JPH0362162B2 - - Google Patents
Info
- Publication number
- JPH0362162B2 JPH0362162B2 JP58198085A JP19808583A JPH0362162B2 JP H0362162 B2 JPH0362162 B2 JP H0362162B2 JP 58198085 A JP58198085 A JP 58198085A JP 19808583 A JP19808583 A JP 19808583A JP H0362162 B2 JPH0362162 B2 JP H0362162B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- photosensitive
- sensitivity
- present
- photocurable resin
- 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 - Lifetime
Links
- 239000011342 resin composition Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- CDSULTPOCMWJCM-UHFFFAOYSA-N 4h-chromene-2,3-dione Chemical class C1=CC=C2OC(=O)C(=O)CC2=C1 CDSULTPOCMWJCM-UHFFFAOYSA-N 0.000 claims description 7
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- -1 coumarin compound Chemical class 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- JQYDECSZBZCKFQ-UHFFFAOYSA-N 3-acetyl-7-(diethylamino)chromen-2-one Chemical compound C1=C(C(C)=O)C(=O)OC2=CC(N(CC)CC)=CC=C21 JQYDECSZBZCKFQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 239000000178 monomer Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- VOPLTTRBWKQQOW-UHFFFAOYSA-N 3-acetyl-5,7-dimethoxychromen-2-one Chemical compound C1=C(C(C)=O)C(=O)OC2=CC(OC)=CC(OC)=C21 VOPLTTRBWKQQOW-UHFFFAOYSA-N 0.000 description 1
- CPVJWBWVJUAOMV-UHFFFAOYSA-N 3-benzoyl-7-(diethylamino)chromen-2-one Chemical compound O=C1OC2=CC(N(CC)CC)=CC=C2C=C1C(=O)C1=CC=CC=C1 CPVJWBWVJUAOMV-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical group C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- QXAMGWKESXGGNV-UHFFFAOYSA-N 7-(diethylamino)-1-benzopyran-2-one Chemical compound C1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 QXAMGWKESXGGNV-UHFFFAOYSA-N 0.000 description 1
- SANIRTQDABNCHF-UHFFFAOYSA-N 7-(diethylamino)-3-[7-(diethylamino)-2-oxochromene-3-carbonyl]chromen-2-one Chemical compound C1=C(N(CC)CC)C=C2OC(=O)C(C(=O)C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=CC2=C1 SANIRTQDABNCHF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 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
- DNFSNYQTQMVTOK-UHFFFAOYSA-N bis(4-tert-butylphenyl)iodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DNFSNYQTQMVTOK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000004775 coumarins Chemical group 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 125000006371 dihalo methyl group Chemical group 0.000 description 1
- HBIYXUCPFAAGLE-UHFFFAOYSA-N dimethyl 3-[5,7-bis(methoxycarbonyl)-2-oxochromene-3-carbonyl]-2-oxochromene-5,7-dicarboxylate Chemical compound C1=C(C(=O)OC)C=C2OC(=O)C(C(=O)C3=CC4=C(C(=O)OC)C=C(C=C4OC3=O)C(=O)OC)=CC2=C1C(=O)OC HBIYXUCPFAAGLE-UHFFFAOYSA-N 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
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 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
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000006372 monohalo methyl group Chemical group 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005593 poly(benzyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Landscapes
