JPH0416104B2 - - Google Patents
Info
- Publication number
- JPH0416104B2 JPH0416104B2 JP11359684A JP11359684A JPH0416104B2 JP H0416104 B2 JPH0416104 B2 JP H0416104B2 JP 11359684 A JP11359684 A JP 11359684A JP 11359684 A JP11359684 A JP 11359684A JP H0416104 B2 JPH0416104 B2 JP H0416104B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- photosensitive material
- salts
- active halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- -1 vinyloxy group Chemical group 0.000 claims description 13
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 8
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 150000003553 thiiranes Chemical group 0.000 claims 1
- 238000006303 photolysis reaction Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LETDRANQSOEVCX-UHFFFAOYSA-N 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 LETDRANQSOEVCX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000976 ink Substances 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
- 238000000034 method Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VPQAFOWBKWKVQQ-UHFFFAOYSA-N (4-methoxyphenyl)methyl-phenyliodanium Chemical compound C1=CC(OC)=CC=C1C[I+]C1=CC=CC=C1 VPQAFOWBKWKVQQ-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- UEIPWOFSKAZYJO-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-[2-(2-ethenoxyethoxy)ethoxy]ethane Chemical compound C=COCCOCCOCCOCCOC=C UEIPWOFSKAZYJO-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QSISWYUKPMXKSO-UHFFFAOYSA-N 2-(2-phenylethenoxymethyl)oxirane Chemical compound C1OC1COC=CC1=CC=CC=C1 QSISWYUKPMXKSO-UHFFFAOYSA-N 0.000 description 1
- IXOJGFDRZRKILF-UHFFFAOYSA-N 2-(chloromethyl)-1,3,5-triazine Chemical compound ClCC1=NC=NC=N1 IXOJGFDRZRKILF-UHFFFAOYSA-N 0.000 description 1
- GUBIZHYTWDOVKO-UHFFFAOYSA-N 2-(dichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)C1=NC=NC=N1 GUBIZHYTWDOVKO-UHFFFAOYSA-N 0.000 description 1
- DUERRGNERQTBAB-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)CC1CO1 DUERRGNERQTBAB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NBTXFNJPFOORGI-UHFFFAOYSA-N 2-ethenoxyethyl prop-2-enoate Chemical compound C=COCCOC(=O)C=C NBTXFNJPFOORGI-UHFFFAOYSA-N 0.000 description 1
- YJNGLOLSVJVXQQ-UHFFFAOYSA-N 3-(2-ethenoxyethoxycarbonyl)benzoic acid Chemical compound C(=C)OCCOC(C1=CC(C(=O)O)=CC=C1)=O YJNGLOLSVJVXQQ-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- VAAQOMZMRHISNB-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C(=O)OCC2OC2)=C1 VAAQOMZMRHISNB-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- UMOGWPSFOULXDY-UHFFFAOYSA-N 4-(2-ethenoxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(=O)OCCOC=C)C=C1 UMOGWPSFOULXDY-UHFFFAOYSA-N 0.000 description 1
