JP4740631B2 - Diimonium salt compound, near infrared absorbing dye and near infrared blocking filter using the same - Google Patents
Diimonium salt compound, near infrared absorbing dye and near infrared blocking filter using the same Download PDFInfo
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- JP4740631B2 JP4740631B2 JP2005119220A JP2005119220A JP4740631B2 JP 4740631 B2 JP4740631 B2 JP 4740631B2 JP 2005119220 A JP2005119220 A JP 2005119220A JP 2005119220 A JP2005119220 A JP 2005119220A JP 4740631 B2 JP4740631 B2 JP 4740631B2
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- -1 salt compound Chemical class 0.000 title claims description 120
- 230000000903 blocking effect Effects 0.000 title description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- 238000010521 absorption reaction Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
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- 229910052709 silver Inorganic materials 0.000 description 8
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- GVNSFLFOZIYBPH-UHFFFAOYSA-N 1-n,1-n-dibutyl-4-n-[4-[4-(dibutylamino)-n-[4-(dibutylamino)phenyl]anilino]phenyl]-4-n-[4-(dibutylamino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N(CCCC)CCCC)=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC(=CC=1)N(CCCC)CCCC)C=1C=CC(=CC=1)N(CCCC)CCCC)C1=CC=C(N(CCCC)CCCC)C=C1 GVNSFLFOZIYBPH-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
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- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 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
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 125000004209 (C1-C8) alkyl group Chemical class 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- LBCLDIXHWKFMST-UHFFFAOYSA-N 4-N-[4-[4-[bis(2,2,2-trifluoroethyl)amino]-N-[4-[bis(2,2,2-trifluoroethyl)amino]phenyl]anilino]phenyl]-4-N-[4-[bis(2,2,2-trifluoroethyl)amino]phenyl]-1-N,1-N-bis(2,2,2-trifluoroethyl)benzene-1,4-diamine Chemical group FC(CN(C1=CC=C(C=C1)N(C1=CC=C(C=C1)N(C1=CC=C(C=C1)N(CC(F)(F)F)CC(F)(F)F)C1=CC=C(C=C1)N(CC(F)(F)F)CC(F)(F)F)C1=CC=C(C=C1)N(CC(F)(F)F)CC(F)(F)F)CC(F)(F)F)(F)F LBCLDIXHWKFMST-UHFFFAOYSA-N 0.000 description 1
- 239000004923 Acrylic lacquer Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002008 alkyl bromide group Chemical group 0.000 description 1
- 125000001930 alkyl chloride group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 150000004986 phenylenediamines Chemical group 0.000 description 1
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- 239000005056 polyisocyanate Substances 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 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
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Images
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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Optical Filters (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
本発明は、ジイモニウム塩化合物並びにこれを利用する近赤外線吸収色素および近赤外線遮断フィルターに関し、更に詳細には、近赤外光領域に吸収を有するジイモニウム塩化合物およびこれを有効成分とする耐湿性、耐熱性に優れた新規な近赤外線吸収色素および該色素を含有してなる近赤外線遮断フィルターに関する。 The present invention relates to a near infrared absorptive dye and a near infrared ray blocking filter utilizing Jiimo two ium salt compounds and which, more particularly, a diimmonium salt compound and an active ingredient which has an absorption in the near infrared region moisture The present invention relates to a novel near-infrared absorbing dye excellent in heat resistance and heat resistance, and a near-infrared shielding filter containing the dye.
近年、ディスプレイの大型化、薄型化の要求が高まる中、プラズマディスプレイパネル（以下、「ＰＤＰ」と略記する）が一般に広く普及し始めている。 In recent years, plasma display panels (hereinafter, abbreviated as “PDP”) are generally becoming widespread as demands for larger and thinner displays increase.
このＰＤＰからは、近赤外線が放出される場合があり、この近赤外線により近赤外線リモコンを使用した電子機器が誤動作を起こしてしまうという問題があった。このため、ＰＤＰには、近赤外線吸収色素を用いたフィルターを使用し、これにより近赤外線を遮断する必要がある。 There is a case where near infrared rays are emitted from this PDP, and there is a problem that an electronic device using a near infrared remote controller causes malfunction due to the near infrared rays. For this reason, it is necessary to use a filter using a near-infrared absorbing dye for the PDP, thereby blocking near-infrared rays.
また、光学レンズ、自動車用ガラス、建材用ガラス等の用途にも近赤外線遮断フィルターが広く利用されている。 Near-infrared blocking filters are also widely used for applications such as optical lenses, automotive glass, and building glass.
これらの用途に用いられる近赤外線遮断フィルターには、可視光領域の光を透過しつつ、効果的に近赤外光領域の光を吸収するだけでなく、更に、耐熱性、耐湿性の特性も高いことが求められている。 Near-infrared blocking filters used in these applications not only effectively absorb near-infrared light while transmitting light in the visible light region, but also have heat and moisture resistance characteristics. It is required to be expensive.
従来、近赤外線遮断フィルターとしては、ジイモニウム塩化合物を含有するものが種々各提案されている（例えば、特許文献１参照）。 Conventionally, various types of near-infrared blocking filters containing diimonium salt compounds have been proposed (see, for example, Patent Document 1).
上記の特許文献１には、ジイモニウム塩系の近赤外線吸収色素が各種例示されているが、これらの中でも比較的耐熱性、耐湿性に優れたものとしては、例えばアニオン成分がビス−ヘキサフルオロアンチモン酸であるＮ,Ｎ,Ｎ',Ｎ'−テトラキス［ｐ−ジ（ｎ−ブチル）アミノフェニル］−ｐ−フェニレンジイモニウム塩が一般的に用いられている。 The above-mentioned Patent Document 1 exemplifies various kinds of diimonium salt-based near-infrared absorbing dyes. Among them, examples of relatively excellent heat resistance and moisture resistance include an anionic component of bis-hexafluoroantimony. The acid N, N, N ′, N′-tetrakis [p-di (n-butyl) aminophenyl] -p-phenylenediimonium salt is commonly used.
