JP5902981B2 - Planographic printing plate making method - Google Patents
Planographic printing plate making method Download PDFInfo
- Publication number
- JP5902981B2 JP5902981B2 JP2012078714A JP2012078714A JP5902981B2 JP 5902981 B2 JP5902981 B2 JP 5902981B2 JP 2012078714 A JP2012078714 A JP 2012078714A JP 2012078714 A JP2012078714 A JP 2012078714A JP 5902981 B2 JP5902981 B2 JP 5902981B2
- Authority
- JP
- Japan
- Prior art keywords
- developer
- compound
- printing plate
- mmol
- lithographic printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims description 39
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- 238000011161 development Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 20
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- 235000019322 gelatine Nutrition 0.000 description 13
- 235000011852 gelatine desserts Nutrition 0.000 description 13
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Landscapes
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Description
本発明は銀錯塩拡散転写法を利用する平版印刷版の製版方法に関するものである。 The present invention relates to a plate making method of a lithographic printing plate using a silver complex diffusion transfer method.
銀錯塩拡散転写法(DTR法)を用いた平版印刷版については、フォーカル・プレス、ロンドン ニューヨーク(1972年)発行、アンドレ ロット及びエディス ワイデ著、「フォトグラフィック・シルバー・ハライド・ディフュージョン・プロセシズ」、第101頁〜第130頁に幾つかの例が記載されている。 For lithographic printing plates using the silver complex diffusion transfer method (DTR method), published by Focal Press, London New York (1972), by Andre Lot and Edith Weide, "Photographic Silver Halide Diffusion Processes", Some examples are described on pages 101-130.
銀錯塩拡散転写法(DTR法)を用いた平版印刷版(以降DTR平版印刷版とも称する)、特にハロゲン化銀乳剤層上に物理現像核層を有する平版印刷版は、例えば、米国特許第3,728,114号明細書、同第4,134,769号明細書、同第4,160,670号明細書、同第4,336,321号明細書、同第4,501,811号明細書、同第4,510,228号明細書、同第4,621,041号明細書等に記載されている。 A lithographic printing plate using a silver complex diffusion transfer method (DTR method) (hereinafter also referred to as a DTR lithographic printing plate), particularly a lithographic printing plate having a physical development nucleus layer on a silver halide emulsion layer is disclosed in, for example, US Pat. No. 4,728,114, No. 4,134,769, No. 4,160,670, No. 4,336,321, No. 4,501,811. No. 4,510,228, No. 4,621,041 and the like.
これらDTR平版印刷版は露光されたハロゲン化銀結晶が現像処理により乳剤層中で化学現像を生起して黒化銀となり、親水性の非画像部を形成する。一方、未露光のハロゲン化銀結晶は、現像液中の銀錯塩形成剤により可溶化した後、表面の物理現像核層まで拡散、更に物理現像核上に現像主薬の還元作用によっていわゆる溶解物理現像を生じ、インキ受容性の画像銀として析出する。従って、DTR平版印刷版は単一の現像処理中に化学現像と溶解物理現像とが同時に進行する機構になっており、平版印刷において良好な印刷物を得るためには非画像部となる化学現像を生じる領域と画像部となる溶解物理現像を生じる領域との明確な差、コントラストが重要になる。 In these DTR lithographic printing plates, the exposed silver halide crystals undergo chemical development in the emulsion layer by the development process to become blackened silver, thereby forming a hydrophilic non-image area. On the other hand, unexposed silver halide crystals are solubilized by a silver complex salt-forming agent in the developer, then diffused to the physical development nucleus layer on the surface, and further so-called dissolution physical development by the reducing action of the developing agent on the physical development nucleus. And is deposited as ink-receptive image silver. Therefore, the DTR lithographic printing plate has a mechanism in which chemical development and dissolution physical development proceed simultaneously during a single development process. In order to obtain a good printed material in lithographic printing, chemical development that becomes a non-image area is performed. A clear difference and contrast between the generated area and the area where the dissolved physical development that becomes the image portion is generated become important.
DTR平版印刷版の製版方法は、露光したDTR平版印刷版を、多量の現像液が貯溜された現像槽中を通過させ、通過後に該印刷版の版面上に残る現像液をローラ間に通過させて絞り取り、更に版面のpHを整えるために中和液(安定液)槽中を通過させ、現像液と同様にして版面上に残る中和液を取り除く方法、いわゆる浸漬現像方式が一般に知られている。また特開昭48−76603号公報、同昭57−115549号公報、米国特許第5,398,092号明細書等には、平版印刷版の版面に現像液を塗布供給して製版する塗布現像方式が開示されている。 The plate making method of the DTR lithographic printing plate is such that the exposed DTR lithographic printing plate is passed through a developing tank in which a large amount of developer is stored, and the developer remaining on the plate surface of the printing plate after passing is passed between rollers. In order to further squeeze out and further adjust the pH of the plate surface, a method of passing through a neutralizing solution (stabilizing solution) tank and removing the neutralizing solution remaining on the plate surface in the same manner as the developing solution, so-called immersion development method is generally known. ing. JP-A-48-76603, JP-A-57-115549, US Pat. No. 5,398,092 and the like describe coating development in which a developer is applied and supplied to the plate surface of a lithographic printing plate. A scheme is disclosed.
従来、DTR平版印刷版の製版は、原稿をカメラによって撮影することが一般的であったが、近年では、コンピュータ及び周辺技術の進歩により、コンピュータのデジタル情報を直接レーザー光源で走査露光を行うComputer−to−plate(CTP)と言われる製版方法が主流となりつつある。これにより、DTR平版印刷版においても高画質化することが容易となり、迅速な製版作業が可能となった反面、DTR平版印刷版のCTP製版速度と該平版印刷版を用いたオフセット印刷時間に大きな乖離が生じた結果、一度に大量の平版印刷版を製版した後、数日かけてオフセット印刷を行うケースが比較的増加している。 Conventionally, the plate making of a DTR lithographic printing plate is generally performed by photographing a document with a camera. However, in recent years, with the advancement of computers and peripheral technologies, a computer that scans digital information of a computer directly with a laser light source is used. A plate making method called -to-plate (CTP) is becoming mainstream. This makes it easy to improve the image quality of a DTR lithographic printing plate and enables rapid plate-making work. However, the CTR plate making speed of the DTR lithographic printing plate and the offset printing time using the lithographic printing plate are large. As a result of the divergence, there is a relatively increasing number of cases where offset printing is performed over several days after making a large amount of lithographic printing plate at a time.
