JP3863195B2 - Phthalocyanine compounds - Google Patents
Phthalocyanine compounds Download PDFInfo
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- JP3863195B2 JP3863195B2 JP10449894A JP10449894A JP3863195B2 JP 3863195 B2 JP3863195 B2 JP 3863195B2 JP 10449894 A JP10449894 A JP 10449894A JP 10449894 A JP10449894 A JP 10449894A JP 3863195 B2 JP3863195 B2 JP 3863195B2
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- Prior art keywords
- phthalocyanine
- compound
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class 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 description 28
- -1 phthalocyanine compound Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- BKAWJIRCKVUVED-UHFFFAOYSA-N 5-(2-hydroxyethyl)-4-methylthiazole Chemical compound CC=1N=CSC=1CCO BKAWJIRCKVUVED-UHFFFAOYSA-N 0.000 description 4
- HOASVNMVYBSLSU-UHFFFAOYSA-N 6-ethoxy-3h-1,3-benzothiazole-2-thione Chemical compound CCOC1=CC=C2N=C(S)SC2=C1 HOASVNMVYBSLSU-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-YYWVXINBSA-N N,N-dimethylformamide-d7 Chemical compound [2H]C(=O)N(C([2H])([2H])[2H])C([2H])([2H])[2H] ZMXDDKWLCZADIW-YYWVXINBSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Filters (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、光記録用色素、カラーフィルター用色素、光電変換素子、電子写真感光体、有機半導体素子、触媒及びガスセンサー、カラーフィルター等に利用可能な新規なフタロシアニン化合物に関する。
【０００２】
【従来の技術】
フタロシアニン化合物は従来から使用されてきた顔料としての用途の他に、光記録用色素、カラーフィルター用色素、光電変換素子、電子写真感光体、有機半導体素子、触媒及びガスセンサー等の材料として注目を集めている。しかしながら、無置換のフタロシアニン化合物は、ほとんどの溶剤に対して難溶若しくは不溶であり、著しく加工性に劣る。例えば、前述の用途に用いるためフタロシアニンを薄膜化する場合には、真空蒸着法か超微粒子分散法が用いられるが、いずれの場合も生産性が低く、これらの媒体や素子等を量産する場合に大きな障害になっている。特に、フタロシアニン化合物の真空蒸着膜を光ディスク用記録膜として用いる場合、蒸着膜を記録特性に合う結晶型に結晶転移することが必要となる。この結晶転移は蒸着した記録膜を熱又は有機溶媒の蒸気に長時間曝す処理によって行なわれ、生産性を著しく損なうため、この方法による光ディスクの生産は実用化されていない。