しかしながら、この色素は、耐熱性、耐湿性が不十分であり、使用中に色素が分解し、近赤外線吸収能力が低下してしまうという問題点や、分解により生成したアミニウム塩が可視光線領域に吸収を生じることから、可視光透過率が低下し、黄色に呈色して色調を損なってしまうという問題点があった。 However, this dye has insufficient heat resistance and moisture resistance, so that the dye is decomposed during use and the near-infrared absorption ability is lowered, and the aminium salt generated by the decomposition is in the visible light region. Since absorption occurs, the visible light transmittance is lowered, and there is a problem that the color tone is deteriorated due to yellow coloration.
さらに、上記色素はアニオン成分として、重金属であるアンチモンを含有しており、大量に使用した場合には環境を汚染するという問題があった。 Further, the above dye contains antimony, which is a heavy metal, as an anion component, and has a problem of polluting the environment when used in a large amount.
従って、本発明の第一の課題は、耐熱性、耐湿性に優れ、長期にわたって近赤外線吸収能力が低下しない新規の近赤外線吸収色素を提供することであり、また、第二の課題は、耐熱性、耐湿性に優れた近赤外線遮断フィルターを提供することである。 Therefore, the first problem of the present invention is to provide a novel near-infrared absorbing dye that is excellent in heat resistance and moisture resistance and does not deteriorate near-infrared absorption ability over a long period of time. It is to provide a near-infrared shielding filter excellent in heat resistance and moisture resistance.
本発明者らは上記課題を解決すべく鋭意研究を行った結果、特定のアニオン成分を有するジイモニウム塩は、近赤外吸収能が高いと共に、耐熱性、耐湿性に優れることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a diimonium salt having a specific anion component has high near-infrared absorption ability and is excellent in heat resistance and moisture resistance. It came to complete.
すなわち本発明は、次の一般式（１）、
で表されるジイモニウム塩化合物である。
That is, the present invention provides the following general formula (1),
The diimonium salt compound represented by these.
また本発明は、上記式（１）で表されるジイモニウム塩化合物を有効成分として含有する近赤外線吸収色素である。 Moreover, this invention is a near-infrared absorption pigment | dye which contains the diimonium salt compound represented by the said Formula (1) as an active ingredient.
更に本発明は、上記の近赤外線吸収色素を含有してなる近赤外線遮断フィルターである。 Furthermore, the present invention is a near-infrared shielding filter containing the above-mentioned near-infrared absorbing dye.
本発明のジイモニウム塩化合物は、近赤外線吸収色素として、耐熱性、耐湿性に優れ、長期間にわたって近赤外線吸収能力が低下することなく、有機溶媒などへの溶解性も高いことから、加工性に優れる特徴を有している。また重金属を含有しないので環境に対する問題がない。 The diimonium salt compound of the present invention is excellent in heat resistance and moisture resistance as a near-infrared absorbing dye, and has a high solubility in organic solvents and the like without decreasing the near-infrared absorbing ability over a long period of time. It has excellent characteristics. Moreover, since it does not contain heavy metals, there are no environmental problems.
従って、本発明のジイモニウム塩化合物を近赤外線吸収色素として含有させた本発明の近赤外線遮断フィルターは、種々の用途、例えばＰＤＰ用近赤外線遮断フィルター、自動車ガラス用ないし建材ガラス用近赤外線遮断フィルター等として利用することができ、特にＰＤＰ用近赤外線遮断フィルターとして好適である。 Therefore, the near-infrared blocking filter of the present invention containing the diimonium salt compound of the present invention as a near-infrared absorbing dye has various uses, for example, a near-infrared blocking filter for PDP, a near-infrared blocking filter for automotive glass or building glass, etc. In particular, it is suitable as a near-infrared shielding filter for PDP.
本発明のジイモニウム塩化合物は、上記一般式（１）で表される化合物である。このうち、式（１）において、Ｒ１がフルオロ基であるものは、ビス（フルオロスルホニル）イミド酸をアニオン成分とするジイモニウム塩化合物であり、式（１）において、Ｒ１がフッ化アルキル基であるものは、フッ化アルカンスルホニル−フルオロスルホニルイミド酸をアニオン成分とするジイモニウムの塩化合物である。
Di Lee Moniumu salt compound of the present invention is a compound represented by the general formula (1). Among these, those in which R 1 is a fluoro group in the formula (1) are diimonium salt compounds having bis (fluorosulfonyl) imidic acid as an anion component. In the formula (1), R 1 is a fluorinated alkyl group. Is a salt compound of diimonium containing alkanesulfonyl fluoride-fluorosulfonylimide acid as an anionic component.
式（１）のＲ１におけるフッ化アルキル基は、置換されているフッ素原子の数や炭素数には特に限定はないが、その好ましい例として、炭素数１〜８のパーフルオロアルキル基が挙げられ、特に、トリフルオロメタン、ペンタフルオロエタン等が近赤外線吸収能力の点で更に好ましい。 The fluorinated alkyl group in R 1 of the formula (1) is not particularly limited in the number of substituted fluorine atoms or the number of carbon atoms. Preferred examples thereof include perfluoroalkyl groups having 1 to 8 carbon atoms. In particular, trifluoromethane, pentafluoroethane, and the like are more preferable in terms of near infrared absorption ability.
本発明のジイモニウム塩化合物の合成方法としては、公知の方法によりジイモニウム化合物を調製した後、そのアニオン部分を上記ビス（フルオロスルホニル）イミド酸またはフッ化アルカンスルホニル−フルオロスルホニルイミド酸と交換すればよい。 As a method for synthesizing the diimonium salt compound of the present invention, after preparing a diimonium compound by a known method, the anion moiety may be exchanged with the above bis (fluorosulfonyl) imidic acid or fluorinated alkanesulfonyl-fluorosulfonylimide acid. .
