JP4465169B2 - Photosensitive planographic printing plate - Google Patents
Photosensitive planographic printing plate Download PDFInfo
- Publication number
- JP4465169B2 JP4465169B2 JP2003277573A JP2003277573A JP4465169B2 JP 4465169 B2 JP4465169 B2 JP 4465169B2 JP 2003277573 A JP2003277573 A JP 2003277573A JP 2003277573 A JP2003277573 A JP 2003277573A JP 4465169 B2 JP4465169 B2 JP 4465169B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- printing plate
- lithographic printing
- photosensitive
- 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 - Fee Related
Links
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- 239000010410 layer Substances 0.000 claims description 68
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- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000011241 protective layer Substances 0.000 claims description 15
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- 239000002245 particle Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
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- 239000011347 resin Substances 0.000 claims description 5
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- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- QNCMIIYBZRXGRX-UHFFFAOYSA-N tert-butyl [4-(2-trimethoxysilylethenyl)phenyl] carbonate Chemical compound CO[Si](OC)(OC)C=CC1=CC=C(OC(=O)OC(C)(C)C)C=C1 QNCMIIYBZRXGRX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000001018 xanthene dye Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Description
本発明はアルミニウム支持体上に光重合性感光層、保護層が形成された感光性平版印刷版に関する。更に詳しくは、露光部と未露光部のディスクリが大きく、かつ高感度の感光性平版印刷版に関する。 The present invention relates to a photosensitive lithographic printing plate in which a photopolymerizable photosensitive layer and a protective layer are formed on an aluminum support. More specifically, the present invention relates to a photosensitive lithographic printing plate having a large discrepancy between an exposed portion and an unexposed portion and having high sensitivity.
従来、平版印刷版としては親水性支持体上に親油性の感光性樹脂層を設けた構成を有するPS版が広く用いられ、その製版方法として、通常はリスフィルムを介してマスク露光後、非画像部を溶解除去することにより所望の印刷版を得ていた。
近年、画像情報をコンピューターにより、電子的に処理、蓄積、出力するディジタル化技術が広く普及し、それに対応した新しい画像出力方式が種々実用化されるようになってきた。その結果レーザー光のような指向性の高い光をディジタル化された画像情報に従って走査し、リスフィルムを介す事無く、直接印刷版を製造するCTP技術が望まれ、これに適応した印刷版用原版を得ることが重要な技術課題となっている。
この光源としてArレーザー(488nm)やFD−YAGレーザー(532nm)、InGaN系半導体レーザー(バイオレットレーザー、350nm〜450nm)が採用され、この光源に感光性を有し、かなりの生産性が確保できる高感度な光重合性感光層を有する平版印刷版が開発され、実用に供されている。
Conventionally, as a lithographic printing plate, a PS plate having a configuration in which a lipophilic photosensitive resin layer is provided on a hydrophilic support is widely used. The desired printing plate was obtained by dissolving and removing the image area.
In recent years, digitization technology for electronically processing, storing, and outputting image information by a computer has become widespread, and various new image output methods corresponding to it have come into practical use. As a result, CTP technology that scans highly directional light such as laser light in accordance with digitized image information and directly produces a printing plate without using a lith film is desired. Obtaining the original edition is an important technical issue.
As this light source, an Ar laser (488 nm), an FD-YAG laser (532 nm), or an InGaN-based semiconductor laser (violet laser, 350 nm to 450 nm) is employed, and this light source has photosensitivity and can ensure considerable productivity. A lithographic printing plate having a sensitive photopolymerizable photosensitive layer has been developed and put into practical use.
高感度技術としては殆んどが光開始系に関するものであり、例えばArレーザー、FD−YAGレーザーに対して高感度な光開始系としては、チタノセンとクマリン色素との組み合わせ(例えば、特許文献1〜3参照。)、スチリル系色素とチタノセンとの組み合わせ(例えば、特許文献4参照。)、五員ヘテロ環酸性核を有する色素とチタノセンの組み合わせ(例えば、特許文献5参照。)がそれぞれ開示されている。
またバイオレットレーザーに対して高感度な光開始系としては、ナフトフラノン系色素とチタノセンとの組み合わせ(例えば、特許文献6参照。)、カルバゾリルスチリル系色素とチタノセンとの組み合わせ(例えば、特許文献7参照。)等が知られているが、CTPの更なる高生産性を実現するためには、更なる高感度化が望まれていた。
Most of the high-sensitivity technologies are related to photoinitiation systems. For example, photoinitiation systems with high sensitivity to Ar lasers and FD-YAG lasers are combinations of titanocene and coumarin dyes (for example, Patent Document 1). 3), a combination of a styryl dye and titanocene (for example, see Patent Document 4), and a combination of a dye having a five-membered heterocyclic acidic nucleus and titanocene (for example, see Patent Document 5). ing.
Further, as a photoinitiating system highly sensitive to a violet laser, a combination of a naphthofuranone dye and titanocene (for example, see Patent Document 6), a combination of a carbazolyl styryl dye and titanocene (for example, Patent Document 7). However, in order to realize higher productivity of CTP, higher sensitivity has been desired.
一方、平版印刷版としての機能を安定して発現するためには、現像処理性として、露光部と未露光部と溶解度差(ディスクリミネーション)が大きいことが求められ、これらに関しては現像液に特定の界面活性剤を加えることである程度改良されることが開示されているが(例えば、特許文献8参照。)、不十分であり、光重合層組成からの改良が望まれていた。
したがって本発明の第一課題は、高感度な光重合性感光層を有する感光性平版印刷版を提供することにある。第二の課題は、未露光部と露光部の溶解度差が大きく、安定した現像処理性が得られる光重合性感光層を有する感光性平版印刷版を提供することにある。 Accordingly, a first object of the present invention is to provide a photosensitive lithographic printing plate having a highly sensitive photopolymerizable photosensitive layer. A second problem is to provide a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer that has a large solubility difference between an unexposed area and an exposed area and that provides stable development processability.
本発明者は、上記目的を達成すべく鋭意検討を重ねた結果、光重合性感光層に平均粒径1〜100nmの下記一般式(1)で表される微粒子を含有させることにより、高感度を示すのみでなく、未露光部の現像速度が著しく速くなることを見出し、本発明に到達した。 As a result of intensive studies to achieve the above object, the present inventor has high sensitivity by incorporating fine particles represented by the following general formula (1) having an average particle diameter of 1 to 100 nm into the photopolymerizable photosensitive layer. As a result, the present inventors have found that the developing speed of the unexposed area is remarkably increased, and have reached the present invention.
P−[(Y)s−{(U1)p−(U2−Z)t}]k (1) P − [(Y) s − {(U 1 ) p − (U 2 −Z) t }] k (1)
式中、Pは微粒子担体を示し、Yはカップリング残基を示し、kは1以上の整数であり、sは0又は1である。U1は第1の連結ユニット、U2は第2の連結ユニットを示し、Zは不飽和二重結合を有する基を示す。pは0又は1、tは1以上の整数を示す。 In the formula, P represents a fine particle carrier, Y represents a coupling residue, k is an integer of 1 or more, and s is 0 or 1. U 1 represents a first connecting unit, U 2 represents a second connecting unit, and Z represents a group having an unsaturated double bond. p represents 0 or 1, and t represents an integer of 1 or more.
本発明の感光性平版印刷版は、光重合性感光層に、平均粒径1〜100nmで不飽和基を有する微粒子を含有することにより、高感度とディスクリミネーションの拡大の両者が実現できた。 The photosensitive lithographic printing plate of the present invention can realize both high sensitivity and increased discrimination by containing fine particles having an average particle diameter of 1 to 100 nm and unsaturated groups in the photopolymerizable photosensitive layer. .
本発明の感光性平版印刷版は、少なくとも支持体上に、光重合性感光層を有するものである。必要に応じ、光重合性感光層の上に保護層を順次積層しても、支持体と光重合性感光層の間に、中間層を設けても良い。
本発明の光重合性感光層(以下、単に感光層とも称する)は、光重合開始系、少なくとも1個のエチレン性不飽和基を有する重合可能な化合物(以下、単にエチレン性不飽和化合物とも称する)、バインダー樹脂、および微粒子を含んでなる。
以下これらの成分について具体的に説明する。
The photosensitive lithographic printing plate of the present invention has a photopolymerizable photosensitive layer on at least a support. If necessary, a protective layer may be sequentially laminated on the photopolymerizable photosensitive layer, or an intermediate layer may be provided between the support and the photopolymerizable photosensitive layer.
The photopolymerizable photosensitive layer of the present invention (hereinafter also simply referred to as photosensitive layer) is a photopolymerization initiation system, a polymerizable compound having at least one ethylenically unsaturated group (hereinafter also simply referred to as ethylenically unsaturated compound). ), A binder resin, and fine particles.
Hereinafter, these components will be specifically described.
〔微粒子〕
本発明に使用される微粒子は、平均粒径が1〜100nmであり、一般式(1)で示される微粒子である。
[Fine particles]
The fine particles used in the present invention are fine particles having an average particle diameter of 1 to 100 nm and represented by the general formula (1).
P−[(Y)s−{(U1)p−(U2−Z)t}]k (1) P − [(Y) s − {(U 1 ) p − (U 2 −Z) t }] k (1)
式中、Pは微粒子担体を示し、Yはカップリング残基を示し、kは1以上の整数であり、sは0又は1である。U1は第1の連結ユニット、U2は第2の連結ユニットを示し、Zは不飽和二重結合を有する基を示す。pは0又は1、tは1以上の整数を示す。 In the formula, P represents a fine particle carrier, Y represents a coupling residue, k is an integer of 1 or more, and s is 0 or 1. U 1 represents a first connecting unit, U 2 represents a second connecting unit, and Z represents a group having an unsaturated double bond. p represents 0 or 1, and t represents an integer of 1 or more.
平均粒径が100nm以下と小さいため、感光層に分散させても濁り等生じることなく透明であり、レーザー露光等、光学的特性上の問題を生じない。また微粒子表面は連結ユニット(U1とU2を総称していう)を介して、Zすなわち不飽和二重結合を有する基で覆われているため、有機溶剤に簡単に分散され、通常の試薬と同様に混合あるいは分散して使用することができる。 Since the average particle size is as small as 100 nm or less, even if dispersed in the photosensitive layer, it is transparent without causing turbidity and the like, and does not cause problems in optical properties such as laser exposure. Further, since the surface of the fine particles is covered with Z, that is, a group having an unsaturated double bond, via a linking unit (collectively referring to U 1 and U 2 ), it is easily dispersed in an organic solvent, Similarly, it can be used by mixing or dispersing.
