JPS6367176B2 - - Google Patents

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Publication number
JPS6367176B2
JPS6367176B2 JP7831681A JP7831681A JPS6367176B2 JP S6367176 B2 JPS6367176 B2 JP S6367176B2 JP 7831681 A JP7831681 A JP 7831681A JP 7831681 A JP7831681 A JP 7831681A JP S6367176 B2 JPS6367176 B2 JP S6367176B2
Authority
JP
Japan
Prior art keywords
polyamide
acid
parts
photosensitive resin
monomer
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
Application number
JP7831681A
Other languages
Japanese (ja)
Other versions
JPS57192461A (en
Inventor
Kohei Umetani
Toshiaki Fujimura
Akira Tomita
Shinichi Tanaka
Hisashi Uhara
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.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
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 Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP7831681A priority Critical patent/JPS57192461A/en
Publication of JPS57192461A publication Critical patent/JPS57192461A/en
Publication of JPS6367176B2 publication Critical patent/JPS6367176B2/ja
Granted legal-status Critical Current

Links

Description

【発明の詳现な説明】[Detailed description of the invention]

本発明は氎珟像可胜なポリアミド系感光性暹脂
組成物に関するものである。 埓来より印刷甚凞板は、感光性暹脂組成物の局
以䞋感光性局ず称すず支持䜓ずからなる感光
性原版の感光性局に透明画像郚を有するネガフむ
ルムたたはポゞフむルムを通じお露光を行ない、
露光郚分の感光性暹脂組成物を硬化させお䞍溶化
した埌、未露光郚分の前蚘暹脂組成物を適圓な珟
像液により溶解陀去しお補造されおいる。このよ
うな感光性暹脂組成物は通垞、光重合可胜な䞍飜
和結合を有する単量䜓、適圓な珟像液に可溶性の
重合䜓でしかも前蚘単量䜓の光重合により䞍溶化
する重合䜓、光増感剀および熱重合防止剀を含
む。未露光郚分においお該感光性暹脂組成物、特
に前蚘重合䜓は適圓な珟像液に可溶性であるが、
露光郚分においお該同䞀溶剀に䞍溶性ずなる。た
た前蚘重合䜓は光重合可胜な䞍飜和結合を有する
単量䜓の光重合埌、機械的匷床が倧きく、有機溶
剀によ぀お膚最したりしない重合䜓である。この
ような重合䜓ずしおは、アルコヌル可溶性共重合
ポリアミドが提案され、たずえば特公昭35―
14719号公報、特公昭35―15513号公報、特公昭45
―7330号公報などに蚘茉されおいる。 ずころが、これら前蚘ポリアミド系感光性暹脂
組成物は党おアルコヌルには可溶であるが、氎に
は䞍溶であり、埓぀お䞊蚘ポリアミド系版材は、
党お未露光郚の暹脂局を溶解陀去する珟像液ずし
お、アルコヌルなどの有機溶剀を䜿甚しなければ
ならない。これらの有機溶剀を珟像液ずしお䜿甚
するこずは取扱い䜜業性、貯蔵、廃液、高䟡な防
爆型珟像装眮などの点で問題があるだけでなく、
䞊蚘ポリアミドがアルコヌルなどの有機溶剀ぞの
溶解速床が小さいためにそれから䜜成される組成
物の珟像に比范的長い時間を必芁ずするなどの欠
点を有する。そこで、これらを解決する方法ずし
お、氎可溶型ポリアミド系重合䜓を䜿甚した氎珟
像可胜型ポリアミド系感光性暹脂組成物が特公昭
54―22229号公報に蚘茉されおいる。この方法に
より補造された氎珟像可胜型ポリアミド系感光性
暹脂版は原図に察しおの再珟性が良奜であり、む
ンキの受理、転移性がさらに向䞊し、又印刷時の
耐刷性も非垞に良奜であるが感光性暹脂組成物が
光硬化しお生成した硬化物以䞋光硬化物ず略
す。が硬いのでこの皮の感光性暹脂は印刷速床
の遅い平台匏印刷機に䟛され、たた印刷される玙
もコヌト玙等の比范的衚面の平らな玙ぞの印刷に
限られおしたう。 しかしながら、近幎印刷の省力化、高速化を目
的ずしお印刷速床の速い茪転匏印刷機の利甚が進
んでおり、たた印刷甚途も䌝祚類、コンピナヌタ
ヌフオヌム類ぞも拡倧しおきおおり、印刷される
玙が䞊質玙等の衚面の粗な玙ぞず広が぀おきおい
る。この様な新たな甚途に぀いおは埓来の光硬化
物のように硬床が比范的硬いものを利甚するず、
玙衚面の凹凞の郚分の凞郚にのみむンキが転䜍さ
れ、凹郚にはむンキののらない印刷物通垞むン
キのカスレず称するものが埗られおしたう。こ
の欠点を解決するためには光硬化物の硬床が比范
的柔らかく、印刷時に加圧される印圧により玙衚
面に接しおいる郚分の光硬化物が玙の凹凞に応じ
お倉圢し、密着䞍良郚がなくなる様にしなくおは
ならない。 本発明者らは以䞊のような欠点を解消すべく、
光硬化物の硬床が柔らかく、高速印刷や衚面の粗
な玙ぞの印刷に䟛しおもむンキのカスレのない良
奜な印刷物を䞎え、しかも機械的匷床に優れ、耐
刷力の優れた、氎珟像可胜型ポリアミド系感光性
暹脂組成物に぀いお皮々鋭意研究した結果、本発
明を完成するに到぀た。すなわち本発明は、塩基
性窒玠を有するポリアミド、光重合可胜な䞍飜和
結合を有する単量䜓および光重合開始剀からなる
感光性暹脂組成物においお、光重合可胜な䞍飜和
結合を有する単量䜓の党郚たたは䞀郚ずしお䞋蚘
䞀般匏(1)で衚わされる化合物を含有するこずを特
城ずする感光性暹脂組成物である。 匏䞭、は炭玠原子数、〜24の二䟡の炭化氎
玠基たたは分子䞭に――、―COO―、―
NHCO―を有する炭玠原子数〜24の二䟡の炭
化氎玠基、は―SO3H、
The present invention relates to a water-developable polyamide photosensitive resin composition. Conventionally, printing convex plates have been produced by exposing the photosensitive layer of a photosensitive original plate consisting of a layer of a photosensitive resin composition (hereinafter referred to as a photosensitive layer) and a support through a negative film or a positive film having a transparent image area. conduct,
After the photosensitive resin composition in the exposed areas is cured and made insolubilized, the resin composition in the unexposed areas is dissolved and removed using a suitable developer. Such photosensitive resin compositions usually contain a monomer having a photopolymerizable unsaturated bond, a polymer that is soluble in a suitable developer and becomes insolubilized by photopolymerization of the monomer, and a photointensifier. Contains a sensitizer and a thermal polymerization inhibitor. In the unexposed areas, the photosensitive resin composition, particularly the polymer, is soluble in a suitable developer;
The exposed areas become insoluble in the same solvent. Further, the polymer has high mechanical strength after photopolymerization of a monomer having a photopolymerizable unsaturated bond, and is not swollen by organic solvents. As such a polymer, an alcohol-soluble copolymer polyamide has been proposed, for example,
