JP6858545B2 - Pigment - Google Patents
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- JP6858545B2 JP6858545B2 JP2016245663A JP2016245663A JP6858545B2 JP 6858545 B2 JP6858545 B2 JP 6858545B2 JP 2016245663 A JP2016245663 A JP 2016245663A JP 2016245663 A JP2016245663 A JP 2016245663A JP 6858545 B2 JP6858545 B2 JP 6858545B2
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- 239000000049 pigment Substances 0.000 title description 5
- 239000002904 solvent Substances 0.000 claims description 42
- 125000001931 aliphatic group Chemical group 0.000 claims description 39
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 29
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 claims description 4
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 56
- 239000000463 material Substances 0.000 description 45
- 238000004040 coloring Methods 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000000126 substance Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002798 polar solvent Substances 0.000 description 14
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- -1 aliphatic hydrocarbon radical Chemical class 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 11
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 11
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 7
- 239000001018 xanthene dye Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- FUCOMWZKWIEKRK-UHFFFAOYSA-N iodocyclohexane Chemical compound IC1CCCCC1 FUCOMWZKWIEKRK-UHFFFAOYSA-N 0.000 description 2
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003732 xanthenes Chemical class 0.000 description 2
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FWXAUDSWDBGCMN-DNQXCXABSA-N [(2r,3r)-3-diphenylphosphanylbutan-2-yl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P([C@H](C)[C@@H](C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-DNQXCXABSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000001634 microspectroscopy Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、色素に関するものである。 The present invention relates to dyes.
キサンテン化合物は、赤〜紫色領域の色相の色素として、各種塗料、水性インキ、油性インキ、インクジェット用インキ、カラーフィルター用など幅広い用途で使用されている。このようなキサンテン化合物の染料として例えば、アシッドレッド２８９やアシッドレッド５２が知られている。 Xanthene compounds are used as pigments in hues in the red to purple region in a wide range of applications such as various paints, water-based inks, oil-based inks, inkjet inks, and color filters. As dyes for such xanthene compounds, for example, Acid Red 289 and Acid Red 52 are known.
ここで、カラーフィルタは、一般的に、透明基板と、透明基板上に形成され、赤、緑、青の三原色の着色パターンからなる着色層と、各着色パターンを区画するように透明基板上に形成された遮光部とを有している。
カラーフィルタの着色層には、色材として顔料や染料を有する着色層形成用樹脂組成物が用いられる。顔料は染料と比較して、一般に、耐熱性や耐光性等、諸耐性に優れているが、製造されたカラーフィルタの輝度が不十分となる場合があった。
一方、色材として染料を用いる場合には、輝度の高いカラーフィルタを製造し得るが、各種耐性やコントラストが不十分となる問題があった。さらに、染料を溶解して用いた着色樹脂組成物は、乾燥工程で塗膜表面に異物が析出しやすいという問題や、耐熱性や耐光性が不十分であったり、染料の蛍光発光によってコントラストが低下するなど、カラーフィルタ用途として使用するには多くの問題があった。
Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.
For the colored layer of the color filter, a resin composition for forming a colored layer having a pigment or a dye as a coloring material is used. Pigments are generally superior in various resistances such as heat resistance and light resistance as compared with dyes, but the brightness of manufactured color filters may be insufficient.
On the other hand, when a dye is used as a coloring material, a color filter having high brightness can be produced, but there is a problem that various resistances and contrasts are insufficient. Further, the colored resin composition used by dissolving the dye has a problem that foreign matter is easily deposited on the surface of the coating film in the drying process, has insufficient heat resistance and light resistance, and has a contrast due to the fluorescence emission of the dye. There were many problems in using it as a color filter, such as deterioration.
近年では、カラーフィルタ用着色層形成用樹脂組成物において、染料を含む色材を組み合わせて用いることが行われている。本発明者らは、輝度及び耐光性に優れた着色層を形成可能なカラーフィルタ用着色樹脂組成物として、特許文献１において、キサンテンを基本骨格として有する特定の色材と、青色色材とを含む、カラーフィルタ用着色樹脂組成物を開示している。
また、特許文献２において、カチオン部位を有する色素構造と、特定の構造を含むアニオン部位とを有し、前記アニオン部位およびカチオン部位が共有結合を介して結合して同一分子内に存在する色素化合物を含む着色組成物が開示され、前記カチオン部位を有する色素構造としてキサンテン色素構造を有する色素化合物が開示されている。
In recent years, in a resin composition for forming a colored layer for a color filter, a color material containing a dye has been used in combination. The present inventors have described in Patent Document 1 a specific coloring material having xanthene as a basic skeleton and a blue coloring material as a coloring resin composition for a color filter capable of forming a coloring layer having excellent brightness and light resistance. Discloses a colored resin composition for a color filter, including the same.
Further, in Patent Document 2, a dye compound having a dye structure having a cation site and an anion site containing a specific structure, and the anion site and the cation site are bonded via a covalent bond and exist in the same molecule. A coloring composition containing the above is disclosed, and a dye compound having a xanthene dye structure is disclosed as a dye structure having the cation moiety.
しかしながら、従来のキサンテン色素である、アシッドレッド２８９やアシッドレッド５２、特許文献１や特許文献２に記載されている色素では、カラーフィルタ用途を始め各種塗料、各種インキ用途に用いるために、未だ、低極性溶媒への溶剤溶解性が不十分であったり、耐光性が不十分であった。
そのため、従来よりも更に、低極性溶媒への溶剤溶解性が向上し、耐光性が向上したキサンテン色素が求められている。
However, the conventional xanthene dyes Acid Red 289 and Acid Red 52, and the dyes described in Patent Document 1 and Patent Document 2 are still used for various paints and inks including color filter applications. The solvent solubility in a low-polarity solvent was insufficient, and the light resistance was insufficient.
Therefore, there is a demand for a xanthene dye having improved solvent solubility in a low-polarity solvent and improved light resistance as compared with the conventional case.
本発明は上記問題点に鑑みてなされたものであり、低極性溶媒への溶剤溶解性が向上し、耐光性が向上したキサンテン色素を提供することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a xanthene dye having improved solvent solubility in a low polar solvent and improved light resistance.
本発明に係る色素は、下記一般式（１）で表される色素である。 The dye according to the present invention is a dye represented by the following general formula (1).
本発明は、低極性溶媒への溶剤溶解性が向上し、耐光性が向上した色素を提供することができる。 The present invention can provide a dye having improved solvent solubility in a low polar solvent and improved light resistance.
本発明に係る色素は、下記一般式（１）で表される色素である。 The dye according to the present invention is a dye represented by the following general formula (1).
従来、カラーフィルタ用着色層にキサンテンを基本骨格として有するキサンテン色素を採用しようとする試みは、特許文献１及び２にも記載されるように行われていた。しかし、従来具体的に用いられていたキサンテン色素は低極性溶媒への溶剤溶解性が劣るものであり、着色層を形成した場合に、染料由来の凝集物である異物を発生し易いものだった。また、着色層の更なる耐光性向上が望まれていた。
一方、本発明に用いられる上記一般式（１）で表される色素は、キサンテンを基本骨格として有することの他、特定の−Ｌ１−Ｎ−−Ｌ２−Ｒ５というアニオン部を含む官能基を１つのみ有し、窒素原子と結合するＲ１〜Ｒ４のいずれも水素原子ではなく、Ｒ３及びＲ４が芳香族炭化水素基又は芳香族複素環基であって、Ｒ３及びＲ４の少なくとも１つの芳香族炭化水素基又は芳香族複素環基は脂肪族炭化水素基で置換されており、Ｒ３及びＲ４が互いに異なるという特徴を有する。このような特徴を有する本発明に係る色素は、従来のキサンテン色素に比べて、低極性溶媒への溶剤溶解性が向上し、耐光性が向上した色素である。
上記効果が得られる作用は、未解明の部分はあるが、以下のように考えられる。上記一般式（１）で表される色素は、１価のカチオン性のキサンテン骨格と、アニオン性の−Ｌ１−Ｎ−−Ｌ２−Ｒ５基１個とを有し、分子内塩のみを有するため、１分子内で電気的に安定化しやすい。一方で、アニオン性の−Ｌ１−Ｎ−−Ｌ２−Ｒ５基においては、Ｒ５において電気陰性度の高いハロゲンが結合していることにより、アニオン部位の電子がＲ５に吸引されやすく、アニオン性が弱まることで分子間でのイオン結合が弱くなっていると推定される。また、上記一般式（１）で表される色素は、窒素原子と結合するＲ１〜Ｒ４のいずれも水素原子ではなく、Ｒ３及びＲ４が芳香族炭化水素基又は芳香族複素環基であって、Ｒ３及びＲ４の少なくとも１つは脂肪族炭化水素基で置換されており、Ｒ３及びＲ４が互いに異なりキサンテン骨格に対して非対称構造であることから、結晶性が低く、且つ溶剤親和性が高くなっていると推定される。これらの相乗効果から、上記一般式（１）で表される色素は、従来に比べて低極性溶媒に対する溶剤溶解性が向上し、また、着色層とした場合に異物の発生が抑制されると推定される。
また、上記一般式（１）で表される色素は、キサンテン骨格に結合した窒素原子が直接水素原子と結合していないため、窒素原子から水素原子が脱離して当該色材が不安定化することはなく、窒素原子が、芳香族炭化水素基又は芳香族複素環基のような芳香族性の置換基を有するため、当該窒素原子が有する孤立電子対が、キサンテン骨格のみならず当該芳香族炭化水素基又は芳香族複素環基とも共鳴することにより、安定性が高い分子構造を有する。また、−Ｌ１−Ｎ−−Ｌ２−Ｒ５基によれば、アニオン性が弱まってキサンテン骨格の電子を吸引する力が弱まると考えられる。そのためキサンテン骨格に結合した窒素原子の電子状態の乱れが少なくなり、更に分子構造の安定性が高くなる。また、Ｒ３及びＲ４が互いに異なりキサンテン骨格に対して非対称構造であることから、結晶性が低下し、着色樹脂組成物中の成分との相溶性が向上して、組成物中にて光照射時の安定性が改善されると推定される。これらの安定性が向上した結果、耐光性が改善すると推定される。
Conventionally, attempts to adopt a xanthene dye having xanthene as a basic skeleton for a colored layer for a color filter have been made as described in Patent Documents 1 and 2. However, the xanthene dyes that have been specifically used in the past are inferior in solvent solubility in low polar solvents, and when a colored layer is formed, foreign substances that are agglomerates derived from the dye are likely to be generated. .. Further, it has been desired to further improve the light resistance of the colored layer.