一般式(1)において、Pは微粒子担体を示し、具体的には有機微粒子担体や無機微粒子担体(たとえばシリカゾル、チタンゾル、アルミゾル、ジルコニウム微粒子)等を指す。またこれらの微粒子担体と活性金属アルコキシドとの反応生成物であってもかまわない。
連結ユニットU1およびU2としては、種々の連結基、例えば、鎖状炭化水素、炭化水素環、ヘテロ原子を有する鎖状炭化水素、複素環、酸素原子、硫黄原子、窒素原子から選択された少なくとも1種を含むユニットで構成できる。例えば、連結ユニットU1およびU2はそれぞれ、下記式で表すことができる。
In the general formula (1), P represents a fine particle carrier, specifically, an organic fine particle carrier, an inorganic fine particle carrier (for example, silica sol, titanium sol, aluminum sol, zirconium fine particle) or the like. Moreover, the reaction product of these fine particle carriers and active metal alkoxides may be used.
The linking units U 1 and U 2 were selected from various linking groups such as chain hydrocarbons, hydrocarbon rings, chain hydrocarbons having heteroatoms, heterocycles, oxygen atoms, sulfur atoms, nitrogen atoms. It can be comprised with the unit containing at least 1 sort. For example, each of the connection units U 1 and U 2 can be represented by the following formula.
−(R1)q−(B)r−、 −(R2)u−(Ar)v− -(R 1 ) q- (B) r -,-(R 2 ) u- (Ar) v-
(式中、R1、R2は同一または異なって、アルキレン基又はアルケニレン基を示し、Bはエステル結合、チオエステル結合、アミド結合、尿素結合、ウレタン結合、チオウレタン結合、イミノ基、硫黄原子または窒素原子を示し、Arは置換基(例えばハロゲン原子、アルキル基など)を有していてもよいアリーレン基またはシクロアルキレン基を示す。q、r、uおよびvは、それぞれ0又は1を示し、q+r+u+v≧1である。)
YはPと連結ユニットをつなぐカップリング残基を指し、具体的にはシランカップリング剤を挙げることができる。
Zは不飽和二重結合を有する基を指し、例えばアクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸等の不飽和カルボン酸、アクリルアミド類等を挙げることができるが、これに限定されるものではない。
Wherein R 1 and R 2 are the same or different and each represents an alkylene group or an alkenylene group, and B represents an ester bond, a thioester bond, an amide bond, a urea bond, a urethane bond, a thiourethane bond, an imino group, a sulfur atom or Represents a nitrogen atom, Ar represents an arylene group or a cycloalkylene group which may have a substituent (for example, a halogen atom, an alkyl group, etc.) q, r, u and v each represents 0 or 1; (q + r + u + v ≧ 1)
Y indicates a coupling residue that connects P and a linking unit, and specific examples include a silane coupling agent.
Z represents a group having an unsaturated double bond, and examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and acrylamides. It is not limited.
本発明で使用される微粒子は前記一般式で示されるものであるが、具体的な例としては、国際公開第02/46841号パンフレット等に記載の日本合成ゴム(株)製 DeSolite Z7500シリーズの微粒子、Z7501、Z7503、Z7521、Z7522、Z7523、Z7524等を挙げることができる。
これらの微粒子の使用量は、後述のエチレン性不飽和化合物100重量部に対し、1〜100重量部、好ましくは3〜50重量部、更に好ましくは5〜30重量部の範囲で用いられる。
The fine particles used in the present invention are those represented by the above general formula. Specific examples thereof include fine particles of DeSolite Z7500 series manufactured by Nippon Synthetic Rubber Co., Ltd. described in WO 02/46841 , Z7501, Z7503, Z7521, Z7522, Z7523, Z7524 and the like.
These fine particles are used in an amount of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound described later.
〔光重合開始系〕
また本発明の感光性平版印刷版の感光層に含有させる光重合開始系(剤)としては、使用する光源の波長により、特許、文献等で公知である種々の光開始剤、あるいは2種以上の光開始剤の併用系(光開始系)を適宜選択して用いることができる。以下に具体例を列挙するがこれらに制限されるものではない。
400nm以上の可視光線、Arレーザー、半導体レーザーの第2高調波、SHG−YAGレーザーを光源とする場合にも、種々の光開始系が提案されており、例えば、米国特許第2,850,445号に記載のある種の光還元性染料、例えばローズベンガル、エオシン、エリスロシンなど、あるいは、染料と開始剤との組み合わせによる系、例えば、染料とアミンの複合開始系(特公昭44−20189号)、ヘキサアリールビイミダゾールとラジカル発生剤と染料との併用系(特公昭45−37377号)、ヘキサアリールビイミダゾールとp−ジアルキルアミノベンジリデンケトンの系(特公昭47−2528号、特開昭54−155292号)、環状シス−α−ジカルボニル化合物と染料の系(特開昭48−84183号)、環状トリアジンとメロシアニン色素の系(特開昭54−151024号)、3−ケトクマリンと活性剤の系(特開昭52−112681号、特開昭58−15503号)、ビイミダゾール、スチレン誘導体、チオールの系(特開昭59−140203号)、有機過酸化物と色素の系(特開昭59−1504号、特開昭59−140203号、特開昭59−189340号、特開昭62−174203号、特公昭62−1641号、米国特許第4766055号)、染料と活性ハロゲン化合物の系(特開昭63−258903号、特開平2−63054号など)染料とボレート化合物の系(特開昭62−143044号、特開昭62−150242号、特開昭64−13140号、特開昭64−13141号、特開昭64−13142号、特開昭64−13143号、特開昭64−13144号、特開昭64−17048号、特開平1−229003号、特開平1−298348号、特開平1−138204号など)ローダニン環を有する色素とラジカル発生剤の系(特開平2−179643号、特開平2−244050号)、チタノセンと3−ケトクマリン色素の系(特開昭63−221110号)、チタノセンとキサンテン色素さらにアミノ基あるいはウレタン基を含む付加重合可能なエチレン性不飽和化合物を組み合わせた系(特開平4−221958号、特開平4−219756号)、チタノセンと特定のメロシアニン色素の系(特開平6−295061号)、チタノセンとベンゾピラン環を有する色素の系(特開平8−334897号)等を挙げることができる。
[Photopolymerization initiation system]
The photopolymerization initiation system (agent) contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention may be various photoinitiators known in patents, literatures, etc., or two or more depending on the wavelength of the light source used. The photoinitiator combination system (photoinitiation system) can be appropriately selected and used. Specific examples are listed below, but are not limited thereto.
Various photoinitiating systems have been proposed in the case of using visible light of 400 nm or more, Ar laser, second harmonic of a semiconductor laser, or SHG-YAG laser as a light source, for example, US Pat. No. 2,850,445. Certain photoreducible dyes described in No. 1, for example, rose bengal, eosin, erythrosine, etc., or a combination of a dye and an initiator, for example, a combined initiator system of a dye and an amine (Japanese Patent Publication No. 44-20189) , Hexaarylbiimidazole, radical generator and dye combination system (Japanese Examined Patent Publication No. 45-37377), hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Examined Patent Publication No. 47-2528, Japanese Patent Laid-Open Publication No. 54- 155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (Japanese Patent Laid-Open No. 48-84183), Azine and merocyanine dye systems (Japanese Patent Laid-Open No. 54-151024), 3-ketocoumarin and activator systems (Japanese Patent Laid-Open Nos. 52-111261, 58-15503), biimidazole, styrene derivatives, thiols System (JP 59-140203 A), organic peroxide and dye system (JP 59-1504, JP 59-140203, JP 59-189340, JP 62-174203). No. 6, JP-B 62-1641, US Pat. No. 4,766,055), dyes and active halogen compounds (JP-A 63-258903, JP-A 2-63054, etc.), dyes and borate compounds (JP A) JP-A-62-143044, JP-A-62-1050242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64- 13143, JP-A 64-13144, JP-A 64-17048, JP-A 1-222903, JP-A-1-298348, JP-A 1-138204, etc.) A dye having a rhodanine ring and a radical generator Systems (JP-A-2-17943, JP-A-2-244050), titanocene and 3-ketocoumarin dye systems (JP-A 63-221110), titanocene and xanthene dyes, addition polymerization containing amino groups or urethane groups A combination of possible ethylenically unsaturated compounds (JP-A-4-221958, JP-A-4-219756), titanocene and a specific merocyanine dye system (JP-A-6-295061), having a titanocene and a benzopyran ring And dye systems (Japanese Patent Laid-Open No. 8-3344897).
また、最近400〜410nmの波長のレーザー(バイオレットレーザー)が開発され、それに感応する450nm以下の波長に高感度を示す光開始系が開発されており、これらの光開始系も使用される。例えば、カチオン色素/ボレート系(特開平11−84647)、メロシアニン色素/チタノセン系(特開2000−147763)、カルバゾール型色素/チタノセン系(特開2001−42524号公報)等を挙げることができる。本発明においては特にチタノセン化合物を用いた系が、感度の点で優れており好ましい。 Recently, a laser having a wavelength of 400 to 410 nm (violet laser) has been developed, and a photoinitiating system exhibiting high sensitivity at a wavelength of 450 nm or less that responds to it has been developed, and these photoinitiating systems are also used. For example, a cationic dye / borate system (Japanese Patent Laid-Open No. 11-84647), a merocyanine dye / titanocene system (Japanese Patent Laid-Open No. 2000-147663), a carbazole type dye / titanocene system (Japanese Patent Laid-Open No. 2001-42524), and the like can be mentioned. In the present invention, a system using a titanocene compound is particularly preferable in view of sensitivity.
チタノセン化合物としては、種々のものを用いることができるが、例えば、特開昭59−152396号、特開昭61−151197号各公報に記載されている各種チタノセン化合物から適宜選んで用いることができる。さらに具体的には、ジ−シクロペンタジエニル−Ti−ジ−クロライド、ジ−シクロペンタジエニル−Ti−ビス−フェニル、ジ−シクロペンタジエニル−Ti−ビス−2,3,4,5,6−ペンタフルオロフェニ−1−イル、ジ−シクロペンタジエニル−Ti−ビス−2,3,5,6−テトラフルオロフェニ−1−イル、ジ−シクロペンタジエニル−Ti−ビス−2,4,6−トリフルオロフェニ−1−イル、ジ−シクロペンタジエニル−Ti−ビス−2,6−ジ−フルオロフェニ−1−イル、ジ−シクロペンタジエニル−Ti−ビス−2,4−ジ−フルオロフェニ−1−イル、ジ−メチルシクロペンタジエニル−Ti−ビス−2,3,4,5,6−ペンタフルオロフェニ−1−イル、ジ−メチルシクロペンタジエニル−Ti−ビス−2,6−ジフルオロフェニ−1−イル、ジ−シクロペンタジエニル−Ti−ビス−2,6−ジフルオロ−3−(ピル−1−イル)−フェニ−1−イル等を挙げることができる。更に上記光開始剤に必要に応じ、2−メルカプトベンズチアゾール、2−メルカプトベンズイミダゾール、2−メルカプトベンズオキサゾール等のチオール化合物、N−フェニルグリシン、N,N−ジアルキルアミノ芳香族アルキルエステル等のアミン化合物等の水素供与性化合物を加えることにより更に光開始能力が高められることが知られている。これらの光重合開始剤(系)の使用量は後述のエチレン性不飽和化合物100重量部に対し、0.05〜100重量部、好ましくは0.1〜70重量部、更に好ましくは0.2〜50重量部の範囲で用いられる。 Various titanocene compounds can be used. For example, various titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used. . More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti -Bis-2, - difluoro-1-yl, di - cyclopentadienyl -Ti- bis-2,6-difluoro-3- (pyrr-1-yl) - can be exemplified 1-yl and the like. Further, if necessary for the above photoinitiator, thiol compounds such as 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, amines such as N-phenylglycine, N, N-dialkylamino aromatic alkyl ester, etc. It is known that the photoinitiating ability can be further enhanced by adding a hydrogen-donating compound such as a compound. The amount of these photopolymerization initiators (systems) used is 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, and more preferably 0.2 to 100 parts by weight of the ethylenically unsaturated compound described later. It is used in the range of ˜50 parts by weight.
