JP5514854B2 - Novel high sensitivity alpha ketoxime ester photoinitiator and photopolymerizable composition containing this compound - Google Patents
Novel high sensitivity alpha ketoxime ester photoinitiator and photopolymerizable composition containing this compound Download PDFInfo
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- JP5514854B2 JP5514854B2 JP2012074092A JP2012074092A JP5514854B2 JP 5514854 B2 JP5514854 B2 JP 5514854B2 JP 2012074092 A JP2012074092 A JP 2012074092A JP 2012074092 A JP2012074092 A JP 2012074092A JP 5514854 B2 JP5514854 B2 JP 5514854B2
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- photosensitive resin
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- 150000001875 compounds Chemical class 0.000 title claims description 89
- 239000000203 mixture Substances 0.000 title claims description 76
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- 239000000049 pigment Substances 0.000 claims description 13
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
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- FKMIBYMTHOJWCY-UHFFFAOYSA-N 2-(2-methylphenyl)acetyl chloride Chemical compound CC1=CC=CC=C1CC(Cl)=O FKMIBYMTHOJWCY-UHFFFAOYSA-N 0.000 description 12
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
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- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 6
- 238000011161 development Methods 0.000 description 5
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 150000003855 acyl compounds Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
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- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- 0 CCC1[C@@]2(C(C)C2)C(*C*C)C(C)C1*C Chemical compound CCC1[C@@]2(C(C)C2)C(*C*C)C(C)C1*C 0.000 description 3
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- 235000000126 Styrax benzoin Nutrition 0.000 description 3
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- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 150000003918 triazines Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- SMFFZOQLHYIRDA-UHFFFAOYSA-N 3,4-dimethoxyphenol Chemical compound COC1=CC=C(O)C=C1OC SMFFZOQLHYIRDA-UHFFFAOYSA-N 0.000 description 2
- AFWPDDDSTUNFBP-UHFFFAOYSA-N 6-phenyl-7-thiabicyclo[4.1.0]hepta-2,4-diene Chemical compound S1C2C=CC=CC12C1=CC=CC=C1 AFWPDDDSTUNFBP-UHFFFAOYSA-N 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
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- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000005441 o-toluyl group Chemical group [H]C1=C([H])C(C(*)=O)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005292 vacuum distillation Methods 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
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Description
本発明は、光開始剤として有用なアルファケトオキシムエステル化合物及びこれを利用した光重合開始剤組成物に関する。 The present invention relates to an alpha ketoxime ester compound useful as a photoinitiator and a photopolymerization initiator composition using the same.
感光性組成物は、エチレン性不飽和結合を有する重合性化合物に光重合開始剤を添加したものであり、このような感光性組成物に３６５ｎｍ、４０５ｎｍ、４３６ｎｍの混合光を照射することによって、重合硬化させることができるので、光硬化性インク、感光性印刷板、各種フォトレジストなどに用いられている。短波長の光源に感度を有する感光性組成物は、微細な印刷が可能なので、特に３６５ｎｍの光源に優れた感度を有する光重合開始剤が要求されている。このような高感度光開始剤としてオキシムエステル化合物が多く使用されていて、そのような特性は、様々な特許文献に多様に記載されていて、また、商用化されたいくつかの商品がある。 The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and by irradiating such photosensitive composition with mixed light of 365 nm, 405 nm, and 436 nm, Since it can be polymerized and cured, it is used in photocurable inks, photosensitive printing plates, various photoresists, and the like. Since a photosensitive composition having sensitivity to a light source having a short wavelength enables fine printing, a photopolymerization initiator having excellent sensitivity to a 365 nm light source is particularly required. Oxime ester compounds are often used as such high-sensitivity photoinitiators, and such characteristics are described in various patent documents and there are several commercialized products.
このようなオキシムエステル光開始剤の場合、主にＬＣＤ分野のフォトレジストに現在応用されている。このような既存の商品は、オキシムエステル化合物とアルファケトオキシム（α
−ｋｅｔｏｘｉｍｅ）エステル化合物とに分けられ、アルファケトオキシムエステル光開始剤の場合、主にレッド、グリーン、ブルーのような色を有するフォトレジストに用いられている。
Such oxime ester photoinitiators are currently applied mainly to photoresists in the LCD field. Such existing products include oxime ester compounds and alpha ketoximes (α
-Ketoxime) ester compounds, and alpha ketoxime ester photoinitiators are mainly used for photoresists having colors such as red, green and blue.
オキシムエステル化合物の場合、ＵＶを受けて光分解が起きる場合、レジストフィルムを変色させるのに対し、アルファケトオキシムエステル開始剤の場合、変色が起きないため、カラーレジストでの色座標の変化を起こさない。このような理由から、カラーフォトレジストにおいてアルファケトオキシムエステル化合物を主に使用しているが、現在の商品化されたアルファケトオキシムエステル光重合開始剤の場合、その感度が高くないため、高い感度のアルファケトオキシムエステル光重合開始剤が要望されている。 In the case of an oxime ester compound, the resist film is discolored when photodegradation occurs upon receiving UV, whereas in the case of an alpha ketoxime ester initiator, no discoloration occurs, resulting in a change in color coordinates in the color resist. Absent. For this reason, alpha ketoxime ester compounds are mainly used in color photoresists, but the sensitivity of current commercialized alpha ketoxime ester photopolymerization initiators is not high, so high sensitivity There is a need for an alpha ketoxime ester photoinitiator.
本発明の目的は、ＵＶ最大吸光が３６５ｎｍ及び４０５ｎｍに近い高感度性であり、且つ、現像性、密着性、耐アルカリ性に優れたアルファケトオキシムエステル化合物及びこれを含む光重合開始剤を提供することにある。 An object of the present invention is to provide an alpha ketoxime ester compound having a UV maximum absorbance close to 365 nm and 405 nm and excellent in developability, adhesion, and alkali resistance, and a photopolymerization initiator containing the same. There is.
上記目的を達成するために、本発明は、下記化学式１及び化学式２で表されるアルファケトオキシムエステル化合物を提供する。 In order to achieve the above object, the present invention provides an alpha ketoxime ester compound represented by the following Chemical Formula 1 and Chemical Formula 2.
上記化学式１及び２で、
Ｒは、１〜５個のメチル基を有するメチルベンゼン基であり、次の化学式Ｒのように例示的に表されることができる。
In the above chemical formulas 1 and 2,
R is a methylbenzene group having 1 to 5 methyl groups, and can be exemplarily represented as the following chemical formula R.
また、上記化学式１及び２で、Ｒ１は、炭素数１〜１０のアルキル基、特にメチル基、ベンゾイル基、または炭素数３〜６のシクロアルキル基であり、
Ｒ２は、−ＣＨ３、−Ｃ２Ｈ５、−プロピル、または−ベンゾイルであり、
Ｒ３は、−Ｈであるか、ａがメチルまたはエチル基であり、ｂがＨまたはメチル基である
R 2 is —CH 3 , —C 2 H 5 , —propyl, or —benzoyl;
R 3 is —H, a is a methyl or ethyl group, and b is H or a methyl group.
また、本発明は、上記化学式１の化合物及び化学式２の化合物から選択された１つ以上の化合物及び溶剤またはアルカリ水溶液に可溶の高分子化合物及び／またはエチレン性不飽和結合を有する光重合性化合物を含むことを特徴とする感光性樹脂組成物を提供する。 In addition, the present invention provides one or more compounds selected from the compound of the above chemical formula 1 and the compound of the chemical formula 2, a high molecular compound soluble in a solvent or an alkaline aqueous solution, and / or a photopolymerizable compound having an ethylenically unsaturated bond. A photosensitive resin composition comprising a compound is provided.
ここで、上記組成物は、着色剤または顔料をさらに含むことができる。 Here, the composition may further include a colorant or a pigment.
また、本発明は、上記感光性樹脂組成物から形成されたカラムスペーサを提供する。 Moreover, this invention provides the column spacer formed from the said photosensitive resin composition.
また、本発明は、上記感光性樹脂組成物から形成されたブラックマトリックスを提供する。 Moreover, this invention provides the black matrix formed from the said photosensitive resin composition.
また、本発明は、上記感光性樹脂組成物から形成されたカラーフィルタ組成物を提供する。 Moreover, this invention provides the color filter composition formed from the said photosensitive resin composition.
また、本発明は、上記感光性樹脂組成物から形成された有機絶縁膜を有する基板を提供する。 Moreover, this invention provides the board | substrate which has an organic insulating film formed from the said photosensitive resin composition.
また、本発明は、上記感光性樹脂組成物をコーティングして形成された膜を有する基材を提供する。ここで、上記膜は、ワープロ、コンピュータ、テレビまたはプラズマディスプレイパネル、液晶表示装置に使用される偏光板の表面、サングラスレンズ、度数があるめがねレンズ、カメラ用ファインダーレンズ、計器のカバー、自動車のガラス、電車のガラス、光輝度向上膜、または光導波路膜として使用されることを特徴とする。 Moreover, this invention provides the base material which has a film | membrane formed by coating the said photosensitive resin composition. Here, the film is a word processor, a computer, a television or plasma display panel, the surface of a polarizing plate used in a liquid crystal display device, a sunglasses lens, a spectacle lens with power, a finder lens for a camera, an instrument cover, an automobile glass It is used as a train glass, a light brightness enhancement film, or an optical waveguide film.
本発明によれば、ＵＶ最大吸光が３６５ｎｍ及び４０５ｎｍに近い高感度性であり、且つ、現像性、密着性、耐アルカリ性に優れたアルファケトオキシムエステル化合物及びこれを含む光重合開始剤を提供することができる。具体的には、本発明によれば、感光性組成物の溶剤として有用なＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）などに対する溶解性に優れたアルファケトオキシムエステル化合物を提供することができ、これにより、光架橋反応時に使用される光開始剤としてのアルファケトオキシムエステル化合物の量を最小化することができ、これを含む感光性組成を薄膜コーティングした後、溶媒を揮発させた時、バインダーと光開始剤との相分離を低減し、架橋後の薄膜特性を向上させることができる。これにより、良質のブラックマトリックス、カラーフィルタ、カラムスペーサ、絶縁膜、光架橋性被膜などを製造することができる。 According to the present invention, there is provided an alpha ketoxime ester compound having a high sensitivity near UV maximum of 365 nm and 405 nm, and excellent in developability, adhesion and alkali resistance, and a photopolymerization initiator containing the same. be able to. Specifically, according to the present invention, it is possible to provide an alpha ketoxime ester compound excellent in solubility in PGMEA (propylene glycol monomethyl ether acetate) and the like useful as a solvent for a photosensitive composition. The amount of alpha ketoxime ester compound used as a photoinitiator during photocrosslinking reaction can be minimized, and after coating the photosensitive composition containing this with a thin film, when the solvent is volatilized, the photoinitiator with the binder The phase separation from the agent can be reduced, and the thin film properties after crosslinking can be improved. Thereby, a good quality black matrix, a color filter, a column spacer, an insulating film, a photocrosslinkable film, etc. can be manufactured.
本発明は、溶媒に対する適切な溶解度と優秀な光感度を達成することができる下記化学式１及び２で表されるアルファケトオキシムエステル化合物を提供する。下記化学式１及び２でアルファケトオキシムエステル構造の窒素原子と二重結合する炭素原子は、メチルベンゼン基と結合されたことを特徴とする。 The present invention provides an alpha ketoxime ester compound represented by the following Chemical Formulas 1 and 2 that can achieve appropriate solubility in a solvent and excellent photosensitivity. In the following chemical formulas 1 and 2, the carbon atom double-bonded to the nitrogen atom of the alpha ketoxime ester structure is bonded to a methylbenzene group.
上記化学式１及び２で、
Ｒは、１〜５個のメチル基を有するメチルベンゼン基であり、次の化学式Ｒのように例示的で表されることができる。
In the above chemical formulas 1 and 2,
R is a methylbenzene group having 1 to 5 methyl groups, and can be exemplarily represented as the following chemical formula R.