- SSGDCFICOXZNJH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)OCC1OC1 SSGDCFICOXZNJH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- BGLGAKMTYHWWKW-UHFFFAOYSA-N acridine yellow Chemical compound [H+].[Cl-].CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=CC2=C1 BGLGAKMTYHWWKW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- YTRKSSYRHCBCIU-UHFFFAOYSA-N bis(2-ethenoxyethyl) butanedioate Chemical compound C=COCCOC(=O)CCC(=O)OCCOC=C YTRKSSYRHCBCIU-UHFFFAOYSA-N 0.000 description 1
- MWPUSWNISCYUNR-UHFFFAOYSA-N bis(3-nitrophenyl)iodanium Chemical compound [O-][N+](=O)C1=CC=CC([I+]C=2C=C(C=CC=2)[N+]([O-])=O)=C1 MWPUSWNISCYUNR-UHFFFAOYSA-N 0.000 description 1
- JQDCYGOHLMJDNA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) butanedioate Chemical compound C1OC1COC(=O)CCC(=O)OCC1CO1 JQDCYGOHLMJDNA-UHFFFAOYSA-N 0.000 description 1
- QTCNFZOTAWKWHS-UHFFFAOYSA-N bis[(4-methoxyphenyl)methyl]iodanium Chemical compound C1=CC(OC)=CC=C1C[I+]CC1=CC=C(OC)C=C1 QTCNFZOTAWKWHS-UHFFFAOYSA-N 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JKXONPYJVWEAEL-UHFFFAOYSA-N oxiran-2-ylmethyl acetate Chemical compound CC(=O)OCC1CO1 JKXONPYJVWEAEL-UHFFFAOYSA-N 0.000 description 1
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
Classifications
-
- 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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、優れた感光度を示す光不溶性樹脂組
成物、さらに詳しく述べれば可視光照射により強
酸を発生し得る光カチオン重合開始系を含有する
ことを特徴とする光硬化性感光材料に関する。
光重合を原理とする光不溶性樹脂の感光速度を
増大させるためには多くの研究がなされている
が、その多くは紫外線に活性な光重合増感剤（開
始剤）に関するものである。一方、感光性樹脂は
フオトレジスト材料、インキ、塗料、ワニス、印
刷製版材料などを越えて、レーザ光を用いる画像
形成材料や銀塩に代る感光材料として注目されて
いるが、この新しい材料としての感光特性は従来
のものでは甚だ不十分なものでしかない。そのた
め、感光波長領域を拡大し、しかも感光速度を飛
躍的に増大させる必要がある。
可視光線に感光する光重合性樹脂としてはいく
つかの提案がなされている。特開始48−36281号
公報においては、エチレン系不飽和によりトリア
ジン環と共役された少なくとも１つのトリハロメ
チル基と少なくとも１つの発色団部分を有するＳ
−トリアジンを重合開始剤とする方法が提案され
ている。また、特開始54−15529号公報において
は、ｐ−ジアルキルアミノアリリデンと共役した
不飽和ケトンを光重合開始剤とする組成物が提案
されている。あるいはまた、特開始52−134692号
公報においては、多環性キノンと三級アミンを光
重合開始系とする組成物が提案されている。
これらはいずれも従来の光重合性樹脂に比し
て、より長波長に感光する材料を与えることが出
来るが、不溶化に関与する反応はラジカルによる
ものであるので、大気中での感度は著しく減ずる
と言う欠点を有している。したがつて、これらの
感光材料が所望の高感度を示すためには、大気中
の酸素をしや断した状態で露光する必要が生ず
る。
一方、このような酸素の影響をうけない重合系
として、光カチオン重合が注目されている。すな
わち、アリールジアゾニウム塩、ジアリールヨー
ドニウム塩、トリアリールスルホニウム塩などの
光分解により、強酸が発生してカチオン重合を開
始する。しかしながら、この種の化合物は著しく
短波長の紫外線ではじめれ光分解するものであ
り、可視光に対しては感光性を示さない。したが
つて、酸素による重合阻害を示さず、しかも、可
視光に感光する感光材料を製造するためには、光
分解を促進する可視光増感剤が不可欠となる。
ジアリールヨードニウム塩やトリアリールスル
ホニウム塩に対する可視光増感剤として、アクリ
ジンオレンジ、アクリジンイエローなどが提案さ
れている（J.V.クリベロ、J.H.W.ハム、高分子科
学誌、高分子化学編、16巻、2441ページ（1978
年）など参照）。しかしながら、この種の増感剤
により構成された感光材料は、著しく感度の低い
ものであつた。
本発明は、光分解により酸を発生するジアリー
ルヨードニウム塩などの増感分解反応を検討する
過程で、アミノフエニル体が効率良くヨードニウ
ム塩などの活性ハロゲン化合物の光分解を増感す
ることを見い出し、その知見に基づいて完成され
たものである。
すなわち、本発明は、(A)一般式（）
（式中のR1、R2はアルキル基を示し、ｎは０ま
たは１であり、Ｘ、Ｙは水素原子、アルコキシカ
ルボニル、フエニル基、置換フエニル基、シアノ
基、カルバモイル基、ホルミル基、アシル基、ア
ンモニオ基から選ばれた残基を示す）
で表わされる共役したジアルキルアミノフエニル
基を持つ化合物を、(B)活性ハロゲン含有化合物
と、(C)カチオン重合能を有する単位を少なくとも
１つ有する化合物とからなることを特徴とする光
架橋性感光材料に関するものである。
成分(A)は成分(B)の光分解を増感するものであ
り、成分(C)は光分解で発生した酸によりカチオン
重合し得るものである。成分(A)である一般式
（）で表わされるアミノフエニル化合物として
は、以下の化合物を例示することができる。
