜が容易である。 In the method for producing a phthalocyanine-based near-infrared absorbing dye of the invention of this application, a pentavalent antimony phthalocyanine complex is produced by an oxidative addition reaction using a trivalent antimony phthalocyanine complex as a raw material. At this time, since the ligands X and Y of the obtained phthalocyanine-based near-infrared absorbing dye are supplied from the oxidizing agent, choices of the dye that can be produced are wider than those of the existing methods. In addition, since the trivalent antimony phthalocyanine complex as a starting material is easily synthesized in high yield from inexpensive substituted phthalonitrile and antimony iodide, it is possible to reduce the production cost of the near infrared absorbing dye. Furthermore, the phthalocyanine-based near-infrared dye obtained by such a method is highly soluble in general organic solvents, so it can be easily purified and can be easily formed by spin coating or solvent casting. It is.
この出願の発明のフタロシアニン系近赤外線吸収色素の製造方法は、次式（II） The method for producing the phthalocyanine-based near-infrared absorbing dye of the invention of this application has the following formula (II):
で表される三価アンチモンフタロシアニン錯体に、置換基ＸおよびＹを有する酸化剤を作用させ、次式（Ｉ） An oxidant having substituents X and Y is allowed to act on the trivalent antimony phthalocyanine complex represented by the following formula (I):
で表される五価アンチモンフタロシアニン錯体を得ることを特徴とするものである。 It is characterized by obtaining a pentavalent antimony phthalocyanine complex represented by the formula:
このとき、式（II）の三価アンチモンフタロシアニン錯体は、本願の発明者らによって見出されたものであり（例えば特許文献２および非特許文献２）、Ｒは各々のベンゼン環に結合する１以上の置換基で、同一または別異に異種原子を有していてもよい炭化水素基である。具体的には、Ｒとしては、メチル、エチル、プロピル、イソプロピル等のアルキル基、フェニル、ナフチル等のアリール基、メトキシ、エトキシ、フェノキシ等のアルコキシ基、アセチル等のアシル基などが例示される。中でも、tert-ブチル基、sec-ブチル
、イソブチル基、およびイソプロピル基等の分岐鎖状アルキル基が好ましいものとして挙げられる。また、Ｒは各ベンゼン環に対して１個ずつ結合していてもよいし、各々のベンゼン環に２〜４個ずつ結合していてもよく、その数、種類、および結合位置は各ベンゼン環毎に異なっていてもよいし、すべてのベンゼン環で同一であってもよい。このような三価アンチモンフタロシアニン錯体は置換フタロニトリルとヨウ化アンチモンを原料として容易に収率高く合成できるが、市販品があればそれを用いてもよい。
At this time, the trivalent antimony phthalocyanine complex of the formula (II) was found by the inventors of the present application (for example, Patent Document 2 and Non-Patent Document 2), and R is bonded to each benzene ring. The above substituents are hydrocarbon groups which may have the same or different hetero atoms. Specifically, examples of R include alkyl groups such as methyl, ethyl, propyl and isopropyl, aryl groups such as phenyl and naphthyl, alkoxy groups such as methoxy, ethoxy and phenoxy, and acyl groups such as acetyl. Among them, branched alkyl groups such as tert-butyl group, sec-butyl group, isobutyl group, and isopropyl group are preferable. One R may be bonded to each benzene ring, or 2 to 4 may be bonded to each benzene ring, and the number, type, and bonding position of each benzene ring Each benzene ring may be different or may be the same. Such a trivalent antimony phthalocyanine complex can be easily synthesized in high yields using substituted phthalonitrile and antimony iodide as raw materials, but any commercially available product may be used.