Publication No. 14719, Special Publication No. 15513, Publication No. 15513, Special Publication No. 15513
- Described in Publication No. 7330, etc. However, all of these polyamide-based photosensitive resin compositions are soluble in alcohol but insoluble in water, so the polyamide-based plate material is
An organic solvent such as alcohol must be used as a developer to dissolve and remove all unexposed areas of the resin layer. The use of these organic solvents as developing solutions not only poses problems in terms of handling, storage, waste liquid, and expensive explosion-proof developing equipment, but also
The above-mentioned polyamide has drawbacks such as a slow dissolution rate in organic solvents such as alcohol, and therefore a relatively long time is required for development of a composition prepared from it. Therefore, as a method to solve these problems, a water-developable polyamide-based photosensitive resin composition using a water-soluble polyamide-based polymer was developed by Tokko Sho.
It is described in Publication No. 54-22229. The water-developable polyamide-based photosensitive resin plate produced by this method has good reproducibility with respect to the original image, further improves ink acceptance and transfer properties, and has excellent printing durability during printing. However, since the cured product produced by photocuring the photosensitive resin composition (hereinafter referred to as photocured product) is hard, this type of photosensitive resin is used in flatbed printing machines with slow printing speeds, and Printing is also limited to paper with a relatively flat surface, such as coated paper. However, in recent years, with the aim of saving labor and speeding up printing, the use of high-speed rotary printing presses has progressed, and printing applications have also expanded to include slips and computer forms. It is spreading to papers with rough surfaces such as high-quality paper. For such new applications, if we use a relatively hard material like the conventional photocured material,
Ink is transferred only to the convex portions of the uneven portion of the paper surface, resulting in printed matter (usually referred to as ink smearing) in which no ink is applied to the concave portions. In order to solve this problem, the hardness of the photocured material is relatively soft, and the pressure applied during printing causes the photocured material in the part that is in contact with the paper surface to deform according to the unevenness of the paper, resulting in poor adhesion. We have to make sure that the parts disappear. In order to eliminate the above drawbacks, the present inventors
A water developable product that has a soft hardness of the photocured material and produces good prints without ink fading even when used for high-speed printing or printing on paper with a rough surface, and has excellent mechanical strength and printing durability. As a result of various intensive studies on photosensitive polyamide-based resin compositions, the present invention has been completed. That is, the present invention provides a photosensitive resin composition comprising a polyamide having basic nitrogen, a monomer having a photopolymerizable unsaturated bond, and a photopolymerization initiator. This is a photosensitive resin composition characterized by containing a compound represented by the following general formula (1) as all or a part of the compound. In the formula, X is the number of carbon atoms, a divalent hydrocarbon group of 1 to 24, or -O-, -COO-, - in the molecule
A divalent hydrocarbon group having 1 to 24 carbon atoms having NHCO-, Y is -SO 3 H,

【匏】【formula】

【匏】を瀺し、は炭玠原子数〜10のアル キル基たたはプニル基を瀺す。 本発明の感光性暹脂組成物は䞻材ずなるポリア
ミドが、塩基性窒玠を有するポリアミドず䞀般匏
(1)で瀺される光重合可胜な䞍飜和結合を有する単
量䜓ず䞀郚もしくは党郚がむオン結合しお生成す
るアンモニりム塩型窒玠原子を有する重合䜓であ
るため、氎に容易に溶解し、氎による珟像が可胜
ずなる。さらに該感光性暹脂組成物は䞀般匏(1)で
衚わされる化合物ずのむオン結合により、䞻材ず
なるポリアミドの氎玠結合が立䜓障害のため枛少
し、可塑効果が働いお柔軟になり、さらに光硬化
した堎合、䞀般匏(1)で衚わされる化合物が単独で
重合あるいは他の光重可胜な䞍飜和結合を有する
単量䜓ず共重合するので、光重合生成物の次元
的結合の網目が粗になり、そのため柔軟になる。
しかも光硬化埌の感光性暹脂では、ポリアミドず
光重合可胜な䞍飜和結合を有する単量䜓の光重合