これらの化合物はいずれもジアルキルアミノベ
ンツアルデヒドの活性メチレン化合物との縮合反
応により、用意に製造することができる。
光重合開始系を構造する成分(B)である活性ハロ
ゲン化合物としては、一般式（）
（式中のR5、R6は水素原子、低級アルキル基、
メトキシ基またはニトロ基を示し、X-はハロゲ
ンイオン、スルホン酸イオン、BF4 -、PF6 -、As
F6 -を示す。）
で表わされるジアリールヨードニウム塩がとくに
好ましい。本発明で用いられる一般式（）で表
わされる化合物としては、Macromolecules、
10、1307（1977）に記載の化合物、たとえば、ジ
フエニルヨードニウム、ジトリルヨードニウム、
フエニル（ｐ−アニシル）ヨードニウム、ビス
（ｍ−ニトロフエニル）ヨードニウム、ビス（ｐ
−tent−ブチルフエニル）ヨードニウムなどのヨ
ードニウムのクロリド、ブロミドあるいはホウフ
ツ化塩、ヘキサフルオロホスフエード塩、ヘキサ
フルオロアルセネート塩をあげることができる。
また、少なくとも１つのモノ、ジ、あるいはド
リハロメチル基により置換されたＳ−トリアジン
化合物も用いることができる。その例として、２
−クロロメチル−Ｓ−トリアジン、２−ジクロロ
メチル−Ｓ−トリアジン、２−メチル−４、６−
ビス（トリクロロメチル）−Ｓ−トリアジン、２
−フエニル−４、６−ビス（トリクロロメチル）
−Ｓ−トリアジン、２、４、６−トリス（トリク
ロロメチル）−Ｓ−トリアジン、をあげることが
できる。これらの活性ハロゲン化合物は、一般式
で表わされる化合物に対して、0.1〜10モル等量、
さらに好ましくは１〜５モル等量を混合すること
により、高効率な光カチオン重合開始系となる。
本発明の光架橋性感光材料を構成する第３の成
分(C)として、カチオン重合能を有する単位を少な
くとも１つ有する化合物が用いられる。ここで言
うカチオン重合能を有する単位とは、たとえば、
東村敏延著、「カチオン重合」、化学同人（1971
年）に記載の官能基をあげることができる。とく
に望ましくは、エポキシ基、エピチオ基、ビニル
エーテル基である。これらの官能基を持つ化合物
としては、低分子化合物でも良いし、また、高分
子量物質でもよい。感度の点からすれば、高分子
量物質がより好ましい。
エポキシ基を持つ化合物としては、グリシドー
ル、エピクロロヒドリン、フエニルグリシジルエ
ーテル、酢酸グリシジル、安息香酸グリシジル、
アクリル酸グリシジル、メタクリル酸グリシジル
コハク酸ジグリシジル、イソフタル酸グリシジ
ル、テレフタル酸グリシジル、ハイドロキノンや
ビスフエノールＡのグリシジル化物、グリシジル
化ノボラツク樹脂、アクリル酸あるいはメタクリ
ル酸グリシジルの（共）重合体、グリシジルオキ
シスチレンの（共）重合体、などをあげることが
できるが、この限りではない。
エピチオ基を持つ化合物としては、アクリル酸
あるいはメタクリル酸のエピチオメチルエステル
およびその（共）重合体が好ましい。
ビニルエーテル基を有する化合物としては、２
−エチルヘキシルビニルエーテル、オクチルエー
テル、フエニルビニルエーテル、オクチルエーテ
ル、フエニルビニルエーテル、ナフチルビニルエ
ーテル、２−クロロエチルビニルエーテル、アク
リル酸２−ビニロキシエチル、メタクリル酸２−
ビニロキシエチル、コハク酸ビス（２−ビニロキ
シエチル）エステル、イソフタル酸（２−ビニロ
キシエチル）エステル、テレフタル酸（２−ビニ
ロキシエチル）エステル、１、４−ジビニロキシ
ブタン、ジエチレングリコールジビニルエーテル
テトラエチレングリコールジビニルエーテル、ハ
イドロキノンやビスフエノールＡのビス（２−ビ
ニロキシエチル）エーテル、ノボラツク樹脂の２
−ビニロキシエチル化物、などをあげることがで
きる。
これらの成分(C)は成分Ａに対して５〜500モル
等量が好ましい。また、成分(C)は上にあげた化合
物の２種以上の混合部であつても良いことは言う
までもない。
本発明の光架橋性組成物は、一般式（）で表
わされる成分(A)が吸収する波長の光にり硬化す
る。このとき、露光後直ちに加熱することにより
一層硬化が効果的に進行する。さらには、大気中
での硬化速度は酸素をしや断した時とほとんど変
わらない。これらの事実は、この光硬化がカチオ
重合により起こつていることを示唆すものであ
る。
本発明の光架橋性樹脂には、所望に応じて着色
剤として顔料もしくは染料を添加しても差しつか
えない。
本発明の感光材料に適した光源としては、高圧
水銀灯、超高圧水銀灯、高圧キセノン灯、ハロゲ
ンランプ、蛍光灯のほかに、He−CdレーザやAr
レーザが利用できる。
本発明の感光材料は酸素により重合阻害を受け
ずに高い感度で硬化するので、インキ、塗料、ワ
ニスなどの基材として有効であるばかりでなく、
平版または凸版用製版材料、リレーフの作成、非
銀塩画像の作成、プリント配線板の作成など巾広
い分野に応用できるほか、レーザ光にも感光する
ところから、ネガレスでの製版用としても有効で
ある。
以下に実施例によりさらに詳細に説明する。
実施例 １〜13
メタクリル酸グリシジル25mlとトルエン25mlの
混合溶液にアゾビスイソブチロニトリル0.13ｇを
加え、アルゴンガス雰囲気中60℃で150分間撹拌
反応させた。反応物を塩化メチレンに溶解してか
らメタノールへ再沈させて単離精製し、ポリメタ
クリル酸グリシジル18.7ｇを得た。このポリマー
をジオキサンに溶解して10重量％とし、この溶液
１ｇにジフエニルヨードニウムヘキサフルオロホ
スフエート10mgおよび表１に示したジアルキルア
ミノフエニル基を有する増感化合物10mgを加え、
さらに、ジオキサン0.5mlで希釈して感光液とし
た。この液をアルミ板上に1000rpmでスピン塗布
し、ステツプタブレツト（イーストマンコダツク
社製No.1A）を適してキセノン灯（0.9ｍＷ／cm2）
で20秒照射した。これを80℃で３分間ポストベー
クした後、ジオキサンで現像した。不溶化段数を
まとめて表１に示す。ベーキングを施こさない場
合には不溶化しないか、あるいは、非常に低感度
であり、エポキシ環のカチオン重合により不溶化
したものと考えられる。また、２−メチル−４、
６−ビス（トリクロロメチル）−Ｓ−トリアジン
もほぼ同様な結果を与えた。
