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JPH0363739B2 - - Google Patents

Info

Publication number
JPH0363739B2
JPH0363739B2 JP57212617A JP21261782A JPH0363739B2 JP H0363739 B2 JPH0363739 B2 JP H0363739B2 JP 57212617 A JP57212617 A JP 57212617A JP 21261782 A JP21261782 A JP 21261782A JP H0363739 B2 JPH0363739 B2 JP H0363739B2
Authority
JP
Japan
Prior art keywords
photosensitive resin
polyvinyl acetate
polymerization
photosensitive
partially saponified
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 - Lifetime
Application number
JP57212617A
Other languages
Japanese (ja)
Other versions
JPS59102228A (en
Inventor
Junichi Fujikawa
Shigetora Kashio
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.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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 Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP21261782A priority Critical patent/JPS59102228A/en
Publication of JPS59102228A publication Critical patent/JPS59102228A/en
Publication of JPH0363739B2 publication Critical patent/JPH0363739B2/ja
Granted legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G03F7/0955Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer one of the photosensitive systems comprising a non-macromolecular photopolymerisable compound having carbon-to-carbon double bonds, e.g. ethylenic compounds

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Description

【発明の詳細な説明】 本発明はすぐれた水現像性と画像再現性を有す
る部分ケン化ポリ酢酸ビニル系感光性樹脂版材に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a partially saponified polyvinyl acetate photosensitive resin plate material having excellent water developability and image reproducibility.

従来から可溶性ポリマと光重合性不飽和化合物
および必要に応じて光開始剤からなる光によつて
不溶化する感光性樹脂組成物は、凸版材、平版
材、凹版材、孔版材などの印刷版材、フオトレジ
スト、感光性塗料、デイスプレイ、画像形成材料
などに用いられている。これらの内でたとえば凸
版印刷用版材は感光性樹脂組成物の層と支持体か
らなる原板の感光層に透明部分を有するネガテイ
ブまたはポジテイブフイルムを通して露光を行な
い、露光部分の感光性樹脂組成物に光重合を起さ
せて不溶化した後に、支持体上にレリーフ像を得
るものである。最近、可溶性ポリマとして部分ケ
ン化ポリ酢酸ビニルを使用し、中性水で現像可能
な感光性樹脂版材が開発されている(たとえば特
公昭52−27561号公報)。
Conventionally, photosensitive resin compositions that are insolubilized by light, which are composed of a soluble polymer, a photopolymerizable unsaturated compound, and, if necessary, a photoinitiator, are used in printing plate materials such as letterpress materials, lithographic materials, intaglio materials, and stencil materials. It is used in photoresists, photosensitive paints, displays, image forming materials, etc. Among these, for example, in the case of a letterpress printing plate material, the photosensitive layer of an original plate consisting of a layer of a photosensitive resin composition and a support is exposed to light through a negative or positive film having a transparent part, and the photosensitive resin composition in the exposed part is exposed to light. A relief image is obtained on a support after photopolymerization and insolubilization. Recently, a photosensitive resin plate material that uses partially saponified polyvinyl acetate as a soluble polymer and can be developed with neutral water has been developed (for example, Japanese Patent Publication No. 52-27561).

部分ケン化ポリ酢酸ビニルの水溶解速度は、重
合度に対する依存性が大であるために、良好な水
現像性を得るためには、重合度200〜1000の範囲
にある比較的低重合度のポリマを使用しなければ
ならない。重合度が1000を越えるものは、水溶解
性の低下が顕著であるために、未露光部分を水中
に溶出除去する現像工程に要する時間が長くなる
欠点が著しい。重合度が200〜1000の範囲にある
部分ケン化ポリ酢酸ビニルを使用した場合には、
上記のように良好な水現像性は有するが、ブラシ
式洗い出し機を使用する場合には、ブラシによる
外力を最も強く受ける感光層表面にある光重合部
分の一部が水中に溶出したり、ブラシの外力で欠
落したりする問題がある。このような点から、部
分ケン化ポリ酢酸ビニル系の感光性版材は一般に
使用されているブラシ式洗い出し機に対する適性
に欠けているのが普通であつた。
The water dissolution rate of partially saponified polyvinyl acetate is highly dependent on the degree of polymerization, so in order to obtain good water developability, it is necessary to use a relatively low degree of polymerization in the range of 200 to 1000. Polymer must be used. When the degree of polymerization exceeds 1000, the water solubility is significantly lowered, so that the disadvantage is that the time required for the development process in which the unexposed areas are eluted and removed in water becomes longer. When using partially saponified polyvinyl acetate with a degree of polymerization in the range of 200 to 1000,
Although it has good water developability as described above, when using a brush-type washing machine, some of the photopolymerized parts on the surface of the photosensitive layer, which is subjected to the strongest external force from the brush, may be eluted into the water or There is a problem that it may be damaged due to external force. From this point of view, partially saponified polyvinyl acetate-based photosensitive printing materials have generally lacked suitability for commonly used brush-type washing machines.

本発明者らは、良好な水現像性を保持して、か
つブラシ洗い出し機での現像時にも良好な画像再
現性を有する部分ケン化ポリ酢酸ビニル系感光性
樹脂版材について鋭意検討した結果、本発明に到
達した。
As a result of intensive studies by the present inventors on a partially saponified polyvinyl acetate-based photosensitive resin plate material that maintains good water developability and has good image reproducibility even when developed with a brush washing machine, the present inventors have found that: We have arrived at the present invention.