より具体的には、例えば、特許文献２に記載の方法に従って調製されたビス（フルオロスルホニル）イミド酸や、例えば、特許文献３などに準じて調製されたフッ化アルカンスルホニル−フルオロスルホニルイミド酸をアニオン成分とし、これに銀を作用させてビス（フルオロスルホニル）イミド酸銀、または、フッ化アルカンスルホニル−フルオロスルホニルイミド酸銀と、下記一般式（４）で表されるイモニウム化合物を、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド（以下、「ＤＭＦ」と略記する）、アセトニトリル等の有機溶媒中、温度３０〜１５０℃で反応させ、析出した銀を濾別した後、水、酢酸エチルまたはヘキサン等の溶媒を加え、生じた沈殿を濾過することにより、本発明のジイモニウム塩化合物を得ることができる。 More specifically, for example, bis (fluorosulfonyl) imidic acid prepared according to the method described in Patent Document 2, or alkanesulfonyl-fluorosulfonylimide acid prepared according to Patent Document 3, for example. As an anion component, silver is allowed to act on the silver bis (fluorosulfonyl) imidate or silver fluoride alkanesulfonyl-fluorosulfonylimidate and an imonium compound represented by the following general formula (4) After reacting at a temperature of 30 to 150 ° C. in an organic solvent such as methyl-2-pyrrolidone, dimethylformamide (hereinafter abbreviated as “DMF”), acetonitrile and the like, the precipitated silver is separated by filtration, and then water, ethyl acetate or hexane Etc. and the resulting precipitate is filtered to obtain the diimonium salt compound of the present invention. That.
なお、本発明のジイモニウム塩化合物（１）において、基Ｒは、アルキル基、シアノアルキル基、アリール基、ヒドロキシル基、フェニル基、フェニルアルキレン基またはアルコキシ基から選ばれる置換基であり、これらは同一であっても、また異なっていてもよい。この基Ｒとしては、上記置換基であれば特に限定はされないが、炭素数１〜８の直鎖若しくは側鎖を有するアルキル基、シアノアルキル基、アルコキシ基等が好ましい。 In the diimonium salt compound (1) of the present invention, the group R is a substituent selected from an alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenyl group, a phenylalkylene group or an alkoxy group, and these are the same. Or may be different. Although it will not specifically limit as this group R if it is the said substituent, The C1-C8 linear or side chain alkyl group, cyanoalkyl group, alkoxy group, etc. are preferable.
より具体的に、一般式（１）中の基Ｒの例としては、例えばメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｉｓｏ−ペンチル基、ｔ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基等のアルキル基が挙げられる。このうち、近赤外線吸収能力、溶解性の点からは、エチル基、ｎ−プロピル基、ｎ−ブチル基が好ましく、また、色素の耐熱性特性の点より、ｉｓｏ−ブチル基、ｉｓｏ−ペンチル基が好ましい。 More specifically, examples of the group R in the general formula (1) include, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group. And alkyl groups such as t-butyl group, n-pentyl group, iso-pentyl group, t-pentyl group, n-hexyl group and n-octyl group. Of these, ethyl group, n-propyl group, and n-butyl group are preferable from the viewpoint of near-infrared absorption ability and solubility, and iso-butyl group and iso-pentyl group are preferable from the viewpoint of heat resistance characteristics of the dye. Is preferred.
また、ハロゲン化アルキル基としては、次の式（３）、
ＣnＸｍＨ（２ｎ＋１−ｍ） （３）
（式中、Ｘは同一または異なってハロゲン原子を示し、ｎは１〜８の正の整数を、ｍは１〜１７の正の整数を示す）
で表される基を挙げることができる。このハロゲン化アルキルのハロゲン原子は、フッ素、塩素、臭素、沃素であり、１種であっても、２種以上であってもよいが、安定性から、特にフッ素原子が好ましい。
As the halogenated alkyl group, the following formula (3),
C n X m H (2n + 1−m) (3)
(Wherein X is the same or different and represents a halogen atom, n represents a positive integer of 1 to 8, and m represents a positive integer of 1 to 17)
The group represented by these can be mentioned. The halogen atom of the alkyl halide is fluorine, chlorine, bromine or iodine, and may be one kind or two or more kinds, but a fluorine atom is particularly preferred from the viewpoint of stability.