- Polymerisation Methods In General (AREA)
Description
本発明は、優れた感度を示す光硬化樹脂組成
物、さらに詳しくは、３−ケトクマリン類とジア
リールヨードニウム塩からなる組合わせを光重合
開始剤として含有することを特徴とする光硬化樹
脂組成物に関するものである。
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、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も注目され
ているが、この新しい材料としての感光特製は従
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。
この場合、感光性樹脂の持つ優れた特性である
高解像性と目的に適した諸物性をも兼ね備えてい
なければならないことは言うまでもない。
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。その中で得開昭52−
112681号広報においてはクマリン化合物を用いる
感光性組成物が提案されている。また、特開昭58
−15503号広報においては３−ケトクマリンに活
性ハロゲン化合物を組合わせた感光性組成物が記
載されている。後者におけるハロゲン化合物とし
ては、芳香族炭化水素還もしくは芳香族複素還に
スルホニルクロル基、モノハロメチル、ジハロメ
チル、トリハロメチル基を少なくとも１つが結合
した化合物が用いられている。しかしながら、レ
ーザ用感光材料や銀塩代替材料などとして利用す
るにはなお一層高度化することが必要である。
本発明は、光分解により酸を発生するジアリー
ルヨードニウム塩の増感分解反応を検討する過程
の中で、３−ケトクマリン類が著しく効率良く増
感分解をひき起こすことを見い出し、その知見に
基づき完成されたものである。
すなわち、本発明は、(A)光重合を有するエチレ
ン性不飽和結合を少なくとも１つ有する化合物お
よび(B)光重合開始剤からなる光硬化樹脂組成物に
おいて、一般式（）
（式中、R1、R2は水素原子、アルコキシ基また
はジアルキルアミノ基を示し、R3は低級アルキ
ル基またはアリール基を示す）
で表わされる３−ケトクマリン類または、
一般式（）
（式中、R1、R2は前記と同じ意味を示す）
で表わされる３位にカルボニル置換されたビスク
マリン類から選ばれた少なくとも１種の化合物お
よびジアリールヨードニウム塩からなる組合わせ
を光重合開始剤とすることを特徴とする光硬化樹
脂組成物に関するものである。
本発明によれば、３−ケト置換クマリンとジア
リールヨードニウム塩とからなる光重合開始系が
極めて高い効率で機能するので、容易に可視光線
に光不溶化する感光材料を製造することができ
る。
本発明の光不溶性樹脂組成物を構成するエチレ
ン性不飽和結合を少なくとも１つ持つ化合物とし
ては、ビニル系モノマーの他にオリゴマーを含
み、さらには、高分子量化合物でもよい。具体的
には、アクリル酸、メタクリル酸、イタコン酸、
マレイン酸、アクリルアミド、メタクリルアミ
ド、ジアセトンアクリルアミド、Ｎ−ビニルカル
バゾールなどの高沸点モノマーがあり、さらに
は、エチレングリコール、ジエチレングリコー
ル、１，３−プロパンジオール、１，４−ブタン
ジオール、１，５−ペンタンジオール、１，６−
ヘキサンジオール、１，10−デカンジオール、ト
リメチロールエタン、ペタンエリスリトール、ソ
ルビトール、マンニトールなどのジあるいはポリ
（メタ）アクリルエステル、さらには、（メタ）ア
クリルされたエポシキ樹脂、ポリエステルアクリ
レートオリゴマー、（メタ）アクリル化ウレタン
オリゴマー、アクロレイン化ポリビニルアルコー
ルなどをあげることができる。
光重合開始剤を構成する一般式（）または
（）で表わされる３−ケトクマリンとしては、
クマリンのベンゼン核にアルコキシ基またはジア
ルキルアミノ基が置換されていることが望まし
い。具体的に一般式（）で表わされる化合物の
例としては、３−アセチル−７−ジエチルアミノ
クマリン、３−アセチル−５，７−ジメトキシク
マリン、３−ベンゾイル−７−ジエチルアミノク
マリン、３−シンナモイル−７−ジエチルアミノ
クマリン、３−（Ｐ−ジエチルアミノシンナモイ
ル）−７−ジエチルアミノクマリンがあり、また、
一般式（）で表わされる化合物の例としては、
３，3′−カルボニルビス（７−ジエチルアミノク
マリン）、３，3′−カルボニルビス（５，７−ジ
メトキシカルボニルクマリン）などをあげること
ができる。
次に、光重合開始系を構成する今一つの成分と
してのジアリールヨードニウム塩は、一般式
（）
（式中、R3、R4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、BF4 -、PF6 -またはAsF6 -を示す）
で表わされる化合物である。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−ｔ−ブチルフエニル）ヨード
ニウムなどのヨードニウムのホウフツ化塩、ヘキ
サフルオロホスフエート塩、ヘキサフルオロアル
セネート塩およびクロリド、ブロミドをあげるこ
とができる。
本発明の光硬化樹脂組成物中含有される光重合
開始剤の量は、光重合開始剤対エチレン性化合物
の重量比で約１：５から約１：500までの広い範
囲をとることが可能であり、好ましくは約１：10
から約１：100の範囲である。また、光重合開始
剤を構成する３−ケトクマリン類とジアリールヨ
ードニウム塩との重量比は約10：１から約１：10
までの範囲であり、好ましくは、約２：１から約
１：５までの範囲である。
本発明の光硬化樹脂組成物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。さらには、公知のバインダー、熱重合
禁止剤、可塑剤などの添加剤を必要に応じて加え
て良い。
本発明の組成物に適した光原としては、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レーザーやAr
レーザーが利用できる。
本発明の光硬化樹脂組成物は従来の光重合性組
成物よりも優れた感度を有しているので、平版ま
たは凸版用製版材料、レリーフの作製、比銀塩画
像の作成、プリント配線板の作成など幅広い分野
に応用できるほか、レーザー光にも感光すること
から、ネガレスでの製版用としても有効である。
以下、実施例をもつて本発明をさらに詳細に説
明するが、本発明はこれに限定されるものではな
い。
実施例 １
クロロメチルスチレンとメタクリル酸メチルと
の50：50共重合体1.26ｇをジメチルホルムアミド
20ｇに溶解し、これにクロロメチルスチレン単位
に対して1.5倍モルのメタクリル酸カリウムを添