即ち、本発明は、支持体上に感光性樹脂組成物
からなる下層と感光性樹脂組成物からなる上層を
この順に積層形成した感光性樹脂版材であつて、
該下層の感光性組成物が次の(1)〜(3)成分 (1) ケン化度60〜99モル%、平均重合度200〜
1000の部分ケン化ポリ酢酸ビニル (2) エチレン性不飽和モノマ (3) 光開始剤 から主としてなり、前記上層の感光性組成物が次
の(1)〜(3)成分 (1) ケン化度60〜99モル%、平均重合度が前記下
層の部分ケン化ポリ酢酸ビニルの平均重合度の
1.25〜10.0倍の範囲である部分ケン化ポリ酢酸
ビニル (2) エチレン性不飽和モノマ (3) 光開始剤 から主としてなることを特徴とする感光性樹脂版
材に関するものである。
That is, the present invention provides a photosensitive resin plate material in which a lower layer made of a photosensitive resin composition and an upper layer made of a photosensitive resin composition are laminated in this order on a support,
The photosensitive composition of the lower layer has the following components (1) to (3): saponification degree of 60 to 99 mol%, average polymerization degree of 200 to
1000 partially saponified polyvinyl acetate (2) an ethylenically unsaturated monomer (3) a photoinitiator, and the photosensitive composition of the upper layer has the following components (1) to (3): (1) degree of saponification; 60 to 99 mol%, the average degree of polymerization is that of the partially saponified polyvinyl acetate in the lower layer.
The present invention relates to a photosensitive resin plate material mainly comprising partially saponified polyvinyl acetate (2), an ethylenically unsaturated monomer (3) and a photoinitiator in a range of 1.25 to 10.0 times.

本発明の感光性樹脂組成物は、上下層ともケン
化度60〜99モル%の部分ケン化ポリ酢酸ビニルを
基体樹脂とするものでなければならない。ケン化
度が60モル%未満であると水溶性が著しく低下
し、ケン化度100モル%の完全ケン化ポリ酢酸ビ
ニルも常温水に対する溶解性に乏しいので水現像
性を得るためにはケン化度は60〜99モル%の範囲
にあることが必要であり、好ましくは70〜90モル
%である。
The photosensitive resin composition of the present invention must contain partially saponified polyvinyl acetate having a degree of saponification of 60 to 99 mol% as a base resin for both the upper and lower layers. If the degree of saponification is less than 60 mol%, the water solubility will decrease significantly, and even fully saponified polyvinyl acetate with a saponification degree of 100 mol% has poor solubility in water at room temperature, so saponification is necessary to obtain water developability. The degree needs to be in the range of 60 to 99 mol%, preferably 70 to 90 mol%.

支持体に接する下層に使用する部分ケン化ポリ
酢酸ビニルは、ブラシ洗い出し機で現像する際に
強く外力を受ける感光層表面部分を形成しないの
で良好な現像性を持つことを主体に選択される。
このような部分ケン化ポリ酢酸ビニルは平均重合
度200〜1000のものである。平均重合度が200未満
であると、光重合部分の耐水性が余りにも劣るた
めに、現像時に光重合部の一部分が水中に溶出す
る問題の発生することが多い。逆に、平均重合度
が1000を越えると急激に水溶解性が低下する。以
上のことから、下層の部分ケン化ポリ酢酸ビニル
の平均重合度は200〜1000の範囲にあることが必
要であり、好ましくは300〜800である。
The partially saponified polyvinyl acetate used in the lower layer in contact with the support is mainly selected so as to have good developability since it does not form a surface portion of the photosensitive layer that is subjected to strong external force during development with a brush washing machine.
Such partially saponified polyvinyl acetate has an average degree of polymerization of 200 to 1,000. When the average degree of polymerization is less than 200, the water resistance of the photopolymerized portion is so poor that a portion of the photopolymerized portion often dissolves into water during development. Conversely, when the average degree of polymerization exceeds 1000, the water solubility decreases rapidly. From the above, it is necessary that the average degree of polymerization of the partially saponified polyvinyl acetate of the lower layer is in the range of 200 to 1000, preferably 300 to 800.

上層に使用する部分ケン化ポリ酢酸ビニルは、
現像時にブラシ等で強く外力を受ける感光性表面
を形成するので下層よりも平均重合度の高いもの
を使用する必要がある。平均重合度が下層の部分
ケン化酢酸ビニルの平均重合度の1.25倍未満であ
ると感光層を2層にする効果が認められない。逆
に、10.0倍をこえると上層部分を水中に溶出する
ために必要とされる時間が非常に長くなるため
に、全体の感光性版材の現像時間に対する影響を
無視することができなくなる。以上の理由から上
層に使用する部分ケン化ポリ酢酸ビニルの平均重
合度は下層に使用する部分ケン化ポリ酢酸ビニル
の平均重合度の1.25〜10.0倍の範囲にあることが
必要であり、好ましくは1.5〜6.0倍である。
The partially saponified polyvinyl acetate used for the upper layer is
Since it forms a photosensitive surface that is strongly subjected to external force by a brush or the like during development, it is necessary to use a material with a higher average degree of polymerization than the lower layer. If the average degree of polymerization is less than 1.25 times the average degree of polymerization of the partially saponified vinyl acetate in the lower layer, the effect of forming two photosensitive layers will not be recognized. On the other hand, if it exceeds 10.0 times, the time required to dissolve the upper layer into water becomes so long that the influence on the development time of the entire photosensitive plate material cannot be ignored. For the above reasons, the average degree of polymerization of the partially saponified polyvinyl acetate used in the upper layer needs to be in the range of 1.25 to 10.0 times the average degree of polymerization of the partially saponified polyvinyl acetate used in the lower layer. It is 1.5 to 6.0 times.

上下層に使用する部分ケン化ポリ酢酸ビニルは
同一ケン化度のものが好ましいが、ケン化度の異
なるものを使用することも可能である。また、部
分ケン化ポリ酢酸ビニルの末端にあるカルボキシ
ル基にグリシジルメタクリレートを反応させて不
飽和基を導入したものや、部分ケン化ポリ酢酸ビ
ニルのもつ水酸基の1部に不飽和基をもつ化合物
を反応させて不飽和基を導入したものや、水酸基
にエチレンオキサイドなどを付加させて変性した
ものも残存する水酸基から決定されるケン化度が
60〜99モル%の範囲内にあれば使用可能である。
It is preferable that the partially saponified polyvinyl acetate used in the upper and lower layers have the same saponification degree, but it is also possible to use polyvinyl acetate having different saponification degrees. In addition, we have introduced unsaturated groups into partially saponified polyvinyl acetate by reacting glycidyl methacrylate with the carboxyl groups at the terminals, and compounds that have unsaturated groups in some of the hydroxyl groups of partially saponified polyvinyl acetate. The degree of saponification determined from the remaining hydroxyl groups of those that have been reacted to introduce unsaturated groups or those that have been modified by adding ethylene oxide etc. to the hydroxyl groups is
It can be used if it is within the range of 60 to 99 mol%.