このハロゲン化アルキル基の一例を挙げると、トリフルオロメチル基、２,２,２−トリフルオロエチル基、３,３,３,−トリフルオロプロピル基、４,４,４−トリフルオロブチル基、５,５,５−トリフルオロペンチル基、６,６,６−トリフルオロヘキシル基、８,８,８−トリフルオロオクチル基、２−メチル−３,３,３−トリフルオロプロピル基、ペルフルオロエチル基、ペルフルオロプロピル基、ペルフルオロブチル基、ペルフルオロヘキシル基、ペルフルオロオクチル基、２−トリフルオロ−ペルフルオロプロピル基等のフッ化アルキル基、トリクロロメチル基、２,２,２−トリクロロエチル基、３,３,３,−トリクロロプロピル基、４,４,４−トリクロロブチル基、５,５,５−トリクロロペンチル基、６,６,６−トリクロロヘキシル基、８,８,８−トリクロロオクチル基、２−メチル−３,３,３−トリクロロプロピル基、ペルクロロエチル基、ペルクロロプロピル基、ペルクロロブチル基、ペルクロロヘキシル基、ペルクロロオクチル基、２−トリクロロ−ペルクロロプロピル基等の塩化アルキル基、トリブロモメチル基、２,２,２−トリブロモエチル基、３,３,３,−トリブロモプロピル基、４,４,４−トリブロモブチル基、５,５,５−トリブロモペンチル基、６,６,６−トリブロモヘキシル基、８,８,８−トリブロモオクチル基、２−メチル−３,３,３−トリブロモプロピル基、パーブロモエチル基、ペルブロモプロピル基、ペルブロモブチル基、ペルブロモヘキシル基、ペルブロモオクチル基、２−トリブロモ−ペルブロモプロピル基等の臭化アルキル基等が挙げられる。 An example of this halogenated alkyl group is a trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 5,5,5-trifluoropentyl group, 6,6,6-trifluorohexyl group, 8,8,8-trifluorooctyl group, 2-methyl-3,3,3-trifluoropropyl group, perfluoroethyl Group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, fluorinated alkyl group such as 2-trifluoro-perfluoropropyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 3,3 , 3, -trichloropropyl group, 4,4,4-trichlorobutyl group, 5,5,5-trichloropentyl group, 6,6,6-trichlorohexyl group, 8,8,8- Trichlorooctyl group, 2-methyl-3,3,3-trichloropropyl group, perchloroethyl group, perchloropropyl group, perchlorobutyl group, perchlorohexyl group, perchlorooctyl group, 2-trichloro-perchloropropyl group Group such as alkyl chloride group, tribromomethyl group, 2,2,2-tribromoethyl group, 3,3,3-tribromopropyl group, 4,4,4-tribromobutyl group, 5,5, 5-tribromopentyl group, 6,6,6-tribromohexyl group, 8,8,8-tribromooctyl group, 2-methyl-3,3,3-tribromopropyl group, perbromoethyl group, per Examples thereof include alkyl bromide groups such as bromopropyl group, perbromobutyl group, perbromohexyl group, perbromooctyl group, and 2-tribromo-perbromopropyl group.
更に、シアノ置換アルキル基の具体例としては、例えばシアノメチル基、２−シアノエチル基、３−シアノプロピル基、２−シアノプロピル基、４−シアノブチル基、３−シアノブチル基、２−シアノブチル基、５−シアノペンチル基、４−シアノペンチル基、３−シアノペンチル基、２−シアノペンチル基、６−シアノヘキシル基、５−シアノヘキシル基、４−シアノヘキシル基、３−シアノヘキシル基、２−シアノヘキシル基等のシアノ置換（Ｃ１〜Ｃ８）アルキル基が挙げられ、アルキル部分の炭素数が２〜５のものが好ましい。更に好ましいものとしてはシアノプロピル基が挙げられる。 Furthermore, specific examples of the cyano-substituted alkyl group include, for example, a cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-cyanopropyl group, 4-cyanobutyl group, 3-cyanobutyl group, 2-cyanobutyl group, 5- Cyanopentyl group, 4-cyanopentyl group, 3-cyanopentyl group, 2-cyanopentyl group, 6-cyanohexyl group, 5-cyanohexyl group, 4-cyanohexyl group, 3-cyanohexyl group, 2-cyanohexyl And a cyano-substituted (C 1 -C 8 ) alkyl group such as a group, and an alkyl moiety having 2 to 5 carbon atoms is preferred. More preferred is a cyanopropyl group.
更にまた、アルコキシ基の具体例としては、例えば、メトキシメチル、２−メトキシエチル、３−メトキシプロピル、２−メトキシプロピル、４−メトキシブチル、３−メトキシブチル、２−メトキシブチル、５−メトキシペンチル、４−メトキシペンチル、３−メトキシペンチル、２−メトキシペンチル、６−メトキシヘキシル、エトキシメチル、２−エトキシエチル、３−エトキシプロピル、２−エトキシプロピル、４−エトキシブチル、３−エトキシブチル、５−エトキシペンチル、４−エトキシペンチル、６−エトキシヘキシル、プロポキシメチル、２−プロポキシエチル、３−プロポキシプロピル、４−プロポキシブチル、５−プロポキシペンチルなどの直鎖あるいは分岐状アルコキシアルキルである Furthermore, specific examples of the alkoxy group include, for example, methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 3-methoxybutyl, 2-methoxybutyl, 5-methoxypentyl. 4-methoxypentyl, 3-methoxypentyl, 2-methoxypentyl, 6-methoxyhexyl, ethoxymethyl, 2-ethoxyethyl, 3-ethoxypropyl, 2-ethoxypropyl, 4-ethoxybutyl, 3-ethoxybutyl, 5 -Linear or branched alkoxyalkyl such as ethoxypentyl, 4-ethoxypentyl, 6-ethoxyhexyl, propoxymethyl, 2-propoxyethyl, 3-propoxypropyl, 4-propoxybutyl, 5-propoxypentyl
また、Ｒの好ましい別の例として、一般式（２）で表されるフェニルアルキレン基を挙げることも出来る。
一般式（２）のフェニルアルキレン基において、アルキレン基の炭素数は、１〜８であることが特に好ましい。また、一般式（２）のフェニルアルキレン基におけるフェニル基は、アルキル基、水酸基、スルホン酸基、アルキルスルホン酸基、ニトロ基、アミノ基、アルコキシ基、ハロゲン化アルキル基またはハロゲンから選ばれる少なくとも１種の置換基を有していてもよいが、好ましいものとしては、置換基を有していないフェニル基を挙げることができる。 In the phenylalkylene group of the general formula (2), the alkylene group preferably has 1 to 8 carbon atoms. The phenyl group in the phenylalkylene group of the general formula (2) is at least one selected from an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, a halogenated alkyl group, or a halogen. Although it may have a substituent of a seed | species, as a preferable thing, the phenyl group which does not have a substituent can be mentioned.
かかるフェニルアルキレン基として具体的には、ベンジル基、フェネチル基、フェニルプロピレン基、フェニル−α−メチルプロピレン基、フェニル−β−メチルプロピレン基、フェニルブチレン基、フェニルペンチレン基、フェニルオクチレン基等が挙げられる。 Specific examples of the phenylalkylene group include benzyl group, phenethyl group, phenylpropylene group, phenyl-α-methylpropylene group, phenyl-β-methylpropylene group, phenylbutylene group, phenylpentylene group, and phenyloctylene group. Is mentioned.