The present invention relates to a photoinsoluble resin composition exhibiting excellent photosensitivity, and more specifically to a photocurable photosensitive material characterized by containing a photocationic polymerization initiation system capable of generating a strong acid upon irradiation with visible light. Many studies have been conducted to increase the photosensitivity speed of photoinsoluble resins based on the principle of photopolymerization, and most of them are related to photopolymerization sensitizers (initiators) that are active to ultraviolet light. On the other hand, photosensitive resins are attracting attention not only as photoresist materials, inks, paints, varnishes, and printing plate materials, but also as image-forming materials that use laser light and photosensitive materials that replace silver salts. The photosensitivity of conventional materials is extremely inadequate. Therefore, it is necessary to expand the photosensitive wavelength range and dramatically increase the photosensitive speed. Several proposals have been made for photopolymerizable resins that are sensitive to visible light. In Japanese Patent Application Publication No. 48-36281, S having at least one trihalomethyl group conjugated to a triazine ring through ethylenic unsaturation and at least one chromophore moiety
- A method using triazine as a polymerization initiator has been proposed. Furthermore, Japanese Patent Application Publication No. 54-15529 proposes a composition using an unsaturated ketone conjugated with p-dialkylaminoallylidene as a photopolymerization initiator. Alternatively, Japanese Patent Application Publication No. 52-134692 proposes a composition using a polycyclic quinone and a tertiary amine as a photopolymerization initiation system. All of these can provide materials that are sensitive to longer wavelengths than conventional photopolymerizable resins, but since the reaction involved in insolubilization is based on radicals, sensitivity in the atmosphere is significantly reduced. It has the disadvantage of. Therefore, in order for these photosensitive materials to exhibit the desired high sensitivity, it is necessary to expose them to light while excluding atmospheric oxygen. On the other hand, cationic photopolymerization is attracting attention as a polymerization system that is not affected by oxygen. That is, photodecomposition of aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, etc. generates strong acids and initiates cationic polymerization. However, this type of compound begins to photodecompose under extremely short wavelength ultraviolet light and does not exhibit photosensitivity to visible light. Therefore, in order to produce a photosensitive material that does not inhibit polymerization due to oxygen and is sensitive to visible light, a visible light sensitizer that promotes photodecomposition is essential. Acridine orange, acridine yellow, etc. have been proposed as visible light sensitizers for diaryliodonium salts and triarylsulfonium salts (JV Crivello, JHW Ham, Journal of Polymer Science, Polymer Chemistry Edition, Volume 16, Page 2441 ( 1978
