JPS5849940A - Photosensitive composition - Google Patents
Photosensitive compositionInfo
- Publication number
- JPS5849940A JPS5849940A JP10062681A JP10062681A JPS5849940A JP S5849940 A JPS5849940 A JP S5849940A JP 10062681 A JP10062681 A JP 10062681A JP 10062681 A JP10062681 A JP 10062681A JP S5849940 A JPS5849940 A JP S5849940A
- Authority
- JP
- Japan
- Prior art keywords
- water
- photosensitive
- plate
- high molecular
- molecular compound
- 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.)
- Pending
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)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 本発明に、感光性組成物に関するものである。[Detailed description of the invention] The present invention relates to a photosensitive composition.
史に詳しくは、平版、凸版等の印刷版、グラフィックア
ートエレメント尋の製造に用いる7オトレジスト、およ
び印刷(ロ)路等の製造に有用な水で現gII可能な感
光性組成物に関する。More specifically, the present invention relates to a water-curable photosensitive composition useful in the production of printing plates such as lithographic plates and letterpress plates, photoresists used in the production of graphic art elements, and printing paths.
従来、水により現儂可能な感光性組成物としては
(1)水溶性高分子化合物と重クロム酸塩類とから成る
組成物
(2)水溶性高分子化合物と水溶性ジアゾ樹脂とから成
る組成物
(3)水溶性高分子化合物と水溶性アジド化合物とから
成る組成物
(4)水溶性光重合組成物
などが知られている。これらの感光性組成物tm設して
得られる感光層は、いずれも水溶性であるために、申り
扱い時に湿気のある手で表面に触れないように細心の注
意を払わなければならず、このため作業性を着しく低下
させる。また、空気中の水分による影響を非常に受けや
すいため、長期間の保存が不可能であった。Conventionally, photosensitive compositions that can be developed with water include (1) compositions comprising a water-soluble polymer compound and dichromate salts, and (2) compositions comprising a water-soluble polymer compound and a water-soluble diazo resin. (3) A composition comprising a water-soluble polymer compound and a water-soluble azide compound, (4) A water-soluble photopolymerizable composition, and the like are known. Since the photosensitive layers obtained by preparing these photosensitive compositions are all water-soluble, great care must be taken not to touch the surface with damp hands when handling them. For this reason, work efficiency is seriously reduced. Furthermore, it is extremely susceptible to the effects of moisture in the air, making it impossible to store it for long periods of time.
さらに、光硬化した皮膜が親水性でもろいため、例えば
印刷版として用いる場合、印刷イン中に対する親和性に
乏しく、印刷適性がきわめて急い。Furthermore, since the photocured film is hydrophilic and brittle, when used as a printing plate, for example, it has poor affinity for printing during printing, and its suitability for printing is extremely poor.
またフォトレジストとしても、耐水性に乏しいため、十
分なレジスト機iII!を果たすに至っていない。Also, as a photoresist, it has poor water resistance, so the resist machine iii! has not yet been achieved.
上記の問題点を解決すべく、水溶性感光層t−験油性樹
脂感光層で核種するという試みがなされ、感光層表面の
性状は疎水性に改良された。しかし、これらの組成分F
iz層系のため、製造が繁雑でコスト高になり、解像力
も恕いという欠点を有していた。−力、単層系において
も上記問題点を解決すべく、いくつかの改良が試みられ
た。例えば特開昭52−2520号公報には、親油性樹
脂の水系エマルジョンと水溶性ジアゾ樹脂からなる組成
−全開示しているが、この組成物は水系エマルジョンを
用いているため、湿気の影響を受けやすく、保存安定性
が悪かった。また、例えば特開昭55−120028号
公報には、竣油性フィルム形成樹脂、フリーラジカル重
合性不飽和化合物、親油性ジアゾ化合物、水溶性樹脂お
よび開始剤の均質混合物からなる組成物が開示されてい
る。しかし、この組成物は、大気中の酸素の影響を受は
子すく、保存安定性が悪かった。さらに、特開昭55−
159433号公報には、エポキシ樹脂と親油性ジアゾ
樹脂からなる組成物が開示されているが、該エポキシ樹
脂の貯蔵時における暗反応のために保存安定性が患かっ
た。このように水で現倫でき、解像力、耐刷力が良好で
酸素の影響をうけず、しかも貯蔵安定性がよいという感
光性組成物は、未だ知られていないのが現状である。In order to solve the above-mentioned problems, an attempt was made to form a nuclide in a water-soluble photosensitive layer and an oil-based resin photosensitive layer, and the surface properties of the photosensitive layer were improved to be hydrophobic. However, these compositions F
Because of the iz layer system, manufacturing is complicated and costly, and the resolution is poor. Several improvements have been attempted in order to solve the above-mentioned problems in single-layer systems as well. For example, JP-A-52-2520 discloses a composition consisting of an aqueous emulsion of a lipophilic resin and a water-soluble diazo resin, but since this composition uses an aqueous emulsion, it is not affected by moisture. It was easy to use and had poor storage stability. Furthermore, for example, JP-A-55-120028 discloses a composition comprising a homogeneous mixture of an oily film-forming resin, a free radical polymerizable unsaturated compound, a lipophilic diazo compound, a water-soluble resin, and an initiator. There is. However, this composition was easily affected by atmospheric oxygen and had poor storage stability. Furthermore, JP-A-55-
Publication No. 159433 discloses a composition comprising an epoxy resin and a lipophilic diazo resin, but storage stability was poor due to dark reaction during storage of the epoxy resin. At present, there is currently no known photosensitive composition that can be processed with water, has good resolution and printing durability, is not affected by oxygen, and has good storage stability.
本発明は、上記従来技術が肩する問題点を解決すべくな
されたものである。The present invention has been made to solve the problems faced by the above-mentioned prior art.
本発明の目的とするところは、保存安定性、親油性、解
像力、耐摩耗性の各々に優れ、がっ#累の影響を受けな
い水で現曽可能な感光性組成物を提供することである。An object of the present invention is to provide a photosensitive composition that has excellent storage stability, lipophilicity, resolution, and abrasion resistance, and can be developed with water without being affected by build-up. be.
また本発明の別の目的は、保存安定性、磯油性、解像力
、耐刷力の各々に優れ、かつM素の影響を受けない水で
現惨可能な平版印刷版を提供することである。Another object of the present invention is to provide a lithographic printing plate which has excellent storage stability, oil resistance, resolution, and printing durability, and which is unaffected by M elements and can be printed with water.
本発明者らは鋭意研究の結果、)記構成の感光性組成物
を用いることによシ上記目的が達成しうることを見い出
した。As a result of intensive research, the present inventors have found that the above object can be achieved by using a photosensitive composition having the following structure.
