JP4898821B2 - エポキシ樹脂を含有する多層画像形成性要素 - Google Patents
エポキシ樹脂を含有する多層画像形成性要素 Download PDFInfo
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- JP4898821B2 JP4898821B2 JP2008537759A JP2008537759A JP4898821B2 JP 4898821 B2 JP4898821 B2 JP 4898821B2 JP 2008537759 A JP2008537759 A JP 2008537759A JP 2008537759 A JP2008537759 A JP 2008537759A JP 4898821 B2 JP4898821 B2 JP 4898821B2
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- 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
- B41C1/1016—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 characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
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- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
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- 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
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- 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
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- 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
- Y10S430/111—Polymer of unsaturated acid or ester
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- 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
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Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Description
アルカリ性現像剤を使用して除去することができる高分子材料を含む内層、および
エポキシ当量130〜1000を提供するのに十分なペンダントエポキシ基を有するポリマーバインダーを含み、そして前記ペンダントエポキシ基のための硬化剤を含まない、画像形成用輻射線による露光前にアルカリ性現像剤を使用して除去することができないインク受容性外層
を有する基板を含んで成るポジ型画像形成性要素を提供する。
A) (上記)本発明のポジ型画像形成性要素を熱的に画像形成し、これにより、画像形成された領域と非画像形成領域とを有する画像形成された要素を形成し、そして
B) 画像形成された領域だけを除去するために、画像形成された要素をアルカリ性現像剤と接触させ、そして
C) 任意選択的に、画像形成され、そして現像された要素をベーキングする
ことを含み、
工程Aで得られた画像形成された要素が、外層のポリマーバインダー中のペンダントエポキシ基が実質的に未反応であることを特徴とする、
画像形成方法を提供する。
特に断らない限り、本明細書中に使用する「画像形成性要素」及び「印刷版前駆体」という用語は、本発明の態様を意味するものとする。
画像形成性要素は多くの方法で使用することができる。好ましい用途は、下でより詳しく説明するような平版印刷版の前駆体としての使用である。しかし、これが、本発明のただ1つの用途であるわけではない。例えば、画像形成性要素は、マスキング要素及びプリント基板を形成するための熱パターン形成系として使用することもできる。
一般に、本発明の画像形成性要素は、基板と、内層(「下層」としても知られる)と、内層上に配置された外層(「トップ層」又は「トップ塗膜」としても知られる)とを含む。熱画像形成前には、外層はアルカリ性現像剤によって除去することはできないが、しかし、熱画像形成後には、外層の画像形成された領域は、アルカリ性現像剤によって除去することができる。内層もアルカリ性現像剤によって除去することができる。赤外線吸収化合物(下記に定義する)が好ましくは内層内に存在し、そして任意選択的には内層と外層との間の分離層内にも存在する。