【０００３】
また、光ディスクなかでもコンパクトディスク（ＣＤ）に関しては、近年特に追記型ＣＤの開発が盛んであり、これまで追記型ＣＤの材料となる有機色素としては、主としてシアニン色素が用いられてきた。この種の色素は、吸光係数が大きいという点では優れているが、耐光性が悪いという欠点があり、これを改善するため一重項酸素クエンチャーなどの光安定剤を添加する方法がとられることもあった。しかし、その効果はまだ十分なものではない。これに対しフタロシアニン色素は高い光安定性を有するが、前述のように有機溶剤への溶解度が低いという問題を有していた。
【０００４】
上記の問題を解決するために、フタロシアニンに置換基を導入して有機溶媒に溶解し得るフタロシアニン化合物となした後、これを塗布することも行なわれている。特開平１−１８０８６５号、特開平２−２６５７８８号、特開平３−２１５４６６号各公報等に開示されているフタロシアニン化合物は、フタロシアニンのベンゼン環に長鎖のアルキル基又はアルコキシ基を導入して炭化水素系有機溶剤に対する溶解性を得たものである。これら以外にも、エステル基、ポリエーテル基、チオエーテル基等の官能基を介して長鎖のアルキル基を導入することが数多く行なわれている。
【０００５】
【発明が解決しようとする課題】
ところが、これらのフタロシアニン化合物は、シアニン色素に比べて吸光係数が低く、特に成膜した場合はフタロシアニン分子間の会合のため長波長部の吸光係数が低下し、光吸収層として必要な屈折率を達成できないという難点があった。
【０００６】
従って、本発明は、置換基により各種の有機溶媒に対する溶解性を向上させたフタロシアニン化合物において、光記録用色素等の用途においても高い性能を持つ化合物を提供することを、その目的とする。
【０００７】
【課題を解決するための手段】
本発明によれば、下記の一般式（Ｉ）で示されるフタロシアニン化合物が提供される。
【化１】
【０００８】
本発明の新規なフタロシアニン化合物は、前記の一般式（Ｉ）で示される構造を有することから、各種の有機溶媒に対し優れた溶解性を有し、しかも光記録用色素等の用途においても高い性能を持つものとなる。
【０００９】
前記一般式（Ｉ）の化合物において、Ｙの好ましい具体例としては、ベンゾチアゾリル基、イソキノリル基、４−メチルチアゾリル基などが挙げられる。また、Ｍの好ましい具体例としては、ＶＯ、ＴｉＯ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｐｄ、Ｃｄ、Ｍｇ、Ｈ2などが挙げられるが、光ディスク材料として用いる場合には、窒素原子との相互作用によって分子会合を防ぎ膜の吸光係数を高める機能を持つｄ５〜ｄ７、ｄ１０、ｄ０の２価金属イオンが好ましく、特に好ましいのはＭｎ、Ｆｅ、Ｃｏ、Ｚｎ、Ｃｄである。また、フタロシアニン骨格上の置換基の位置については、α位置換体の方が分子会合を防ぐ効果が大きく、膜の吸光係数を高める点で好ましい。
【００１０】
前記一般式（Ｉ）のフタロシアニン化合物は、対応するフタロニトリル（３又は４位の炭素にＸＹが結合したもの）を（必要により金属塩とともに）強有機塩基である１，８−ジアザビシクロ［５，４，０］−７−ウンデセン等の存在下、アルコール系溶媒中で反応させることにより合成することができる。
【００１１】
本発明のフタロシアニン化合物は、アルコール系極性溶剤や炭化水素系溶剤、或いはそれらの混合物などに容易に溶けて青色ないし緑色を呈する。例えば、そのエチルセロソルブ溶液をポリカーボネート基板にスピンコートすると、均質な薄膜を形成することができる。
【００１２】
