JPS61117548A - Photosensitive lithographic plate - Google Patents

Photosensitive lithographic plate

Info

Publication number
JPS61117548A
JPS61117548A JP23758384A JP23758384A JPS61117548A JP S61117548 A JPS61117548 A JP S61117548A JP 23758384 A JP23758384 A JP 23758384A JP 23758384 A JP23758384 A JP 23758384A JP S61117548 A JPS61117548 A JP S61117548A
Authority
JP
Japan
Prior art keywords
plate
photosensitive
diazo
printing plate
diazo resin
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.)
Granted
Application number
JP23758384A
Other languages
Japanese (ja)
Other versions
JPH06103390B2 (en
Inventor
Shigeki Shimizu
茂樹 清水
Masayuki Onose
小野瀬　優幸
Shinichi Fumiya
文屋　信一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Kasei Corp
Original Assignee
Mitsubishi Kasei Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Priority to JP59237583A priority Critical patent/JPH06103390B2/en
Publication of JPS61117548A publication Critical patent/JPS61117548A/en
Publication of JPH06103390B2 publication Critical patent/JPH06103390B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/016—Diazonium salts or compounds
    • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
    • G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

PURPOSE:To enhance image reproducibility an film strength, and to obtain high printing resistance by forming a photosensitive layer contg. a hydrophilic polymer having OH groups and a diazo compd. on an Al plate provided with a specified anodized layer. CONSTITUTION:The photosensitive layer contg. a hydrophilic polymer having OH groups, such as acrylamide having OH groups, and a diazo compd.is formed on the Al plate having the anodized layer obtained by anodizing Al in an electrolyte contg. phosphoric acid alone or as a main component and having an average bore diameter of 20-90nm and a bore density of 100-1,000/mum2. The diazo resin to be used is a condensation product of aldehyde and p-diazophenylamine represented by the formula shown on the right in which R<1>, R<2>, and R<3> are each H, alkyl, or alkoxy; R is H, alkyl, or phenyl; X is PF6 or BF4; and n is an integer of 1-200. The photosensitive compsn. consisting of said polymer, said diazo resin, and necesary additives is applied to the Al plate to obtain a lithographic plate material. It is exposed to a light image of the object to be printed, and developed to obtain a printing plate, thus permitting the obtained plate to be high in film strength and printing resistance, to be erased well, and to be prevented from back ground stains, and superior in storage stability.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、感光性平版印刷版に係ル、詳しくは膜強度が
強く、高耐刷力で保存安定性が良く、しかも画像再現性
が良好な感光性平版印刷版に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate, and more specifically, the present invention relates to a photosensitive lithographic printing plate, which has strong film strength, high printing durability, good storage stability, and image reproducibility. Concerning a good photosensitive lithographic printing plate.

〔従来の技術〕[Conventional technology]

従来、芳香族ジアゾニウム塩、例えば、ジフェニルアミ
ン−４−ジアゾニウム塩と活性カルボニル化合物、例え
ばホルムアルデヒドを反応させたジアゾ樹脂は公知であ
る。特に印刷分野ではジアゾ樹脂の光分解による溶解性
の変化を利用して、オフセット印刷用平版の製版用感光
性物質として広く利用されている。Conventionally, diazo resins are known, which are prepared by reacting an aromatic diazonium salt, such as diphenylamine-4-diazonium salt, with an active carbonyl compound, such as formaldehyde. Particularly in the printing field, diazo resins are widely used as photosensitive materials for plate making of planographic plates for offset printing, taking advantage of the change in solubility caused by photodecomposition of diazo resins.

ジアゾ樹脂をバインダー等と混合し、それを親水性の金
属、紙、好ましくはアルミニウム等に塗布することによ
ルオフセット印刷版が得られる。この版は、像様霧光す
ることによシ露光部が硬化し、現像液に不溶となり、こ
れを現像液によ、多処理することによ）版面上に親水性
部分と親油性部分が得られ水と脂肪性インキを用いて印
刷することができる。An offset printing plate can be obtained by mixing a diazo resin with a binder and applying the mixture to a hydrophilic metal, paper, preferably aluminum. The exposed areas of this plate are hardened by imagewise mist light and become insoluble in the developer, and by multiple treatments with the developer, a hydrophilic area and a lipophilic area are formed on the plate surface. The obtained can be printed using water and fatty ink.

高分子化合物とジアゾ化合物とからなる感光性物質は、
ジアゾ化合物単独のものと比較して、後でラッカー盛）
等の必要性がなく、安定した印刷版が得られる等優れた
性能を示すことが知られている。A photosensitive substance consisting of a polymer compound and a diazo compound is
(later lacquered) compared to the diazo compound alone
It is known that it exhibits excellent performance, such as being able to obtain stable printing plates without the need for

高分子化合物に関しては、種々のものが検討されている
が、親水性の高分子化合物であると現像性やジアゾ樹脂
との相溶性に優れているものの保存安定性や、感脂性が
悪く実用上支障がある。一方、高分子化合物が親油性で
あると保存安定性や感脂性は優れているものの現像性特
に水系の現像液での現像性が悪い（特開ｌ＠５６−４１
４４号、同５４−９８６１４号各公報参照）。Various polymer compounds have been studied, but while hydrophilic polymer compounds have excellent developability and compatibility with diazo resin, they have poor storage stability and poor oil sensitivity, making them difficult to use in practice. There is a problem. On the other hand, if the polymer compound is lipophilic, it has excellent storage stability and oil sensitivity, but has poor developability, especially in an aqueous developer (Japanese Patent Application Laid-Open No. 56-41
No. 44 and No. 54-98614).

ジアゾ樹脂に関しても種々検討されている。Various studies have also been made regarding diazo resins.

例えば特公昭４７−１１６７号公報又は米国特許第３３
００３０９号明細書でれ、ジアゾのアニオンとして有機
スルホン酸塩等の有機塩が記載されている。また特開昭
５４−９８６１５号公報ではジアゾのアニオンとしてハ
ロゲン化ルイス酸塩が記載されている。For example, Japanese Patent Publication No. 47-1167 or U.S. Patent No. 33
No. 00309 describes organic salts such as organic sulfonates as diazo anions. Further, in JP-A-54-98615, a halogenated Lewis acid salt is described as an anion of diazo.

また近年、作業性尋の点から、印刷版の耐刷力と画像再
現性の向上が強く望まれている。耐刷力を向上させるた
めに、感光層の膜厚や陽極酸化被膜の膜厚を厚くすると
いう手段が使われているが、これは、画像再現性が不良
となシ使用範囲が限定される。Furthermore, in recent years, from the viewpoint of workability, it has been strongly desired to improve printing durability and image reproducibility of printing plates. In order to improve printing durability, methods are used to increase the thickness of the photosensitive layer and the anodic oxide film, but this results in poor image reproducibility and limits the range of use. .

