JP3757543B2 - Printing plate material and image forming method - Google Patents
Printing plate material and image forming method Download PDFInfo
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- JP3757543B2 JP3757543B2 JP13097397A JP13097397A JP3757543B2 JP 3757543 B2 JP3757543 B2 JP 3757543B2 JP 13097397 A JP13097397 A JP 13097397A JP 13097397 A JP13097397 A JP 13097397A JP 3757543 B2 JP3757543 B2 JP 3757543B2
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- hydrogen atom
- alkyl group
- photosensitive layer
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- 239000000463 material Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 239000006096 absorbing agent Substances 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229920003986 novolac Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
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- 125000005462 imide group Chemical group 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 4
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- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
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- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 22
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- 238000002474 experimental method Methods 0.000 description 9
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
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- -1 alkyl boron Chemical compound 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 5
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 230000005540 biological transmission Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
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- 238000007789 sealing Methods 0.000 description 3
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
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- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- 238000007743 anodising Methods 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
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Description
【０００１】
【発明の属する技術分野】
本発明は、赤外線の照射によってアルカリ性現像液に対して不溶化する感光層を有する画像形成材料及びそれを用いた画像形成方法に関する。
【０００２】
【従来の技術】
赤外線感光性のネガ型の感光層を有する画像形成材料として、米国特許第５，３４０，６９９号明細書には、酸発生剤、レゾール樹脂、ノボラック樹脂及び赤外線吸収剤を含有する感光層を有し、画像露光の後、現像処理前に加熱処理を施すことによりネガ型の画像形成材料として使用され、上記加熱処理を施さないとポジ型の画像形成材料として使用される技術が開示されている。
【０００３】
しかし、該画像形材料は、赤外線に対する感度が十分でなく、半導体レーザ等による画像露光（描画）に時間がかかる問題がある。また、現像性についても、支持体上に色素が残存し印刷で地汚れが発生するなどの問題がある。
【０００４】
特開昭６２−１６４０４９号公報には、ブロックイソシアネート及びイソシアネートと反応し得る活性水素を有するポリマーを含有する感性層を設け、かつ光熱変換物質を含有させた平版印刷原版が開示されているが、現像性が十分でなく地汚れを生じ、また耐刷性が十分でない問題がある。
【０００５】
特開平９−４３８４５号公報には、熱により架橋反応を起こす高分子化合物と、光を吸収し熱を発生する物質とを有するネガ型画像記録材料が開示されているが、現像性が十分でなく地汚れを生じる問題がある。
【０００６】
【本発明が解決しようとする課題】
本発明の目的は、赤外線による露光における感度が高く、現像性が向上し、地汚れが防止された画像形成材料及び画像形成方法を提供することである。
【０００７】
【課題を解決するための手段】
本発明の上記目的を達成する本発明は下記（１）〜（５）である。
【０００８】
（１）支持体上に、下記一般式（１）又は（２）で表される化合物、下記一般式（３）又は（４）で表される赤外吸収剤、ノボラック樹脂及びカルボン酸基、アミノ基又はヒドロキシル基を側鎖に有するビニル重合体を含有する感光層を有することを特徴とする印刷版材料。
【０００９】
【化３】
式中、Ｘ1、Ｘ2及びＸ3は各々水素原子又は置換基を表し、Ｘ1、Ｘ2及びＸ3の少なくとも１つは−ＮＲ1−ＣＯ−Ｏ−Ｒ2である。Ｒ1は水素原子又はアルキル基を表し、Ｒ2はアルキル基、アラルキル基、イミド基、トリアゾリル基、ピリジル基、スルホニル基、ピラゾリル基、ハロゲン原子又は芳香環基を表す。
【００１１】
【化４】
式中、Ｘ1、Ｘ2、Ｘ3及びＸ4は各々水素原子又は置換基を表し、Ｘ1及びＸ2の少なくとも１つ、並びにＸ3及びＸ4の少なくとも１つは−ＮＲ1−ＣＯ−Ｏ−Ｒ2である。Ｒ1は水素原子又はアルキル基を表し、Ｒ2はアルキル基、アラルキル基、イミド基、トリアゾリル基、ピリジニウム基、スルホニル基、ピラゾリル基、ハロゲン原子又は芳香環基を表す。Ｒ3及びＲ4は各々Ｒ1と同義である。
【００１３】
【化Ｂ】
【００１６】
（２）前記感光層を塗布する際に、塗布溶剤として、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、メチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブ、エチルセロソルブアセテート、ジメチルホルムアミド、ジメチルスルホキシド、ジオキサン、アセトン、シクロヘキサノン、トリクロロエチレン、メチルエチルケトンから選ばれる溶剤を用いることを特徴とする上記（１）に記載の印刷版材料。