(上記式中、R2はOH、COOH、又はSO2NH2であり、そしてR3はH、又はメチルである)の1種又は2種以上のモノマーから誘導された20〜75モル%、好ましくは35〜60モル%の反復単位、及び任意選択的に、構造:
(上記式中、R4はOH、COOH、又はSO2NH2であり、そしてR5はH、又はメチルである)の1種又は2種以上のモノマーから誘導された1〜30モル%、好ましくは、存在するならば3〜20モル%の反復単位を含むコポリマーを含む。
画像形成性要素は、基板の表面(及びその上に設けられた任意のその他の親水性層)上に内層配合物を順次適用し、次いでコンベンショナルな塗布法又はラミネーション法を用いて、内層上に外層配合物を適用することによって調製することができる。内層配合物と外層配合物との混和を回避することが重要である。
使用中、画像形成性要素は、波長600〜1200 nm、好ましくは700〜1200 nmの赤外線レーザーを使用して、好適な赤外線源に当てられる。本発明の画像形成部材に露光を施すために使用されるレーザーは、ダイオード・レーザー・システムの信頼性及びメンテナンスの手間の少なさにより、好ましくはダイオード・レーザーであるが、しかし他のレーザー、例えば気体又は固体レーザーを使用することもできる。レーザー画像形成のための出力、強度、及び露光時間の組み合わせは、当業者には容易に明らかである。目下、商業的に入手可能な画像セッターにおいて使用される高性能レーザー又はレーザー・ダイオードは、波長800〜850 nm又は1040〜1120 nmの赤外線を放射する。
MEKは、メチルエチルケトンである。
DEKは、ジエチルケトンである。
PGMEは、1-メトキシプロパ-2-オールである。これはDowanol PMとしても知られる。
BLOは、γ-ブチロラクトンである。
加熱マントル、温度計、空気式撹拌器、水冷式還流冷却器、Claisenアダプター(Corning 9040 Ace Glass #4015)、及び窒素掃気部を備えた1リットル4首フラスコ内に、506.62グラムの1,3-ジオキソラン、16.99グラムのスチレン、23.19グラムのグリシジルメタクリレート、及び0.84グラムの1-ドデカンチオールを入れた。
ポリマーAの合成におけるように、494グラムの1,3-ジオキソラン、1.39グラムのメタクリルアミド、15.98グラムのスチレン、21.80グラムのグリシジルメタクリレート、及び0.83グラムの1-ドデカンチオールの反応溶液を形成した。
494グラムの1,3-ジオキソラン、2.83グラムのメタクリルアミド、15.36グラムのスチレン、20.97グラムのグリシジルメタクリレート、及び0.84グラムの1-ドデカンチオールで、上述のように反応溶液を形成した。
加熱マントル、温度調節器、機械的撹拌器、凝縮器、均圧添加漏斗、及び窒素入口を備えた1000 ml 4首磨りガラス・フラスコ内で、353.5 gのプロピレングリコールメチルエーテルアセテート、22.0 gのグリシジルメタクリレート、及び15.5 gのメチルメタクリレートを用いて、反応溶液を形成した。反応混合物を、1時間にわたって窒素パージ下で80℃まで加熱した。窒素流を変化させて溶液の上方に保持した後、0.375 gのAIBNを添加した。66.0 gのグリシジルメタクリレートと、46.5 gのメチルメタクリレートと、0.75 gのAIBNとの予混合溶液を、80℃で2時間にわたって添加した。重合反応をさらに7時間続け、この時間中に、0.375 gのAIBNをインターバルを置いて添加した。その結果生じたポリマーDは、不揮発分%の測定に基づいて>99 %の変換率で得られた。粘度(G.H'33)は「+T」(ほぼ570 cps)であった。ポリマーDは、グリシジルメタクリレートとメチルメタクリレートとの重量比が60:40であった。
加熱マントル、温度調節器、機械的撹拌器、凝縮器、均圧添加漏斗、及び窒素入口を備えた1000 ml 4首磨りガラス・フラスコ内で、235.6 gのプロピレングリコールメチルエーテルアセテート、20.0 gのグリシジルメタクリレート、及び5.0 gのメチルメタクリレートを用いて、反応混合物を形成した。反応混合物を、1時間にわたって窒素パージ下で80℃まで加熱した。窒素流を変化させて溶液の上方に保持した後、0.25 gのAIBNを添加した。60.0 gのグリシジルメタクリレートと、15.0 gのメチルメタクリレートと、0.5 gのAIBNとの予混合溶液を、80℃で2時間にわたって添加した。重合反応をさらに7時間続け、この時間中に、0.25 gのAIBNをインターバルを置いて添加した。その結果生じたポリマーEは、不揮発分%の測定に基づいて>99 %の変換率で得られた。粘度(G.H'33)は「O」(ほぼ370 cps)であった。ポリマーEは、グリシジルメタクリレートとメチルメタクリレートとの重量比が80:20であった。