䜓ずがむオン結合しおいるので、耐湿性、耐溶剀
性がよく、か぀力孊的特性、特に耐摩耗性のすぐ
れたものが埗られる。 本発明においお、光重合可胜な䞍飜和結合を有
する単量䜓の党郚たたは䞀郚ずしお䜿甚される䞀
般匏(1)で衚わされる化合物は、たずえば䞋蚘匏で
瀺される化合物である。 などがある。これらの単量䜓を単独あるいは皮
以䞊混合しお䜿甚する。これらの単量䜓は塩基性
窒玠を含有するポリアミドに察しお四玚化剀ずし
お反応する。四玚化剀ずしお䞀般匏(1)で瀺す化合
物の他に、塩酞、硫酞などの無機酞、蟻酞、酢
酞、クロル酢酞、マレむン酞、フタル酞、アゞピ
ン酞、アクリル酞、メタクリル酞などの有機酞も
利甚できる。たた、前蚘䞀般匏(1)で瀺す化合物を
含む四玚化剀の添加量はポリアミド䞭に存圚する
塩基性窒玠の量、氎に察する溶解性などを考慮し
お適宜遞択するこずができる。ポリアミド䞭に存
圚する塩基性窒玠の量に察しお、䞀般匏(1)で衚わ
される化合物がモル以䞊特に50〜100モル
存圚するこずが必芁である。䞀般匏(1)で衚わされ
る化合物がモル未満では光架橋埌の感光性暹
脂組成物の必芁な柔軟性が欠けるので奜たしくな
い。 本発明においお、䜵甚可胜な前蚘䞀般匏(1)で瀺
される化合物以倖の光重合し埗る䞍飜和結合を有
する単量䜓ずしおは、たずえばメチルアクリレヌ
ト、メチルメタアクリレヌト、ベンゞルアクリレ
ヌト、トリブロムプニルアクリレヌト、シクロ
ヘキシルアクリレヌト、―ヒドロキシプロピル
アクリレヌト、アクリルアミド、メタアクリルア
ミド、―メチロヌルアクリルアミド、―ブト
キシメチルアクリルアミド、iso―ブトキシメチ
ルアクリルアミド、――ブチルアクリルアミ
ド、アクリロニトリル、スチレン、ビニルピリゞ
ン等の䞍飜和二重結合を個有する単量䜓、或い
はアリルメタアクリレヌト、゚チレングリコヌル
ゞアクリレヌト、゚チレングリコヌルゞメタアク
リレヌト、―プロパンゞオヌルゞアクリレ
ヌト、―プロパンゞオヌルメタアクリレヌ
ト、―ブタンゞオヌルゞアクリレヌト、
―ブタンゞオヌルメタアクリレヌト、
―ヘキサンゞオヌルゞアクリレヌト、―
ヘキサンゞオヌルゞメタアクリレヌト、トリメチ
ロヌルプロパントリアクレヌト、トリメチロヌル
プロパントリメタアクリレヌト、テトラメチロヌ
ルメタントリアクリレヌト、トリアクリロむルオ
キシ゚チルホスプむト、メチレンビスアクリル
アミド、゚チレンビスアクリルアミド、プロピレ
ンビスアクリルアミド、ブチレンビスアクリルア
ミド、メチレンビスメタクリルアミド、゚チレン
ビスメタクリルアミド、プロピレンビスメタクリ
ルアミド等の䞍飜和二重結合を個以䞊有する単
量䜓がある。 尚、ポリアミド䞭に存圚する塩基性窒玠の量に
察しお、䞀般匏(1)で衚わされる化合物ず䜵甚した
前蚘四玚化剀の和の量の比が100モル以䞊にな
る堎合、塩基性窒玠のモル量から䜵甚した四玚化
剀のモル量を匕き、さらに匏(1)の化合物から残䜙
の等モル量にした量以䞊の匏(1)の化合物は䟿宜
䞊、本発明に斌お、䜵甚可胜な四玚化剀以倖の光
重合可胜な䞍飜和結合を有する単量䜓の類䞭に入
れる。 本発明においお塩基性窒玠を有するポリアミド
ずは、たずえば䞋蚘䞀般匏〜で瀺さ
れる単量䜓を重合原料ずしお埗られるものであ
る。 䞊蚘䞀般匏〜においお、
R′は氎玠原子たたは炭玠原子数〜10個の炭化
氎玠残基、R1R2R3は炭玠原子数〜15個の
アルキレン基、R4R5は炭玠原子数〜10個の
炭化氎玠残基、は―NH2、―COOH、―
COOR″を瀺し、ずは同時に同じあるいは盞
違しおもよい。ここでR″は炭玠原子数〜10個
の炭化氎玠残基を瀺す。 䞊蚘䞀般匏においお、R6R7は炭玠
原子数〜10個の炭化氎玠残基を瀺す。R6ずR7
は共同しお環や異節環を圢成しおも良い。たた
R8は炭玠原子数〜個の䜎玚アルキル基ある
いは
[Formula] is shown, and R represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. In the photosensitive resin composition of the present invention, the main material polyamide is a polyamide having basic nitrogen and the general formula
It is an ammonium salt-type nitrogen atom-containing polymer produced by partially or fully ionic bonding with the photopolymerizable unsaturated bond-containing monomer shown in (1), so it easily dissolves in water. Development with water becomes possible. Furthermore, due to the ionic bonding with the compound represented by general formula (1), the hydrogen bonds in the polyamide, which is the main material, are reduced due to steric hindrance, and the photosensitive resin composition becomes flexible due to the plasticizing effect, and furthermore, the photosensitive resin composition becomes flexible and photosensitive. When cured, the compound represented by formula (1) is polymerized alone or copolymerized with other photopolymerizable monomers having unsaturated bonds, so that the three-dimensional bond network of the photopolymerized product is It becomes coarser and therefore more flexible.
In addition, in the photosensitive resin after photocuring, the polyamide and the monomer photopolymer having photopolymerizable unsaturated bonds are ionicly bonded, so it has good moisture resistance, solvent resistance, and mechanical properties. In particular, products with excellent abrasion resistance can be obtained. In the present invention, the compound represented by the general formula (1) used as all or part of the monomer having a photopolymerizable unsaturated bond is, for example, a compound represented by the following formula. and so on. These monomers may be used alone or in combination. These monomers react as quaternizing agents for polyamides containing basic nitrogen. In addition to the compound represented by general formula (1) as a quaternizing agent, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as formic acid, acetic acid, chloroacetic acid, maleic acid, phthalic acid, adipic acid, acrylic acid, and methacrylic acid Also available. Further, the amount of the quaternizing agent containing the compound represented by the general formula (1) can be appropriately selected in consideration of the amount of basic nitrogen present in the polyamide, the solubility in water, and the like. The amount of the compound represented by general formula (1) is 5 mol% or more, especially 50 to 100 mol%, based on the amount of basic nitrogen present in the polyamide.