このようにして得られた薄膜の吸収スペクトルは、通常のフタロシアニン誘導体を用いた薄膜で見られるような可視部における吸光係数の低下が見られず、可視部において高い吸光係数を持つので、光記録媒体等の用途に用いるのにも適している。吸収スペクトルにおけるこのような好ましい特性は、本発明のフタロシアニン化合物が電子供与性の置換基を持ち、これが中心金属に配位結合することによって、フタロシアニン骨格の分子会合を防ぐためと考えられる。
【００１３】
【実施例】
以下、本発明を実施例により更に具体的に説明する。
実施例１
テトラα−〔２−（６−エトキシベンゾチアゾリル）チオ〕フタロシアニンの合成；
１）フタロニトリル誘導体の合成２−メルカプト−６−エトキシベンゾチアゾール６．３ｇ、３−ニトロフタロニトリル５．２ｇ、無水炭酸カリウム８．４ｇ、ジメチルスルホキシド２０ｍｌを仕込み、７０℃で７時間反応させた。反応物に水を加え、析出した結晶を凝集、乾燥して、６．６ｇのフタロニトリル誘導体を得た。このフタロニトリル誘導体の分析データは、下記の通りである。
ＩＲスペクトル（ＫＢｒ） ：２３２０ｃｍ−１（νＣＮ）
マススペクトル ：３３７（Ｍ+）
融点 ：１５６℃
【００１４】
２）環化反応上記で得たフタロニトリル誘導体３．４ｇに、塩化亜鉛０．３５ｇとＤＢＵ（１，８−ジアザビシクロ〔５，４，０〕−７−ウンデンセン）２．３ｇ、１−ペンタノール３０ｍｌを加えて、窒素雰囲気下、１００℃で１０時間反応させた。反応物を濾過した後、メタノールで洗浄し、２．７ｇの粗製品を得た。この粗製品をカラムクロマトグラフィーを用いて精製し、１．１ｇの精製フタロシアニン（化合物１）を得た。
【００１５】
実施例２
テトラα−〔５−（４−メチルチアゾリル）エトキシ〕亜鉛フタロシアニンの合成；
１）フタロニトリル誘導体の合成５−（２−ヒドロキシエチル）−４−メチルチアゾール５．１ｇ、３−ニトロフタロニトリル５．２ｇ、無水炭酸カリウム８．４ｇ、ジメチルスルホキシド２０ｍｌを仕込み、７０℃で５時間反応させた。反応物に水３００ｍｌを加え、析出した結晶を凝集、乾燥して、７．０ｇのフタロニトリル誘導体を得た。このフタロニトリル誘導体の分析データは、下記の通りである。
ＩＲスペクトル（ＫＢｒ） ：２３２０ｃｍ−１（νＣＮ）
マススペクトル ：２６９（Ｍ+）
融点 ：１５２℃
【００１６】
２）環化反応上記で得たフタロニトリル誘導体３．５ｇに、塩化亜鉛０．５９ｇとＤＢＵ３．５ｇ、１−ペンタノール２０ｍｌを加えて、窒素雰囲気下、１１０℃で７時間反応させた。反応液にメタノール５０ｍｌ、水５０ｍｌを加え、析出物を濾過した後、メタノールで洗浄し、２．１ｇの粗製品を得た。この粗製品をカラムクロマトグラフィーを用いて精製し、１．０ｇの精製フタロシアニン（化合物２）を得た。このフタロシアニン誘導体の元素分析値は、次のようであった。
Ｃ（％） Ｈ（％） Ｎ（％）
実測値 ５８．７４ ３．９２ １４．７８
計算値 ５８．８６ ３．８８ １４．７１（Ｃ５６Ｈ４４Ｎ１２Ｏ４Ｓ４Ｚｎ）
【００１７】
実施例３
実施例１の１）の反応において、２−メルカプト−６−エトキシベンゾチアゾールに代えて２−メルカプト−６−ｎ−ヘキシルオキシベンゾチアゾールを原料として用いたこと以外は、実施例１と同様にしてフタロシアニン誘導体（化合物３）を得た。
【００１８】
参考例１
実施例１の１）の反応において、２−メルカプト−６−エトキシベンゾチアゾールに代えて２−メルカプトピリミジンを用いたこと以外は、実施例１と同様にしてフタロシアニン誘導体（化合物４）を得た。
【００１９】
参考例２
実施例２の１）の反応において、３−ニトロフタロニトリルに代えて４−ニトロフタロニトリルを原料として用いたこと以外は、実施例２と同様にしてフタロシアニン誘導体（化合物５）を得た。
【００２０】
実施例４
実施例２の２）の環化反応において、塩化亜鉛に代えて塩化コバルトを用いたこと以外は、実施例２と同様にしてフタロシアニン誘導体（化合物６）を得た。