（３）上記（１）又は（２）記載の印刷版材料の感光層上に赤外線を用いて画像を描画した後、アルカリ性現像液で未露光部を除去することを特徴とする画像形成方法。
【００１７】
以下、本発明について詳述する。
【００１８】
本発明の画像形成材料の感光層が含有する一般式（１）又は（２）で表される化合物（以下「本発明のブロック化イソシアネート」という）について説明する。
【００１９】
一般式（１）又は（２）におけるＸ1〜Ｘ4が表す−ＮＲ1−ＣＯ−Ｏ−Ｒ2において、Ｒ2が表すアルキル基としては炭素数１〜４のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基等）が好ましく、Ｒ2が表すイミド基としては例えば
【００２０】
【化５】
（Ｒ5及びＲ6は、各々水素原子、スルホ基、アルキル基又はヒドロキシル基を表す。）が挙げられる。Ｒ2が表すピリジル基は置換されていてもよく、例えば、
【００２２】
【化６】
（Ｌは、水素原子、アルキル基、ヒドロキシル基、又は置換もしくは無置換のアミノ基を表す。）が挙げられる。Ｒ2が表すスルホニル基としては例えば−ＳＯ2−Ｌ2（Ｌ2は上記Ｌと同義である。）が挙げられる。Ｒ2が表す芳香環基としては例えば
【００２４】
【化７】
が挙げられる。
【００２６】
Ｘ1〜Ｘ4が表す−ＮＲ1−ＣＯ−Ｏ−Ｒ2以外の置換基としては、置換若しくは無置換のアルキル基、置換若しくは無置換の芳香環基、置換若しくは無置換のアミノ基、アミド基（ＲＣＯＮＨ−、Ｒは鎖式又は環式の炭化水素基）又はハロゲン原子が好ましいが、これらに限定されない。
【００２７】
一般式（１）で表される化合物は、−ＮＲ1−ＣＯ−Ｏ−Ｒ2を２以上有することが好ましく、一般式（２）で表される化合物は、−ＮＲ1−ＣＯ−Ｏ−Ｒ2を４以上有することが好ましい。
【００２８】
本発明のブロック化イソシアネートは特開平７−２８０４号公報を参考として合成することができる。
【００２９】
本発明に用いられる赤外線吸収剤としては、波長７００ｎｍ以上の可視光線から赤外領域に吸収を持つ赤外吸収色素、カーボンブラック、磁性粉等を使用することができる。特に好ましい赤外線吸収剤は７００〜８５０ｎｍに吸収ピークを有し、ピークでのモル吸光係数εが１０5以上である赤外吸収色素である。
【００３０】
上記赤外吸収色素としては、シアニン系色素、スクアリウム系色素、クロコニウム系色素、アズレニウム系色素、フタロシアニン系色素、ナフタロシアニン系色素、ポリメチン系色素、ナフトキノン系色素、チオピリリウム系色素、ジチオール金属錯体系色素、アントラキノ系色素、インドアニリン金属錯体系色素、分子間ＣＴ色素等が挙げられる。
【００３１】
また、上記赤外吸収色素として、特開昭６３−１３９１９１号、同６４−３３５４７号、特開平１−１６０６８３号、同１−２８０７５０号、同１−２９３３４２号、同２−２０７４号、同３−２６５９３号、同３−３０９９１号、同３−３４８９１号、同３−３６０９３号、同３−３６０９４号、同３−３６０９５号、同３−４２２８１号、同３−１０３４７６号等に記載の化合物が挙げられる。
【００３２】
本発明において、赤外線吸収剤として、下記一般式（３）又は（４）で表されるシアニン染料が特に好ましい。
【００３３】
【化８】
一般式（３）及び（４）において、Ｚ1及びＺ2は各々硫黄原子、セレン原子又は酸素原子を表し、Ｘ1及びＸ2は各々置換基を有していてもよいベンゾ縮合環又はナフト縮合環を形成するのに必要な非金属原子群を表し、Ｒ1及びＲ2は各々置換基を表し、Ｒ1及びＲ2のどちらか一方はアニオン性解離性基を有する。Ｒ3、Ｒ4、Ｒ5及びＲ6は各々炭素原子数１〜３のアルキル基、水素原子又はハロゲン原子を表す。Ｌは炭素原子数５〜１３の共役結合の連鎖を表す。〕
本発明において、赤外線吸収剤として、前記一般式（３）又は（４）で表されるシアニン染料が特に好ましい。
【００３５】
一般式（３）又は（４）で表されるシアニン色素は、該一般式（３）又は（４）がカチオンを形成し、対アニオンを有するものを包含する。この場合、対アニオンとしては、Ｃｌ-、Ｂｒ-、ＣｌＯ4 -、ＢＦ4 -、ｔ−ブチルトリフェニルホウ素等のアルキルホウ素等が挙げられる。
【００３６】
一般式（３）及び（４）において、Ｌで表される共役結合の連鎖の炭素原子数（ｎ）は、画像露光の光源として赤外線を放射するレーザーが使用される場合、該レーザーの発信波長に合わせて有効な値を選択することが好ましい。例えば、発信波長１０６０ｎｍのＹＡＧレーザーを使用する場合は、ｎは９〜１３が好ましい。また、この共役結合部分は任意の置換基を有することができ、また、共役結合部分は複数の置換基により環を形成させてもよい。
【００３７】
一般式（３）及び（４）において、Ｘ1で表される環及びＸ2で表される環には任意の置換基を有することができる。該置換基としてハロゲン原子、炭素原子数１〜５のアルキル基、炭素原子数１〜５のアルコキシ基、−ＳＯ3Ｍ及び−ＣＯＯＭ（Ｍは水素原子又はアルカリ金属原子）から選ばれる基が好ましい。
【００３８】
Ｒ1及びＲ2は各々任意の置換基であるが、好ましくは、炭素原子数１〜５のアルキル基若しくは炭素原子数１〜５のアルコキシ基；−（ＣＨ2）n−Ｏ−）k−（ＣＨ2）mＯＲ（ｎ及びｍは各々１〜３の整数、ｋは０又は１、Ｒは炭素原子数１〜５のアルキル基を表す。）；Ｒ1及びＲ2の一方が−Ｒ−ＳＯ3Ｍで他方が−Ｒ−ＳＯ3 -（Ｒは炭素原子数１〜５のアルキル基、Ｍはアルカリ金属原子を表す）；又はＲ1及びＲ2の一方が−Ｒ−ＣＯＯＭで他方が−Ｒ−ＣＯＯ-（Ｒは炭素原子数１〜５のアルキル基、Ｍはアルカリ金属原子を表す。）である。Ｒ1及びＲ2は、感度及び現像性の点から、Ｒ1及びＲ2の一方が−Ｒ−ＳＯ3 -又は−Ｒ−ＣＯＯ-、他方が−Ｒ−ＳＯ3Ｍ又は−Ｒ−ＣＯＯＭであることが好ましい。
【００３９】
一般式（３）又は（４）で表されるシアニン色素は、画像露光の光源として半導体レーザーを使用する場合は７５０〜９００ｎｍにおいて、ＹＡＧレーザーを使用する場合は９００〜１２００ｎｍにおいて吸収ピークを示し、ε＞１×１０5のモル吸光係数を有するものが好ましい。
【００４０】
本発明に好ましく用いられる赤外線吸収剤の代表的具体例を以下に挙げるが、これらに限定されるものではない。
【００４１】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
【化１４】
【化１５】
【化１６】
【化１７】
【化１８】
【化１９】
【化２０】
【化２１】
【化２２】
これらの色素は公知の方法によって合成することができるが、下記のような市販品を用いることもできる。
【００５６】
日本化薬：ＩＲ７５０（アントラキノン系）；ＩＲ００２，ＩＲ００３（アルミニウム系）；ＩＲ８２０（ポリメチン系）；ＩＲＧ０２２，ＩＲＧ０３３（ジインモニウム系）；ＣＹ−２，ＣＹ−４，ＣＹ−９，ＣＹ−２０
三井東圧：ＫＩＲ１０３，ＳＩＲ１０３（フタロシアニン系）；ＫＩＲ１０１，ＳＩＲ１１４（アントラキノン系）；ＰＡ１００１，ＰＡ１００５，ＰＡ１００６，ＳＩＲ１２８（金属錯体系）
大日本インキ化学：Ｆａｓｔｏｇｅｎ ｂｌｕｅ８１２０
みどり化学：ＭＩＲ−１０１，１０１１，１０２１
その他、日本感光色素、住友化学、富士写真フィルム等の各社からも市販されている。
【００５７】
本発明において、赤外線吸収剤の添加量は、０．５〜５ｗｔ％の範囲が好ましい。該添加量が５ｗｔ％を越えると非画像部（未露光部）の現像性が低下し、０．５ｗｔ％未満では画像部の耐現像性が低下する。
【００５８】
本発明の画像形成材料の感性層にはアルカリ可溶性ポリマーを含有させることが好ましい。アルカリ可溶性ポリマーとしては、ノボラック、及びカルボン酸基、アミノ基又はヒドロキシル基を側鎖に有するビニル重合体が好ましい。
【００５９】
ノボラックとしては、例えばフェノール・ホルムアルデヒド樹脂、クレゾール・ホルムアルデヒド樹脂、特開昭５５−５７８４１号公報に記載されているようなフェノール・クレゾール・ホルムアルデヒド共重縮合体樹脂、特開昭５５−１２７５５３号公報に記載されているような、ｐ−置換フェノールとフェノールもしくはクレゾールとホルムアルデヒドとの共重縮合体樹脂等が挙げられる。