即ち、本発明の水で現俸可能な感光性組成物は、[A]
ジアゾ樹脂、〔B〕水軟化性高分子化合物、及び[C]
主鎖又はIIIIIK架倫成分として−CH−C−C0
−基(Rけ水帛摩子、シアノ基又はハロゲン原子を表わ
す。)を南する感光性高分子化合物を含むことを特徴と
する〇
本発明に係る感光性組成物は、上記[C]酸成分ある感
光性高分子化合物が6加されているため皮III強度が
著しく強固になり、かつ本発明に係る感光性組成物が平
版印III版に使用されたときには、耐刷力が著しく改
善される。That is, the water-dispersible photosensitive composition of the present invention has [A]
Diazo resin, [B] water-softening polymer compound, and [C]
-CH-C-C0 as main chain or IIIK linkage component
The photosensitive composition according to the present invention is characterized in that it contains a photosensitive polymer compound containing a - group (representing R, a cyano group, or a halogen atom). Since 6 is added with a certain photosensitive polymer compound, the skin III strength is significantly increased, and when the photosensitive composition according to the present invention is used in a lithographic printing III plate, printing durability is significantly improved. .
次に、本発明について詳細に説明する。Next, the present invention will be explained in detail.
ジアゾ樹脂としては、例えば米国特許第2,06363
1号および同第2667415号の各明細書に開示され
ているジアゾニウム塩とアルドールやアセメールのよう
な反応性カルボニル基を含有する有機縮合剤との反応生
成物であるジフェニルアミン−p−ジアゾニウム塩とフ
ォルムアルデヒドとの縮合物、fftこれらの水溶性ジ
アゾ化合物を特開昭54−98613号公報に開示され
た刀GK j F) BF4−、 PF6−.5iF6
−″、8bF6−″″。As the diazo resin, for example, U.S. Pat. No. 2,06363
Diphenylamine-p-diazonium salt, which is a reaction product of the diazonium salt disclosed in the specifications of No. 1 and No. 2667415, and an organic condensing agent containing a reactive carbonyl group such as aldol or acemer, and form Condensates with aldehydes, fft These water-soluble diazo compounds are used in the katana GK j F) BF4-, PF6-. 5iF6
-'', 8bF6-''''.
BaF2 なるアニオン成分で置換した如きハロゲ
ン化ルイス酸塩が含まれる。Included are halogenated Lewis acid salts such as those substituted with an anionic component of BaF2.
該ジアゾ樹脂の添加量は、感光性組成物を皮膜にした感
光層の総重量に対してl〜50重量優重量当であり、3
〜301i量憾が好ましい。The amount of the diazo resin added is 1 to 50 weight equivalents based on the total weight of the photosensitive layer made of the photosensitive composition, and 3.
~301i amount is preferred.
本発明に用いられる水軟化性高分子化合物は、極性有機
溶媒系にも可溶の水溶性高分子化合物であり、好ましく
は相対湿wIL80’lVcおける吸湿率(水蒸気)が
5〜60憾のものである。The water-softening polymer compound used in the present invention is a water-soluble polymer compound that is also soluble in polar organic solvent systems, and preferably has a moisture absorption rate (water vapor) of 5 to 60 at relative humidity wIL80'lVc. It is.
該水軟化性高分子化合物の添加量によって決定さねるこ
とであるが、該吸湿率が60%以下のときは、耐水性親
油性のある感光性組成物が得られるという点で一段と優
れており、また保存安定性も一段と優れたものとなる。Although it does not depend on the amount of the water-softening polymer compound added, when the moisture absorption rate is 60% or less, it is even better in that a water-resistant and lipophilic photosensitive composition can be obtained. , storage stability is also improved.
又、5憾以上では、水による現像性が著しく優れたもの
となる。#吸湿率は「材料と水分ハンドブック」(高分
子学会編、共立出版1968年)ill 77頁に記歇
の秤量ビン法により測定されたものである。Further, when the number is 5 or more, the developability with water becomes extremely excellent. #The moisture absorption rate was measured by the weighing bottle method as described in "Handbook of Materials and Moisture" (edited by the Society of Polymer Science and Technology, Kyoritsu Publishing, 1968) ill, page 77.
本発明の水軟化性高分子化合物の中でも好ましいものは
、セルロース鍔導体、ポリビニルアルコールn導体、ポ
リビニルビクリトン、ポリヒドロキシスチレン、及びア
クリル酸、メタクリル酸、アクリルアミド系、メタクリ
ルアミド系、ヒドロキシル基を不するアクリルエステル
系またはヒドロキシル基1kiするメタクリルエステル
系の単量体単位を含む単独重合体または共重合体からな
る群から選ばj−たものを少くともla[含むものであ
る。Among the water-softening polymer compounds of the present invention, preferred are cellulose tsuba conductor, polyvinyl alcohol n-conductor, polyvinyl vicritone, polyhydroxystyrene, and acrylic acid, methacrylic acid, acrylamide type, methacrylamide type, and those having no hydroxyl group. At least one selected from the group consisting of homopolymers or copolymers containing acrylic ester-based or methacrylic ester-based monomer units containing hydroxyl groups.
本発明に用いられるセルロース誘導体は、代表的なもの
として、セルロースの水酸基の水Ia原子の少なくとも
1つがアルキル基、ヒドロキシアルキル基および/又は
アシル基で置きかえられた構造のものがあげられる。核
セルロース酵導体の具体的な例としては、とドロキシメ
チルセルロース、ヒドロキシエチルセルロース、ヒドロ
キシプロピルセルロース、ヒドロキシプロピルメチルセ
ルロースフタレート、ヒドロキシプロピルメチルセルロ
ースへキサヒドロフタレート、メチルセルロース、エチ
ルセルロース、プロピルセルロース等カある。Typical cellulose derivatives used in the present invention include those having a structure in which at least one of the water Ia atoms in the hydroxyl group of cellulose is replaced with an alkyl group, a hydroxyalkyl group, and/or an acyl group. Specific examples of the core cellulose enzyme conductor include hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose hexahydrophthalate, methylcellulose, ethylcellulose, propylcellulose, and the like.
本発明に用いられるポリビニルアルコール篩導体の具体
的例としては、例えばケン化1120〜5゜暢のポリビ
ニルアルコール、
2H5
H
(各々、分子量1,000〜100,000)等がある
。Specific examples of the polyvinyl alcohol sieve conductor used in the present invention include polyvinyl alcohol with saponification of 1120 to 5 degrees, 2H5H (each having a molecular weight of 1,000 to 100,000), and the like.
本発明におけるアクリルアミド系、メタクリルアミド系
、ヒドロキシル基を有するアクリルエステル系及びヒド
ロキシル基を有するメタクリルアミド系の単量体単位と
しては、下記一般式[T]で示すものがあげられる。Examples of the acrylamide type, methacrylamide type, hydroxyl group-containing acrylic ester type and hydroxyl group-containing methacrylamide type monomer units in the present invention include those represented by the following general formula [T].