従来よシ、陽極酸化処理層を設けるとアルミニウム板の
表面硬度が向上し、画像部のアルミニウム板との接着性
も向上することは知られていた。またリン酸あるいはリ
ン酸を主成分とした電解液中で陽極酸化されたアルミニ
ウム板の方が、硫酸やシュウ酸等の電解液中で処理した
ものよシ接着性が良好なことは既に公知である。Conventionally, it has been known that providing an anodized layer improves the surface hardness of the aluminum plate and also improves the adhesion of the image area to the aluminum plate. Furthermore, it is already known that aluminum plates anodized in phosphoric acid or an electrolyte containing phosphoric acid as a main component have better adhesion than those treated in an electrolyte such as sulfuric acid or oxalic acid. be.

したがって、感光層として光二量化型フォトポリマーや
アジド系フォトポリマーといった比較的接着力の劣るも
のを使用する場合には、リン酸の陽極酸化層が使用され
ることが多い（特公昭４６−２６５２１号、同５４−３
７５２２号、同５７−２２０５５号、同５７−２２０５
５号各公報、及び米国特許第５５９４２８９号明細書参
照）。Therefore, when using a material with relatively poor adhesive strength such as a photodimerizable photopolymer or an azide-based photopolymer as a photosensitive layer, a phosphoric acid anodized layer is often used (Japanese Patent Publication No. 46-26521). , 54-3
No. 7522, No. 57-22055, No. 57-2205
5 and US Pat. No. 5,594,289).

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

ところが、ジアゾ系の場合は、接着性が強すぎるために
、リン酸の陽極酸化層を使用すると地汚れが発生したシ
、消去が不能となる等の傾向があシ、実用上難点が多い
とされている。However, in the case of diazo-based materials, the adhesiveness is too strong, so when a phosphoric acid anodized layer is used, there is a tendency for background smearing to occur and erasing to be impossible, and there are many practical difficulties. has been done.

したがって、本発明の目的は、画像再現性を向上し、し
かも膜強度が強く、高耐刷力の印刷版を提供することに
ある。Therefore, an object of the present invention is to provide a printing plate that improves image reproducibility, has strong film strength, and has high printing durability.

また、本発明の更に別の目的は、消去性が良好で地汚れ
が発生せず、保存安定性の良い印刷版を提供することに
ある。Still another object of the present invention is to provide a printing plate that has good erasability, does not cause scumming, and has good storage stability.

ｃ問題点を解決するための手段〕 本発明を概説すれば、本発明は感光性平版印刷版に関す
る発明であって、該印刷版が、リン酸又はリン酸を主成
分とする電解液中で陽極酸化処理して得られる平均ボア
径が２００〜９００Ｘでボア密度が１００〜１０００個
／μｍ２の陽極酸化層を有するアルミニウム板上に、水
酸基を有する親油性高分子化合物とジアゾ樹脂を含有す
る感光層を設けたものであることを特徴とする。Means for Solving Problems c] To summarize the present invention, the present invention relates to a photosensitive lithographic printing plate, wherein the printing plate is immersed in phosphoric acid or an electrolytic solution containing phosphoric acid as a main component. A photosensitive material containing a lipophilic polymer compound having a hydroxyl group and a diazo resin on an aluminum plate having an anodized layer having an average bore diameter of 200 to 900X and a bore density of 100 to 1000/μm2 obtained by anodizing treatment. It is characterized by having layers.

本発明者等鉱鋭意研究を菖ねた結果、上記の印刷版は、
特異的に画像再現性が向上し、高耐刷力で、保存安定性
及び消去性が良好であシ、しかも地汚れの発注しないｌ
＆光性平版印刷版であることを見出し、本発明を完成し
た。As a result of intensive research by the present inventors, the above printed version is
It has uniquely improved image reproducibility, high printing durability, good storage stability and erasability, and does not cause background smudges.
& A photosensitive lithographic printing plate was discovered, and the present invention was completed.

以下、本発明を具体的に説明する。The present invention will be explained in detail below.

本発明に使用されるジアゾ樹脂は、公知の方法、例えば
、フォトグラフィック　サイエンスアンド　エンジニア
リング（Ｐｈｏｔｏ、ＳｃｉＪｎｇ　）第１７巻、第３
３頁（１９７３）、米国特許第２０６３６５１号、同第
２６７９４９８号各明細書に記載の方法に従い、硫酸や
リン酸あるいは塩酸中でジアゾニウム塩とアルデヒド類
例えばバラホルムアルデヒド、アセトアルデヒド、ベン
ズアルデヒドとを重縮合させることによって得られる。The diazo resin used in the present invention can be prepared by a known method, for example, Photographic Science and Engineering (Photo, SciJng) Volume 17, Volume 3.
3 (1973), U.S. Patent Nos. 2063651 and 2679498, a diazonium salt and an aldehyde such as paraformaldehyde, acetaldehyde, and benzaldehyde are polycondensed in sulfuric acid, phosphoric acid, or hydrochloric acid. obtained by

その際、ジアゾニウム塩とアルデヒド類をモル比で通常
１：０．５〜１：２、好ましくは、１：０．６〜１：　
＋、Ｓで仕込み、低温で短時間、例えば１００以下３時
間程度反応させることによシ高感度ジアゾ樹脂が得られ
る。At that time, the molar ratio of diazonium salt and aldehyde is usually 1:0.5 to 1:2, preferably 1:0.6 to 1:
A highly sensitive diazo resin can be obtained by charging with + and S and reacting at a low temperature for a short time, for example, 100 or less, for about 3 hours.

本発明においては、ジアゾ樹脂のＰＦ６塩又はＢＦ４塩
が好ましく、特に下記一般式■で示され、かつ数式にお
けるｎが５以上である樹脂を２０モル％以上、好ましく
は、２０〜６０モル％含有するジアゾ樹脂が好ましい。In the present invention, PF6 salt or BF4 salt of diazo resin is preferable, and in particular contains 20 mol% or more, preferably 20 to 60 mol%, of a resin represented by the following general formula (1) and where n in the formula is 5 or more. A diazo resin is preferred.

Ｃ式中、Ｂ　、Ｒ及びＲは水素原子、アルキル基又はア
ルコキシ基を示し、Ｒは水素原子、アルキル基又はフェ
ニル基を示し、ＸはＰＦ６又はＢＦ４を示し、ｎは１〜
２００の数を示す）かくして得られたジアゾ樹脂は、例
えば、水ｗＲ１ｔｓを有する親油性高分子化合物と混合
して使用する。この目的に使用しりろ水酸基を有する親
油性高分子化合物としては、例えば、下記の様な水酸基
を有するアクリルアミド類、メタクリルアミド類、アク
リル酸エステル類又はメタクリル酸エステル類等の単量
体から誘導される構成単位を含有する通常２万〜２０万
の分子量をもつ共重合体が挙げられる。In formula C, B, R and R represent a hydrogen atom, an alkyl group or an alkoxy group, R represents a hydrogen atom, an alkyl group or a phenyl group, X represents PF6 or BF4, and n is 1 to
200) The diazo resin thus obtained is used, for example, in a mixture with a lipophilic polymer compound having water wR1ts. Examples of lipophilic polymer compounds having a hydroxyl group used for this purpose include those derived from monomers such as acrylamides, methacrylamides, acrylic esters, or methacrylic esters having a hydroxyl group as shown below. Examples include copolymers containing constitutional units having a molecular weight of usually 20,000 to 200,000.