Ｒ１は、炭素数１〜１０のアルキル基、特にメチル基、ベンゾイル基、または炭素数３〜６のシクロアルキル基であり、Ｒ２は、−ＣＨ３、−Ｃ２Ｈ５、−プロピル、または−ベンゾイルであり、特にエチル基が好ましく、Ｒ３は、−Ｈであるか、ａがメチルまたはエチル基であり、ｂがＨまたはメチル基である R 1 is an alkyl group having 1 to 10 carbon atoms, particularly a methyl group, a benzoyl group, or a cycloalkyl group having 3 to 6 carbon atoms, and R 2 is —CH 3 , —C 2 H 5 , —propyl, or - benzoyl, particularly preferably an ethyl group, R 3 is either -H, a is a methyl or ethyl group, b is H or a methyl group
また、上記化学式２で、Ｘは、−Ｏ−、−Ｓ−、または−Ｓｅ−であり、特に−Ｏ−、−Ｓ−であることが好ましい。 In the above chemical formula 2, X is —O—, —S—, or —Se—, and is particularly preferably —O— or —S—.
上記化学式１〜２で表される化合物の好ましい具体例は、次の化学式３〜３２で表されるものを含む。しかし、本発明は、下記例示によって限定されない。 Preferred specific examples of the compounds represented by the above chemical formulas 1 and 2 include those represented by the following chemical formulas 3 to 32. However, the present invention is not limited by the following examples.
［カルバゾール構造を含む化学式１のアルファケトオキシムエステル化合物の合成］
前記化学式１で表される化合物を製造する方法は、例えば、下記の反応式１で説明される合成過程によって合成されることができる。しかし、これに限定されるものではない。
[Synthesis of Alpha-Ketoxime Ester Compound of Formula 1 Containing Carbazole Structure]
The method for producing the compound represented by Chemical Formula 1 can be synthesized by, for example, a synthesis process described in Reaction Formula 1 below. However, it is not limited to this.
まず、カルバゾール化合物とカルボン酸クロライドとｎ−メチルカルボン酸クロライドとを順次に塩化アルミニウムの存在下に反応させてアシル化合物を得る。このアシル化合物を塩基触媒の下でイソアミルニトリトと反応させて、アルファケトオキシム化合物を得る。次に、アルファケトオキシム化合物とカルボン酸クロライドをトリエチルアミン触媒の下で反応させて、上記化学式１で表されるアルファケトオキシムエステル化合物を得る。 First, an acyl compound is obtained by sequentially reacting a carbazole compound, a carboxylic acid chloride, and an n-methylcarboxylic acid chloride in the presence of aluminum chloride. This acyl compound is reacted with isoamylnitrite under a base catalyst to give an alpha ketoxime compound. Next, the alpha ketoxime compound and carboxylic acid chloride are reacted in the presence of a triethylamine catalyst to obtain the alpha ketoxime ester compound represented by Formula 1 above.
［ジフェニル構造を含む化学式２のアルファケトオキシムエステル化合物の合成］
上記化学式２で表される化合物を製造する方法は、例えば、下記の反応式２で説明される合成過程によって合成されることができる。しかし、これに限定されるものではない。
[Synthesis of Alpha-Ketooxime Ester Compound of Chemical Formula 2 Containing Diphenyl Structure]
The method for producing the compound represented by Chemical Formula 2 can be synthesized by, for example, a synthesis process described in Reaction Formula 2 below. However, it is not limited to this.
まず、ジフェニル化合物とカルボン酸クロライドとｎ−メチルカルボン酸クロライドとを順次に塩化アルミニウムの存在の下に反応させてアシル化合物を得る。このアシル化合物を塩基触媒の下でイソアミルニトリトと反応させてアルファケトオキシム化合物を得る。次に、アルファケトオキシム化合物とカルボン酸クロライドをトリエチルアミン触媒下で反応させて、上記化学式２で表されるアルファケトオキシムエステル化合物を得る。 First, an acyl compound is obtained by sequentially reacting a diphenyl compound, a carboxylic acid chloride, and an n-methylcarboxylic acid chloride in the presence of aluminum chloride. This acyl compound is reacted with isoamylnitrite under a base catalyst to obtain an alpha ketoxime compound. Next, the alpha ketoxime compound and the carboxylic acid chloride are reacted in the presence of a triethylamine catalyst to obtain the alpha ketoxime ester compound represented by the chemical formula 2.
本発明は、光開始剤として上記化学式１〜２のいずれか１つで表されるアルファケトオキシムエステル化合物を含む感光性樹脂組成物を提供する。 The present invention provides a photosensitive resin composition comprising an alpha ketoxime ester compound represented by any one of Chemical Formulas 1-2 as a photoinitiator.
上記感光性樹脂組成物は、光開始剤として上記化学式１〜２のいずれか１つで表されるアルファケトオキシムエステル化合物を１つ以上含むことができる。また、上記感光性樹脂組成物は、公知の光開始剤がさらに含まれることができる。 The photosensitive resin composition may include one or more alpha ketoxime ester compounds represented by any one of Chemical Formulas 1-2 as a photoinitiator. The photosensitive resin composition may further include a known photoinitiator.
本発明によるアルファケトオキシムエステル化合物１種以上と他の公知の光開始剤を混合して使用する場合には、本発明によるアルファケトオキシムエステル化合物の含量が全体光開始剤の総重量に対して５０重量％以上含むことが好ましい。すなわち、全体光開始剤の総重量に対して５０重量％を含むことによって、本発明によるアルファケトオキシムエステル化合物による光開始剤の感度の維持効果を達成することができる。 When one or more alpha ketoxime ester compounds according to the present invention are mixed with other known photoinitiators, the content of the alpha ketoxime ester compound according to the present invention is based on the total weight of the total photoinitiator. It is preferable to contain 50% by weight or more. That is, by including 50% by weight with respect to the total weight of the total photoinitiator, the effect of maintaining the sensitivity of the photoinitiator by the alpha ketoxime ester compound according to the present invention can be achieved.
ここで、上記公知の光開始剤の一例としては、アセトフェノン、２、２−ジエトキシアセトフェノン、ｐ−ジメチルアセトフェノン、ｐ−ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、ｐ−ｔｅｒｔ−ブチルアセトフェノンなどのアセトフェノン類や、ベンゾフェノン、２−クロロベンゾフェノン、ｐ、ｐ’−ビスジメチルアミノベンゾフェノンなどのベンゾフェノン類や、ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテルなどのベンゾインエーテル類や、ベンジルジメチルケタル、チオキサンテン、２−クロロチオキサンテン、２、４−ジエチルチオキサンテン、２−メチルチオキサンテン、２−イソプロピルチオキサンテンなどのスルファ化合物や、２−エチルアントラキノン、オクタメチルアントラキノン、１、２−ベンズアントラキノン、２、３−ジフェニルアントラキノンなどのアントラキノン類や、アゾビスイソブチロニトリル、ベンゾイルペルオキシド、クメンペルオキシドなどの有機過酸化物や、２−メルカプトベンゾイミダゾール、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾチアゾールなどのチオール（ｔｈｉｏｌ）化合物や、２−（ｏ−クロロフェニル）−４、５−ジ（ｍ−メトキシフェニル）−イミダゾリル二量体などのイミダゾリル化合物や、ｐ−メトキシトリアジンなどのトリアジン化合物や、２、４、６−トリス（卜リクロロメチル）−ｓ−トリアジン、２−メチル−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−［２−（５−メチルフラン−２−イル）エテニル］−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−［２−（フラン−２−イル）エテニル］−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−［２−（４−ジエチルアミノ−２−メチルフェニル）エテニル］−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−［２−（３、４−ジメトキシフェノール）エテニル］−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−（４−メトキシフェニル）−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−（４−エトキシスチリル）−４、６−ビス（卜リクロロメチル）−ｓ−トリアジン、２−（４−ｎ−ブトキシフェニル）−４、６−ビス（卜リクロロメチル）−ｓ−トリアジンなどのハロメチル基を有するトリアジン化合物、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１オンなどのアミノケトン化合物を挙げることができる。 Here, examples of the known photoinitiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and the like. Acetophenones, benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl Dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthate Sulfa compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, Oxides, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl)- Imidazolyl compounds such as imidazolyl dimer, triazine compounds such as p-methoxytriazine, 2,4,6-tris (卜 lichloromethyl) -s-triazine, 2-methyl-4,6-bis (卜 lichloromethyl)- s-tria , 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (卜 lichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 , 6-bis (卜 trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4, 6-bis (卜 trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) ethenyl] -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (卜 trichloromethyl) -s-triazine and the like Examples thereof include triazine compounds having a romethyl group and aminoketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.
また、本発明の感光性樹脂組成物は、増感剤として、サイニン、キサンテン、オキサジン、チアジン、ジアリールメタン、トリアリールメタン及びピリリウムなどの陽イオン染料、メロシアニン、クマリン、インジゴ、芳香族アミン類、フタロシアニン、アゾ、キノン及びチオキサンテン感光染料などの中性染料、及びベンゾフェノン類、アセトフェノン類、ベンゾイン類、チオキサントン類、アントラキノン類、イミダゾール類、ビイミダゾール類、クマリン類、ケトクマリン類、トリフェニルピリリウム類、トリアジン類及びベンゾイン酸などの化合物などをさらに含むことができる。 In addition, the photosensitive resin composition of the present invention includes, as sensitizers, cation dyes such as cynin, xanthene, oxazine, thiazine, diarylmethane, triarylmethane and pyrylium, merocyanine, coumarin, indigo, aromatic amines, Neutral dyes such as phthalocyanine, azo, quinone and thioxanthene photosensitive dyes, and benzophenones, acetophenones, benzoins, thioxanthones, anthraquinones, imidazoles, biimidazoles, coumarins, ketocoumarins, triphenylpyryliums Further, compounds such as triazines and benzoic acid can be further included.
本発明の感光性樹脂組成物には、溶剤またはアルカリ水溶液に可溶である高分子化合物単独またはこれらの高分子化合物とエチレン性不飽和結合を有する光重合性化合物の混合物を含むことができる。ここで、溶剤またはアルカリ水溶液に可溶である高分子化合物やエチレン性不飽和結合を有する光重合性化合物の一例としては、具体的には、アクリル酸、メタクリル酸、フマル酸、マレイン酸、フマル酸モノメチル、フマル酸モノエチル、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、エチレングリコールモノメチルエーテルアクリレート、エチレングリコールモノメチルエーテルメタクリレート、エチレングリコールモノエチルエーテルアクリレート、エチレングリコールモノエチルエーテルメタクリレート、グリセロールアクリレート、グリセロールメタクリレート、アクリル酸アミド、メタクリル酸アミド、アクリロニトリル、メタクリロニトリル、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、イソブチルアクリレート、イソブチルメタクリレート、２−エチルヘキシルアクリレート、２−エチルヘキシルメタクリレート、ベンジルアクリレート、ベンジルメタクリレート、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、テトラエチレングリコールジメタクリレート、ブチレングリコールジメタクリレート、プロピレングリコールジアクリレート、プロピレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、テトラメチロールプロパンテトラアクリレート、テトラメチロールプロパンテトラメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、１、６−ヘキサンジオールジアクリレート、１、６−ヘキサンジオールジメタクリレート、カルドエポキシジアクリレートなどのモノマー、オリゴマー類；多価アルコール類と１塩基酸または多塩基酸を縮合して得られるポリエステルプレポリマーに（メタ）アクリル酸を反応して得られるポリエステル（メタ）アクリレート、ポリオール基と２個のイソシアネート基を有する化合物を反応させた後、（メタ）アクリル酸を反応して得られるポリウレタン（メタ）アクリレート；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールまたはクレゾールノボラック型エポキシ樹脂、レゾール型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ポリカルボキシ酸ポリグリシジルエステル、ポリオールポリグリシジルエステル、脂肪族または指環式エポキシ樹脂、アミンエポキシ樹脂、ジヒドロキシベンゼン型エポキシ樹脂などのエポキシ樹脂と（メタ）アクリル酸を反応して得られるエポキシ（メタ）アクリレート樹脂などを挙げることができる。さらに、上記エポキシ（メタ）アクリレート樹脂に多塩基酸無水物を反応させた樹脂を使用することができる。これら光重合性化合物は、カルド系樹脂であってもよい。 The photosensitive resin composition of the present invention can contain a polymer compound that is soluble in a solvent or an alkaline aqueous solution alone or a mixture of these polymer compounds and a photopolymerizable compound having an ethylenically unsaturated bond. Here, as an example of a polymer compound soluble in a solvent or an alkaline aqueous solution or a photopolymerizable compound having an ethylenic unsaturated bond, specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, fumaric acid, Monomethyl acid, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate , Acrylic amide, methacrylic amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl Acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethyl Roll propane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, di Monomers, oligomers such as pentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate; polyhydric alcohols and monobasic acid or polybasic acid Obtained by reacting the resulting polyester prepolymer with (meth) acrylic acid Polyester (meth) acrylate, polyurethane (meth) acrylate obtained by reacting a compound having a polyol group and two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type Epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or finger ring epoxy resin, amine Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as an epoxy resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Furthermore, a resin obtained by reacting a polybasic acid anhydride with the epoxy (meth) acrylate resin can be used. These photopolymerizable compounds may be cardo resins.