【００６０】
上記カルボン酸基、アミノ基又はヒドロキシル基を側鎖に有するビニル重合体としては、例えばノボラック樹脂やヒドロキシスチレン単位を有する重合体や後記一般式（５）で表される構造単位を有する重合体、その他公知のアクリル樹脂等を挙げることができる。
【００６１】
ヒドロキシスチレン単位を有する重合体としては、例えば特公昭５２−４１０５０号公報に記載されているポリヒドロキシスチレンやヒドロキシスチレン共重合体などを挙げることをことができる。
【００６２】
上記一般式（５）で表される構造単位を有する重合体とは、該構造単位のみの繰り返し構造を有する単独重合体、あるいは該構造単位と他のビニル系単量体の不飽和二重結合を開裂せしめた構造で示される構造単位１種以上とを組み合わせた共重合体である。
【００６３】
【化２３】
一般式（５）において、Ｒ1及びＲ2は各々、水素原子、メチル基やエチル基等のアルキル基又はカルボン酸基を表し、好ましくは水素原子である。Ｒ3は水素原子、塩素原子や臭素原子等のハロゲン原子又はメチル基、エチル基等のアルキル基を表し、好ましくは水素原子又はメチル基である。Ｒ4は水素原子、メチル基やエチル基等のアルキル基、フェニル基又はナフチル基を表す。
【００６５】
Ｙは置換基を有するものも含むフェニレン基又はナフチレン基を表し、該置換基としてはメチル基やエチル基等のアルキル基、塩素原子や臭素原子等のハロゲン原子、カルボン酸基、メトキシ基やエトキシ基等のアルコキシ基、ヒドロキシル基、スルホ基、シアノ基、ニトロ基、アシル基等が挙げられるが、好ましくは置換基を有しないか、あるいはメチル基で置換されているものである。
【００６６】
Ｘは窒素原子と芳香族炭素原子とを連結する２価の有機基で、ｎは０〜５の整数を表し、好ましくはｎが０である。
【００６７】
一般式（５）で表される構造単位を有する重合体は、さらに具体的に、例えば（ａ）〜（ｈ）で表すことができる。
【００６８】
【化２４】
（ａ）〜（ｈ）において、Ｒ1〜Ｒ5は各々水素原子、アルキル基又はハロゲン原子を表し、Ｘはアルキル基又はハロゲン原子を表す。また、ｍ、ｎ、ｌ、ｋ及びｓはそれぞれの構造単位のモル％を表す。
【００７０】
また、ノボラック樹脂、ヒドロキシスチレン単位を有する重合体、及び前記一般式（５）で表される構造単位を有する重合体は併用することもできる。
【００７１】
更に、本発明の感光性組成物には、該感光性組成物の感脂性を向上するために親油性の樹脂を添加することができる。
【００７２】
前記親油性の樹脂としては、例えば、特開昭５０−１２５８０６号公報に記載されているような、炭素数３〜１５のアルキル基で置換されたフェノール類とアルデヒドの縮合物、例えばｔブチルフェノールホルムアルデヒド樹脂などが使用可能である。
【００７３】
本発明の画像形成材料の感光層には必要に応じて、更に上記以外の色素、顔料、増感剤等を含有させることができる。
【００７４】
本発明の感性層は、前記各成分を溶解する下記の溶媒に溶解させて、これらを適当な支持体の表面に塗布乾燥させることにより感性層を設けて本発明の画像形成材料とすることができる。
【００７５】
上記溶媒としては、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、メチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブ、エチルセロソルブアセテート、ジメチルホルムアミド、ジメチルスルホキシド、ジオキサン、アセトン、シクロヘキサノン、トリクロロエチレン、メチルエチルケトン等が挙げられる。これら溶媒は、単独であるいは２種以上混合して使用する。
【００７６】
塗布方法は、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が可能である。塗布量は用途により異なるが、例えば、感光性平版印刷版についていえば固形分として０．５〜５．０ｇ／ｍ2が好ましい。
【００７７】
本発明の感光層を設ける支持体は、アルミニウム、亜鉛、鋼、銅等の金属板、並びにクロム、亜鉛、銅、ニッケル、アルミニウム、鉄等がメッキ又は蒸着された金属板、紙、プラスチックフィルム及びガラス板、樹脂が塗布された紙、アルミニウム等の金属箔が張られた紙、親水化処理したプラスチックフィルム等が挙げられる。このうち好ましいのはアルミニウム板である。本発明を感光性平版印刷版に適用するとき、支持体として、砂目立て処理、陽極酸化処理及び必要に応じて封孔処理等の表面処理等が施されているアルミニウム板を用いることが好ましい。これらの処理には公知の方法を適用することができる。
【００７８】
砂目立て処理の方法としては、例えば機械的方法、電解によりエッチングする方法が挙げられる。機械的方法としては、例えばボール研磨法、ブラシ研磨法、液体ホーニングによる研磨法、バフ研磨法等が挙げられる。アルミニウム材の組成等に応じて上述の各種方法を単独あるいは組合わせて用いることができる。
【００７９】
電解によりエッチングするには、リン酸、硫酸、塩酸、硝酸等の無機の酸を単独ないし２種以上混合した浴を用いて行われる。砂目立て処理の後、必要に応じてアルカリあるいは酸の水溶液によってデスマット処理を行い中和して水洗する。
【００８０】
陽極酸化処理は、電解液として、硫酸、クロム酸、シュウ酸、リン酸、マロン酸等を１種又は２種以上含む溶液を用い、アルミニウム板を陽極として電解して行われる。形成された陽極酸化被膜量は１〜５０ｍｇ／ｄｍ2が適当であり、好ましくは１０〜４０ｍｇ／ｄｍ2であり、特に好ましくは２５〜４０ｍｇ／ｄｍ2である。陽極酸化被膜量は、例えばアルミニウム板をリン酸クロム酸浴液（リン酸８５％液：３５ｍｌ、酸化クロム（IV）：２０ｇを１ｌの水に溶解して作製）に浸漬し、酸化被膜を溶解し、板の被膜溶解前後の重量変化測定から求められる。
【００８１】
封孔処理は、沸騰水処理、水蒸気処理、ケイ酸ソーダ処理、重クロム酸塩水溶液処理等が具体例として挙げられる。この他にアルミニウム板支持体に対して、水溶性高分子化合物や、フッ化ジルコン酸等の金属塩の水溶液による下引き処理を施すこともできる。
【００８２】
本発明の画像形成材料は赤外線を放射する光源を用いて画像露光を行うことができる。該光源としては、半導体レーザー、Ｈｅ−Ｎｅレーザー、ＹＡＧレーザー、炭酸ガスレーザー等が挙げられる。出力は５０ｍＷ以上が適当であり、好ましくは１００ｍＷ以上である。
【００８３】
本発明の画像形成材料の現像に用いられる現像液としては、水系アルカリ現像液が好適である。水系アルカリ現像液（以下、本発明の現像液という。）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前記アルカリ金属塩の濃度は０．０５〜２０重量％の範囲で用いるのが好適であり、より好ましくは、０．１〜１０重量％である。
【００８４】
本発明の画像形成方法において、現像液には、必要に応じアニオン性界面活性剤、両性界面活性剤やアルコール等の有機溶剤を加えることができる。
【００８５】
有機溶剤としては、プロピレングリコール、エチレングリコールモノフェニルエーテル、ベンジンアルコール、ｎ−プロピルアルコール等が有用である。
【００８６】
【実施例】
次に、本発明を実施例で更に具体的に説明する。なお、以下の実施例及び比較例において「部」は「重量部」を意味する。
【００８７】
実施例１
支持体の作成
厚さ０．２４ｍｍのアルミニウム板（材質１０５０、調質Ｈ１６）を５％苛性ソーダ水溶液中で６０℃で１分間脱脂処理を行った後、０．５モル１ｌの塩酸水溶液中で温度；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った。次いで、５％苛性ソーダ水溶液中で６０℃、１０秒間のデスマット処理を施した後、２０％硫酸溶液中で温度；２０℃、電流密度；３Ａ／ｄｍ2、処理時間；１分間の条件で陽極酸化処理を行った、更に又、３０℃の熱水で２０秒間、熱水封孔処理を行い、平版印刷版材料用支持体であるアルミニウム板を作製した。