（リ　芳香族性水酸基を有するモノマー、例えばＮ−（
４−ヒドロキシフェニル）アクリルア＜　）”　Ｘ　ｕ
　Ｎ　−（４−とド目キシフェニル）メタクリルアミド
、Ｏ−，１１−、ｐ−ヒト田キシスチレン、０−２曹−
９ｐ−ヒトルキシフェニル−アクリレート又はメタクリ
レート（２）　　脂肪族水酸基を有するモノマー、例え
ば２−ヒドロキシエチルアクリレ−）又＃ｉ２−ヒドロ
キシエチルメタクリレート 共重合する他のモノマーとしては、 （１）　　アクリル酸、メタクリル酸、無水マレイン酸
等のα、β−不飽和カルボン酸 （２）　　アクリル酸メチル、アクリル酸エチル、アク
リル酸プ四ビル、アクリル酸ブチル、アクリル酸アミル
、アクリル酸ヘキシル、アクリル酸オクチル、アクリル
酸−２−クロロエチル、２−ヒトジキシエチルアクリレ
ート、グリシジルアクリレート、Ｈ−ジメチルアミノエ
チルアクリレート等の（置換）アルキルアクリレート （３）　　メチルメタクリレート、エチルメタクリレー
ト、プロピルメタクリレート、プ、チルメタクリレート
、アミルメタクリレート、シクロへキシルメタクリレー
ト、２−ヒト日キシエチルメタクリレート、４−とドμ
キシブチルメタクリレート、グリシジルメタクリレート
、Ｈ−ジメチルアミノエチルメタクリレート等の（置換
）アルキルメタクリレート （４）　　アクリルアミド、メタクリルアミド、Ｎ−メ
チロールアクリルアミド、Ｎ−メチロールメタクリルア
ミド、Ｎ−エチルアクリルアミド、Ｎ−へキシルメタク
リルアミド、Ｎ−シクロヘキシルアクリルアミド、Ｎ−
ヒドロキシエチルアクリルアミド、Ｎ−フェニルアクリ
ルアミド、Ｎ−二ト四フェニルアクリルアミド、Ｎ−エ
チル−Ｎ−フェニルアクリルアミド等のアクリルアミド
若しくはメタクリルアミド類 （５１エチルビニルエーテル、２−／ロロエチルビニル
エーテル、ヒト四キシエチルビニルエーテル、フロビル
ビニルエーテル、　７’−ＩＦ−ルビニルエーテル、オ
クチルビニルエーテル、フェニルビニルエーテル等ノビ
ニルエーテル類（６）　　ビニルアセテート、ビニルク
ロロアセテート、ビニルブチレート、安息香酸ビニル等
のビニルエステル類 （７）　　スチレン、α−メチルスチレン、メチルスチ
レン、クロロメチルスチレン等のスチレン類 （８）メチルビニルケトン、エチルビニルケトン、プロ
ピルビニルケトン、フェニルビニルケトン等のビニルケ
トン類 （９）　　エチレン、プ目ピレン、イソブチレン、ブタ
ジェン、イソプレン等のオレフィン類αυ　Ｎ−ビニル
ピロリドン、Ｎ−ビニルカルバゾール、４−ビニルピリ
ジン、アクリロニトリル、メタクリレートリル等 が挙げられるが、その他、水酸基を含有するモノマーと
共重合しうるモノマーであれば良く、これに限定される
ものではない。また、これ以外にも必要に応じて、ポリ
ビニルブチラール樹脂、ポリウレタン樹脂、ポリアミド
樹脂、エポキシ樹脂、ノボラック樹脂、天然樹脂等を添
加してもよい。(Li) A monomer having an aromatic hydroxyl group, such as N-(
4-Hydroxyphenyl)acryla< )”X u
N-(4-xyphenyl)methacrylamide, O-, 11-, p-hydroxystyrene, 0-2-
9p-Hydroxyphenyl acrylate or methacrylate (2) A monomer having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate) or #i2-hydroxyethyl methacrylate Other monomers to be copolymerized include (1) acrylic acid; α, β-unsaturated carboxylic acids such as methacrylic acid and maleic anhydride (2) Methyl acrylate, ethyl acrylate, tetravir acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic (Substituted) alkyl acrylates such as acid-2-chloroethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, H-dimethylaminoethyl acrylate (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2-human xyethyl methacrylate, 4- and deμ
(Substituted) alkyl methacrylates such as xybutyl methacrylate, glycidyl methacrylate, H-dimethylaminoethyl methacrylate (4) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide , N-cyclohexyl acrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-dithotetraphenylacrylamide, N-ethyl-N-phenylacrylamide (51 ethyl vinyl ether, 2-/roloethyl vinyl ether, human tetraxyethyl vinyl ether, Novinyl ethers such as flobyl vinyl ether, 7'-IF-ruvinyl ether, octyl vinyl ether, and phenyl vinyl ether (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate (7) Styrene, α- Styrenes such as methylstyrene, methylstyrene, and chloromethylstyrene (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone (9) Ethylene, pyrene, isobutylene, butadiene, isoprene, etc. Examples of olefins αυ include N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylatetrile, etc., but any other monomer that can be copolymerized with a monomer containing a hydroxyl group may be used, and is limited to these. In addition, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolak resin, natural resin, etc. may be added as required.

本発明に用いられる水酸基を有する親油性の高分子化合
物は、感光性組成物の固形分中に通常４０〜９９０〜９
９重量しくは５０〜９５重量％含有させる。また、ジア
ゾ樹脂は通常１〜６０重蓋％、好ましくは３〜３０重量
％含有させる。The lipophilic polymer compound having a hydroxyl group used in the present invention usually contains 40 to 990 to 9
9% by weight or 50 to 95% by weight. The diazo resin is usually contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

本発明の感光性組成物には、更に性能を向上させるため
に以下に示した種々の公知の添加剤を加えることができ
る。Various known additives shown below can be added to the photosensitive composition of the present invention in order to further improve performance.

（１）　　画像を可視画化することを目的とした染料（
２）塗布性を改良するためのフッ素系界面活性痢やアル
キルエーテル類 （３）塗膜の柔軟性、耐摩耗性を付与するための可塑剤 （４）感脂化剤 （５）　　安定剤 これらの添加量は一般に全固形分に対し０．１〜３０重
量％である。(1) Dye for the purpose of visualizing images (
2) Fluorinated surfactants and alkyl ethers to improve coating properties (3) Plasticizers to impart flexibility and abrasion resistance to the coating film (4) Sensitizers (5) Stabilizers The amount added is generally 0.1 to 30% by weight based on the total solid content.