特に溶剤またはアルカリ水溶液に可溶性である高分子は、透明性が高い高分子重合体であって、現像液（溶剤またはアルカリ水溶液）に可溶性のものである。このような高分子重合体としては、熱硬化性樹脂、熱可塑性樹脂、感光性樹脂などを挙げることができ、単独または２種以上の混合物として使用される。特に耐熱性、耐溶剤性、耐薬品性に優れたものが好ましい。 In particular, a polymer that is soluble in a solvent or an aqueous alkali solution is a polymer having high transparency and is soluble in a developer (solvent or aqueous alkali solution). Examples of such a high molecular polymer include a thermosetting resin, a thermoplastic resin, a photosensitive resin, and the like, and they are used alone or as a mixture of two or more. In particular, those excellent in heat resistance, solvent resistance and chemical resistance are preferred.
エチレン性不飽和結合を有する化合物としては、露光感度及び効果後の様々な耐性の面から多作用性（メタ）アクリル系モノマーを使用することが有利であることができる。 As the compound having an ethylenically unsaturated bond, it may be advantageous to use a multi-functional (meth) acrylic monomer in terms of exposure sensitivity and various resistances after the effect.
一方、感光性樹脂組成物は、一例としてカラーフィルタやブラックマトリックス形成用レジストに適用するために顔料または着色剤を含有することができる。 On the other hand, the photosensitive resin composition can contain a pigment or a colorant for application to a color filter or a resist for forming a black matrix, for example.
着色剤としては、レッド、グリーン、ブルーと紺色混合系のシアン、マゼンダ、イエロ、ブラック顔料を挙げることができる。顔料としては、Ｃ．Ｉ．ピグメントイエロ１２、１３、１４、１７、２０、２４、５５、８３、８６、９３、１０９、１１０、１１７、１２５、１３７、１３９、１４７、１４８、１５３、１５４、１６６、１６８、Ｃ．Ｉ．ピグメントオレンジ３６、４３、５１、５５、５９、６１、Ｃ．Ｉ．ピグメントレッド９、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９、３０、３７、４０、５０、Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：４、１５：６、２２、６０、６４、Ｃ．Ｉ．ピグメントグリーン７、３６、Ｃ．Ｉ．ピグメントブラウン２３、２５、２６、Ｃ．Ｉ．ピグメントブラック７、及びチタンブラックなどを挙げることができる。 Examples of the colorant include red, green, blue and amber mixed cyan, magenta, yellow and black pigments. Examples of the pigment include C.I. I. Pigment yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, C.I. I. And CI pigment black 7 and titanium black.
本発明によれば、このような感光性樹脂組成物からカラムスペーサ、ブラックマトリックス、カラーフィルタ、有機絶縁膜を有する基板、これをコーティングして形成された膜を有する基材を提供し、ここでの膜は、ワープロ、コンピュータ、テレビ、プラズマディスプレイパネル、液晶表示装置に使用される偏光板の表面、サングラスレンズ、度数があるメガネレンズ、カメラ用ファインダーレンズ、計器のカバー、自動車のガラス、電車のガラス、光輝度向上膜、または光導波路膜として使用されるものであることができる。 According to the present invention, a column spacer, a black matrix, a color filter, a substrate having an organic insulating film from such a photosensitive resin composition, and a substrate having a film formed by coating the substrate are provided, Film of word processor, computer, TV, plasma display panel, polarizing plate surface used in liquid crystal display device, sunglasses lens, power glasses lens, camera finder lens, instrument cover, automobile glass, train It can be used as glass, a light brightness enhancement film, or an optical waveguide film.
このような感光性組成物を使用してパターンを形成する方法としては、基板または基板上に感光性樹脂組成物を塗布し、塗布された感光性組成物層から溶剤など揮発成分を除去し、フォトマスクを介して揮発成分が除去された層を露光した後、現像する方法を挙げることができる。これより、本発明では、このような硬化過程を経て得られる硬化膜を提供する。 As a method of forming a pattern using such a photosensitive composition, a photosensitive resin composition is applied on a substrate or a substrate, volatile components such as a solvent are removed from the applied photosensitive composition layer, An example is a method in which a layer from which a volatile component has been removed is exposed through a photomask and then developed. Thus, the present invention provides a cured film obtained through such a curing process.
基板としては、例えば、ガラス基板、シリコン基板、ポリカーボネート基板、ポリエステル基板、芳香族ポリアミド基板、ポリアミドイミド基板、ポリイミド基板、アルミニウム基板、ＧａＡｓ基板などの表面が平坦な基板などを挙げることができる。 Examples of the substrate include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a substrate having a flat surface such as a GaAs substrate, and the like.
基板上に感光性樹脂組成物を塗布する方法としては、限定されるものではないが、一例としてスピンコーティング法、キャスティング法、ロール塗布法、スリット＆スピンコーティング法、スピンレスコーターなどのコーターを使用して塗布するなどの公知された塗布方法などで基板などの上に塗布することができる。 The method for applying the photosensitive resin composition on the substrate is not limited. For example, a coater such as a spin coating method, a casting method, a roll coating method, a slit & spin coating method, or a spinless coater is used. It can apply | coat on a board | substrate etc. by the well-known application | coating methods etc. which apply | coat.
次に、溶剤などの揮発成分を加熱によって揮発させることができる。このようにして、基板などの上に感光性組成物の固形分よりなる層が形成される。次に、感光性組成物の固形分よりなる層を露光し、例えば、フォトマスクを介して選択的に活性エネルギー線を照射することができる。露光光源としては、通常、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、金属ハロゲンランプなどが適当である。また、レーザー光線なども露光用活性エネルギー線として使用することができる。その他、電子線、α線、β線、γ線、Ｘ線、中性子線なども使用可能である。活性エネルギー線は、フォトマスクを介して照射され、ここで、フォトマスクは、例えば、ガラス板の表面に活性エネルギー線を遮蔽する遮光層が設けられたものである。ガラス板中の遮光層が設けられていない部分は、活性エネルギー線が透過する透光部であり、この透光部のパターンによるパターンで感光性組成物が露光され、活性エネルギー線が照射されない未照射領域と活性エネルギー線が照射された照射領域が生ずる。 Next, volatile components such as a solvent can be volatilized by heating. Thus, the layer which consists of solid content of a photosensitive composition is formed on a board | substrate etc. Next, the layer which consists of solid content of a photosensitive composition can be exposed, and an active energy ray can be selectively irradiated through a photomask, for example. As the exposure light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halogen lamp, or the like is usually suitable. A laser beam or the like can also be used as the exposure active energy ray. In addition, electron beams, α rays, β rays, γ rays, X rays, neutron rays and the like can also be used. The active energy ray is irradiated through a photomask. Here, the photomask has, for example, a light shielding layer that shields the active energy ray on the surface of a glass plate. The portion of the glass plate where the light-shielding layer is not provided is a translucent part through which active energy rays are transmitted, and the photosensitive composition is exposed with a pattern based on the pattern of the translucent part and is not irradiated with active energy rays. An irradiation region and an irradiation region irradiated with active energy rays are generated.
このように露光を行った基板は、一例として、薄いアルカリ水溶液で現像する。現像を行うときには、例えば、露光後の感光性組成物層を薄いアルカリ水溶液と接触させることができ、具体的には、その表面上に感光性組成物層が形成された状態の基板を薄いアルカリ水溶液に浸漬するか、薄いアルカリ水溶液をシャワー形態で噴き出すことができる。薄いアルカリ水溶液としては、例えば、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムヒドロキシド、有機アミンなどのアルカリ性化合物の水溶液などを挙げることができる。現像によって感光性組成物層中の活性エネルギー線が照射されていない未照射領域は除去される。一方、活性エネルギー線の照射領域は、そのまま残ってパターンを構成する。 The substrate thus exposed is developed with a thin alkaline aqueous solution as an example. When developing, for example, the photosensitive composition layer after exposure can be brought into contact with a thin alkaline aqueous solution. Specifically, a substrate having a photosensitive composition layer formed on the surface thereof is thinly alkaline. It can be immersed in an aqueous solution or a thin alkaline aqueous solution can be ejected in the form of a shower. Examples of the thin alkaline aqueous solution include aqueous solutions of alkaline compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and organic amines. The unirradiated area that is not irradiated with the active energy rays in the photosensitive composition layer is removed by development. On the other hand, the irradiation region of the active energy ray remains as it is to form a pattern.
このように現像を行った基板は、通常、水洗して乾燥させることによって、目的するパターンを得ることができる。 The substrate thus developed is usually washed with water and dried to obtain the desired pattern.
以下、本発明を実施例によりさらに詳細に説明する。しかし、これらの実施例は、本発明を例示的に説明するためのものであって、本発明の範囲がこれら実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only and the scope of the present invention is not limited by these examples.
［実施例１］
［１段階：２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）の合成］
窒素雰囲気下で２−（ｏ−トルイル）酢酸（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｉｃ ａｃｉｄ）（１００ｇ）とチオニルクロライド（２３７ｇ）を入れ、温度を徐々に上げて９５℃で４時間還流させた。４時間後、同一温度で蒸留装置を設置し、常圧でチオニルクロライドを蒸留した。反応器の温度を常温に冷却した後、真空蒸留装置を利用して残余のチオニルクロライドを除去した。残留の粘性液体を石油エーテルに沈澱、濾過し、黄色の結晶を得た。黄色の結晶は、１１２ｇで、収率は７１％であった。
ＧＣ Ｐｕｒｉｔｙ：９９％
ＧＣ ＭＡＳＳ：ｍ／ｚ＝１６８．０３
[Step 1: Synthesis of 2- (o-tolyl) acetyl chloride]
Under a nitrogen atmosphere, 2- (o-tolyl) acetic acid (100 g) and thionyl chloride (237 g) were added, the temperature was gradually raised, and the mixture was refluxed at 95 ° C. for 4 hours. After 4 hours, a distillation apparatus was installed at the same temperature, and thionyl chloride was distilled at normal pressure. After cooling the reactor temperature to room temperature, the remaining thionyl chloride was removed using a vacuum distillation apparatus. The residual viscous liquid was precipitated in petroleum ether and filtered to obtain yellow crystals. The yellow crystals were 112 g and the yield was 71%.