上記一般式（２）で示されるフェニルアルキレン基を用いると、耐熱性の向上を図ることができ、最も好ましいものとして、ベンジル基及びフェネチル基を挙げることができる。 When the phenylalkylene group represented by the general formula (2) is used, the heat resistance can be improved, and most preferable examples include a benzyl group and a phenethyl group.
以上説明した、本発明の式（１）で表されるジイモニウム塩化合物においては、特に耐熱性・耐湿熱性、溶解性が高く、８５０ｎｍ付近の吸収も大きいことから、全ての置換基がハロゲン化アルキル基であることがより好ましい。 In the diimonium salt compound represented by the formula (1) of the present invention described above, since the heat resistance, the heat-and-moisture resistance and the solubility are particularly high and the absorption near 850 nm is large, all the substituents are alkyl halides. More preferably, it is a group.
このようにして得られた本発明のジイモニウム塩化合物は、近赤外線吸収色素として有用なものであるが、これを利用し、キャスト法や溶融押し出し法等の公知の方法により、近赤外線遮断フィルターを作製することができる。 The diimonium salt compound of the present invention thus obtained is useful as a near-infrared absorbing dye. By utilizing this, a near-infrared blocking filter is formed by a known method such as a casting method or a melt extrusion method. Can be produced.
このうちキャスト法は、本発明のジイモニウム塩化合物（近赤外線吸収色素）を、高分子樹脂及び溶剤を混合させた溶液中に、溶解または分散させた後、ポリエステルやポリカーボネート等の透明なフィルム、パネルまたはガラス基板上に該溶液を塗布、乾燥させてフィルム状に成膜させる方法である。 Among these, the cast method is a method in which the diimonium salt compound (near infrared absorbing dye) of the present invention is dissolved or dispersed in a solution in which a polymer resin and a solvent are mixed, and then a transparent film or panel such as polyester or polycarbonate. Alternatively, the solution is applied on a glass substrate and dried to form a film.
上記樹脂としては、透明な樹脂が用いられ、例えば、アクリル系樹脂、ポリエステル系樹脂、ポリカーボネート、ウレタン系樹脂、セルロース系樹脂、ポリイソシアナート、ポリアリレート、エポキシ系樹脂等があげられる。 As the resin, a transparent resin is used, and examples thereof include acrylic resins, polyester resins, polycarbonates, urethane resins, cellulose resins, polyisocyanates, polyarylate, and epoxy resins.
また、上記溶媒としては、樹脂を溶解することが可能であれば特に限定はされないが、例えば、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、テトラヒドロフラン、１,４−ジオキサン等の有機溶剤またはこれらを混合させた溶媒を用いることができる。 The solvent is not particularly limited as long as it can dissolve the resin, but for example, an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, 1,4-dioxane, or a mixture thereof. Can be used.
一方、溶融押し出し法は、本発明のジイモニウム塩化合物を高分子樹脂中に、溶融、混練させた後、押し出し成型によりパネル状に成型させるものである。 On the other hand, in the melt extrusion method, the diimonium salt compound of the present invention is melted and kneaded in a polymer resin and then molded into a panel by extrusion molding.
上記樹脂としては、透明な樹脂が用いられ、例えば、アクリル系樹脂、ポリエステル系樹脂、ポリカーボネート等が挙げられる。 A transparent resin is used as the resin, and examples thereof include acrylic resins, polyester resins, and polycarbonates.
本発明のジイモニウム塩化合物は、近赤外線吸収色素としてこれを単独で用いるか、あるいは、波長８５０ｎｍ付近の近赤外線遮断性能を補うため、フタロシアニン類やジチオール系金属錯体等の公知色素を添加させて用いることができる。また、耐光性を向上させるためにベンゾフェノン系やベンゾトリアゾール系等の紫外線吸収色素を添加させて用いてもよい。さらに、必要に応じて、可視光領域に吸収を持つ公知色素を添加させて、色調を調えてもよい。 The diimonium salt compound of the present invention is used alone as a near-infrared absorbing dye, or is used by adding a known dye such as phthalocyanines or dithiol-based metal complexes in order to supplement near-infrared blocking performance near a wavelength of 850 nm. be able to. Further, in order to improve light resistance, an ultraviolet absorbing dye such as benzophenone or benzotriazole may be added and used. Furthermore, if necessary, a known dye having absorption in the visible light region may be added to adjust the color tone.
本発明の近赤外線遮断フィルターの近赤外線透過率は、近赤外線吸収色素であるジイモニウム塩化合物の高分子樹脂に対する混合率を変えることで制御でき、該色素の高分子樹脂に対する混合率は０.０１〜３０％の範囲である。混合率が０.０１％未満の場合、近赤外線遮断能力が不十分であり、３０％以上の場合、可視光線透過率が低下し、不都合である。 The near-infrared transmittance of the near-infrared blocking filter of the present invention can be controlled by changing the mixing ratio of the diimonium salt compound, which is a near-infrared absorbing dye, to the polymer resin, and the mixing ratio of the dye to the polymer resin is 0.01. It is in the range of -30%. When the mixing ratio is less than 0.01%, the near infrared ray blocking ability is insufficient, and when it is 30% or more, the visible light transmittance is lowered, which is inconvenient.
本発明のジイモニウム塩化合物は、近赤外線吸収色素として、耐熱性、耐湿性に優れ、長期間にわたって近赤外線吸収能力が低下せず、また重金属を含有しないので環境に対する問題がない。 The diimonium salt compound of the present invention is excellent in heat resistance and moisture resistance as a near-infrared absorbing dye, does not deteriorate near-infrared absorbing ability over a long period of time, and does not contain a heavy metal, thereby causing no environmental problems.