さらに、上記の式（II）におけるＷおよび式（Ｉ）におけるＷ’は対陰イオンを表すが、これらの対陰イオンは三価アンチモンフタロシアニン錯体および五価アンチモンフタロシアニン錯体の物性にほとんど影響を及ぼさないことから、安定でアンチモンフタロシアニンの陽イオン部位と反応しないものであればよく、その種類はとくに限定されない。例えばI3 -、Ｆ-、Ｃｌ-、Ｂｒ-、Ｂｒ3 -等が例示される。これらＷおよびＷ’は同一であっても異なっていてもよい。つまり、式（II）における対陰イオンＷは、三価アンチモンフタロシアニン錯体と酸化剤の酸化的付加反応後、通常は変化しないが、酸化剤の酸化力が対イオンよりも強い場合には、Ｗが酸化され、Ｗ’に変化する。例えば、対陰イオンＷがＩ3 -の場合、酸化剤をＢｒ2とすれば、対陰イオンの酸化が起こり、Ｗ’はＩＢｒ2 -にな
るが、対陰イオンＷがＦ-やＣｌ-あるいはＢｒ-の場合には、Ｂｒ2を酸化剤としても酸化反応は起こらず、Ｗ’はＷと同じものとなる。
Further, W in the above formula (II) and W ′ in the formula (I) represent counter anions, but these counter anions have little influence on the physical properties of the trivalent antimony phthalocyanine complex and the pentavalent antimony phthalocyanine complex. Since it does not exist, what is necessary is just what is stable and does not react with the cation part of antimony phthalocyanine, and the kind is not specifically limited. Examples thereof include I 3 − , F − , Cl − , Br − , Br 3 − and the like. These W and W ′ may be the same or different. That is, the counter anion W in the formula (II) does not normally change after the oxidative addition reaction of the trivalent antimony phthalocyanine complex and the oxidizing agent, but when the oxidizing power of the oxidizing agent is stronger than the counter ion, W Is oxidized and changed to W ′. For example, when the counter anion W is I 3 − , if the oxidizing agent is Br 2 , the counter anion is oxidized and W ′ becomes IBr 2 − , but the counter anion W is F − or Cl −. Alternatively, in the case of Br − , no oxidation reaction occurs even if Br 2 is used as an oxidizing agent, and W ′ is the same as W.
この出願の発明のフタロシアニン系近赤外線吸収色素の製造方法において、前記の三価アンチモンフタロシアニン錯体と反応させる酸化剤は、アンチモンフタロシアニン錯体の中心金属に配位しうる基ＸおよびＹを有するものであればよく、とくに限定されない。このとき、ＸとＹは一価の陰イオンであってもよいし、多価イオンでもよく、さらに中性分子であっても陽イオンであってもよい。具体的には、酸化剤としては、Cl2、Br2、ClBr等のハロゲンや次式（III）におけるa〜fの有機過酸化物が例示される。とくに、e〜fでは
、ＸおよびＹが中性および陽イオン性置換基となっている。
In the method for producing a phthalocyanine-based near-infrared absorbing dye of the invention of this application, the oxidizing agent to be reacted with the trivalent antimony phthalocyanine complex is one having groups X and Y that can coordinate to the central metal of the antimony phthalocyanine complex. There is no particular limitation. At this time, X and Y may be a monovalent anion, a polyvalent ion, a neutral molecule, or a cation. Specifically, examples of the oxidizing agent include halogens such as Cl 2 , Br 2 , and ClBr, and organic peroxides a to f in the following formula (III). In particular, in ef, X and Y are neutral and cationic substituents.
さらに、酸化剤はＸＹで表されるものに限定されず、塩化スルフリル（ＳＯ2Ｃｌ2：このときＸおよびＹは各々Ｃｌであり、スルフリル基は反応に関与しない）等の酸ハロゲン化物であってもよい。 Further, the oxidizing agent is not limited to those represented by XY, but may be an acid halide such as sulfuryl chloride (SO 2 Cl 2, where X and Y are each Cl, and the sulfuryl group does not participate in the reaction). May be.