GC Purity: 99%
GC MASS: m / z = 168.03
［２段階：１−（９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル）−２−（ｏ−トルイル）エタノン（１−（９−ｅｔｈｙｌ−６−（２−ｍｅｔｈｙｌｂｅｎｚｏｙｌ）−９Ｈ−ｃａｒｂａｚｏｌ−３−ｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下でＮ−エチルカルバゾール２０．０ｇと乾燥したＣＨ２Ｃｌ２ １２０ｍｌを加えて溶かした。反応物を０℃に冷却した後、ＡｌＣｌ３ １４．０７ｇをゆっくり投入した。これにｏ−トルイルクロリド（ｏ−ｔｏｌｕｏｙｌ ｃｈｌｏｒｉｄｅ） １６．３１ｇを内部温度５℃以下でゆっくり滴加した。反応温度を常温にして約５時間撹拌した後、内部温度を０℃以下に下げ、ＡｌＣｌ３ １４．０７ｇをゆっくり投入した。この反応物に２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ） １７．７９ｇを内部温度５℃以下でゆっくり滴加した。反応温度を常温にして約８時間撹拌した後、内部温度を０℃以下に下げ、氷水３００ｍｌに反応器の溶液をゆっくり加え、１時間撹拌後、層分離し、さらに１％ＮａＯＨ ２００ｍｌで中和、洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、回転蒸発器で溶媒を除去し、エチルアセテートとメチレンクロライドに再結晶し、収率７７％の白色固体３５ｇを得た。
[Two steps: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (o-toluyl) ethanone (1- (9-ethyl-6- (2- Synthesis of methylbenzoyl) -9H-carbazol-3-yl) -2- (o-tolyl) ethanol)
Under a nitrogen atmosphere, 20.0 g of N-ethylcarbazole and 120 ml of dried CH 2 Cl 2 were added and dissolved. After the reaction was cooled to 0 ° C., 14.07 g of AlCl 3 was slowly added. To this, 16.31 g of o-toluoyl chloride was slowly added dropwise at an internal temperature of 5 ° C. or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature was lowered to 0 ° C. or lower, and 14.07 g of AlCl 3 was slowly added. To this reaction product, 17.79 g of 2- (o-tolyl) acetyl chloride was slowly added dropwise at an internal temperature of 5 ° C. or less. After stirring the reaction temperature at room temperature for about 8 hours, lower the internal temperature to below 0 ° C., slowly add the reactor solution to 300 ml of ice water, stir for 1 hour, separate the layers, and neutralize with 200 ml of 1% NaOH. After washing, the organic layer was dried with MgSO 4 , the solvent was removed by a rotary evaporator, and recrystallized from ethyl acetate and methylene chloride to obtain 35 g of a white solid having a yield of 77%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：１．３７（ｔ、３Ｈ）、２．３４（ｓ、３Ｈ）、２．４８（ｓ、３Ｈ）、４．１４（ｓ、２Ｈ）、４．５１（ｑ、２Ｈ）、７．１４〜７．１６（ｍ、２Ｈ）、７．３４〜７．３６（ｍ、２Ｈ）、７．４０（ｍ、２Ｈ）、７．５２〜７．６６（ｍ、４Ｈ）、７．８３（ｄ、１Ｈ）、７．９８（ｄ、１Ｈ）、８．６５（ｓ、１Ｈ）、８．７４（ｓ１Ｈ） 1 H-NMR (d, ppm) CDCl 3 : 1.37 (t, 3H), 2.34 (s, 3H), 2.48 (s, 3H), 4.14 (s, 2H), 4. 51 (q, 2H), 7.14 to 7.16 (m, 2H), 7.34 to 7.36 (m, 2H), 7.40 (m, 2H), 7.52 to 7.66 ( m, 4H), 7.83 (d, 1H), 7.98 (d, 1H), 8.65 (s, 1H), 8.74 (s1H)
［３段階：（Ｅ）−１−（９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル）−２−（ヒドロキシイミノ）−２−（ｏ−トルイル）エタノン（（Ｅ）−１−（９−ｅｔｈｙｌ−６−（２−ｍｅｔｈｙｌｂｅｎｚｏｙｌ）−９Ｈ−ｃａｒｂａｚｏｌ−３−ｙｌ）−２−（ｈｙｄｒｏｘｙｉｍｉｎｏ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
反応器に１８０ｍＬのジメチルホルムアミドを入れ、上記２段階で収得した化合物３０ｇを添加して溶かした。反応水の温度を１５℃でソジウムメトキシド１．８２ｇをゆっくり添加した。この反応物にイソペンチルニトリト８．１３ｇを内部温度１５℃に維持しながらゆっくり滴加した。その後、２５℃まで昇温した後、８時間撹拌した。この反応物に溶媒エチルアセテート２００ｍＬと蒸留水２００ｍＬを添加して水洗した。２回追加水洗し、ジメチルホルムアミドを除去した後、飽和炭酸カルシウムで中和洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、減圧蒸留し、液状の化合物を得た。この液状の化合物にメタノールとメチレンクロライドを加え、再結晶した。薄い黄色の結晶２０ｇを得た。収率は、６３％であった。
[Three stages: (E) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (hydroxyimino) -2- (o-toluyl) ethanone (( E) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (hydroxyimino) -2- (o-tolyl) ethanol)]
180 mL of dimethylformamide was placed in the reactor, and 30 g of the compound obtained in the above two steps was added and dissolved. The reaction water temperature was 15 ° C. and 1.82 g of sodium methoxide was slowly added. To this reaction, 8.13 g of isopentylnitrite was slowly added dropwise while maintaining an internal temperature of 15 ° C. Then, after heating up to 25 degreeC, it stirred for 8 hours. To this reaction product, 200 mL of solvent ethyl acetate and 200 mL of distilled water were added and washed with water. After washing twice with additional water to remove dimethylformamide and neutralizing and washing with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Methanol and methylene chloride were added to this liquid compound and recrystallized. 20 g of pale yellow crystals were obtained. The yield was 63%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＤＭＳＯｄ６：１．２９（ｔ、３Ｈ）、２．４４（ｓ、６Ｈ）、４．５３（ｑ、２Ｈ）、７．１４〜７．１６（ｍ、２Ｈ）、７．３４〜７．３６（ｍ、２Ｈ）、７．４０（ｍ、２Ｈ）、７．５２〜７．６６（ｍ、４Ｈ）、７．８３（ｄ、１Ｈ）、７．９８（ｄ、１Ｈ）、８．６０（ｓ、１Ｈ）、８．７４（ｓ１Ｈ）、１２．５（ｓ、１Ｈ、−ＯＨ） 1 H-NMR (d, ppm) DMSOd 6 : 1.29 (t, 3H), 2.44 (s, 6H), 4.53 (q, 2H), 7.14 to 7.16 (m, 2H) ), 7.34 to 7.36 (m, 2H), 7.40 (m, 2H), 7.52 to 7.66 (m, 4H), 7.83 (d, 1H), 7.98 ( d, 1H), 8.60 (s, 1H), 8.74 (s1H), 12.5 (s, 1H, -OH)
［４段階：（Ｅ）−２−（アセトキシイミノ）−１−（９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル）−２−（ｏ−トルイル）エタノン（（Ｅ）−２−（ａｃｅｔｏｘｙｉｍｉｎｏ）−１−（９−ｅｔｈｙｌ−６−（２−ｍｅｔｈｙｌｂｅｎｚｏｙｌ）−９Ｈ−ｃａｒｂａｚｏｌ−３−ｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下で内部温度を０℃以下に下げ、上記３段階で収得した化合物２０ｇ、メチレンクロライド１２０ｍＬとトリエチレンアミン４．４０ｇを添加し、アセチルクロライド３．４２ｇをメチレンクロライド１０ｍＬに溶解した溶液をゆっくり加えた。内部温度を１０℃に上げた後、３時間撹拌した。反応溶液に水を数回添加し、有機層を洗浄し、減圧蒸留して得られた固体化合物をエチルアセテートとメチレンクロライドを加えて再結晶した。濾過し、収率７８％の薄い黄色の固体１７ｇを得た。上記薄い黄色の結晶は、目的物である化合物（化学式３）であることが確認された。分析結果を以下に整理した。
[Step 4: (E) -2- (acetoxyimino) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (o-toluyl) ethanone (( E) 2- (acetoxyimino) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (o-tolyl) ethanol)
Under a nitrogen atmosphere, the internal temperature was lowered to 0 ° C. or lower, 20 g of the compound obtained in the above three steps, 120 mL of methylene chloride and 4.40 g of triethyleneamine were added, and a solution in which 3.42 g of acetyl chloride was dissolved in 10 mL of methylene chloride. Slowly added. After raising the internal temperature to 10 ° C., the mixture was stirred for 3 hours. Water was added to the reaction solution several times, the organic layer was washed, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding ethyl acetate and methylene chloride. Filtration gave 17 g of a pale yellow solid with a yield of 78%. The pale yellow crystals were confirmed to be the target compound (Chemical Formula 3). The analysis results are summarized below.
分析結果
（１）融点：１７２．８℃
（２）１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：１．２９（ｔ、３Ｈ）、２．２８（ｓ、３Ｈ）、２．４８（ｓ、６Ｈ）、４．５３（ｑ、２Ｈ）、７．１４〜７．１６（ｍ、２Ｈ）、７．３４〜７．３６（ｍ、２Ｈ）、７．４０（ｍ、２Ｈ）、７．５２〜７．６６（ｍ、４Ｈ）、７．８３（ｄ、１Ｈ）、７．９８（ｄ、１Ｈ）、８．６５（ｓ、１Ｈ）、８．７４（ｓ１Ｈ）
（３）ＵＶスペクトル測定（メチレンクロライド）
λｍａｘ：２４２、３３２
Analysis result (1) Melting point: 172.8 ° C
(2) 1 H-NMR (d, ppm) CDCl 3 : 1.29 (t, 3H), 2.28 (s, 3H), 2.48 (s, 6H), 4.53 (q, 2H) 7.14 to 7.16 (m, 2H), 7.34 to 7.36 (m, 2H), 7.40 (m, 2H), 7.52 to 7.66 (m, 4H), 7 .83 (d, 1H), 7.98 (d, 1H), 8.65 (s, 1H), 8.74 (s1H)
(3) UV spectrum measurement (methylene chloride)
λmax: 242, 332
［実施例２］
［１段階：２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）の合成］
実施例１の１段階と同様の方法で２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）を合成した。
[Step 1: Synthesis of 2- (o-tolyl) acetyl chloride]
2- (o-tolyl) acetyl chloride (2- (o-tolyl) acetyl chloride) was synthesized in the same manner as in Step 1 of Example 1.