加熱マントル、温度調節器、機械的撹拌器、凝縮器、均圧添加漏斗、及び窒素入口を備えた1000 ml 4首磨りガラス・フラスコ内で、235.6 gのプロピレングリコールメチルエーテルアセテート、15.0 gのグリシジルメタクリレート、及び8.7 gのメチルメタクリレート、及び1.2 gのt-ブチルアクリレートを用いて、反応混合物を形成した。反応混合物を、1時間にわたって窒素パージ下で80℃まで加熱した。窒素流を変化させて溶液の上方に保持した後、0.25 gのAIBNを添加した。45.0 gのグリシジルメタクリレートと、26.3 gのメチルメタクリレートと、3.8 gのt-ブチルアクリレートと、0.5 gのAIBNとの予混合物を2時間で80℃で添加した。重合反応をさらに8時間続け、この時間中に、0.5 gのAIBNをインターバルを置いて添加した。ポリマーEの変換率は、不揮発分のパーセントの測定に基づいて>99 %であった。粘度(G.H'33)は「O」(ほぼ370 cps)であった。ポリマーFは、グリシジルメタクリレートとメチルメタクリレートとt-ブチルアクリレートとの重量比が60:35:5であった。
ここに記載した種々のエポキシ含有ポリマーを外(トップ)層内に含有する画像形成性要素を、下記のように調製した:
下記表IVに記載した成分を用いて内層配合物を調製し、そして、0.012インチ(0.03 cm)巻線バーを使用して基板Aに適用し、そして135℃で30秒間にわたって乾燥させることにより、ほぼ1.5 g/cm2の乾燥塗膜を提供した。
現像剤可溶性:
水及びTSD01(5:1 v/v)の現像剤溶液の液滴を、180秒間にわたって10秒のインターバルを置いて各要素に適用した。現像剤溶液を、すぐに水で洗い落とした。表面(上層)劣化が始まるのに必要な時間(秒)を記録した。
商業的に入手可能なScreen PlateRite 4300シリーズ版セッターを使用して、各要素に画像を形成した。C1 2400Dpi内部試験パターンを、50、55、60、65、70、75、80、85及び90 %出力の露光を用いて、1000 rpmのドラムスピードで施した。その結果生じた画像形成された印刷版を、水及びTSD01(5:1 v/v)の現像剤溶液を含有するKodak Polychrome Graphics PK910II処理装置内で、12秒間にわたって30℃で処理した。現像された版を次いで、クリーンアウト(すなわちきれいな画像を生成するのに必要な最小露光)、及び最良露光(すなわち、最良の画質を生成する露光)に関して評価した。
これらの比較要素の外層が米国特許第6,152,036号明細書(上記)における教示内容に従った硬化型エポキシ含有ポリマーを含有することを除けば、例1〜6に記載された画像形成性要素と同様に、画像形成性要素を調製し、画像形成し、そして評価した。層配合物を下記表VIIに記載する。
内層配合物を、0.012インチ(0.03 cm)巻線バーを使用して基板Aに適用することにより、ほぼ1.5 g/cm2の乾燥塗膜を提供した。その結果生じた層を、135℃で30秒間にわたって乾燥させ、その後で、外層配合物を、0.006インチ(0.015 cm)巻線バーを使用して適用することにより、ほぼ0.60 g/cm2の乾燥塗膜重量を提供した。この外層を、135℃で40秒間にわたって乾燥させた。
現像剤可溶性:水/TSD01(4:1)の液滴を、最大120秒間にわたって10秒のインターバルを置いて要素試料に適用し、そして現像剤を、すぐに水で洗い落とした。現像剤が外層を攻撃し始めるのにかかる時間を記録した。
外層配合物をほぼ160℃で60秒間にわたって乾燥させることを除けば、比較例1に記載されているように、画像形成性要素を調製し、そして評価した。試験結果を下記表VIIIに示す。
Claims (9)
- 順に:
アルカリ性現像剤を使用して除去することができる高分子材料を含む内層、および
エポキシ当量130〜1000を提供するのに十分なペンダントエポキシ基を有するポリマーバインダーを含み、そして前記ペンダントエポキシ基のための硬化剤を含まない、画像形成用輻射線による露光前にアルカリ性現像剤を使用して除去することができないインク受容性外層
を有する基板を含んで成るポジ型画像形成性要素であって、
前記内層中に、赤外線吸収化合物を含むポジ型画像形成性要素。 - 前記外層ポリマーバインダーが、エポキシ当量140〜750を提供するのに十分なペンダントエポキシ基を有する、請求項1に記載の要素。
- 前記外層ポリマーバインダーが、1種又は2種以上のエチレン系不飽和型重合性モノマーから誘導されたアクリル樹脂であり、該モノマーうちの少なくとも1種が、ペンダントエポキシ基を含む、請求項1又は2に記載の要素。