It is necessary to exist. If the amount of the compound represented by general formula (1) is less than 5 mol %, the photosensitive resin composition after photocrosslinking will lack the necessary flexibility, which is not preferred. In the present invention, monomers having a photopolymerizable unsaturated bond other than the compound represented by the general formula (1) that can be used in combination include, for example, methyl acrylate, methyl methacrylate, benzyl acrylate, tribromphenyl acrylate. , cyclohexyl acrylate, 2-hydroxypropyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide, n-butoxymethylacrylamide, iso-butoxymethylacrylamide, Nt-butylacrylamide, acrylonitrile, styrene, vinylpyridine, etc. Monomers having one heavy bond, or allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol methacrylate, 1,4-butanediol diacrylate,
1,4-butanediol methacrylate, 1,
6-hexanediol diacrylate, 1,6-
Hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, triacryloyloxyethyl phosphate, methylenebisacrylamide, ethylenebisacrylamide, propylenebisacrylamide, butylenebisacrylamide, methylenebis There are monomers having two or more unsaturated double bonds, such as methacrylamide, ethylenebismethacrylamide, and propylenebismethacrylamide. In addition, when the ratio of the sum of the quaternizing agent used in combination with the compound represented by general formula (1) to the amount of basic nitrogen present in the polyamide is 100 mol% or more, the basic nitrogen For convenience, in the present invention, the compound of formula (1) in an amount equal to or more than the equivalent molar amount of the compound of formula (1) after subtracting the molar amount of the quaternizing agent used in combination from the molar amount of nitrogen, It is included in the category of monomers having photopolymerizable unsaturated bonds other than quaternizing agents that can be used in combination. In the present invention, the polyamide having basic nitrogen is obtained, for example, by using monomers represented by the following general formulas () to () as polymerization raw materials. (In the above general formulas () to (), R,
R' is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, R 1 , R 2 , and R 3 are alkylene groups having 1 to 15 carbon atoms, and R 4 and R 5 are 1 to 1 carbon atoms. 10 hydrocarbon residues, A and B are -NH 2 , -COOH, -
COOR'', and A and B may be the same or different at the same time.R'' represents a hydrocarbon residue having 1 to 10 carbon atoms. ) (In the above general formula (), R 6 and R 7 represent hydrocarbon residues having 1 to 10 carbon atoms. R 6 and R 7
may join together to form a ring or a heterocyclic ring. Also
R 8 is a lower alkyl group having 1 to 3 carbon atoms or

【匏】を瀺す。ここではR6R7は 前述の基である。はγ―アミノプロピル基を瀺
す。 前蚘䞀般匏で瀺される具䜓的な単量䜓ず
しおはN′―ビスアミノメチル―ピペラ
ゞン、N′―ビスβ―アミノ゚チル―ピ
ペラゞン、N′―ビスβ―アミノ゚チル
―メチルピペラゞン、―アミノメチル―
N′―β―アミノ゚チル―ピペラゞン、
N′―ビスγ―アミノプロピル―ピペラゞン
等のゞアミン類、N′―ビス―カルボキシ
メチル―ピペラゞン、N′―ビスカルボ
キシメチル―メチルピペラゞン、N′―ビ
スカルボキシメチル――ゞメチルピペ
ラゞン、N′―ビスβ―カルボキシ゚チル
―ピペラゞン、N′―ビスγ―カルボキシ
プロピル―ピペラゞン、―β―カルボキシ
゚チル―N′―カルボキシメチル―ピペラ
ゞンなどのゞカルボン酞類あるいはこれらの䜎玚
アルキル゚ステル、酞ハロゲン化物および―
アミノメチル―N′―カルボキシメチル―
ピペラゞン、―アミノメチル―N′―β
―カルボキシ゚チル―ピペラゞン、―β―
アミノ゚チル―N′―β―カルボキシ゚チル
―ピペラゞン、―アミノメチル―N′―
カルボキシメチル――メチルピペラゞンな