しかしながらDTR平版印刷版は製版後、数日経過した場合に一旦非画像部に付着したインキ汚れが解消できなくなる(以下インキ脱離不良)場合があり、改善が望まれていた。インキ脱離不良が発生する平版印刷版を用いて印刷すると、印刷途中に印刷機を一旦停機した場合、再印刷時にインキ汚れが発生して印刷の続行が不可能になり、しばしば一連の印刷を完了させるために複数の平版印刷版を準備することがあった。 However, the DTR lithographic printing plate may not be able to remove ink stains once attached to the non-image area after several days have passed since the plate making (hereinafter referred to as ink detachment failure), and improvement has been desired. When printing using a lithographic printing plate that causes ink detachment failure, if the printer is temporarily stopped during printing, ink stains will occur during reprinting, making it impossible to continue printing. Several lithographic printing plates were prepared to complete.
本発明の目的は、製版後、数日間放置した平版印刷版であってもインキ脱離不良の発生が無く、且つ耐刷不良が発生しない平版印刷版の製版方法を提供することである。 An object of the present invention is to provide a plate making method for a lithographic printing plate which does not cause ink detachment failure and does not cause printing failure even if it is a lithographic printing plate left for several days after plate making.
本発明の上記課題は、以下の平版印刷版の製版方法により達成された。
1.支持体上に少なくともハロゲン化銀乳剤層及び物理現像核層を少なくともこの順に有する平版印刷版を、アルカノールアミン化合物の含有量が30mmol/L以下であり、且つアミノアルキル基を有するピペラジン化合物もしくはアミノアルキル基を有するモルホリン化合物と、チオエーテル化合物を含有し、アミノアルキル基を有するピペラジン化合物もしくはアミノアルキル基を有するモルホリン化合物の含有量が、チオエーテル化合物の2〜8倍(モル比)である現像液で現像処理する平版印刷版の製版方法。
The above object of the present invention has been achieved by the following plate making method of a lithographic printing plate.
1. A lithographic printing plate having at least a silver halide emulsion layer and a physical development nucleus layer in this order on a support, a piperazine compound or aminoalkyl having an alkanolamine compound content of 30 mmol / L or less and having an aminoalkyl group Developed with a developer containing a morpholine compound having a thioether compound and a piperazine compound having an aminoalkyl group or a morpholine compound having an aminoalkyl group that is 2 to 8 times (molar ratio) of the thioether compound A process for making a lithographic printing plate to be processed .
本発明により、製版後、数日間放置した平版印刷版であってもインキ脱離不良の発生が無く、且つ耐刷不良が発生しない平版印刷版の製版方法を提供することが可能となる。 According to the present invention, it is possible to provide a plate making method of a lithographic printing plate that does not cause ink detachment failure and does not cause printing failure even if it is a lithographic printing plate left for several days after plate making.
以下、本発明で利用される現像液に関して詳細に説明する。
銀錯塩拡散転写法を利用した平版印刷版の製版で利用される現像液において、ハロゲン化銀溶剤としてアルカノールアミンを利用する方法は広く一般的であり、且つ必要不可欠であった。好適にはN−(2−アミノエチル)エタノールアミンが利用されることが多いが、本発明の課題を達成するためには現像液中のアルカノールアミン化合物の含有量を1L当たり30mmol以下、より好ましくは0mmolにする必要がある。
Hereinafter, the developer used in the present invention will be described in detail.
In a developer used for making a lithographic printing plate using the silver complex diffusion transfer method, a method using an alkanolamine as a silver halide solvent has been widely used and indispensable. Preferably, N- (2-aminoethyl) ethanolamine is often used, but in order to achieve the object of the present invention, the content of the alkanolamine compound in the developer is preferably 30 mmol or less per liter, more preferably Needs to be 0 mmol.
本発明において現像液が含有するアミノアルキル基を有するピペラジン化合物もしくはアミノアルキル基を有するモルホリン化合物としては、好ましくは下記一般式1〜3で示される化合物を利用することができる。 In the present invention, as the piperazine compound having an aminoalkyl group or the morpholine compound having an aminoalkyl group contained in the developer, compounds represented by the following general formulas 1 to 3 can be preferably used.
式中L1、L2、L3及びL4はアルキレン基を表し、R1、R2、R3及びR4はそれぞれ直鎖または分岐のアルキル基、アリール基もしくは水素原子を表す。L1〜L4のアルキレン基としてはエチレン基、プロピレン基、ブチレン基等が挙げられ、好ましくはエチレン基である。またR1〜R4は水素原子であることが好ましい。これらの化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 In the formula, L 1 , L 2 , L 3 and L 4 represent an alkylene group, and R 1 , R 2 , R 3 and R 4 each represent a linear or branched alkyl group, an aryl group or a hydrogen atom. Examples of the alkylene group of L 1 to L 4 include an ethylene group, a propylene group, and a butylene group, and an ethylene group is preferable. R 1 to R 4 are preferably hydrogen atoms. Specific examples of these compounds are shown below, but the present invention is not limited thereto.
本発明において、アミノアルキル基を有するピペラジン化合物もしくはアミノアルキル基を有するモルホリン化合物は好適には、現像液1L当たり40〜800mmol含有することが好ましい。 In the present invention, the piperazine compound having an aminoalkyl group or the morpholine compound having an aminoalkyl group is preferably contained in an amount of 40 to 800 mmol per liter of the developer.