〔少なくとも1個のエチレン性不飽和基を有する重合可能な化合物〕
エチレン性不飽和化合物とは、光重合性組成物が活性光線の照射を受けた時、光重合開始剤の作用により付加重合し、架橋、硬化するようなエチレン性不飽和結合を有する化合物である。付加重合可能なエチレン性不飽和結合を含む化合物は、末端エチレン性不飽和結合を少なくとも1個、好ましくは2個以上有する化合物の中から任意に選択することができる。例えばモノマー、プレポリマー、すなわち2量体、3量体およびオリゴマー、またはそれらの混合物ならびにそれらの共重合体などの化学的形態をもつものである。
[Polymerizable compound having at least one ethylenically unsaturated group]
An ethylenically unsaturated compound is a compound having an ethylenically unsaturated bond that undergoes addition polymerization, crosslinking and curing by the action of a photopolymerization initiator when the photopolymerizable composition is irradiated with actinic rays. . The compound containing an ethylenically unsaturated bond capable of addition polymerization can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.
モノマーおよびその共重合体の例としては、不飽和カルボン酸(例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など)と脂肪族多価アルコール化合物とのエステル、不飽和カルボン酸と脂肪族多価アミン化合物とのアミド等が挙げられる。脂肪族多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、1,3−ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリ(アクリロイルオキシプロピル)エ−テル、トリメチロールエタントリアクリレート、ヘキサンジオールジアクリレート、1,4−シクロヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、トリ(アクリロイルオキシエチル)イソシアヌレート、ポリエステルアクリレートオリゴマー等がある。 Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and aliphatic polyvalent amine compounds. Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrelane , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester Examples include acrylate oligomers.
メタクリル酸エステルとしては、テトラメチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、エチレングリコールジメタクリレート、1,3−ブタンジオールジメタクリレート、ヘキサンジオールジメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールペンタメタアクリレート、ソルビトールトリメタクリレート、ソルビトールテトラメタクリレート、ビス[p−(3−メタクリルオキシ−2−ヒドロキシプロポキシ)フェニル]ジメチルメタン、ビス−[p−(メタクリルオキシエトキシ)フェニル]ジメチルメタン等がある。 Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [ - (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p-(methacryloxyethoxy) phenyl] dimethyl methane.
イタコン酸エステルとしては、エチレングリコールジイタコネート、プロピレングリコールジイタコネート、1,5−ブタンジオールジイタコネート、1,4−ブタンジオールジイタコネート、テトラメチレングリコールジイタコネート、ペンタエリスリトールジイタコネート、ソルビトールテトライタコネート等がある。クロトン酸エステルとしては、エチレングリコールジクロトネート、テトラメチレングリコールジクロトネート、ペンタエリスリトールジクロトネート、ソルビトールテトラジクロトネート等がある。イソクロトン酸エステルとしては、エチレングリコールジイソクロトネート、ペンタエリスリトールジイソクロトネート、ソルビトールテトライソクロトネート等がある。 Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,5-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
マレイン酸エステルとしては、エチレングリコールジマレート、トリエチレングリコールジマレート、ペンタエリスリトールジマレート、ソルビトールテトラマレート等がある。さらに、前述のエステルモノマーの混合物も挙げることができる。また、脂肪族多価アミン化合物と不飽和カルボン酸とのアミドのモノマーの具体例としては、メチレンビス−アクリルアミド、メチレンビス−メタクリルアミド、1,6−ヘキサメチレンビス−アクリルアミド、1,6−ヘキサメチレンビス−メタクリルアミド、ジエチレントリアミントリスアクリルアミド、キシリレシビスアクリルアミド、キシリレンビスメタクリルアミド等がある。 Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, the mixture of the above-mentioned ester monomer can also be mentioned. Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.
その他の例としては、特公昭48−41708号公報中に記載されている1分子中に2個以上のイソシアネート基を有するポリイソシアネート化合物に、下記の一般式(A)で示される水酸基を含有するビニルモノマーを付加せしめた1分子中に2個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。 As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708 contains a hydroxyl group represented by the following general formula (A). Examples thereof include a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer is added.
CH2=C(R)COOCH2CH(R')OH (A)
(ただし、RおよびR'はHあるいはCH3を示す。)
CH 2 = C (R) COOCH 2 CH (R ') OH (A)
(However, R and R ′ represent H or CH 3. )
また、特開昭51−37193号、特公平2−32293号の各公報に記載されているようなウレタンアクリレート類、特開昭48−64183号、特公昭49−43191号、特公昭52−30490号各公報に記載されているようなポリエステルアクリレート類、エポキシ樹脂と(メタ)アクリル酸を反応させたエポキシアクリレート類等の多官能のアクリレートやメタクリレートを挙げることができる。さらに日本接着協会誌Vo1.20, No.7, 300〜308ぺ−ジ(1984年)に光硬化性モノマーおよびオリゴマーとして紹介されているものも使用することができる。なお、これらエチレン性不飽和結合含有化合物の使用量は、感光層全成分の5〜80質量%、好ましくは30〜70質量%の範囲で使用される。 Further, urethane acrylates as described in JP-A-51-37193 and JP-B-2-32293, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, as described in each publication. Furthermore, those introduced as photo-curable monomers and oligomers in the Japan Adhesion Association magazine Vo 1.20, No. 7, pages 300 to 308 (1984) can also be used. In addition, the usage-amount of these ethylenically unsaturated bond containing compounds is 5-80 mass% of the photosensitive layer whole component, Preferably it is used in 30-70 mass%.
〔バインダー樹脂〕
本発明の感光性平版印刷版の感光層に用いられるバインダー樹脂(高分子結合剤)としては、該感光層の皮膜形成剤としてだけでなく、アルカリ現像液に溶解する必要があるため、アルカリ水に可溶性または膨潤性である有機高分子重合体が使用される。
この様な有機高分子重合体としては、側鎖にカルボン酸基を有する付加重合体、例えば特開昭59−44615号、特公昭54−34327号、特公昭58−12577号、特公昭54−25957号、特開昭54−92723号、特開昭59−53836号、特開昭59−71048号に記載されているもの、すなわち、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等がある。
[Binder resin]
The binder resin (polymer binder) used in the photosensitive layer of the photosensitive lithographic printing plate of the present invention is not only used as a film forming agent for the photosensitive layer but also needs to be dissolved in an alkaline developer. Organic polymer that is soluble or swellable is used.
Examples of such an organic polymer include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-. No. 25957, JP 54-92723, JP 59-53836, JP 59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer Examples include polymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers.
また同様に側鎖にカルボン酸基を有する酸性セルロース誘導体がある。この外に水酸基を有する付加重合体に環状酸無水物を付加させたものなどが有用である。特にこれらの中で〔ベンジル(メタ)アクリレート/(メタ)アクリル酸/必要に応じてその他の付加重合性ビニルモノマー〕共重合体及び〔アリル(メタ)アクリレート(メタ)アクリル酸/必要に応じてその他の付加重合性ビニルモノマー〕共重合体が好適である。この他に水溶性有機高分子として、ポリビニルピロリドンやポリエチレンオキサイド等が有用である。また硬化皮膜の強度を上げるためにアルコール可溶性ポリアミドや2,2−ビス−(4−ヒドロキシフェニル)−プロパンとエピクロロヒドリンのポリエーテル等も有用である。
また特公平7−120040号、特公平7−120041号、特公平7−120042号、特公平8−12424号、特開昭63−287944号、特開昭63−287947号、特開平1−271741号、特開平11−352691号に記載のポリウレタン樹脂も本発明の用途には有用である。
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful. Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate (meth) acrylic acid / as required Other addition polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
JP-B-7-120040, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271741 And JP-A-11-352691 are also useful for the use of the present invention.
これら高分子重合体は側鎖にラジカル反応性基を導入することにより硬化皮膜の強度を向上させることができる。付加重合反応し得る官能基としてエチレン性不飽和結合基、アミノ基、エポキシ基等が、又光照射によりラジカルになり得る官能基としてはメルカプト基、チオール基、ハロゲン原子、トリアジン構造、オニウム塩構造等が、又極性基としてカルボキシル基、イミド基等が挙げられる。上記付加重合反応し得る官能基としては、アクリル基、メタクリル基、アリル基、スチリル基などエチレン性不飽和結合基が特に好ましいが、又アミノ基、ヒドロキシ基、ホスホン酸基、燐酸基、カルバモイル基、イソシアネート基、ウレイド基、ウレイレン基、スルフォン酸基、アンモニオ基から選ばれる官能基も有用である。 These polymer polymers can improve the strength of the cured film by introducing a radical reactive group into the side chain. Functional groups that can undergo an addition polymerization reaction include ethylenically unsaturated bond groups, amino groups, and epoxy groups, and functional groups that can become radicals upon light irradiation include mercapto groups, thiol groups, halogen atoms, triazine structures, and onium salt structures. In addition, examples of the polar group include a carboxyl group and an imide group. The functional group capable of undergoing addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acryl group, a methacryl group, an allyl group, or a styryl group, but also an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, or a carbamoyl group. A functional group selected from an isocyanate group, a ureido group, a ureylene group, a sulfonic acid group, and an ammonio group is also useful.
感光層の現像性を維持するためには、高分子結合剤は適当な分子量、酸価を有することが好ましく、重量平均分子量で5000〜30万、酸価20〜200の高分子重合体が有効に使用される。
これらの有機高分子重合体は感光層全組成中に任意な量を混和させることができる。好ましくは10〜90%、より好ましくは30〜80%である。90重量%以下の場合には形成される画像強度等の点で好ましい結果を与えるため好ましい。また光重合可能なエチレン性不飽和化合物と有機高分子重合体は、重量比で1/9〜9/1の範囲とするのが好ましい。より好ましい範囲は2/8〜8/2てあり、更に好ましくは3/7〜7/3である。
In order to maintain the developability of the photosensitive layer, the polymer binder preferably has an appropriate molecular weight and acid value, and a polymer having a weight average molecular weight of 5000 to 300,000 and an acid value of 20 to 200 is effective. Used for.