このとき、酸化剤の三価アンチモンフタロシアニン錯体に対する添加量はとくに限定されない。三価アンチモンフタロシアニン錯体が過剰であっても、精製工程において生成した五価アンチモンフタロシアニン錯体のみを単離すればよく、酸化剤が過剰の場合には、残存する酸化剤を除去すればよい。好ましくは、酸化剤を三価アンチモンフタロシアニン錯体に対して１〜１０倍モル添加する。 At this time, the amount of the oxidizing agent added to the trivalent antimony phthalocyanine complex is not particularly limited. Even if the trivalent antimony phthalocyanine complex is excessive, it is sufficient to isolate only the pentavalent antimony phthalocyanine complex produced in the purification step. If the oxidizing agent is excessive, the remaining oxidizing agent may be removed. Preferably, the oxidizing agent is added in a molar amount of 1 to 10 times with respect to the trivalent antimony phthalocyanine complex.
このような三価アンチモンフタロシアニン錯体と酸化剤の反応は、三価アンチモンフタロシアニン錯体を溶媒に溶解して行ってもよいし、溶媒を使用することなく行ってもよい。溶媒を使用する場合には、出発物質である三価アンチモンフタロシアニン錯体や生成物の五価アンチモンフタロシアニン錯体と反応せず、これらを溶解できるものが好ましい。本願の発明者らにより、ジクロロメタン、クロロホルム、ベンゼン、トルエン、クロロベンゼン、アセトニトリル等の各種の有機溶媒が適用できることが確認されている。 Such a reaction between the trivalent antimony phthalocyanine complex and the oxidizing agent may be performed by dissolving the trivalent antimony phthalocyanine complex in a solvent, or may be performed without using the solvent. When a solvent is used, it is preferable to use a solvent that does not react with the starting material trivalent antimony phthalocyanine complex or the product pentavalent antimony phthalocyanine complex and can dissolve them. The inventors of the present application have confirmed that various organic solvents such as dichloromethane, chloroform, benzene, toluene, chlorobenzene, and acetonitrile can be applied.
さらにこの出願の発明のフタロシアニン系近赤外線吸収色素の製造方法においては、反応温度はとくに限定されず、例えば反応に溶媒を使用する場合には、溶媒の分解が起こらない温度や溶媒の乾留温度付近とすることができる。また、溶媒を用いない場合には、三価アンチモンフタロシアニン錯体が分解しない温度、具体的には400℃未満の温度とする
ことができる。
Furthermore, in the method for producing a phthalocyanine-based near-infrared absorbing dye of the invention of this application, the reaction temperature is not particularly limited. For example, when a solvent is used for the reaction, the temperature at which the solvent does not decompose or near the dry distillation temperature of the solvent. It can be. When no solvent is used, the temperature can be set such that the trivalent antimony phthalocyanine complex is not decomposed, specifically, a temperature of less than 400 ° C.
そして、以上のとおりの反応により、次式（Ｉ） Then, by the reaction as described above, the following formula (I)
で表される五価アンチモンフタロシアニン錯体がフタロシアニン系近赤外線吸収色素として得られる。このとき、Ｒは前記と同じ置換基を表し、Ｗ’は前記のとおり、Ｗと同じ対陰イオンであってもＷが酸化剤により酸化されたものであってもよい。さらに、ＸおよびＹは各々前記の酸化剤由来の配位子である。 Is obtained as a phthalocyanine-based near-infrared absorbing dye. In this case, R represents the same substituent as described above, and W ′ may be the same counter anion as W as described above, or W may be oxidized by an oxidizing agent. Furthermore, X and Y are each a ligand derived from the oxidizing agent.
この出願の発明の方法により得られるフタロシアニン系近赤外線吸収色素は、近赤外領域に強い光吸収と蛍光を示す。 The phthalocyanine near-infrared absorbing dye obtained by the method of the invention of this application exhibits strong light absorption and fluorescence in the near-infrared region.