本発明において現像液が含有するチオエーテル化合物としては、例えば特開平10−282674号公報に記載されている化合物が利用できるが、3,6−ジチア−1,8−オクタンジオール、2,2′−チオジエタノールを用いることが好ましい。これら化合物は現像液1L当たり1〜300mmol含有することが好ましく、より好ましくは5〜200mmolである。 As the thioether compound contained in the developer in the present invention, for example, compounds described in JP-A-10-282684 can be used, but 3,6-dithia-1,8-octanediol, 2,2′- It is preferable to use thiodiethanol. These compounds are preferably contained in an amount of 1 to 300 mmol, and more preferably 5 to 200 mmol, per liter of the developer.
前記したアミノアルキル基を有するピペラジン化合物もしくはアミノアルキル基を有するモルホリン化合物の含有量と、チオエーテル化合物の含有量の比率には好ましい範囲が存在し、アミノアルキル基を有するピペラジン化合物もしくはアミノアルキル基を有するモルホリン化合物の含有量が、チオエーテル化合物の2〜8倍(モル比)であることが好ましい。これによりインキ脱離性にとりわけ優れた製版方法を得ることができる。 There is a preferable range in the ratio of the content of the piperazine compound having an aminoalkyl group or the morpholine compound having an aminoalkyl group and the content of the thioether compound, and the piperazine compound having an aminoalkyl group or the aminoalkyl group has an aminoalkyl group. The content of the morpholine compound is preferably 2 to 8 times (molar ratio) of the thioether compound. This makes it possible to obtain a plate making method that is particularly excellent in ink detachability.
本発明に用いる現像液のpHは11.0〜14.0であることが好ましく、より好ましくはpH12.5〜14.0である。pH調整剤としてはアルカリ性物質、例えば水酸化カリウム、水酸化ナトリウム等が利用できる。 The pH of the developer used in the present invention is preferably 11.0 to 14.0, more preferably 12.5 to 14.0. As the pH adjuster, an alkaline substance such as potassium hydroxide or sodium hydroxide can be used.
現像液に含有できる他の成分としては、保恒剤として例えば亜硫酸塩を含有することが好ましい。亜硫酸塩の具体例としては亜硫酸ナトリウム、亜硫酸カリウム、重亜硫酸ナトリウム、重亜硫酸カリウム等が挙げられる。更にはチオ硫酸塩、チオサリチル酸、メソイオン化合物、環状イミド化合物等を含有することができる。 As other components that can be contained in the developer, it is preferable to contain, for example, sulfite as a preservative. Specific examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like. Furthermore, thiosulfate, thiosalicylic acid, mesoionic compounds, cyclic imide compounds and the like can be contained.
更に本発明で利用される現像液には、銀画像部のインキ受理性を向上させるために、親油化剤としてメルカプト基またはチオン基を有する化合物を含有させることが好ましい。かかる化合物としては例えば特公昭48−29723号公報、特開昭58−127928号公報等に記載されている化合物が挙げられる。特に炭素数が3〜12のアルキル基、アリール基、アルケニル基等の親油性基を有する含窒素複素環化合物が好ましい。 Further, the developer used in the present invention preferably contains a compound having a mercapto group or a thione group as a lipophilic agent in order to improve the ink acceptability of the silver image portion. Examples of such compounds include compounds described in JP-B-48-29723, JP-A-58-127928 and the like. A nitrogen-containing heterocyclic compound having a lipophilic group such as an alkyl group having 3 to 12 carbon atoms, an aryl group, or an alkenyl group is particularly preferable.
上記化合物の具体例としては、2−メルカプト−4−フェニルイミダゾール、2−メルカプト−1−ベンジルイミダゾール、2−メルカプト−1−ブチル−ベンズイミダゾール、1,3−ジベンジル−イミダゾリジン−2−チオン、2−メルカプト−4−フェニルチアゾール、3−ブチル−ベンゾチアゾリン−2−チオン、3−ドデシル−ベンゾチアゾリン−2−チオン、2−メルカプト−4,5−ジフェニルオキサゾール、3−ペンチル−ベンゾオキサゾリン−2−チオン、1−フェニル−3−メチルピラゾリン−5−チオン、3−メルカプト−4−アリル−5−ペンタデシル−1,2,4−トリアゾール、3−メルカプト−5−ノニル−1,2,4−トリアゾール、3−メルカプト−4−アセタミド−5−ヘプチル−1,2,4−トリアゾール、3−メルカプト−4−アミノ−5−ヘプタデシル−1,2,4−トリアゾール、2−メルカプト−5−フェニル−1,3,4−チアジアゾール、2−メルカプト−5−n−ヘプチル−オキサチアゾール、2−メルカプト−5−n−ヘプチル−オキサジアゾール、2−メルカプト−5−フェニル−1,3,4−オキサジアゾール、2−ヘプタデシル−5−フェニル−1,3,4−オキサジアゾール、5−メルカプト−1−フェニル−テトラゾール、3−メルカプト−4−メチル−6−フェニル−ピリダジン、2−メルカプト−5,6−ジフェニル−ピラジン、2−メルカプト−4,6−ジフェニル−1,3,5−トリアジン、2−アミノ−4−メルカプト−6−ベンジル−1,3,5−トリアジン等が挙げられるが、これらに限定されるものではない。 Specific examples of the compound include 2-mercapto-4-phenylimidazole, 2-mercapto-1-benzylimidazole, 2-mercapto-1-butyl-benzimidazole, 1,3-dibenzyl-imidazolidine-2-thione, 2-mercapto-4-phenylthiazole, 3-butyl-benzothiazoline-2-thione, 3-dodecyl-benzothiazoline-2-thione, 2-mercapto-4,5-diphenyloxazole, 3-pentyl-benzoxazoline-2 -Thione, 1-phenyl-3-methylpyrazolin-5-thione, 3-mercapto-4-allyl-5-pentadecyl-1,2,4-triazole, 3-mercapto-5-nonyl-1,2,4-triazole 3-mercapto-4-acetamido-5-heptyl-1,2,4-tria 3-mercapto-4-amino-5-heptadecyl-1,2,4-triazole, 2-mercapto-5-phenyl-1,3,4-thiadiazole, 2-mercapto-5-n-heptyl-oxa Thiazole, 2-mercapto-5-n-heptyl-oxadiazole, 2-mercapto-5-phenyl-1,3,4-oxadiazole, 2-heptadecyl-5-phenyl-1,3,4-oxadi Azole, 5-mercapto-1-phenyl-tetrazole, 3-mercapto-4-methyl-6-phenyl-pyridazine, 2-mercapto-5,6-diphenyl-pyrazine, 2-mercapto-4,6-diphenyl-1, 3,5-triazine, 2-amino-4-mercapto-6-benzyl-1,3,5-triazine, and the like, but are not limited thereto. Not.