上下層の部分ケン化ポリ酢酸ビニルに、ポリエ
チレンオキサイドやメチルセルロースなどのセル
ロース誘導体、およびα−(N,N′−ジメチルア
ミノ)−ε−カプロラクタムの開環重合体やα−
(N,N′−ジメチルアミノ)−ε−カプロラクタ
ムとε−カプロラクタムの開環共重合体などの他
の水溶性ポリマを部分ケン化ポリ酢酸ビニルの20
重量%以下の少量混合して併用することも可能で
ある。
The upper and lower layers of partially saponified polyvinyl acetate are coated with cellulose derivatives such as polyethylene oxide and methylcellulose, and ring-opening polymers of α-(N,N'-dimethylamino)-ε-caprolactam and α-
(N,N'-dimethylamino)-ε-caprolactam and other water-soluble polymers such as ring-opened copolymers of ε-caprolactam are partially saponified with polyvinyl acetate.
It is also possible to mix and use a small amount of less than % by weight.

上下層の感光性樹脂組成物に使用される光重合
性の不飽和モノマとしては全てのものが使用でき
るが、具体的には次のようなものが挙げられる。
2−ヒドロキシエチル(メタ)アクリレート、2
−ヒドロキシプロピル(メタ)アクリレート、3
−クロロ−2−ヒドロキシプロピル(メタ)アク
リレートなどの水酸基をもつ単官能ビニルモノ
マ、エチレンゴリコールジグリシジルエーテルな
どの2〜5価のグリシジルエーテルと(メタ)ア
クリル酸の付加反応によつて得られる2〜5個の
水酸基および同数の(メタ)アクリロイル基を有
する多官能ビニルモノマ、グリシジル(メタ)ア
クリレートと(メタ)アクリル酸などの不飽和カ
ルボン酸の付加反応物、グリシジル(メタ)アク
リレートとリンゴ酸などの2〜6価の飽和カルボ
ン酸の付加反応物、グリシジル(メタ)アクリレ
ートとキシリレンジアミンなどの1級また2級ア
ミンとの付加反応物などの分子中に水酸基と2〜
6個の不飽和結合をもつ多官能ビニルモノマ、ア
クリルアミド、メチレンビスアクリルアミドなど
のアクリルアミド類などである。
All photopolymerizable unsaturated monomers can be used in the photosensitive resin compositions of the upper and lower layers, and specific examples include the following.
2-hydroxyethyl (meth)acrylate, 2
-Hydroxypropyl (meth)acrylate, 3
2 obtained by the addition reaction of a monofunctional vinyl monomer having a hydroxyl group such as -chloro-2-hydroxypropyl (meth)acrylate, a di- to pentavalent glycidyl ether such as ethylene golicol diglycidyl ether, and (meth)acrylic acid. Polyfunctional vinyl monomers having ~5 hydroxyl groups and the same number of (meth)acryloyl groups, addition reaction products of glycidyl (meth)acrylate and unsaturated carboxylic acids such as (meth)acrylic acid, glycidyl (meth)acrylate and malic acid, etc. Addition reaction products of di- to hexavalent saturated carboxylic acids, addition reaction products of glycidyl (meth)acrylate and primary or secondary amines such as xylylene diamine, etc.
These include polyfunctional vinyl monomers having six unsaturated bonds, acrylamides, and acrylamides such as methylenebisacrylamide.

部分ケン化ポリ酢酸ビニルとこれらの光重合性
不飽和モノマの相溶性を改良するために、エチレ
ングリコール、ジエチレングリコール、グリセリ
ン、ジグリセリン、トリメチロールプロパン、ト
リメチロールエタン、分子量200〜1000のポリエ
チレングリコール、分子量200〜600のポリプロピ
レングリコールなどの水酸基を有する飽和化合物
を添加することもできる。
In order to improve the compatibility of partially saponified polyvinyl acetate with these photopolymerizable unsaturated monomers, ethylene glycol, diethylene glycol, glycerin, diglycerin, trimethylolpropane, trimethylolethane, polyethylene glycol with a molecular weight of 200 to 1000, A saturated compound having a hydroxyl group such as polypropylene glycol having a molecular weight of 200 to 600 can also be added.

本発明の感光性樹脂の光重合を速かに行わせる
ために、公知の光開始剤は全て使用することがで
きる。このような光開始剤としては、ベンゾフエ
ノン類、ベンジル類、ベンゾイル類、アセトンフ
エノン類、ジアセチル類などが挙げられる。
All known photoinitiators can be used to rapidly photopolymerize the photosensitive resin of the present invention. Such photoinitiators include benzophenones, benzyls, benzoyls, acetonephenones, diacetyls, and the like.

本発明の感光性樹脂の熱安定性を改良するため
の熱安定剤としては、公知のものが全て使用可能
である。このようなものとしては、トリフエニル
フオスインのようなリン化合物、ハイドロキノン
やハイドロキノンモノメチルエーテル、t−ブチ
ルカテコールなどの熱重合禁止剤などが挙げられ
る。この他に、染料、顔料、紫外線吸収剤、消泡
剤、界面活性剤等の微量成分を添加することもで
きる。
All known thermal stabilizers can be used to improve the thermal stability of the photosensitive resin of the present invention. Examples of such substances include phosphorus compounds such as triphenylphosin, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and t-butylcatechol. In addition, trace components such as dyes, pigments, ultraviolet absorbers, antifoaming agents, and surfactants may also be added.

本発明の上下層の感光性樹脂層において、光重
合性不飽和モノマや光開始剤、熱安定剤などとし
て別々のものを使用することも可能であるが、長
期的には上下層の基体ポリマ以外の組成は均一化
する傾向にあるので余り得策ではない。むしろ、
上下層の基体ポリマ以外の組成は同一または近似
したものとする方が品質の安定性の点で良好であ
る。
Although it is possible to use separate photopolymerizable unsaturated monomers, photoinitiators, heat stabilizers, etc. in the upper and lower photosensitive resin layers of the present invention, in the long term, the base polymers of the upper and lower layers Other compositions tend to be uniform and are not a good idea. Rather,
It is better from the viewpoint of quality stability that the compositions of the upper and lower layers other than the base polymer are the same or similar.