どのω―アミノ酞である。 䞊蚘䞀般匏で瀺される具䜓的な単量䜓ず
しおは、―β―アミノ゚チルピペラゞン、
―γ―アミノプロピルピペラゞン、―
ω―アミノヘキシルピペラゞン、―Ύ―
アミノシクロヘキシルピペラゞン、―β―
アミノ゚チル――メチルピペラゞン、―
β―アミノ゚チル――ゞメチルピペラ
ゞン、―β―アミノプロピル――メチル
ピペラゞン、―γ―アミノプロピル―
―ゞメチルピペラゞンなどのゞアミン類、―
カルボキシメチルピペラゞン、―β―カルボ
キシ゚チル―ピペラゞン、―γ―カルボキ
シプロピルピペラゞン、―ω―カルボキシ
ヘキシルピペラゞン、―Ύ―カルボキシシ
クロヘキシルピペラゞン、―β―カルボキ
シ゚チル――メチルピペラゞン、―β―
カルボキシ゚チル――ゞメチルピペラゞ
ンなどのω―アミノ酞あるいはこれらの䜎玚アル
キル゚ステル類などである。 前蚘䞀般匏で瀺される具䜓的な単量䜓ず
しおは、―ゞβ―アミノ゚チル゚チル
アミン、―ゞγ―アミノプロピルメチ
ルアミン、―ゞβ―アミノ゚チル―メ
チルアミン、N′―ゞγ―アミノプロピル
―゚チルアミン、―ゞγ―アミノプロピ
ルむ゜プロピルアミン、―ゞγ―アミ
ノプロピル―シクロヘキシルアミン、―
ゞΎ―アミノ――ブチルプニルアミン、
―メチル――β―アミノ゚チル―
―プロパンゞアミンなどのゞアミン類、―
ゞカルボキシメチル―メチルアミン、
―ゞβ―カルボキシ゚チルメチルアミン、
―ゞβ―カルボキシ゚チル―メチルア
ミン、―ゞβ―カルボキシ゚チル―む
゜プロピルアミン、―カルボキシメチル――
β―カルボキシ゚チル―メチルアミンなどの
ゞカルボン酞類あるいはこれらの䜎玚アルキル゚
ステル、酞ハロゲン化物、および―アミノメ
チル――カルボキシメチル―メチルアミ
ン、―β―アミノ゚チル――β―カル
ボキシ゚チル―メチルアミン、―アミノメ
チル――β―カルボキシル゚チル―む゜
プロピルアミン、―γ―アミノプロピル―
―γ―カルボキシプロピル―む゜プロピル
アミン、―γ―アミノプロピル――β
―カルボキシ゚チル―メチルアミンなどのω―
アミン酞類である。 前蚘䞀般匏で瀺される具䜓的な単量䜓ず
しおは、N′―ゞメチル―N′―ゞ―γ
―アミノプロピル―゚チレンゞアミン、
N′―ゞメチル―N′―ゞ―γ―アミノプロ
ピル―テトラメチレンゞアミン、N′―ゞ
む゜ブチル―N′―ゞ―γ―アミノプロピ
ル―ヘキサメチレンゞアミン、N′―ゞシ
クロヘキシル―N′―ゞ―γ―アミノプロ
ピル―ヘキサメチレンゞアミン、N′―ゞ
―γ―アミノプロピル――トリメ
チル―ヘキサメチレンゞアミンなどのゞアミン
類、N′―ゞメチル―N′―ゞカルボキ
シメチル―゚チレンゞアミン、N′―ゞメ
チル―N′―ゞ―β―カルボキシ゚チル
―゚チレンゞアミン、N′―ゞメチル―
N′―ゞ―γ―カルボキシプロピル―ヘキサ
メチレンゞアミンなどのゞカルボン酞類あるいは
これらの䜎玚アルキル゚ステル、酞ハロゲン化物
およびN′―ゞメチル――アミノメチル
―N′―カルボキシメチル―゚チレンゞアミ
ン、N′―ゞメチル――βアミノ゚チル
―N′―β―カルボキシ゚チル―゚チレンゞ
アミン、N′―ゞメチル――アミノメチ
ル―N′―カルボキシ゚チル―ヘキサメチ
レンゞアミンなどのω―アミノ酞である。 䞊蚘䞀般匏で瀺される具䜓的な単量䜓ず
しおは、―メチル――N′―ゞメチル
アミノメチル――ゞオキサ―りンデカン
ゞアミン、―メチル――N′―ゞ゚チ
ルアミノメチル――ゞオキサ―りンデカ
ンゞアミン、―゚チル―――ゞメチ
ルアミノメチル――ゞオキサ―りンデカ
ンゞアミン、―ビス―ゞメチルア
ミノメチル――ゞオキサンりンデカンゞ
アミンなどのゞアミン類である。 これら塩基性窒玠をゆうする単量䜓を単独もし
くは皮以䞊甚いお瞮重合を行いポリアミドを圢
成する。すなわち、䞊蚘単量䜓がω―アミノ酞あ
るいはそのアルキル゚ステル類などのように単独
重合によ぀おポリアミドを圢成し埗る単量䜓は単
独で甚いるこずができる。䞀方、䞊蚘単量䜓がゞ
カルボン酞あるいはそのアルキル゚ステル類、酞
ハロゲン化物などであればゞアミンず、たた䞊蚘
単量䜓がゞアミンであればゞカルボン酞あるいは
その誘導䜓ず、瞮重合させるこずによ぀おポリア
ミドを圢成せしめる。 さらに本発明に甚いるポリアミドの重合原料ず
しおは、前蚘䞀般匏〜で瀺される単
量䜓のほかに、通垞のポリアミドの重合に甚いら
れる脂肪族およびたたは芳銙族のゞカルボン
酞、ゞアミン、ω―アミノ酞、ラクタムなどを䜵
甚しおもよい。䜵甚可胜なゞカルボン酞ずしお
は、たずえばコハク酞、アゞピン酞、グルタル
酞、アれラむン酞、セバシン酞、デカンゞカルボ
ン酞、テレフタル酞、む゜フタル酞、シクロヘキ
サンゞカルボン酞などの脂肪族およびたたは芳
銙族のゞカルボン酞あるいはこれらの酞の䜎玚ア
ルキル゚ステル、酞ハロゲン化物などを甚いる。
ゞアミンずしおはたずえばテトラメチレンゞアミ
ン、ペンタメチレンゞアミン、ヘキサメチレンゞ
アミン、ヘプタメチレンゞアミン、オクタメチレ
ンゞアミン、ノナメチレンゞアミン、デカメチレ
ンゞアミン、などの盎鎖飜和脂肪族ゞアミン、メ
タキシリレンゞアミン、パラキシリレンゞアミン
などの芳銙族ゞアミン、シクロヘキサンビスメチ
ルアミンなどの脂肪族ゞアミンなどを甚いる。ω
―アミノ酞ずしおは、たずえばアミノカプロン
酞、アミノヘプタン酞、アミノカプリル酞、アミ
ノカプロン酞、アミノラりリル酞などを甚いる。
ラクタムずしおは、たずえばε―カプロラクタ
ム、α―メチル―εカプロラクタム、ε―メチル
―εカプロラクタム、シクロヘプタノンむ゜オキ
シム、シクロオクタノンむ゜オキシムなどを甚い
る。 以䞊の単量䜓から埗られる塩基性窒玠原子を有
するポリアミドの重合方法は埓来公知のポリアミ
ドの補造方法に埓぀お行なうこずができる。塩基
性窒玠を含有する単量䜓成分は党ポリアミド構成
成分の〜100モルであり、特に20〜50モル
であるこずが奜たしい。なお、䞊述に瀺される塩
基性窒玠を含有する単量䜓の他に、䞀般匏
で瀺される化合物ず反応し第四玚アンモニりム塩
を生成する様な窒玠を含有する単量䜓はすべお利
甚できる。 以䞊の単量䜓を単独あるいは皮以䞊混合しお
䜿甚する。特に䞍飜和二重結合を少なくずも個
以䞊有する単量䜓を単独で甚いるかあるいは少な
くずも皮以䞊含む単量䜓混合物を甚いるこずが
望たしい。該単量䜓の䜿甚量は、感光性暹脂組成
物䞭のポリアミドに察し、〜150重量、特に
10〜100重量であるこずが奜たしい。該単量䜓
が重量未満であるず、露光郚の溶剀に察する
䞍溶化が充分でなくなる。たた150重量を越え
るず、感光性局の露光埌、機械匷床が損なわれ
る。 光増感剀は前蚘ポリアミドのマトリツクス内で
の前蚘単量䜓の重合反応を促進させるために添加
する。このような光増感剀ずしおは埓来公知のも
のを䜿甚するこずができる。たずえば10―ア
ントラキノン、―クロルアントラキノン、―
クロルアントラキノンなどのアントラキノン類、
ベンゟプノン、―アミノベンゟプノン、
―クロルベンゟプノンなどのベンゟプノン
類、ベンゟむン、ベンゟむンメチル゚ヌテル、ベ
ンゟむン゚チル゚ヌテル、α―メチルベンゟむン
などのベンゟむン類、あるいはベンゞル類があ
る。光増感剀の䜿甚量は前蚘ポリアミド、䞀般匏
で瀺される化合物および光重合可胜な䞍飜
和結合を有する単量䜓ずの総量に察し、0.01〜
重量、特に0.1〜重量であるこずが奜たし
い。 熱重合防止剀は感光性暹脂組成物の調合、成
型、加工時の加熱による光重合可胜な䞍飜和基を
有する単量䜓の熱重合あるいは該感光性暹脂組成
物の保存䞭の暗反応を防止するために添加する。