本発明の感光性組成物は適当な溶媒、例えばメチルセロ
ソルブ、メチルエチルケトン、エチルセロソルブ、シク
μヘキサノン、ジオキサン、酢酸エチル、ベンジルアル
コール、ジアセトンアルコール等に溶解して支持体に塗
布する。塗布量としては、乾燥重量で通常約０．５〜約
ｓｌ／ｍ２である。このとき、用いるアルミニウム板は
リン酸又はリン酸を主成分とする電解液中で陽極酸化処
理しておく。例えば、アルミニウム板を１０〜５０重量
％、好ましくは、２０〜４０重量％のリン酸を含む水溶
液中、又は、かかるリン酸と全酸中２５重量％以下、好
ましくは、１０重量％以下の他の酸、例えば、硫酸、シ
ュウ酸等との混酸を含む水溶液中、浴温１０〜５０Ｃ１
好ましくは、２５〜４５Ｃで、電流密度０．２〜１０　
Ａ／ｕｔ、好ましくは、１〜７　Ａ　／　ａ凱２で、１
０秒〜１０分、好ましくは、２０秒〜３分の範囲で、得
られる陽極酸化層の゛　　　　　　　　　、平均ボア径
が２００〜９００Ａ、好ましくは、３００〜９００Ａ。The photosensitive composition of the present invention is dissolved in a suitable solvent such as methyl cellosolve, methyl ethyl ketone, ethyl cellosolve, cyclohexanone, dioxane, ethyl acetate, benzyl alcohol, diacetone alcohol, etc., and applied to a support. The coating amount is usually about 0.5 to about sl/m<2 >in terms of dry weight. At this time, the aluminum plate used is anodized in phosphoric acid or an electrolytic solution containing phosphoric acid as a main component. For example, the aluminum plate may be placed in an aqueous solution containing 10 to 50% by weight, preferably 20 to 40% by weight of phosphoric acid, or 25% by weight or less, preferably 10% by weight or less of such phosphoric acid and the total acid. in an aqueous solution containing a mixed acid with an acid such as sulfuric acid, oxalic acid, etc., at a bath temperature of 10 to 50 C1.
Preferably, the current density is 0.2-10 at 25-45C.
A/ut, preferably 1 to 7 A/a kai 2, 1
In the range of 0 seconds to 10 minutes, preferably 20 seconds to 3 minutes, the resulting anodized layer has an average bore diameter of 200 to 900A, preferably 300 to 900A.

特に好ましくは４００〜９００Ａで、ボア密度が１００
〜１，０００個／μｍ２、好ましくは、１００〜５００
個／　ｐｍ２、特に好ましく　ハ１００〜５５０個／μ
ｍ２となるように陽極酸化処理したものを使用する。Particularly preferably 400 to 900 A and a bore density of 100
~1,000 pieces/μm2, preferably 100-500
pieces/pm2, particularly preferably 100 to 550 pieces/μ
Use one that has been anodized so that it becomes m2.

本発明においては、陽極酸化処理の前後に、それぞれ周
知の方法に従いブラシ研摩、電解エツチング等の砂目型
て処理、及び／又は親水化処理等の表面処理を行ってお
くことが好ましい０親水化処理として紘熱水封孔やケイ
酸ソーダ処理が挙げられるが接着性やジアゾ残シ、現像
性の点からは、ケイ酸ソーダ処理が好ましい。In the present invention, it is preferable to perform surface treatment such as brush polishing, grain forming treatment such as electrolytic etching, and/or hydrophilic treatment according to well-known methods before and after the anodizing treatment. Treatments include hot water sealing and sodium silicate treatment, but sodium silicate treatment is preferred from the viewpoint of adhesiveness, diazo residue, and developability.

ケイ酸ソーダ処理の条件としては濃度０．１〜５％のメ
タケイ酸ソーダ溶液中に、温度５０Ｃ〜９５Ｃで１０秒
間〜５分間浸漬して行われる。The sodium silicate treatment is carried out by immersion in a sodium metasilicate solution having a concentration of 0.1 to 5% at a temperature of 50C to 95C for 10 seconds to 5 minutes.

好ましくは、その後に６０Ｃ〜１００Ｃの水に１０秒間
〜５分間浸漬して処理される。Preferably, it is then treated by immersion in water at 60C to 100C for 10 seconds to 5 minutes.

こうして製造した感光性平版印刷版上に、常法に従って
被写物を重ねて露光するか電子線等を照射して画像の書
込みを行った後、現像液を用いて現像すれば支持体上に
対応する画像を形成させることができる。露光に好適な
光源としては、メタルハライドランプ、水銀灯、カーボ
ンアーク灯等が挙げられる。After writing an image on the photosensitive lithographic printing plate produced in this way by overlapping the subject and exposing it to light or irradiating it with an electron beam, etc., in accordance with a conventional method, it is developed using a developer to form an image on the support. A corresponding image can be formed. Light sources suitable for exposure include metal halide lamps, mercury lamps, carbon arc lamps, and the like.

本発明に係る感光性印刷版の現像処理に用いられる現像
液は公知のいずれのものであっても良いが、好ましくは
以下のものがよい。すなわち本発明に係る感光性印刷版
を現像する現像液は、水、あるいは特定の有機溶媒及び
／又はアルカリ剤を含む水溶液が挙げられる。ここに特
定の有機溶媒とは、現像液中に含有させたとき上述の感
光性組成物層の非露光部（非画像部）を溶解又は膨潤す
ることができ、しかも常温（２０Ｃ）において水に対す
る溶解度が１０重量％以下の有機溶媒をいう。このよう
な有機溶媒としては上記のような特性を有するものであ
シさえすればよく、以下のもののみに限定されるもので
はないが、これらを例示するならば、例えば酢酸エチル
、酢酸グロビル、酢酸ブチル、酢酸アミル、酢酸ベンジ
ル、エチレングリコールモノブチルアセテート、乳酸ブ
チル、レブリン酸ブチルのようなカルボン酸エステル；
エチルブチルケトン、メチルイソブチルケトン、シクロ
ヘキサノンのよりなケトン類；エチレングリコールモツ
プチルエーテル、エチレンクリコールベンジルエーテル
、エチレングリコールモノフェニルエーテル、ベンジル
アル：ｌ−ル、）１チルフエニルカルビノール、ｎ−ア
ミルアルコール、メチルアミルアルコールのｊ５なアル
コール類；キシレンのようなアルキル置換芳香族炭化水
素；メチレンジクロライド、エチレンジクロライド、モ
ノクロロベンゼンのようなノ１０グン化炭化水素などが
ある。これら有機溶媒は一種以上用いてもよい。これら
有機溶媒の中でハ、エチレンクリコールモノフェニルエ
ーテルとベンジルアルコールが特に有効である。また、
これら有機溶媒の現像液中における含有量はおおむね１
〜２０重量％であシ、特に２〜１０重量％のときよシ好
ましい結果を得る。The developer used in the development of the photosensitive printing plate according to the present invention may be any known developer, but the following are preferred. That is, the developer for developing the photosensitive printing plate according to the present invention may be water or an aqueous solution containing a specific organic solvent and/or alkaline agent. The specific organic solvent herein means that when it is contained in the developer, it can dissolve or swell the non-exposed area (non-image area) of the above-mentioned photosensitive composition layer, and that it is resistant to water at room temperature (20C). An organic solvent with a solubility of 10% by weight or less. Such organic solvents only need to have the characteristics described above, and are not limited to the following, examples of which include ethyl acetate, globil acetate, Carboxylic acid esters such as butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate;
Ketones such as ethyl butyl ketone, methyl isobutyl ketone, and cyclohexanone; ethylene glycol motsubutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alkyl, )1 tylphenyl carbinol, n- Examples include alcohols such as amyl alcohol and methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; and oxidized hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. Also,
The content of these organic solvents in the developer is approximately 1
Favorable results are obtained at up to 20% by weight, especially between 2 and 10% by weight.