On the other hand, the dye represented by the above general formula (1) used in the present invention has xanthene as a basic skeleton and is functionally containing a specific anion portion of −L 1 −N − −L 2 −R 5. None of R 1 to R 4 having only one group and bonded to a nitrogen atom is a hydrogen atom, and R 3 and R 4 are aromatic hydrocarbon groups or aromatic heterocyclic groups, and R 3 and at least one aromatic hydrocarbon or aromatic heterocyclic group of R 4 is substituted with an aliphatic hydrocarbon radical, having the feature that R 3 and R 4 are different from each other. The dye according to the present invention having such characteristics is a dye having improved solvent solubility in a low-polarity solvent and improved light resistance as compared with conventional xanthene dyes.
The action to obtain the above effect is considered as follows, although there are some unclear points. The dye represented by the above general formula (1) has a monovalent cationic xanthene skeleton and one anionic −L 1 −N − −L 2 −R 5 groups, and has only an intramolecular salt. Therefore, it is easy to be electrically stabilized in one molecule. On the other hand, anionic -L 1 -N - in -L 2 -R 5 group, by bonded high electronegativity halogen in R 5, easy electron anionic sites is attracted to R 5 It is presumed that the weakening of the anionic property weakens the ionic bond between the molecules. Further, in the dye represented by the above general formula (1), none of R 1 to R 4 bonded to the nitrogen atom is a hydrogen atom, and R 3 and R 4 are aromatic hydrocarbon groups or aromatic heterocyclic groups. a is at least one of R 3 and R 4 is substituted with an aliphatic hydrocarbon group, since R 3 and R 4 are asymmetrical structure with respect to different xanthene skeleton together, have low crystallinity, Moreover, it is presumed that the solvent affinity is high. Due to these synergistic effects, the dye represented by the above general formula (1) has improved solvent solubility in a low polar solvent as compared with the conventional one, and when it is used as a colored layer, the generation of foreign substances is suppressed. Presumed.
Further, in the dye represented by the above general formula (1), since the nitrogen atom bonded to the xanthene skeleton is not directly bonded to the hydrogen atom, the hydrogen atom is desorbed from the nitrogen atom and the coloring material becomes unstable. Since the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone electron pair of the nitrogen atom is not only the xanthene skeleton but also the aromatic. It has a highly stable molecular structure by resonating with a hydrocarbon group or an aromatic heterocyclic group. Further , according to the 5 groups of −L 1 − N − − L 2 −R, it is considered that the anionic property is weakened and the ability to attract electrons in the xanthene skeleton is weakened. Therefore, the disturbance of the electronic state of the nitrogen atom bonded to the xanthene skeleton is reduced, and the stability of the molecular structure is further improved. Further, since R 3 and R 4 are different from each other and have an asymmetric structure with respect to the xanthene skeleton, the crystallinity is lowered, the compatibility with the components in the colored resin composition is improved, and light is emitted in the composition. It is presumed that the stability during irradiation will be improved. As a result of these improvements in stability, it is presumed that the light resistance will improve.
また、上記一般式（１）で表される色素は、アニオン性の−Ｌ１−Ｎ−−Ｌ２−Ｒ５基においては、Ｒ５において電気陰性度の高いハロゲンが結合していることにより、長波長側の吸収が強くなり、赤味が少なくなる。そのため色度座標においてxの小さい黄味の領域で輝度を向上させやすい。
更に、上記一般式（１）で表される色素は、Ｒ３及びＲ４の少なくとも１つの芳香族炭化水素基又は芳香族複素環基が脂肪族炭化水素基で置換されており、Ｒ３及びＲ４が互いに異なるため、色素同士が凝集し難く、かつ溶剤溶解性が高いことから異物も発生し難いため、着色層の透過光量を減衰させることもない。
また、上記一般式（１）で表される色素は、Ｒ３及びＲ４が互いに異なり、分子設計の幅が広いことから、分光特性等の調整幅も広いため、当該色素を目標色度に近づけ、さらに輝度を向上することが容易である。
上記一般式（１）で表される色素は、前述のように安定性が高い分子構造を有することからカラーフィルタ製造工程のベイク後の輝度低下が抑制されること、カラーフィルタ製造工程において色素の凝集や異物の発生が抑制されること、所望の色度に合わせて構造を設計して分光特性等を調整できることにより、着色層の輝度も向上することができると推定される。
これらのことから、色材として上記一般式（１）で表される色素を含むことにより、異物の発生が抑制され、輝度が向上した着色層を形成することができる。
Further, dyes represented by the general formula (1), the anionic -L 1 -N - in -L 2 -R 5 group, by halogen high electronegativity is attached at R 5 , The absorption on the long wavelength side becomes stronger and the redness becomes less. Therefore, it is easy to improve the brightness in the yellowish region where x is small in the chromaticity coordinates.
Further, in the dye represented by the above general formula (1), at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 3 and R 4 is replaced with an aliphatic hydrocarbon group, and R 3 and Since R 4 is different from each other, the dyes are less likely to aggregate with each other, and foreign matter is less likely to be generated because the dyes are highly soluble in the solvent, so that the amount of transmitted light in the colored layer is not attenuated.
Further, since R 3 and R 4 of the dye represented by the above general formula (1) are different from each other and the range of molecular design is wide, the range of adjustment of spectral characteristics and the like is also wide, so that the dye is set as the target chromaticity. It is easy to bring them closer and further improve the brightness.
Since the dye represented by the above general formula (1) has a highly stable molecular structure as described above, the decrease in brightness after baking in the color filter manufacturing process is suppressed, and the dye in the color filter manufacturing process It is presumed that the brightness of the colored layer can be improved by suppressing aggregation and generation of foreign matter, and by designing the structure according to the desired chromaticity and adjusting the spectral characteristics and the like.
From these facts, by including the dye represented by the above general formula (1) as the coloring material, it is possible to suppress the generation of foreign substances and form a colored layer having improved brightness.
前記一般式（１）で表される色素について、詳細に説明する。
前記一般式（１）において、Ｒ１及びＲ２における脂肪族炭化水素基とは、直鎖状、分岐状、環状のいずれであってもよく、特に限定されないが、例えば、炭素数１以上２０以下の直鎖又は分岐状脂肪族炭化水素基、或いは、炭素数５以上８以下の環状脂肪族炭化水素基（脂環式炭化水素基）等が挙げられ、炭素数が１０以下であることが、耐光性の点から好ましい。脂肪族炭化水素基としては、飽和脂肪族炭化水素基である、直鎖状、分岐状、環状のアルキル基が好ましい。
当該脂肪族炭化水素基が有してもよい置換基としては、特に限定されないが、例えば、ハロゲン原子、芳香族炭化水素基、カルバモイル基、−ＣＯ−Ｏ−Ｒａで示される一価の基、−Ｏ−ＣＯ−Ｒａ’で示される一価の基、−ＳＯ２−Ｒａ”で示される一価の基、−Ｒｂ−ＣＯ−Ｏ−Ｒｃで示される一価の基、−Ｒｂ’−Ｏ−ＣＯ−Ｒｃ’で示される一価の基、及び−Ｒｂ”−ＳＯ２−Ｒｃ”で示される一価の基等が挙げられる。
Ｒ１〜Ｒ４における芳香族炭化水素基とは、特に限定されないが、例えば、置換基を有していてもよい炭素数６以上２０以下の芳香族炭化水素基が挙げられ、中でも、フェニル基、ナフチル基等を有する基が好ましい。
Ｒ３及びＲ４における芳香族複素環基とは、特に限定されないが、置換基を有していてもよい炭素数５以上２０以下の芳香族複素環基が挙げられ、ヘテロ原子として、例えば、窒素原子、酸素原子、硫黄原子を含むものが好ましい。また、芳香族複素環基として具体的には例えば、フラン、チオフェン、ピロール、ピリジン等が挙げられる。
芳香族炭化水素基又は芳香族複素環基が有してもよい置換基としては、特に限定されないが、例えば、脂肪族炭化水素基、ハロゲン原子、アルコキシ基、水酸基、カルバモイル基、−ＣＯ−Ｏ−Ｒａで示される一価の基、−Ｏ−ＣＯ−Ｒａ’で示される一価の基、−ＳＯ２−Ｒａ”で示される一価の基、−Ｒｂ−ＣＯ−Ｏ−Ｒｃで示される一価の基、−Ｒｂ’−Ｏ−ＣＯ−Ｒｃ’で示される一価の基、−Ｒｂ”−ＳＯ２−Ｒｃ”で示される一価の基等が挙げられる。前記Ｒａ、Ｒａ’、Ｒａ”、Ｒｂ、Ｒｂ’、Ｒｂ”、Ｒｃ、Ｒｃ’及びＲｃ”は、脂肪族炭化水素基を示す。これらの置換基は、耐熱性等に悪影響を及ぼさない点から好適に用いられる。これらの置換基による電子吸引性及び電子供与性を調整することにより、分光特性の調整をすることが可能である。また、ここでの脂肪族炭化水素基は、Ｒ１及びＲ２における脂肪族炭化水素基と同様であって良い。
The dye represented by the general formula (1) will be described in detail.