本発明に用いられる現像液は、上記化合物の他に増粘剤、例えばヒドロキシメチルセルロース、カルボキシメチルセルロース等、かぶり防止剤、例えば臭化カリウム、特開昭47−26201号公報記載の化合物等を含有することができる。 The developer used in the present invention contains, in addition to the above compounds, thickeners such as hydroxymethylcellulose and carboxymethylcellulose, antifoggants such as potassium bromide, and compounds described in JP-A-47-26201. be able to.
本発明の現像液を塗布現像方式に適用する場合には、表面張力を下げる目的で界面活性剤を含有することが好ましい。界面活性剤の具体例としては例えば、ポリオキシエチレングリコールアルキルエーテル、ポリオキシプロピレングリコールアルキルエーテル、ポリオキシエチレングリコールソルビタンアルキルエステル、ポリオキシエチレンアセチレニックグリコールエーテル、ポリオキシエチレンソルビタンモノオレエート等のノニオン性界面活性剤、ポリオキシエチレングリコールアルキル硫酸、ポリオキシプロピレングリコールアルキル硫酸、ポリオキシエチレングリコールアルキルカルボン酸、ポリオキシプロピレングリコールアルキルカルボン酸、ポリオキシエチレングリコールアルキルリン酸、ポリオキシプロピレングリコールアルキルリン酸等のアニオン性界面活性剤、ラウリルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルヒドロキシスルホプロピルベタイン等の両性界面活性剤が挙げられる。 When the developer of the present invention is applied to a coating and developing system, it is preferable to contain a surfactant for the purpose of reducing the surface tension. Specific examples of the surfactant include, for example, polyoxyethylene glycol alkyl ether, polyoxypropylene glycol alkyl ether, polyoxyethylene glycol sorbitan alkyl ester, polyoxyethylene acetylenic glycol ether, polyoxyethylene sorbitan monooleate and the like. Nonionic surfactant, polyoxyethylene glycol alkyl sulfuric acid, polyoxypropylene glycol alkyl sulfuric acid, polyoxyethylene glycol alkyl carboxylic acid, polyoxypropylene glycol alkyl carboxylic acid, polyoxyethylene glycol alkyl phosphoric acid, polyoxypropylene glycol alkyl phosphoric acid Anionic surfactants such as acids, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldi Chiruamino betaine, amphoteric surfactants such as coconut oil fatty acid amide propyl dimethyl hydroxypropyl sulfopropyl betaine.
本発明における製版方法においては、現像処理に引き続いて、安定処理を行うことが好ましい。安定処理の主な機能は、現像処理において、アルカリ性になった版面を中和することである。従って、安定液のpHは中性から酸性に調整されていることが好ましい。安定液のpHは7.5以下であることが好ましく、より好ましくは4〜7である。 In the plate making method of the present invention, it is preferable to carry out a stabilization process subsequent to the development process. The main function of the stabilization process is to neutralize the alkaline plate surface in the development process. Therefore, the pH of the stabilizer is preferably adjusted from neutral to acidic. The pH of the stabilizing solution is preferably 7.5 or less, more preferably 4-7.
安定液には更に上記pH付近に緩衝性能を付与することが好ましい。緩衝剤としてはリン酸とその塩あるいはトリエタノールアミンのごとくアミン類を使用することが好ましい。リン酸塩を緩衝剤として使用する場合、その含有量は使用液にして0.05モル/L以上、好ましくは0.1〜1.0モル/Lの範囲で添加する。リン酸塩としてはカリウム塩、ナトリウム塩、アンモニウム塩、あるいは前述のトリエタノールアミンのごとくアミン類との塩等を用いることができる。 It is preferable that the stabilizing solution is further provided with a buffering performance near the pH. As the buffer, it is preferable to use amines such as phosphoric acid and its salts or triethanolamine. When using a phosphate as a buffering agent, the content is 0.05 mol / L or more, preferably 0.1 to 1.0 mol / L in the use solution. As the phosphate, potassium salt, sodium salt, ammonium salt, or a salt with amines such as triethanolamine described above can be used.
また、現像液同様、安定液にも銀画像部のインキ受理性を向上させるために、親油化剤としてメルカプト基またはチオン基を有する化合物を含有させることができる。これらの化合物は、安定液においても現像液と同様の化合物を用いることができる。 Similarly to the developer, the stabilizer may contain a compound having a mercapto group or a thione group as a lipophilic agent in order to improve the ink acceptability of the silver image area. As these compounds, the same compounds as in the developer can be used in the stabilizer.
本発明に用いられる銀錯塩拡散転写法を応用した平版印刷版の好ましい実施態様は、支持体上に少なくとも下塗層、ハロゲン化銀乳剤層及び物理現像核層を順次塗布されてなる平版印刷版である。これら順次塗布された層の総ゼラチン量は1〜4.5g/m2であることが好ましい。 A preferred embodiment of a lithographic printing plate to which the silver complex diffusion transfer method used in the present invention is applied is a lithographic printing plate in which at least a subbing layer, a silver halide emulsion layer and a physical development nucleus layer are successively coated on a support. It is. The total gelatin amount of these sequentially applied layers is preferably 1 to 4.5 g / m 2 .