他方、現像液中に含有されるアルカリ剤としては、 （Ａ）　　ケイ酸ナトリウム、ケイ酸カリウム、水酸化
カリウム、水酸化ナトリウム、水酸化リチウム、第−二
又は第三リン酸のナトリウム又はアンモニウム塩、メタ
ケイ酸ナトリウム、炭酸ナトリウム、アンモニ・ア４１
等の無機アルカリ剤 （Ｂ）　　モノ、ジ又はトリメチルアミン、モノ、ジ又
はトリエチルアミン、モノ又はジイソプロピルアミン、
ｎ−ブチルアミン、モノ、ジ又はトリエタノールアミン
、モノ、ジ又はトリイソプロパツールアミン、エチレン
イミン、エチレンジアミン等の有機アミン化合物等が挙
げられる。On the other hand, the alkaline agents contained in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium salt of di- or tri-phosphoric acid; , sodium metasilicate, sodium carbonate, ammonia 41
Inorganic alkaline agents (B) such as mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine,
Examples include organic amine compounds such as n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, and ethylenediamine.

これらアルカリ剤の現像液中における含有量鉱通常０．
０５〜４重量％で、好ましくは０．５〜２重量％である
。The content of these alkaline agents in the developer is usually 0.
05 to 4% by weight, preferably 0.5 to 2% by weight.

また、保存安定性、耐刷性等をよシ以上に高めるために
は、水溶性亜硫酸塩を現像液中に含有させることが好ま
しい。このような水溶性亜硫酸塩としては、亜硫酸のア
ルカリ又はアルカリ土類金属塩が好ましく、例えば亜硫
酸ナトリウム、亜硫酸カリウム、亜硫酸リチウム、亜硫
酸マグネシウム々とがある。これらの亜硫酸塩の現像液
組成物における含有量は通常０．０５〜４重量％で、好
ましくは０．１〜１重量％である。Further, in order to further improve storage stability, printing durability, etc., it is preferable to include a water-soluble sulfite in the developer. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The content of these sulfites in the developer composition is usually 0.05 to 4% by weight, preferably 0.1 to 1% by weight.

また、上述の有機溶媒の水への溶解を助けるために一定
の可溶化剤を含有させることもできる。このよう、な可
溶化剤としては、本発明の所期の効果を実現するため、
用いる有機溶媒よシ水易溶性で、低分子のアルコール、
ケトン類を用いるのがよい。また、アニオン活性剤、両
性活性剤等も用いることができる。仁のようなアルコー
ル、ケトン類としては、例えばメタノール、エタノール
、グロパノール、ブタノール、アセトン、メチルエチル
ケトン、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、メトキシブタノー
ル、エトキシブタノール、４−メトキシ−４−メチルブ
タノール、Ｎ−メチルピロリドン等を用いることが好ま
しい。また、活性剤としては例えばイソプロピルナフタ
レンスルホン酸ナトリウム、ｎ−ブチルナフタレンスル
ホン酸ナトリウム、Ｎ−メチル−Ｎ−ペンタデシルアミ
ノ酢酸ナトリウム、ラウリルサルフェートナトリウム塩
等が好ましい。これらアルコール、ケトン類等の可溶化
剤の使用量については特に制限社ないが、一般に現像液
全体に対し約３０重量％以下とすることが好ましい。Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water. In order to achieve the desired effect of the present invention, the solubilizing agent is as follows:
The organic solvent used is a water-soluble, low-molecular alcohol,
It is better to use ketones. Furthermore, anionic activators, amphoteric activators, etc. can also be used. Examples of alcohols and ketones include methanol, ethanol, gropanol, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-methoxy-4-methylbutanol, It is preferable to use N-methylpyrrolidone or the like. Preferred examples of the activator include sodium isopropylnaphthalene sulfonate, sodium n-butylnaphthalene sulfonate, sodium N-methyl-N-pentadecylaminoacetate, and sodium lauryl sulfate. Although there are no particular restrictions on the amount of solubilizers such as alcohols and ketones to be used, it is generally preferred that the amount be about 30% by weight or less based on the entire developer.

本発明に係る感光性印刷版は、像様露光した後、上述の
現像液に接触させたシ、あるいはこすったルすれば、お
おむね常温〜４ＱＣにて１０〜６０秒後には、感光性組
成物層の露光部に悪影響を及ぼすことなく、非露光部の
感光性組成物が完全に除去されることになる。After the photosensitive printing plate according to the present invention has been imagewise exposed, if it is brought into contact with the above-mentioned developer or rubbed, the photosensitive composition is formed after 10 to 60 seconds at room temperature to 4QC. The photosensitive composition in the unexposed areas will be completely removed without adversely affecting the exposed areas of the layer.

以下、本発明で使用する砂目、ジアゾ樹脂及びポリマー
の製造例を示す。Examples of producing the grain, diazo resin, and polymer used in the present invention are shown below.

〔砂目−１〕 アルミニウム板を１７Ｉ／ノの塩酸浴中で浴温度２５Ｃ
にて５０　Ａ　／　６ＴｒＬ２で２５秒間電解研摩処理
を行い、最大粗さ４μｍの砂目板を得た。[Grain-1] Aluminum plate was placed in a 17 I/no hydrochloric acid bath at a bath temperature of 25 C.
Electrolytic polishing was performed at 50 A/6TrL2 for 25 seconds to obtain a grained plate with a maximum roughness of 4 μm.