また、本発明の近赤外線吸収色素を含有した本発明の近赤外線遮断フィルターは、種々の用途に用いることができ、例えばＰＤＰ用近赤外線遮断フィルター、自動車ガラス用ないし建材ガラス用近赤外線遮断フィルター等があげられ、特にＰＤＰ用近赤外線遮断フィルターとして好適である。 Moreover, the near-infrared blocking filter of the present invention containing the near-infrared absorbing dye of the present invention can be used for various applications, for example, a near-infrared blocking filter for PDP, a near-infrared blocking filter for automobile glass or building glass, etc. Especially, it is suitable as a near infrared ray blocking filter for PDP.
更に、本発明の近赤外線吸収色素は、従来の用途である、ＣＤ−Ｒ、ＤＶＤ−Ｒ等の光記録媒体用の色素またはクエンチャーとしても用いることができる。 Furthermore, the near-infrared absorbing dye of the present invention can also be used as a dye or quencher for optical recording media such as CD-R and DVD-R, which are conventional applications.
以下、発明の実施の形態を、実施例に基づき説明する。なお、本発明は、実施例により、なんら限定されない。実施例中、「部」は「質量部」を表す。 Hereinafter, embodiments of the invention will be described based on examples. In addition, this invention is not limited at all by the Example. In the examples, “part” represents “part by mass”.
実 施 例 １
（１）アセトニトリル２５０部に、ビス（フルオロスルホニル）イミド酸銀１０部及びＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジアミン１３.３部を加え、６０℃で２時間反応させ、生成した銀を濾別した。
Example 1
(1) 10 parts of silver bis (fluorosulfonyl) imidate and 13.3 parts of N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine are added to 250 parts of acetonitrile, The reaction was carried out at 2 ° C. for 2 hours, and the produced silver was filtered off.
ついで、該濾液に水２００部を添加し、生成した沈殿を濾過後、メタノール５０部で洗浄、洗浄後、６０℃減圧において乾燥を行ない、ビス［ビス（フルオロスルホニル）イミド酸］Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジイモニウム１６.７部を得た。このものは、近赤外線吸収色素として、最大吸収波長（以下、「λｍａｘ」と略記する。）が１０７４ｎｍ、モル吸光係数（以下、「ε」と略記する。）が１０５０００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は２０質量％以上であった。 Next, 200 parts of water was added to the filtrate, and the resulting precipitate was filtered, washed with 50 parts of methanol, washed and dried at 60 ° C. under reduced pressure to give bis [bis (fluorosulfonyl) imidic acid] N, N, 16.7 parts of N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium were obtained. As a near-infrared absorbing dye, this has a maximum absorption wavelength (hereinafter abbreviated as “λmax”) of 1074 nm, a molar extinction coefficient (hereinafter abbreviated as “ε”) of 105000, and methyl ethyl ketone and toluene. The solubility in the 1: 1 mass mixed solvent was 20 mass% or more.
（２）ついで、アクリルラッカー系樹脂（綜研化学(株)登録商標サーモラックＬＰ−４５Ｍ）６０部に、メチルエチルケトン２５部及びトルエン１３部を加えた溶液中に、該色素
２部を溶解させた。この溶液を隙間寸法４６μｍのバーコーターを使用して、市販のポリメタクリル樹脂フィルム（厚み１２５μｍ）上に塗布した。
(2) Next, 2 parts of the dye was dissolved in a solution obtained by adding 25 parts of methyl ethyl ketone and 13 parts of toluene to 60 parts of an acrylic lacquer resin (Soken Chemical Co., Ltd., Thermolac LP-45M). This solution was applied onto a commercially available polymethacrylic resin film (thickness 125 μm) using a bar coater having a gap size of 46 μm.
更に、これを温度１２０℃で３分間乾燥させて、本発明の近赤外線遮断フィルターを得、該フィルターの光線透過率を測定した。この測定結果を図１に示す。 Furthermore, this was dried at a temperature of 120 ° C. for 3 minutes to obtain a near-infrared shielding filter of the present invention, and the light transmittance of the filter was measured. The measurement results are shown in FIG.
実 施 例 ２
実施例１のビス(フルオロスルホニル)イミド酸銀に代えて、トリフロロメタンスルホニル−フルオロスルホニルイミド酸銀を用いた以外は、実施例１と同様にしてビス(トリフロロメタンスルホニル−フルオロスルホニルイミド酸）Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジイモニウムの近赤外線吸収色素を得た。該色素はλｍａｘが１０７４ｎｍ、εが１０４０００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は２５質量％以上であった。以下、実施例１と同様にして近赤外線遮断フィルターを作製した。
Example 2
Bis (trifluoromethanesulfonyl-fluorosulfonylimide acid) was used in the same manner as in Example 1 except that instead of silver bis (fluorosulfonyl) imidate in Example 1, silver trifluoromethanesulfonyl-fluorosulfonylimide acid was used. ) N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium near-infrared absorbing dye was obtained. The dye had a λmax of 1074 nm and an ε of 104000, and the solubility in a 1: 1 mass mixed solvent of methyl ethyl ketone and toluene was 25% by mass or more. Thereafter, a near-infrared shielding filter was produced in the same manner as in Example 1.
実 施 例 ３
実施例１のＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジアミンをＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジイソブチルアミノフェニル）−ｐ−フェニレンジアミンに代えた以外は、実施例１と同様にして、ビス(トリフルオロメタンスルホニル)イミド酸Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジイモニウムの近赤外線吸収色素を得た。該色素はλｍａｘが１０７９ｎｍ、εが１０５０００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は２０質量％以上であった。以下、実施例１と同様にして近赤外線遮断フィルターを作製した。
Example 3
N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine of Example 1 was converted to N, N, N ′, N′-tetrakis (p-diisobutylaminophenyl) -p-phenylene. Near-infrared absorption of bis (trifluoromethanesulfonyl) imidic acid N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium, except that diamine was used A dye was obtained. The dye had a λmax of 1079 nm and an ε of 105000, and the solubility in a 1: 1 mass mixed solvent of methyl ethyl ketone and toluene was 20% by mass or more. Thereafter, a near-infrared shielding filter was produced in the same manner as in Example 1.