総ゼラチン量が1g/m2未満では、印刷版として必要な被膜強度が得られない場合がある。また、4.5g/m2を超えると、印刷時のインキ受理性及びインキ脱離が遅く、印刷作業性が低下する場合がある。 If the total gelatin amount is less than 1 g / m 2 , the coating strength required for a printing plate may not be obtained. On the other hand, if it exceeds 4.5 g / m 2 , ink acceptability and ink detachment during printing are slow, and printing workability may be reduced.
本発明のDTR平版印刷版はバインダーとしてゼラチンを含有しており、その含有層は下塗層であり、乳剤層であり、また物理現像核層でもありうる。また、ゼラチンの一部を澱粉、デキストリン、アルブミン、アルギン酸ナトリウム、ヒドロキシルエチルセルロース、アラビアゴム、ポリビニルアルコール、ポリビニルピロリドン、カルボキシメチルセルロース、ポリアクリルアミド、スチレン−無水マレイン酸共重合体、ポリビニルルチルエーテル−無水マレイン酸共重合体等の親水性高分子の一種または二種以上で置換することもできる。 The DTR lithographic printing plate of the present invention contains gelatin as a binder, and the containing layer is an undercoat layer, an emulsion layer, or a physical development nucleus layer. Part of gelatin is starch, dextrin, albumin, sodium alginate, hydroxyl ethyl cellulose, gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyacrylamide, styrene-maleic anhydride copolymer, polyvinyl rutile ether-maleic anhydride. It can also be substituted with one or more hydrophilic polymers such as copolymers.
これらのゼラチン含有層は、ゼラチン硬膜剤で硬化することができる。ゼラチン硬膜剤としては、例えば、クロムミョウバンのような無機化合物、ホルマリン、グリオギザール、マレアルデヒド、グルタルアルデヒドのようなアルデヒド類、尿素やエチレン尿素、ムコクロル酸、2,3−ジヒドロキシ−1,4−ジオキサンのようなアルデヒド等価体、2,4−ジクロロ−6−ヒドロキシ−s−トリアジンや、2,4−ジヒドロキシ−6−クロロ−s−トリアジンのような活性ハロゲンを有する化合物、ジビニルスルホン、ジビニルケトンやN,N,N−トリアクロイルヘキサヒドロトリアジン、活性な三員環であるエチレンイミノ基やエポキシ基を分子中に二個以上有する化合物類、高分子硬膜剤としてのジアルデヒド澱粉等の種々の化合物の一種もしくは二種以上を用いることができる。 These gelatin-containing layers can be hardened with a gelatin hardener. Examples of gelatin hardeners include inorganic compounds such as chromium alum, aldehydes such as formalin, gliogizar, malealdehyde, and glutaraldehyde, urea, ethylene urea, mucochloric acid, and 2,3-dihydroxy-1,4. Aldehyde equivalents such as dioxane, compounds having active halogen such as 2,4-dichloro-6-hydroxy-s-triazine and 2,4-dihydroxy-6-chloro-s-triazine, divinyl sulfone, divinyl Ketones, N, N, N-triacloylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups or epoxy groups in the molecule, dialdehyde starch as a polymer hardener, etc. One or two or more of these various compounds can be used.
硬膜剤は全ての層に添加することもでき、幾つかまたは一層にのみ添加することも可能である。もちろん、拡散性の硬膜剤は二層以上を同時塗布する場合には、何れか一層にのみ添加することが可能である。添加方法は塗液製造時に添加、もしくは塗布時にインラインで添加することもできる。 The hardener can be added to all layers, or it can be added to some or only one layer. Of course, the diffusible hardener can be added to only one layer when two or more layers are applied simultaneously. The addition method can be added at the time of producing the coating liquid or in-line at the time of coating.
本発明においては、DTR平版印刷版の感光面側の構成層中に平均粒子サイズが0.3〜8.0μmであるマット化剤を用いることが好ましい。本発明に用いるマット化剤は、例えば、シリカ粒子、スチレン等の有機物粒子等がある。 In the present invention, it is preferable to use a matting agent having an average particle size of 0.3 to 8.0 μm in the constituent layer on the photosensitive surface side of the DTR lithographic printing plate. Examples of the matting agent used in the present invention include silica particles and organic particles such as styrene.
本発明においては、前記マット化剤は支持体とハロゲン化銀乳剤層の間の下塗層に含まれることが好ましい。マット化剤の添加量は、種々の条件により異なるが、感光面側の構成層中に0.1〜5.0g/m2の範囲で含まれることが好ましく、好ましくは0.3〜3.5g/m2の範囲である。 In the present invention, the matting agent is preferably contained in an undercoat layer between the support and the silver halide emulsion layer. The addition amount of the matting agent varies depending on various conditions, but is preferably included in the constituent layer on the photosensitive surface side in the range of 0.1 to 5.0 g / m 2 , preferably 0.3 to 3. The range is 5 g / m 2 .
下塗層にはハレーション防止の目的でカーボンブラック等の顔料、染料等を含ませることができる。更に現像主薬等の写真用添加物も含むことができる。また下塗層は特開昭48−5503号公報、同昭48−100203号公報、同昭49−16507号公報に記載のような下塗り層であってもよい。 The undercoat layer can contain a pigment such as carbon black, a dye or the like for the purpose of preventing halation. Furthermore, photographic additives such as developing agents can also be included. The undercoat layer may be an undercoat layer as described in JP-A-48-5503, JP-A-48-100203, and JP-A-49-16507.
本発明の実施に用いられるDTR平版印刷版のハロゲン化銀乳剤は、塩化銀、臭化銀、塩臭化銀、塩ヨウ化銀、塩臭ヨウ化銀等が使用でき、好ましくは塩化銀が70モル%以上のハロゲン化銀である。これらを含有するハロゲン化銀乳剤は分光増感剤(光源、用途に応じた分光増感色素)、ゼラチン硬化剤、塗布助剤、かぶり防止剤、可塑剤、現像剤、マット剤等を含むことができる。 As the silver halide emulsion of the DTR lithographic printing plate used in the practice of the present invention, silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, etc. can be used, preferably silver chloride is used. 70 mol% or more of silver halide. Silver halide emulsions containing these contain spectral sensitizers (light sources, spectral sensitizing dyes depending on the application), gelatin hardeners, coating aids, antifoggants, plasticizers, developers, matting agents, etc. Can do.