加して75℃で４時間撹拌した。反応液から分離し
精製したポリマーのジオキサン溶液を調製し、次
いで、これにポリマーに対して10重量％のジフエ
ニルヨードニウム・ヘキサフルオロホスフエート
と５重量％のビス（７−ジエチルアミノ−３−ク
マリル）ケトンを添加して感光液とした。この溶
液を陽極酸化アルミ板にスピン塗布し、ゴダツク
ステツプタブレツトNo.１越しに露光して感度を測
定したところ、市販のポリビニル桂皮酸系感光材
［東京応化工業(株)：TPR］の約128倍の感度を示
した。この感度は、脱気真空下でもほとんど変化
しなかつた。また、この感光性樹脂組成物をガラ
ス板に塗布し、アルゴンレーザの488ｍの光
（0.28ｍＷ／cm2）を照射して残膜率を測定したと
ころ、約10ｍＪ／cm2の露光量でほぼ定量的に不溶
化し、１ｍＪ／cm2の露光量で約20％の残膜が認め
られた。
実施例 ２
クロロメチルスチレンとメタクリル酸メチルと
の50：50共重合体とアクリル酸カリウムとの反応
で得たポリマーと、ポリマーに対して10重量％の
ジフエニルヨードニウム・ヘキサフルオロホスフ
エートと５重量％のビス（７−ジエチルアミノ−
３−クマリル）ケトンとからなる感光性樹脂組成
物のジオキサン溶液を調製し、その感度を測定し
たところ、TPRの約256倍の感度を示した。
実施例 ３〜６
実施例１で用いたポリマー１部、３−アセチル
−７−ジエチルアミノクマリン0.01部および表１
に示すヨードニウム塩のジオキサン溶液を調製
し、その感度をXe光を用いて測定した。結果を
表１にまとめた。
The present invention relates to a photocurable resin composition exhibiting excellent sensitivity, and more particularly to a photocurable resin composition characterized by containing a combination of 3-ketocoumarins and diaryliodonium salt as a photopolymerization initiator. It is something. 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 can replace silver salts. Conventional photosensitive special products are extremely inadequate. Therefore, it is necessary to expand the photosensitive wavelength range and dramatically increase the photosensitive speed. In this case, it goes without saying that the photosensitive resin must have both high resolution, which is an excellent characteristic, and various physical properties suitable for the purpose. Several proposals have been made for photopolymerizable resins that are sensitive to visible light. Among them, Tokukai 52-
Publication No. 112681 proposes a photosensitive composition using a coumarin compound. Also, JP-A-58
Publication No. 15503 describes a photosensitive composition in which 3-ketocoumarin is combined with an active halogen compound. As the halogen compound in the latter, a compound in which at least one of a sulfonylchloro group, monohalomethyl, dihalomethyl, or trihalomethyl group is bonded to an aromatic hydrocarbon ring or an aromatic heterocyclic ring is used. However, in order to use it as a photosensitive material for lasers, a silver salt substitute material, etc., it is necessary to make it even more sophisticated. The present invention was completed based on the discovery that 3-ketocoumarins cause sensitized decomposition with remarkable efficiency during the process of investigating the sensitized decomposition reaction of diaryliodonium salts that generate acid through photolysis. It is what was done. That is, the present invention provides a photocurable resin composition comprising (A) a compound having at least one photopolymerizable ethylenically unsaturated bond and (B) a photopolymerization initiator, which has the general formula () (In the formula, R 1 and R 2 represent a hydrogen atom, an alkoxy group or a dialkylamino group, and R 3 represents a lower alkyl group or an aryl group) or 3-ketocoumarins represented by the general formula () (In the formula, R 1 and R 2 have the same meanings