実 施 例 ４
実施例１のＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジアミンをＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジフェネチルアミノフェニル）−ｐ−フェニレンジアミンに代えた以外は、実施例１と同様にして、ビス(トリフルオロメタンスルホニル)イミド酸Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジイモニウムの近赤外線吸収色素を得た。該色素はλｍａｘが１０８０ｎｍ、εが１０４５００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は１５％以上であった。以下、実施例１と同様にして近赤外線遮断フィルターを作製した。
Example 4
N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine of Example 1 was converted to N, N, N ′, N′-tetrakis (p-diphenethylaminophenyl) -p- Near-infrared of bis (trifluoromethanesulfonyl) imidic acid N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium, except that it was replaced with phenylenediamine An absorbing dye was obtained. The dye had a λmax of 1080 nm and an ε of 104500, and the solubility in a 1: 1 mass mixed solvent of methyl ethyl ketone and toluene was 15% or more. Thereafter, a near-infrared shielding filter was produced in the same manner as in Example 1.
実 施 例 ５
実施例１の実施例１のＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジアミンをＮ,Ｎ,Ｎ',Ｎ'−テトラキス［ｐ−ジ（４,４,４−トリフルオロブチル）アミノフェニル］−ｐ−フェニレンジアミンに代えた以外は、実施例１と同様にして、ビス(トリフルオロメタンスルホニル)イミド酸Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス［ｐ−ジ（４,４,４−トリフルオロブチル）アミノフェニル］−ｐ−フェニレンジイモニウムの近赤外線吸収色素を得た。該色素はλｍａｘが１０４８ｎｍ、εが１０３６００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は２５％以上であった。以下、実施例１と同様にして近赤外線遮断フィルターを作製した。
Example 5
The N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine of Example 1 of Example 1 was replaced with N, N, N ′, N′-tetrakis [p-di (4, Bis (trifluoromethanesulfonyl) imidic acid N, N, N ′, N′-tetrakis [4] in the same manner as in Example 1 except that 4,4-trifluorobutyl) aminophenyl] -p-phenylenediamine was used. A near-infrared absorbing dye of p-di (4,4,4-trifluorobutyl) aminophenyl] -p-phenylenediimonium was obtained. The dye had a λmax of 1048 nm and an ε of 103600, and the solubility in a 1: 1 mass mixed solvent of methyl ethyl ketone and toluene was 25% or more. Thereafter, a near-infrared shielding filter was produced in the same manner as in Example 1.
実 施 例 ６
実施例１の実施例１のＮ,Ｎ,Ｎ',Ｎ'−テトラキス（ｐ−ジブチルアミノフェニル）−ｐ−フェニレンジアミンをＮ,Ｎ,Ｎ',Ｎ'−テトラキス［ｐ−ジ（２,２,２−トリフルオロエチル）アミノフェニル］−ｐ−フェニレンジアミンに代えて以外は、実施例１と同様にして、ビス(トリフルオロメタンスルホニル)イミド酸Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス［ｐ−ジ（２,２,２−トリフルオロエチル）アミノフェニル］−ｐ−フェニレンジイモニウムの近赤外線吸収色素を得た。該色素はλｍａｘが１０４５ｎｍ、εが１０２６００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は３０％以上であった。以下、実施例１と同様にして近赤外線遮断フィルターを作製した。
Example 6
The N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine of Example 1 of Example 1 was replaced with N, N, N ′, N′-tetrakis [p-di (2, 2,2-trifluoroethyl) aminophenyl] -p-phenylenediamine, except that bis (trifluoromethanesulfonyl) imidic acid N, N, N ′, N′-tetrakis [ A near-infrared absorbing dye of p-di (2,2,2-trifluoroethyl) aminophenyl] -p-phenylenediimonium was obtained. The dye had a λmax of 1045 nm and an ε of 102600, and the solubility in a 1: 1 mass mixed solvent of methyl ethyl ketone and toluene was 30% or more. Thereafter, a near-infrared shielding filter was produced in the same manner as in Example 1.
比 較 例
実施例１において、ビス(フルオロスルホニル)イミド酸銀に代えて６フッ化アンチモン酸銀を用いた以外は実施例１と同様にして、ビス（ヘキサフルオロアンチモン酸）Ｎ,Ｎ,Ｎ',Ｎ'−テトラキス［ｐ−ジ（ｎ−ブチル）アミノフェニル］−ｐ−フェニレンジイモニウムの近赤外線吸収色素を得た。該色素はλｍａｘが１０７４ｎｍ、εが１０１０００であり、メチルエチルケトンとトルエンの１：１質量混合溶媒への溶解度は５％であった。以下、実施例１と同様にして近赤外線遮断フィルターを作製した。
Comparative Example In the same manner as in Example 1 except that silver hexafluoroantimonate was used in place of silver bis (fluorosulfonyl) imidate in Example 1, bis (hexafluoroantimonic acid) N, N, N A near-infrared absorbing dye of ', N'-tetrakis [p-di (n-butyl) aminophenyl] -p-phenylenediimonium was obtained. The dye had a λmax of 1074 nm and an ε of 101000, and the solubility in a 1: 1 mass mixed solvent of methyl ethyl ketone and toluene was 5%. Thereafter, a near-infrared shielding filter was produced in the same manner as in Example 1.