本発明は、現像中にブラシなどからの外力を最
も強く受ける感光層の表面に近い部分を形成する
上層に平均重合度の高い強靭な部分ケン化ポリ酢
酸ビニルを基体ポリマとする感光性樹脂組成物を
使用することによつて現像中に微細な光重合部分
が水中に溶出したり、欠落することを防止するも
のである。平均重合度の高い部分ケン化ポリ酢酸
ビニルを全感光層に使用すると現像時間が著しく
長くなるが、この点を防止するために下層の感光
層には、平均重合度200〜1000の良好な水溶性を
もつ部分ケン化ポリ酢酸ビニルを基体ポリマとす
る感光性樹脂層を使用することによつて、このよ
うな問題点を解決するものである。現像時間をあ
まり長くしないためには、上層は比較的薄くし、
下層を厚くする方が有利である。このような点か
ら、感光層の全厚のうち1/2以上は下層が占める
必要がある。好ましい層の厚さは下層が0.1〜1
mm、好ましくは0.02〜0.5mmである。
The present invention uses a photosensitive resin composition in which the base polymer is a tough partially saponified polyvinyl acetate with a high average degree of polymerization in the upper layer, which forms the part closest to the surface of the photosensitive layer that receives the strongest external force from a brush or the like during development. This prevents fine photopolymerized portions from being eluted into water or missing during development. If partially saponified polyvinyl acetate, which has a high average degree of polymerization, is used in all photosensitive layers, the development time will be significantly longer, but in order to prevent this, the lower photosensitive layer is made of a material with good water solubility and an average degree of polymerization of 200 to 1000. These problems can be solved by using a photosensitive resin layer whose base polymer is partially saponified polyvinyl acetate having the properties of polyvinyl acetate. In order not to make the development time too long, the upper layer should be relatively thin.
It is advantageous to make the lower layer thicker. From this point of view, it is necessary that the lower layer occupies 1/2 or more of the total thickness of the photosensitive layer. The preferred layer thickness is 0.1 to 1 for the lower layer.
mm, preferably 0.02 to 0.5 mm.

本発明に用いられる支持体としては、スチー
ル、アルミニウム、銅、亜鉛などの金属素材、ポ
リエステル、ポリプロピレン、ポリ塩化ビニルな
どの合成樹脂素材が挙げられ、形状としては板状
のもの以外に、円筒状のものも使用される。金属
素材はそのまま使用することもできるが、リン酸
処理、クロメート処理、エツチング処理、砂目立
処理を行つたものや、亜鉛メツキ、クロムメツキ
などのメツキを行つたものも使用できる。また防
錆のためにエポキシ系塗料などを塗布キユアした
ものも可能である。さらに、感光性樹脂層との接
着性を良くするために、部分ケン化ポリ酢酸ビニ
ルとフエノール樹脂およびエポキシ樹脂から成る
接着剤や、部分ケン化ポリ酢酸ビニルと光重合性
モノマから成る層を塗布後、全面光硬化した接着
層などを設けたものも使用可能である。
Examples of the support used in the present invention include metal materials such as steel, aluminum, copper, and zinc, and synthetic resin materials such as polyester, polypropylene, and polyvinyl chloride. are also used. Metal materials can be used as they are, but metal materials that have been subjected to phosphoric acid treatment, chromate treatment, etching treatment, grain treatment, or plating such as zinc plating or chrome plating can also be used. It is also possible to apply and cure epoxy paint to prevent rust. Furthermore, in order to improve the adhesion with the photosensitive resin layer, an adhesive made of partially saponified polyvinyl acetate, a phenol resin, and an epoxy resin, or a layer made of partially saponified polyvinyl acetate and a photopolymerizable monomer is applied. It is also possible to use an adhesive layer which is then photo-cured over the entire surface.

本発明に使用する感光性樹脂組成物の通常の製
造は、下層用組成物として平均重合度200〜1000
の部分ケン化ポリ酢酸ビニルを水または水/アル
コールの混合溶媒に加熱溶解した後に、光重合性
不飽和モノマや光開始剤、場合によつては水酸基
をもつ飽和化合物や熱安定剤を添加して十分に撹
拌し混合する。このようにして、下層用の感光性
樹脂溶液が得られる。上層用組成物は、部分ケン
化ポリ酢酸ビニルとして平均重合度が下層の部分
ケン化ポリ酢酸ビニルとして平均重合度が下層の
部分ケン化ポリ酢酸ビニルの1.25〜10.0倍の範囲
にあるものを使用する以外は同様の手法で上層用
感光性樹脂溶液が得られる。
In the usual production of the photosensitive resin composition used in the present invention, the average degree of polymerization is 200 to 1000 as the composition for the lower layer.
After heating and dissolving the partially saponified polyvinyl acetate in water or a mixed solvent of water/alcohol, a photopolymerizable unsaturated monomer, a photoinitiator, and in some cases a saturated compound with a hydroxyl group or a heat stabilizer are added. Stir thoroughly to mix. In this way, a photosensitive resin solution for the lower layer is obtained. The composition for the upper layer is a partially saponified polyvinyl acetate whose average degree of polymerization is in the range of 1.25 to 10.0 times that of the partially saponified polyvinyl acetate of the lower layer. A photosensitive resin solution for the upper layer can be obtained in the same manner except for the following steps.