【００８８】
実施例１
前記アルミニウム板の支持体上に下記組成の感光層塗布液を乾燥後の膜厚が２ｇ／ｍ2になるように回転塗布機を用いて塗布し１００℃で２分間乾燥して画像形成材料を得た。
【００８９】
感光層塗布液の組成
赤外線吸収剤 例示化合物ＩＲ４９ １０部
本発明のブロック化イソシアネートＡ ２０部
【００９０】
【化２５】
ノボラック樹脂Ａ ７０部
【００９２】
【化２６】
プロピレングルコールモノメチルエーテル １０００部
この画像形成材料を、半導体レーザー（波長８３０ｎｍ、出力５００ｍＷ）で感光層表面に画像露光を行った。レーザー光径はピークにおける強度の１／ｅ2で１３μｍであった。また、解像度は走査方向、副走査方向とも２０００ＤＰＩとした。露光後、赤外線ヒーターを用い感光層を１２０℃で３０秒間熱処理した。さらに、コニカＰＳ版用現像液ＳＤＲ−１（コニカ（株）製）を水で容積比６倍に希釈した２７℃の現像液に２５秒間浸漬し、非画像部（未露光部）を除去した後、水洗し平版印刷版を製造した。
【００９４】
上記条件において、感度を露光部が現像されない硬化に必要な露光エネルギー（ｍＪ／ｃｍ2）で評価し、印刷による非画像部の汚れ（印刷汚れ）の発生状況、及び印刷版の非画像部で汚れが発生するまでの印刷枚数で耐刷性を評価した。
【００９５】
実施例２
感光層塗布液の組成中の赤外線吸収剤を例示化合物ＩＲ１４に変え、かつ画像露光用の光源を発信波長１０６４ｎｍのＹＡＧレーザーに変えた以外は実施例１と同様の実験を行った。
【００９６】
実施例３
感光層塗布液の組成中の赤外線吸収剤をカーボンブラックに変えた以外は実施例１と同様の実験を行った。
【００９７】
実施例４
感光層塗布液の組成中の赤外線吸収剤をカーボンブラックに変え、かつ画像露光用の光源を発信波長１０６４ｎｍのＹＡＧレーザーに変えた以外は実施例１と同様の実験を行った。
【００９８】
実施例５
感光層塗布液の組成を下記に変えた以外は実施例１と同様の実験を行った。
【００９９】
感光層塗布液の組成
赤外線吸収剤 例示化合物ＩＲ４９ １０部
本発明のブロック化イソシアネートＡ（前記） ２０部
ノボラック樹脂Ａ（前記） ５０部
ビニル重合体Ａ ２０部
（４−ヒドロキシフェニルメクリルアミド／アクリロニトリル／メチルメタクリレート／アクリル酸＝３０／３０／１０／３０（モル比）の共重合体、重量平均分子量３万）
プロピレングルコールモノメチルエーテル １０００部
実施例６
感光層塗布液の組成中のビニル重合体Ａを下記ビニル重合体Ｂに変えた以外は実施例５と同様の実験を行った。
【０１００】
ビニル重合体Ｂは、４−ヒドロキシフェニルメクリルアミド／アクリロニトリル／メチルメタクリレート／２−ヒドロキシエチルメタクリレート＝３０／３０／１０／３０（モル比）の共重合体、重量平均分子量３万である。
【０１０１】
実施例７
感光層塗布液の組成中のビニル重合体Ａを下記ビニル重合体Ｃに変えた以外は実施例５と同様の実験を行った。
【０１０２】
ビニル重合体Ｃは、４−ヒドロキシフェニルメクリルアミド／アクリルアミド／メチルメタクリレート／２−ヒドロキシエチルメタクリレート＝３０／３０／１０／３０（モル比）の共重合体、重量平均分子量３万である。
【０１０３】
実施例８
感光層塗布液の組成中のビニル重合体Ａを下記ビニル重合体Ｄに変えた以外は実施例５と同様の実験を行った。
【０１０４】
ビニル重合体Ｄは、スチレン／マレイン酸＝５０／５０（モル比）の共重合体、重量平均分子量３万である。
【０１０５】
比較例１
実施例１の感光層塗布液の組成中の本発明のブロック化イソシアネートＡを特開平９−４３８４５号公報記載の合成例７の高分子化合物（ベンジルオキシカルボニルアミノエチルメタクリレート／４−メチルフェニルスルホニルメタクリルアミド＝２０／８０（モル比）の共重合体、重量平均分子量４．５万）に変えた以外は実施例５と同様の実験を行った。
【０１０６】
比較例２
実施例１の感光層塗布液の組成中の本発明のブロック化イソシアネートＡを特開昭６２−１６４０４９号公報記載の合成例１に従って合成したブロックイソシアネートに変えた以外は実施例５と同様の実験を行った。
【０１０７】
以上の結果を下記表１に示す。
【０１０８】
【表１】
【発明の効果】
本発明の目的は、赤外線による露光に対して優れた感度を有し、現像性が向上し、地汚れが防止された画像形成材料及び画像形成方法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming material having a photosensitive layer that is insolubilized in an alkaline developer by infrared irradiation, and an image forming method using the same.
[0002]
[Prior art]
As an image forming material having an infrared-sensitive negative photosensitive layer, US Pat. No. 5,340,699 has a photosensitive layer containing an acid generator, a resole resin, a novolac resin, and an infrared absorber. In addition, a technique is disclosed that is used as a negative-type image forming material by performing heat treatment after image exposure and before development processing, and is used as a positive-type image forming material without performing the heat treatment. .
[0003]
However, the image-shaped material has insufficient sensitivity to infrared rays, and there is a problem that it takes time for image exposure (drawing) with a semiconductor laser or the like. In addition, the developing property also has a problem such that the dye remains on the support and the background stain is generated by printing.
[0004]
JP-A-62-164049 discloses a lithographic printing plate precursor provided with a photosensitive layer containing a blocked isocyanate and a polymer having active hydrogen capable of reacting with isocyanate and containing a photothermal conversion substance. There are problems in that developability is insufficient and background staining occurs, and printing durability is not sufficient.
[0005]