フタロシアニンは、一般的に、高濃度溶液中で自己会合し、吸収極大が短波長側にシフトしたり、吸収帯の広幅化により吸光強度や蛍光が減少することが知られているが、この出願の発明のフタロシアニン系近赤外線吸収色素の製造方法によって製造されるフタロシアニン系近赤外線吸収色素では、吸光光度法による検出限界までの濃度範囲で会合が発生しないことが確認されている（特許文献１、非特許文献１）。 Phthalocyanine is generally known to self-associate in a high-concentration solution, the absorption maximum shifts to the short wavelength side, and the absorption intensity and fluorescence decrease by broadening the absorption band. In the phthalocyanine near-infrared absorbing dye produced by the method for producing a phthalocyanine near-infrared absorbing dye of the present invention, it has been confirmed that no association occurs in the concentration range up to the detection limit by the spectrophotometric method (Patent Document 1, Non-patent document 1).
また、このようなフタロシアニン系近赤外線吸収色素は、薄膜形成に通常使用されるジクロロメタン、トルエン、ベンゼン、アセトン等の各種有機溶媒に対して高い溶解性を示すため、スピンコート法や溶媒キャスト法により容易に成膜することができる。 In addition, such phthalocyanine-based near-infrared absorbing dyes exhibit high solubility in various organic solvents such as dichloromethane, toluene, benzene, and acetone that are usually used for thin film formation. A film can be easily formed.
したがって、この出願の発明のフタロシアニン系近赤外線吸収色素の製造方法により、半導体レーザーの波長に近い波長領域に強い光吸収を有し、光ディスク等のメモリー、光伝導体、光通信ならびに近赤外発光材料等の広範囲の分野において有用なフタロシアニン系近赤外線吸収色素が、安価に、かつ簡便な方法で得られる。 Therefore, the method for producing a phthalocyanine-based near-infrared absorbing dye of the invention of this application has strong light absorption in a wavelength region close to the wavelength of a semiconductor laser, a memory such as an optical disk, a photoconductor, optical communication, and near-infrared light emission. A phthalocyanine-based near-infrared absorbing dye useful in a wide range of fields such as materials can be obtained at a low cost by a simple method.
以下、実施例を示し、この発明の実施の形態についてさらに詳しく説明する。この発明は以下の例に限定されるものではなく、細部については様々な態様が可能であることは言うまでもない。 Hereinafter, examples will be shown, and the embodiments of the present invention will be described in more detail. The present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail.
＜実施例１＞
119 mgのアンチモン-テトラtert-ブチル置換フタロシアニン錯体（以下[Sb(tbpc)]+I3
とする）（0.10 mmol）を20 mlのジクロロメタンに溶解し、室温で激しく攪拌しながら0.4 ml（7.8 mmol）の臭素を滴下し、さらに３時間攪拌を続けた。
<Example 1>
119 mg of antimony-tetra-tert-butyl-substituted phthalocyanine complex (hereinafter [Sb (tbpc)] + I 3
(0.10 mmol) was dissolved in 20 ml of dichloromethane, 0.4 ml (7.8 mmol) of bromine was added dropwise with vigorous stirring at room temperature, and stirring was continued for another 3 hours.
吸収スペクトルで原料の［Sb(tbpc)]+I3 -が消失したのを確認した（図１）後、ロータ
リーエバポレーターで溶媒と過剰の臭素を留去した。得られた固体を20 mlのジクロロメ
タンに溶かし、ろ過して不溶物を除去した後、ロータリーエバポレーターで乾固させた。
[Sb (TBPC)] of the material in the absorption spectrum + I 3 - After it was confirmed that the disappeared (FIG. 1), to distill off excess bromine and the solvent on a rotary evaporator. The obtained solid was dissolved in 20 ml of dichloromethane, filtered to remove insoluble matters, and then dried with a rotary evaporator.
この固体を10 mlのジクロロメタンに溶かし、80 mlのヘキサンを加えて固体を析出させた。この操作を、上澄みが無色になるまで繰り返した。 This solid was dissolved in 10 ml of dichloromethane, and 80 ml of hexane was added to precipitate the solid. This operation was repeated until the supernatant became colorless.