as above) Photopolymerize a combination consisting of at least one compound selected from biscoumarins substituted with carbonyl at the 3-position and a diaryliodonium salt. The present invention relates to a photocurable resin composition characterized by using an initiator. According to the present invention, a photopolymerization initiation system consisting of a 3-keto-substituted coumarin and a diaryliodonium salt functions with extremely high efficiency, so that it is possible to produce a photosensitive material that is easily photoinsolubilized by visible light. The compound having at least one ethylenically unsaturated bond constituting the photoinsoluble resin composition of the present invention includes oligomers in addition to vinyl monomers, and may also be high molecular weight compounds. Specifically, acrylic acid, methacrylic acid, itaconic acid,
There are high-boiling monomers such as maleic acid, acrylamide, methacrylamide, diacetone acrylamide, N-vinylcarbazole, and also ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-
Di- or poly(meth)acrylic esters such as hexanediol, 1,10-decanediol, trimethylolethane, petaneerythritol, sorbitol, mannitol, etc., as well as (meth)acrylated epoxy resins, polyester acrylate oligomers, (meth)acrylic esters, etc. Examples include acrylated urethane oligomers and acroleinated polyvinyl alcohol. As the 3-ketocoumarin represented by the general formula () or () constituting the photopolymerization initiator,
It is desirable that the benzene nucleus of coumarin is substituted with an alkoxy group or a dialkylamino group. Specific examples of compounds represented by the general formula () include 3-acetyl-7-diethylaminocoumarin, 3-acetyl-5,7-dimethoxycoumarin, 3-benzoyl-7-diethylaminocoumarin, and 3-cinnamoyl-7. -diethylaminocoumarin, 3-(P-diethylaminocinnamoyl)-7-diethylaminocoumarin, and
Examples of compounds represented by the general formula () are:
Examples include 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(5,7-dimethoxycarbonylcoumarin). Next, the diaryliodonium salt as another component constituting the photopolymerization initiation system has the general formula () (In the formula, R 3 and R 4 are hydrogen atoms, lower alkyl groups,
It represents a methoxy group or a nitro group, and X - represents a halogen ion, BF 4 - , PF 6 - or As F 6 - . 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-t-butylphenyl)iodonium, etc. Mention may be made of iodonium borofluoride salts, hexafluorophosphate salts, hexafluoroarsenate salts, and chlorides and bromides. The amount of the photopolymerization initiator contained in the photocurable resin composition of the present invention can range widely from about 1:5 to about 1:500 in weight ratio of photopolymerization initiator to ethylenic compound. and preferably about 1:10
The range is approximately 1:100. In addition, the weight ratio of the 3-ketocoumarins and diaryliodonium salt constituting the photopolymerization initiator is about 10:1 to about 1:10.