該砂目板を４０重量％のリン酸浴中で、浴温度４０Ｃに
て４　Ａ　／　ｅ１ｍ２で３０秒間陽極酸化処理を行い
、充分に水洗後風乾した。得られた陽極酸化処理層を電
子顕微鏡で解析したところ、平均ボア径７５０Ａのボア
が１７５個／μｍ確認された。The grained board was anodized in a 40% by weight phosphoric acid bath at a bath temperature of 40 C and 4 A/e1 m2 for 30 seconds, thoroughly washed with water, and then air-dried. When the obtained anodized layer was analyzed using an electron microscope, 175 bores/μm with an average bore diameter of 750 A were confirmed.

［砂目−２〕 〔砂目−１〕と同様にして砂目立て処理されたアルミニ
ウム板を３０重量％のリン酸と２．５重量％の硫酸との
混酸浴中で、浴温度４０Ｃにて４Ａ／ｄｍ２で３０秒間
陽極酸化処理を行い充分に水洗後風乾した。得られたｌ
ｉｌ！極酸化極層化処理層顕微鏡で解析したところ、平
均ボア径５００ＸＯボアが２２０個／ｐｍ２確認された
。[Grain-2] An aluminum plate grained in the same manner as [Grain-1] was placed in a mixed acid bath of 30% by weight phosphoric acid and 2.5% by weight sulfuric acid at a bath temperature of 40C. Anodizing was performed at 4 A/dm2 for 30 seconds, thoroughly washed with water, and then air-dried. obtained l
Il! When analyzed using a polar oxide layered layer microscope, 220 bores/pm2 with an average bore diameter of 500XO were confirmed.

〔砂目−３〕 〔砂目−２〕と同様にして、３０重量％のリン酸と５重
量％の硫酸との混酸浴中で、他は同一条件にて得られた
陽極酸化処理層は平均ボア径３５０ムのボアが３５０個
／μｍ形成されたことが確認された。[Sand Grain-3] In the same manner as [Sand Grain-2], the anodized layer was obtained in a mixed acid bath of 30% by weight phosphoric acid and 5% by weight sulfuric acid under the same conditions. It was confirmed that 350 bores/μm with an average bore diameter of 350 μm were formed.

〔砂目−４〕 〔砂目−２〕と同様にして、３０重量％のリン酸と３０
重量％の硫酸との混酸浴中で、他は同一条件にて得られ
た陽極酸化処理層は平均ボア径２５０Ｘのボアが１００
０個／μｍ２形成されたことが確認された。[Sand Grain-4] In the same manner as [Sand Grain-2], 30% by weight of phosphoric acid and 30% by weight of phosphoric acid were added.
The anodized layer obtained under otherwise identical conditions in a mixed acid bath with sulfuric acid of 100% by weight had an average bore diameter of 250
It was confirmed that 0 pieces/μm2 were formed.

〔砂目−５〕 〔砂目−１〕と同様にして砂目立て処理されたアルミニ
ウム板を３０重量％の硫酸浴中で、浴温度３０Ｃにて６
Ａ／ｄＴｒＬ２で３０秒間陽極酸化処理を行い、充分に
水洗後風乾した。得られた陽極酸化処理層を参考例１と
同様にして解析したところ、平径ボア径１３０Ｘのボア
が１０００個／μｍ以上確認された。[Grain-5] An aluminum plate grained in the same manner as [Grain-1] was heated in a 30% by weight sulfuric acid bath at a bath temperature of 30C for 6 hours.
Anodic oxidation treatment was performed for 30 seconds using A/dTrL2, thoroughly washed with water, and then air-dried. When the obtained anodized layer was analyzed in the same manner as in Reference Example 1, more than 1000 bores/μm with a flat bore diameter of 130X were confirmed.

〔砂目−６〕 〔砂目−５〕と同様にして、電流密度を４Ａ７６ｙ１　
で他は同一条件にして得られた陽極酸化処理層は平均ボ
ア径８０Ａのボアが１０００個／μｍ以上形成されたこ
とが確認され友。[Grain-6] Same as [Grain-5], change the current density to 4A76y1
It was confirmed that more than 1000 bores/μm with an average bore diameter of 80 A were formed in the anodized layer obtained under the same conditions.

〔砂目−７〕 〔砂目−１〕と同様にして電流密度を９Ａ／ａｉａ２で
他は同一条件にして得られた陽極酸化処理層は平均ボア
径９５０Ｘのボアが１００個／μ雷確認された。[Sand Grain-7] The anodized layer obtained in the same manner as [Sand Grain-1] at a current density of 9A/AIA2 and the other same conditions had 100 bores/μ lightning with an average bore diameter of 950X. It was done.

〔ポリマー１の合成〕 Ｎ−（４−ヒト−キシフェニル）メタクリルアミド１０
，０７７、アクリ四ニトリル２５ＩＩ、エチルアクリレ
−）　６０　、！ｉＪ、メタクリル酸５１ｉ及びアゾビ
スイソブチロニトリル１．６４２　、Ｐを７セトンーメ
タノール１：１混合溶媒１１２−に溶解し、窒素置換し
た後６０Ｃで８時間加熱した。[Synthesis of Polymer 1] N-(4-Huto-xyphenyl) methacrylamide 10
,077, Acrytetranitrile 25II, Ethyl acryle) 60,! iJ, methacrylic acid 51i, azobisisobutyronitrile 1.642, and P were dissolved in a 1:1 mixed solvent of 7cetone and methanol (112-), and the mixture was purged with nitrogen and then heated at 60C for 8 hours.

反応終了後反応液を水５ノ中にかくはん下注ぎ、生じた
白色沈殿をｐ取乾燥してポリマー１を９０Ｉｉ得た。After the reaction was completed, the reaction solution was poured into 50ml of water with stirring, and the resulting white precipitate was removed and dried to obtain 90Ii of Polymer 1.

コノホリマーヲゲルハーミエーションクロマトグラフイ
ー（以下ＧＰＣと略記する）によシ分子量の測定をした
ところ、重量平均分子量は８．５万でめった。When the molecular weight was measured by conophoric gel hermeation chromatography (hereinafter abbreviated as GPC), the weight average molecular weight was found to be 85,000.

〔ポリマー２の合成〕 ２−ヒドロキシエチルメタクリレート４５ｇ、アクリロ
ニトリル１０Ｉ、エチルメタクリレート４５．９、メタ
クリル酸２Ｉｉと１．２Ｉの過酸化ベンゾイルの混合液
を、１００Ｃに加熱したエチレングリコールモノメチル
エーテル５００Ｉに２時間かけて滴下した。滴下終了後
エチレングリコールモノメチルエーテル３００Ｉと過酸
化ベンゾイル０．５Ｉを加えてそのまま４時間反応させ
た。反応終了後メタノールで希釈して水５−ｅ中Ｋかく
はん下注ぎ生じた白色沈殿をＦ取乾燥してポリマー２を
９５１１’４ｆｃ−０このポリマーをｅｐｃによシ分子
量の測定をしたところ、重量平均分子量は６．５万であ
った。[Synthesis of Polymer 2] A mixture of 45 g of 2-hydroxyethyl methacrylate, 10 I of acrylonitrile, 45.9 I of ethyl methacrylate, 2Ii of methacrylic acid, and 1.2 I of benzoyl peroxide was added to 500 I of ethylene glycol monomethyl ether heated to 100 C for 2 hours. It dripped. After the dropwise addition was completed, 300 I of ethylene glycol monomethyl ether and 0.5 I of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After the reaction was completed, it was diluted with methanol and poured into water with stirring. The average molecular weight was 65,000.

