JP3797381B2 - ポジ型感光性組成物 - Google Patents
ポジ型感光性組成物 Download PDFInfo
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- JP3797381B2 JP3797381B2 JP2005084185A JP2005084185A JP3797381B2 JP 3797381 B2 JP3797381 B2 JP 3797381B2 JP 2005084185 A JP2005084185 A JP 2005084185A JP 2005084185 A JP2005084185 A JP 2005084185A JP 3797381 B2 JP3797381 B2 JP 3797381B2
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- Prior art keywords
- dye
- photosensitive composition
- light
- positive photosensitive
- compound
- 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.)
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- 239000011347 resin Substances 0.000 claims abstract description 48
- -1 quinolinium compound Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims description 43
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 claims description 4
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZLBAMQINIRRJEN-UHFFFAOYSA-N benzyl naphthalene-1-sulfonate Chemical compound C=1C=CC2=CC=CC=C2C=1S(=O)(=O)OCC1=CC=CC=C1 ZLBAMQINIRRJEN-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 230000008543 heat sensitivity Effects 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
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- AMZOVRCWZOIZHH-UHFFFAOYSA-N phenyl naphthalene-2-sulfonate Chemical compound C=1C=C2C=CC=CC2=CC=1S(=O)(=O)OC1=CC=CC=C1 AMZOVRCWZOIZHH-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
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- 239000002798 polar solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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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 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