【００２１】
実施例５及び参考例３〜６
実施例１の１）の反応において、２−メルカプト−６−エトキシベンゾチアゾールに代えて表１に示した置換基Ｙ−（ＣＨ2）n−Ｘに対応した原料Ｙ−（ＣＨ2）n−ＸＨを用い、且つ２）の反応においては、塩化亜鉛に代えて表１に示した金属Ｍの塩化物を用いたこと以外は、実施例１と同様にしてそれぞれ表１に示すα−置換フタロシアニン（化合物７〜１１）を得た。
【００２２】
参考例７〜８
参考例２の１）の反応において、５−（２−ヒドロキシエチル）−４−メチルチアゾールに代えて表１に示した置換基Ｙ−（ＣＨ2）n−Ｘに対応した原料Ｙ−（ＣＨ2）n−ＸＨを用い、且つ２）の反応においては、塩化亜鉛に代えて表１に示した金属Ｍの塩化物を用いたこと以外は、参考例２と同様にしてそれぞれ表１に示すβ−置換フタロシアニンを得た。
【００２３】
以上の各実施例及び各参考例で得られたフタロシアニン化合物の置換基〔−Ｘ−（ＣＨ2）n−Ｙ〕と置換位置、Ｍの種類及びクロロホルム溶液における吸収スペクトルの極大波長λｍａｘを、それぞれ表１に示す。このうち化合物２の1Ｈ−ＮＭＲスペクトル（ＤＭＦ−ｄ７）は、下記の通りである。
δ（ｐｐｍ ｆｒｏｍ ＴＭＳ）：２．２（８Ｈ，ｑ），３．４（１２Ｈ，ｓ），４．８（８Ｈ，ｍ），７．５（４Ｈ，ｍ），７．８（４Ｈ，ｍ），８．０（４Ｈ，ｓ），８．７（４Ｈ，ｍ）
【００２４】
【表１】
表１に記載されたフタロシアニン化合物の一部にについて、有機溶剤への溶解度を調べた。その結果を表２に示す。
【００２６】
【表２】
応用例直径１２０ｍｍ、厚さ１．２ｍｍのポリカーボネイト基板の表面上に深さ約１，２００Åの案内溝凸凹パターンを有する基板を用意し、前記Ｎｏ．２の化合物を２，２，３，３−テトラフロロプロパノールを塗布溶媒としてスピンコートすることにより、基板上に光吸収層を設けた。この光吸収層の膜厚は約１，５００Åであった。次に、光吸収層の上にＡｕスパッタ法によりＡｕを約８００Åの厚さに設け反射層とし、更にその上に紫外線硬化樹脂からなる保護層を約５μｍの厚さに設けて追記型ＣＤを作製した。このＣＤに波長７８５ｎｍ、Ｎ．Ａ、０．５、線速１．４ｍ／ｓの条件でＥＦＭ信号を記録し、再生を行なったところ、Ｉｔｏｐは６６％、Ｃ１エラーは２２０以下であり、ＣＤ規格を満足する値であった。
【００２８】
応用比較例応用例において、前記Ｎｏ．２の化合物の代わりにα−２メチルフェニルチオＺｎフタロシアニンを用い、且つそれをアモルファスポリオレフィン基板上に１，２ジクロロエタンを用いてスピンコートしたこと以外は、応用例と同様にして追記型ＣＤを作製し評価したところ、Ｉｔｏｐは３８％、Ｃ１エラーは２２０以上であり、ＣＤ規格を満足できなかった。
【００２９】
【発明の効果】
本発明のフタロシアニン化合物は、前記一般式（Ｉ）で示される構造を有することから、種々の有機溶媒に室温で容易に溶解する。そのため、該化合物は膜形成などの加工性に優れたものとして利用が期待でき、特に光記録用材料に優れた特性を与えることができる。[0001]
[Industrial application fields]
The present invention relates to a novel phthalocyanine compound that can be used for optical recording dyes, color filter dyes, photoelectric conversion elements, electrophotographic photosensitive members, organic semiconductor elements, catalysts and gas sensors, color filters, and the like.