上記の感光性樹脂溶液から、本発明の積層構造
をもつ感光性樹脂版材を得るには、下記のような
方法をとることができる。例えば、支持体上に下
層用樹脂溶液を所定厚さに流延した後に、乾燥装
置で溶剤を除去し、次いでこの上に上層用樹脂溶
液で所定厚さに流延した後に乾燥装置で溶剤を除
去する方法。また、乾式製膜法で下層用の感光層
シートを得た後に、このシートを支持体にラミネ
ートし、次いで上層用樹脂溶液を薄くこの上に塗
布しつつポリエステルフイルムなどのカバーフイ
ルムをかぶせ、上層用樹脂溶液の溶媒が下層シー
トに拡散することによつて、上層の感光層を形成
する方法もある。下層用樹脂溶液の全部または大
部分の溶媒を真空で留去した後に、基板上に直接
溶融製膜した後に、上層用組成物を同様にしてこ
の上に溶融状態で流延する方法も可能である。
The following method can be used to obtain the photosensitive resin plate material having the laminated structure of the present invention from the above photosensitive resin solution. For example, after a resin solution for the lower layer is cast onto a support to a predetermined thickness, the solvent is removed using a drying device, and then a resin solution for the upper layer is cast onto the support to a predetermined thickness, and then the solvent is removed using a dryer. How to remove. In addition, after obtaining a photosensitive layer sheet for the lower layer using a dry film forming method, this sheet is laminated onto a support, and then a resin solution for the upper layer is applied thinly thereon and a cover film such as a polyester film is placed over the upper layer. There is also a method in which the upper photosensitive layer is formed by diffusing the solvent of the resin solution into the lower layer sheet. It is also possible to distill off all or most of the solvent in the resin solution for the lower layer in a vacuum, form a film by melting it directly on the substrate, and then similarly cast the composition for the upper layer thereon in a molten state. be.

このようにして得られた感光性樹脂版材の上層
の表面にネガテイブまたはポジテイブの原図フイ
ルムを密着させ、原図フイルムを通して超高圧水
銀灯、高圧水銀灯、メタルハライドランプ、キセ
ノンランプ、カーボンアーク灯、ケミカル灯など
からの活性光線を照射し、感光層の露光部分に光
重合を起こさせる。その後、中性水を入れたブラ
シ式洗い出し機またはスプレ式洗い出し機で未露
光部分を水中に溶解除去すると支持体上にレリー
フ像が得られる。
A negative or positive original image film is closely attached to the upper layer surface of the photosensitive resin plate material obtained in this way, and an ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, chemical lamp, etc. The photosensitive layer is irradiated with actinic light to cause photopolymerization in the exposed areas of the photosensitive layer. Thereafter, the unexposed areas are dissolved and removed in water using a brush type washing machine or a spray type washing machine containing neutral water to obtain a relief image on the support.

本発明の積層構造を有する感光性樹脂版材は凸
版材として使用されるときに最もその効果を発揮
するが、平版材、凹版材、孔版材、フオトレジス
トとして使用することも可能である。
The photosensitive resin plate material having a laminated structure of the present invention exhibits its effects most when used as a letterpress material, but it can also be used as a planographic material, an intaglio material, a stencil material, and a photoresist.

以下に実施例で本発明をさらに具体的に説明す
る。
The present invention will be explained in more detail below using Examples.

実施例 1 下層用の感光性樹脂組成物の基体ポリマとして
ケン化度82モル%、平均重合度600の部分ケン化
ポリ酢酸ビニルを選んだ。この部分ケン化ポリ酢
酸ビニル100重量部をエタノール/水=50/50(重
量比)混合溶剤150重量部に80℃で溶解した。次
いで、光重合性不飽和モノマとしてプロピレング
リコールジグリシジルエーテルとアクリル酸の付
加反応物を70重量部、相溶助剤としてジエチレン
グリコールを28重量部、光開始剤としてジメチル
ベンジルケタール2重量部、熱重合禁止剤として
ハイドロキノンモノメチルエーテルを0.1重量部
添加して十分に撹拌混合した。このようにして下
層用の感光性樹脂溶液を得た。
Example 1 Partially saponified polyvinyl acetate having a degree of saponification of 82 mol% and an average degree of polymerization of 600 was selected as the base polymer of the photosensitive resin composition for the lower layer. 100 parts by weight of this partially saponified polyvinyl acetate was dissolved in 150 parts by weight of a mixed solvent of ethanol/water = 50/50 (weight ratio) at 80°C. Next, 70 parts by weight of an addition reaction product of propylene glycol diglycidyl ether and acrylic acid as a photopolymerizable unsaturated monomer, 28 parts by weight of diethylene glycol as a compatibility aid, 2 parts by weight of dimethylbenzyl ketal as a photoinitiator, and thermal polymerization. 0.1 part by weight of hydroquinone monomethyl ether was added as an inhibitor and thoroughly stirred and mixed. In this way, a photosensitive resin solution for the lower layer was obtained.

上層用の感光性樹脂組成物の基体ポリマとして
ケン化度82モル%、平均重合度1800のものを選ん
だ。このポリマ100重量部をエタノール/水=
50/50(重量比)の混合溶剤250重量部に80℃で溶
解した。次いで、光重合性モノマとして下層と同
じものを70重量部、ジエチレングリコール28重量
部、光開始剤としてジメチルベンジルケタール2
重量部、熱安定剤としてハイドロキノンモノメチ
ルエーテル0.1重量部を添加して十分に撹拌混合
して上層用感光性樹脂溶液を得た。
As the base polymer of the photosensitive resin composition for the upper layer, one having a degree of saponification of 82 mol% and an average degree of polymerization of 1800 was selected. Add 100 parts by weight of this polymer to ethanol/water =
It was dissolved in 250 parts by weight of a 50/50 (weight ratio) mixed solvent at 80°C. Next, 70 parts by weight of the same material as in the lower layer was used as a photopolymerizable monomer, 28 parts by weight of diethylene glycol, and 2 parts by weight of dimethylbenzyl ketal as a photoinitiator.
parts by weight, and 0.1 part by weight of hydroquinone monomethyl ether as a heat stabilizer were added and thoroughly stirred and mixed to obtain a photosensitive resin solution for the upper layer.