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- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- 230000007704 transition Effects 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- OTAPGXWPDKYADF-UHFFFAOYSA-N tributyl 1,3,5-triazine-2,4,6-tricarboxylate Chemical compound CCCCOC(=O)C1=NC(C(=O)OCCCC)=NC(C(=O)OCCCC)=N1 OTAPGXWPDKYADF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- DBPYGJOORSXBMI-UHFFFAOYSA-N trinaphthalen-1-yl phosphate Chemical compound C1=CC=C2C(OP(OC=3C4=CC=CC=C4C=CC=3)(OC=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 DBPYGJOORSXBMI-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
- B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/127—Spectral sensitizer containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/145—Infrared
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Printing Plates And Materials Therefor (AREA)
Description
特に、高出力の半導体レーザーやYAGレーザーを用いる、高解像度のレーザー感光ダイレクト製版システムは、小型化、製版作業時の環境光や版材コストの面から、その実現が強く望まれていた。
また、更にこれに類する技法として赤外線吸収色素、潜伏性ブレンステッド酸、レゾール樹脂およびノボラック樹脂を含む感光層を半導体レーザー等により像状に露光し平版印刷版を作製する技術が提案されており(特開平7−20629号公報)、更に、前記潜伏性ブレンステッド酸に代えs−トリアジン化合物を用いる技術も開示されている(特開平7−271029号公報)。
更に、大きな問題点として、通常、このような化学増幅型感光版の場合は露光後の加熱処理工程が必須であり、この後、加熱処理条件等の振れに起因して、得られる画像の品質安定性は必ずしも充分でなく、従ってこの工程を含まない技術が望まれていた。前述の特開平7−20629号、7−271029号各公報には、前記の後加熱処理を経ずにポジ画像を得る手法が提案されているが具体的な実施例は示されておらず、ポジ画像を得た事実及びその具体的手法は全く示されていない。また、これらの技術は、感材が紫外光に対しても感光するため、紫外光を含まない黄色灯の下で作業する必要があり、作業性の点で問題があった。
又、特開昭60−175046号公報には、アルカリ可溶性フェノール樹脂と輻射線感光性オニウム塩とからなり、組成物が光可溶化性である輻射線感光性組成物が開示され、該組成物は、オニウム塩の光分解的分解が樹脂に溶解度を回復させ、光可溶化系の基本的要請を満たすこと、更に、オニウム塩はUVから可視へそして赤外の中に至る広範囲の電磁スペクトルに対して増感されうることが示されている。
従来より、ポジ型感光性組成物としては、アルカリ可溶性樹脂及び感光性付与成分としてo−キノンジアジド基含有化合物を含んだ系が知られている。この系では、o−キノンジアジド基含有化合物が吸収可能な紫外光を照射することにより、ジアゾ部分が分解し最終的にカルボン酸が生成することによって、樹脂のアルカリ可溶性が増加し、即ち露光部分のみがアルカリ現像液に溶解することによって画像が形成するものと考えられている。又、前述の特開昭60−175046号に記載の組成物は、オニウム塩の光分解的分解が樹脂の溶解性に関与している。従って、これらの系は感光性組成物中の成分が化学変化を伴うものである。
本発明の感光性組成物がこのような優れた効果を奏する理由は必ずしも明らかではないが、光熱変換分解物質によって吸収された光エネルギーが、熱に変換され、その熱を受けた部分のアルカリ可溶性樹脂がコンフォメーション変化等の何らかの化学変化以外の変化を起こし、その部分のアルカリ可溶性が高まることによって、アルカリ現像液により画像が形成されるものと考えられる。