Japanese Patent Application Laid-Open No. 9-43845 discloses a negative image recording material having a polymer compound that undergoes a crosslinking reaction by heat and a substance that absorbs light and generates heat, but has sufficient developability. There is a problem that causes soiling.
[0006]
[Problems to be solved by the present invention]
An object of the present invention is to provide an image forming material and an image forming method that have high sensitivity in exposure with infrared rays, improve developability, and prevent background contamination.
[0007]
[Means for Solving the Problems]
The present invention that achieves the above object of the present invention includes the following (1) to (5).
[0008]
(1) On a support, a compound represented by the following general formula (1) or (2), an infrared absorber represented by the following general formula (3) or (4), a novolak resin and a carboxylic acid group, A printing plate material comprising a photosensitive layer containing a vinyl polymer having an amino group or a hydroxyl group in a side chain .
[0009]
[Chemical 3]
In the formula, each of X 1 , X 2 and X 3 represents a hydrogen atom or a substituent, and at least one of X 1 , X 2 and X 3 is —NR 1 —CO—O—R 2 . R 1 represents a hydrogen atom or an alkyl group, and R 2 represents an alkyl group, an aralkyl group, an imide group, a triazolyl group, a pyridyl group, a sulfonyl group, a pyrazolyl group, a halogen atom or an aromatic ring group.
[0011]
[Formula 4]
In the formula, each of X 1 , X 2 , X 3 and X 4 represents a hydrogen atom or a substituent, and at least one of X 1 and X 2 and at least one of X 3 and X 4 is —NR 1 —CO. it is -O-R 2. R 1 represents a hydrogen atom or an alkyl group, and R 2 represents an alkyl group, an aralkyl group, an imide group, a triazolyl group, a pyridinium group, a sulfonyl group, a pyrazolyl group, a halogen atom or an aromatic ring group. R 3 and R 4 are each synonymous with R 1 .
[0013]
[Chemical B]
[0016]
(2) When coating the photosensitive layer, as a coating solvent, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone The printing plate material as described in (1) above, wherein a solvent selected from cyclohexanone, trichloroethylene, and methyl ethyl ketone is used.
( 3 ) An image forming method comprising: drawing an image using infrared rays on the photosensitive layer of the printing plate material according to (1) or (2) above; and removing an unexposed portion with an alkaline developer.
[0017]
Hereinafter, the present invention will be described in detail.
[0018]
The compound represented by the general formula (1) or (2) contained in the photosensitive layer of the image forming material of the present invention (hereinafter referred to as “blocked isocyanate of the present invention”) will be described.
[0019]
In —NR 1 —CO—O—R 2 represented by X 1 to X 4 in General Formula (1) or (2), the alkyl group represented by R 2 is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, Ethyl group, propyl group, butyl group, etc.), and the imide group represented by R 2 is, for example,
[Chemical formula 5]
(R 5 and R 6 each represent a hydrogen atom, a sulfo group, an alkyl group, or a hydroxyl group). The pyridyl group represented by R 2 may be substituted, for example
[0022]
[Chemical 6]
(L represents a hydrogen atom, an alkyl group, a hydroxyl group, or a substituted or unsubstituted amino group). Examples of the sulfonyl group represented by R 2 include —SO 2 —L 2 (L 2 has the same meaning as L above). Examples of the aromatic ring group represented by R 2 include:
[Chemical 7]
Is mentioned.