このような熱重合防止剀ずしおは埓来公知のもの
を甚いるこずができる。たずえばハむドロキノ
ン、モノ――ブチルハむドロキノンなどのハむ
ドロキノン類、ベンゟキノン、―ゞ――
ベンゟキノンなどのベンゟキノン類、カテコヌ
ル、――ブチルカテコヌルなどのカテコヌル
類、ピクリン酞類などがある。熱重合防止剀の䜿
甚量は前蚘ポリアミドず、匏で瀺される化
合物および光重合可胜な䞍飜和結合を有する単量
䜓ずの総量に察し、0.001〜重量、特に0.05
〜0.5重量であるこずが奜たしい。 以䞊、䞀般匏で瀺される化合物、塩基性
窒玠を有するポリアミド、光重合可胜な䞍飜和結
合を有する単量䜓、光増感剀および熱重合防止剀
を含有する本発明の感光性暹脂組成物は、氎、メ
タノヌル、゚タノヌル、四塩化炭玠、トル゚ンあ
るいはキシレンなどの溶媒に溶解し、この溶液か
ら溶媒のみを蒞発させお均䞀に混合するこずによ
぀お容易に埗られる。 本発明の感光性暹脂組成物は通垞シヌト状物な
どに成圢しお感光性暹脂原版ずしお甚いる。即ち
䞊述の組成からなる混合物を熱プレス、泚型ある
いは溶融抌出しなどの方法により所望の厚さの
板、フむルムたたは箔などのシヌト状物ずする。 たたこのシヌト状物を接着剀を介しおあるいは
介さずに支持䜓䞊に積局する。支持䜓ずしおはス
チヌル、アルミニりム、ガラス、プラスチツクフ
むルムなど任意のものが䜿甚できる。 埗られた感光性暹脂原版は感光性局に透明画像
郚を有するネガフむルムたたはポゞフむルムを密
着しお重ね合せ、その䞊方から掻性光線を照射す
るず、露光郚のみ䞍溶化ならびに硬化する。この
ような掻性光線を発する光源ずしおは各皮氎銀
灯、炭玠アヌク灯、キセノンランプ、玫倖線、螢
光灯などが䜿甚できる。 光照射埌は適圓な溶剀により非露光郚分を溶解
陀去するず、鮮明な画像郚を有する凞版が埗られ
る。本発明においおは、基材に䞀般匏で瀺
される化合物ず塩基性窒玠を有するポリアミドず
が反応しおできるアンモニりム塩型窒玠原子を有
するポリアミドを䜿甚するため、単なる氎によ぀
お容易に速かに珟像するこずができる。もちろん
各皮酞氎溶液、氎ずアルコヌルの混合液、䜎玚脂
肪族アルコヌル、䜎玚玙肪族アルコヌルず塩化カ
ルシりムもしくは塩化亜鉛など結合材のポリアミ
ドを可溶化し埗る溶剀によ぀おも珟像できる。 このようにしお埗られる本発明の凞版は、露光
および珟像に芁する時間が極めお短いため埗られ
る画像は非垞にシダヌプな茪廓を有する。しかも
該凞版は、匏で瀺される化合物の効果によ
り非垞に柔軟になり、䞊質玙等粗面を有する玙䞊
にもきれいにむンキが転移し、茪転印刷機で高速
印刷しおもむンキのカスレがなく、非垞に鮮明で
ある。 以䞋本発明を実斜䟋により詳现に説明する。な
お、実斜䟋䞭においお単に郚ずあるのはいずれも
重量郚を瀺す。 参考䟋  ―ビスγ―アミノプロピルピペラゞ
ンアゞペヌト40郚ずε―カプロラクタム60郚を反
応容噚に加え、充分な窒玠眮換を行぀たのち、密
閉しお埐々に加熱した。内圧が10Kgm2に達した
時点から、その圧力を保持できなくなるたで氎を
留出させ、玄時間で垞圧にもどし、その埌1.5
時間垞圧で反応させた。埗られた重合䜓は比粘床
1.59、軟化点110℃の乳癜色ポリアミドであり、
䞭性氎には実質的に䞍溶であ぀た。 実斜䟋  䞋蚘匏で瀺される化合物34郚、参考䟋
で埗られたポリアミド100郚、゚チレングリコヌ
ルゞグリシゞル゚ヌテルずアクリル酞の瞮
合物30郚、ベンゟプノン郚およびハむドロキ
ノン0.2郚をメタノヌル300郚に加え加熱しお溶解
した。この溶液をガラス板䞊に流延しお枛圧䞋に
攟眮しお完党にメタノヌルを陀去するず厚さ0.6
mmの透明なフむルム状の感光性暹脂組成物が埗ら
れた。この組成物は垞枩の氎に容易に溶解した。 埗られたフむルムを、厚さ0.25mmのポリ゚ステ
ルフむルム䞊に貌着しお、感光性原版を埗た。 この原版の感光性局に、133線の網分解した写
真像ネガフむルムを密着させお、倧日本スクリヌ
ン補露光機―113―で分間露光した。露光
埌、倧日本スクリヌン補プリンタむトりオツシダ
ヌBR―A3で分間珟像し、也燥埌埌露光した。
埗られた凞版は原像を忠実に再珟しおいた。次に
この凞版を浮田工業補凞版茪転印刷機BF―201に
装着しお印刷を行぀たずころ、シダドり郚のカス
レがなく、たたハむラむト郚の倪りもなく、非垞
に良奜な印刷物が埗られた。たた䞊蚘凞版の20
℃、65RHでの硬床は28゜シペア―でかな
り柔軟であ぀た。 実斜䟋  䞋蚘匏(2)で瀺される化合物63郚、参考䟋で埗
られたポリアミド100郚、゚チレングリコヌルゞ
グリシゞル゚ヌテルずアクリル酞の瞮合物
30郚、ベンゟプノン郚、ハむドロキノン0.2
郚をメタノヌル300郚に加え加熱しお溶解した。
この溶液から実斜䟋ず同様な方法で感光性原版
を埗、露光、珟像、也燥、埌露光を行぀た。埗ら
れた凞版は原像を再珟し、良奜な印刷物が埗られ
た。たた硬床は30゜シペア―であ぀た。 実斜䟋  䞋蚘匏(3)で瀺される化合物29郚、参考䟋で埗
られたポリアミド100郚、゚チレングリコヌルゞ
グリシゞル゚ヌテルずアクリル酞瞮合物30
郚、ベンゟプノン郚、ハむドロキノン0.2郚
をメタノヌル300郚に加え加熱しお溶解した。こ
の溶液から実斜䟋ず同様な方法で感光性原版を
埗、露光、珟像、也燥、埌露光を行぀た。埗られ
た凞版は原像を再珟しおいた。このレリヌフを実
斜䟋ず同様に印刷したずころ非垞に良奜な印刷
物が埗られた。たた凞版の硬床は33゜であ぀た。 比范䟋  メタアクリル酞10郚、参考䟋で埗られたポリ
アミド100郚、゚チレングリコヌルゞグリシゞル
゚ヌテルずアクリル酞瞮合物30郚、ベンゟ
プノン郚、ハむドロキノン0.2郚をメタノヌ
ル300郚に加え加熱しお溶解した。この溶液から
実斜䟋ず同様な方法で感光性原版を埗、露光、
珟像、也燥、埌露光を行぀た。埗られた凞版を甚
いお実斜䟋ず同様にしお印刷を行぀たずころ、
シダドり郚にカスレを生じ、印刷物は良奜でなか
぀た。たた凞版の硬床は50゜シペア―であり
柔軟性に欠けおいた。 実斜䟋  䞋蚘匏(4)で瀺される化合物21郚、参考䟋で埗
られたポリアミド100郚、゚チレングリコヌルゞ
グリシゞル゚ヌテルずアクリル酞瞮合物30
郚、ベンゟプノン郚、ハむドロキノン0.2郚
をメタノヌル300郚に加え加熱しお溶解した。こ
の溶液から実斜䟋ず同様な方法で感光性原版を
埗、露光、珟像、也燥、埌露光を行぀た。埗られ
た凞版は原像を再珟しおいた。このレリヌフを実
斜䟋ず同様に印刷したずころ非垞に良奜な印刷
物が埗られた。たた凞版の硬床は33゜であ぀た。
[Formula] is shown. Here, R 6 and R 7 are the aforementioned groups. Y represents a γ-aminopropyl group. ) Specific monomers represented by the above general formula () include N,N'-bis(aminomethyl)-piperazine, N,N'-bis(β-aminoethyl)-piperazine, N,N'- Bis(β-aminoethyl)
-Methylpiperazine, N-(aminomethyl)-
N′-(β-aminoethyl)-piperazine, N,