〔ポリマー３の合成〕 メタクリル酸メチル６０ｇ、アクリロニトリル３０９、
メタクリル酸１０１／及びアゾビスイソブチロニトリル
１．５ｇをメチルセロソルブ２００Ｉに溶解し、悩素を
通じながらａｏＣにおいて４時間重合させた。この反応
混合物を５１の水中に滴下し、生じた白色沈殿をＦ取乾
燥してポリマー３を７０．ｐ得た。[Synthesis of Polymer 3] Methyl methacrylate 60g, acrylonitrile 309,
Methacrylic acid 101 and 1.5 g of azobisisobutyronitrile were dissolved in methyl cellosolve 200I, and polymerized for 4 hours in aoC while passing through the solution. This reaction mixture was dropped into 70% of water, and the resulting white precipitate was taken and dried to obtain Polymer 3 at 70% of water. I got p.

このポリマーをＧＰＣによル分子量の測定をした所１重
量平均分子量は６万であった。When the molecular weight of this polymer was measured by GPC, the weight average molecular weight was 60,000.

〔ポリマー４の合成〕 メタクリル酸エチル７０，９、アクリロニトリル２０１
１メタクリル酸１０ｇをポリマー３の合成例と同様な方
法で重合させポリマー４を得た。[Synthesis of Polymer 4] Ethyl methacrylate 70,9, acrylonitrile 201
Polymer 4 was obtained by polymerizing 10 g of 1 methacrylic acid in the same manner as in the synthesis example of Polymer 3.

このポリマーをＧＰＯによシ分子量の測定をした所、重
量平均分子量は６．３万であった。When the molecular weight of this polymer was measured by GPO, the weight average molecular weight was 63,000.

〔ジアゾ樹脂−１の合成〕 ｐ−ジアゾジフェニルアミン硫酸塩１４，５．９（５０
ミリモル）を水冷下で４０．９．９の濃硫酸に溶解した
。この反応液に１．２．９　（４０ミリモル）のパラホ
ルムアルデヒドをゆつ＜ｊｌ）ｍ下した。この際、反応
温度が１ＤＣを超えないように添加していった。その後
、２時間氷冷下かく紘んを了けた。[Synthesis of diazo resin-1] p-diazodiphenylamine sulfate 14,5.9 (50
mmol) was dissolved in 40.9.9 mm concentrated sulfuric acid under water cooling. To this reaction solution, 1.2.9 (40 mmol) of paraformaldehyde was added. At this time, the addition was carried out so that the reaction temperature did not exceed 1 DC. Thereafter, the mixture was cooled on ice for 2 hours.

この反応混合物を水冷下、５００−のエタノールに滴下
し、生じた沈殿を濾過した。エタノールで洗浄後、この
沈殿物を１００１の純水に溶解し、この液に６．８ＩＯ
塩化亜鉛を溶解した冷濃厚水溶液を加えた。住じた沈殿
を炉遇した後エタノールで洗浄し、これを１５０−の純
水に溶解した。この液に８１ｉのへキサフルオロリン酸
アンモニウムを溶解した冷濃厚水溶液を加えた。生じた
沈殿を沖取し水洗した後、３０Ｃ１１昼夜乾燥してジア
ゾ樹脂−１を得た。This reaction mixture was added dropwise to 500-ml ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 1001% pure water, and 6.8IO
A cold concentrated aqueous solution of zinc chloride was added. The precipitate was dissolved in a furnace, washed with ethanol, and dissolved in 150-pure water. A cold concentrated aqueous solution of ammonium hexafluorophosphate 81i was added to this liquid. The resulting precipitate was taken off and washed with water, and then dried on 30C11 day and night to obtain diazo resin-1.

このジアゾ樹脂−１をＧＰＯによシ分子量の測定をした
ところ、５量体以上が約５５モル％含まれていた。When the molecular weight of this diazo resin-1 was measured by GPO, it was found that it contained about 55 mol% of pentamers or more.

〔ジアゾ樹脂−２の合成〕 ジアゾ樹脂−１と同様にし合成し、最後のへキサフルオ
ロリン酸アンモニウムの代シに２一ヒド日キシー４−メ
トキシーベンゾフェノン−５−スルホン酸１５．９を溶
解した水溶ｉで処理しジアゾ樹脂−２を得た。[Synthesis of diazo resin-2] Synthesize in the same manner as diazo resin-1, and dissolve 15.9 g of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in place of the final ammonium hexafluorophosphate. Diazo resin-2 was obtained by treatment with water-soluble i.

このジアゾ樹脂−２をＧＰＣによル測定したところ、５
１１体以上が約３２モル％含まれていた。When this diazo resin-2 was measured by GPC, it was found that 5
About 32 mol% of 11 or more bodies was contained.

〔実施例〕〔Example〕

以下、本発明を実施例によシ更に具体的に説明するが、
本発明はこれら実施例に限定されない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

実施例１〜４、比較例１〜３ 上記製造例で得た砂目１〜７に次のような組成を有する
感光液−１をホワラーを用いて塗布した。その後８５Ｃ
の温度で３分間乾燥し感光性平版印刷版を得た。塗布量
は乾燥重量で２．０＃　／　ｍ２であった。Examples 1 to 4, Comparative Examples 1 to 3 Photosensitive liquid 1 having the following composition was applied to grains 1 to 7 obtained in the above production example using a whirler. Then 85C
A photosensitive lithographic printing plate was obtained by drying at a temperature of 3 minutes. The coating amount was 2.0#/m2 in terms of dry weight.

（感光液−１） 得られた感光性平版印刷版を３裂の超高圧水銀灯で６０
ｃｍの距離から３０秒間露光し、現像液−１で現像し、
平版印刷版を得た。(Photosensitive liquid-1) The obtained photosensitive planographic printing plate was heated at 60°C using a 3-fiber ultra-high pressure mercury lamp.
Exposure for 30 seconds from a distance of cm, develop with developer-1,
A lithographic printing plate was obtained.

（現像液−１） 得られた平版印刷版の感度、点大ｂｉｔ、耐刷力、消去
性及び保存安定性を測定した。その結果を表１に示した
。(Developer Solution-1) The sensitivity, dot size, bit, printing durability, erasability, and storage stability of the obtained lithographic printing plate were measured. The results are shown in Table 1.