These organic high molecular polymers can be mixed in an arbitrary amount in the entire composition of the photosensitive layer. Preferably it is 10 to 90%, More preferably, it is 30 to 80%. In the case of 90% by weight or less, it is preferable because a preferable result is given in terms of the strength of the formed image. The photopolymerizable ethylenically unsaturated compound and the organic polymer are preferably in the range of 1/9 to 9/1 by weight. A more preferable range is 2/8 to 8/2, still more preferably 3/7 to 7/3.
〔その他の成分〕
また、本発明の感光性平版印刷版の感光層においては、以上の基本成分の他に感光層用組成物(以下、感光性組成物ともいう)の製造中あるいは保存中において重合可能なエチレン性不飽和化合物の不要な熱重合を阻止するために少量の熱重合禁止剤を添加することが望ましい。適当な熱重合禁止剤としてはハロイドキノン、p−メトキシフェノール、ジ−t−ブチル−p−クレゾール、ピロガロール、t−ブチルカテコール、ベンゾキノン、4,4′−チオビス(3−メチル−6−t−ブチルフェノール)、2,2′−メチレンビス(4−メチル−6−t−ブチルフェノール)、N−ニトロソフェニルヒドロキシルアミン第一セリウム塩、N−ニトロソフェニルヒドロキシルアミンアルミニウム塩等が挙げられる。熱重合禁止剤の添加量は、感光層の固形分に対して約0.01%〜約5%が好ましい。また必要に応じて、酸素による重合阻害を防止するためにベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加して、塗布後の乾燥の過程で感光層の表面に偏在させてもよい。高級脂肪酸誘導体の添加量は、感光層の固形分に対して約0.5%〜約10%が好ましい。
[Other ingredients]
In addition, in the photosensitive layer of the photosensitive lithographic printing plate of the present invention, in addition to the above basic components, an ethylenic polymerisable during production or storage of a composition for a photosensitive layer (hereinafter also referred to as a photosensitive composition). It is desirable to add a small amount of a thermal polymerization inhibitor to prevent unwanted thermal polymerization of unsaturated compounds. Suitable thermal polymerization inhibitors include haloid quinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitrosophenylhydroxylamine aluminum salt, and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% with respect to the solid content of the photosensitive layer. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% with respect to the solid content of the photosensitive layer.
更に感光層の着色を目的として、着色剤を添加してもよい。着色剤としては、例えば、フタロシアニン系顔料(C.I.Pigment Blue 15:3、15:4、15:6など)、アゾ系顔料、カーボンブラック、酸化チタンなどの顔料、エチルバイオレット、クリスタルバイオレット、アゾ染料、アントラキノン系染料、シアニン系染料がある。染料および顔料の添加量は感光層用全組成物の約0.5%〜約20%が好ましい。加えて、硬化皮膜の物性を改良するために、無機充填剤やジオクチルフタレート、ジメチルフタレート、トリクレジルホスフェート等の可塑剤等の添加剤を加えてもよい。これらの添加量は感光層用全組成物の10%以下が好ましい。 Further, a coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the colorant include phthalocyanine pigments (CI Pigment Blue 15: 3, 15: 4, 15: 6, etc.), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, There are azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% to about 20% of the total composition for the photosensitive layer. In addition, in order to improve the physical properties of the cured film, an additive such as an inorganic filler or a plasticizer such as dioctyl phthalate, dimethyl phthalate, or tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total composition for the photosensitive layer.
〔感光性平版印刷版の形成方法〕
本発明の感光性平版印刷版の感光層組成物を後述のアルミニウム支持体上に塗布する際には、種々の有機溶剤に溶かして使用に供される。ここで使用する溶媒としては、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、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、アセチルアセトン、シクロヘキサノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3−メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート−3−メトキシプロピルアセテート、N,N−ジメチルホルムアミド、ジメチルスルホキシド、γ−ブチロラクトン、乳酸メチル、乳酸エチルなどがある。これらの溶媒は、単独あるいは混合して使用することができる。そして、塗布溶液中の固形分の濃度は1〜50重量%が適当である。
[Method for forming photosensitive lithographic printing plate]
When the photosensitive layer composition of the photosensitive lithographic printing plate of the present invention is coated on an aluminum support described later, it is dissolved in various organic solvents and used. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate-3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 1 to 50% by weight.
本発明の感光性平版印刷版の感光層には、塗布面質を向上するために界面活性剤を添加することができる。感光層の被覆量は乾燥後の重量で約0.1g/m2〜約10g/m2の範囲が適当である。より好ましくは0.3〜5g/m2である。更に好ましくは0.5〜3g/m2である。 A surfactant can be added to the photosensitive layer of the photosensitive lithographic printing plate of the present invention in order to improve the coating surface quality. The coverage of the photosensitive layer is suitably ranges from about 0.1 g / m 2 ~ about 10 g / m 2 in weight after drying. More preferably from 0.3 to 5 g / m 2. More preferably, it is 0.5-3 g / m < 2 >.
〔保護層〕
本発明の感光性平版印刷版においては、通常、露光を大気中で行うため、感光層の上に、さらに、保護層を設ける事が好ましい。保護層は、感光層中で露光により生じる画像形成反応を阻害する大気中に存在する酸素や塩基性物質等の低分子化合物の感光層への混入を防止し、大気中での露光を可能とする。従って、この様な保護層に望まれる特性は、酸素等の低分子化合物の透過性が低いことであり、さらに、露光に用いる光の透過は実質阻害せず、感光層との密着性に優れ、かつ、露光後の現像工程で容易に除去できる事が望ましい。この様な、保護層に関する工夫が従来よりなされており、米国特許第3,458,311号、特開昭55−49729号に詳しく記載されている。
[Protective layer]
In the photosensitive lithographic printing plate of the present invention, since exposure is usually performed in the air, it is preferable to further provide a protective layer on the photosensitive layer. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to allow exposure in the atmosphere. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure. Such a device for the protective layer has been conventionally devised, which is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729.
保護層に使用できる材料としては、例えば、比較的、結晶性に優れた水溶性高分子化合物を用いる事がよく、具体的には、ポリビニルアルコール、ポリビニルピロリドン、酸性セルロース類、ゼラチン、アラビアゴム、ポリアクリル酸などのような水溶性ポリマーが知られていが、これらの内、ポリビニルアルコールを主成分として用いる事が、酸素遮断性、現像除去性といった基本特性的にもっとも良好な結果を与える。保護層に使用するポリビニルアルコールは、必要な酸素遮断性と水溶性を有するための、未置換ビニルアルコール単位を含有する限り、一部がエステル、エーテル、およびアセタールで置換されていても良い。また、同様に一部が他の共重合成分を有していても良い。ポリビニルアルコールの具体例としては71〜100%加水分解され、分子量が300から2400の範囲のものを挙げる事ができる。 As a material that can be used for the protective layer, for example, a water-soluble polymer compound that is relatively excellent in crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as polyacrylic acid are known, but among these, the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400.
具体的には、株式会社クラレ製のPVA−105、PVA−110、PVA−117、PVA−117H、PVA−120、PVA−124、PVA−124H、PVA−CS、PVA−CST、PVA−HC、PVA−203、PVA−204、PVA−205、PVA−210、PVA−217、PVA−220、PVA−224、PVA−217EE、PVA−217E、PVA−220E、PVA−224E、PVA−405、PVA−420、PVA−613、L−8等が挙げられる。 Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.
保護層の成分(PVAの選択、添加剤の使用)、塗布量等は、酸素遮断性・現像除去性の他、カブリ性や密着性・耐傷性を考慮して選択される。一般には使用するPVAの加水分解率が高い程(保護層中の未置換ビニルアルコール単位含率が高い程)、膜厚が厚い程酸素遮断性が高くなり、感度の点で有利である。しかしながら、極端に酸素遮断性を高めると、製造時・生保存時に不要な重合反応が生じたり、また画像露光時に、不要なカブリ、画線の太りが生じたりという問題を生じる。また、画像部との密着性や、耐傷性も版の取り扱い上極めて重要である。即ち、水溶性ポリマーからなる親水性の層を親油性の重合層に積層すると、接着力不足による膜剥離が発生しやすく、剥離部分が酸素の重合阻害により膜硬化不良などの欠陥を引き起こす。 Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic polymer layer, film peeling due to insufficient adhesion tends to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization.
これに対し、これら2層間の接着性を改善すべく種々の提案がなされている。たとえば米国特許第292,501号、米国特許第44,563号には、主にポリビニルアルコールからなる親水性ポリマー中に、アクリル系エマルジョンまたは水不溶性ビニルピロリドン−ビニルアセテート共重合体などを5〜80重量%混合し、重合層の上に積層することにより、十分な接着性が得られることが記載されている。本発明における保護層に対しては、これらの公知の技術をいずれも適用する事ができる。このような保護層の塗布方法については、例えば米国特許第3,458,311号、特開昭55−49729号に詳しく記載されている。 On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, in US Pat. No. 292,501 and US Pat. No. 44,563, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer is added to a hydrophilic polymer mainly composed of polyvinyl alcohol in an amount of 5 to 80. It is described that sufficient adhesion can be obtained by mixing by weight% and laminating on the polymerized layer. Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.
さらに、保護層に他の機能を付与する事もできる。例えば、露光に使う、350nmから450nmの光の透過性に優れ、かつ500nm以上の光を効率良く吸収しうる、着色剤(水溶性染料等)の添加により、感度低下を起こすことなく、セーフライト適性をさらに高める事ができる。 Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that is excellent in the transmission of light from 350 nm to 450 nm and that can absorb light of 500 nm or more, which is used for exposure, it is safe light without causing a decrease in sensitivity. The aptitude can be further enhanced.
〔支持体〕
次に、本発明の感光性平版印刷版の支持体について説明する。本発明にて用いられる支持体は、特に限定されないが、アルミニウム支持体が好ましい。アルミニウム支持体は、寸度的に安定なアルミニウムまたはその合金(例えば珪素、銅、マンガン、マグネシウム、クロム、亜鉛、鉛、ビスマス、ニッケルとの合金)、またはアルミニウム、アルミニウム合金がラミネートもしくは蒸着されたプラスチックフィルムまたは紙を意味し、通常その厚さは0.05mm〜1mm程度である。また特開昭48−18327号に記載の複合シートも使用することができる。
[Support]
Next, the support for the photosensitive lithographic printing plate of the present invention will be described. The support used in the present invention is not particularly limited, but an aluminum support is preferable. Aluminum supports are dimensionally stable aluminum or alloys thereof (eg, alloys with silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel), or aluminum or aluminum alloys laminated or deposited. It means a plastic film or paper, and its thickness is usually about 0.05 mm to 1 mm. A composite sheet described in JP-A-48-18327 can also be used.