[0026]
Examples of the substituent other than —NR 1 —CO—O—R 2 represented by X 1 to X 4 include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic ring group, a substituted or unsubstituted amino group, and an amide A group (RCONH-, R is a chain or cyclic hydrocarbon group) or a halogen atom is preferable, but is not limited thereto.
[0027]
The compound represented by the general formula (1) preferably has two or more —NR 1 —CO—O—R 2, and the compound represented by the general formula (2) represents —NR 1 —CO—O—. It is preferable to have 4 or more R 2 .
[0028]
The blocked isocyanate of the present invention can be synthesized with reference to JP-A-7-2804.
[0029]
As the infrared absorbent used in the present invention, an infrared absorbing dye having absorption in the infrared region from visible light having a wavelength of 700 nm or more, carbon black, magnetic powder and the like can be used. A particularly preferred infrared absorber is an infrared absorbing dye having an absorption peak at 700 to 850 nm and a peak molar absorption coefficient ε of 10 5 or more.
[0030]
Examples of the infrared absorbing dye include a cyanine dye, a squalium dye, a croconium dye, an azurenium dye, a phthalocyanine dye, a naphthalocyanine dye, a polymethine dye, a naphthoquinone dye, a thiopyrylium dye, and a dithiol metal complex dye. , Anthraquino dyes, indoaniline metal complex dyes, intermolecular CT dyes, and the like.
[0031]
Examples of the infrared absorbing dye include JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, and JP-A-3-20374. -26593, 3-30991, 3-34891, 3-36093, 3-36094, 3-36095, 3-42281, 3-103476, etc. Is mentioned.
[0032]
In the present invention, as the infrared absorber, a cyanine dye represented by the following general formula (3) or (4) is particularly preferable.
[0033]
[Chemical 8]
In the general formulas (3) and (4), Z 1 and Z 2 each represent a sulfur atom, a selenium atom or an oxygen atom, and X 1 and X 2 each represent a benzo-fused ring or naphtho which may have a substituent. It represents a nonmetallic atom group necessary for forming a condensed ring, R 1 and R 2 each represent a substituent, and either one of R 1 and R 2 has an anionic dissociative group. R 3 , R 4 , R 5 and R 6 each represent an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a halogen atom. L represents a chain of conjugated bonds having 5 to 13 carbon atoms. ]
In the present invention, as the infrared absorber, the cyanine dye represented by the general formula (3) or (4) is particularly preferable.
[0035]
The cyanine dyes represented by the general formula (3) or (4) include those in which the general formula (3) or (4) forms a cation and has a counter anion. In this case, examples of the counter anion include Cl − , Br − , ClO 4 − , BF 4 − , alkyl boron such as t-butyltriphenyl boron, and the like.
[0036]
In the general formulas (3) and (4), the number of carbon atoms (n) of the conjugated bond represented by L is the emission wavelength of the laser when a laser emitting infrared rays is used as a light source for image exposure. It is preferable to select an effective value in accordance with. For example, when a YAG laser having a transmission wavelength of 1060 nm is used, n is preferably 9 to 13. In addition, the conjugated bond portion may have an arbitrary substituent, and the conjugated bond portion may form a ring with a plurality of substituents.
[0037]
In the general formulas (3) and (4), the ring represented by X 1 and the ring represented by X 2 may have an arbitrary substituent. The substituent is preferably a group selected from a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, —SO 3 M and —COOM (M is a hydrogen atom or an alkali metal atom). .
[0038]
R 1 and R 2 are each an arbitrary substituent, preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; — (CH 2 ) n —O—) k — (CH 2 ) m OR (n and m are each an integer of 1 to 3, k is 0 or 1, R represents an alkyl group having 1 to 5 carbon atoms); one of R 1 and R 2 is —R -SO 3 M on the other hand is -R-SO 3 - (R is an alkyl group having 1 to 5 carbon atoms, M is an alkali represents a metal atom); on the other hand, or one of R 1 and R 2 is -R-COOM Is —R—COO − (wherein R represents an alkyl group having 1 to 5 carbon atoms, and M represents an alkali metal atom). R 1 and R 2 are, in terms of sensitivity and developability, R 1 and R one of the 2 -R-SO 3 - or -R-COO -, the other is at -R-SO 3 M or -R-COOM Preferably there is.
[0039]
The cyanine dye represented by the general formula (3) or (4) exhibits an absorption peak at 750 to 900 nm when a semiconductor laser is used as a light source for image exposure, and at 900 to 1200 nm when a YAG laser is used, Those having a molar extinction coefficient of ε> 1 × 10 5 are preferred.
[0040]
Specific examples of infrared absorbers preferably used in the present invention are listed below, but are not limited thereto.
[0041]
[Chemical 9]
[Chemical Formula 10]
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Although these pigment | dyes can be synthesize | combined by a well-known method, the following commercial items can also be used.
[0056]
Nippon Kayaku: IR750 (anthraquinone); IR002, IR003 (aluminum); IR820 (polymethine); IRG022, IRG033 (diimmonium); CY-2, CY-4, CY-9, CY-20
Mitsui Toatsu: KIR103, SIR103 (phthalocyanine series); KIR101, SIR114 (anthraquinone series); PA1001, PA1005, PA1006, SIR128 (metal complex series)
Dainippon Ink Chemical: Fastogen blue8120
Midori Chemical: MIR-101, 1011, 1021
In addition, they are also commercially available from companies such as Nippon Photosensitive Dye, Sumitomo Chemical and Fuji Photo Film.
[0057]
In the present invention, the addition amount of the infrared absorber is preferably in the range of 0.5 to 5 wt%. The additive amount is reduced developability of non-image portions and exceeds 5 wt% (unexposed portion), development resistance of the image portion is lowered less than 0.5 wt%.
[0058]
The sensitive layer of the image forming material of the present invention preferably contains an alkali-soluble polymer. As the alkali-soluble polymer, a novolak and a vinyl polymer having a carboxylic acid group, an amino group or a hydroxyl group in the side chain are preferable.