一般式〔I〕
1
−CH2−C−
C二〇
2
上記一般式[T]で示される単量体単位を与える単量体
としては、例えばアクリルアミド、p−ヒドロキシフェ
ニルメタクリルアミド、ヒドロキシメチルメタクリレー
ト、ヒドロキシエチルメタクリレート、ヒドロキシプロ
ピルメタクリレート等がある。General formula [I] 1 -CH2-C- C202 Monomers that provide the monomer unit represented by the above general formula [T] include, for example, acrylamide, p-hydroxyphenyl methacrylamide, hydroxymethyl methacrylate, Examples include hydroxyethyl methacrylate and hydroxypropyl methacrylate.
本発明において、単量体単位としてアクリル酸、メタク
リル酸、またはアクリルアミド系、メタクリルアミド系
、ヒドロキシル基を有するアクリルエステル系若しくは
ヒドロキシル基を有するメタクリルエステル系のものを
含む共重合体は、これら単量体単位を少なくとも181
含んでいればよい。In the present invention, copolymers containing acrylic acid, methacrylic acid, acrylamide type, methacrylamide type, acrylic ester type having a hydroxyl group, or methacrylic ester type having a hydroxyl group as monomer units are At least 181 body units
It is sufficient if it is included.
又、共重合体中のこれら単量体単位の比率は30重重量
板上であることが好ましい。Further, the ratio of these monomer units in the copolymer is preferably on a 30-weight plate.
上記構造単位を少なくとも一程含む単独重合体乃至共重
合体の具体例としては、例えば次のものが挙げられる。Specific examples of homopolymers or copolymers containing at least one of the above structural units include the following.
()内は単量体単位の重量比を表わす。The numbers in parentheses represent the weight ratio of monomer units.
[13ポリヒドロキシエチルメタクリレート〔2〕
ポリ−p−ヒトジキシフェニルメタクリルアミド
【3〕 ヒドロキシエチルメタクリレート/ブチルア
クリレート/スチレン(40:15:35)の共重合体
〔4〕 ヒドロキシエチルメタクリレート/ブチルア
クリレート/アクリル酸/スチレン(40:25:to
:25)の共重合体
〔5〕p−ヒドロキシフ、エニルメメクリルアミド/ア
クリロニトリル/ブチルアクリレート/アクリル酸(2
0:20:40:20)の共重合体
【6〕 プチルメ!クリレート/アクリル酸/スチレ
ン(25:50:25)の共重合体
【7〕 メチルメタクリレート/ブチルアクリレート
/アクリル酸/スチレン(10:10:50:30)の
共重合体
〔8〕 ブチルアクリレート/アクリル酸/ヒドロキ
シエチルアクリレ−)(30:30:40)の共重合体
[9]フチルアクリレート/メタクリル酸(SO:50
)の共重合体
本発明に用いられる感光性高分子化合物としては、次の
ものが挙げられる。[13 Polyhydroxyethyl methacrylate [2]
Poly-p-hydroxyphenylmethacrylamide [3] Copolymer of hydroxyethyl methacrylate/butyl acrylate/styrene (40:15:35) [4] Hydroxyethyl methacrylate/butyl acrylate/acrylic acid/styrene (40:25) :to
:25) copolymer [5] p-hydroxyph, enylmemethrylamide/acrylonitrile/butyl acrylate/acrylic acid (2
0:20:40:20) copolymer [6] Petitilme! Copolymer of acrylate/acrylic acid/styrene (25:50:25) [7] Copolymer of methyl methacrylate/butyl acrylate/acrylic acid/styrene (10:10:50:30) [8] Butyl acrylate/acrylic copolymer of acid/hydroxyethyl acrylate (30:30:40) [9] phthyl acrylate/methacrylic acid (SO:50)
) Photosensitive polymer compounds used in the present invention include the following.
n:8〜200)、例えば特開昭55−40415号公
報に示されるごとく、フエニレンジエfルアクリレート
、水嵩添加したビスフェノールAおよびトリエチレング
リコールからなるポリエステル化合物がある。n: 8 to 200), for example, as shown in JP-A-55-40415, there is a polyester compound consisting of phenylene diethyl acrylate, bisphenol A to which water has been added and triethylene glycol.
例えはポリエーテル、ポリビニlレアフレコール ポリ
ヒドロキシフェニルアミ/アクリレート、ホリヒドロキ
シスチレン、ノボラック樹脂等の樹脂に等のスチリルI
導体を反応させたものがあシ、具体色としては、例えd
次のものを挙げることができる。Examples include styryl I, polyether, polyvinyl rarefrecol, polyhydroxyphenyl amide/acrylate, polyhydroxystyrene, novolak resin, etc.
The one that reacts with the conductor is the one, and the specific color is, for example, d
The following can be mentioned:
CN
〔イロし、上&l:+ll〜αの中、m、n/ri整数
で、l 00 ) −) 0.01 である。〕上記感
光性高分子化合物の使用に対しては増感剤を用いること
が好ましい。増感剤としては、ニドロアリール化合物、
アントロン類、ジアミノベンゾフェノンイミド類、ジア
ミノジフェニルメタン類、ジアミノジフェニルケトン類
、ジアミノジフェニルカルピトール類等が好適に用いら
れる。CN [Iro, top & l: +ll to α, m, n/ri integer, l 00 ) −) 0.01. ] It is preferable to use a sensitizer when using the above photosensitive polymer compound. As a sensitizer, a nidroaryl compound,
Anthrones, diaminobenzophenonimides, diaminodiphenylmethanes, diaminodiphenylketones, diaminodiphenylcalpitols, and the like are preferably used.
該増感剤は感光性高分子化合物100重量部に対して0
.1〜50重量部用いられる。上記感光性高分子化合物
は、活性光線の照射により、自己架橋しておよび/また
拡充分解したジアゾと反応して網目構造を形成して硬化
す慝。The sensitizer is used in an amount of 0 per 100 parts by weight of the photosensitive polymer compound.
.. 1 to 50 parts by weight are used. When irradiated with active light, the photosensitive polymer compound self-crosslinks and/or reacts with expanded decomposed diazo to form a network structure and harden.
本発明に係る感光性組成物中には、二種の感光−]が含
まれている。すなわち、ジアゾ樹脂と感光性高分子化合
物である。The photosensitive composition according to the present invention contains two types of photosensitive compounds. That is, they are a diazo resin and a photosensitive polymer compound.