このようにして得た下層用の感光性樹脂溶液を
あらかじめエポキシ系接着剤を塗布してある厚さ
250μのスチール基板上に感光層の厚さが600μに
なるように流延した後に60℃のオーブンに3時間
入れて溶媒を除去した。この基板で裏打ちされた
下層の上に、乾燥後の厚さが100μとなるように
先に得られた上層用の感光性樹脂溶液を流延し、
60℃のオーブンに1時間入れて乾燥した。このよ
うにして、基板を含む全厚が950μの2層感光層
を有する版材が得られた。
The photosensitive resin solution for the lower layer obtained in this way is coated with epoxy adhesive in advance.
The photosensitive layer was cast onto a 250μ steel substrate to a thickness of 600μ, and then placed in an oven at 60°C for 3 hours to remove the solvent. On the lower layer lined with this substrate, the photosensitive resin solution for the upper layer obtained earlier is cast so that the thickness after drying is 100μ,
It was dried by placing it in an oven at 60°C for 1 hour. In this way, a plate material having two photosensitive layers having a total thickness of 950 μm including the substrate was obtained.

この版材の感光層上にテスト用ネガフイルム
(133線3%、5%、10%網点、直径200μ、300μ
独立点、線幅50μ、70μの細線部あり)を真空密
着して、高圧水銀灯で2分間露光した。次いで、
中性水を入つたブラシ式洗い出し機(水温30℃)
で2分間で未露光部を完全に溶解除去してレリー
フ像を得た。
Test negative film (133 line 3%, 5%, 10% halftone dots, diameter 200μ, 300μ) was placed on the photosensitive layer of this plate material.
The independent points (with thin line parts with line widths of 50μ and 70μ) were vacuum-adhered and exposed for 2 minutes using a high-pressure mercury lamp. Then,
Brush type washing machine with neutral water (water temperature 30℃)
The unexposed area was completely dissolved and removed in 2 minutes to obtain a relief image.

得られたレリーフは非常にシヤープであり、3
%網点、200μ独立点、50μ細線など微細な部分ま
で完全に再現していることを確認した。
The relief obtained is very sharp and 3
It was confirmed that even minute details such as % halftone dots, 200μ independent points, and 50μ fine lines were completely reproduced.

比較例 1 実施例1で得られた下層用感光性樹脂組成物を
実施例1と同じ基板上に感光層の厚さが700μと
なるように流延し、60℃のオーブンに4時間入れ
て乾燥した。このようにして、1層構造の感光層
から成る感光性樹脂版材を得た。
Comparative Example 1 The lower layer photosensitive resin composition obtained in Example 1 was cast onto the same substrate as in Example 1 so that the photosensitive layer had a thickness of 700μ, and placed in an oven at 60°C for 4 hours. Dry. In this way, a photosensitive resin plate material consisting of a single-layered photosensitive layer was obtained.

この版材を実施例1と同様のテストネガフイル
ムを使用し、同一条件で露光を行なつた。次いで
実施例1と同じブラシ式洗い出し機で未露光部を
実施例より10秒短い1分50秒で完全に溶解除去し
て基板上にレリーフ像を得た。
This plate material was exposed to light using the same test negative film as in Example 1 under the same conditions. Then, using the same brush type washing machine as in Example 1, the unexposed areas were completely dissolved and removed in 1 minute and 50 seconds, 10 seconds shorter than in Example 1, to obtain a relief image on the substrate.

このレリーフを調べたところ、3%の網点は頂
点が完全に水中に溶出しており、5%の網点も部
分的に欠けていることがわかつた。また、200μ
の独立点はシヨルダが溶出してシヤープさがな
く、50μの細線にも欠けが見られた。このように
下層のみから成る版材は画層再現性が不十分であ
つた。
When this relief was examined, it was found that the tops of the 3% halftone dots were completely eluted into the water, and that the 5% halftone dots were also partially missing. Also, 200μ
At the independent point, the shoulder was eluted and there was no sharpness, and chipping was also observed in the 50μ thin line. In this way, the plate material consisting only of the lower layer had insufficient image layer reproducibility.

比較例 2 実施例1の上層用感光性樹脂溶液を使用して、
実施例1と同じ基板上に感光層の厚さが700μと
なるように流延し、60℃のオーブンに5時間入れ
て溶剤を除去した。
Comparative Example 2 Using the photosensitive resin solution for the upper layer of Example 1,
The photosensitive layer was cast onto the same substrate as in Example 1 to a thickness of 700 μm, and placed in an oven at 60° C. for 5 hours to remove the solvent.

このようにして得られた感光性樹脂版材を、実
施例1と同じネガフイルムを使用し、同一条件で
露光を行なつた。次いで、実施例1と同じブラシ
式洗い出し機で現像を行なつたところ、未露光部
分を完全に溶解除去するには6分間を要し、これ
は実施例1の3倍であつた。
The thus obtained photosensitive resin plate material was exposed to light using the same negative film as in Example 1 under the same conditions. Next, when development was carried out using the same brush type washing machine as in Example 1, it took 6 minutes to completely dissolve and remove the unexposed areas, which was three times as long as in Example 1.

得られたレリーフ自体は実施例1で得られたも
のと同等のシヤープさを有していたが、50μの細
線は、現像時間が余り長いために水で膨潤して曲
がりが発生していた。このように上層用の感光性
樹脂層のみから成る版材は、非常に長い現像時間
が必要であり、水現像性の劣ることがわかつた。
The obtained relief itself had the same sharpness as that obtained in Example 1, but the 50μ thin line was swollen with water and bent due to the excessively long development time. It has been found that a plate material consisting only of the upper photosensitive resin layer requires a very long development time and has poor water developability.

実施例 2 下層用感光性樹脂組成物溶液として実施例1と
全く同じものを調整した。
Example 2 The same solution as in Example 1 was prepared as a lower layer photosensitive resin composition solution.