In the general formula (1), the aliphatic hydrocarbon group in R 1 and R 2 may be linear, branched, or cyclic, and is not particularly limited, but for example, it has 1 or more carbon atoms and 20 carbon atoms. Examples thereof include the following linear or branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups having 5 or more and 8 or less carbon atoms (alicyclic hydrocarbon groups), and the like, and the number of carbon atoms is 10 or less. , Preferred from the viewpoint of light resistance. As the aliphatic hydrocarbon group, a linear, branched, or cyclic alkyl group, which is a saturated aliphatic hydrocarbon group, is preferable.
The substituent that the aliphatic hydrocarbon group may have is not particularly limited, but is, for example, a halogen atom, an aromatic hydrocarbon group, a carbamoyl group, or a monovalent group represented by −CO—O—R a. , A monovalent group represented by -O-CO-R a' , a monovalent group represented by -SO 2- R a" , a monovalent group represented by -R b- CO-O-R c , -R b '-O-CO-R c' monovalent group represented by, and -R b monovalent group represented by "-SO 2 -R c" and the like.
The aromatic hydrocarbon groups in R 1 to R 4 are not particularly limited, and examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent, and among them, a phenyl group. , A group having a naphthyl group or the like is preferable.
The aromatic heterocyclic group in R 3 and R 4 is not particularly limited, and examples thereof include an aromatic heterocyclic group having 5 to 20 carbon atoms which may have a substituent, and examples of the hetero atom include, for example, an aromatic heterocyclic group. Those containing a nitrogen atom, an oxygen atom, and a sulfur atom are preferable. Specific examples of the aromatic heterocyclic group include furan, thiophene, pyrrole, and pyridine.
The substituent which the aromatic hydrocarbon group or the aromatic heterocyclic group may have is not particularly limited, but for example, an aliphatic hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, a carbamoyl group, -CO-O. A monovalent group represented by -R a , a monovalent group represented by -O-CO-R a' , a monovalent group represented by -SO 2- R a" , -R b- CO-O- monovalent groups represented by R c, monovalent group represented by -R b '-O-CO-R c', monovalent group is represented by -R b "-SO 2 -R c" R a , R a' , R a " , R b , R b' , R b" , R c , R c'and R c " indicate an aliphatic hydrocarbon group. These substituents are preferably used because they do not adversely affect heat resistance and the like. It is possible to adjust the spectral characteristics by adjusting the electron attracting property and the electron donating property of these substituents. Further, the aliphatic hydrocarbon group here may be the same as the aliphatic hydrocarbon group in R 1 and R 2 .
Ｒ１及びＲ２の少なくとも１つは、脂肪族炭化水素基であることが好ましく、低極性溶媒への溶剤溶解性が向上する点から、Ｒ１及びＲ２が脂肪族炭化水素基であることが好ましく、中でも直鎖脂肪族炭化水素基であることが好ましく、中でも直鎖アルキル基であることが好ましい。前記脂肪族炭化水素基としては、炭素数１以上１０以下であることが好ましく、更に炭素数１以上６以下の直鎖アルキル基であることが、異物の発生が抑制され、輝度が向上した着色層を形成可能な点から好ましい。
Ｒ３及びＲ４の少なくとも１つは、芳香族炭化水素基であることが好ましく、Ｒ３及びＲ４が芳香族炭化水素基であることが好ましい。当該芳香族炭化水素基としては、炭素数６以上１０以下の芳香族炭化水素基であることが好ましく、更にフェニル基であることが、耐光性の点、及び、異物の発生が抑制され、輝度が向上した着色層を形成可能な点から好ましい。
また、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基であるＲ３及びＲ４の少なくとも１つは脂肪族炭化水素基で置換されており、Ｒ３及びＲ４が互いに異なるものである。
当該芳香族炭化水素基又は芳香族複素環基の水素原子と置換されている脂肪族炭化水素基としては、中でも直鎖脂肪族炭化水素基であることが好ましい。当該脂肪族炭化水素基としては、炭素数１以上１０以下であることが好ましく、更に炭素数１以上６以下の直鎖アルキル基であることが好ましい。また、Ｒ３及びＲ４の両方共が、前記のような脂肪族炭化水素基で置換されていることが好ましい。
また、Ｒ３及びＲ４の少なくとも１つの芳香族炭化水素基又は芳香族複素環基は、１つの芳香族炭化水素基又は芳香族複素環基当たり、２つ以上の脂肪族炭化水素基で置換されていることが、低極性溶媒への溶剤溶解性が向上する点、異物の発生が抑制され、輝度が向上した着色層を形成可能な点から好ましい。
また、Ｒ１、Ｒ２、Ｒ３及びＲ４に含まれる脂肪族炭化水素基のいずれか１つが、炭素数２以上、更に炭素数３以上の直鎖アルキル基である場合には、分子中の電子密度を調整し易い傾向がある。
Ｒ１及びＲ２の少なくとも１つが直鎖肪族炭化水素基で置換されている場合であって、Ｒ３及びＲ４の少なくとも１つの芳香族炭化水素基又は芳香族複素環基が、炭素数２以上の直鎖アルキル基で置換されている場合には、低極性溶媒への溶剤溶解性が向上し、異物の発生が抑制され易く、輝度が向上した着色層が形成され易い傾向がある。
At least one of R 1 and R 2 is preferably an aliphatic hydrocarbon group, and R 1 and R 2 are aliphatic hydrocarbon groups from the viewpoint of improving the solvent solubility in a low polar solvent. Is preferable, and a linear aliphatic hydrocarbon group is preferable, and a linear alkyl group is particularly preferable. The aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, and further, a linear alkyl group having 1 or more and 6 or less carbon atoms suppresses the generation of foreign substances and improves the brightness. It is preferable because a layer can be formed.
At least one of R 3 and R 4 is preferably an aromatic hydrocarbon group, and R 3 and R 4 are preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 or more and 10 or less carbon atoms, and further, a phenyl group is used in terms of light resistance and the generation of foreign substances is suppressed, and the brightness is increased. It is preferable because it is possible to form a colored layer having an improved content.
Further, at least one of R 3 and R 4 , which are aromatic hydrocarbon groups or aromatic heterocyclic groups which may have a substituent, is substituted with an aliphatic hydrocarbon group, and R 3 and R 4 are substituted. Are different from each other.
The aliphatic hydrocarbon group substituted with the hydrogen atom of the aromatic hydrocarbon group or the aromatic heterocyclic group is preferably a linear aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, and more preferably a linear alkyl group having 1 or more and 6 or less carbon atoms. Further, it is preferable that both R 3 and R 4 are substituted with the above-mentioned aliphatic hydrocarbon group.
Further, at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 3 and R 4 is replaced with two or more aliphatic hydrocarbon groups per aromatic hydrocarbon group or aromatic heterocyclic group. This is preferable because the solubility in a low-polarity solvent is improved, the generation of foreign substances is suppressed, and a colored layer having improved brightness can be formed.
When any one of the aliphatic hydrocarbon groups contained in R 1 , R 2 , R 3 and R 4 is a linear alkyl group having 2 or more carbon atoms and further 3 or more carbon atoms, it is contained in the molecule. It tends to be easy to adjust the electron density of.
When at least one of R 1 and R 2 is substituted with a linear aliphatic hydrocarbon group, at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 3 and R 4 has a carbon number of carbon atoms. When it is substituted with two or more linear alkyl groups, the solvent solubility in a low polar solvent is improved, the generation of foreign substances is easily suppressed, and a colored layer with improved brightness tends to be easily formed.