先ず、本発明のポジ型感光性組成物に用いられる第1成分である、光熱変換物質(以下、光吸収色素と称す)について説明する。該物質としては、吸収した光を熱に変換しうる化合物であれば特に限定されないが、波長域650〜1300nmの一部又は全部に吸収帯を有する光吸収色素(a)が特に有効である。本発明に用いられる光吸収色素は、650〜1300nmの波長域の光を効率よく吸収する一方、紫外領域の光は、ほとんど吸収しないか、吸収しても実質的に感応せず、白色灯に含まれるような弱い紫外線によっては、感光性組成物を変成させる作用のない化合物である。これらの光吸収色素の具体例を第1表に示す。
これらの内、シアニン色素、ポリメチン色素、スクアリリウム色素、クロコニウム色素、ピリリウム色素、チオピリリウム色素が好ましい。更に、シアニン色素、ポリメチン色素、ピリリウム色素、チオピリリウム色素がより好ましい。
これらの内、特に好ましい色素は、波長域650〜900nmにおいては下記一般式[I]で表されるシアニン色素または一般式[II]で表されるポリメチン色素であり、波長域800〜1300nmにおいては下記一般式[III]表されるピリリウム色素またはチオピリリウム色素である。
、フェニル基、フェノキシ基、アルコキシ基、スルホン酸基、カルボキシル基であり;Q1は置換基を有していても良いヘプタメチン基であり、該置換基は、C8以下のアルキル基、ハロゲン原子、アミノ基であるか、該ヘプタメチン基がその2つのメチン炭素上の置換基が相互に結合して形成された置換基を有していても良いシクロヘキセン環またはシクロペンテン環を含むものであっても良く、該置換基はC8以下のアルキル基またはハロゲン
原子であり;m1、m2は各々が0または1であり;Z1、Z2は含窒素複素環を形成するに必要な原子群であり;X− は対アニオンを示す。]
アリール基であり、該アリール基は、フェニル基、ナフチル基、フリル基またはチエニル基であり、該置換基はC4以下のアルキル基、C8以下のアルキル基を有するジアルキルアミノ基、C8以下のアルコキシ基およびハロゲン原子である。Q2はトリメチン基またはペンタメチン基を示し;X-は対アニオンを示す。]
C8以下のアルコキシ基であり;l1とl2は各々独立に0または1を示し;R9〜R14は水素原子またはC8以下のアルキル基を示すかあるいは各々独立にR9とR10、R11とR12またはR13とR14とが相互に結合して
。)の連結基を形成しても良く;Z3はハロゲン原子または水素原子;X-は対アニオンを示す。]
以上の[I]、[II]および[III]式における対アニオンX-を具体的に示すに、例え
ば、Cl-、Br-、I-、ClO4 -、BF4 -、PF6 -等の無機酸アニオン、ベンゼンスル
ホン酸、p−トルエンスルホン酸、ナフタレン−1−スルホン酸、酢酸の様な有機酸アニオンを挙げることができる。
これらの光吸収色素の本発明のポジ型感光性組成物中における使用割合は、重量比で好ましくは0.1〜30%、より好ましくは1〜20%である。
縮合物であるノボラック樹脂が好ましい。
又、t−ブトキシカルボニル基、ピラニル基、フラニル基などでポリビニルフェノール類の一部のOH基を保護した樹脂でもよい。ポリビニルフェノール樹脂のMwは、好ましくは1,000〜100,000、特に好ましくは1,500〜50,000のものが用いられる。
以上のノボラック樹脂またはポリビニルフェノール樹脂のMwが、上記範囲よりも小さいと十分な塗膜が得られず、この範囲よりも大きいと未露光部分のアルカリ現像液に対する溶解性が小さくなり、パターンが得られない傾向にある。
本発明で用いられる前記の成分(a)及び成分(b)から成るポジ型感光性組成物中におけるこれら樹脂の使用割合は重量比で好ましくは70%〜99.9%であり、特に好ましくは80%〜99%である。
本発明の感光性組成物は、その成分として、光吸収色素(a)と、前記アルカリ可溶性樹脂(b)から成る配合物のアルカリ性現像液に対する溶解速度を低減し得る溶解抑止剤(c)(以下、単に溶解抑止剤と称す)を更に含んでいてもよい。
該溶解抑止剤は、少なくとも、それの添加により前記成分(a)及び(b)からなる配合物のアルカリ現像液に対する溶解速度を80%以下に抑制する化合物でなければならないが、好ましくは、該溶解速度が50%以下に、更に好ましくは30%以下に抑制する化合物である。
本発明に使用する感光性組成物を支持体表面に設ける際に用いる塗布方法としては、従来公知の方法、例えば、回転塗布、ワイヤーバー塗布、ディップ塗布、エアーナイフ塗布、ロール塗布、ブレード塗布及びカーテン塗布等を用いることが可能である。塗布量は用途により異なるが、例えば0.1〜10.0g/m2(固形分として)が好ましい。また