［２段階：１−（９−エチル−６−（チオフェン−２−カルボニル）−９Ｈ−カルバゾール−３−イル）−２−（ｏ−トルイル）エタノン（１−（９−ｅｔｈｙｌ−６−（ｔｈｉｏｐｈｅｎｅ−２−ｃａｒｂｏｎｙｌ）−９Ｈ−ｃａｒｂａｚｏｌ−３−ｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下でＮ−エチルカルバゾール３０．０ｇと乾燥したＣＨ２Ｃｌ２ １８０ｍｌを加えて溶かした。反応物を０℃に冷却した後、ＡｌＣｌ３ ２１．１ｇをゆっくり投入した。これに２−チオニルクロリド（２−ｔｈｙｏｎｙｌ ｃｈｌｏｒｉｄｅ） ２３．１９ｇを内部温度５℃以下でゆっくり滴加した。反応温度を常温にして約５時間撹拌した後、内部温度を０℃以下に下げ、ＡｌＣｌ３ ２１．１ｇをゆっくり投入した。この反応物に２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ） ２６．６８ｇを内部温度５℃以下でゆっくり滴加した。反応温度を常温にして約８時間撹拌した後、内部温度を０℃以下に下げ、氷水５００ｍｌに反応器の溶液をゆっくり加え、１時間撹拌後、層分離し、さらに１％ＮａＯＨ ５００ｍｌで中和、洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、回転蒸発器で溶媒を除去し、メタノールとメチレンクロライドに再結晶し、収率７６％の薄い黄色の固体５１ｇを得た。
[Two steps: 1- (9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl) -2- (o-toluyl) ethanone (1- (9-ethyl-6- (thiophene) Synthesis of 2-carbonyl) -9H-carbazol-3-yl) -2- (o-tolyl) ethanol)
Under a nitrogen atmosphere, 30.0 g of N-ethylcarbazole and 180 ml of dried CH 2 Cl 2 were added and dissolved. After the reaction was cooled to 0 ° C., 21.1 g of AlCl 3 was slowly added. To this, 23.19 g of 2-thionyl chloride was slowly added dropwise at an internal temperature of 5 ° C. or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature was lowered to 0 ° C. or lower, and 21.1 g of AlCl 3 was slowly added. To this reaction product, 26.68 g of 2- (o-tolyl) acetyl chloride was slowly added dropwise at an internal temperature of 5 ° C. or less. After stirring the reaction temperature at room temperature for about 8 hours, lower the internal temperature to below 0 ° C., slowly add the reactor solution to 500 ml of ice water, stir for 1 hour, separate the layers, and neutralize with 500 ml of 1% NaOH. After washing, the organic layer was dried with MgSO 4 , the solvent was removed by a rotary evaporator, and recrystallized from methanol and methylene chloride to obtain 51 g of a pale yellow solid with a yield of 76%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：１．２８（ｔ、３Ｈ）、２．３２（ｓ、３Ｈ）、４．１６（ｓ、２Ｈ）、４．５３（ｑ、２Ｈ）、７．１４（ｍ、１Ｈ）、７．２７（ｔ、１Ｈ）、７．３４（ｄ、１Ｈ）、７．４２（ｍ、２Ｈ）、７．６１〜７．６６（ｍ、２Ｈ）、７．９２（ｄ、１Ｈ）、７．９８（ｄ、１Ｈ）、８．１３（ｄ、１Ｈ）、８．６４（ｓ、１Ｈ）、８．８４（ｓ、１Ｈ） 1 H-NMR (d, ppm) CDCl 3 : 1.28 (t, 3H), 2.32 (s, 3H), 4.16 (s, 2H), 4.53 (q, 2H), 7. 14 (m, 1H), 7.27 (t, 1H), 7.34 (d, 1H), 7.42 (m, 2H), 7.61 to 7.66 (m, 2H), 7.92 (D, 1H), 7.98 (d, 1H), 8.13 (d, 1H), 8.64 (s, 1H), 8.84 (s, 1H)
［３段階：（Ｅ）−１−（９−エチル−６−（チオフェン−２−カルボニル）−９Ｈ−カルバゾール−３−イル）−２−（ヒドロキシイミノ）−２−（ｏ−トルイル）エタノン（（Ｅ）−１−（９−ｅｔｈｙｌ−６−（ｔｈｉｏｐｈｅｎｅ−２−ｃａｒｂｏｎｙｌ）−９Ｈ−ｃａｒｂａｚｏｌ−３−ｙｌ）−２−（ｈｙｄｒｏｘｙｉｍｉｎｏ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
反応器に１８０ｍＬのジメチルホルムアミドを入れ、上記２段階で収得した化合物４０ｇを添加して溶かした。反応水の温度を１５℃でソジウムメトキシド２．４６ｇをゆっくり添加した。この反応物にイソペンチルニトリト１１．０３ｇを内部温度１５℃に維持しながらゆっくり滴加したた。滴加後、２５℃まで昇温した後、８時間撹拌した。この反応物に溶媒エチルアセテート２００ｍＬと蒸留水２００ｍＬを添加して水洗した。２回追加水洗し、ジメチルホルムアミドを除去した後、飽和炭酸カルシウムで中和洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、減圧蒸留し、液状の化合物を得た。この液状の化合物にエタノールとメチレンクロライドを加えて再結晶した。黄色の結晶３５ｇを得た。収率は８２％であった。
[Three stages: (E) -1- (9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl) -2- (hydroxyimino) -2- (o-toluyl) ethanone ( Synthesis of (E) -1- (9-ethyl-6- (thiophene-2-carbonyl) -9H-carbazol-3-yl) -2- (hydroxyimino) -2- (o-tolyl) ethanol)
180 mL of dimethylformamide was placed in the reactor, and 40 g of the compound obtained in the above two steps was added and dissolved. The reaction water temperature was 15 ° C., and 2.46 g of sodium methoxide was slowly added. To this reaction product, 11.03 g of isopentylnitrite was slowly added dropwise while maintaining the internal temperature at 15 ° C. After the dropwise addition, the mixture was heated to 25 ° C. and stirred for 8 hours. To this reaction product, 200 mL of solvent ethyl acetate and 200 mL of distilled water were added and washed with water. After washing twice with additional water to remove dimethylformamide and neutralizing and washing with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Ethanol and methylene chloride were added to this liquid compound for recrystallization. 35 g of yellow crystals were obtained. The yield was 82%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＤＭＳＯｄ６：１．３０（ｔ、３Ｈ）、２．４６（ｓ、３Ｈ）、４．５３（ｑ、２Ｈ）、７．２３〜７．２７（ｍ、４Ｈ）、７．５６（ｄ、１Ｈ）、７．７３（ｍ、２Ｈ）、７．９２（ｄ、１Ｈ）、７．９８（ｄ、１Ｈ）、８．０６（ｄ、１Ｈ）、８．１４（ｄ、１Ｈ）、８．６２（ｓ、１Ｈ）、８．８５（ｓ、１Ｈ）、１２．１（ｓ、１Ｈ、−ＯＨ） 1 H-NMR (d, ppm) DMSOd 6 : 1.30 (t, 3H), 2.46 (s, 3H), 4.53 (q, 2H), 7.23 to 7.27 (m, 4H ), 7.56 (d, 1H), 7.73 (m, 2H), 7.92 (d, 1H), 7.98 (d, 1H), 8.06 (d, 1H), 8.14 (D, 1H), 8.62 (s, 1H), 8.85 (s, 1H), 12.1 (s, 1H, -OH)
［４段階：（Ｅ）−２−（アセトキシイミノ）−１−（９−エチル−６−（チオフェン−２−カルボニル）−９Ｈ−カルバゾール−３−イル）−２−（ｏ−トルイル）エタノン（（Ｅ）−２−（ａｃｅｔｏｘｙｉｍｉｎｏ）−１−（９−ｅｔｈｙｌ−６−（ｔｈｉｏｐｈｅｎｅ−２−ｃａｒｂｏｎｙｌ）−９Ｈ−ｃａｒｂａｚｏｌ−３−ｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気の下で内部温度を０℃以下に下げ、上記３段階で収得した化合物３０ｇ、メチレンクロライド１８０ｍＬとトリエチレンアミン６．７０ｇを添加し、アセチルクロライド５．２０ｇをメチレンクロライド１０ｍＬに溶解した溶液をゆっくり加えた。内部温度を１０℃に上げた後、４時間撹拌した。反応溶液に水を数回添加し、有機層を洗浄し、減圧蒸留して得られた固体化合物をエチルアセテートとメタノールを加えて再結晶した。濾過し、薄い黄色の固体を収率８０％、２６ｇを得た。上記薄い黄色の結晶は、目的した化学式９の化合物であることを確認した。分析結果は、下記の通りである。
[Step 4: (E) -2- (acetoxyimino) -1- (9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl) -2- (o-toluyl) ethanone ( Synthesis of (E) -2- (acetoxyimino) -1- (9-ethyl-6- (thiophene-2-carbonyl) -9H-carbazol-3-yl) -2- (o-tolyl) ethanol)
A solution in which 30 g of the compound obtained in the above three steps, 180 mL of methylene chloride and 6.70 g of triethyleneamine were added, and 5.20 g of acetyl chloride was dissolved in 10 mL of methylene chloride under an atmosphere of nitrogen reduced to 0 ° C. or lower. Was added slowly. After raising the internal temperature to 10 ° C., the mixture was stirred for 4 hours. Water was added to the reaction solution several times, the organic layer was washed, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding ethyl acetate and methanol. Filtration gave a pale yellow solid, yield 80%, 26 g. The pale yellow crystals were confirmed to be the target compound of Formula 9. The analysis results are as follows.
分析結果
（１）融点：１７６．４℃
（２）１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：１．２９（ｔ、３Ｈ）、２．２７（ｓ、３Ｈ）、２．４８（ｓ、３Ｈ）、４．５３（ｑ、２Ｈ）、７．２３〜７．２８（ｍ、４Ｈ）、７．５６（ｄ、１Ｈ）、７．７２（ｍ、２Ｈ）、７．９２（ｄ、１Ｈ）、８．０１（ｄ、１Ｈ）、８．１０（ｍ、２Ｈ）、８．６０（ｓ、１Ｈ）、８．８５（ｓ、１Ｈ）
（３）ＵＶスペクトル測定（メチレンクロライド）
λｍａｘ：２７８、３３４
Analysis result (1) Melting point: 176.4 ° C
(2) 1 H-NMR (d, ppm) CDCl 3 : 1.29 (t, 3H), 2.27 (s, 3H), 2.48 (s, 3H), 4.53 (q, 2H) 7.23-7.28 (m, 4H), 7.56 (d, 1H), 7.72 (m, 2H), 7.92 (d, 1H), 8.01 (d, 1H), 8.10 (m, 2H), 8.60 (s, 1H), 8.85 (s, 1H)
(3) UV spectrum measurement (methylene chloride)
λmax: 278, 334
［実施例３］
［１段階：２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）の合成］
実施例１の１段階と同様の方法で２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）を合成した。
[Step 1: Synthesis of 2- (o-tolyl) acetyl chloride]
2- (o-tolyl) acetyl chloride (2- (o-tolyl) acetyl chloride) was synthesized in the same manner as in Step 1 of Example 1.
［２段階：１−（４−（フェニルチオ）フェニル）−２−ｏ−トルイルエタノン（１−（４−（ｐｈｅｎｙｌｔｈｉｏ）ｐｈｅｎｙｌ）−２−ｏ−ｔｏｌｙｌｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下でビフェニルスルファイド９０．０ｇと乾燥したＣＨ２Ｃｌ２ ５４０ｍｌを加えて溶かした。反応物を０℃に冷却した後、ＡｌＣｌ３ ６６．３４ｇをゆっくり投入した。これに２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ） ８３．９ｇを内部温度５℃以下でゆっくり滴加した。反応温度を常温にして約５時間撹拌した後、内部温度を０℃以下に下げ、氷水７００ｍｌに反応器の溶液をゆっくり加え、１時間撹拌した後、層分離し、さらに１％ＮａＯＨ７００ｍｌで中和、洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、回転蒸発器で溶媒を除去し、エチルアセテートに再結晶し、収率９１％の白色固体１４０ｇを得た。
[Two steps: Synthesis of 1- (4- (phenylthio) phenyl) -2-o-toluylethanone (1- (4- (phenylthio) phenyl) -2-o-tolylethanone)]
Under a nitrogen atmosphere, 90.0 g of biphenyl sulfide and 540 ml of dried CH 2 Cl 2 were added and dissolved. After the reaction was cooled to 0 ° C., 66.34 g of AlCl 3 was slowly added. To this, 83.9 g of 2- (o-tolyl) acetyl chloride (2- (o-tolyl) acetyl chloride) was slowly added dropwise at an internal temperature of 5 ° C. or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature is lowered to 0 ° C. or lower, the reactor solution is slowly added to 700 ml of ice water, the mixture is stirred for 1 hour, the layers are separated, and neutralized with 700 ml of 1% NaOH. After washing, the organic layer was dried with MgSO 4 , the solvent was removed by a rotary evaporator and recrystallized in ethyl acetate to obtain 140 g of a white solid having a yield of 91%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：２．２３（ｓ、３Ｈ）、４．２２（ｓ、２Ｈ）、７．０８〜７．２１（ｍ、７Ｈ）、７．３９〜７．４０（ｍ、２Ｈ）、７．４９〜７．５１（ｍ、２Ｈ）、７．８７（ｄ、２Ｈ） 1 H-NMR (d, ppm) CDCl 3 : 2.23 (s, 3H), 4.22 (s, 2H), 7.08 to 7.21 (m, 7H), 7.39 to 7.40 (M, 2H), 7.49-7.51 (m, 2H), 7.87 (d, 2H)
［３段階：（Ｅ）−２−（ヒドロキシイミノ）−１−（４−（フェニルチオ）フェニル）−２−ｏ−トルイルエタノン（（Ｅ）−２−（ｈｙｄｒｏｘｙｉｍｉｎｏ）−１−（４−（ｐｈｅｎｙｌｔｈｉｏ）ｐｈｅｎｙｌ）−２−ｏ−ｔｏｌｙｌｅｔｈａｎｏｎｅ）の合成］
反応器に５４０ｍＬのジメチルホルムアミドを入れ、上記２段階で収得した化合物９０ｇを添加して溶かした。反応物の温度を１５℃でソジウムメトキシド７．６３ｇをゆっくり添加した。この反応物にイソペンチルニトリト３６．４２ｇを内部温度１５℃に維持しながらゆっくり滴加した。滴加後、２５℃まで昇温した後、８時間撹拌した。この反応物に溶媒エチルアセテート７００ｍＬと蒸留水７００ｍＬを添加し、水洗した。２回追加水洗し、ジメチルホルムアミドを除去した後、飽和炭酸カルシウムで中和洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、減圧蒸留し、液状の化合物を得た。この液状の化合物にヘキサンとメチレンクロライドを加えて再結晶した。薄い黄色の結晶７０ｇを得、収率は７１％であった。
[Three steps: (E) -2- (hydroxyimino) -1- (4- (phenylthio) phenyl) -2-o-toluylethanone ((E) -2- (hydroxyimino) -1- (4- (phenylthio)) phenyl) -2-o-tolylethanone)]
540 mL of dimethylformamide was added to the reactor, and 90 g of the compound obtained in the above two steps was added and dissolved. At a temperature of 15 ° C., 7.63 g of sodium methoxide was slowly added. To this reaction, 36.42 g of isopentylnitrite was slowly added dropwise while maintaining an internal temperature of 15 ° C. After the dropwise addition, the mixture was heated to 25 ° C. and stirred for 8 hours. To this reaction product, 700 mL of solvent ethyl acetate and 700 mL of distilled water were added and washed with water. After washing twice with additional water to remove dimethylformamide and neutralizing and washing with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Hexane and methylene chloride were added to this liquid compound and recrystallized. 70 g of pale yellow crystals were obtained, and the yield was 71%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：２．２５（ｓ、３Ｈ）、２．５３（ｓ、１Ｈ、−ＯＨ）、７．１９〜７．３２（ｍ、６Ｈ）、７．３８〜７．４２（ｍ、３Ｈ）、７．５１〜７．５３（ｍ、２Ｈ）、７．９５（ｄ、２Ｈ） 1 H-NMR (d, ppm) CDCl 3 : 2.25 (s, 3H), 2.53 (s, 1H, —OH), 7.19 to 7.32 (m, 6H), 7.38 to 7.42 (m, 3H), 7.51 to 7.53 (m, 2H), 7.95 (d, 2H)
［４段階：（Ｅ）−２−（アセトキシイミノ）−１−（４−（フェニルチオ）フェニル）−２−ｏ−トルイルエタノン（（Ｅ）−２−（ａｃｅｔｏｘｙｉｍｉｎｏ）−１−（４−（ｐｈｅｎｙｌｔｈｉｏ）ｐｈｅｎｙｌ）−２−ｏ−ｔｏｌｙｌｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下で内部温度を０℃以下に下げ、上記３段階で収得した化合物５０ｇ、メチレンクロライド３００ｍＬとトリエチレンアミン１５．０ｇを添加し、アセチルクロライド１１．６ｇをメチレンクロライド２０ｍＬに溶解した溶液をゆっくり加えた。内部温度を１０℃に上げた後、３時間撹拌した。反応溶液に水を数回添加し、有機層を洗浄し、減圧蒸留して得られた固体化合物を石油エーテルとメチレンクロライドを加えて再結晶した。濾過し、収率８９％の薄い黄色の固体５０ｇを得た。上記薄い黄色の結晶は、目的物である化学式１５の化合物であることを確認し、分析結果は下記の通りである。
[Four stages: (E) -2- (acetoxyimino) -1- (4- (phenylthio) phenyl) -2-o-toluylethanone ((E) -2- (acetoxyimino) -1- (4- (phenylthio)) phenyl) -2-o-tolylethanone)]
Reduce the internal temperature to 0 ° C. or lower under a nitrogen atmosphere, add 50 g of the compound obtained in the above three steps, 300 mL of methylene chloride and 15.0 g of triethyleneamine, and add a solution of 11.6 g of acetyl chloride in 20 mL of methylene chloride. Slowly added. After raising the internal temperature to 10 ° C., the mixture was stirred for 3 hours. Water was added several times to the reaction solution, the organic layer was washed, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding petroleum ether and methylene chloride. Filtration gave 50 g of a pale yellow solid with a yield of 89%. The pale yellow crystals were confirmed to be the target compound of Formula 15, and the analysis results are as follows.