また、Ｒ１〜Ｒ４における脂肪族炭化水素基は、無置換であるか、分岐状又は直鎖状のアルキル基の場合は置換基が芳香族炭化水素基であることが好ましく、芳香族炭化水素基又は芳香族複素環基の置換基は、脂肪族炭化水素基であることが好ましい。このような場合、前記一般式（１）で表される色素は極性が低下するため、ＰＧＭＥＡ等の低極性溶媒に対する親和性が向上するからである。また、前記色材を溶剤に溶解させる場合においてもより低極性溶媒を用いることができ、低極性溶媒を用いる着色組成物の安定性が向上する。中でも、低極性溶媒に対する親和性が向上する点からは、芳香族炭化水素基又は芳香族複素環基の置換基としては、脂肪族炭化水素基のみを有することが好ましい。 Further, the aliphatic hydrocarbon group in R 1 to R 4 is preferably unsubstituted, or in the case of a branched or linear alkyl group, the substituent is preferably an aromatic hydrocarbon group, and aromatic carbide is used. The substituent of the hydrogen group or the aromatic heterocyclic group is preferably an aliphatic hydrocarbon group. In such a case, the dye represented by the general formula (1) has a reduced polarity, so that the affinity for a low-polarity solvent such as PGMEA is improved. Further, even when the coloring material is dissolved in a solvent, a lower polar solvent can be used, and the stability of the coloring composition using the low polar solvent is improved. Above all, it is preferable to have only an aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group or the aromatic heterocyclic group from the viewpoint of improving the affinity for the low polar solvent.
−Ｌ１−Ｎ−−Ｌ２−Ｒ５基における、Ｌ１及びＬ２は各々独立に、直接結合、―ＳＯ２―、又は―ＣＯ―であるが、中でも、―ＳＯ２―、又は―ＣＯ―であることが好ましく、更に、―ＳＯ２―であることが、低極性溶媒への溶剤溶解性が向上し、耐光性、耐熱性が向上する点から好ましい。 -L 1 -N - in -L 2 -R 5 group, L 1 and L 2 are each independently a direct bond, -SO 2 -, or -CO- a but, among them, -SO 2 -, or - It is preferably CO-, and more preferably -SO 2- because the solvent solubility in a low polar solvent is improved and the light resistance and heat resistance are improved.
−Ｌ１−Ｎ−−Ｌ２−Ｒ５基における、Ｒ５はハロゲン化脂肪族炭化水素基であるが、当該ハロゲンとしては、フッ素原子、塩素原子、ヨウ素原子等が挙げられ、中でもフッ素原子であることが好ましい。Ｒ５のハロゲン化脂肪族炭化水素基としては、炭素数が１以上８以下の直鎖又は分岐のハロゲン化脂肪族炭化水素基であることが好ましく、炭素数が１以上５以下の直鎖又は分岐のハロゲン化脂肪族炭化水素基であることがより好ましく、炭素数が１以上３以下の直鎖又は分岐のハロゲン化脂肪族炭化水素基であることがより更に好ましい。中でも脂肪族炭化水素基におけるハロゲン原子の置換率（ハロゲン原子数／脂肪族炭化水素基の水素原子の合計数）は、５０％以上であることが好ましく、更に７０％以上であることが好ましく、中でも１００％であることが好ましい。
Ｒ５としては、中でも炭素数が１以上５以下の直鎖又は分岐のパーフルオロアルキル基であることが好ましい。
In the −L 1 −N − −L 2 −R 5 groups, R 5 is a halogenated aliphatic hydrocarbon group, and examples of the halogen include a fluorine atom, a chlorine atom, an iodine atom and the like, and among them, a fluorine atom. Is preferable. The halogenated aliphatic hydrocarbon group of R 5 is preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 8 carbon atoms, and a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 5 carbon atoms. It is more preferably a branched halogenated aliphatic hydrocarbon group, and even more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. Among them, the substitution rate of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms / total number of hydrogen atoms of the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more. Above all, it is preferably 100%.
The R 5, among them it is preferable carbon number of 1 to 5 linear or branched perfluoroalkyl group.
また、前記一般式（１）において、キサンテン骨格に結合したベンゼン環が有する−Ｌ１−Ｎ−−Ｌ２−Ｒ５基の置換位置は、特に限定されないが、キサンテン骨格に対して、オルト位又はパラ位であることが好ましく、−Ｌ１−Ｎ−−Ｌ２−Ｒ５基がキサンテン骨格に対してオルト位に置換されていることが、前記一般式（１）で表される色素の耐光性及び各種耐性の点から好ましい。その作用機構は明らかではないが、−Ｌ１−Ｎ−−Ｌ２−Ｒ５基がオルト位にあると、ベンゼン環が結合しているキサンテン骨格の炭素原子と共鳴して環構造を形成でき、分子の安定性が高くなり、そのために色材の各種耐性が向上すると推定される。 Further, in the general formula (1), the substitution position of 5 groups of −L 1 −N − −L 2 −R of the benzene ring bonded to the xanthene skeleton is not particularly limited, but the ortho position with respect to the xanthene skeleton. Alternatively, it is preferably in the para position, and the fact that 5 groups of −L 1 −N − −L 2 −R are substituted in the ortho position with respect to the xanthene skeleton is the dye represented by the general formula (1). It is preferable from the viewpoint of light resistance and various resistances. The mechanism of action is not clear, but when the -L 1- N - L 2- R 5 groups are in the ortho position, they can resonate with the carbon atoms of the xanthene skeleton to which the benzene ring is bonded to form a ring structure. It is presumed that the stability of the molecule is increased, and therefore the resistance of various coloring materials is improved.
前記一般式（１）で表される色素の製造方法は、特に限定されないが、具体的には例えば下記の方法が挙げられる。
スルホフルオラン化合物とＲ３及びＲ４に対応するアミン化合物を溶媒中６０℃で還流させ、この反応液を６０℃でろ過して不溶解分を除いた後、溶媒の一部を除き、６％塩酸に注ぐ。次いで、大量の水を加えて室温で３０分間攪拌した後、ウェットケーキをろ取する。このウェットケーキを水やお湯で洗浄後、乾燥させることにより上記一般式（１）で表される色素の中間体が得られる。なお、本発明においては、Ｒ３及びＲ４の一部の構造が異なり、キサンテン環に対して非対称である一般式（１）の色素を製造するため、対応する半分のアミン化合物を、大希釈のスルホフルオラン化合物メタノール溶液に、少量ずつ滴下し、反応後、残る一方のアミン化合物を滴下したり、各アミン化合物の１：１溶液をスルホフルオラン化合物メタノール溶液にゆっくり滴下したりすることにより、高収率で非対称の一般式（１）で表される色素の中間体を得ることができる。
なお、スルホフルオラン化合物とＲ３及びＲ４に対応するアミン化合物との反応温度は、６０℃以上１４０℃以下が好ましく、６０℃以上１００℃以下が好ましい。
次いで一般式（１）で表される色素の中間体を、１−メチル−２−ピロリジノン等の極性溶媒中炭酸カリウム等の塩基存在下で、Ｒ１及びＲ２に対応するハロゲン化物と、８０℃で２時間、撹拌して反応させる。反応終了後、反応溶液を室温まで放冷した後、反応溶液を０〜１０℃の１７．５％塩酸に滴下して１時間、撹拌をする。その後、析出物をろ取して、残渣を６０℃で２４時間、乾燥することにより、一般式（１）で表される色素の前駆体を得る。
なお、一般式（１）で表される色素の中間体とＲ１及びＲ２に対応するハロゲン化物との反応温度は、６０℃以上１００℃以下が好ましく、６０℃以上８０℃以下が好ましい。
次いで、非対称の一般式（１）で表される色素の前駆体に、トリフルオロメチルスルホンアミドをクロロホルムに溶解させ、トリエチルアミンを滴下し、反応させる。その後、得られた反応溶液を水洗し、次いで有機層を分取する。この有機層を硫酸ナトリウムにて乾燥させ、カラムクロマトグラフィーにて精製し、減圧濃縮することにより、上記一般式（１）で表される色素を得ることができる。
また、Ｌ１が−ＣＯ−で表される場合は、スルホフルオラン化合物の代わりにフルオラン化合物を用い、以降同様にして上記一般式（１）で表される色素を得ることができる。
The method for producing the dye represented by the general formula (1) is not particularly limited, and specific examples thereof include the following methods.
The sulfofluorane compound and the amine compounds corresponding to R 3 and R 4 were refluxed in a solvent at 60 ° C., and the reaction solution was filtered at 60 ° C. to remove insoluble matter, and then a part of the solvent was removed. Pour into% hydrochloric acid. Then, a large amount of water is added and the mixture is stirred at room temperature for 30 minutes, and then the wet cake is collected by filtration. By washing this wet cake with water or hot water and then drying it, an intermediate of the pigment represented by the above general formula (1) can be obtained. In the present invention, in order to produce a dye of the general formula (1) in which some structures of R 3 and R 4 are different and asymmetric with respect to the xanthene ring, the corresponding half of the amine compound is drastically diluted. By dropping little by little into the sulfofluorane compound methanol solution of the above, and after the reaction, the remaining amine compound is added dropwise, or a 1: 1 solution of each amine compound is slowly added dropwise to the sulfofluorane compound methanol solution. , A high-yield, asymmetric dye intermediate represented by the general formula (1) can be obtained.