- R1が、水素、メチル、又はクロロであり、Lが、-C(O)O-アルキレン、-C(O)O-アルキレン-フェニレン、又は-C(O)O-フェニレンであり、アルキレンの炭素原子数が1〜4であり、xが40〜95重量%であり、yが5〜60重量%であり、そしてR2が、グリシジル、又は3,4-エポキシシクロヘキシル基である、請求項4に記載の要素。
- xが、40〜95重量%であり、そしてペンダントエポキシ基を含む反復単位が、グリシジルアクリレート、グリシジルメタクリレート、3,4-エポキシシクロヘキシルメタクリレート、及び3,4-エポキシシクロヘキシルアクリレートのうちの1種又は2種以上から誘導される、請求項4又は5に記載の要素。
- A) 請求項1〜6のいずれか一項に記載のポジ型画像形成性要素を熱的に画像形成し、
これにより、画像形成された領域と非画像形成領域とを有する画像形成された要素を形成し、そして
B) 前記画像形成された領域だけを除去するために、前記画像形成された要素をアルカリ性現像剤と接触させ、そして
C) 任意選択的に、前記画像形成され、そして現像された要素をベーキングする
ことを含んで成り、
工程Aで得られた画像形成された要素が、前記外層の前記ポリマーバインダー中のペンダントエポキシ基が実質的に無反応であることを特徴とする、
画像形成方法。 - 前記現像剤が、チオ硫酸塩、又は少なくとも1つのN-水素原子と、ヒドロキシ又は酸性基又はポリエチレンオキシド鎖で置換されたアルキル基とを有するアミノ化合物を含む、請求項7に記載の方法。
- 請求項7又は8に記載の方法から得られた画像。
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US11/257,864 | 2005-10-25 | ||
US11/257,864 US7160653B1 (en) | 2005-10-25 | 2005-10-25 | Multilayer imageable element containing epoxy resin |
PCT/US2006/040316 WO2007050336A2 (en) | 2005-10-25 | 2006-10-16 | Multilayer imageable element containing epoxy resin |
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US7163770B1 (en) * | 2006-01-23 | 2007-01-16 | Eastman Kodak Company | Multilayer imageable element containing sulfonamido resin |
JP5068681B2 (ja) * | 2008-02-27 | 2012-11-07 | 富士フイルム株式会社 | 平版印刷版原版 |
EP2194429A1 (en) | 2008-12-02 | 2010-06-09 | Eastman Kodak Company | Gumming compositions with nano-particles for improving scratch sensitivity in image and non-image areas of lithographic printing plates |
ATE555904T1 (de) | 2009-08-10 | 2012-05-15 | Eastman Kodak Co | Lithografische druckplattenvorläufer mit betahydroxy-alkylamid-vernetzern |
EP2293144B1 (en) | 2009-09-04 | 2012-11-07 | Eastman Kodak Company | Method of drying lithographic printing plates after single-step-processing |
US20110097666A1 (en) | 2009-10-27 | 2011-04-28 | Celin Savariar-Hauck | Lithographic printing plate precursors |
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EP1940621B1 (en) | 2014-01-08 |
CN101296798A (zh) | 2008-10-29 |
EP1940621A2 (en) | 2008-07-09 |
WO2007050336A3 (en) | 2007-06-21 |
US7160653B1 (en) | 2007-01-09 |
CN101296798B (zh) | 2010-10-20 |
JP2009514018A (ja) | 2009-04-02 |
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