本発明の平版印刷版に用いられる支持体は、紙、各種フィルム、プラスチック、樹脂様物質で被覆した紙、金属等が使用できる。 As the support used in the lithographic printing plate of the present invention, paper, various films, plastic, paper coated with a resin-like substance, metal, or the like can be used.
物理現像核層に使用される物理現像核は、この種の薬品の例として周知であって、アンチモン、ビスマス、カドミウム、コバルト、パラジウム、ニッケル、銀、鉛、亜鉛等の金属及びこれらの硫化物が使用できる。また、特開平5−265164号公報記載の物理現像核を用いることもできる。物理現像核層にも現像主薬を含んでもよく、バインダーを含んでもよい。 The physical development nuclei used in the physical development nuclei layer are well known as examples of this type of chemical, and include metals such as antimony, bismuth, cadmium, cobalt, palladium, nickel, silver, lead, zinc, and sulfides thereof. Can be used. Also, physical development nuclei described in JP-A-5-265164 can be used. The physical development nucleus layer may also contain a developing agent or a binder.
また、本発明により作製された平版印刷版の印刷方法あるいは使用する不感脂化液、給湿液等は、一般によく知られている方法によることができる。 Moreover, the printing method of the lithographic printing plate produced by this invention or the desensitizing liquid used, the moisturizing liquid, etc. can be based on a generally well-known method.
以下、実施例により本発明を詳細に説明するが、本発明の意図を逸脱しない限り、これらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, unless it deviates from the meaning of this invention, it is not limited to these.
(実施例1)
DTR平版印刷版を製版するための現像装置は、三菱製紙株式会社より市販されているSDP−Eco1630IIIR(塗布現像方式)を用いた。この装置は、波長630nmの赤色レーザーを用い、デジタルデータを走査露光方式によりDTR印刷版にデータ画像の潜像を形成させ、引き続いて、現像、安定処理を行い、製版する自動製版装置である。現像液の塗布量は30〜50mlであり、現像液が塗布されてから安定液に接するまでの時間は12秒である。
(Example 1)
As a developing device for making a DTR planographic printing plate, SDP-Eco1630IIIR (coating and developing method) commercially available from Mitsubishi Paper Industries Co., Ltd. was used. This apparatus is an automatic plate making apparatus that uses a red laser having a wavelength of 630 nm to form a latent image of a data image on a DTR printing plate by digital exposure using a scanning exposure method, and subsequently performs development and stabilization processing to make a plate. The application amount of the developer is 30 to 50 ml, and the time from the application of the developer to the contact with the stabilizing solution is 12 seconds.
DTR平版印刷版は、厚さ175μmのポリエチレンテレフタレートベースの片面に裏塗り層として2g/m2の酸化チタン及び平均粒子サイズ5μmのシリカマット剤を含有するマット化層を設け、反対側の面にカーボンブラックを含み、写真用ゼラチンに対して20質量%の平均粒径7μmのシリカマット剤を含む下塗層(pH4.5に調整)と、ハイポ及び金化合物で化学増感された後に、2−メルカプト安息香酸を加えたハロゲン化銀乳剤層(pH4.5に調整)とを設ける。 The DTR lithographic printing plate is provided with a matting layer containing 2 g / m 2 of titanium oxide and a silica matting agent having an average particle size of 5 μm as a backing layer on one side of a 175 μm-thick polyethylene terephthalate base. An undercoat layer (adjusted to pH 4.5) containing a silica matting agent containing carbon black and containing 20% by mass of an average particle diameter of 7 μm with respect to photographic gelatin, and after chemical sensitization with hypo and gold compounds, 2 -A silver halide emulsion layer (adjusted to pH 4.5) containing mercaptobenzoic acid is provided.
ハロゲン化銀乳剤は公知の方法によって赤色に色素増感させた。 The silver halide emulsion was dye sensitized to red by a known method.
下塗層のゼラチンは3.0g/m2、ハロゲン化銀乳剤層のゼラチンは1.0g/m2、硝酸銀に換算したハロゲン化銀は1.0g/m2となるように塗布した。この下塗層と乳剤層は硬膜剤としてホルマリンをゼラチン1gに対して30mg含んでいる。 The gelatin of the undercoat layer was applied at 3.0 g / m 2 , the gelatin of the silver halide emulsion layer was 1.0 g / m 2 , and the silver halide converted to silver nitrate was 1.0 g / m 2 . The undercoat layer and the emulsion layer contain 30 mg of formalin as a hardener with respect to 1 g of gelatin.
下塗層のゼラチンはジメトキシフェニドンを0.105g/m2、ハロゲン化銀乳剤層は0.024g/m2、物理現像核層は0.006g/m2含んでいる。 Gelatin 0.105 g / m 2 dimethoxy phenidone subbing layer, a silver halide emulsion layer 0.024 g / m 2, the physical development nuclei layer contains 0.006 g / m 2.
下塗り層とハロゲン化銀乳剤層を塗布した後、50℃で2日間加温し、ハロゲン化銀乳剤層の上に特開昭57−86835号公報の実施例1にある核塗液を塗布した。このようにして設けた物理現像核層は0.001g/m2の硫化パラジウムを含んでいる。 After coating the undercoat layer and the silver halide emulsion layer, the mixture was heated at 50 ° C. for 2 days, and the core coating solution described in Example 1 of JP-A-57-86835 was coated on the silver halide emulsion layer. . The physical development nucleus layer thus provided contains 0.001 g / m 2 of palladium sulfide.