Diamines such as N'-bis(γ-aminopropyl)-piperazine, N,N'-bis-(carboxymethyl)-piperazine, N,N'-bis(carboxymethyl)-methylpiperazine, N,N'- Bis(carboxymethyl)-2,6-dimethylpiperazine, N,N'-bis(β-carboxyethyl)
-Dicarboxylic acids such as piperazine, N,N'-bis(γ-carboxypropyl)-piperazine, N-(β-carboxyethyl)-N'-(carboxymethyl)-piperazine, or their lower alkyl esters and acid halides and N-
(aminomethyl)-N'-(carboxymethyl)-
Piperazine, N-(aminomethyl)-N'-(β
-carboxyethyl)-piperazine, N-(β-
aminoethyl)-N′-(β-carboxyethyl)
-Piperazine, N-(aminomethyl)-N'-
(carboxymethyl)-2-methylpiperazine and other ω-amino acids. Specific monomers represented by the above general formula () include N-(β-aminoethyl)piperazine,
N-(γ-aminopropyl)piperazine, N-
(ω-aminohexyl)piperazine, N-(ÎŽ-
aminocyclohexyl)piperazine, N-(β-
aminoethyl)-3-methylpiperazine, N-
(β-aminoethyl)-2,5-dimethylpiperazine, N-(β-aminopropyl)-3-methylpiperazine, N-(γ-aminopropyl)-2,
Diamines such as 5-dimethylpiperazine, N-
Carboxymethylpiperazine, N-(β-carboxyethyl)-piperazine, N-(γ-carboxypropyl)piperazine, N-(ω-carboxyhexyl)piperazine, N-(ÎŽ-carboxycyclohexyl)piperazine, N-(β- carboxyethyl)-3-methylpiperazine, N-(β-
These include ω-amino acids such as (carboxyethyl)-2,5-dimethylpiperazine, or lower alkyl esters thereof. Specific monomers represented by the general formula () include N,N-di(β-aminoethyl)ethylamine, N,N-di(γ-aminopropyl)methylamine, and N,N-di( β-aminoethyl)-methylamine, N,N'-di(γ-aminopropyl)
-Ethylamine, N,N-di(γ-aminopropyl)isopropylamine, N,N-di(γ-aminopropyl)-cyclohexylamine, N,N-
di(ÎŽ-amino-n-butyl)phenylamine,
N-methyl-N-(β-aminoethyl)-1,3
-Diamines such as propanediamine, N,N-
Di(carboxymethyl)-methylamine, N,N
-di(β-carboxyethyl)methylamine,
N,N-di(β-carboxyethyl)-methylamine, N,N-di(β-carboxyethyl)-isopropylamine, N-carboxymethyl-N-
Dicarboxylic acids such as (β-carboxyethyl)-methylamine or their lower alkyl esters, acid halides, and N-(aminomethyl)-N-(carboxymethyl)-methylamine, N-(β-aminoethyl) -N-(β-carboxyethyl)-methylamine, N-(aminomethyl)-N-(β-carboxylethyl)-isopropylamine, N-(γ-aminopropyl)-
N-(γ-carboxypropyl)-isopropylamine, N-(γ-aminopropyl)-N-(β
-Carboxyethyl)-ω of methylamine, etc.-
They are amino acids. A specific monomer represented by the general formula () is N,N'-dimethyl-N,N'-di-(γ
-aminopropyl)-ethylenediamine, N,
N'-dimethyl-N,N'-di-(γ-aminopropyl)-tetramethylenediamine, N,N'-diisobutyl-N,N'-di-(γ-aminopropyl)-hexamethylenediamine, N, N'-dicyclohexyl-N,N'-di-(γ-aminopropyl)-hexamethylenediamine, N,N'-di-(γ-aminopropyl)-2,2,4-trimethyl-hexamethylenediamine, etc. Diamines, N,N'-dimethyl-N,N'-di(carboxymethyl)-ethylenediamine, N,N'-dimethyl-N,N'-di-(β-carboxyethyl)
-ethylenediamine, N,N'-dimethyl-N,
Dicarboxylic acids such as N'-di-(γ-carboxypropyl)-hexamethylene diamine or their lower alkyl esters, acid halides, and N,N'-dimethyl-N-(aminomethyl)
-N'-(carboxymethyl)-ethylenediamine, N,N'-dimethyl-N-(βaminoethyl)