[0002]
[Prior art]
Phthalocyanine compounds are attracting attention as materials for pigments for optical recording, dyes for color filters, photoelectric conversion elements, electrophotographic photoreceptors, organic semiconductor elements, catalysts, gas sensors, etc., in addition to their conventional use as pigments. Collecting. However, unsubstituted phthalocyanine compounds are hardly soluble or insoluble in most solvents and are extremely inferior in processability. For example, when thinning phthalocyanine for use in the above-mentioned applications, vacuum deposition or ultrafine particle dispersion is used, but in either case, productivity is low, and these media and devices are mass-produced. It is a big obstacle. In particular, when a vacuum-deposited film of a phthalocyanine compound is used as a recording film for an optical disc, it is necessary to crystal-transform the deposited film into a crystal type that matches the recording characteristics. This crystal transition is performed by a process in which the deposited recording film is exposed to heat or vapor of an organic solvent for a long time, and the productivity is remarkably impaired. Therefore, production of an optical disk by this method has not been put to practical use.
[0003]
In addition, with regard to compact discs (CDs) among optical discs, write-once CDs have been especially developed in recent years, and cyanine dyes have been mainly used as organic dyes as materials for write-once CDs. This type of dye is superior in that it has a large extinction coefficient, but has the disadvantage of poor light resistance, and a method of adding a light stabilizer such as a singlet oxygen quencher is taken to improve this. There was also. However, the effect is not enough. In contrast, phthalocyanine dyes have high light stability, but have the problem of low solubility in organic solvents as described above.
[0004]
In order to solve the above problem, a phthalocyanine compound that can be dissolved in an organic solvent by introducing a substituent into phthalocyanine is then applied. The phthalocyanine compounds disclosed in JP-A-1-180865, JP-A-2-265788, JP-A-3-215466, etc. are carbonized by introducing a long-chain alkyl group or alkoxy group into the benzene ring of phthalocyanine. It has obtained solubility in a hydrogen-based organic solvent. In addition to these, many long-chain alkyl groups have been introduced through functional groups such as ester groups, polyether groups, and thioether groups.
[0005]
[Problems to be solved by the invention]
However, these phthalocyanine compounds have a lower extinction coefficient than cyanine dyes, and in particular when formed into a film, the extinction coefficient in the long wavelength portion is lowered due to the association between phthalocyanine molecules, and the refractive index necessary for the light absorption layer is reduced. There was a difficulty that could not be achieved.
[0006]
Accordingly, an object of the present invention is to provide a phthalocyanine compound whose solubility in various organic solvents is improved by a substituent, and a compound having high performance in applications such as optical recording dyes.
[0007]
[Means for Solving the Problems]
According to the present invention, a phthalocyanine compound represented by the following general formula (I) is provided.
[Chemical 1]
[0008]
Since the novel phthalocyanine compound of the present invention has the structure represented by the general formula (I), it has excellent solubility in various organic solvents and is also high in applications such as optical recording dyes. It will have performance.
[0009]
In the compound of the general formula (I), preferred specific examples of Y include benzothiazolyl group, isoquinolyl group, 4-methylthiazolyl group and the like. Preferable specific examples of M include VO, TiO, Mn, Fe, Co, Ni, Cu, Zn, Pd, Cd, Mg, H 2 and the like. Divalent metal ions d5 to d7, d10, and d0 having a function of preventing molecular association by the interaction with and increasing the absorption coefficient of the film are preferable, and Mn, Fe, Co, Zn, and Cd are particularly preferable. As for the position of the substituent on the phthalocyanine skeleton, the α-position substitution product is more effective in preventing molecular association and is preferable in terms of increasing the absorption coefficient of the film.
[0010]
The phthalocyanine compound represented by the general formula (I) includes 1,8-diazabicyclo [5, which is a strong organic base (corresponding to XY bonded to 3 or 4 position carbon) (along with a metal salt if necessary). It can be synthesized by reacting in an alcohol solvent in the presence of 4,0] -7-undecene or the like.
[0011]
The phthalocyanine compound of the present invention easily dissolves in an alcohol-based polar solvent, a hydrocarbon-based solvent, or a mixture thereof and exhibits a blue or green color. For example, when the ethyl cellosolve solution is spin-coated on a polycarbonate substrate, a homogeneous thin film can be formed.