このようにして得たDTR平版印刷版を幅400mm、長さ61mのロール状にし、上記SDP−Eco1630IIIR自動製版装置に装填し、露光及び製版処理を行った後、室温にて14日間保存し、印刷評価を実施した。 The DTR lithographic printing plate thus obtained was rolled into a width of 400 mm and a length of 61 m, loaded into the SDP-Eco1630IIIR automatic plate making apparatus, subjected to exposure and plate making processing, and stored at room temperature for 14 days. A print evaluation was performed.
上記製版処理において、用いた現像液を以下に示す。
<現像液A>
水酸化ナトリウム 15g
水酸化カリウム 20g
無水亜硫酸ナトリウム 50g
2−メルカプト−5−n−ヘプチルオキサジアゾール 0.4g
チオサリチル酸 0.5g
ポリオキシエチレンアセチレニックグリコールエーテル 0.2g
ポリオキシエチレンソルビタンモノオレエート 0.25g
ヤシ油脂肪酸アミドプロピルジメチルヒドロキシスルホプロピルベタイン 0.5g
純水で1リットルとする。
pHは水酸化カリウムで13.7に調整した。
The developer used in the plate making process is shown below.
<Developer A>
Sodium hydroxide 15g
Potassium hydroxide 20g
Anhydrous sodium sulfite 50g
0.4 g of 2-mercapto-5-n-heptyloxadiazole
Thiosalicylic acid 0.5g
Polyoxyethylene acetylenic glycol ether 0.2g
Polyoxyethylene sorbitan monooleate 0.25g
Coconut oil fatty acid amidopropyldimethylhydroxysulfopropylbetaine 0.5g
Make up to 1 liter with pure water.
The pH was adjusted to 13.7 with potassium hydroxide.
<現像液B>
上記現像液Aの作製において、更にN−(2−アミノエチル)エタノールアミンを115mmol添加した以外は現像液Aと同様にして現像液Bを得た。
<Developer B>
Developer B was obtained in the same manner as Developer A except that 115 mmol of N- (2-aminoethyl) ethanolamine was further added.
<現像液C>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol添加した以外は現像液Aと同様にして現像液Cを得た。
<Developer C>
In the preparation of the developer A, a developer C was obtained in the same manner as the developer A except that 80 mmol of the compound 1-1 was further added.
<現像液D>
上記現像液Aの作製において、更に3,6−ジチア−1,8−オクタンジオールを10mmol添加した以外は現像液Aと同様にして現像液Dを得た。
<Developer D>
In the preparation of the developer A, a developer D was obtained in the same manner as the developer A except that 10 mmol of 3,6-dithia-1,8-octanediol was further added.
<現像液E>
上記現像液Aの作製において、更にエチレンジアミンを80mmol、前記した化合物1−1を80mmol添加した以外は現像液Aと同様にして現像液Eを得た。
<Developer E>
In the preparation of the developer A, a developer E was obtained in the same manner as the developer A except that 80 mmol of ethylenediamine and 80 mmol of the compound 1-1 were added.
<現像液F>
上記現像液Aの作製において、更にエチレンジアミンを80mmol、3,6−ジチア−1,8−オクタンジオールを10mmol添加した以外は現像液Aと同様にして現像液Fを得た。
<Developer F>
Developer F was obtained in the same manner as Developer A except that 80 mmol of ethylenediamine and 10 mmol of 3,6-dithia-1,8-octanediol were further added in the preparation of Developer A.
<現像液G>
上記現像液Aの作製において、更にトリエチレンテトラアミンを80mmol、前記した化合物1−1を80mmol添加した以外は現像液Aと同様にして現像液Gを得た。
<Developer G>
In the production of the developer A, a developer G was obtained in the same manner as the developer A except that 80 mmol of triethylenetetraamine and 80 mmol of the compound 1-1 were added.
<現像液H>
上記現像液Aの作製において、更にN−(2−アミノエチル)エタノールアミンを96mmol、3,6−ジチア−1,8−オクタンジオールを27mmol添加した以外は現像液Aと同様にして現像液Hを得た。
<Developer H>
In the preparation of the developer A, a developer H was prepared in the same manner as the developer A except that 96 mmol of N- (2-aminoethyl) ethanolamine and 27 mmol of 3,6-dithia-1,8-octanediol were further added. Got.
<現像液I>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、3,6−ジチア−1,8−オクタンジオールを10mmol添加した以外は現像液Aと同様にして現像液Iを得た。
<Developer I>
Developer I was obtained in the same manner as Developer A except that 80 mmol of Compound 1-1 and 10 mmol of 3,6-dithia-1,8-octanediol were further added in the preparation of Developer A.
<現像液J>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、3,6−ジチア−1,8−オクタンジオールを40mmol添加した以外は現像液Aと同様にして現像液Jを得た。
<Developer J>
In the production of the developer A, a developer J was obtained in the same manner as the developer A except that 80 mmol of the compound 1-1 and 40 mmol of 3,6-dithia-1,8-octanediol were added.
<現像液K>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、3,6−ジチア−1,8−オクタンジオールを80mmol添加した以外は現像液Aと同様にして現像液Kを得た。
<Developer K>
Developer K was obtained in the same manner as Developer A, except that 80 mmol of Compound 1-1 and 80 mmol of 3,6-dithia-1,8-octanediol were further added.
<現像液L>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、3,6−ジチア−1,8−オクタンジオールを120mmol添加した以外は現像液Aと同様にして現像液Lを得た。
<Developer L>
In the preparation of the developer A, a developer L was obtained in the same manner as the developer A except that 80 mmol of the compound 1-1 and 120 mmol of 3,6-dithia-1,8-octanediol were further added.
<現像液M>
上記現像液Aの作製において、更に前記した化合物1−1を700mmol、3,6−ジチア−1,8−オクタンジオールを10mmol添加した以外は現像液Aと同様にして現像液Mを得た。
<Developer M>
Developer M was obtained in the same manner as Developer A, except that 700 mmol of Compound 1-1 and 10 mmol of 3,6-dithia-1,8-octanediol were further added.