The reaction temperature of the sulfofluorane compound and the amine compound corresponding to R 3 and R 4 is preferably 60 ° C. or higher and 140 ° C. or lower, and preferably 60 ° C. or higher and 100 ° C. or lower.
Next, the intermediate of the dye represented by the general formula (1) was mixed with a halide corresponding to R 1 and R 2 in the presence of a base such as potassium carbonate in a polar solvent such as 1-methyl-2-pyrrolidinone, and 80. Stir and react at ° C. for 2 hours. After completion of the reaction, the reaction solution is allowed to cool to room temperature, and then the reaction solution is added dropwise to 17.5% hydrochloric acid at 0 to 10 ° C. and stirred for 1 hour. Then, the precipitate is collected by filtration and the residue is dried at 60 ° C. for 24 hours to obtain a precursor of the dye represented by the general formula (1).
The reaction temperature between the intermediate of the dye represented by the general formula (1) and the halide corresponding to R 1 and R 2 is preferably 60 ° C. or higher and 100 ° C. or lower, and preferably 60 ° C. or higher and 80 ° C. or lower.
Next, trifluoromethylsulfonamide is dissolved in chloroform in the precursor of the dye represented by the asymmetric general formula (1), and triethylamine is added dropwise to cause a reaction. Then, the obtained reaction solution is washed with water, and then the organic layer is separated. The organic layer is dried over sodium sulfate, purified by column chromatography, and concentrated under reduced pressure to obtain a dye represented by the above general formula (1).
When L1 is represented by −CO−, a fluorane compound is used instead of the sulfofluorane compound, and a dye represented by the above general formula (1) can be obtained in the same manner thereafter.
本発明の前記一般式（１）で表される色素は、低極性溶媒に対しても溶剤溶解性が高いので、アルコール性水酸基を有する溶剤を用いなくても、着色層用途に必要な濃度での溶剤溶解性を有する。本発明で用いられる前記一般式（１）で表される色素は、プロピレングリコールモノメチルエーテルアセテート、３−メトキシ−３−メチル−１−ブチルアセテート、及びジエチレングリコールエチルメチルエーテルの少なくとも１つに対して、２３℃における前記一般式（１）で表される色素の溶解度が２．０（ｇ／１００ｇ溶剤）以上であることが好ましく、２．５（ｇ／１００ｇ溶剤）以上であることがより好ましい。 Since the dye represented by the general formula (1) of the present invention has high solvent solubility even in a low polar solvent, the concentration required for the colored layer application can be obtained without using a solvent having an alcoholic hydroxyl group. Has solvent solubility. The dye represented by the general formula (1) used in the present invention is based on at least one of propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, and diethylene glycol ethyl methyl ether. The solubility of the dye represented by the general formula (1) at 23 ° C. is preferably 2.0 (g / 100 g solvent) or more, and more preferably 2.5 (g / 100 g solvent) or more.
本発明の前記一般式（１）で表される色素は、低極性溶媒に対しても溶剤溶解性が向上し、耐光性が向上したものであるため、着色組成物として、例えば、各種塗料、油性インキ、インクジェット用インキ等の印刷用インキ、感熱記録材料におけるインクシート、電子写真用のカラートナー、各種繊維用の染色のための染色液や樹脂着色のためなどの各種着色組成物、カラーフィルター用着色組成物等に好適に用いられる。
また、本発明の前記一般式（１）で表される色素は、太陽電池の色素増感用色素として用いても良い。更に、蛍光色素として、各種マーカーとして用いても良い。
The dye represented by the general formula (1) of the present invention has improved solvent solubility even in a low polar solvent and improved light resistance. Therefore, as a coloring composition, for example, various paints, etc. Printing inks such as oil-based inks and inkjet inks, ink sheets for heat-sensitive recording materials, color toners for electrophotographic, dyeing solutions for dyeing various fibers, various coloring compositions for resin coloring, color filters, etc. It is preferably used for coloring compositions for use.
Further, the dye represented by the general formula (1) of the present invention may be used as a dye for dye sensitization of a solar cell. Further, it may be used as a fluorescent dye and as various markers.
以下、本発明について実施例を示して具体的に説明する。これらの記載により本発明を制限するものではない。 Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
（実施例１：色材Ａの合成）
以下の手順により、下記構造式で表される中間体Ｉ−１を合成した。
５００ｍｌの４つ口フラスコに、下記化学式（３）のスルホフルオラン化合物１８．０質量部、メタノール３１２質量部、２，６−キシリジン ５．４質量部及びｏ−トルイジン ４．８質量部を仕込み、６０℃で３０時間還流させた。この反応液を６０℃でろ過して不溶解分を除いた後、反応液が約７０ｍｌになるまで減圧下で溶媒を除き、６％塩酸２００質量部に注いだ。次いで、水６００質量部を加えて室温で３０分間攪拌した後、ウェットケーキをろ取した。このウェットケーキを１００質量部の水に懸濁させて６０℃で２時間攪拌した後、再びろ取して６０℃の湯で水洗後、乾燥させることにより、下記化学式の中間体Ｉ−１ ２１．９質量部を得た。
(Example 1: Synthesis of color material A)
Intermediate I-1 represented by the following structural formula was synthesized by the following procedure.
In a 500 ml four-necked flask, 18.0 parts by mass of the sulfofluorane compound of the following chemical formula (3), 312 parts by mass of methanol, 5.4 parts by mass of 2,6-xylidine and 4.8 parts by mass of o-toluidine were charged. , 60 ° C. for 30 hours. This reaction solution was filtered at 60 ° C. to remove insoluble matter, and then the solvent was removed under reduced pressure until the reaction solution became about 70 ml, and the mixture was poured into 200 parts by mass of 6% hydrochloric acid. Then, 600 parts by mass of water was added, and the mixture was stirred at room temperature for 30 minutes, and then the wet cake was collected by filtration. This wet cake is suspended in 100 parts by mass of water, stirred at 60 ° C. for 2 hours, collected again, washed with hot water at 60 ° C., and dried. 9.9 parts by mass was obtained.
次に中間体Ｉ−１ ２０質量部、１−メチル−２−ピロリジノン１３５．３質量部、炭酸カリウム７．８質量部およびヨウ化メチル１６．２質量部の混合物を８０℃で２時間、撹拌をした。反応終了後、反応溶液を室温まで放冷した後、反応溶液を０〜１０℃の１７．５％塩酸５４１．２質量部に滴下して１時間、撹拌をした。その後、析出物をろ取して、残渣を６０℃で２４時間、乾燥することにより、結晶２０．４質量部を得た。
得られた結晶２０質量部及びオキシ塩化リン １０６質量部をフラスコへ入れ、６０℃で２時間撹拌した。得られた反応溶液を室温まで放冷し、氷水１５００質量部へ反応液を滴下し、３０分撹拌した。得られた結晶を濾別し、水２００質量部で洗浄し、乾燥を１０時間行った。この結晶 ７質量部、トリフルオロメチルスルホンアミド １．８質量部をクロロホルム ４０質量部に溶解させ、トリエチルアミン１．５５質量部を滴下して、室温で１時間撹拌した。その後得られた反応溶液に水１００質量部を入れて水洗し、次いで有機層を分取した。有機層を硫酸ナトリウムにて乾燥させて精製し、減圧濃縮して下記化学式の色材Ａ ６．８質量部を得た。（収率８０％）
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝ ７２０
１Ｈ-ＮＭＲ (５００ＭＨｚ, ＣＤ３ＯＤ)： δ２．００〜２．２５ (ｍ, ９Ｈ) , ３．４４〜３．６０ (ｍ, ６Ｈ), ５．８５〜６．３０ (ｍ, ２Ｈ), ６．９０〜７．５４ (ｍ, １２Ｈ), ７．６８〜７．８５ (ｍ, ２Ｈ), ８．２０〜８．４０ (ｍ, １Ｈ)
Next, a mixture of 20 parts by mass of Intermediate I-1, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate and 16.2 parts by mass of methyl iodide was stirred at 80 ° C. for 2 hours. Did. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10 ° C., and the mixture was stirred for 1 hour. Then, the precipitate was collected by filtration, and the residue was dried at 60 ° C. for 24 hours to obtain 20.4 parts by mass of crystals.