なお、耐刷力は枚葉オフセット印刷機で上質紙に印刷し
、平網のカスレあるいは着肉不良が起こった枚数を耐刷
力とした。In addition, printing durability was determined by printing on high-quality paper using a sheet-fed offset printing machine, and the number of sheets on which fading of the flat mesh or poor inking occurred was defined as the printing durability.

実施例８、比較例６．７ 砂目−１、−５、−６に以下の感光液−３を塗布した。Example 8, Comparative Example 6.7 The following photosensitive liquid 3 was applied to the grains -1, -5, and -6.

これを露光、現像して、感度と、膜強度を測定した。そ
の結果を表３に示した。塗布量は乾燥重量で１．５１１
　／　ｍ２でめった。This was exposed and developed, and the sensitivity and film strength were measured. The results are shown in Table 3. Application amount is 1.511 in dry weight
/ m2 was rare.

（感光液−３） 表３ ％％膜強度：露光後、現像液−１に１０分間浸漬し、摩
耗布で強こすシしてヤラ レ具合を観察して評価 表３から、本発明の印刷成鉱、膜強度が極めて優れてい
ることがわかる。(Photosensitive solution-3) Table 3 %% Film strength: After exposure, it was immersed in developer-1 for 10 minutes, rubbed vigorously with an abrasion cloth, and observed the degree of wear. From Table 3, the printing composition of the present invention was evaluated. It can be seen that the mineral and film strength are extremely excellent.

〔発明の効果〕〔Effect of the invention〕

以上詳細に説明したように、本発明の感光性平版印刷版
は、画像再現性が向上し、高耐刷力で、保存安定性及び
消去性が良好であシ、しかも地汚れが発生しないという
優れた効果を奏するものである。As explained in detail above, the photosensitive lithographic printing plate of the present invention has improved image reproducibility, high printing durability, good storage stability and erasability, and does not cause scumming. It has excellent effects.

Claims (1)

【特許請求の範囲】 １、リン酸又はリン酸を主成分とする電解液中で陽極酸
化処理して得られる平均ボア径が２００〜９００Åでボ
ア密度が１００〜１０００個／μｍ＾２の陽極酸化層を
有するアルミニウム板上に、水酸基を有する親油性高分
子化合物とジアゾ樹脂を含有する感光層を設けたもので
あることを特徴とする感光性平版印刷版。 ２、該高分子化合物が、水酸基を有するアクリルアミド
類、メタクリルアミド類、アクリル酸エステル類及びメ
タクリル酸エステル類よりなる群から選択した単量体か
ら誘導される構成単位を含有する高分子化合物である特
許請求の範囲第１項記載の感光性平版印刷版。 ３、該ジアゾ樹脂が、置換又は非置換のｐ−ジアゾジフ
ェニルアミンとアルデヒド類との縮合物であつて、アニ
オンがＰＦ＿６又はＢＦ＿４である特許請求の範囲第１
項記載の感光性平版印刷版。 ４、該ジアゾ樹脂が、下記一般式 I ： ▲数式、化学式、表等があります▼・・・・・・〔 I
〕 （式中、Ｒ＾１、Ｒ＾２及びＲ＾３は水素原子、アルキ
ル基又はアルコキシ基を示し、Ｒは水素原子、アルキル
基又はフェニル基を示し、ＸはＰＦ＿６又はＢＦ＿４を
示し、ｎは１〜２００の数を示す）で表され、かつ該式
におけるｎが５以上の樹脂を２０モル％以上含有するも
のである特許請求の範囲第１項記載の感光性平版印刷版
。 ５、該陽極酸化層の平均ボア径が３００〜９００Åであ
り、ボア密度が１００〜５００個／μｍ＾２である特許
請求の範囲第１項記載の感光性平版印刷版。[Claims] 1. An anode having an average bore diameter of 200 to 900 Å and a bore density of 100 to 1000/μm^2 obtained by anodizing in phosphoric acid or an electrolyte containing phosphoric acid as a main component. 1. A photosensitive lithographic printing plate, characterized in that a photosensitive layer containing a lipophilic polymer compound having a hydroxyl group and a diazo resin is provided on an aluminum plate having an oxidized layer. 2. The polymer compound is a polymer compound containing a structural unit derived from a monomer selected from the group consisting of hydroxyl group-containing acrylamides, methacrylamides, acrylic esters, and methacrylic esters. A photosensitive lithographic printing plate according to claim 1. 3. Claim 1, wherein the diazo resin is a condensate of substituted or unsubstituted p-diazodiphenylamine and aldehydes, and the anion is PF_6 or BF_4.
The photosensitive lithographic printing plate described in Section 1. 4. The diazo resin has the following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
] (In the formula, R^1, R^2 and R^3 represent a hydrogen atom, an alkyl group or an alkoxy group, R represents a hydrogen atom, an alkyl group or a phenyl group, X represents PF_6 or BF_4, n represents a number from 1 to 200), and contains 20 mol% or more of a resin in which n in the formula is 5 or more. 5. The photosensitive lithographic printing plate according to claim 1, wherein the anodized layer has an average bore diameter of 300 to 900 Å and a bore density of 100 to 500/μm^2.
JP59237583A 1984-11-13 1984-11-13 Photosensitive lithographic printing plate Expired - Lifetime JPH06103390B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59237583A JPH06103390B2 (en) 1984-11-13 1984-11-13 Photosensitive lithographic printing plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59237583A JPH06103390B2 (en) 1984-11-13 1984-11-13 Photosensitive lithographic printing plate

Publications (2)

Publication Number Publication Date
JPS61117548A true JPS61117548A (en) 1986-06-04
JPH06103390B2 JPH06103390B2 (en) 1994-12-14

Family

ID=17017467

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59237583A Expired - Lifetime JPH06103390B2 (en) 1984-11-13 1984-11-13 Photosensitive lithographic printing plate

Country Status (1)

Country Link
JP (1) JPH06103390B2 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5517580A (en) * 1978-07-26 1980-02-07 Mitsubishi Chem Ind Ltd Preparation of supporter for printing plate
JPS56121031A (en) * 1980-02-28 1981-09-22 Konishiroku Photo Ind Co Ltd Photosensitive composition
JPS58153698A (en) * 1982-02-23 1983-09-12 ヘキスト・アクチエンゲゼルシヤフト Manufacture of supporter material for offset printing plate
JPS5997136A (en) * 1982-11-26 1984-06-04 Fuji Photo Film Co Ltd Photosensitive composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5517580A (en) * 1978-07-26 1980-02-07 Mitsubishi Chem Ind Ltd Preparation of supporter for printing plate
JPS56121031A (en) * 1980-02-28 1981-09-22 Konishiroku Photo Ind Co Ltd Photosensitive composition
JPS58153698A (en) * 1982-02-23 1983-09-12 ヘキスト・アクチエンゲゼルシヤフト Manufacture of supporter material for offset printing plate
JPS5997136A (en) * 1982-11-26 1984-06-04 Fuji Photo Film Co Ltd Photosensitive composition

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