). However, photosensitive materials composed of this type of sensitizer have extremely low sensitivity. In the process of investigating the sensitized decomposition reaction of diaryliodonium salts, etc., which generate acids upon photolysis, the present invention discovered that aminophenyl compounds efficiently sensitize the photodecomposition of active halogen compounds such as iodonium salts. It was completed based on knowledge. That is, the present invention provides (A) general formula () (In the formula, R 1 and R 2 represent an alkyl group, n is 0 or 1, and X and Y are a hydrogen atom, alkoxycarbonyl, phenyl group, substituted phenyl group, cyano group, carbamoyl group, formyl group, acyl (B) an active halogen-containing compound and (C) at least one unit having cationic polymerization ability. The present invention relates to a photocrosslinkable photosensitive material characterized by comprising a compound having the following properties. Component (A) is a component that sensitizes the photodecomposition of component (B), and component (C) is a component that can be cationically polymerized by the acid generated by photolysis. As the aminophenyl compound represented by the general formula () which is component (A), the following compounds can be exemplified. All of these compounds can be readily produced by a condensation reaction of dialkylaminobenzaldehyde with an active methylene compound. The active halogen compound which is the component (B) structuring the photopolymerization initiation system has the general formula () (R 5 and R 6 in the formula are hydrogen atoms, lower alkyl groups,
Represents a methoxy group or a nitro group, and X - is a halogen ion, sulfonate ion, BF 4 - , PF 6 - , A s
Indicates F 6 - . ) Diaryliodonium salts represented by these are particularly preferred. The compounds represented by the general formula () used in the present invention include Macromolecules,
10, 1307 (1977), such as diphenyliodonium, ditolyliodonium,
Phenyl(p-anisyl)iodonium, bis(m-nitrophenyl)iodonium, bis(p-anisyl)iodonium
Examples include iodonium chloride, bromide, or borofluoride salts, hexafluorophosphate salts, and hexafluoroarsenate salts such as -tent-butylphenyl)iodonium. S-triazine compounds substituted with at least one mono-, di-, or dolihalomethyl group can also be used. As an example, 2
-chloromethyl-S-triazine, 2-dichloromethyl-S-triazine, 2-methyl-4,6-
Bis(trichloromethyl)-S-triazine, 2
-phenyl-4,6-bis(trichloromethyl)
Examples include -S-triazine and 2,4,6-tris(trichloromethyl)-S-triazine. These active halogen compounds are used in an amount of 0.1 to 10 molar equivalents, based on the compound represented by the general formula.