20 parts by mass of the obtained crystals and 106 parts by mass of phosphorus oxychloride were placed in a flask and stirred at 60 ° C. for 2 hours. The obtained reaction solution was allowed to cool to room temperature, the reaction solution was added dropwise to 1500 parts by mass of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of the crystal and 1.8 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution and washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified, and concentrated under reduced pressure to obtain 6.8 parts by mass of a coloring material A having the following chemical formula. (Yield 80%)
MALDI-MS: [M + H] + = 720
1 1 H-NMR (500 MHz, CD 3 OD): δ2.00 to 2.25 (m, 9H), 3.44 to 3.60 (m, 6H), 5.85 to 6.30 (m, 2H) , 6.90 to 7.54 (m, 12H), 7.68 to 7.85 (m, 2H), 8.20 to 8.40 (m, 1H)
（実施例２：色材Ｂの合成）
実施例１において、ヨウ化メチル１６．２質量部を、ヨウ化シクロヘキシル２４．０質量部に変えた以外は実施例１と同様にして、下記化学式の色材Ｂ ８．１質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝８５６
(Example 2: Synthesis of color material B)
In Example 1, 8.1 parts by mass of the coloring material B having the following chemical formula was obtained in the same manner as in Example 1 except that 16.2 parts by mass of methyl iodide was changed to 24.0 parts by mass of cyclohexyl iodide. ..
MALDI-MS: [M + H] + = 856
（実施例３：色材Ｃの合成）
実施例１において、ヨウ化メチル１６．２質量部を、ヨウ化ｎ−プロピル１９．４質量部に変えた以外は実施例１と同様にして、下記化学式の色材Ｃ ７．３質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝７７６
(Example 3: Synthesis of color material C)
In Example 1, 7.3 parts by mass of the coloring material C having the following chemical formula was used in the same manner as in Example 1 except that 16.2 parts by mass of methyl iodide was changed to 19.4 parts by mass of n-propyl iodide. Obtained.
MALDI-MS: [M + H] + = 776
（実施例４：色材Ｄの合成）
実施例１において、ヨウ化メチル１６．２質量部を、ヨウ化ｎ−ブチル２１．０質量部に変えた以外は実施例１と同様にして、下記化学式の色材Ｄ ７．６質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝８０４
(Example 4: Synthesis of color material D)
In Example 1, 7.6 parts by mass of the coloring material D having the following chemical formula was used in the same manner as in Example 1 except that 16.2 parts by mass of methyl iodide was changed to 21.0 parts by mass of n-butyl iodide. Obtained.
MALDI-MS: [M + H] + = 804
（実施例５：色材Ｅの合成）
まず、以下の手順により、下記構造式で表される中間体Ｉ−２を合成した。
実施例１の中間体Ｉ−１を合成する工程において、ｏ−トルイジン ４．８質量部を、２−メチル−６−エチルアニリン ６．０質量部に替えた以外は、実施例１の中間体Ｉ−１と同様にして、下記化学式の中間体Ｉ−２ ２３．０質量部を得た。
(Example 5: Synthesis of color material E)
First, Intermediate I-2 represented by the following structural formula was synthesized by the following procedure.
The intermediate of Example 1 except that 4.8 parts by mass of o-toluidine was replaced with 6.0 parts by mass of 2-methyl-6-ethylaniline in the step of synthesizing the intermediate I-1 of Example 1. In the same manner as I-1, 23.0 parts by mass of an intermediate I-2 having the following chemical formula was obtained.
次に、実施例１において、中間体Ｉ−１ ２０質量部を、中間体Ｉ−２ ２０質量部に変え、ヨウ化メチル１６．２質量部を、ヨウ化メチル１５．４質量部に変え、トリフルオロメチルスルホンアミド １．８質量部を、トリフルオロメチルスルホンアミド １．７質量部に変えた以外は実施例１と同様にして、下記化学式の色材Ｅ ６．７質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝７４８
１Ｈ-ＮＭＲ (５００ＭＨｚ, ＣＤ３ＯＤ)： δ１．０７〜１．２９ (ｍ, ３Ｈ) , ２．００〜２．２２ (ｍ, ９Ｈ), ２．３１〜２．６２ (ｍ, ２Ｈ), ３．４０〜３．５８ (ｍ, ６Ｈ), ５．９２〜６．２３ (ｍ, ２Ｈ), ６．９５〜７．１０ (ｍ, ２Ｈ), ７．１７〜７．４５ (ｍ, ９Ｈ), ７．６５〜７．８５ (ｍ, ２Ｈ), ８．１２〜８．３４ (ｍ, １Ｈ)
Next, in Example 1, 20 parts by mass of intermediate I-1 was changed to 20 parts by mass of intermediate I-2, and 16.2 parts by mass of methyl iodide was changed to 15.4 parts by mass of methyl iodide. In the same manner as in Example 1 except that 1.8 parts by mass of trifluoromethylsulfonamide was changed to 1.7 parts by mass of trifluoromethylsulfonamide, 6.7 parts by mass of a coloring material E having the following chemical formula was obtained.
MALDI-MS: [M + H] + = 748
1 1 H-NMR (500 MHz, CD 3 OD): δ1.07 to 1.29 (m, 3H), 2.00 to 2.22 (m, 9H), 2.31 to 2.62 (m, 2H) , 3.40 to 3.58 (m, 6H), 5.92 to 6.23 (m, 2H), 6.95 to 7.10 (m, 2H), 7.17 to 7.45 (m, 9H), 7.65 to 7.85 (m, 2H), 8.12 to 8.34 (m, 1H)
（実施例６：色材Ｆの合成）
実施例５において、ヨウ化メチル１５．４質量部を、ヨウ化シクロヘキシル２２．８質量部に変えた以外は実施例５と同様にして、下記化学式の色材Ｆ ８．０質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝８８４
(Example 6: Synthesis of color material F)
In Example 5, 8.0 parts by mass of the coloring material F having the following chemical formula was obtained in the same manner as in Example 5 except that 15.4 parts by mass of methyl iodide was changed to 22.8 parts by mass of cyclohexyl iodide. ..
MALDI-MS: [M + H] + = 884
（実施例７：色材Ｇの合成）
実施例５において、ヨウ化メチル１５．４質量部を、ヨウ化ｎ−プロピル１８．５質量部に変えた以外は実施例５と同様にして、下記化学式の色材Ｇ ７．２質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝８０４
(Example 7: Synthesis of color material G)
In Example 5, in the same manner as in Example 5 except that 15.4 parts by mass of methyl iodide was changed to 18.5 parts by mass of n-propyl iodide, 7.2 parts by mass of the coloring material G having the following chemical formula was used. Obtained.
MALDI-MS: [M + H] + = 804
（実施例８：色材Ｈの合成）
実施例５において、ヨウ化メチル１５．４質量部を、ヨウ化ｎ−ブチル２０．０質量部に変えた以外は実施例５と同様にして、下記化学式の色材Ｈ ７．５質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝８３２
(Example 8: Synthesis of color material H)
In Example 5, 7.5 parts by mass of the coloring material H having the following chemical formula was used in the same manner as in Example 5 except that 15.4 parts by mass of methyl iodide was changed to 20.0 parts by mass of n-butyl iodide. Obtained.
MALDI-MS: [M + H] + = 832
（実施例９：色材Ｉの合成）
まず、以下の手順により、下記構造式で表される中間体Ｉ−３を合成した。
実施例１の中間体Ｉ−１を合成する工程において、ｏ−トルイジン ４．８質量部を、２，６−ジイソプロピルアニリン ７．９質量部に替えた以外は、実施例１の中間体Ｉ−１と同様にして、下記化学式の中間体Ｉ−３ ２６．８質量部を得た。
(Example 9: Synthesis of color material I)
First, Intermediate I-3 represented by the following structural formula was synthesized by the following procedure.
Intermediate I- of Example 1 except that 4.8 parts by mass of o-toluidine was replaced with 7.9 parts by mass of 2,6-diisopropylaniline in the step of synthesizing Intermediate I-1 of Example 1. In the same manner as in No. 1, 26.8 parts by mass of Intermediate I-3 having the following chemical formula was obtained.
次に、実施例１において、中間体Ｉ−１ ２０質量部を、中間体Ｉ−３ ２０質量部に変え、ヨウ化メチル１６．２質量部を、ヨウ化メチル１４．４質量部に変え、トリフルオロメチルスルホンアミド １．８質量部を、トリフルオロメチルスルホンアミド １．６質量部に変えた以外は実施例１と同様にして、下記化学式の色材Ｉ ６．６質量部を得た。
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝７７８
Next, in Example 1, 20 parts by mass of Intermediate I-1 was changed to 20 parts by mass of Intermediate I-3, and 16.2 parts by mass of methyl iodide was changed to 14.4 parts by mass of methyl iodide. 6.6 parts by mass of the coloring material I having the following chemical formula was obtained in the same manner as in Example 1 except that 1.8 parts by mass of trifluoromethylsulfonamide was changed to 1.6 parts by mass of trifluoromethylsulfonamide.
MALDI-MS: [M + H] + = 778
（比較例１：比較色材Ｊの合成）
まず、以下の手順により、下記構造式で表される中間体Ｉ−４を合成した。
実施例１の中間体Ｉ−１を合成する工程において、ｏ−トルイジン ４．８質量部を用いず、ｏ−トルイジン １０．８質量部に替えた以外は、実施例１の中間体Ｉ−１と同様にして、下記化学式の中間体Ｉ−４ ２２．５質量部を得た。
(Comparative Example 1: Synthesis of Comparative Color Material J)
First, Intermediate I-4 represented by the following structural formula was synthesized by the following procedure.