and preferably from about 2:1 to about 1:5. A pigment or dye may be added to the photocurable resin composition of the present invention as a coloring agent, if desired. Furthermore, known additives such as binders, thermal polymerization inhibitors, and plasticizers may be added as necessary. Suitable light sources for the compositions of the present invention include high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, halogen lamps, fluorescent lamps, as well as He-Cd lasers and Ar
Laser available. The photocurable resin composition of the present invention has a sensitivity superior to that of conventional photopolymerizable compositions, so it can be used as a plate-making material for planography or letterpress, in the production of reliefs, in the production of specific silver salt images, and in printed wiring boards. In addition to being applicable to a wide range of fields such as creation, it is also sensitive to laser light, making it effective for negativeless plate making. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 1.26 g of a 50:50 copolymer of chloromethylstyrene and methyl methacrylate was dissolved in dimethylformamide.
20 g of potassium methacrylate was added thereto in an amount of 1.5 times the mole per chloromethylstyrene unit, and the mixture was stirred at 75° C. for 4 hours. A dioxane solution of the polymer separated and purified from the reaction solution was prepared, and then 10% by weight of diphenyliodonium hexafluorophosphate and 5% by weight of bis(7-diethylamino-3-coumaryl) were added to the polymer. A photosensitive solution was prepared by adding ketones. This solution was spin-coated on an anodized aluminum plate and exposed through a Godax Step Tablet No. 1 to measure the sensitivity. The sensitivity was approximately 128 times higher. This sensitivity hardly changed even under degassed vacuum. In addition, when this photosensitive resin composition was coated on a glass plate and irradiated with 488 m of argon laser light (0.28 mW/cm 2 ) to measure the residual film rate, it was found that approximately 10 mJ/cm 2 of exposure amount resulted in approximately It was quantitatively insolubilized, and approximately 20% of the film remained after an exposure dose of 1 mJ/cm 2 . Example 2 A polymer obtained by reacting a 50:50 copolymer of chloromethylstyrene and methyl methacrylate with potassium acrylate and 5% by weight of diphenyliodonium hexafluorophosphate, based on the polymer. % bis(7-diethylamino-
When a dioxane solution of a photosensitive resin composition comprising 3-coumaryl) ketone was prepared and its sensitivity was measured, it showed a sensitivity approximately 256 times that of TPR. Examples 3 to 6 1 part of the polymer used in Example 1, 0.01 part of 3-acetyl-7-diethylaminocoumarin, and Table 1
A solution of the iodonium salt shown in dioxane was prepared, and its sensitivity was measured using Xe light. The results are summarized in Table 1.
【表】
実施例 ７
ポリメタクリル酸ベンジル一部、ペンタエリス
リトールトリアクリレート１部、３−アセチル−
７−ジエチルアミノクマリン0.1部およびジフエ
ニルヨードニウム・ヘキサフルオロホスフエート
0.1部からなる感光性樹脂組成物のジオキサン溶
液を調製し、これを陽極酸化アルミ板上に塗布し
て感度を測定した。その結果、TPRに対して約
４倍の感度を示した。[Table] Example 7 One part of polybenzyl methacrylate, one part of pentaerythritol triacrylate, 3-acetyl-
0.1 part of 7-diethylaminocoumarin and diphenyliodonium hexafluorophosphate
A dioxane solution of a photosensitive resin composition containing 0.1 part was prepared, and the solution was coated on an anodized aluminum plate to measure the sensitivity. As a result, the sensitivity was approximately four times higher than that of TPR.