<現像液N>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、3,6−ジチア−1,8−オクタンジオールを10mmol、及びN−(2−アミノエチル)エタノールアミンを30mmol添加した以外は現像液Aと同様にして現像液Nを得た。
<Developer N>
In the preparation of the developer A, except that 80 mmol of the compound 1-1, 10 mmol of 3,6-dithia-1,8-octanediol, and 30 mmol of N- (2-aminoethyl) ethanolamine were further added. In the same manner as Developer A, Developer N was obtained.
<現像液O>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、3,6−ジチア−1,8−オクタンジオールを10mmol、及びN−(2−アミノエチル)エタノールアミンを35mmol添加した以外は現像液Aと同様にして現像液Oを得た。
<Developer O>
In the preparation of the developer A, except that 80 mmol of the compound 1-1, 10 mmol of 3,6-dithia-1,8-octanediol, and 35 mmol of N- (2-aminoethyl) ethanolamine were further added. In the same manner as Developer A, Developer O was obtained.
<現像液P>
上記現像液Aの作製において、更に前記した化合物1−1を80mmol、2,2′−チオジエタノールを10mmol添加した以外は現像液Aと同様にして現像液Pを得た。
<Developer P>
Developer P was obtained in the same manner as Developer A except that 80 mmol of Compound 1-1 and 10 mmol of 2,2′-thiodiethanol were further added in the preparation of Developer A.
<現像液Q>
上記現像液Aの作製において、更に前記した化合物1−5を80mmol、3,6−ジチア−1,8−オクタンジオールを10mmol添加した以外は現像液Aと同様にして現像液Qを得た。
<Developer Q>
Developer Q was obtained in the same manner as Developer A, except that 80 mmol of Compound 1-5 and 10 mmol of 3,6-dithia-1,8-octanediol were further added.
安定液には、下記に示すものを使用した。
<安定液>
第一リン酸カリウム 20g
トリエタノールアミン 5g
2−メルカプト−5−n−ヘプチルオキサジアゾール 0.4g
リン酸でpHを6に調整し、純水で1Lとする。
The stabilizer shown below was used.
<Stabilizer>
Primary potassium phosphate 20g
Triethanolamine 5g
0.4 g of 2-mercapto-5-n-heptyloxadiazole
The pH is adjusted to 6 with phosphoric acid and adjusted to 1 L with pure water.
平版印刷版の印刷試験は印刷機(リョービイマジクス株式会社製RYOBI660H)、インキ(DIC株式会社製スペースカラーフュージョンG墨ノーマルタイプ及びスペースカラーフュージョンG紅ノーマルタイプ)及び給湿液(富士フイルム株式会社製エコリティ2を0.5質量%で使用)を使用した。スペースカラーフュージョンG墨ノーマルタイプインキを用いた印刷では通常の印刷方法にて2万枚の印刷を行い、銀画像部の消失度合いを判定する耐刷試験を行い、スペースカラーフュージョンG紅ノーマルタイプインキを用いた印刷では一旦、非画像部全面にインキを付着させた後、通常印刷を行うことで非画像部のインキ汚れの回復を判定するインキ脱離試験を行った。 The printing test of the planographic printing plate is performed by a printing press (RYOBI 660H RYOBI660H), ink (DIC Corporation Space Color Fusion G Black Normal Type and Space Color Fusion G Red Normal Type), and dampening liquid (Fuji Film Co., Ltd.). Ecolite 2 manufactured at 0.5% by mass) was used. In printing using Space Color Fusion G black normal type ink, 20,000 sheets are printed by a normal printing method, a printing durability test is performed to determine the disappearance degree of the silver image portion, and Space Color Fusion G Red normal type ink is printed. In the printing using, an ink detachment test was carried out to determine the recovery of ink stains in the non-image area by performing normal printing after the ink was once deposited on the entire surface of the non-image area.
耐刷試験では、2400dpiで出力した175線5%の網点面積の変化率で評価した。印刷開始を100%とし、2万枚印刷時に80%以上の画像面積を維持している場合は○、50%以上80%未満の場合は△、50%未満に減少した場合は×とした。また、インキ脱離試験では、上記した一連の印刷方法を1セットとし、5セット以上繰り返した場合であっても非画像部のインキ汚れが回復した場合は○、3セットもしくは4セットでインキ汚れが回復しなくなった場合は△、2セット以下の印刷で回復しなかった場合は×と評価した。結果を表1に示す。 In the printing durability test, evaluation was performed based on the change rate of the dot area of 175 lines and 5% output at 2400 dpi. The printing start was set to 100%, and when the image area of 80% or more was maintained at the time of printing 20,000 sheets, it was marked as ◯, when it was 50% or more and less than 80%, and when it decreased to less than 50%. In addition, in the ink detachment test, if the above-mentioned series of printing methods is set as one set and the ink stain on the non-image area is recovered even when it is repeated 5 sets or more, the ink stain is obtained with 3 sets or 4 sets. When no recovery occurred, Δ was evaluated, and when it did not recover after printing of 2 sets or less, it was evaluated as ×. The results are shown in Table 1.
(実施例2)
実施例1の平版印刷版の製版に利用した自動製版装置を三菱製紙株式会社より市販されているFREDIA(浸漬現像方式)に変更した以外は実施例1と同様にして試験した。
(Example 2)
The test was conducted in the same manner as in Example 1 except that the automatic plate making apparatus used for plate making of the lithographic printing plate of Example 1 was changed to FREDIA (immersion development method) commercially available from Mitsubishi Paper Corporation.
製版して印刷を行った結果、実施例1と同様の結果を得られたことから、本発明の製版方法は浸漬現像方式においても有用であることが証明された。 As a result of plate-making and printing, the same results as in Example 1 were obtained, so that the plate-making method of the present invention was proved to be useful in the immersion development method.
以上の結果から明らかなように、本発明により、製版後14日間保管した場合であっても、非画像部のインキ脱離不良の発生が無く、且つ耐刷不良が発生しない平版印刷版が得られることが判る。 As is clear from the above results, according to the present invention, a lithographic printing plate in which no ink detachment failure occurs in the non-image area and printing failure does not occur even when stored for 14 days after plate making is obtained. You can see that
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