[0012]
The absorption spectrum of the thin film thus obtained does not show a decrease in the extinction coefficient in the visible part as seen in a thin film using ordinary phthalocyanine derivatives, and has a high extinction coefficient in the visible part. It is also suitable for use as a medium. Such a preferable characteristic in the absorption spectrum is considered to prevent molecular association of the phthalocyanine skeleton by the phthalocyanine compound of the present invention having an electron-donating substituent, which is coordinated to the central metal.
[0013]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
Synthesis of tetra α- [2- (6-ethoxybenzothiazolyl) thio] phthalocyanine;
1) Synthesis of phthalonitrile derivative 6.3 g of 2-mercapto-6-ethoxybenzothiazole, 5.2 g of 3-nitrophthalonitrile, 8.4 g of anhydrous potassium carbonate, and 20 ml of dimethyl sulfoxide were charged and reacted at 70 ° C. for 7 hours. . Water was added to the reaction product, and the precipitated crystals were agglomerated and dried to obtain 6.6 g of a phthalonitrile derivative. Analysis data of this phthalonitrile derivative is as follows.
IR spectrum (KBr): 2320 cm −1 (νCN)
Mass spectrum: 337 (M +)
Melting point: 156 ° C
[0014]
2) Cyclization reaction To 3.4 g of the phthalonitrile derivative obtained above, 0.35 g of zinc chloride, 2.3 g of DBU (1,8-diazabicyclo [5,4,0] -7-undencene), 1-pentanol 30 ml was added and reacted at 100 ° C. for 10 hours under a nitrogen atmosphere. The reaction product was filtered and washed with methanol to obtain 2.7 g of a crude product. This crude product was purified using column chromatography to obtain 1.1 g of purified phthalocyanine (Compound 1).
[0015]
Example 2
Synthesis of tetra α- [5- (4-methylthiazolyl) ethoxy] zinc phthalocyanine;
1) Synthesis of phthalonitrile derivative 5.1 g of 5- (2-hydroxyethyl) -4-methylthiazole, 5.2 g of 3-nitrophthalonitrile, 8.4 g of anhydrous potassium carbonate, and 20 ml of dimethyl sulfoxide were charged at 70 ° C. Reacted for hours. 300 ml of water was added to the reaction product, and the precipitated crystals were aggregated and dried to obtain 7.0 g of a phthalonitrile derivative. Analysis data of this phthalonitrile derivative is as follows.
IR spectrum (KBr): 2320 cm −1 (νCN)
Mass spectrum: 269 (M +)
Melting point: 152 ° C
[0016]
2) Cyclization reaction To 3.5 g of the phthalonitrile derivative obtained above, 0.59 g of zinc chloride, 3.5 g of DBU, and 20 ml of 1-pentanol were added and reacted at 110 ° C. for 7 hours in a nitrogen atmosphere. 50 ml of methanol and 50 ml of water were added to the reaction solution, and the precipitate was filtered and washed with methanol to obtain 2.1 g of a crude product. This crude product was purified using column chromatography to obtain 1.0 g of purified phthalocyanine (Compound 2). The elemental analysis values of this phthalocyanine derivative were as follows.
C (%) H (%) N (%)
Actual value 58.74 3.92 14.78
Calculated 58.86 3.88 14.71 (C 56 H 44 N 12 O 4 S 4 Zn)
[0017]
Example 3
In the reaction of Example 1 1), except that 2-mercapto-6-n-hexyloxybenzothiazole was used as a raw material instead of 2-mercapto-6-ethoxybenzothiazole, the same procedure as in Example 1 was performed. A phthalocyanine derivative (Compound 3) was obtained.
[0018]
Reference example 1
A phthalocyanine derivative (Compound 4) was obtained in the same manner as in Example 1 except that 2-mercaptopyrimidine was used in place of 2-mercapto-6-ethoxybenzothiazole in the reaction of Example 1).
[0019]
Reference example 2
A phthalocyanine derivative (Compound 5) was obtained in the same manner as in Example 2 except that 4-nitrophthalonitrile was used as a raw material in place of 3-nitrophthalonitrile in the reaction of Example 2 1).