More preferably, by mixing 1 to 5 molar equivalents, a highly efficient photocationic polymerization initiation system can be obtained. As the third component (C) constituting the photocrosslinkable photosensitive material of the present invention, a compound having at least one unit having cationic polymerization ability is used. The unit having cationic polymerization ability mentioned here is, for example,
Toshinobu Higashimura, “Cationic Polymerization,” Kagaku Doujin (1971)
Examples include the functional groups described in 2010). Particularly preferred are an epoxy group, an epithio group, and a vinyl ether group. The compound having these functional groups may be a low molecular weight compound or a high molecular weight substance. From the viewpoint of sensitivity, high molecular weight substances are more preferable. Compounds with epoxy groups include glycidol, epichlorohydrin, phenyl glycidyl ether, glycidyl acetate, glycidyl benzoate,
Glycidyl acrylate, glycidyl methacrylate, diglycidyl succinate, glycidyl isophthalate, glycidyl terephthalate, glycidyl compounds of hydroquinone and bisphenol A, glycidylated novolac resins, (co)polymers of glycidyl acrylic acid or methacrylate, glycidyloxystyrene Examples include (co)polymers, but are not limited thereto. As the compound having an epithio group, epithiomethyl esters of acrylic acid or methacrylic acid and (co)polymers thereof are preferable. As a compound having a vinyl ether group, 2
-Ethylhexyl vinyl ether, octyl ether, phenyl vinyl ether, octyl ether, phenyl vinyl ether, naphthyl vinyl ether, 2-chloroethyl vinyl ether, 2-vinyloxyethyl acrylate, methacrylic acid 2-
Vinyloxyethyl, bis(2-vinyloxyethyl) succinate, isophthalic acid (2-vinyloxyethyl) ester, terephthalic acid (2-vinyloxyethyl) ester, 1,4-divinyloxybutane, diethylene glycol divinyl ether, tetraethylene glycol divinyl ether, hydroquinone, etc. Bis(2-vinyloxyethyl)ether of bisphenol A, 2 of novolac resin
- vinyloxyethylated products, etc. These components (C) are preferably used in an amount of 5 to 500 molar equivalents relative to component A. It goes without saying that component (C) may be a mixture of two or more of the above-mentioned compounds. The photocrosslinkable composition of the present invention is cured by light having a wavelength absorbed by component (A) represented by the general formula (). At this time, curing proceeds more effectively by heating immediately after exposure. Furthermore, the curing speed in the atmosphere is almost the same as when oxygen is excluded. These facts suggest that this photocuring occurs through cationic polymerization. A pigment or dye may be added to the photocrosslinkable resin of the present invention as a coloring agent, if desired. Light sources suitable for the photosensitive material of the present invention include high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, halogen lamps, and fluorescent lamps, as well as He-Cd lasers and Ar
Laser available. Since the photosensitive material of the present invention cures with high sensitivity without being inhibited by oxygen, it is not only effective as a base material for inks, paints, varnishes, etc.
It can be applied to a wide range of fields such as lithographic or letterpress plate-making materials, relief relief creation, non-silver halide image creation, and printed wiring board production, and because it is sensitive to laser light, it is also effective for negativeless plate-making. be. This will be explained in more detail with reference to Examples below. Examples 1 to 13 0.13 g of azobisisobutyronitrile was added to a mixed solution of 25 ml of glycidyl methacrylate and 25 ml of toluene, and the mixture was stirred and reacted at 60° C. for 150 minutes in an argon gas atmosphere. The reaction product was dissolved in methylene chloride and then reprecipitated into methanol for isolation and purification to obtain 18.7 g of polyglycidyl methacrylate. This polymer was dissolved in dioxane to a concentration of 10% by weight, and 10 mg of diphenyliodonium hexafluorophosphate and 10 mg of a sensitizing compound having a dialkylaminophenyl group shown in Table 1 were added to 1 g of this solution.