乾燥温度としては、例えば20〜150℃、好ましくは30〜120℃が採用される。
J/s・cm2)に依存することがある。ここで、レーザービームの光強度(mJ/s・
cm2)は、版面上でのレーザービームの単位時間当たりのエネルギー量(mJ/s)を
光パワーメーターにより測定し、また感光材表面におけるビーム径(照射面積;cm2)
を測定し、単位時間当たりのエネルギー量を照射面積で除することにより求めることができる。レーザービームの照射面積は、通常、レーザーピーク強度の1/e2強度を超える
部分の面積で定義されるが、簡易的には相反則を示す感光材を感光させて測定することもできる。
ることが好ましく、1.0×107 mJ/s・cm2以上であることが更に好ましい。光
強度が上記の範囲であれば、本発明のポジ型平版印刷版の感度特性が向上し、走査露光時間が短くすることができ実用的に大きな利点が得られる。
上記アルカリ現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、メタケイ酸ナトリウム、メタケイ酸カリウム、第二リン酸ナトリウム、第三リン酸ナトリウム等のアルカリ金属塩の水溶液が挙げられる。アルカリ金属塩の濃度は0.1〜20重量%が好ましい。又、該現像液中に必要に応じアニオン性界面活性剤、両性界面活性剤等やアルコール等の有機溶媒を加えることができる。
〔平版印刷版の作製〕
〔アルミニウム板(1)の作製〕
厚さ0.24mmのアルミニウム板(材質1050、調質H16)を、5重量%の水酸化ナトリウム水溶液中で60℃で1分間脱脂処理を行なった後、0.5モル/リットルの濃度の塩酸水溶液中において、温度25℃、電流密度60A/dm2、処理時間30秒の
条件で電解エッチング処理を行なった。次いで5重量%水酸化ナトリウム水溶液中で60℃、10秒間のデスマット処理を施した後、20重量%硫酸溶液中で、温度20℃、電流密度3A/dm2、処理時間1分の条件で陽極酸化処理を行なった。更に、80℃の熱水で20秒間熱水封孔処理を行ない、平版印刷版用支持体のアルミニウム板(1)を作製した。
下記成分よりなる感光液を前述の方法で作製したアルミニウム板(1)上にワイヤーバーで塗布し、85℃にて2分間乾燥させた後、55℃のオーブン中で安定させ、膜厚24mg/dm2の感光性層を設け、感光性平版印刷版を得た。
〔感光液〕
高分子化合物:第2表記載のノボラック樹脂 0.9g
光吸収色素:第2表記載の化合物 第2表記載の配合量
色材:ビクトリアピュアーブルーBOH 0.008g
溶媒:シクロヘキサノン 9g
次にこれらの感光性平版印刷版の一部に関し次の方法によりレーザー光の光強度の影響を調べた。
即ち、感光材表面での前記半導体レーザー(830nm)の受光エネルギーを40mwに固定し、光強度はレンズによる集光度を調節し適宜変化させ、それぞれに対応した感度を求めた。感度は露光ビーム径を再現する画線(ポジ)を与えるドラム回転数より求めた。なおレーザー受光エネルギーは光パワーメーターTQ8210(アドバンテスト社製)を用いて測定した。
得られた感度mJ/cm2の結果を第3表に示した。
下記成分によりなる感光液を前述の方法で作製したアルミニウム板(1)上にワイヤーバーで塗布し、85℃にて2分間乾燥させた後、55℃のオープン中で安定させ、膜厚20mg/dm2の感光性層を設け、感光性平版印刷版を得た。
光吸収色素:第4表記載の化合物 0.015g
高分子化合物:ノボラック樹脂:前記のSK−188 0.5g
溶解抑止剤:第4表に記載の化合物 0.1g
溶媒:シクロヘキサノン 5.3g
続いて以下の項目について評価した。その結果を第4表に示す。
上記感光性平版印刷版に関して実施例1と同様な方法により、感度をエネルギー値として求めた。但し、アルカリ性現像液SDR−1を標準倍率(6倍)で希釈し使用した。
上記感光性平版印刷版をアルカリ性現像液に浸漬し、感光性層が全て溶解するまでの時間(秒)を計測した。溶解抑止効果の値を下記式により求めた。
実施例20と同一の組成比から成る感光層を塗設した感光性平版印刷版を作成、同例と同条件の半導体レーザーを用いて150mJ/cm2の露光量で印刷用パターンを焼き付
け、印刷版を作成した。これを用いて4万枚の印刷を行なった結果、良好な印刷画像を得ることができた。
実施例20と同一の感光材料を40Wの白色蛍光灯2本(FLR40SW、三菱電機社製)の光源から2mの距離において2時間全面暴露した後実施例20と同様な方法により画像露光を行なった。その結果、実施例20と同様な良好なポジ画像が得られ特に異状は認められなかった。