分析結果
（１）融点：９５．１℃
（２）１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：２．０９（ｓ、３Ｈ）、２．２６（ｓ、３Ｈ）、７．１７〜７．２７（ｍ、５Ｈ）、７．３２（ｔ、１Ｈ）、７．４２（ｔ、３Ｈ）、７．５３〜７．５５（ｍ、２Ｈ）、８．０７（ｄ、２Ｈ）
（３）ＵＶスペクトル測定（メチレンクロライド）
λｍａｘ：２４８、３３４
Analysis result (1) Melting point: 95.1 ° C
(2) 1 H-NMR (d, ppm) CDCl 3 : 2.09 (s, 3H), 2.26 (s, 3H), 7.17 to 7.27 (m, 5H), 7.32 ( t, 1H), 7.42 (t, 3H), 7.53 to 7.55 (m, 2H), 8.07 (d, 2H)
(3) UV spectrum measurement (methylene chloride)
λmax: 248, 334
［実施例４］
［１段階：２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）の合成］
実施例１の１段階と同様の方法で２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ）を合成した。
[Step 1: Synthesis of 2- (o-tolyl) acetyl chloride]
2- (o-tolyl) acetyl chloride (2- (o-tolyl) acetyl chloride) was synthesized in the same manner as in Step 1 of Example 1.
［２段階：１−（４−（（４−（２−メチルベンゾイル）フェニル）チオ）フェニル）−２−（ｏ−トルイル）エタノン（１−（４−（（４−（２−ｍｅｔｈｙｌｂｅｎｚｏｙｌ）ｐｈｅｎｙｌ）ｔｈｉｏ）ｐｈｅｎｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下でビフェニルスルファイド５０．０ｇと乾燥したＣＨ２Ｃｌ２ ３００ｍｌを加えて溶かした。反応物を０℃に冷却した後、ＡｌＣｌ３ ３６．８７ｇをゆっくり投入した。これにｏ−トルイルクロリド（ｏ−ｔｏｌｕｙｌ ｃｈｌｏｒｉｄｅ） ４２．７４ｇをメチレンクロライド８０ｍＬに希釈し、ゆっくり滴加した。反応温度を常温にして８時間撹拌後、内部温度を０℃以下に下げ、ＡｌＣｌ３ ３６．８７ｇをゆっくり投入した。この反応物に２−（ｏ−トルイル）アセチルクロリド（２−（ｏ−ｔｏｌｙｌ）ａｃｅｔｙｌ ｃｈｌｏｒｉｄｅ） ４６．６２ｇをメチレンクロライド８０ｍＬに希釈し、内部温度５℃以下でゆっくり滴加した。反応温度を常温にして約５時間撹拌後、内部温度を０℃以下に下げ、氷水５００ｍｌに反応器の溶液をゆっくり加えて１時間撹拌後、層分離し、さらに１％ＮａＯＨ５００ｍｌで中和、洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、回転蒸発器で溶媒を除去し、メタノールに再結晶し、収率６４％の白色固体７５ｇを得た。
[Two steps: 1- (4-((4- (2-methylbenzoyl) phenyl) thio) phenyl) -2- (o-toluyl) ethanone (1- (4-((4- (2-methylbenzoyl) phenyl) ) Thio) phenyl) -2- (o-tolyl) ethanolone)]
Under a nitrogen atmosphere, 50.0 g of biphenyl sulfide and 300 ml of dried CH 2 Cl 2 were added and dissolved. After the reaction was cooled to 0 ° C., 36.87 g of AlCl 3 was slowly added. To this, 42.74 g of o-toluyl chloride was diluted in 80 mL of methylene chloride and slowly added dropwise. After stirring the reaction temperature at room temperature for 8 hours, the internal temperature was lowered to 0 ° C. or lower, and 36.87 g of AlCl 3 was slowly added. To this reaction product, 46.62 g of 2- (o-tolyl) acetyl chloride (2- (o-tolyl) acetyl chloride) was diluted in 80 mL of methylene chloride and slowly added dropwise at an internal temperature of 5 ° C. or lower. After stirring at about room temperature for about 5 hours, the internal temperature is lowered to 0 ° C. or lower, the solution of the reactor is slowly added to 500 ml of ice water, stirred for 1 hour, separated into layers, and further neutralized and washed with 500 ml of 1% NaOH. After drying the organic layer with MgSO 4 , the solvent was removed with a rotary evaporator and recrystallized in methanol to obtain 75 g of a white solid with a yield of 64%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：２．３４（ｓ、３Ｈ）、２．４８（ｓ、３Ｈ）、４．１４（ｓ、２Ｈ）、７．１５（ｍ、２Ｈ）、７．３４〜７．４０（ｍ、４Ｈ）、７．５１〜７．５８（ｍ、７Ｈ）、７．６６（ｄ、１Ｈ）、７．７４（ｄ、２Ｈ） 1 H-NMR (d, ppm) CDCl 3 : 2.34 (s, 3H), 2.48 (s, 3H), 4.14 (s, 2H), 7.15 (m, 2H), 7. 34-7.40 (m, 4H), 7.51-7.58 (m, 7H), 7.66 (d, 1H), 7.74 (d, 2H)
［３段階：１−（４−（（４−（２−メチルベンゾイル）フェニル）チオ）フェニル）−２−（ｏ−トルイル）エタン−１、２−ジオン（１−（４−（（４−（２−ｍｅｔｈｙｌｂｅｎｚｏｙｌ）ｐｈｅｎｙｌ）ｔｈｉｏ）ｐｈｅｎｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｅ−１、２−ｄｉｏｎｅ）の合成］
反応器に３００ｍＬのジメチルホルムアミドを入れ、上記２段階で得た化合物５０ｇを添加して溶かした。反応物の温度を１５℃でソジウムメトキシド３．０９ｇをゆっくり添加した。この反応物にイソペンチルニトリト１３．８２ｇを内部温度１５℃に維持しながらゆっくり滴加した。滴加後、２５℃まで昇温した後、８時間撹拌する。この反応物に溶媒エチルアセテート４００ｍＬと蒸留水４００ｍＬを添加して水洗した。２回追加水洗し、ジメチルホルムアミドを除去した後、飽和炭酸カルシウムで中和洗浄した後、有機層をＭｇＳＯ４で乾燥させた後、減圧蒸留し、液状の化合物を得た。この液状の化合物にヘキサンとメタノールを加えて再結晶した。薄い黄色の結晶３５ｇを得た。収率は６６％であった。
[Three stages: 1- (4-((4- (2-methylbenzoyl) phenyl) thio) phenyl) -2- (o-toluyl) ethane-1,2-dione (1- (4-((4- Synthesis of (2-methylbenzoyl) phenyl) thio) phenyl) -2- (o-tolyl) ethane-1,2-dione)]
300 mL of dimethylformamide was placed in the reactor, and 50 g of the compound obtained in the above two steps was added and dissolved. The reaction temperature was 15 ° C. and 3.09 g of sodium methoxide was slowly added. To this reaction, 13.82 g of isopentylnitrite was slowly added dropwise while maintaining an internal temperature of 15 ° C. After the dropwise addition, the mixture is heated to 25 ° C. and stirred for 8 hours. To this reaction product, 400 mL of solvent ethyl acetate and 400 mL of distilled water were added and washed with water. After washing twice with additional water to remove dimethylformamide and neutralizing and washing with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Hexane and methanol were added to this liquid compound for recrystallization. 35 g of pale yellow crystals were obtained. The yield was 66%.
１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：２．４８（ｓ、６Ｈ）、２．００（ｓ、１Ｈ、−ＯＨ）、７．１６〜７．３６（ｍ、５Ｈ）、７．５１〜７．６９（ｍ、１０Ｈ） 1 H-NMR (d, ppm) CDCl 3 : 2.48 (s, 6H), 2.00 (s, 1H, —OH), 7.16 to 7.36 (m, 5H), 7.51 7.69 (m, 10H)
［４段階：（Ｚ）−２−（アセトキシイミノ）−１−（４−（（４−（２−メチルベンゾイル）フェニル）チオ）フェニル）−２−（ｏ−トルイル）エタノン（（Ｚ）−２−（ａｃｅｔｏｘｙｉｍｉｎｏ）−１−（４−（（４−（２−ｍｅｔｈｙｌｂｅｎｚｏｙｌ）ｐｈｅｎｙｌ）ｔｈｉｏ）ｐｈｅｎｙｌ）−２−（ｏ−ｔｏｌｙｌ）ｅｔｈａｎｏｎｅ）の合成］
窒素雰囲気下で内部温度を０℃以下に下げ、上記３段階で得た化合物３０ｇ、メチレンクロライド１８０ｍＬとトリエチレンアミン６．７２ｇを添加し、アセチルクロライド５．２１ｇをメチレンクロライド１０ｍＬに溶解した溶液をゆっくり加えた。内部温度を１０℃に上げた後、３時間撹拌した。反応溶液に水を数回添加し、有機層を洗浄し、減圧蒸留して得られた固体化合物をノルマルヘキサンとメチレンクロライドを加えて再結晶した。濾過し、収率７９％の薄い黄色の固体２６ｇを得た。上記薄い黄色の結晶は、目的した化合物である化学式２１で表される化合物であることを確認し、その分析結果は、下記の通りである。
[Four stages: (Z) -2- (acetoxyimino) -1- (4-((4- (2-methylbenzoyl) phenyl) thio) phenyl) -2- (o-toluyl) ethanone ((Z)- 2- (acetoxymino) -1- (Synthesis of 4-((4- (2-methylbenzoyl) phenyl) thio) phenyl) -2- (o-tolyl) ethanol)
The internal temperature was lowered to 0 ° C. or lower under a nitrogen atmosphere, 30 g of the compound obtained in the above three steps, 180 mL of methylene chloride and 6.72 g of triethyleneamine were added, and a solution in which 5.21 g of acetyl chloride was dissolved in 10 mL of methylene chloride was added. Slowly added. After raising the internal temperature to 10 ° C., the mixture was stirred for 3 hours. Water was added to the reaction solution several times, the organic layer was washed, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding normal hexane and methylene chloride. Filtration gave 26 g of a pale yellow solid with a yield of 79%. The pale yellow crystal was confirmed to be a compound represented by Chemical Formula 21, which is the target compound, and the analysis results are as follows.