Furthermore, it was diluted with 0.5 ml of dioxane to prepare a photosensitive solution. This solution was spin-coated onto an aluminum plate at 1000 rpm, and a step tablet (No. 1A manufactured by Eastman Kodak Co.) was used to apply a xenon lamp (0.9 mW/cm 2 ).
It was irradiated for 20 seconds. After post-baking this at 80°C for 3 minutes, it was developed with dioxane. The number of insolubilization stages is summarized in Table 1. If baking is not performed, the insolubilization does not occur or the sensitivity is extremely low, and it is thought that the insolubilization occurs due to cationic polymerization of the epoxy ring. Also, 2-methyl-4,
6-bis(trichloromethyl)-S-triazine gave almost similar results.
【表】【table】
Claims (1)
たは１であり、Ｘ、Ｙは水素原子、アルコキシカ
ルボニル、フエニル基、置換フエニル基、シアノ
基、カルバモイル基、ホルミル基、アシル基、ア
ンモニオ基から選ばれた残基を示す。）で表わさ
れる共役したジアルキルアミノフエニル基を持つ
化合物と、(B)活性ハロゲン含有化合物と、(C)カチ
オン重合能を有する単位を少なくとも１つ有する
化合物とからなることを特徴とする光架橋性感光
材料。 ２ 活性ハロゲン含有化合物が、ジアリールヨー
ドニウム塩または少なくとも１つのモノ、ジある
いはトリハロメチル基により置換されたＳ−トリ
アジン化合物から選ばれた少なくとも１種の化合
物である特許請求の範囲第１項記載の光架橋性感
光材料。 ３ カチオン重合能を有する単位が、ビニルオキ
シ基、ビニルチオ基、エポキシ基、エピスルフイ
ド基である特許請求の範囲第１項記載の光架橋性
感光材料。[Claims] 1 (A) General formula (In the formula, R 1 and R 2 represent an alkyl group, n is 0 or 1, and X and Y are a hydrogen atom, alkoxycarbonyl, phenyl group, substituted phenyl group, cyano group, carbamoyl group, formyl group, acyl (B) an active halogen-containing compound, and (C) at least one unit having cationic polymerization ability. A photocrosslinkable photosensitive material comprising a compound having: 2. The light according to claim 1, wherein the active halogen-containing compound is at least one compound selected from diaryliodonium salts and S-triazine compounds substituted with at least one mono-, di-, or trihalomethyl group. Crosslinkable photosensitive material. 3. The photocrosslinkable photosensitive material according to claim 1, wherein the unit having cationic polymerizability is a vinyloxy group, a vinylthio group, an epoxy group, or an episulfide group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11359684A JPS60257444A (en) | 1984-06-01 | 1984-06-01 | Photobridgeable photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11359684A JPS60257444A (en) | 1984-06-01 | 1984-06-01 | Photobridgeable photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60257444A JPS60257444A (en) | 1985-12-19 |
| JPH0416104B2 true JPH0416104B2 (en) | 1992-03-23 |
Family
ID=14616213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11359684A Granted JPS60257444A (en) | 1984-06-01 | 1984-06-01 | Photobridgeable photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60257444A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH063546B2 (en) * | 1986-02-04 | 1994-01-12 | 東洋紡績株式会社 | Photopolymerizable composition |
| JPH0816783B2 (en) * | 1989-09-11 | 1996-02-21 | 工業技術院物質工学工業技術研究所長 | Visible light recording material |
| JPH0816784B2 (en) * | 1989-09-27 | 1996-02-21 | 工業技術院物質工学工業技術研究所長 | Visible light resin composition |
| JPH04181944A (en) * | 1990-11-16 | 1992-06-29 | Toyo Ink Mfg Co Ltd | Visible light photosensitive composition |
| AT412427B (en) * | 1999-12-21 | 2005-02-25 | Ciba Sc Holding Ag | Radiation sensitive composition, useful for production of e.g. paint and inks, contains cationic or acid catalysed polymerizable compound and novel dirayliodonium salt |
| JP2024038756A (en) * | 2022-09-08 | 2024-03-21 | 日東電工株式会社 | Photocurable resin sheet |
-
1984
- 1984-06-01 JP JP11359684A patent/JPS60257444A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60257444A (en) | 1985-12-19 |
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