上層用感光性樹脂用の部分ケン化ポリ酢酸ビニ
ルとして、ケン化度75モル%、平均重合度900の
ものを選んだ。この平均重合度は、下層用の部分
ケン化ポリ酢酸ビニルの平均重合度の1.50倍であ
る。このポリマ100重量部を、エタノール/水=
60/40(重量比)の混合溶剤120重量部に加温溶解
し、次いで下層と同じ光重合性モノマを70重量
部、相溶助剤としてジエチレングリコール28重量
部、光開始剤としてジメチルベンジルケタノール
2重量部、熱安定剤としてハイドロキノンモノメ
チルエーテル0.1重量部を添加して十分に撹拌混
合した。
As the partially saponified polyvinyl acetate for the photosensitive resin for the upper layer, one with a degree of saponification of 75 mol% and an average degree of polymerization of 900 was selected. This average degree of polymerization is 1.50 times the average degree of polymerization of the partially saponified polyvinyl acetate for the lower layer. 100 parts by weight of this polymer, ethanol/water =
Dissolve under heating in 120 parts by weight of a 60/40 (weight ratio) mixed solvent, then add 70 parts by weight of the same photopolymerizable monomer as the lower layer, 28 parts by weight of diethylene glycol as a compatibility aid, and dimethylbenzyl ketanol as a photoinitiator. 2 parts by weight and 0.1 part by weight of hydroquinone monomethyl ether as a heat stabilizer were added and thoroughly stirred and mixed.

あらかじめポリエステル系接着剤を塗布した厚
さ200μのポリエステルフイルム上に、下層用感
光性樹脂溶液を乾燥後の厚さが700μとなるよう
に流延し、60℃のオーブンに5時間入れて溶剤を
除去した。このようにして、ホリエステルフイル
ムで裏打ちされた感光層を得た。この感光層上
に、上層用の感光性樹脂溶液を厚さ50μに塗布す
ると同時に、表面がケミカルエツチングでマツト
化された厚さ100μのポリエステルフイルムをラ
ミネートした。このようにして、支持体と2層の
感光層の厚さの合計が950μのカバーフイルムつ
き版材を得た。
The photosensitive resin solution for the lower layer was cast onto a 200μ thick polyester film coated with a polyester adhesive in advance so that the dry thickness would be 700μ, and the solution was placed in an oven at 60°C for 5 hours to remove the solvent. Removed. In this way, a photosensitive layer lined with a polyester film was obtained. On this photosensitive layer, a photosensitive resin solution for the upper layer was applied to a thickness of 50 .mu.m, and at the same time, a 100 .mu.m thick polyester film whose surface had been matted by chemical etching was laminated thereon. In this way, a plate material with a cover film having a total thickness of the support and two photosensitive layers of 950 μm was obtained.

この版材を、暗所に10日間保存して上層の溶剤
が下層に完全に拡散するのを待つてから、カバー
フイルムをハク離した。カバーフイルムをハク離
した感光層表面は、ケミカルエツチングのマツト
面が完全に転写したマツト形状をもつていた。こ
の版材表面は実施例1と同じネガフイルムを非常
に容易に真空密着することができた。次いで、ケ
ミカル灯で6分間露光を行ない、水温30℃のブラ
シ式洗い出し機で現像を行なつた。現像時間は1
分50秒であり、実施例1よりも約10秒短い時間で
あつた。
This plate material was stored in a dark place for 10 days to allow the solvent in the upper layer to completely diffuse into the lower layer, and then the cover film was peeled off. The surface of the photosensitive layer from which the cover film was peeled off had a matte shape in which the chemically etched matte surface was completely transferred. The same negative film as in Example 1 could be vacuum-adhered to the surface of this plate very easily. Next, exposure was performed for 6 minutes using a chemical lamp, and development was performed using a brush-type washing machine at a water temperature of 30°C. Development time is 1
The time was 50 minutes, which was about 10 seconds shorter than in Example 1.

得られたレリーフを調べたところ、3%網点、
200μ独立点、50μ細線など微細な部分まで十分再
現されていることを確認した。
When I examined the obtained relief, I found that there were 3% halftone dots,
It was confirmed that fine details such as 200μ independent points and 50μ thin lines were sufficiently reproduced.

実施例 3 下層用の部分ケン化ポリ酢酸ビニルとして、ケ
ン化度88モル%、平均重合度300のものを選んだ。
このポリマ100重量部を、エタノール/水=40/
60(重量比)の混合溶剤100重量部に加温溶解し
た。次いで、光重合性モノマとしてグリシジルメ
タクリレートとメタクリル酸の付加反応物を100
重量部を添加し、さらに分子量400のポリエチレ
ングリコール40重量部、光開始剤としてベンゾイ
ンメチルエーテル3重量部、熱安定剤としてトリ
フエニルフオスイン2重量部とt−ブチルカテコ
ール0.1重量部を添加して十分に撹拌混合した。
このようにして、下層用の感光性樹脂溶液を調整
した。
Example 3 As the partially saponified polyvinyl acetate for the lower layer, one having a degree of saponification of 88 mol% and an average degree of polymerization of 300 was selected.
Add 100 parts by weight of this polymer to ethanol/water = 40/
It was heated and dissolved in 100 parts by weight of a mixed solvent of 60% (weight ratio). Next, as a photopolymerizable monomer, an addition reaction product of glycidyl methacrylate and methacrylic acid was added at 100%
40 parts by weight of polyethylene glycol having a molecular weight of 400, 3 parts by weight of benzoin methyl ether as a photoinitiator, 2 parts by weight of triphenylphosin and 0.1 part by weight of t-butylcatechol as heat stabilizers. Stir and mix thoroughly.
In this way, a photosensitive resin solution for the lower layer was prepared.

上層用の部分ケン化ポリ酢酸ビニルとして、ケ
ン化度88モル%、平均重合度1800のものを選ん
だ。このポリマの平均重合度は、下層用のポリマ
の6.0倍である。上層用の部分ケン化ポリ酢酸ビ
ニル100重量部をエタノール/水=40/60(重量
比)の混合溶剤250重量部に溶解した。次いで、
下層と同じ光重合性モノマの120重量部、分子量
400のホリエチレングリコール20重量部、光開始
剤としてベンゾインメチルエーテル3重量部、耐
熱安定剤としてトリフエニルフオスイン2重量部
とt−ブチルカテコール0.1重量部を添加した十
分に撹拌混合した。
As the partially saponified polyvinyl acetate for the upper layer, one with a degree of saponification of 88 mol% and an average degree of polymerization of 1800 was selected. The average degree of polymerization of this polymer is 6.0 times that of the polymer for the lower layer. 100 parts by weight of partially saponified polyvinyl acetate for the upper layer was dissolved in 250 parts by weight of a mixed solvent of ethanol/water = 40/60 (weight ratio). Then,
120 parts by weight of the same photopolymerizable monomer as the lower layer, molecular weight
400 polyethylene glycol, 3 parts by weight of benzoin methyl ether as a photoinitiator, 2 parts by weight of triphenylphosin and 0.1 part by weight of t-butylcatechol as heat-resistant stabilizers were added and mixed with thorough stirring.