[0059]
Examples of novolaks include phenol / formaldehyde resins, cresol / formaldehyde resins, phenol / cresol / formaldehyde copolycondensation resins as described in JP-A-55-57841, and JP-A-55-127553. Examples thereof include a co-polycondensation resin of p-substituted phenol and phenol or cresol and formaldehyde as described.
[0060]
Examples of the vinyl polymer having a carboxylic acid group, amino group or hydroxyl group in the side chain include, for example, a novolak resin, a polymer having a hydroxystyrene unit, and a polymer having a structural unit represented by the following general formula (5), Other known acrylic resins can also be mentioned.
[0061]
Examples of the polymer having a hydroxystyrene unit include polyhydroxystyrene and hydroxystyrene copolymer described in JP-B-52-41050.
[0062]
The polymer having the structural unit represented by the general formula (5) is a homopolymer having a repeating structure of only the structural unit, or an unsaturated double bond of the structural unit and another vinyl monomer. Is a copolymer obtained by combining at least one structural unit represented by a structure obtained by cleaving.
[0063]
Embedded image
In the general formula (5), R 1 and R 2 each represent a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxylic acid group, preferably a hydrogen atom. R 3 represents a hydrogen atom, a halogen atom such as a chlorine atom or a bromine atom, or an alkyl group such as a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group. R 4 represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a phenyl group, or a naphthyl group.
[0065]
Y represents a phenylene group or a naphthylene group including those having a substituent, such as an alkyl group such as a methyl group or an ethyl group, a halogen atom such as a chlorine atom or a bromine atom, a carboxylic acid group, a methoxy group or an ethoxy group. Examples thereof include an alkoxy group such as a group, a hydroxyl group, a sulfo group, a cyano group, a nitro group, and an acyl group, but preferably have no substituent or are substituted with a methyl group.
[0066]
X is a divalent organic group linking a nitrogen atom and an aromatic carbon atom, n represents an integer of 0 to 5, and n is preferably 0.
[0067]
More specifically, the polymer having the structural unit represented by the general formula (5) can be represented by, for example, (a) to (h).
[0068]
Embedded image
In (a) to (h), R 1 to R 5 each represent a hydrogen atom, an alkyl group, or a halogen atom, and X represents an alkyl group or a halogen atom. Moreover, m, n, l, k, and s represent mol% of each structural unit.
[0070]
A novolac resin, a polymer having a hydroxystyrene unit, and a polymer having a structural unit represented by the general formula (5) can also be used in combination.
[0071]
Furthermore, an oleophilic resin can be added to the photosensitive composition of the present invention in order to improve the oil sensitivity of the photosensitive composition.
[0072]
Examples of the lipophilic resin include condensates of phenols and aldehydes substituted with an alkyl group having 3 to 15 carbon atoms, such as t-butylphenol formaldehyde, as described in JP-A-50-125806. Resin etc. can be used.
[0073]
If necessary, the photosensitive layer of the image forming material of the present invention may further contain other dyes, pigments, sensitizers and the like.
[0074]
The sensitive layer of the present invention is dissolved in the following solvent that dissolves each of the above-described components, and these are applied to the surface of a suitable support and dried to provide the sensitive layer to obtain the image forming material of the present invention. it can.
[0075]
Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents are used alone or in admixture of two or more.
[0076]
As a coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount varies depending on the application. For example, in the case of a photosensitive lithographic printing plate, the solid content is preferably 0.5 to 5.0 g / m 2 .
[0077]
The support on which the photosensitive layer of the present invention is provided is a metal plate such as aluminum, zinc, steel, copper, and a metal plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic film, and Examples thereof include a glass plate, paper coated with a resin, paper coated with a metal foil such as aluminum, and a plastic film subjected to hydrophilic treatment. Of these, an aluminum plate is preferred. When the present invention is applied to a photosensitive lithographic printing plate, it is preferable to use an aluminum plate that has been subjected to surface treatment such as graining treatment, anodizing treatment, and if necessary, sealing treatment. A known method can be applied to these processes.
[0078]
Examples of the graining method include a mechanical method and a method of etching by electrolysis. Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.
[0079]
Etching by electrolysis is performed using a bath in which inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid are used alone or in combination. After the graining treatment, if necessary, it is desmutted with an alkali or acid aqueous solution, neutralized and washed with water.
[0080]
The anodizing treatment is performed by electrolysis using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid and the like as an electrolytic solution, and using an aluminum plate as an anode. The amount of the anodic oxide film formed is suitably 1 to 50 mg / dm 2 , preferably 10 to 40 mg / dm 2 , and particularly preferably 25 to 40 mg / dm 2 . The amount of anodic oxide coating is, for example, by immersing an aluminum plate in a chromic phosphate bath solution (phosphoric acid 85% solution: 35 ml, chromium oxide (IV): 20 g dissolved in 1 liter of water) to dissolve the oxide coating. It is obtained from the weight change measurement before and after dissolution of the film on the plate.
[0081]
Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, and the like. In addition, the aluminum plate support can be subjected to a subbing treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconic acid.
[0082]
The image forming material of the present invention can perform image exposure using a light source that emits infrared rays. Examples of the light source include a semiconductor laser, a He—Ne laser, a YAG laser, and a carbon dioxide gas laser. The output is suitably 50 mW or more, preferably 100 mW or more.
[0083]
As the developer used for developing the image forming material of the present invention, an aqueous alkaline developer is suitable. Examples of the aqueous alkaline developer (hereinafter referred to as the developer of the present invention) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and triphosphoric acid. The concentration of the alkali metal salt including an aqueous solution of an alkali metal salt such as sodium is preferably used in the range of 0.05 to 20% by weight, and more preferably 0.1 to 10% by weight.
[0084]
In the image forming method of the present invention, an anionic surfactant, an amphoteric surfactant or an organic solvent such as alcohol can be added to the developer as necessary.
[0085]
As the organic solvent, propylene glycol, ethylene glycol monophenyl ether, benzine alcohol, n-propyl alcohol and the like are useful.
[0086]
【Example】
Next, the present invention will be described more specifically with reference to examples. In the following Examples and Comparative Examples, “part” means “part by weight”.