ジアゾ樹脂と親油性樹脂よりなるアルカリ現俸性の感光
性組成物はよく知られているが、これらは平版印刷版と
して使用した際、高耐刷性が得られlいという国有の欠
点を廟し、−力、感光性高分子化合物と親油性樹脂から
なるアルカリ現俸性の感光性組成物吃また、よく知られ
ているが、これらは一般に感度が低いという欠点を有し
ていた。Alkaline-current photosensitive compositions made of diazo resins and lipophilic resins are well known, but they suffer from the disadvantage of not being able to provide high printing durability when used as lithographic printing plates. However, alkaline-current photosensitive compositions comprising a photosensitive polymer compound and a lipophilic resin are also well known, but they generally have the drawback of low sensitivity.
本発明者らは、ジアゾ樹脂、感光性高分子化合物および
水軟化性高分子化合物を組み合わせることにより、高I
IAltで、耐摩耗性が極めて優れており、しかも水で
現像できる感光性組成物を完成したものである。By combining a diazo resin, a photosensitive polymer compound, and a water-softening polymer compound, the present inventors have developed
A photosensitive composition made of IAlt that has extremely excellent abrasion resistance and can be developed with water has been completed.
該感光性組成物を印刷版として用いると、高感度、高耐
刷性で、しかも水で税健できる印刷版が得られて非常に
有利である。When the photosensitive composition is used as a printing plate, it is very advantageous to obtain a printing plate that has high sensitivity, high printing durability, and can be washed with water.
本発明に係る感光性組成物には、充填剤が添加されるこ
とが望ましい。該充填剤1i活性光IIt透過しジアゾ
樹脂、水軟化性高分子化合物等罠対して不活性なもので
ある。具体的な例としては、例えばアスベスト、アルミ
ナ、アタパルジャイト、カオリンクレー、グラフチ1ト
、微粉珪酸、珪藻土、酸化チタン、酸化ケイ素、石英粉
、タルク等の無機充填剤、例えば7タロシアニン、ジオ
キサジン、アントラキノン系等の有機顔料、特開昭55
−149326号公報に1叡されているような有機溶媒
に分散さt″した疎水性ポリマー等がある。上記充填剤
は粒径1mn〜100μが適当であシ、l rnp〜I
onが好ましく用いられる。tた上記無機元項削、#i
料は前述した水軟化性高分子化合物を保静剤として有機
溶媒に分散したものが好適に用いられる。It is desirable that a filler is added to the photosensitive composition according to the present invention. The filler 1i is a material that transmits active light IIt and is inert to traps such as diazo resin and water-softening polymer compounds. Specific examples include inorganic fillers such as asbestos, alumina, attapulgite, kaolin clay, graphite, finely divided silicic acid, diatomaceous earth, titanium oxide, silicon oxide, quartz powder, and talc, such as 7-talocyanine, dioxazine, and anthraquinone. Organic pigments such as
There are hydrophobic polymers dispersed in an organic solvent as described in Japanese Patent No. 149326.The particle size of the filler is suitably 1 mm to 100μ, and lrnp to I
on is preferably used. Deleting the above inorganic element, #i
Preferably, the material used is one in which the water-softening polymer compound described above is dispersed in an organic solvent as a preservative.
従来、充填剤の添加にょシ感度、1I9IJ度が改善さ
れることは知られていたが、本発明者らは充填剤を添加
することにより、水現儂性が改善されることを見い出し
た。この事実は、充填剤の添加によシ感光性組成物を構
成する高分子化合物間の分子間力が減少するためである
と考えられるが明らかでない。上記充填−]の添加量は
、感光層総重量のl〜60重量憾重量当であり、3〜4
5重量係が好ましい。It has been known in the past that the addition of a filler improves the sensitivity and 1I9IJ degree, but the present inventors have discovered that the addition of a filler improves the water extensibility. This fact is thought to be because the addition of the filler reduces the intermolecular force between the polymer compounds constituting the photosensitive composition, but it is not clear. The amount of the above-mentioned filling is 1 to 60 liters of the total weight of the photosensitive layer, and 3 to 4 liters of the total weight of the photosensitive layer.
5 weight ratio is preferable.
水による現像性に対しては、水軟化性高分子化合物の吸
湿率およびその添加量並びKm光性高分子化合物の添加
量が大きく影響する。The water developability is greatly influenced by the moisture absorption rate of the water-softening polymer compound and the amount thereof added, as well as the amount of the Km photosensitive polymer compound added.
該水軟化性高分子化合物、該感光性高分子化合物、各々
の添加量Fi該氷水軟化性高分子化合物検知によシ、保
存安定性、耐摩耗性、現像性等の性能が最良になるよう
に決定されるものであるが、一般的に1感光層のa’t
r iに対して該水軟化性高分子化合物の添加量は10
〜7oilii1%、好オしくけ15〜60重量係であ
り、該感光性高分子化合物の添加量は10〜8011を
嘔、好ましくFi30〜701ii鳴である。The water-softening polymer compound, the photosensitive polymer compound, and the respective additive amounts Fi should be adjusted so that the performance of the ice-water softening polymer compound in terms of detection, storage stability, abrasion resistance, developability, etc. is maximized. Generally, a't of one photosensitive layer is determined by
The amount of the water softening polymer compound added to r i is 10
The amount of the photosensitive polymer compound added is preferably 10 to 8011%, preferably 30 to 701% by weight.
本発明の感光性組成物は、必要に応じて種々の添加剤を
含有することができる。露光fIt画倫を可視化するた
めの露光可視画剤、例えばアクリジン染料、シアニン染
料、メロシアニン染料、スチリル染料、トリフェニルメ
タン染料等の染料、前述した7タロシアニン、ジオキサ
ジン、アントラキノン系等の有wk餉料、例えば芳香族
アンド、カルボニルアジド、スルホニルアジド、ポリハ
ロメチル化合物等とロイコ染料等の組み合わせ、例えば
特公昭44−6413号公報に記載されているような、
筒先により変色するスピロピラン化合物等を添加するこ
とができる。その添加’lけ、目的とする町視惜の度合
によって異なるが、感光層総重量に対して1〜5重量憾
程度である。なお、充填剤として有機顔料を用いた場合
には、上記の露光可視画剤は、特に必要としない。tた
、更に、安定化剤、界面活性剤、可塑剤、増粘剤、レベ
リング剤等も適宜添加できる。The photosensitive composition of the present invention can contain various additives as necessary. Exposure visualization agents for visualizing the exposure fIt image, such as dyes such as acridine dyes, cyanine dyes, merocyanine dyes, styryl dyes, and triphenylmethane dyes, and pigments such as the aforementioned 7-talocyanine, dioxazine, anthraquinone, etc. For example, combinations of aromatic and, carbonyl azide, sulfonyl azide, polyhalomethyl compounds, etc. and leuco dyes, etc., such as those described in Japanese Patent Publication No. 44-6413,
A spiropyran compound or the like that changes color depending on the tip of the tube can be added. The amount of addition thereof varies depending on the desired degree of opacity, but is approximately 1 to 5% by weight based on the total weight of the photosensitive layer. In addition, when an organic pigment is used as a filler, the above-mentioned exposed visible image agent is not particularly required. Furthermore, stabilizers, surfactants, plasticizers, thickeners, leveling agents, etc. can also be added as appropriate.