アルミニウム支持体は適宜、後述の基板表面処理が施される。
(砂目立て処理)
砂目立て処理方法は、特開昭56−28893号に開示されているような機械的砂目立て、化学的エッチング、電解グレインなどがある。さらに塩酸または硝酸電解液中で電気化学的に砂目立てする電気化学的砂目立て方法、及びアルミニウム表面を金属ワイヤーでひっかくワイヤーブラシグレイン法、研磨球と研磨剤でアルミニウム表面を砂目立てするボールグレイン法、ナイロンブラシと研磨剤で表面を砂目立てするブラシグレイン法のような機械的砂目立て法を用いることができ、上記砂目立て方法を単独あるいは組み合わせて用いることもできる。その中でも本発明に有用に使用される表面粗さを作る方法は、塩酸または硝酸電解液中で化学的に砂目立てする方法であり、適する電流密度は100C/dm2〜400C/dm2の範囲である。さらに具体的には、0.1〜50%の塩酸または硝酸を含む電解液中、温度20〜100℃、時間1秒〜30分、電流密度100C/dm2〜400C/dm2の条件で電解を行うことが好ましい。
The aluminum support is appropriately subjected to substrate surface treatment described below.
(Graining treatment)
Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, electrochemical graining method that electrochemically grains in hydrochloric acid or nitric acid electrolyte, and wire brush grain method that scratches aluminum surface with metal wire, and ball grain method that graines aluminum surface with abrasive balls and abrasives Further, a mechanical graining method such as a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination. The method is a method of chemically graining in a hydrochloric acid or nitric acid electrolytic solution, suitable current density of 100C / dm 2 ~400C / dm 2 ranges to make the surface roughness usefully employed in the present invention among them It is. More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm 2 ~400C / dm 2 It is preferable to carry out.
このように砂目立て処理したアルミニウム支持体は、酸またはアルカリにより化学的にエッチングされる。酸をエッチング剤として用いる場合は、微細構造を破壊するのに時間がかかり、工業的に本発明を適用するに際しては不利であるが、アルカリをエッチング剤として用いることにより改善できる。本発明において好適に用いられるアルカリ剤は、苛性ソーダ、炭酸ソーダ、アルミン酸ソーダ、メタケイ酸ソーダ、リン酸ソーダ、水酸化カリウム、水酸化リチウム等を用い、濃度と温度の好ましい範囲はそれぞれ1〜50%、20〜100℃であり、Alの溶解量が5〜20g/m3となるような条件が好ましい。エッチングのあと表面に残留する汚れ(スマット)を除去するために酸洗いが行われる。用いられる酸は硝酸、硫酸、リン酸、クロム酸、フッ酸、ホウフッ化水素酸等が用いられる。特に電気化学的粗面化処理後のスマット除去処理方法としては、好ましくは特開昭53−12739号公報に記載されているような50〜90℃の温度の15〜65重量%の硫酸と接触させる方法及び特公昭48−28123号公報に記載されているアルカリエッチングする方法が挙げられる。なお、本発明で有効に用いられるAl支持体の表面粗さ(Ra)は0.3〜0.7μmである。 The grained aluminum support is chemically etched with acid or alkali. When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent. As the alkali agent suitably used in the present invention, caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like are used, and preferred ranges of concentration and temperature are 1 to 50 respectively. %, 20 to 100 ° C., and conditions such that the dissolution amount of Al is 5 to 20 g / m 3 are preferable. Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65% by weight sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123. Note that the surface roughness (Ra) of the Al support effectively used in the present invention is 0.3 to 0.7 μm.
(陽極酸化処理)
以上のようにして処理されたアルミニウム支持体は、さらに陽極酸化処理が施される。陽極酸化処理はこの分野で従来より行われている方法で行うことができる。具体的には、硫酸、リン酸、クロム酸、シュウ酸、スルファミン酸、ベンゼンスルフォン酸等あるいはこれらの二種以上を組み合わせて水溶液または非水溶液中でアルミニウムに直流または交流を流すとアルミニウム支持体表面に陽極酸化皮膜を形成することができる。陽極酸化処理の条件は使用される電解液によって種々変化するので一概に決定され得ないが、一般的には電解液の濃度が1〜80%、液温5〜70℃、電流密度0.5〜60アンペア/dm2、電圧1〜100V、電解時間10〜100秒の範囲が適当である。
(Anodizing treatment)
The aluminum support treated as described above is further anodized. The anodizing treatment can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution by combining sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. An anodized film can be formed. The conditions for anodizing treatment vary depending on the electrolyte used, and therefore cannot be determined in general. In general, the concentration of the electrolyte is 1 to 80%, the solution temperature is 5 to 70 ° C., and the current density is 0.5. A range of ˜60 amperes / dm 2 , a voltage of 1 to 100 V, and an electrolysis time of 10 to 100 seconds is appropriate.
これらの陽極酸化処理のうちでも特に英国特許第1,412,768号明細書に記載されている、硫酸中で高電流密度で陽極酸化する方法及び米国特許第3,511,661号明細書に記載されているリン酸を電解浴として陽極酸化する方法が好ましい。本発明においては、陽極酸化皮膜は1〜10g/m2であることが好ましく、1g/m2以上であると版に傷が入り難く、10g/m2以下であると製造に多大な電力が不要となり、経済的に有利である。好ましくは、1.5〜7g/m2である。更に好ましくは、2〜5g/m2である。 Among these anodizing treatments, a method for anodizing at a high current density in sulfuric acid and U.S. Pat. No. 3,511,661, particularly described in British Patent 1,412,768. A method of anodizing the described phosphoric acid as an electrolytic bath is preferred. In the present invention, the anodized film is preferably from 1~10g / m 2, 1g / m 2 or more plate on difficult to enter scratches If it is, a great deal power production and is 10 g / m 2 or less This is unnecessary and is economically advantageous. Preferably, a 1.5~7g / m 2. More preferably 2-5 g / m 2.
更に、本発明においては、砂目立て処理及び陽極酸化後、アルミニウム支持体に封孔処理を施してもかまわない。かかる封孔処理は、熱水又は無機塩または有機塩を含む熱水溶液への基板の浸漬ならびに水蒸気浴などによって行われる。また本発明のアルミニウム支持体にはアルカリ金属珪酸塩によるシリケート処理又はシリケート処理以外の処理、たとえば弗化ジルコニウム酸カリウム、燐酸塩等の水溶液への浸漬処理などの表面処理がなされてもかまわない。 Furthermore, in the present invention, the aluminum support may be subjected to sealing treatment after graining treatment and anodizing. Such sealing treatment is performed by immersing the substrate in hot water or a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. The aluminum support of the present invention may be subjected to a surface treatment such as a silicate treatment with an alkali metal silicate or a treatment other than the silicate treatment, for example, an immersion treatment in an aqueous solution of potassium fluorinated zirconate or phosphate.
上記の如く表面処理を施されたアルミニウム支持体上に、前記の光重合性組成物からなる感光層を形成することで、本発明の感光性平版印刷版を作製するが、感光層を塗設する前に必要に応じて有機または無機の中間層が設けられてもかまわない。 The photosensitive lithographic printing plate of the present invention is produced by forming a photosensitive layer comprising the photopolymerizable composition on the aluminum support that has been surface-treated as described above. An organic or inorganic intermediate layer may be provided as necessary before the treatment.
〔中間層〕
本発明における感光性平版印刷版には、感光層と基板との間の密着性や汚れ性を改善する目的で、中間層を設けてもよい。このような中間層の具体例としては、特公昭50−7481号、特開昭54−72104号、特開昭59−101651号、特開昭60−149491号、特開昭60−232998号、特開平3−56177号、特開平4−282637号、特開平5−16558号、特開平5−246171号、特開平7−159983号、特開平7−314937号、特開平8−202025号、特開平8−320551号、特開平9−34104号、特開平9−236911号、特開平9−269593号、特開平10−69092号、特開平10−115931号、特開平10−161317号、特開平10−260536号、特開平10−282682号、特開平11−84674号、特開平10−69092号、特開平10−115931号、特開平11−38635号、特開平11−38629号、特開平10−282645号、特開平10−301262号、特開平11−24277号、特開平11−109641号、特開平10−319600号、特開平11−84674号、特開平11−327152号、特開2000−10292号、特開2000−235254号、特開2000−352824号、特願平11−284091号明細書、特開2001−209170号等に記載のものを挙げることができる。
[Middle layer]
In the photosensitive lithographic printing plate according to the invention, an intermediate layer may be provided for the purpose of improving the adhesion and soiling between the photosensitive layer and the substrate. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, JP-A-10-69092, JP-A-10-115931, Kaihei 11-38635, JP-A-11-38629, JP-A-10-282645, JP-A-10-301262, JP-A-11-24277, JP-A-11-109641, JP-A-10-319600, JP-A-10-319600 No. 11-84684, No. 11-327152, No. 2000-10292, No. 2000-235254, No. 2000-352824, Japanese Patent Application No. 11-284091, No. 2001-209170, etc. Can be mentioned.
〔画像形成〕
本発明における感光性平版印刷版を、例えば、カーボンアーク灯、高圧水銀灯、キセノンランプ、メタルハライドランプ、蛍光ランプ、タングステンランプ、ハロゲンランプ、ヘリウムカドミニウムレーザー、アルゴンイオンレーザー、FD・YAGレーザー、ヘリウムネオンレーザー、半導体レーザー(350nm〜600nm)等の従来公知の活性光線で画像露光した後、現像処理することにより、アルミニウム板支持体表面に画像を形成することができる。画像露光後、現像までの間に、重合性感光層の硬化率を高める目的で50℃〜150℃の温度で1秒〜5分の時間の加熱プロセスを設けることを行っても良い。
(Image formation)
The photosensitive lithographic printing plate in the present invention is, for example, a carbon arc lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, an argon ion laser, an FD / YAG laser, a helium neon laser. An image can be formed on the surface of the aluminum plate support by exposing the image with a conventionally known actinic ray such as a semiconductor laser (350 nm to 600 nm) and then developing it. A heating process for 1 second to 5 minutes may be performed at a temperature of 50 ° C. to 150 ° C. for the purpose of increasing the curing rate of the polymerizable photosensitive layer after image exposure and development.