分析結果
（１）融点：１２６．１℃
（２）１Ｈ−ＮＭＲ（ｄ、ｐｐｍ）ＣＤＣｌ３：２．２７（ｓ、３Ｈ）、２．４５（ｓ、６Ｈ）、７．１６〜７７．３６（ｍ、５Ｈ）、７．５１〜７．７１（ｍ、１１Ｈ）
（３）ＵＶスペクトル測定（メチレンクロライド）
λｍａｘ：２４９、３３６
Analysis result (1) Melting point: 126.1 ° C
(2) 1 H-NMR (d, ppm) CDCl 3 : 2.27 (s, 3H), 2.45 (s, 6H), 7.16 to 77.36 (m, 5H), 7.51 7.71 (m, 11H)
(3) UV spectrum measurement (methylene chloride)
λmax: 249, 336
上記実施例１〜実施例４と同様の方法で次の表１のように本発明によるアルファケトオキシムエステル化合物を合成した。 Alpha ketoxime ester compounds according to the present invention were synthesized in the same manner as in Examples 1 to 4 as shown in Table 1 below.
［実施例１１］
透明レジスト組成物の製造
アクリル系バインダー樹脂３０ｇ、光重合単量体（ジペンタエリスリトールヘキサアクリレート、Ｎｉｈｏｎ Ｋａｙａｋｕ Ｋｏｇｙｏｕ社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）３０ｇ、上記実施例１で得た化合物１．０ｇ及びＰＧＭＥＡ２００ｇ、界面活性剤（３Ｍ社製、ＦＣ−４３０）５００ｐｐｍを含む透明感光性レジスト組成物を製造した。
[Example 11]
Production of Transparent Resist Composition 30 g of acrylic binder resin, 30 g of photopolymerizable monomer (dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA), 1.0 g of compound obtained in Example 1 and 200 g of PGMEA, interface A transparent photosensitive resist composition containing 500 ppm of an activator (manufactured by 3M, FC-430) was produced.
［実施例１２］
ブラックレジスト組成物の製造
カーボンブラック３０ｇ、チタンブラック２０ｇ、ポリエステルバインダー樹脂、光重合単量体（ジペンタエリスリトールヘキサアクリレート、Ｎｉｈｏｎ Ｋａｙａｋｕ Ｋｏｇｙｏｕ社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）１０ｇ、上記実施例１で得た化合物２．５ｇ及びＰＧＭＥＡ３００ｇ、界面活性剤（３Ｍ社製、ＦＣ−４３０）５００ｐｐｍを含むブラック感光性レジスト組成物を製造した。
[Example 12]
Production of Black Resist Composition Carbon Black 30 g, Titanium Black 20 g, Polyester Binder Resin, Photopolymerization Monomer (Dipentaerythritol Hexaacrylate, Nihon Kayaku Kogyou Co., Ltd., KAYARAD DPHA) 10 g, Compound 2 obtained in Example 1 above A black photosensitive resist composition containing 0.5 g, 300 g of PGMEA, and 500 ppm of a surfactant (manufactured by 3M, FC-430) was prepared.
［実施例１３］
レッドレジスト組成物の製造
アクリル系共重合体１０ｇに対して光重合単量体（ジペンタエリスリトールヘキサアクリレート、Ｎｉｈｏｎ Ｋａｙａｋｕ Ｋｏｇｙｏｕ社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）１０ｇ、実施例１で得た化合物１．５ｇ、ピグメントレッドＲｅｄ １７７：Ｃｉｂａ社ＣＲＯＭＯＰＨＴＡＬＲＥＤ Ａ２Ｂ １０ｇ及びプロピレングリコールモノエチルエーテル２００ｇを入れ、界面活性剤（ＤｉｓｐｅｒＢＹＫ−１１１）５００ｐｐｍを含むブラック感光性レジスト組成物を製造した。
[Example 13]
Production of Red Resist Composition 10 g of photopolymerizable monomer (dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Kogyou Co., Ltd., KAYARAD DPHA) per 10 g of acrylic copolymer, 1.5 g of the compound obtained in Example 1, and pigment Red Red 177: Ciba CROMOPHTALRED A2B 10 g and propylene glycol monoethyl ether 200 g were added to prepare a black photosensitive resist composition containing 500 ppm of a surfactant (DisperBYK-111).
［実施例１４］
透明レジスト組成物の製造
実施例１で得た化合物の代わりに、実施例２で得た化合物１．０ｇを添加することを除いて、実施例１１と同一の条件で透明感光性レジデントスト組成物を製造した。
[Example 14]
Production of transparent resist composition Transparent photosensitive resident tost composition under the same conditions as in Example 11 except that 1.0 g of the compound obtained in Example 2 was added instead of the compound obtained in Example 1. Manufactured.
［実施例１５］
ブラックレジスト組成物の製造
実施例１で得た化合物の代わりに、実施例２で得た化合物２．５ｇを添加することを除いて、実施例１２と同一の条件でブラック感光性レジスト組成物を製造した。
[Example 15]
Production of Black Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Example 12 except that 2.5 g of the compound obtained in Example 2 was added instead of the compound obtained in Example 1. Manufactured.
［実施例１６］
レッドレジスト組成物の製造
実施例１で得た化合物の代わりに、実施例２で得た化合物１．５ｇを添加することを除いて、実施例１３と同一の条件でブラック感光性レジスト組成物を製造した。
[Example 16]
Production of Red Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Example 13, except that 1.5 g of the compound obtained in Example 2 was added instead of the compound obtained in Example 1. Manufactured.
［実施例１７］
透明レジスト組成物の製造
実施例１で得た化合物の代わりに、実施例３で得た化合物１．０ｇを添加することを除いて、実施例１１と同一の条件で透明感光性レジスト組成物を製造した。
[Example 17]
Production of transparent resist composition A transparent photosensitive resist composition was prepared under the same conditions as in Example 11 except that 1.0 g of the compound obtained in Example 3 was added instead of the compound obtained in Example 1. Manufactured.
［実施例１８］
ブラックレジスト組成物の製造
実施例１で得た化合物の代わりに、実施例３で得た化合物２．５ｇを添加することを除いて、実施例１２と同一の条件でブラック感光性レジスト組成物を製造した。
[Example 18]
Production of Black Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Example 12 except that 2.5 g of the compound obtained in Example 3 was added instead of the compound obtained in Example 1. Manufactured.
［実施例１９］
レッドレジデントスト組成物の製造
実施例１で得た化合物の代わりに、実施例３で得た化合物１．５ｇを添加することを除いて、実施例１３と同一の条件でブラック感光性レジスト組成物を製造した。
[Example 19]
Production of Red Resistant Composition Black photosensitive resist composition under the same conditions as in Example 13 except that 1.5 g of the compound obtained in Example 3 was added instead of the compound obtained in Example 1. Manufactured.
［実施例２０］
透明レジスト組成物の製造
実施例１で得た化合物の代わりに、実施例４で得た化合物１．０ｇを添加することを除いて、実施例１１と同一の条件で透明感光性レジスト組成物を製造した。
[Example 20]
Production of transparent resist composition A transparent photosensitive resist composition was prepared under the same conditions as in Example 11 except that 1.0 g of the compound obtained in Example 4 was added instead of the compound obtained in Example 1. Manufactured.
［実施例２１］
ブラックレジスト組成物の製造
実施例１で得た化合物の代わりに、実施例４で得た化合物２．５ｇを添加することを除いて、実施例１２と同一の条件でブラック感光性レジスト組成物を製造した。
[Example 21]
Production of Black Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Example 12 except that 2.5 g of the compound obtained in Example 4 was added instead of the compound obtained in Example 1. Manufactured.
［実施例２２］
レッドレジスト組成物の製造
実施例１で得た化合物の代わりに、実施例４で得た化合物１．５ｇを添加することを除いて、実施例１３と同一の条件でブラック感光性レジスト組成物を製造した。
[Example 22]
Production of Red Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Example 13, except that 1.5 g of the compound obtained in Example 4 was added instead of the compound obtained in Example 1. Manufactured.
［比較例］
本発明によるアルファケトオキシムエステル化合物との特性比較のために下記化学式３３及び３４で表される比較化合物を使用して感光性レジスト組成物を製造し、これを上記実施例と比較評価した。なお、これらの比較化合物も、上記実施例１〜実施例４と同様の方法で製造された。
[Comparative example]
In order to compare the properties with the alpha ketoxime ester compounds according to the present invention, photosensitive resist compositions were prepared using comparative compounds represented by the following chemical formulas 33 and 34, and were compared with the above examples. These comparative compounds were also produced in the same manner as in Examples 1 to 4 above.
［比較例１］
透明レジスト組成物の製造
アクリル系バインダー樹脂３０ｇ、光重合単量体（ジペンタエリスリトールヘキサアクリレート、Ｎｉｈｏｎ Ｋａｙａｋｕ Ｋｏｇｙｏｕ社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）３０ｇ、上記化学式３３で表される化合物１．０ｇ及びＰＧＭＥＡ２００ｇ、界面活性剤（３Ｍ社製、ＦＣ−４３０）５００ｐｐｍを含む透明感光性レジスト組成物を製造した。
[Comparative Example 1]
Production of Transparent Resist Composition 30 g of acrylic binder resin, 30 g of photopolymerizable monomer (dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA), 1.0 g of compound represented by the above chemical formula 33 and 200 g of PGMEA, interface A transparent photosensitive resist composition containing 500 ppm of an activator (manufactured by 3M, FC-430) was produced.
［比較例２］
ブラックレジスト組成物の製造
カーボンブラック３０ｇ、チタンブラック２０ｇ、ポリエステルバインダー樹脂、光重合単量体（ジペンタエリスリトールヘキサアクリレート、Ｎｉｈｏｎ Ｋａｙａｋｕ Ｋｏｇｙｏｕ社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）１０ｇ、上記化学式３３で表される化合物２．５ｇ及びＰＧＭＥＡ３００ｇ、界面活性剤（３Ｍ社製、ＦＣ−４３０）５００ｐｐｍを含むブラック感光性レジスト組成物を製造した。
[Comparative Example 2]
Production of Black Resist Composition Carbon Black 30 g, Titanium Black 20 g, Polyester Binder Resin, Photopolymerization Monomer (Dipentaerythritol Hexaacrylate, Nihon Kayaku Kogyou Co., Ltd., KAYARAD DPHA) 10 g, Compound 2 represented by Formula 33 above A black photosensitive resist composition containing 0.5 g, 300 g of PGMEA, and 500 ppm of a surfactant (manufactured by 3M, FC-430) was prepared.