下層用の感光性樹脂溶液をエポキシ系接着剤を
塗布した厚さ300μのアルミニウム支持体上に乾
燥後の感光層の厚さが300μとなるように流延し、
60℃のオーブンに2時間入れて溶剤を除去した。
このアルミニウム基板で裏打ちされた感光層上
に、上層用の感光性樹脂溶液を乾燥後の厚さが
100μとなるように流延し、60℃のオーブンに1
時間入れて乾燥した。このようにして、全体の厚
さが700μ、2層構造をもつ感光層の厚さが400μ
の感光性樹脂版材が得られた。
A photosensitive resin solution for the lower layer was cast onto a 300μ thick aluminum support coated with an epoxy adhesive so that the photosensitive layer would have a thickness of 300μ after drying.
The solvent was removed by placing it in an oven at 60°C for 2 hours.
On the photosensitive layer lined with this aluminum substrate, a photosensitive resin solution for the upper layer is applied to a dry thickness.
Cast it to a thickness of 100μ and place it in an oven at 60℃.
It took some time to dry. In this way, the total thickness is 700μ, and the thickness of the photosensitive layer with a two-layer structure is 400μ.
A photosensitive resin plate material was obtained.

この版材を、実施例1と同じ方法で露光し、実
施例1と同じ中性水の入つたブラシ式洗い出し機
で現像したところ、現像時間1分で未露光部分が
完全に水中に溶解除去されてレリーフ像が得られ
た。
When this plate material was exposed in the same manner as in Example 1 and developed in the same brush-type washing machine containing neutral water as in Example 1, the unexposed areas were completely dissolved and removed in water within 1 minute of development time. A relief image was obtained.

得られたレリーフを調べたところ、微細な部分
まで十分再現されていることを確認した。この版
材を使用して印刷テストを行なつたが、シヤープ
な刷り上がりの印刷物が得られ、印刷中のレリー
フクラツクなどのトラブルも全く発生しなかつ
た。
When we examined the resulting relief, we confirmed that even the smallest details were sufficiently reproduced. A printing test was conducted using this plate material, and the printed matter had a sharp finish, and no troubles such as relief cracks occurred during printing.

Claims (1)

【特許請求の範囲】 1 支持体上に感光性樹脂組成物からなる下層と
感光性樹脂組成物からなる上層をこの順に積層形
成した感光性樹脂版材であつて、該下層の感光性
組成物が次の(1)〜(3)成分 (1) ケン化度60〜99モル%、平均重合度200〜
1000の部分ケン化ポリ酢酸ビニル (2) 光重合性性不飽和モノマ (3) 光開始剤 から主としてなり、前記上層の感光性組成物が次
の(1)〜(3)成分 (1) ケン化度60〜99モル%、平均重合度が前記下
層の部分ケン化ポリ酢酸ビニルの平均重合度の
1.25〜10.0倍の範囲である部分ケン化ポリ酢酸
ビニル (2) 光重合性不飽和モノマ (3) 光開始剤 から主としてなることを特徴とする感光性樹脂版
材。
[Scope of Claims] 1. A photosensitive resin plate material in which a lower layer made of a photosensitive resin composition and an upper layer made of a photosensitive resin composition are laminated in this order on a support, wherein the photosensitive composition of the lower layer is the following (1) to (3) component (1) degree of saponification 60 to 99 mol%, average degree of polymerization 200 to
1000 partially saponified polyvinyl acetate (2) a photopolymerizable unsaturated monomer (3) a photoinitiator, and the photosensitive composition of the upper layer contains the following components (1) to (3): The degree of polymerization is 60 to 99 mol%, and the average degree of polymerization is the average degree of polymerization of the partially saponified polyvinyl acetate in the lower layer.
1. A photosensitive resin plate material mainly comprising partially saponified polyvinyl acetate (2) a photopolymerizable unsaturated monomer (3) a photoinitiator in the range of 1.25 to 10.0 times.
JP21261782A 1982-12-06 1982-12-06 Photosensitive resin plate material Granted JPS59102228A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21261782A JPS59102228A (en) 1982-12-06 1982-12-06 Photosensitive resin plate material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21261782A JPS59102228A (en) 1982-12-06 1982-12-06 Photosensitive resin plate material

Publications (2)

Publication Number Publication Date
JPS59102228A JPS59102228A (en) 1984-06-13
JPH0363739B2 true JPH0363739B2 (en) 1991-10-02

Family

ID=16625638

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21261782A Granted JPS59102228A (en) 1982-12-06 1982-12-06 Photosensitive resin plate material

Country Status (1)

Country Link
JP (1) JPS59102228A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61103150A (en) * 1984-10-26 1986-05-21 Toray Ind Inc Photosensitive resin composition
WO2017038970A1 (en) * 2015-09-03 2017-03-09 東レ株式会社 Photosensitive resin printing plate precursor, and method for manufacturing printing plate
US20230333473A1 (en) * 2020-09-14 2023-10-19 Toray Industries, Inc. Photosensitive resin printing plate precursor, and method of manufacturing printing plate using said precursor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5245402A (en) * 1975-10-07 1977-04-09 Murakami Screen Kk Photoosensitive composition and photoosensitive film for screen plate
JPS5785048A (en) * 1980-11-17 1982-05-27 Daicel Chem Ind Ltd Exposed photosensitive diazo film for making screen plate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5245402A (en) * 1975-10-07 1977-04-09 Murakami Screen Kk Photoosensitive composition and photoosensitive film for screen plate
JPS5785048A (en) * 1980-11-17 1982-05-27 Daicel Chem Ind Ltd Exposed photosensitive diazo film for making screen plate

Also Published As

Publication number Publication date
JPS59102228A (en) 1984-06-13

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