また、本発明における感光性平版印刷版の感光層の上には、前述したように、通常、酸素遮断性を有するオーバーコート層が設けてあり、本発明における現像液を用いて、オーバーコート層の除去と感光層未露光部の除去を同時に行う方法、または、水、温水でオーバーコート層を先に除外し、その後未露光部の感光層を現像で除去する方法が知られている。これらの水または温水には特開平10−10754号公報に記載の防腐剤等、特開平8−278636号公報に記載の有機溶剤等を含有させることができる。 In addition, as described above, an overcoat layer having oxygen barrier properties is usually provided on the photosensitive layer of the photosensitive lithographic printing plate in the present invention. Using the developer in the present invention, the overcoat layer is provided. There is known a method of removing the photosensitive layer and the unexposed portion of the photosensitive layer at the same time, or a method of removing the overcoat layer first with water and warm water and then removing the photosensitive layer of the unexposed portion by development. These water or warm water can contain a preservative described in JP-A-10-10754, an organic solvent described in JP-A-8-278636, and the like.
本発明における感光性平版印刷版の前記現像液による現像は、常法に従って、0〜60℃、好ましくは15〜40℃程度の温度で、例えば、露光処理した感光性平版印刷版を現像液に浸漬してブラシで擦る等により行う。 The development of the photosensitive lithographic printing plate in the present invention with the developer is performed at a temperature of about 0 to 60 ° C., preferably about 15 to 40 ° C., for example, using a light-sensitive photosensitive lithographic printing plate as a developer according to a conventional method. It is performed by dipping and rubbing with a brush.
さらに自動現像機を用いて現像処理を行う場合、処理量に応じて現像液が疲労してくるので、補充液または新鮮な現像液を用いて処理能力を回復させても良い。このようにして現像処理された感光性平版印刷版は特開昭54−8002号、同55−115045号、同59−58431号などの各公報に記載されているように、水洗水、界面活性剤等を含有するリンス液、アラビアガムやデンプン誘導体等を含む不感脂化液で後処理される。本発明において感光性平版印刷版の後処理にはこれらの処理を種々組み合わせて用いることができる。上記のような処理により得られた印刷版は特開2000−89478号公報に記載の方法による後露光処理やバーニングなどの加熱処理により、耐刷性を向上させることができる。このような処理によって得られた平版印刷版はオフセット印刷機に掛けられ、多数枚の印刷に用いられる。 Further, when developing using an automatic developing machine, the developing solution becomes fatigued according to the amount of processing, so that the processing capability may be restored using a replenishing solution or a fresh developing solution. The photosensitive lithographic printing plate thus developed is washed with water, surface active as described in JP-A Nos. 54-8002, 55-1115045 and 59-58431. It is post-treated with a rinsing solution containing an agent and the like, a desensitizing solution containing gum arabic, starch derivatives and the like. In the present invention, these treatments can be used in various combinations for the post-treatment of the photosensitive lithographic printing plate. The printing plate obtained by the above treatment can be improved in printing durability by post-exposure treatment or heating treatment such as burning according to the method described in JP-A-2000-89478. The planographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.
〔現像液〕
上述の感光性平版印刷版を従来公知の現像液を用いて現像し、画像形成することが可能であるが、特に以下に示す特殊な現像液を用いるのが、画像形成性、現像カスの点から好ましい。これらの従来公知の現像液としては、特公昭57−7427号に記載されているような現像液が挙げられ、ケイ酸ナトリウム、ケイ酸カリウム、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、第三リン酸ナトリウム、第二リン酸ナトリウム、第三リン酸アンモニウム、第二リン酸アンモニウム、メタケイ酸ナトリウム、重炭酸ナトリウム、アンモニア水などのような無機アルカリ剤やモノエタノールアミンまたはジエタノールアミンなどのような有機アルカリ剤の水溶液が適当である。このようなアルカリ溶液の濃度が0.1〜10重量%、好ましくは0.5〜5重量%になるように添加される。
[Developer]
The above-described photosensitive lithographic printing plate can be developed with a conventionally known developer to form an image. In particular, the following special developer is used in terms of image formability and development residue. To preferred. Examples of these conventionally known developers include developers described in JP-B-57-7427, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, Such as inorganic alkaline agents such as sodium triphosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. and monoethanolamine or diethanolamine etc. An aqueous solution of an organic alkali agent is suitable. Such an alkaline solution is added so that the concentration is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
また、このようなアルカリ性水溶液には、必要に応じて界面活性剤やベンジルアルコール、2−フェノキシエタノール、2−ブトキシエタノールのような有機溶媒を少量含むことができる。例えば、米国特許第3375171号および同第3615480号に記載されているものを挙げることができる。さらに、特開昭50−26601号、同58−54341号、特公昭56−39464号、同56−42860号の各公報に記載されている現像液も挙げることができる。 Such an alkaline aqueous solution may contain a small amount of a surfactant, an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480. Furthermore, the developing solution described in each gazette of Unexamined-Japanese-Patent No. 50-26601, 58-54341, Japanese Patent Publication No. 56-39464, and 56-42860 can also be mentioned.
また、好ましい例としては、無機アルカリ塩とポリオキシアルキレンエーテル基を有するノニオン系界面活性剤を含有し、pHが11.0〜12.5である。現像液が挙げられる。
無機アルカリ塩としては適宜使用可能であるが、例えば、水酸化ナトリウム、同カリウム、同アンモニウム、同リチウム、珪酸ナトリウム、同カリウム、同アンモニウム、同リチウム、第3リン酸ナトリウム、同カリウム、同アンモニウム、炭酸ナトリウム、同カリウム、同アンモニウム、炭酸水素ナトリウム、同カリウム、同アンモニウム、硼酸ナトリウム、同カリウム、及び同アンモニウム等の無機アルカリ剤が挙げられる。これらは単独でも、二種以上を組み合わせて用いても良い。
Moreover, as a preferable example, the nonionic surfactant which has an inorganic alkali salt and a polyoxyalkylene ether group is contained, and pH is 11.0-12.5. A developer is mentioned.
The inorganic alkali salt can be used as appropriate. For example, sodium hydroxide, potassium, ammonium, lithium, sodium silicate, potassium, ammonium, lithium, tribasic sodium phosphate, potassium, ammonium Inorganic alkaline agents such as sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium, sodium borate, potassium, and ammonium. These may be used alone or in combination of two or more.
珪酸塩を使用する場合には、珪酸塩の成分である酸化珪素SiO2とアルカリ酸化物M2O(Mはアルカリ金属を表す。)との混合比率及び濃度の調製により、現像性を容易に調節することが出来る。前記アルカリ水溶液の中でも前記酸化珪素SiO2とアルカリ酸化物M2Oとの混合比率(SiO2/M2O:モル比)が0.5〜3.0のものが好ましく、1.0〜2.0のものが好ましい。前記SiO2/M2Oが0.5以上であると、アルカリ強度が強くなり過ぎず、感光性平版印刷版の支持体として汎用のアルミニウム板をエッチングしてしまうといった弊害を生ずることがなく、4.0以下であると、現像性が向上する。また、現像液中のSiO2濃度は現像液の総重量に対し、1〜10質量%が好ましく、3〜8質量%がより好ましく、4〜7質量%が最も好ましい。この濃度が1質量%以上であると現像性、処理能力が向上するため好ましく、10質量%以下であれば沈殿や結晶を生成し難くなり、さらに廃液時の中和の際にゲル化し難くなり、廃液処理に支障をきたすことがないため、好ましい。 When silicate is used, developability is easily achieved by adjusting the mixing ratio and concentration of silicon oxide SiO 2 and alkali oxide M 2 O (M represents alkali metal), which is a component of silicate. Can be adjusted. Among the alkaline aqueous solutions, those having a mixing ratio (SiO 2 / M 2 O: molar ratio) of silicon oxide SiO 2 and alkali oxide M 2 O of 0.5 to 3.0 are preferable, and 1.0 to 2 0.0 is preferred. When the SiO 2 / M 2 O is 0.5 or more, the alkali strength is not too strong, and there is no adverse effect such as etching a general-purpose aluminum plate as a support for a photosensitive lithographic printing plate, When it is 4.0 or less, developability is improved. Further, the SiO 2 concentration in the developer is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, and most preferably 4 to 7% by mass with respect to the total weight of the developer. When the concentration is 1% by mass or more, developability and processing ability are improved. When the concentration is 10% by mass or less, it is difficult to form precipitates and crystals, and further, gelation is difficult to neutralize in the waste liquid. It is preferable because it does not hinder the waste liquid treatment.
また、アルカリ濃度の微少な調整、感光層の溶解性の補助の目的で、補足的に有機アルカリ剤を併用してもよい。有機アルカリ剤としては、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、n−ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン、テトラメチルアンモニウムヒドロキシド等を挙げることができる。これらのアルカリ剤は、単独もしくは2種以上を組み合わせて用いられる。 In addition, an organic alkali agent may be supplementarily used for the purpose of finely adjusting the alkali concentration and assisting the solubility of the photosensitive layer. Examples of the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Examples thereof include diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide and the like. These alkali agents are used alone or in combination of two or more.
上記現像液には、ポリオキシアルキレンエーテル基を有するノニオン界面活性剤を含有され、この界面活性剤添加により、未露光部の感光層の溶解促進、露光部への現像液の浸透性の低減が可能となる。ポリオキシアルキレンエーテル基を含有する界面活性剤としては、下記一般式(I)の構造を有する物が好適に使用される。 The developer contains a nonionic surfactant having a polyoxyalkylene ether group, and the addition of this surfactant promotes dissolution of the photosensitive layer in the unexposed area and reduces the permeability of the developer to the exposed area. It becomes possible. As the surfactant containing a polyoxyalkylene ether group, those having the structure of the following general formula (I) are preferably used.
R40−O−(R41-O)pH (I) R 40 −O− (R 41 -O) p H (I)
式中、R40は、置換基を有しても良い炭素数3〜15のアルキル基、置換基を有しても良い炭素数6〜15の芳香族炭化水素基、又は置換基を有しても良い炭素数4〜15の複素芳香族環基(尚、置換基としては炭素数1〜20のアルキル基、Br、Cl、I等のハロゲン原子、炭素数6〜15の芳香族炭化水素基、炭素数7〜17のアラルキル基、炭素数1〜20のアルコキシ基、炭素数2〜20のアルコキシ−カルボニル基、炭素数2〜15のアシル基が挙げられる。)を示し、R41は、置換基を有しても良い炭素数1〜100のアルキレン基(尚、置換基としては、炭素数1〜20のアルキル基、炭素数6〜15の芳香族炭化水素基が挙げられる。)を示し、pは1〜100の整数を表す。 In the formula, R 40 has an alkyl group having 3 to 15 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent, or a substituent. A heteroaromatic cyclic group having 4 to 15 carbon atoms (wherein the substituent is an alkyl group having 1 to 20 carbon atoms, a halogen atom such as Br, Cl, or I, or an aromatic hydrocarbon having 6 to 15 carbon atoms) R 41 represents a group, an aralkyl group having 7 to 17 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy-carbonyl group having 2 to 20 carbon atoms, or an acyl group having 2 to 15 carbon atoms. , An optionally substituted alkylene group having 1 to 100 carbon atoms (in addition, examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 15 carbon atoms). P represents an integer of 1 to 100.