試 験 例
実施例１ないし６および比較例で得られた近赤外線遮断フィルターを、温度１０５℃の雰囲気下で保存して耐熱性試験を行い、分光光度計において１１００ｎｍ付近の極大吸収波長における吸光度を測定した。初期の吸光度を１００％とし、所定時間経過後の吸光度の百分率を色素残存率として算出した。また、フィルターの変色の測定として、Ｄ65光源を使用し、１０度視野の透過色調の測定を行ない、初期透過色調ｘ、ｙに対する所定時間経過後のΔｘ及びΔｙの測定を行なった。これらの結果を表１に示す。
Test Example The near-infrared cut-off filters obtained in Examples 1 to 6 and the comparative example were stored in an atmosphere at a temperature of 105 ° C. to conduct a heat resistance test, and the spectrophotometer measured the absorbance at the maximum absorption wavelength near 1100 nm. It was measured. The initial absorbance was taken as 100%, and the percentage of absorbance after the lapse of a predetermined time was calculated as the dye residual rate. In addition, as a measure of the discoloration of the filter, a D65 light source was used to measure the transmission color tone of the 10 ° visual field, and Δx and Δy after a predetermined time with respect to the initial transmission color tone x and y were measured. These results are shown in Table 1.
また、温度８５℃、湿度８５％の雰囲気下に保存して耐湿熱性試験を行い、色素残存率及びフィルターに透過色調変化を測定した。これらの結果を表２に示す。 Further, the sample was stored in an atmosphere at a temperature of 85 ° C. and a humidity of 85%, and a heat and humidity resistance test was performed. These results are shown in Table 2.
表１に示すように、従来の近赤外線吸収色素（比較例）は、耐熱性、耐湿性が低く、時間の経過と共に分解し、波長１1００ｎｍ付近の近赤外線領域の吸光度が低下し、さらには分解により生成したアミニウム塩化合物の吸収が、可視光線領域に生じてしまい可視光透過率が低下し、黄色に呈色して色調を損なってしまった。これに対して、本発明の実施例１から６の近赤外線吸収色素を含有させた近赤外線遮断フィルターは、耐熱性、耐湿性が高く、近赤外線領域の吸収低下が少なく、色素の分解による可視光領域の呈色も発生し難い。さらに、透明樹脂の溶解に一般に使用される事が多い、メチルエチルケトン、トルエン混合溶媒などに溶解性が高い事から、従来の近赤外線吸収色素（比較例）等と比較して加工性に優れる特徴も有している。 As shown in Table 1, the conventional near-infrared absorbing dye (comparative example) has low heat resistance and moisture resistance, decomposes with time, decreases the absorbance in the near-infrared region near the wavelength of 100 nm, and further decomposes. The absorption of the aminium salt compound produced by the above method occurs in the visible light region, the visible light transmittance is lowered, and the color tone is deteriorated by yellowing. On the other hand, the near-infrared blocking filter containing the near-infrared absorbing dyes of Examples 1 to 6 of the present invention has high heat resistance and moisture resistance, little absorption decrease in the near-infrared region, and visible due to decomposition of the dyes. Coloring in the light region is unlikely to occur. In addition, it is commonly used for dissolving transparent resins, and is highly soluble in methyl ethyl ketone and toluene mixed solvents. Therefore, it also has excellent processability compared to conventional near-infrared absorbing dyes (comparative examples). Have.
Claims (12)
で表されるジイモニウム塩化合物。 The following general formula (1),
The diimonium salt compound represented by these.
で表されるフェニルアルキレン基である請求項１ないし請求項６のいずれかに記載のジイモニウム塩化合物。 R is the following formula (2),
The diimonium salt compound according to any one of claims 1 to 6, which is a phenylalkylene group represented by the formula:
ＣnＸｍＨ（２ｎ＋１−ｍ） （３）
（式中、Ｘは同一または異なってハロゲン原子を示し、ｎは１〜８の正の整数を、ｍは１〜１７の正の整数を示す）
で表されるハロゲン化アルキル基である請求項１ないし３のいずれかに記載のジイモニウム塩化合物。 R is the following formula (3),
C n X m H (2n + 1−m) (3)
(Wherein X is the same or different and represents a halogen atom, n represents a positive integer of 1 to 8, and m represents a positive integer of 1 to 17)
The diimonium salt compound according to any one of claims 1 to 3, which is a halogenated alkyl group represented by the formula:
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| US9575213B2 (en) | 2011-10-14 | 2017-02-21 | Jsr Corporation | Optical filter, and solid-state image pickup device and camera module using the optical filter |
| US9791596B2 (en) | 2011-10-14 | 2017-10-17 | Jsr Corporation | Optical filter, and solid-state image pickup device and camera module using the optical filter |
| US9791606B2 (en) | 2011-10-14 | 2017-10-17 | Jsr Corporation | Optical filter, and solid-state image pickup device and camera module using the optical filter |
| US9746595B2 (en) | 2012-06-25 | 2017-08-29 | Jsr Corporation | Solid-state image capture element optical filter and application thereof |
| US9606275B2 (en) | 2013-10-17 | 2017-03-28 | Jsr Corporation | Optical filter, solid-state image pickup device and camera module |
| US9966402B2 (en) | 2014-12-04 | 2018-05-08 | Jsr Corporation | Solid-state imaging device |
| US10473836B2 (en) | 2015-07-28 | 2019-11-12 | Jsr Corporation | Optical filter and ambient light sensor including optical filter |
| US11226442B2 (en) | 2015-07-28 | 2022-01-18 | Jsr Corporation | Optical filter and ambient light sensor including optical filter |
| US11163098B2 (en) | 2016-06-08 | 2021-11-02 | Jsr Corporation | Optical filter and optical sensor device |
| WO2018190560A1 (en) * | 2017-04-10 | 2018-10-18 | 주식회사 엘엠에스 | Optical article and optical filter including same |
| US10908081B2 (en) | 2017-04-10 | 2021-02-02 | Lms Co., Ltd | Optical article and optical filter including same |
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| Publication number | Publication date |
|---|---|
| JP2006298989A (en) | 2006-11-02 |
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