本発明に係る感光性組成物は、支持体上Kal設して感
光層として用いることができる。支持体としては紙、プ
ラスチックフィルム(例えば二酢酸セルロース、三酢i
!セルロース、ポリエチレンテレフタレート、ポリスチ
レン)、アルミニウム板、咎鉛板、銅板、クロムメッキ
した鉄板等が好適に用いられる。The photosensitive composition according to the present invention can be used as a photosensitive layer by disposing it on a support. Supports include paper, plastic films (e.g. cellulose diacetate, triacetate
! Cellulose, polyethylene terephthalate, polystyrene), aluminum plates, lead plates, copper plates, chrome-plated iron plates, etc. are preferably used.
また、金属、特にアルミニウムの表面を有する支持体の
場合には、砂目立て処理、珪酸ナトリウム、弗化ジルコ
ニウム酸カリウム、燐1[等の水溶液への浸漬処理、あ
るいは陽極酸化処理などの袋面処理がなされていること
が好ましい。米国特許第2,714,066号明細書に
記載されているように、砂目立てしたのちに、珪酸ナト
リウム水溶液に浸漬処理されたアルミニウム板、特公昭
47−5125号公報に記載されているように1アルミ
ニウム板を陽極級化したのちに、アルカリ金属珪#に塩
の水溶液に浸漬処理したもの等が好適に用いられる。In addition, in the case of a support having a surface of metal, especially aluminum, bag surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphorus 1, etc., or anodizing treatment, etc. It is preferable that the As described in U.S. Patent No. 2,714,066, an aluminum plate is grained and then immersed in an aqueous sodium silicate solution; 1. After anodizing an aluminum plate, an alkali metal silicon plate immersed in an aqueous salt solution is preferably used.
支持体上に設けられる感光層の塗布量は、本発明に係る
感光性組成物の使用目的によシ異なるが、約0.5q/
d−〜約100q/dm’が適当であシ、好ましくは約
5.0 my/dm” 〜約501111/drp/テ
1bルOIII布方法は、公知の塗布方法、例えばディ
ップ塗布、ロー5111布、回転塗布、エアーナイフI
11布、スプレー塗布等が利用できる。塗布液lII変
Fi塗布方式、塗布条件、塗布量から決定される。The coating amount of the photosensitive layer provided on the support varies depending on the purpose of use of the photosensitive composition according to the present invention, but is about 0.5q/
d- to about 100 q/dm' is suitable, preferably about 5.0 my/dm' to about 501111/drp/t1b OIII cloth method can be performed using known coating methods such as dip coating, low 5111 cloth. , rotation coating, air knife I
11 cloth, spray coating, etc. can be used. Coating liquid lII modified Fi is determined from the coating method, coating conditions, and coating amount.
本発明に係る感光性組成物から得られる感光層と支持体
との閾に、所謂ヌケ性を改善する目的で、下引き層とし
て水溶性化合物層あるいは水溶性感光層を設けても差し
つかえないが、該下引き層の被種量が多いと、保存安定
性、解像力の低)につながるため、該下引き層の薔榎蓋
は、約0.111Vdn?〜5q/dイが適当である。A water-soluble compound layer or a water-soluble photosensitive layer may be provided as an undercoat layer between the photosensitive layer obtained from the photosensitive composition according to the present invention and the support for the purpose of improving so-called opacity. However, if the amount of seeds in the undercoat layer is large, it will lead to poor storage stability and low resolution. ~5q/d is appropriate.
このようにして′製造した感光性重曹形成材料はi儂筒
先稜、水で現像される。The photosensitive sodium bicarbonate-forming material thus produced is then developed with water.
画gI篇光に使用される光源は、感光層の感光波長域の
光を含むものが使用される。一般的には、300〜45
Q nmの波長を含むものが適当であ7/
す、例えば水銀灯、カーボンアーク灯、キセノン灯、メ
タルハライドランプ等が利用される。The light source used for image gI is one that includes light in the wavelength range to which the photosensitive layer is sensitive. Generally, 300-45
A lamp including a wavelength of Q nm is suitable; for example, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, etc. are used.
感光層の旋光部分は現像の際に伺ら変化しないが、未謝
光部分はその表面を例えは脱脂綿、スポンジ等で軽く擦
ることによシ容易に除去される。The optically rotating portion of the photosensitive layer does not change during development, but the optically rotating portion is easily removed by lightly rubbing the surface with, for example, absorbent cotton or a sponge.
かくして支持体上に、親油性疎水性の樹脂画像が形成さ
れる。A lipophilic and hydrophobic resin image is thus formed on the support.
以下、不発8J4を実施例に基づいて釘に詳細に説明す
るが、本発明の実施態様がこれにょシ限定されるもので
はない。なお、以下に示す吸湿率は相対f1180%に
おける値である。Hereinafter, the unexploded 8J4 will be described in detail as a nail based on an example, but the embodiments of the present invention are not limited thereto. Note that the moisture absorption rates shown below are values at relative f1180%.
合成例L
30gのポリヒドロキシスチレン(丸善石油化学製2分
子量約10,000)t4007!(D乾燥ピリジンと
r−ブチロラクトン60−の混合溶媒に完全に溶解し、
50℃に保持してα−シアノケイ皮酸クロライド9.8
5 g i少しずつ添加し、添加終了後、50℃で5時
間反応させると、反応混合物は淡黄色の透明溶液となっ
た。これを室温で一晩放置後、氷水31とIIk塩酸8
0−の混合溶液中に攪拌下に注入して沈澱を生成させ、
吸引ろ過して、水洗、乾燥後35gのポリマー(感光性
高分子化合物)を得た。Synthesis Example L 30g of polyhydroxystyrene (Maruzen Petrochemical 2 molecular weight approximately 10,000) t4007! (Completely dissolved in a mixed solvent of D dry pyridine and r-butyrolactone 60-,
α-cyanocinnamic acid chloride 9.8 at 50°C
5 g i was added little by little, and after the addition was completed, the reaction was allowed to proceed at 50° C. for 5 hours, and the reaction mixture turned into a pale yellow transparent solution. After leaving this overnight at room temperature, ice water 31 and IIk hydrochloric acid 8
0- into a mixed solution under stirring to generate a precipitate,
After suction filtration, washing with water, and drying, 35 g of polymer (photosensitive polymer compound) was obtained.