固体を回収し、60℃で3時間乾燥した後、128 mgの生成物をIBr2塩として得た（収率90 %）。 After collecting the solid and drying at 60 ° C. for 3 hours, 128 mg of product was obtained as an IBr 2 salt (90% yield).
元素分析による同定結果を表１に示した。 The identification results by elemental analysis are shown in Table 1.
発色部分が[Sb(tbpc)Br2]+であることは、ESI-TOF質量分析スペクトルから確認した。
対陰イオンであるIBr2 -は、原料の対陰イオンI3 -が臭素によって酸化されたものであり、近赤外の吸収に影響を与えなかったが、既知の[Sb(tbpc)C12]+と同様の方法（特許文献１、非特許文献１）により過塩素酸塩等に変換した。
It was confirmed from the ESI-TOF mass spectrometry spectrum that the colored portion was [Sb (tbpc) Br 2 ] + .
The counter anion, IBr 2 − , was obtained by oxidizing the raw material counter anion I 3 − with bromine and did not affect the near-infrared absorption, but the known [Sb (tbpc) C1 2 ] + a similar manner to (Patent Document 1, non-Patent Document 1) it was converted to the perchlorate salt or the like by.
生成物の元素分析による同定結果を表２に示した。 The identification results of the product by elemental analysis are shown in Table 2.
以上詳しく説明したとおり、この出願の発明のフタロシアニン系近赤外線吸収色素の製造方法により、様々なフタロシアニン系近赤外線吸収色素を安価に収率高く製造するための簡便な方法が提供される。 As described in detail above, the method for producing a phthalocyanine-based near infrared absorbing dye of the invention of this application provides a simple method for producing various phthalocyanine-based near infrared absorbing dyes at a low cost and in a high yield.
この発明のフタロシアニン系近赤外線吸収色素の製造方法では、フタロシアニン系近赤外線吸収色素が簡便に合成、精製、製膜できるため、近赤外吸収色素やその薄膜が安価に製造できる。したがって、近赤外線吸収フィルターとしてSPD機器の高性能化や、プラズ
マディスプレイパネル（PDP）の普及、半導体レーザー技術の拡大等が期待され、有用性
が高い。
In the method for producing a phthalocyanine-based near-infrared absorbing dye of the present invention, a phthalocyanine-based near-infrared absorbing dye can be easily synthesized, purified, and formed into a film, so that the near-infrared absorbing dye and its thin film can be produced at low cost. Therefore, it is highly useful as a near-infrared absorption filter because it is expected to improve the performance of SPD devices, spread plasma display panels (PDP), expand semiconductor laser technology, and so on.
Claims (3)
（ただし、Ｒは各々のベンゼン環に結合する１以上の置換基であって、同一または別異であってよく、異種原子を有していてもよい炭化水素基であり、ＸおよびＹは同一または別異に、アンチモンに配位しうる基であり、Ｗ’は対陰イオンである）
で表されるフタロシアニン系近赤外線吸収色素の製造方法であって、次式（II）
（ただし、Ｒは前記と同じ置換基であり、Ｗは対陰イオンである）
で表される三価アンチモンフタロシアニン錯体を、ＸおよびＹを含有する酸化剤にて酸化し、前記式ＩのＸ、Ｙの置換基を生成することを特徴とする五価アンチモンフタロシアニン錯体よりなるフタロシアニン系近赤外線吸収色素の製造方法。 Formula (I)
(However, R is one or more substituents bonded to each benzene ring, which may be the same or different, and may be a hydrocarbon group which may have different atoms, and X and Y are the same. Or, alternatively, a group capable of coordinating with antimony, and W ′ is a counter anion)
A phthalocyanine-based near-infrared absorbing dye represented by the following formula (II)
(Wherein R is the same substituent as above, and W is a counter anion)
The in trivalent antimony phthalocyanine complex represented, phthalocyanine oxidized by oxidizing agents containing X and Y, consisting of pentavalent antimony phthalocyanine complex and generating an X, Y substituents of formula I Of manufacturing near-infrared absorbing dyes.
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