実施例33と同一の感光材料を実施例44と同様な条件下で評価し同様な良好なポジ画像を得た。
実施例46
実施例25と同一の感光材料を実施例44と同様な条件下で評価し、同様に良好なポジ画像を得た。
実施例20と同一の光吸収色素を用いて下記組成から成る感光液を用いて同様に塗布、乾燥し化学増幅型のネガ型感光材料を作成した。
高分子化合物;実施例20と同一のもの 0.5g
光吸収色素;実施例20と同一のもの 0.015g
架橋剤サイメル300 (三井サイアナミッド社製) 0.1g
トリス−(トリクロロメチル)−s−トリアジン 0.015g
得られた感光材料を実施例44と同様な条件で全面暴露の後同様に画像露光し、100℃3分間加熱後、同様な現像液で現像した。その結果全面に強いカブリが生じネガ画像は得られなかった。
市販ポジ型PS版KM−3 (コニカ社製)を用いて実施例44と同一の条件で全面暴露し同様な現像液で現像した。その結果、画像は全面溶解しポジ画像は全く得られなかった。
下記成分によりなる感光液を前述の方法で作製したアルミニウム板(1)上にワイヤーバーで塗布し、85℃にて2分間乾燥させた後、55℃のオープン中で安定させ、膜厚24mg/dm2の感光性層を設け、第5表に記載の感光性平版印刷版(A〜F)を得た。
光吸収色素:S−53(第1表記載の化合物) 0.0135g
高分子化合物:前記のSK−188 0.5g
溶解抑止剤:第5表に記載の化合物 0.15g
色材:ビクトリアピュアーブルーBOH 0.004g
溶媒:シクロヘキサノン 5.5g
光強度は第6表に示す通り、4段階に変化させ、それぞれに対応した感度を求めた。
得られた結果を第6表に示す。
下記成分よりなる感光液を前述の方法で作製したアルミニウム板(1)上にワイヤーバーで塗布し、85℃にて2分間乾燥させた後、55℃のオーブン中で安定させ、膜厚24mg/dm2の感光性層を設け、感光性平版印刷版を得た。
[感光液]
高分子化合物:ノボラック樹脂SK−135 0.9g
光吸収色素:第7表記載の化合物 0.027g
色材:ビクトリアピュアーブルーBOH 0.008g
溶媒:シクロヘキサノン/クロロホルム(=3V/1V) 12g
次にこれらの感光性平版印刷版の一部に関し次の方法によりYAGレーザー光の光強度の影響を調べた。
即ち、実施例11において半導体レーザー(830nm、40mw)を前記のYAGレーザー(1064nm、480mw)に変更した以外は同様の方法、即ち、光強度はレンズによる集光度を調節し、適宜変化させ、それぞれのビーム径に対応した感度を実施例11と同様の方法により感度を求めた。
得られた感度の結果を第8表に示した。
れなかった(画線部の抜けなし)事を意味する。
本発明のポジ画像の形成機構は以下の参考例に示される様に従来の光化学変化を伴うポジ画像のそれとは顕著に異なる。即ち、本発明の感光層に於いてはレーザー露光部分に生じた溶解性の増加現象が加温処理することにより容易に減退もしくは消失する挙動を示す。以下、それを具体的に例示する。
厚さ0.24mmのアルミニウム板(材質1050、調質H16)を、5重量%の水酸化ナトリウム水溶液中で60℃で1分間脱脂処理を行なった後、0.5モル/リットルの濃度の塩酸水溶液中において、温度28℃、電流密度55A/dm2、処理時間40秒の
条件で電解エッチング処理を行なった。次いで4重量%水酸化ナトリウム水溶液中で60℃、12秒間のデスマット処理を施した後、20重量%硫酸溶液中で、温度20℃、電流密度3.5A/dm2、処理時間1分の条件で陽極酸化処理を行なった。更に、80℃の
熱水で20秒間熱水封孔処理を行ない、平版印刷版用支持体のアルミニウム板(2)を作製した。
下記成分よりなる感光液を前述の方法で作製したアルミニウム板(2)上にワイヤーバーで塗布し、85℃にて2時間、乾燥した。感光層の塗膜量は2.5g/m2であった。
得られた感光性印刷版の試料に関し、以下の手順に従って、露光部の溶解特性の変化挙動を調べた。
高分子化合物:第9表に記載のもの 3.6g
光吸収色素:S−53 0.12g
溶解抑止剤:使用する場合は第9表記載のもの 0.72g
色材:ビクトリアピュアーブルーBOH 0.032g
シクロヘキサノン 37g
トを介し、クリヤー段数1段を与える光量で行なった。次いで、それら試料を実施例1同様に現像した。