@数例2
30gのポリビニルアルコール[日本合成化学工業■製
、GL−05]を400dの乾燥ピリジンとr−ブチロ
ラクトン60−の混合溶tsに完全に溶解し、50℃に
保持して、α−シアノケイ皮酸クロライド6.18 g
を少しずつ添加し、添加終了後、50℃で5時間反応さ
せると、反応混合物は淡黄色の透明溶液となった。これ
を室温で一晩放置後、氷水3tと#虐@SO−の混合溶
諌忙攪拌下に注入して沈澱を生成させ、吸引ろ過して、
水洗、乾燥920gのポリマー(g光性高分子化@物)
を得た。@Example 2 30g of polyvinyl alcohol [manufactured by Nippon Gosei Kagaku Kogyo ■, GL-05] was completely dissolved in 400d of a mixed solution of dry pyridine and r-butyrolactone 60-ts, kept at 50°C, and α- Cyanocinnamic acid chloride 6.18 g
was added little by little, and after the addition was completed, the reaction mixture was allowed to react at 50° C. for 5 hours, and the reaction mixture turned into a pale yellow transparent solution. After leaving this overnight at room temperature, it was poured into a mixed solution of 3 tons of ice water and #SO- under vigorous stirring to form a precipitate, which was filtered with suction.
Washed with water and dried 920g of polymer (g photopolymerization @ thing)
I got it.
実施例1
Ifo、24箇の38アルミニウム板ヲナイロンブラシ
と400メツシユのパミストン水懸濁液ヲ用いてその表
面を砂目立てした後、水で洗浄し、10幅水酸化ナトリ
ウム水溶液中で50℃、20秒間エツチングし友。これ
を30暢硝酸溶液中に室温で20秒間浸漬してデスマッ
ト処理を行ない、更に、倣酸溶液中で、温度40℃、電
圧tOV。Example 1 Ifo, the surface of 24 38 aluminum plates was grained using a nylon brush and a 400 mesh pumice stone water suspension, washed with water, and heated at 50°C in a 10 mm sodium hydroxide aqueous solution. Etching my friend for 20 seconds. This was desmutted by immersing it in a nitric acid solution for 20 seconds at room temperature, and then in a mimic acid solution at a temperature of 40° C. and a voltage of tOV.
電流密度2A/dm’、時間5分で陽極酸化処理を行な
った。次に、III!度5僑、温度80℃のケイ酸ナト
リウム溶液に5分間浸漬し、封孔処理を行なった。得ら
れたアルミニウム板の砂目の粗さはRZ=4.5a(D
IN規格)であり、陽極酸化皮IItFi1511t/
d−であった。Anodic oxidation treatment was performed at a current density of 2 A/dm' for 5 minutes. Next, III! It was immersed in a sodium silicate solution at a temperature of 80° C. for 5 minutes to seal the holes. The grain roughness of the obtained aluminum plate was RZ=4.5a (D
IN standard), anodized skin IItFi1511t/
It was d-.
この基板上に1下記組成の感光液を用いて、乾燥後の被
1重量が27〜30”F/dm’になるように回転塗布
磯で塗布し、その後55℃で1時間乾燥を行なって平版
臼刷版を得た。A photosensitive solution having the following composition was coated on this substrate using a spin coating surface so that the weight of the coating after drying was 27 to 30 F/dm', and then dried at 55°C for 1 hour. A lithographic mortar plate was obtained.
し感光液〕
上記の平版印刷版上にネガフィルムを合着させ、アイド
ルフィン2000[1崎亀機■製、2KWメタルハライ
ドランプ〕で、距離1m、版面強度8mW/−で40秒
間露光後、約18℃の水道水に30秒間浸漬稜、脱脂綿
で1分間軽くとすシ、非画線部を暇り去った。乾燥後、
上記露光機て2分間露光したガム引き処理をおこなった
後、この印刷版を枚葉オフセット印刷*@小森スプリン
トL−25B’にセットし、ウルトラキング(東洋イン
ク製)レッドの印刷インキを使用して印刷したところ、
インキIIi度のよくのった良好な印刷物が10万枚以
上得られた。Photosensitive solution] A negative film was bonded onto the above lithographic printing plate, and after exposure for 40 seconds at a distance of 1 m and a plate surface strength of 8 mW/- using an Idolfin 2000 [manufactured by Ichizaki Kame Kiku ■, 2 KW metal halide lamp], approximately The edges were immersed in tap water at 18° C. for 30 seconds, then gently wiped with absorbent cotton for 1 minute, and the non-printed areas were removed. After drying,
After performing gumming treatment by exposing for 2 minutes using the above exposure machine, this printing plate was set in sheet-fed offset printing*@Komori Sprint L-25B', and Ultra King (manufactured by Toyo Ink) red printing ink was used. When I printed it,
More than 100,000 good prints with good ink quality were obtained.
比較例1
比験として、本発明の感光性高分子化合物の代シに、光
重合系としてフリーラジカル重合性のポリエチレン性不
飽和化合物および7リ一ラジカル光重合開始剤を用いた
下記の組成の感光液を、実織例1と同じようK1m1布
し乾燥した。Comparative Example 1 As a comparative example, the following composition was prepared using a free radical polymerizable polyethylenically unsaturated compound and a 7-radical photopolymerization initiator as a photopolymerization system in place of the photosensitive polymer compound of the present invention. The photosensitive solution was applied to a K1ml cloth in the same manner as in Fabrication Example 1 and dried.
上記比較の印刷版と実施例1の本発明の印刷版とを各々
三分割し、湯皺55℃、湿WIL3〜4暢RHで、3日
間、6日間、9日間だけ、それぞれ強制伽存した。その
後、上lピロ種の平版印刷版上にコダツクステップメプ
レット−2を密着させ、実施例1と同様に露光した。1
8℃の水道水で30秒間浸漬後、脱脂綿で60秒間軽く
こすって埃儂した。現**のステップタブレットのベタ
段数を表1に示し虎。また、現僚後の印桐版tガム引き
処理後、オフセット印刷機に増シ付け、500枚印刷後
の印刷物を次の3段階で評価した。○:良好、ム:やや
汚れ、X:汚れ。その結果f:表1に示す。The printing plate of the above comparison and the printing plate of the present invention of Example 1 were each divided into three parts and subjected to forced storage at a water temperature of 55°C and a humidity of 3 to 4 degrees RH for 3 days, 6 days, and 9 days, respectively. . Thereafter, Kodak Step Meplet-2 was brought into close contact with the upper 1 pyro type lithographic printing plate, and exposed in the same manner as in Example 1. 1
After immersing it in tap water at 8°C for 30 seconds, it was lightly rubbed with absorbent cotton for 60 seconds to remove dust. Table 1 shows the number of solid steps of the current step tablet. In addition, after the Inkuri version was treated with T-gumming, the offset printing machine was added with additional markings, and the printed matter after printing 500 sheets was evaluated on the following three levels. ○: Good, Mu: Slightly dirty, X: Stained. The results f: are shown in Table 1.