上記式(I)の定義において、「芳香族炭化水素基」の具体例としては、フェニル基、トリル基、ナフチル基、アンスリル基、ビフェニル基、フェナンスリル基等が挙げられ、また「複素芳香族環基」の具体例としては、フリル基、チオニル基、オキサゾリル基、イミダゾリル基、ピラニル基、ピリジニル基、アクリジニル基、ベンゾフラニル基、ベンゾチオニル基、ベンゾピラニル基、ベンゾオキサゾリル基、ベンゾイミダゾリル基等が挙げられる。 In the definition of the above formula (I), specific examples of the “aromatic hydrocarbon group” include phenyl group, tolyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like, and “heteroaromatic ring” Specific examples of the “group” include furyl group, thionyl group, oxazolyl group, imidazolyl group, pyranyl group, pyridinyl group, acridinyl group, benzofuranyl group, benzothionyl group, benzopyranyl group, benzooxazolyl group, benzoimidazolyl group, and the like. It is done.
また式(I)の(R41−O)pの部分は、上記範囲であれば、2種又は3種の基であっても良い。具体的にはエチレンオキシ基とプロピレンオキシ基、エチレンオキシ基とイソプロピルオキシ基、エチレンオキシ基とブチレンオキシ基、エチレンオキシ基とイソブチレン基等の組み合わせのランダム又はブロック状に連なったもの等が挙げられる。本発明において、ポリオキシアルキレンエーテル基を有する界面活性剤は単独又は複合系で使用され、現像液中1〜30質量%、好ましくは2〜20質量%添加することが効果的である。添加量が少ないと現像性の低下がみられ、逆に多すぎると現像のダメージが強くなり、印刷版の耐刷性を低下させてしまう。 In addition, the part of (R 41 —O) p in the formula (I) may be two or three groups as long as it is in the above range. Specific examples include a combination of random or block combinations of ethyleneoxy and propyleneoxy, ethyleneoxy and isopropyloxy, ethyleneoxy and butyleneoxy, ethyleneoxy and isobutylene, and the like. . In the present invention, the surfactant having a polyoxyalkylene ether group is used alone or in a composite system, and it is effective to add 1 to 30% by mass, preferably 2 to 20% by mass in the developer. If the addition amount is small, the developability is deteriorated. On the other hand, if the amount is too large, the development damage becomes strong and the printing durability of the printing plate is lowered.
また上記式(I)で表されるポリオキシアルキレンエーテル基を有するノニオン界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンナフチルエーテル等のポリオキシエチレンアリールエーテル類、ポリオキシエチレンメチルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類が挙げられる。 Examples of the nonionic surfactant having a polyoxyalkylene ether group represented by the above formula (I) include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether. Polyoxyethylene aryl ethers such as polyoxyethylene phenyl ether and polyoxyethylene naphthyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Kind.
さらに以下に記す、その他の界面活性剤を加えてもよい。その他の界面活性剤としては、ポリオキシエチレンステアレート等のポリオキシエチレンアルキルエステル類、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタンジステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ソルビタントリオレエート等のソルビタンアルキルエステル類、グリセロールモノステアレート、グリセロールモノオレート等のモノグリセリドアルキルエステル類等のノニオン界面活性剤; ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩類、ブチルナフタレンスルホン酸ナトリウム、ペンチルナフタレンスルホン酸ナトリウム、ヘキシルナフタレンスルホン酸ナトリウム、オクチルナフタレンスルホン酸ナトリウム等のアルキルナフタレンスルホン酸塩類、ラウリル硫酸ナトリウム等のアルキル硫酸塩類、ドデシルスルホン酸ソーダ等のアルキルスルホン酸塩類、ジラウリルスルホコハク酸ナトリウム等のスルホコハク酸エステル塩類等のアニオン界面活性剤; ラウリルベタイン、ステアリルベタイン等のアルキルベタイン類、アミノ酸類等の両性界面活性剤等が使用可能であるが、特に好ましいのはアルキルナフタレンスルホン酸塩類等のアニオン界面活性剤である。 Further, other surfactants described below may be added. Other surfactants include polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate Nonionic surfactants such as sorbitan alkyl esters such as glycerol monostearate and monoglyceride alkyl esters such as glycerol monooleate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; sodium butylnaphthalenesulfonate; pentylnaphthalenesulfonic acid Alkylnaphthalenesulfonic acid such as sodium, sodium hexylnaphthalenesulfonate, sodium octylnaphthalenesulfonate , Alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinic acid ester salts such as sodium dilauryl sulfosuccinate; alkyl betaines such as lauryl betaine and stearyl betaine Amphoteric surfactants such as amino acids can be used, and anionic surfactants such as alkylnaphthalene sulfonates are particularly preferred.
これら界面活性剤は、単独もしくは組み合わせて使用することができる。また、これら界面活性剤の現像液中における含有量は有効成分換算で0.1〜20質量%の範囲が好適に使用される。 These surfactants can be used alone or in combination. Further, the content of these surfactants in the developer is preferably in the range of 0.1 to 20% by mass in terms of active ingredients.
上記現像液のpHは、11.0〜12.7が好ましくは、より好ましくは11.5〜12.5である。11.0以上であると画像形成がより確実に可能となり、12.7以下であると過現像にならず、露光部の現像でのダメージが少なく好ましい。 The pH of the developer is preferably 11.0 to 12.7, more preferably 11.5 to 12.5. When it is 11.0 or more, image formation can be performed more reliably, and when it is 12.7 or less, over-development is not caused, and damage in development at the exposed portion is small.
また、上記現像液の導電率は、3〜30mS/cmである事が好ましい。3mS/cm以上であると、通常、アルミニウム板支持体表面の感光性組成物の溶出が容易となり、印刷で汚れを伴うことなく、30mS/cm以下であると、塩濃度が低いため、感光層の溶出速度が充分となり、未露光部に残膜が生じることがないため、好ましい。特に好ましい導電率は、5〜20mS/cmの範囲である。 The conductivity of the developer is preferably 3 to 30 mS / cm. When it is 3 mS / cm or more, the photosensitive composition on the surface of the aluminum plate support is usually easily eluted, and when it is 30 mS / cm or less without being soiled by printing, the salt concentration is low. This is preferable because the elution rate of is sufficient and no residual film is formed in the unexposed area. Particularly preferred conductivity is in the range of 5-20 mS / cm.
以下に本発明を実施例によって具体的に説明するが、勿論、本発明の範囲はこれらにより再現されるものではない。
〔実施例1〜5〕
厚さ0.3mmの材質1Sのアルミニウム板を水でよく洗浄し、10%水酸化ナトリウムに70℃60秒間浸漬してエッチングした後、流水で水洗、その後20%硝酸で中和洗浄、水洗した。これをVA=12.7Vの条件下で正弦波の交番波形電流を用いて、1.5%硝酸水溶液中で270クーロン/dm2の陽極時電気量で電解粗面化処理を行った。その表面粗さを測定したところ、0.30μm(Ra表示)であった。引き続いて、30%の硫酸水溶液中に浸漬し、40℃で2分間デスマットした後、33℃、20%硫酸水溶液中で、砂目立てした面に陰極を配置して、電流密度5A/dm2において、50秒陽極酸化したところ厚さが2.7g/m2であった。
このように処理されたアルミニウム版上に、下記組成の中間層用塗布液を塗布し、乾燥塗布重量が2mg/m2に塗布し、100℃で3分乾燥した。
EXAMPLES The present invention will be specifically described below with reference to examples, but of course, the scope of the present invention is not reproduced by these examples.
[Examples 1 to 5]
A 0.3 mm thick material 1S aluminum plate was thoroughly washed with water, etched by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, then neutralized and washed with 20% nitric acid, and washed with water. . This was subjected to an electrolytic surface roughening treatment in a 1.5% nitric acid aqueous solution with an electric quantity at the anode of 270 coulomb / dm 2 using a sinusoidal alternating current under the condition of V A = 12.7V. When the surface roughness was measured, it was 0.30 μm (Ra indication). Subsequently, after dipping in a 30% sulfuric acid aqueous solution and desmutting at 40 ° C. for 2 minutes, a cathode was placed on a grained surface in a 33 ° C., 20% sulfuric acid aqueous solution at a current density of 5 A / dm 2 . When anodized for 50 seconds, the thickness was 2.7 g / m 2 .
On the aluminum plate thus treated, an intermediate layer coating solution having the following composition was applied, applied to a dry coating weight of 2 mg / m 2, and dried at 100 ° C. for 3 minutes.
<中間層用塗布液>
下記組成を混合攪拌し、約5分後に発熱が見られ、60分間反応させた後、メタノール20,000gを加えた液。
<Coating liquid for intermediate layer>
A solution in which the following composition was mixed and stirred, exotherm was observed after about 5 minutes, and after reacting for 60 minutes, 20,000 g of methanol was added.
メタノール 100g
DDP−8(燐酸化合物:日光ケミカル製) 15g
水 10g
燐酸 5g
テトラエトキシシラン 50g
3−メタクリロキシプロピルトリエトキシシラン 50g
Methanol 100g
DDP-8 (phosphate compound: manufactured by Nikko Chemical) 15g
10g of water
Phosphoric acid 5g
Tetraethoxysilane 50g
3-Methacryloxypropyltriethoxysilane 50g
この下塗り層上に、下記組成の高感度光重合性組成物1〜5を乾燥塗布重量が1.5g/m2になるように塗布し、100℃で90秒間乾燥させ感光層を形成した。 On this undercoat layer, high-sensitivity photopolymerizable compositions 1 to 5 having the following composition were applied so that the dry coating weight was 1.5 g / m 2 and dried at 100 ° C. for 90 seconds to form a photosensitive layer.
<光重合性組成物1〜5>
エチレン性不飽和結合含有化合物(A1) 1.8g
線状有機高分子バインダー(B1) 1.5g
増感剤(C1) 0.15g
光開始剤(D1) 0.2g
β−フタロシアニン(F1)分散物 0.2g
微粒子(表1に記載)
フッ素系ノニオン界面活性剤メガファックF177(DIC製) 0.03g
メチルエチルケトン 10g
プロピレングリコールモノメチルエーテルアセテート 10g
<Photopolymerizable composition 1-5>
1.8g of ethylenically unsaturated bond-containing compound (A1)
Linear organic polymer binder (B1) 1.5g
Sensitizer (C1) 0.15 g
Photoinitiator (D1) 0.2g
β-phthalocyanine (F1) dispersion 0.2 g
Fine particles (listed in Table 1)
Fluorine-based nonionic surfactant Megafac F177 (manufactured by DIC) 0.03g
Methyl ethyl ketone 10g
10g of propylene glycol monomethyl ether acetate
このように形成された光重合性感光層上にポリビニルアルコール(ケン化度98モル%、重合度500)の3重量%の水溶液を乾燥塗布重量が2.5g/m2になるように塗布し、100℃で90秒間乾燥させ、感光性平版印刷版を得た。 A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied on the photopolymerizable photosensitive layer thus formed so that the dry coating weight was 2.5 g / m 2. And dried at 100 ° C. for 90 seconds to obtain a photosensitive lithographic printing plate.