か様にして得られたポジ画像の露光部に於ける感光層残存率は当然0%であるが、次に、これと同一で他の感光性印刷版を同様の条件で露光した後、現像工程前に55℃にて20時間保持する加温処理工程を挿入した場合、露光部の可溶化特性は減退し、得られるポジ画像部分は、もはや、必ずしも感光層が充分除去されず、通常、残膜が観察される。この場合の露光部に於ける感光層残存率[X]はそれら露光部、未露光部の溶解速度を測定することにより求める事ができ、この値は可逆性の度合いを示す目安となる。得られた結果を第9表に示す。
*1,*2:住友デュレス社製
。
下記成分よりなる感光液を前述の方法で作成したアルミニウム板(1)上にワイヤーバーで塗布し、85度にて2分間乾燥させた後、55度のオーブンで安定させ、膜厚20mg/dm2の感光層を設け、感光性平版印刷版を得た。
[感光液]
光吸収色素;第10表記載の化合物 0.02g
アルカリ可溶樹脂;m−クレゾール/p−クレゾール/
フェノールノボラック樹脂(SK−188)0.5g
溶解抑止剤;第10表記載の化合物 第10表に記載の量
溶媒;シクロヘキサノン 5.5g
尚、続いて以下の項目について評価した。その結果を第10表に示す。
上記感光性平版印刷版を40W2本の白色灯下1.5mの位置にて5時間曝露し、コニカ社製ポジ現像液SDR−1の6倍希釈現像液にて現像し、マクベス社製反射濃度計にて反射濃度を測定し残膜率に換算した。
1;ピロガロール−アセトン樹脂(Mw=2500)のナフチルスルホン酸エ
ステル(エステル化率20%)
2;ピロガロール−アセトン樹脂(Mw=2500)のp−トルエンスルホン
酸エステル(エステル化率20%)
3;p−トルエンスルホン酸2−フェニルエチル
4;ジフェニルヨードニウムp−トルエンスルホネート
5;トリフェニルスルホニウム−トリフルオロメタンスルホネート
Claims (6)
- 露光部と非露光部においてアルカリ現像液に対する溶解性に差異を生ずるポジ型感光性組成物において、該ポジ型感光性組成物が、該溶解性に差異を生ぜしめる本質的成分として(a)波長域650nm〜1.06μmの一部又は全部に吸収帯を有する光吸収色素、及び、(b)高分子化合物としてノボラック樹脂及び/又はポリビニルフェノール樹脂を含有し、該組成物が、更に、(c)本質的に(a)成分の光吸収色素及び(b)成分の高分子化合物からなる配合物のアルカリ性現像液に対する溶解速度を低減し得る溶解抑止剤を含有し、該組成物が紫外光に対して感光性を有しないことを特徴とするポジ型感光性組成物。
(但し、下記(ア)又は(イ)の場合を除く。
(ア)感光性組成物が、下記染料A及びカーボンブラックを含有する場合
(イ)感光性組成物が、下記染料B並びに、下記染料A、1−エチル−4−メチルキノリニウムブロミド、イミダゾリン化合物、ベンゾチアゾリウム化合物、セチルピリジニウムブロミド、エチルバイオロゲンジブロミド及びセトルイミドの何れかを含有する場合)
染料A
- 前記光吸収色素が、シアニン色素、ポリメチン色素、スクアリリウム色素、クロコニウム色素、ピリリウム色素及びチオピリリウム色素より選ばれた少なくとも一つの化合物であることを特徴とする請求項1に記載のポジ型感光性組成物。
- 前記高分子化合物がノボラック樹脂を含むことを特徴とする請求項1又は2に記載のポジ型感光性組成物。
- 前記溶解抑止剤が(a)成分の光吸収色素及び(b)成分の高分子化合物からなる配合物のアルカリ性現像液に対する溶解速度を50%以下に低減し得る化合物であることを特徴とする請求項1〜3の何れか1項に記載のポジ型感光性組成物。
- 前記溶解抑止剤が、スルホン酸エステル類、リン酸エステル類、芳香族カルボン酸エステル類、カルボン酸無水物類、芳香族ケトン類、芳香族アルデヒド類、芳香族アミン類及び芳香族エーテル類から選ばれた少なくとも1つであることを特徴とする請求項1〜4の何れか1項に記載のポジ型感光性組成物。
- 40Wの白色蛍光灯2本の光源から2mの距離において2時間全面暴露した後にポジ画像形成可能であることを特徴とする請求項1〜5の何れか1項に記載のポジ型感光性組成物。
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EP (4) | EP1747884B2 (ja) |
JP (3) | JP3814961B2 (ja) |
AT (3) | ATE281932T1 (ja) |
DE (3) | DE69731513T2 (ja) |
DK (3) | DK1655132T3 (ja) |
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