表 I
表1から明らかなように1光重合系を使用した比較の印
刷版は、熱による劣化が著しいが、2F発明に%る感光
性組成物の実施態様である印刷版は保存性が着しく優れ
ていることがわかる。Table I As is clear from Table 1, the comparative printing plate using the photopolymerization system 1 shows significant deterioration due to heat, but the printing plate which is an embodiment of the photosensitive composition according to the 2F invention has a good shelf life. It can be seen that it is excellent.
夾−例2
上記組成の感光液を用いて、現儂後の後露光を省略した
点を除いては実施例1と全く同様に行なった。この印刷
版を用いて8万枚印刷したところ原画に忠実な印刷物が
得られた。Example 2 The same procedure as in Example 1 was carried out except that the photosensitive solution having the above composition was used and the post-exposure after exposure was omitted. When 80,000 copies were printed using this printing plate, printed matter faithful to the original image was obtained.
実施例3
上記組成の感光tf&を用いたほかは、実施例1と全く
同様に行なった。実施例1と同じく、この印刷版につい
て印刷したところ、原画に忠実な印刷物が9万枚以上得
られ次。Example 3 The same procedure as in Example 1 was carried out except that photosensitive tf& having the above composition was used. As in Example 1, when this printing plate was printed, more than 90,000 prints faithful to the original were obtained.
実施例4
上記組成の感光液を実施例1のアルミニウム板に実施例
1と同様に塗布、乾燥、m光し、水道水で現像したとこ
ろ、解像力、インク着肉性の優れた平版印刷版が8万枚
以上得られた。Example 4 A photosensitive solution having the above composition was applied to the aluminum plate of Example 1 in the same manner as in Example 1, dried, exposed to light, and developed with tap water. As a result, a lithographic printing plate with excellent resolution and ink receptivity was obtained. Over 80,000 copies were obtained.
実施例5
厚さ1004mのポリエチレンテレフタレートフィルム
の片面にアルミニウムを500ム真空蒸儀し、該アルミ
ニウム面上に実施例1の感光液で乾燥後の被覆重量が3
0 q/d−になるように、回転塗布機を用いて塗布し
た。55℃で1時間放置して乾燥させた後、上記感光性
フィルム上にネガフィルムを密着させ、実施例1と同様
に露光した。Example 5 500 μm of aluminum was vacuum vaporized on one side of a polyethylene terephthalate film with a thickness of 1004 m, and the photosensitive solution of Example 1 was coated on the aluminum surface with a coating weight of 3 after drying.
It was coated using a rotary coater so that the coating was 0 q/d-. After drying at 55° C. for 1 hour, a negative film was adhered onto the photosensitive film and exposed in the same manner as in Example 1.
18℃の水道水に1分間浸漬後、脱脂綿で1分間擦り末
筒先部を除去して下層のアルミニウムを算出させた。After immersing in tap water at 18° C. for 1 minute, the tip of the tube was removed by rubbing with absorbent cotton for 1 minute, and the aluminum in the lower layer was calculated.
次に、水100mにリン酸20wtを含む溶液に1分間
浸漬後、水洗、乾燥した。その結果、ピンホールのない
itgIIl光性の極めて高いポジフィルムが得られた
。Next, it was immersed for 1 minute in a solution containing 20 wt of phosphoric acid in 100 m of water, washed with water, and dried. As a result, a positive film with extremely high itgIIl optical properties without pinholes was obtained.
冥怖例6
銅/プラスチック板の銅面上に下記の組成の感光液で乾
燥後の被覆重量が30w/diKなるように回転塗布l
lIを用いて塗布した。Horror Example 6 Spinning a photosensitive solution with the following composition on the copper surface of a copper/plastic plate so that the coating weight after drying is 30w/diK.
It was coated using II.
55℃で1時間乾燥させ、その後上記感光性銅板上にプ
リント配線用ネガフィルムt−密着させ、実権例1と同
様に露光、現俸を行ない、下層の銅板を算出させた。次
に、40暢の塩化第2鉄水溶液中に浸漬して腐食を行な
ったところ、欠陥のない良好なプリント配線板が得られ
た。After drying at 55° C. for 1 hour, a negative film for printed wiring was brought into close contact with the photosensitive copper plate, and exposure and exposure were performed in the same manner as in Example 1 to calculate the copper plate of the lower layer. Next, when the board was immersed in 40 g of ferric chloride aqueous solution for corrosion, a good printed wiring board with no defects was obtained.
特許出願人 小西六写真工業株式会社代理人 弁理士
坂 O信 昭
(aか1名)
手続補正書岨発)
1−′J和57年9月29日
!t!i許庁長官庁長官杉 和 夫 殿1 °IIイ′
1の表示
昭和56年 特 許願第100626 号2・ 発明
の名称
111す1
r’L’ ”;’、 (?+M・)(127)小西六写
真工業株式会社4、代 理 人〒105
/
6 補正により増加する発明の数
8、補正の内容
別紙の通り
V 補正の内容
1 明細書中筒11行〜第12行に「アルドールやアセ
タールのような」とあるを削除する。Patent applicant Konishi Roku Photo Industry Co., Ltd. Agent Patent attorney Akira Oshin Saka (a or 1 person) Procedural amendment (Issue) 1-'JSeptember 29, 1957! T! i Mr. Kazuo Sugi, Director-General of the Office of the Director General 1 ° II I'
1 Indication 1982 Patent Application No. 100626 2. Name of the invention 111s1 r'L'”;', (?+M・) (127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 〒105/6 The number of inventions increased by 8 due to the amendment. Contents of the amendment V. Contents of the amendment 1 The words "aldol and acetal" are deleted from lines 11 to 12 of the central cylinder of the specification.
2 同第9頁第6行〜第7行に「メタクリルアミド系の
単量体」とあるを「メタクリルエステル系の車社体」と
補正する。2. On page 9, lines 6 to 7, the phrase "methacrylamide-based monomer" is corrected to "methacrylic ester-based car body."
3 同停止1負第11行にr40 : 15 : 35
Jとあるをr50 : 15 : 35Jと補正する。3 Same stop 1 negative 11th line r40: 15: 35
J is corrected to r50: 15: 35J.
4 同第13自第8行にl’f :CHO−、NH,
1とあるを[R: 11− 、CHO−、N)l −J
と補正する。4 On the 8th line of the 13th car, l'f: CHO-, NH,
1 [R: 11-, CHO-, N)l-J
and correct it.
と補正する。and correct it.