〔比較例1〕
実施例1より微粒子を除いた他は、実施例1と全く同様な操作を繰り返し、比較用の感光性平版印刷版を作成した。
[Comparative Example 1]
Except that the fine particles were removed from Example 1, the same operation as in Example 1 was repeated to prepare a photosensitive lithographic printing plate for comparison.
〔実施例6〜10〕
厚さ0.30mmの材質1Sのアルミニウム板を8号ナイロンブラシと800メッシュのパミストンの水懸濁液を用い、その表面を砂目立てした後、よく水で洗浄した。10%水酸化ナトリウムに70℃で60秒間浸漬してエッチングした後、流水で水洗後、20%HNO3で中和洗浄、水洗した。これをVA=12.7Vの条件下で正弦波の交番波形電流を用いて、1%硝酸水溶液中で300クーロン/dm2の陽極時電気量で電解粗面化処理を行った。その表面粗さを測定したところ、0.45μm(Ra表示)であった。引き続いて、30%のH2SO4水溶液中に浸漬し、55℃で2分間デスマットした後、33℃、20%H2SO4水溶液中で、砂目立てした面に陰極を配置して、電流密度5A/dm2において50秒間陽極酸化したところ、厚さが2.7g/m2の陽極酸化被膜が形成された。
[Examples 6 to 10]
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After etching by immersing in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, neutralized and washed with 20% HNO 3 and washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with a quantity of electricity at the anode of 300 coulomb / dm 2 using a sinusoidal alternating waveform current under the condition of V A = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Subsequently, after dipping in a 30% H 2 SO 4 aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on the grained surface in a 33 ° C., 20% H 2 SO 4 aqueous solution. When anodization was performed for 50 seconds at a density of 5 A / dm 2 , an anodized film having a thickness of 2.7 g / m 2 was formed.
上記の陽極酸化被膜が形成されたアルミニウム板に、メチルメタクリレート/エチルアクリレート/2−アクリルアミド−2−メチルプロパンスルホン酸ナトリウム共重合体(60/25/15モル比、分子量Mn=3万)を、水/メタノール=5g/95gに溶解した液を塗布量が3mg/m2となるように塗布し、80℃、30秒間乾燥させたものを支持体とした。 On the aluminum plate on which the anodized film is formed, methyl methacrylate / ethyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (60/25/15 molar ratio, molecular weight Mn = 30,000) A support obtained by applying a solution dissolved in water / methanol = 5 g / 95 g so that the coating amount was 3 mg / m 2 and drying at 80 ° C. for 30 seconds was used.
この中間層上に、下記組成の高感度光重合性組成物6〜10を乾燥塗布重量が1.5g/m2になるように塗布し、100℃で90秒間乾燥させ感光層を形成した。 On this intermediate layer, high-sensitivity photopolymerizable compositions 6 to 10 having the following composition were applied so that the dry coating weight was 1.5 g / m 2 and dried at 100 ° C. for 90 seconds to form a photosensitive layer.
<光重合性組成物6〜10>
エチレン性不飽和結合含有化合物(A2) 1.5g
線状有機高分子バインダー(B2) 1.8g
増感剤(C2) 0.1g
上記光開始剤(D1) 0.2g
β−フタロシアニン(F1)分散物 0.2g
微粒子(表1に記載)
フッ素系ノニオン界面活性剤メガファックF177(DIC製) 0.03g
メチルエチルケトン 10g
プロピレングリコールモノメチルエーテルアセテート 10g
<Photopolymerizable composition 6-10>
Ethylenically unsaturated bond-containing compound (A2) 1.5 g
Linear organic polymer binder (B2) 1.8g
Sensitizer (C2) 0.1g
0.2 g of the above photoinitiator (D1)
β-phthalocyanine (F1) dispersion 0.2 g
Fine particles (listed in Table 1)
Fluorine-based nonionic surfactant Megafac F177 (manufactured by DIC) 0.03g
Methyl ethyl ketone 10g
10g of propylene glycol monomethyl ether acetate
このように形成された光重合性感光層上にポリビニルアルコール(ケン化度98モル%、重合度500)の3重量%の水溶液を乾燥塗布重量が2.5g/m2になるように塗布し、100℃で90秒間乾燥させ、感光性平版印刷版を得た。 A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied on the photopolymerizable photosensitive layer thus formed so that the dry coating weight was 2.5 g / m 2. And dried at 100 ° C. for 90 seconds to obtain a photosensitive lithographic printing plate.
〔比較例2〕
実施例6より微粒子を除いた他は、実施例6と全く同様な操作を繰り返し、比較用の感光性平版印刷版を作成した。
[Comparative Example 2]
Except for removing the fine particles from Example 6, the same operation as in Example 6 was repeated to prepare a photosensitive lithographic printing plate for comparison.
〔比較例3〕
実施例6の微粒子を二次粒子径が1μmのシリカ粒子アエロゾルR972(日本アエロゾル社製)に変えた他は、実施例6と全く同様の操作を繰り返し、比較用の感光性平版印刷版を作成した。
[Comparative Example 3]
Except that the fine particles of Example 6 were changed to silica particle aerosol R972 (manufactured by Nippon Aerosol Co., Ltd.) having a secondary particle diameter of 1 μm, the same operation as in Example 6 was repeated to prepare a photosensitive lithographic printing plate for comparison. did.
〔実施例11〕
1−(2−トリメトキシシリルビニル)−4−(t−ブトキシカルボニルオキシ)ベンゼン)5g、コロイダルシリカ(NPC−ST,日産化学工業(株)製、シリカゾル含量30質量%)33g、0.05モル/Lの塩酸2.5gとを混合し、16時間室温で攪拌し、シリカゾルを修飾した。
実施例1の微粒子のかわりに上記修飾したシリカゾルに変えた他は、実施例1と全く同様の操作を繰り返し、実施例11の感光性平版印刷版を作成した。
Example 11
1- (2-trimethoxysilylvinyl) -4- (t-butoxycarbonyloxy) benzene) 5 g, colloidal silica (NPC-ST, manufactured by Nissan Chemical Industries, Ltd., silica sol content 30% by mass) 33 g, 0.05 2.5 g of mol / L hydrochloric acid was mixed and stirred at room temperature for 16 hours to modify the silica sol.
A photosensitive lithographic printing plate of Example 11 was prepared by repeating exactly the same operation as in Example 1 except that the modified silica sol was used instead of the fine particles of Example 1.
これらの感光性平版印刷版の内、実施例1〜5、11、比較例1はFD・YAGレーザー(CSI社製プレートジェット4)で、実施例6〜10、比較例2〜3はVioletレーザー(富士写真フイルム社製ルクセルVx9600CTP)にて、露光量を変え、2400dpiで175線の条件で画像露光した。
現像は下記組成の現像液およびフィニッシングガム液FP−2W(富士写真フイルム社製)を仕込んだ自動現像機(富士写真フイルム社製LP−850P2)で標準処理を行った。
Among these photosensitive lithographic printing plates, Examples 1 to 5 and 11 and Comparative Example 1 are FD • YAG lasers (Plate Jet 4 manufactured by CSI), Examples 6 to 10 and Comparative Examples 2 to 3 are Violet lasers. (Luxel Vx9600CTP manufactured by Fuji Photo Film Co., Ltd.) The exposure amount was changed, and image exposure was performed at 2400 dpi under the condition of 175 lines.
Development was carried out by standard processing using an automatic processor (LP-850P2 manufactured by Fuji Photo Film Co., Ltd.) charged with a developer having the following composition and finishing gum solution FP-2W (Fuji Photo Film Co., Ltd.).
(現像液)
水酸化カリウム 0.15g
ポリオキシエチレンフェニルエーテル(n=10) 5.0g
キレスト400(キレート剤) 0.1g
水 94.75g
(Developer)
Potassium hydroxide 0.15g
Polyoxyethylene phenyl ether (n = 10) 5.0 g
Kirest 400 (chelating agent) 0.1g
94.75 g of water
プレヒートの条件は版面到達温度が100℃、現像液温度は30℃、現像液の浸漬時間は12秒であった。
このようにして得られた画像のベタ濃度が飽和になる露光量を感度とした。値が小さい方が高感度を示す。
The preheating conditions were a plate surface temperature of 100 ° C., a developer temperature of 30 ° C., and a developer immersion time of 12 seconds.
The exposure amount at which the solid density of the image thus obtained was saturated was defined as sensitivity. Smaller values indicate higher sensitivity.
また現像液に、未露光の版材を2秒間隔で2〜30秒まで浸漬し、その後水洗し、未露光部の感光層が完全に無くなる時間を、現像時間として求めた。値が小さい方が、現像速度が大きいことを示す。
これらの評価の結果を表1に示す。
Further, the unexposed plate material was immersed in the developer at intervals of 2 seconds to 2 to 30 seconds, and then washed with water, and the time for completely removing the photosensitive layer in the unexposed area was determined as the development time. A smaller value indicates a higher development speed.
The results of these evaluations are shown in Table 1.
実施例1〜11は比較例1〜3に比較し、感度が高く、未露光部の現像速度が大きいことが明らかである。 It is clear that Examples 1 to 11 have higher sensitivity and higher development speed in the unexposed areas than Comparative Examples 1 to 3.
Claims (3)
P−[(Y)s−{(U1)p−(U2−Z)t}]k (1)
式中、Pは微粒子担体を示し、Yはカップリング残基を示し、kは1以上の整数であり、sは0又は1である。U1は第1の連結ユニット、U2は第2の連結ユニットを示し、Zは不飽和二重結合を有する基を示す。pは0又は1、tは1以上の整数を示す。 In a photosensitive lithographic printing plate having a polymerizable photosensitive layer on a support, fine particles represented by the following general formula (1) having an average particle diameter of 1 to 100 nm, at least one ethylenic layer on the polymerizable photosensitive layer A photosensitive lithographic printing plate comprising a polymerizable compound having an unsaturated group and a binder resin .
P-[(Y) s -{(U 1 ) p- (U 2 -Z) t }] k (1)
In the formula, P represents a fine particle carrier, Y represents a coupling residue, k is an integer of 1 or more, and s is 0 or 1. U 1 represents a first connecting unit, U 2 represents a second connecting unit, and Z represents a group having an unsaturated double bond. p represents 0 or 1, and t represents an integer of 1 or more.
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