Claims (1)
なくとも１つ有する化合物および(B)光重合開始剤
からなる光硬化樹脂組成物において、３−ケトク
マリン類とジアリールヨードニウム塩との組合わ
せを光重合開始剤とすることを特徴とする光硬化
樹脂組成物。1. In a photocurable resin composition consisting of (A) a compound having at least one ethylenically unsaturated bond with polymerization ability and (B) a photopolymerization initiator, the combination of 3-ketocoumarins and diaryliodonium salt is A photocurable resin composition characterized by containing a polymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19808583A JPS6088005A (en) | 1983-10-21 | 1983-10-21 | Photocurable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19808583A JPS6088005A (en) | 1983-10-21 | 1983-10-21 | Photocurable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6088005A JPS6088005A (en) | 1985-05-17 |
| JPH0362162B2 true JPH0362162B2 (en) | 1991-09-25 |
Family
ID=16385254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19808583A Granted JPS6088005A (en) | 1983-10-21 | 1983-10-21 | Photocurable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6088005A (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2539810B2 (en) * | 1987-01-22 | 1996-10-02 | 日本ペイント株式会社 | High-sensitivity photopolymerizable composition |
| JPH02144539A (en) * | 1988-11-28 | 1990-06-04 | Sumitomo Bakelite Co Ltd | Photosensitive resin composition |
| JPH02238002A (en) * | 1989-03-10 | 1990-09-20 | Nippon Paint Co Ltd | Photosensitive composition |
| JP3141517B2 (en) | 1992-05-14 | 2001-03-05 | ブラザー工業株式会社 | Photocurable composition |
| US5738974A (en) | 1994-09-05 | 1998-04-14 | Mitsubishi Chemical Corporation | Photopolymerizable composition and photosensitive lithographic printing plate |
| DE69620723T2 (en) | 1995-12-22 | 2002-12-05 | Mitsubishi Chem Corp | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
| EP2078978A3 (en) | 2004-04-26 | 2009-07-22 | Mitsubishi Chemical Corporation | LCD backlight containing a LED with adapted light emission and suitable colour filters |
| JP4257295B2 (en) | 2005-01-07 | 2009-04-22 | 日東電工株式会社 | Photorefractive index modulation polymer composition, hologram recording material, and refractive index control method |
| TW200807104A (en) | 2006-04-19 | 2008-02-01 | Mitsubishi Chem Corp | Color image display device |
| EP2242119A4 (en) | 2008-02-07 | 2012-03-07 | Mitsubishi Chem Corp | Semiconductor light emitting device, backlighting device, color image display device and phosphor used for those devices |
| CN102344504B (en) | 2011-07-29 | 2013-03-13 | 华中科技大学 | Visible light photoinitiation system for preparing high diffraction efficiency holographic photopolymer material |
| EP3147335A1 (en) | 2015-09-23 | 2017-03-29 | BYK-Chemie GmbH | Colorant compositions containing wettting and/or dispersing agents with low amine number |
| KR101970730B1 (en) | 2017-04-20 | 2019-04-23 | 한국화학연구원 | Azobenzen compound and composition for hologram recording comprising thereof |
| KR101869388B1 (en) | 2017-05-15 | 2018-06-21 | 한국화학연구원 | Photoisomerizable diphenyldiacetylene-azobenzen mesogens and polymers there of |
| KR102407377B1 (en) | 2017-11-15 | 2022-06-13 | 비와이케이-케미 게엠베하 | block copolymer |
| KR102407380B1 (en) | 2017-11-15 | 2022-06-13 | 비와이케이-케미 게엠베하 | block copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52112681A (en) * | 1976-02-02 | 1977-09-21 | Eastman Kodak Co | Sensitive composition |
| JPS5815503A (en) * | 1981-07-20 | 1983-01-28 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
-
1983
- 1983-10-21 JP JP19808583A patent/JPS6088005A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52112681A (en) * | 1976-02-02 | 1977-09-21 | Eastman Kodak Co | Sensitive composition |
| JPS5815503A (en) * | 1981-07-20 | 1983-01-28 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6088005A (en) | 1985-05-17 |
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