［比較例３］
レッドレジスト組成物の製造
アクリル系共重合体１０ｇに対して光重合単量体（ジペンタエリスリトールヘキサアクリレート、Ｎｉｈｏｎ Ｋａｙａｋｕ Ｋｏｇｙｏｕ社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）１０ｇ、上記化学式３３で表される化合物１．５ｇ、ピグメントレッドＲｅｄ１７７：Ｃｉｂａ社ＣＲＯＭＯＰＨＴＡＬＲＥＤ Ａ２Ｂ １０ｇ及びプロピレングリコールモノエチルエーテル２００ｇを入れ、界面活性剤（ＤｉｓｐｅｒＢＹＫ−１１１）５００ｐｐｍを含むブラック感光性レジスト組成物を製造した。
[Comparative Example 3]
Production of Red Resist Composition 10 g of photopolymerizable monomer (dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Kogyou Co., Ltd., KAYARAD DPHA) with respect to 10 g of the acrylic copolymer, 1.5 g of the compound represented by the above chemical formula 33, Pigment Red Red 177: Ciba CROMOPHTALRED A2B (10 g) and propylene glycol monoethyl ether (200 g) were added to prepare a black photosensitive resist composition containing 500 ppm of a surfactant (DisperBYK-111).
［比較例４］
透明レジスト組成物の製造
化学式３３で表される化合物の代わりに、化学式３４で表される化合物１．０ｇを添加することを除いて、比較例１と同一の条件で透明感光性レジスト組成物を製造した。
[Comparative Example 4]
Production of transparent resist composition A transparent photosensitive resist composition was prepared under the same conditions as in Comparative Example 1 except that 1.0 g of the compound represented by the chemical formula 34 was added instead of the compound represented by the chemical formula 33. Manufactured.
［比較例５］
ブラックレジスト組成物の製造
化学式３３で表現される化合物の代わりに、化学式３４で表される化合物２．５ｇを添加することを除いて、比較例２と同一の条件でブラック感光性レジスト組成物を製造した。
[Comparative Example 5]
Production of Black Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Comparative Example 2 except that 2.5 g of the compound represented by Chemical Formula 34 was added instead of the compound represented by Chemical Formula 33. Manufactured.
［比較例６］
レッドレジスト組成物の製造
化学式３３で表される化合物の代わりに、化学式３４で表される化合物１．５ｇを添加することを除いて、比較例３と同一の条件でブラック感光性レジスト組成物を製造した。
[Comparative Example 6]
Production of Red Resist Composition A black photosensitive resist composition was prepared under the same conditions as in Comparative Example 3 except that 1.5 g of the compound represented by Chemical Formula 34 was added instead of the compound represented by Chemical Formula 33. Manufactured.
［物性評価］
上記実施例１１〜２２及び比較例１〜６で得た感光性組成物の評価は、下記のように行った。上記感光性組成物をスピンコーターに８００〜９００ｒｐｍで１５秒間塗布した後、ホットプレートで９０℃で１００秒間乾燥した。所定のマスクを利用して、光源として超高圧水銀ランプを利用して露光した後、０．０４％水酸化カリウム溶液に２５℃で６０秒間スピン現像した後、水洗した。水洗乾燥後、２３０℃で４０分間ベークし、パターンを得た。得られたパターンに対して以下の評価を進行した。各感光性組成物として利用した光重合開始剤と各種評価結果を表１に示した。
[Evaluation of the physical properties]
Evaluation of the photosensitive composition obtained in the said Examples 11-22 and Comparative Examples 1-6 was performed as follows. The photosensitive composition was applied to a spin coater at 800 to 900 rpm for 15 seconds, and then dried on a hot plate at 90 ° C. for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source using a predetermined mask, spin development was performed in a 0.04% potassium hydroxide solution at 25 ° C. for 60 seconds, followed by washing with water. After washing with water and drying, baking was performed at 230 ° C. for 40 minutes to obtain a pattern. The following evaluation proceeded on the obtained pattern. Table 1 shows the photopolymerization initiator used as each photosensitive composition and various evaluation results.
（１）密着性
ＪＩＳ Ｄ ０２０２の試験方法によって、露光現像後、２００℃で３０分間加熱した塗膜に格子形状でクロスカットを入れ、次に、セロハンテープによってピーリングテストを行い、格子形状の剥離状態を観察して評価した。全然剥離がない場合、○、剥離が認められたものを×で表示した。
(1) Adhesiveness According to the test method of JIS D 0202, after exposure and development, the coating film heated at 200 ° C. for 30 minutes is cross-cut with a lattice shape, and then a peeling test is performed with a cellophane tape to separate the lattice shape. The state was observed and evaluated. When there was no peeling at all, ◯ and those where peeling was recognized were indicated by ×.
（２）耐アルカリ性
現像後、２３０℃で３０分間ベークした後、塗膜を５％ＮａＯＨに２４時間、４％ＫＯＨ
５０℃で１０分間、１％ＮａＯＨ ８０℃で５分間浸漬した後、状態を観察した。外観変化もなく、剥離もない場合○、レジスト浮き上がりが認められたものを△、レジストの剥離が認められたものを×で表示した。
(2) Alkali resistance After development, after baking at 230 ° C. for 30 minutes, the coating film was subjected to 5% NaOH for 24 hours and 4% KOH.
After immersing at 50 ° C. for 10 minutes and 1% NaOH at 80 ° C. for 5 minutes, the state was observed. When there was no change in appearance and there was no peeling, ○ was indicated when the resist lift was observed, and × when the resist peeling was recognized.
（３）感度評価
上記組成された各々の感光性樹脂組成物をスピンコーターでガラス基板（三星コーニング社製、Ｅａｇｌｅ２０００）に塗布し、ホットプレートで９０℃、１分間乾燥した。乾燥後、触針式膜厚測定器（ＫＬＡ−Ｔｅｎｃｏｒ社製、α−ｓｔｅｐ
５００）で測定して得られたブラックレジスト及び透明ネガティブレジストの膜厚は、各々１ミクロン及び５ミクロンであった。次に、このサンプルをマスクを介して高圧水銀灯に露光した。その後、濃度０．０４％水酸化カリウム水溶液でスプレイ現像し、レジストパターンを得た。４０ミクロンのマスクパターンのような寸法を形成することができる適正露光量（ｍＪ／ｓｑｃｍ）を表示した。すなわち、露光量が少ないレジストは、少ない光エネルギーでも画像形成が可能なので、高感度であることを示す。
(3) Sensitivity evaluation Each photosensitive resin composition having the above composition was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning) with a spin coater, and dried on a hot plate at 90 ° C. for 1 minute. After drying, a stylus type film thickness measuring device (manufactured by KLA-Tencor, α-step)
The film thicknesses of the black resist and the transparent negative resist obtained by measuring 500) were 1 micron and 5 microns, respectively. Next, this sample was exposed to a high-pressure mercury lamp through a mask. Thereafter, spray development was performed with a 0.04% aqueous potassium hydroxide solution to obtain a resist pattern. An appropriate exposure amount (mJ / sqcm) capable of forming a dimension like a mask pattern of 40 microns was displayed. That is, a resist with a small exposure amount can form an image with a small amount of light energy, and thus shows high sensitivity.
（４）白化現象
合成された光開始剤を含んで組成された各々の感光性樹脂組成物をスピンコーターで有機基板に塗布した。この際、光開始剤の溶解度によって回転塗布時に結晶が生成され、塗布面が非常に不良な場合を×で表示し、フィルム生成後、乾燥中に結晶が生成され、表面が曇っている場合を△で表示し、レジスト組成物によく溶解された状態で、フィルム形成時に結晶が生成せずに表面がきれいな場合を○で表示する。
(4) Whitening phenomenon Each photosensitive resin composition containing the synthesized photoinitiator was applied to an organic substrate with a spin coater. At this time, crystals are generated at the time of spin coating due to the solubility of the photoinitiator, and the case where the coated surface is very poor is indicated by x, and after the film is formed, crystals are generated during drying and the surface is cloudy. A symbol △ indicates that the surface is clean without forming crystals during film formation in a state well dissolved in the resist composition.
このような評価結果を下記表２に示した。 Such evaluation results are shown in Table 2 below.
上記結果から、本発明によるオキシムエステル系化合物及びアルファケトオキシムエステル系化合物を含む感光性組成物の場合、密着性及び耐アルカリ性に優れていて、薄膜の白化現象もないことが分かる。また、本発明によるオキシムエステル系化合物及びアルファケトオキシムエステル系化合物は、感度に優れていることが分かる。 From the above results, it can be seen that the photosensitive composition containing the oxime ester compound and the alpha keto oxime ester compound according to the present invention is excellent in adhesion and alkali resistance and does not have a whitening phenomenon of the thin film. Moreover, it turns out that the oxime ester type compound and alpha keto oxime ester type compound by this invention are excellent in the sensitivity.
例えば、実施例１１〜１６は、比較例１〜３よりも優秀な感度を示す。実施例１７〜１９について、レッドレジストは比較例１〜３よりも優秀な感度を示す。したがって、化学式１５の化合物は従来のものよりも優秀であるといえる。実施例２０〜２２は、比較例１〜３よりも優秀な感度を示す。 For example, Examples 11 to 16 show better sensitivity than Comparative Examples 1 to 3. About Examples 17-19, a red resist shows the sensitivity superior to Comparative Examples 1-3. Therefore, it can be said that the compound of Formula 15 is superior to the conventional one. Examples 20-22 show a sensitivity superior to Comparative Examples 1-3.
（５）変色性
アルファケトオキシムエステル光重合開始剤の変色有無を確認するために、Ｌａｍｂｄａ Ｖｉｓｉｏｎ社の顕微分光器（ｍｏｄｅｌ：ＴＦＣＡＭ７００）を使用してレッドに該当する組成物を露光の前後に対して色座標を測定した。その結果を下記表３に示した。
(5) Discoloration In order to confirm the presence or absence of discoloration of the alpha ketoxime ester photopolymerization initiator, a composition corresponding to red was applied before and after exposure using a microspectroscope (model: TFCAM700) manufactured by Lambda Vision. The color coordinates were measured. The results are shown in Table 3 below.
上記表３から明らかなように、本発明によるアルファケトオキシムエステル化合物を含む感光性組成物の場合、露光前及び露光後の色座標を比較した時、その差異がほとんどなかった。したがって、本発明による感光性組成物の場合、変色が容易に生じないことを確認することができた。 As apparent from Table 3 above, in the case of the photosensitive composition containing the alpha ketoxime ester compound according to the present invention, there was almost no difference when comparing the color coordinates before and after exposure. Therefore, in the case of the photosensitive composition according to the present invention, it was confirmed that no discoloration easily occurred.
以上、添付図面を参照しながら本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
Claims (10)
Ｒ１は、炭素数１〜１０のアルキル基、ベンゾイル基、または炭素数３〜６のシクロアルキル基であり、
Ｒ２は、−ＣＨ３、−Ｃ２Ｈ５、−プロピル、または−ベンゾイルであり、
Ｒ３は、−Ｈであるか、ａがメチルまたはエチル基であり、ｂがＨまたはメチル基である
R 1 is an alkyl group having 1 to 10 carbon atoms, a benzoyl group, or a cycloalkyl group having 3 to 6 carbon atoms,
R 2 is —CH 3 , —C 2 H 5 , —propyl, or —benzoyl;
R 3 is —H, a is a methyl or ethyl group, and b is H or a methyl group.
Ｒ１は、炭素数１〜１０のアルキル基、ベンゾイル基、または炭素数３〜６のシクロアルキル基であり、
Ｒ３は、−Ｈであるか、ａがメチルまたはエチル基であり、ｂがメチル基である
R 1 is an alkyl group having 1 to 10 carbon atoms, a benzoyl group, or a cycloalkyl group having 3 to 6 carbon atoms,
R 3 is —H, a is a methyl or ethyl group, and b is a methyl group
溶剤またはアルカリ水溶液に可溶の高分子化合物及び／またはエチレン性不飽和結合を有する光重合性化合物；
を含むことを特徴とする感光性樹脂組成物。 One or more compounds selected from a compound of formula 1 according to claim 1 and a compound of formula 2 according to claim 2; and a polymer compound and / or ethylenically unsaturated which is soluble in a solvent or an aqueous alkaline solution. A photopolymerizable compound having a bond;
The photosensitive resin composition characterized by including.
The film is a word processor, computer, television or plasma display panel, polarizing plate surface used in liquid crystal display devices, sunglasses lens, power glasses lens, camera finder lens, instrument cover, automobile glass, train The base material according to claim 9, wherein the base material is used for glass, a light brightness enhancement film, or an optical waveguide film.
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