[0087]
Example 1
Preparation of support body An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was degreased in a 5% aqueous sodium hydroxide solution at 60 ° C. for 1 minute, and then heated in 0.5 mol / l of hydrochloric acid aqueous solution. Electrolytic etching treatment was performed under conditions of 25 ° C., current density; 60 A / dm 2 , treatment time; 30 seconds. Next, after desmutting at 60 ° C. for 10 seconds in a 5% aqueous sodium hydroxide solution, anodization was performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm 2 , a treatment time of 1 minute. Furthermore, the hot water sealing process was performed for 20 seconds with 30 degreeC hot water, and the aluminum plate which is a support body for a lithographic printing plate material was produced.
[0088]
Example 1
A photosensitive layer coating solution having the following composition is coated on the support of the aluminum plate using a rotary coater so that the film thickness after drying is 2 g / m 2 and dried at 100 ° C. for 2 minutes to obtain an image forming material. Obtained.
[0089]
Composition of photosensitive layer coating solution Infrared absorber Illustrative compound IR49 10 parts Blocked isocyanate A of the present invention 20 parts
Embedded image
70 parts of novolac resin A
Embedded image
1000 parts of propylene glycol monomethyl ether This image forming material was subjected to image exposure on the surface of the photosensitive layer with a semiconductor laser (wavelength: 830 nm, output: 500 mW). The laser beam diameter was 13 μm at 1 / e 2 of the intensity at the peak. The resolution was 2000 DPI in both the scanning direction and the sub-scanning direction. After the exposure, the photosensitive layer was heat-treated at 120 ° C. for 30 seconds using an infrared heater. Further, Konica PS plate developer SDR-1 (manufactured by Konica) was immersed in a developer at 27 ° C. diluted with water to a volume ratio of 6 times for 25 seconds to remove non-image areas (unexposed areas). Thereafter, it was washed with water to produce a lithographic printing plate.
[0094]
Under the above conditions, the sensitivity is evaluated by the exposure energy (mJ / cm 2 ) necessary for curing where the exposed area is not developed, and the occurrence of stains (print stains) on the non-image area due to printing and the non-image area of the printing plate The printing durability was evaluated based on the number of printed sheets until smearing occurred.
[0095]
Example 2
An experiment similar to that of Example 1 was performed, except that the infrared absorber in the composition of the photosensitive layer coating solution was changed to Exemplified Compound IR14 and the light source for image exposure was changed to a YAG laser having a transmission wavelength of 1064 nm.
[0096]
Example 3
The same experiment as in Example 1 was performed except that the infrared absorber in the composition of the photosensitive layer coating solution was changed to carbon black.
[0097]
Example 4
The same experiment as in Example 1 was performed except that the infrared absorber in the composition of the photosensitive layer coating solution was changed to carbon black and the light source for image exposure was changed to a YAG laser having a transmission wavelength of 1064 nm.
[0098]
Example 5
The same experiment as in Example 1 was performed except that the composition of the photosensitive layer coating solution was changed as follows.
[0099]
Composition of photosensitive layer coating solution Infrared absorber Exemplified compound IR49 10 parts Blocked isocyanate A of the present invention (above) 20 parts Novolak resin A (above) 50 parts Vinyl polymer A 20 parts (4-hydroxyphenylmethacrylamide / acrylonitrile) / Methyl methacrylate / acrylic acid = 30/30/10/30 (molar ratio) copolymer, weight average molecular weight 30,000)
Propylene glycol monomethyl ether 1000 parts Example 6
The same experiment as in Example 5 was performed except that the vinyl polymer A in the composition of the photosensitive layer coating solution was changed to the following vinyl polymer B.
[0100]
Vinyl polymer B is a copolymer of 4-hydroxyphenylmethacrylamide / acrylonitrile / methyl methacrylate / 2-hydroxyethyl methacrylate = 30/30/10/30 (molar ratio), and has a weight average molecular weight of 30,000.
[0101]
Example 7
The same experiment as in Example 5 was performed except that the vinyl polymer A in the composition of the photosensitive layer coating solution was changed to the following vinyl polymer C.
[0102]
The vinyl polymer C is a copolymer of 4-hydroxyphenylmethacrylamide / acrylamide / methyl methacrylate / 2-hydroxyethyl methacrylate = 30/30/10/30 (molar ratio), and has a weight average molecular weight of 30,000.
[0103]
Example 8
The same experiment as in Example 5 was performed except that the vinyl polymer A in the composition of the photosensitive layer coating solution was changed to the following vinyl polymer D.
[0104]
The vinyl polymer D is a copolymer of styrene / maleic acid = 50/50 (molar ratio) and has a weight average molecular weight of 30,000.
[0105]
Comparative Example 1
The blocked isocyanate A of the present invention in the composition of the photosensitive layer coating solution of Example 1 was replaced with the polymer compound of Synthesis Example 7 described in JP-A-9-43845 (benzyloxycarbonylaminoethyl methacrylate / 4-methylphenylsulfonyl methacrylate). The same experiment as in Example 5 was performed except that the copolymer was changed to an amide = 20/80 (molar ratio) copolymer and a weight average molecular weight of 45,000).
[0106]
Comparative Example 2
The same experiment as in Example 5 except that the blocked isocyanate A of the present invention in the composition of the photosensitive layer coating solution of Example 1 was changed to the blocked isocyanate synthesized according to Synthesis Example 1 described in JP-A-62-164049. Went.
[0107]
The above results are shown in Table 1 below.
[0108]
[Table 1]
【The invention's effect】
An object of the present invention is to provide an image forming material and an image forming method which have excellent sensitivity to exposure by infrared rays, improve developability, and prevent background contamination.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13097397A JP3757543B2 (en) | 1997-05-21 | 1997-05-21 | Printing plate material and image forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13097397A JP3757543B2 (en) | 1997-05-21 | 1997-05-21 | Printing plate material and image forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10319591A JPH10319591A (en) | 1998-12-04 |
| JP3757543B2 true JP3757543B2 (en) | 2006-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13097397A Expired - Fee Related JP3757543B2 (en) | 1997-05-21 | 1997-05-21 | Printing plate material and image forming method |
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| JP (1) | JP3757543B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6949327B2 (en) | 2003-07-09 | 2005-09-27 | Kodak Polychrome Graphics Llc | On-press developable lithographic printing plate |
| JP6601394B2 (en) * | 2014-04-22 | 2019-11-06 | 日本ゼオン株式会社 | Radiation-sensitive resin composition, resin film, and electronic component |
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1997
- 1997-05-21 JP JP13097397A patent/JP3757543B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH10319591A (en) | 1998-12-04 |
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