1−
6 同第23頁第9行〜第10行に[何ら変化しないが
、」とあるを「除去されないが、Jと補正する。1-6 On page 23, lines 9 and 10, the phrase ``No change, but'' is corrected to ``Not removed, but J.''
7、 同第25頁第12行に「6藤Jとあるを「水溶液
」と補正する。7. On page 25, line 12, ``6 Fuji J'' is corrected to read ``aqueous solution''.
8 同第26頁第1行に「バラジフェニルアミン」とあ
るを「パラジアゾジフェニルアミンJさ補正する。8 In the first line of page 26 of the same document, the phrase ``baradiphenylamine'' is corrected to ``paradiazodiphenylamine J.''
以上
2−
手続補正書(方向
昭和57年11月4日
特許庁長官若杉和夫 殿
1、事件の表示
昭和56年特 許 願第100626 号2、 発明
0名s 感光性組成物
3、 補正をする者
事件との関係 特許出願人
4・ 代 理 人 〒105
6、補正により増加する発明の数
7、補正の対象
/
昭和57年9月29日付提出の手続補寸書゛の補正の内
容、1.1
8u紙の通り
補正の内容
1 昭和57年1月4日付提出の手続補正書の補正の内
容中、1項を「明細1中第5自第11行〜第12行に「
アルドールやアセタールのような」とあるを削除する。Above 2 - Procedural amendment (direction: November 4, 1980 Kazuo Wakasugi, Commissioner of the Patent Office, 1, Indication of the case, Patent Application No. 100626 filed in 1982, 2, Inventors: 0, Photosensitive composition, 3, Make amendments) Relationship with the Patent Applicant's Case Patent Applicant 4/Agent 105 6, Number of Inventions Increased by Amendment 7, Subject of Amendment/Contents of Amendment to Procedural Supplementary Statement Submitted on September 29, 1980, 1 .1 Contents of amendment as per paper 8u 1 In the contents of the amendment to the procedural amendment submitted on January 4, 1981, paragraph 1 was changed to ``In the 5th paragraph lines 11 to 12 of Specification 1''.
Delete "like aldol or acetal."
」と肝玉する。” he exclaims.
以 上that's all
Claims (1)
び(C)主鎖または1lIl@に架橋成分として−CH
= C−Co−基(Rti水素原子、シアノ基 /%ロ
ケン原子t−表わす。)1に有する感光性高分子化合物
を含むことを特徴とする水で現偉可能な感光性組成物。[Scope of Claims] [A] Diazo resin, [B] water-softening polymer compound, and (C) -CH as a crosslinking component in the main chain or 1lIl@
= C-Co- group (represented by Rti hydrogen atom, cyano group/% Loken atom t-).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10062681A JPS5849940A (en) | 1981-06-30 | 1981-06-30 | Photosensitive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10062681A JPS5849940A (en) | 1981-06-30 | 1981-06-30 | Photosensitive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5849940A true JPS5849940A (en) | 1983-03-24 |
Family
ID=14279038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10062681A Pending JPS5849940A (en) | 1981-06-30 | 1981-06-30 | Photosensitive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5849940A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62175730A (en) * | 1986-01-30 | 1987-08-01 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPS62175729A (en) * | 1986-01-30 | 1987-08-01 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPH0212250A (en) * | 1988-04-20 | 1990-01-17 | Hoechst Celanese Corp | Water developing, negatively acting overlayer or transfer type color proof system |
US6258507B1 (en) | 1998-03-26 | 2001-07-10 | Sumitomo Chemical Company, Limited | Photoresist compositions |
EP1468822A2 (en) | 2003-04-18 | 2004-10-20 | Konica Minolta Medical & Graphic, Inc. | Development process on a press of planographic printing plate material and printing process |
-
1981
- 1981-06-30 JP JP10062681A patent/JPS5849940A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62175730A (en) * | 1986-01-30 | 1987-08-01 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPS62175729A (en) * | 1986-01-30 | 1987-08-01 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPH0544018B2 (en) * | 1986-01-30 | 1993-07-05 | Fuji Photo Film Co Ltd | |
JPH0212250A (en) * | 1988-04-20 | 1990-01-17 | Hoechst Celanese Corp | Water developing, negatively acting overlayer or transfer type color proof system |
US6258507B1 (en) | 1998-03-26 | 2001-07-10 | Sumitomo Chemical Company, Limited | Photoresist compositions |
EP1468822A2 (en) | 2003-04-18 | 2004-10-20 | Konica Minolta Medical & Graphic, Inc. | Development process on a press of planographic printing plate material and printing process |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3346866B2 (en) | Water developable diazo-based lithographic printing plate | |
JP3381208B2 (en) | Lithographic base and method for producing a lithographic printing plate using the same | |
US5445912A (en) | Lithographic base and a method for making a lithographic printing plate therewith | |
JP3381209B2 (en) | Lithographic base and method for producing a lithographic printing plate using the same | |
US5786128A (en) | On-press development of a lithographic printing plate having an aryldiazosulfonate resin in a photosensitive layer | |
JP3150756B2 (en) | Radiation-sensitive substance | |
US4511640A (en) | Aqueous developable diazo lithographic printing plates with admixture of polyvinyl acetate and styrene maleic acid ester copolymer | |
JPH0519460A (en) | Diazo-base lithographic plate capable of being developed by water | |
JPH06180504A (en) | Lithographic printing plate based on resin containing aryl diazo sulfonate | |
JPH09249712A (en) | Production of acid anhydride-modified polyvinyl acetal useful for photosensitive composition | |
US5639586A (en) | Lithographic base and a lithographic printing plate | |
US5402725A (en) | Lithographic base with a modified dextran or pullulan hydrophilic layer | |
JPH0720630A (en) | Improvement of storage stability of image formation material of diazo base to make printing-plate forming material | |
JPS5849940A (en) | Photosensitive composition | |
JPH09235438A (en) | Water-developable negative photosensitive composition having improved image contrast | |
JPH0272A (en) | Pre-sensitized image forming material ideal for use as lithographic plate | |
EP0727714A1 (en) | A diazo based imaging element having improved resistance against physical damage | |
US4539285A (en) | Photosensitive negative diazo composition with two acrylic polymers for photolithography | |
JPS6255503B2 (en) | ||
US5264318A (en) | Positive type photosensitive composition developable with water comprising a photocrosslinking agent, a water-soluble resin and an aqueous synthetic resin | |
JPH08152712A (en) | Improvement of storage stability of diazo-based image forming material for manufacturing printing plate | |
JPH09179311A (en) | Developing method of diazo base printing plate in printing machine | |
US4914000A (en) | Three dimensional reproduction material diazonium condensates and use in light sensitive | |
JPS6119027B2 (en) | ||
EP0068902A1 (en) | Water-developable lithographic printing plate material |