[0020]
Example 4
A phthalocyanine derivative (Compound 6) was obtained in the same manner as in Example 2 except that cobalt chloride was used in place of zinc chloride in the cyclization reaction of Example 2).
[0021]
Example 5 and Reference Examples 3-6
In the reaction 1) of Example 1, instead of 2-mercapto-6-ethoxybenzothiazole, the raw material Y- (CH 2 ) n — corresponding to the substituent Y— (CH 2 ) n —X shown in Table 1 Α-Substituted phthalocyanine shown in Table 1 in the same manner as in Example 1 except that XH was used and the metal M chloride shown in Table 1 was used instead of zinc chloride in the reaction of 2) (Compounds 7 to 11) were obtained.
[0022]
Reference Examples 7-8
In the reaction of 1) of Reference Example 2, instead of 5- (2-hydroxyethyl) -4-methylthiazole, the raw material Y- (CH corresponding to the substituent Y— (CH 2 ) n —X shown in Table 1 2 ) In the reaction of 2 ), n- XH was used, and in the same manner as in Reference Example 2, except that the metal M chloride shown in Table 1 was used instead of zinc chloride, Table 1 shows each. β-substituted phthalocyanine was obtained.
[0023]
The substituent [—X— (CH 2 ) n —Y] and substitution position of the phthalocyanine compound obtained in each of the above Examples and Reference Examples, the type of M, and the maximum wavelength λmax of the absorption spectrum in a chloroform solution, Table 1 shows. Among these, the 1 H-NMR spectrum (DMF-d7) of Compound 2 is as follows.
δ (ppm from TMS): 2.2 (8H, q), 3.4 (12H, s), 4.8 (8H, m), 7.5 (4H, m), 7.8 (4H, m ), 8.0 (4H, s), 8.7 (4H, m)
[0024]
[Table 1]
A part of the phthalocyanine compounds described in Table 1 was examined for solubility in organic solvents. The results are shown in Table 2.
[0026]
[Table 2]
Application Example A substrate having a guide groove uneven pattern having a depth of about 1,200 mm on the surface of a polycarbonate substrate having a diameter of 120 mm and a thickness of 1.2 mm is prepared. The compound 2 was spin-coated using 2,2,3,3-tetrafluoropropanol as a coating solvent to provide a light absorption layer on the substrate. The thickness of this light absorption layer was about 1,500 mm. Next, Au is deposited on the light absorption layer by Au sputtering to a thickness of about 800 mm to form a reflective layer, and a protective layer made of ultraviolet curable resin is further formed on the light-absorbing layer to a thickness of about 5 μm. Produced. This CD has a wavelength of 785 nm, N.I. When an EFM signal was recorded and reproduced under the conditions of A, 0.5, and a linear velocity of 1.4 m / s, Itop was 66% and C1 error was 220 or less, which was a value satisfying the CD standard. .
[0028]
Application Comparative Example In the application example, the above-mentioned No. A write-once CD was prepared in the same manner as in the application example except that α-2 methylphenylthio Zn phthalocyanine was used in place of compound 2 and spin coated with 1,2 dichloroethane on an amorphous polyolefin substrate. As a result, it was found that Itop was 38%, C1 error was 220 or more, and the CD standard could not be satisfied.
[0029]
【The invention's effect】
Since the phthalocyanine compound of the present invention has the structure represented by the general formula (I), it is easily dissolved in various organic solvents at room temperature. For this reason, the compound can be expected to be used as a material having excellent processability such as film formation, and can give particularly excellent characteristics to an optical recording material.
Claims (1)
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| JP10449894A JP3863195B2 (en) | 1994-04-20 | 1994-04-20 | Phthalocyanine compounds |
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| JP10449894A JP3863195B2 (en) | 1994-04-20 | 1994-04-20 | Phthalocyanine compounds |
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