In the step of synthesizing the intermediate I-1 of Example 1, 4.8 parts by mass of o-toluidine was not used and replaced with 10.8 parts by mass of o-toluidine, except that the intermediate I-1 of Example 1 was used. In the same manner as above, 22.5 parts by mass of Intermediate I-4 having the following chemical formula was obtained.
次に、得られた中間体Ｉ−４ ２０質量部及びオキシ塩化リン １０６質量部をフラスコへ入れ、６０℃で２時間撹拌した。得られた反応溶液を室温まで放冷し、氷水１５００質量部へ反応液を滴下し、３０分撹拌した。得られた結晶を濾別し、水２００質量部で洗浄し、乾燥を１０時間行った。この結晶 ７質量部、トリフルオロメチルスルホンアミド １．７質量部をクロロホルム ４０質量部に溶解させ、トリエチルアミン１．５５質量部を滴下して、室温で１時間撹拌した。その後得られた反応溶液に水１００質量部を入れて水洗し、次いで有機層を分取した。有機層を硫酸ナトリウムにて乾燥させて精製し、減圧濃縮して下記化学式の比較色材Ｊ ７．５質量部を得た。（収率８０％）
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝７０６
Next, 20 parts by mass of the obtained intermediate I-4 and 106 parts by mass of phosphorus oxychloride were placed in a flask, and the mixture was stirred at 60 ° C. for 2 hours. The obtained reaction solution was allowed to cool to room temperature, the reaction solution was added dropwise to 1500 parts by mass of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of the crystal and 1.7 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution and washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified, and concentrated under reduced pressure to obtain 7.5 parts by mass of a comparative coloring material J having the following chemical formula. (Yield 80%)
MALDI-MS: [M + H] + = 706
（比較例２：比較色材Ｋの合成）
実施例１と同様にして得られた中間体Ｉ−１ ２０質量部、１−メチル−２−ピロリジノン１３５．３質量部、炭酸カリウム７．８質量部およびヨウ化メチル１６．２質量部の混合物を８０℃で２時間、撹拌をした。反応終了後、反応溶液を室温まで放冷した後、反応溶液を０〜１０℃の１７．５％塩酸５４１．２質量部に滴下して１時間、撹拌をした。その後、析出物をろ取して、残渣を６０℃で２４時間、乾燥することにより、下記化学式の比較色材Ｋ １６．７質量部を得た（収率８０％）
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝５８９
(Comparative Example 2: Synthesis of Comparative Color Material K)
A mixture of 20 parts by mass of Intermediate I-1, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate and 16.2 parts by mass of methyl iodide obtained in the same manner as in Example 1. Was stirred at 80 ° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10 ° C., and the mixture was stirred for 1 hour. Then, the precipitate was collected by filtration and the residue was dried at 60 ° C. for 24 hours to obtain 16.7 parts by mass of the comparative coloring material K having the following chemical formula (yield 80%).
MALDI-MS: [M + H] + = 589
（比較例３：比較色材Ｌの合成）
実施例５と同様にして得られた中間体Ｉ−２ ２０質量部、１−メチル−２−ピロリジノン１３５．３質量部、炭酸カリウム７．８質量部およびヨウ化メチル１５．４質量部の混合物を８０℃で２時間、撹拌をした。反応終了後、反応溶液を室温まで放冷した後、反応溶液を０〜１０℃の１７．５％塩酸５４１．２質量部に滴下して１時間、撹拌をした。その後、析出物をろ取して、残渣を６０℃で２４時間、乾燥することにより、下記化学式の比較色材Ｌ １６．６質量部を得た（収率８０％）
ＭＡＬＤＩ−ＭＳ：[Ｍ＋Ｈ]＋ ＝６１７
(Comparative Example 3: Synthesis of Comparative Color Material L)
A mixture of 20 parts by mass of Intermediate I-2, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate and 15.4 parts by mass of methyl iodide obtained in the same manner as in Example 5. Was stirred at 80 ° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10 ° C., and the mixture was stirred for 1 hour. Then, the precipitate was collected by filtration and the residue was dried at 60 ° C. for 24 hours to obtain 16.6 parts by mass of the comparative coloring material L having the following chemical formula (yield 80%).
MALDI-MS: [M + H] + = 617
＜評価：溶剤への溶解性＞
上記合成した色材Ａ〜Ｉ、及び、比較色材Ｊ〜Ｌについて、以下の手順で各下記の溶剤に対する溶解性の評価を行った。
２０ｍＬサンプル管瓶に、各色材を０．２ｇ投入し、次いで各溶剤１０ｇを量りとって投入し、密栓した後に超音波で３分間処理した。得られた液は２３℃のウォーターバスで６０分間静置保管後、目視で確認した。結果を表１に示す。
溶剤１： プロピレングリコールモノメチルエーテルアセテート
溶剤２： プロピレングリコールモノメチルエーテル
溶剤３： ３−メトキシ−３−メチル−１−ブチルアセテート
溶剤４： ジエチレングリコールエチルメチルエーテル
溶剤５：３−エトキシプロピオン酸エチル
（評価基準）
Ａ：全て溶解
Ｂ：一部溶解せず沈殿
Ｃ：ほとんど溶解せず沈殿
<Evaluation: Solubility in solvent>
The solubility of the synthesized color materials A to I and the comparative color materials J to L in the following solvents was evaluated by the following procedure.
0.2 g of each coloring material was put into a 20 mL sample tube bottle, then 10 g of each solvent was weighed and put into a bottle, and after sealing, the mixture was treated with ultrasonic waves for 3 minutes. The obtained liquid was stored in a water bath at 23 ° C. for 60 minutes, and then visually confirmed. The results are shown in Table 1.
Solvent 1: Propylene glycol monomethyl ether acetate solvent 2: Propylene glycol monomethyl ether solvent 3: 3-Methoxy-3-methyl-1-butyl acetate solvent 4: Diethylene glycol ethyl methyl ether solvent 5: Ethyl 3-ethoxypropionate (evaluation criteria)
A: All dissolved B: Partially dissolved and precipitated C: Almost dissolved and precipitated
表１の結果から、本発明で用いられる前記一般式（１）で表される色素である、色材Ａ〜Ｉは、それぞれプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールエチルメチルエーテル、又は３−エトキシプロピオン酸エチルのような、アルコール性水酸基を有しない低極性溶媒に対しても、溶剤溶解性に優れることが示された。 From the results in Table 1, the coloring materials A to I, which are the dyes represented by the general formula (1) used in the present invention, are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol ethyl methyl ether, respectively. Alternatively, it has been shown to be excellent in solvent solubility even in a low-polarity solvent having no alcoholic hydroxyl group, such as ethyl 3-ethoxypropionate.
＜評価：耐光性、異物発生、光学特性＞
（１）着色樹脂組成物の調製
まず、アルカリ可溶性樹脂としてメタクリル酸／メタクリル酸メチル／メタクリル酸シクロヘキシル共重合体（モル比：１３．８／２６．２／５０.０、重量平均分子量：９０００、酸価：９０ｍｇＫＯＨ／ｇ、有効成分含量４０質量％）４０．０質量部、多官能性モノマーとしてジペンタエリスリトールヘキサアクリレート（日本化薬社製、「ＫＡＹＡＲＡＤ ＤＰＨＡ」）４８．０質量部、光開始剤として２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン（ＢＡＳＦジャパン社製、「ＩＲＧＡＣＵＲＥ９０７」）１２．０質量部、ジエチルチオキサントン（日本化薬社製、「ＤＥＴＸ−Ｓ」）４．０質量部及び溶媒としてＰＧＭＥＡ ９６．０質量部を添加した後、均一になるまで混合し、感光性バインダー成分（ＣＲ−１）を得た。
次に、実施例及び比較例で得られた色材 ０．８５質量部を ＰＧＭＥＡ ７２．３質量部に溶解して色材溶液を調製し、一方で、前記感光性バインダー成分（ＣＲ−１）２６．６質量部、シランカップリング剤ＫＢＭ−５０３（信越シリコーン製）０．２質量部、界面活性剤メガファックＦ５５９（ＤＩＣ製）０．０２質量部を混合し、これにさらに前記色材溶液を混合することにより、実施例及び比較例の色材をそれぞれ含む評価用の着色樹脂組成物を得た。
<Evaluation: Light resistance, foreign matter generation, optical characteristics>
(1) Preparation of Colored Resin Composition First, as an alkali-soluble resin, a methacrylate / methyl methacrylate / cyclohexyl methacrylate copolymer (molar ratio: 13.8 / 26.2 / 50.0, weight average molecular weight: 9000, Acid value: 90 mgKOH / g, active ingredient content 40% by mass) 40.0 parts by mass, dipentaerythritol hexaacrylate (manufactured by Nippon Kayakusha, "KAYARAD DPHA") 48.0 parts by mass as a polyfunctional monomer, start of light As an agent, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan, "IRGACURE907") 12.0 parts by mass, diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) , "DETX-S") 4.0 parts by mass and 96.0 parts by mass of PGMEA as a solvent were added and then mixed until uniform to obtain a photosensitive binder component (CR-1).
Next, 0.85 parts by mass of the coloring material obtained in Examples and Comparative Examples was dissolved in 72.3 parts by mass of PGMEA to prepare a coloring material solution, while the photosensitive binder component (CR-1). 26.6 parts by mass, 0.2 parts by mass of the silane coupling agent KBM-503 (manufactured by Shinetsu Silicone), and 0.02 parts by mass of the surfactant Megafuck F559 (manufactured by DIC) are mixed, and the colorant solution is further mixed. Was mixed to obtain a colored resin composition for evaluation containing the coloring materials of Examples and Comparative Examples, respectively.
（２）耐光性評価
実施例及び比較例の色材をそれぞれ含む各着色樹脂組成物を、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製、「ＮＡ３５」）上に、スピンコーターを用いて塗布した。その後、８０℃のホットプレート上で３分間加熱乾燥を行った。フォトマスクを介さずに超高圧水銀灯を用いて６０ｍＪ／ｃｍ２の紫外線を照射した。その後、着色膜が形成されたガラス板を２３０℃のクリーンオーブンで３０分間ポストベークすることによって硬化膜（着色膜）を得た。それぞれ、ポストベーク後の膜厚（Ｔ；μｍ）が１．５となるようにした。
大気下試料はキセノンランプ（アトラス社製Ｃｉ４０００ウェザメータ、内側フィルター：石英、外側フィルター：ソーダライム＆赤外線吸収コーティング（ＣＩＲＡ））を用い、４２０ｎｍの波長で、照度を１．２ｍＷ／ｍ２として、７０時間（３００ｋＪ／ｍ２相当）した前後でΔＥａｂ値を測定した。ΔＥａｂ値の絶対値が小さいほど耐光性に優れているといえる。
ポストベーク処理された着色膜のＬ、ａ、ｂを測定し、Ｌ１、ａ１、ｂ１とした。耐光試験後の着色膜のＬ、ａ、ｂを再び測定し、Ｌ３、ａ３、ｂ３とした。ΔＥａｂは下記式より算出される。
ΔＥａｂ＝｛（Ｌ３−Ｌ１）２＋（ａ３−ａ１）２＋（ｂ３−ｂ１）２｝１／２
(2) Light resistance evaluation A spin coater is placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm for each colored resin composition containing the coloring materials of Examples and Comparative Examples. Used to apply. Then, it was heated and dried on a hot plate at 80 ° C. for 3 minutes. Ultraviolet rays of 60 mJ / cm 2 were irradiated using an ultra-high pressure mercury lamp without using a photomask. Then, the glass plate on which the colored film was formed was post-baked in a clean oven at 230 ° C. for 30 minutes to obtain a cured film (colored film). The film thickness (T; μm) after post-baking was adjusted to 1.5 for each.
For the atmospheric sample, a xenon lamp (Ci4000 weather meter manufactured by Atlas, inner filter: quartz, outer filter: soda lime & infrared absorption coating (CIRA)) is used, and the illuminance is 1.2 mW / m 2 at a wavelength of 420 nm and 70. The ΔEab value was measured before and after the time (corresponding to 300 kJ / m 2). It can be said that the smaller the absolute value of ΔEab value, the better the light resistance.
L, a, and b of the post-baked colored film were measured and used as L 1 , a 1 , and b 1 . The L, a, and b of the colored film after the light resistance test were measured again and used as L 3 , a 3 , and b 3 . ΔEab is calculated by the following formula.
ΔEab = {(L 3- L 1 ) 2 + (a 3- a 1 ) 2 + (b 3- b 1 ) 2 } 1/2
（３）光学特性評価
光学特性評価は以下のように行った。着色樹脂組成物をそれぞれ、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製、「ＮＡ３５」）上に、スピンコーターを用いて塗布した。塗布後の基板の溶剤を減圧乾燥機で除いた後、８０℃のホットプレート上で３分間加熱乾燥を行った。フォトマスクを介さずに超高圧水銀灯を用いて６０ｍＪ／ｃｍ２の紫外線を照射することによって硬化膜を得た。乾燥硬化後の膜厚（Ｔ；μｍ）は後述のポストベーク後の色度がｙ＝０．１７となるようにした。着色層が形成されたガラス板を２３０℃のクリーンオーブンで３０分間ポストベークし、得られた着色層の色度（ｘ、ｙ）及び輝度（Ｙ）をオリンパス製顕微分光測定装置ＯＳＰ−ＳＰ２００を用いて測定した。
(3) Evaluation of optical characteristics The evaluation of optical characteristics was performed as follows. Each of the colored resin compositions was applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm using a spin coater. After removing the solvent of the substrate after coating with a vacuum dryer, heat drying was performed on a hot plate at 80 ° C. for 3 minutes. A cured film was obtained by irradiating ultraviolet rays of 60 mJ / cm 2 using an ultra-high pressure mercury lamp without using a photomask. The film thickness (T; μm) after drying and curing was adjusted so that the chromaticity after post-baking, which will be described later, was y = 0.17. The glass plate on which the colored layer was formed was post-baked in a clean oven at 230 ° C. for 30 minutes, and the chromaticity (x, y) and brightness (Y) of the obtained colored layer were measured by using an Olympus microspectroscopy measuring device OSP-SP200. Measured using.
（４）異物発生評価
着色樹脂組成物をそれぞれ、ガラス基板上に、スピンコーターを用いて乾燥後膜厚が２μｍとなるように塗布後、減圧乾燥機で溶剤を除いた後の塗膜を目視確認し、異物の発生評価をした。
（評価基準）
Ａ：減圧乾燥後の塗膜に析出なし
Ｂ：減圧乾燥後の塗膜の一部に析出
Ｃ：減圧乾燥後の塗膜全面に析出
(4) Evaluation of foreign matter generation Each of the colored resin compositions is applied onto a glass substrate using a spin coater so that the film thickness becomes 2 μm after drying, and then the coating film after removing the solvent with a vacuum dryer is visually observed. After confirming, the generation of foreign matter was evaluated.
(Evaluation criteria)
A: No precipitation on the coating film after vacuum drying B: Precipitation on a part of the coating film after vacuum drying C: Precipitation on the entire surface of the coating film after vacuum drying
表２の結果から、本発明の前記一般式（１）で表される色素である、色材Ａ〜色材Ｉをそれぞれ用いた場合、耐光性に優れ、低極性溶媒への溶剤溶解性が向上し、異物の発生が抑制され、輝度が向上した着色層が得られることが示された。
一方で、特許文献２に記載されている比較色材Ｊ、及び特許文献１に記載されている比較色材Ｋ及びＬをそれぞれ用いた場合、耐光性が劣り、異物が発生した着色層が得られ、輝度の点でも劣っていた。
実施例の中でも、Ｒ１及びＲ２が直鎖アルキル基である場合に輝度が向上する傾向がみられ、特に、Ｒ１及びＲ２がｎ−プロピル基である場合に特に輝度が向上する傾向がみられた。
From the results in Table 2, when the color materials A to I, which are the dyes represented by the general formula (1) of the present invention, are used, the light resistance is excellent and the solvent solubility in a low polar solvent is high. It was shown that the colored layer was improved, the generation of foreign substances was suppressed, and the brightness was improved.
On the other hand, when the comparative color materials J described in Patent Document 2 and the comparative color materials K and L described in Patent Document 1 are used, respectively, the light resistance is inferior and a colored layer in which foreign matter is generated is obtained. It was also inferior in terms of brightness.
Among the examples , the brightness tends to be improved when R 1 and R 2 are linear alkyl groups, and the brightness tends to be particularly improved when R 1 and R 2 are n-propyl groups. Was seen.
Claims (6)
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| US6020481A (en) * | 1996-04-01 | 2000-02-01 | The Perkin-Elmer Corporation | Asymmetric benzoxanthene dyes |
| US6008379A (en) * | 1997-10-01 | 1999-12-28 | The Perkin-Elmer Corporation | Aromatic-substituted xanthene dyes |
| WO2004101709A1 (en) * | 2003-05-09 | 2004-11-25 | Applera Corporation | Phenyl xanthene dyes |
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| JP5647279B2 (en) * | 2013-02-08 | 2014-12-24 | 大日本印刷株式会社 | Colorant dispersion, method for producing colorant dispersion, colored resin composition for color filter, color filter, liquid crystal display device, and organic light emitting display device |
| JP5646663B2 (en) * | 2013-02-08 | 2014-12-24 | 株式会社Ｄｎｐファインケミカル | Colored resin composition for color filter, color material dispersion, color filter, liquid crystal display device, and organic light emitting display device |
| TWI644905B (en) * | 2013-05-31 | 2018-12-21 | 南韓商東友精細化工有限公司 | Compound and coloring curable resin composition |
| JP6333604B2 (en) * | 2013-07-09 | 2018-05-30 | 富士フイルム株式会社 | Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging device, and image display device |
| JP6162084B2 (en) * | 2013-09-06 | 2017-07-12 | 富士フイルム株式会社 | Colored composition, cured film, color filter, method for producing color filter, solid-state imaging device, image display device, polymer, xanthene dye |
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