-N'-(β-carboxyethyl)-ethylenediamine, N,N'-dimethyl-N-(aminomethyl)-N'-(carboxyethyl)-hexamethylenediamine, and other ω-amino acids. Specific monomers represented by the above general formula () include 6-methyl-6-(N,N'-dimethylaminomethyl)-4,8-dioxa-undecanediamine, 6-methyl-6-( N,N'-diethylaminomethyl)-4,8-dioxa-undecanediamine, 6-ethyl-6-(N,N-dimethylaminomethyl)-4,8-dioxa-undecanediamine, 6,6-bis(N , N-dimethylaminomethyl)-4,8-dioxane undecane diamine. Polyamide is formed by condensation polymerization using one or more of these monomers containing basic nitrogen. That is, monomers that can form polyamide by homopolymerization, such as ω-amino acids or alkyl esters thereof, can be used alone. On the other hand, if the monomer is a dicarboxylic acid, its alkyl esters, acid halides, etc., it can be condensed with a diamine, and if the monomer is a diamine, it can be condensed with a dicarboxylic acid or a derivative thereof to form a polyamide. to form. Furthermore, as polymerization raw materials for polyamide used in the present invention, in addition to the monomers represented by the above general formulas () to (), aliphatic and/or aromatic dicarboxylic acids and diamines used in ordinary polyamide polymerization are used. , ω-amino acids, lactams, etc. may be used in combination. Examples of dicarboxylic acids that can be used in combination include aliphatic and/or aromatic dicarboxylic acids such as succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, and cyclohexanedicarboxylic acid; Lower alkyl esters, acid halides, etc. of these acids are used.
Examples of diamines include linear saturated aliphatic diamines such as tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, and decamethylene diamine, metaxylylene diamine, and paraxylylene diamine. Aromatic diamines such as cyclohexane bismethylamine, aliphatic diamines such as cyclohexane bismethylamine, etc. are used. ω
- As the amino acid, for example, aminocaproic acid, aminoheptanoic acid, aminocaprylic acid, aminocaproic acid, aminolauric acid, etc. are used.
Examples of the lactam used include ε-caprolactam, α-methyl-ε-caprolactam, ε-methyl-ε-caprolactam, cycloheptanone isoxime, and cyclooctanone isoxime. Polyamides having basic nitrogen atoms obtained from the above-mentioned monomers can be polymerized according to conventionally known methods for producing polyamides. The monomer component containing basic nitrogen accounts for 5 to 100 mol% of the total polyamide constituents, especially 20 to 50 mol%.
It is preferable that In addition to the basic nitrogen-containing monomers shown above, general formula ()
Any nitrogen-containing monomer that reacts with the compound represented by to form a quaternary ammonium salt can be used. The above monomers may be used alone or in combination of two or more. In particular, it is desirable to use a single monomer having at least two or more unsaturated double bonds or to use a monomer mixture containing at least one kind. The amount of the monomer used is 5 to 150% by weight, especially 5 to 150% by weight, based on the polyamide in the photosensitive resin composition.
It is preferably 10 to 100% by weight. If the monomer content is less than 5% by weight, the exposed area will not be sufficiently insolubilized in the solvent. Moreover, if it exceeds 150% by weight, the mechanical strength of the photosensitive layer will be impaired after exposure. A photosensitizer is added to accelerate the polymerization reaction of the monomers within the polyamide matrix. As such a photosensitizer, conventionally known ones can be used. For example, 9,10-anthraquinone, 1-chloranthraquinone, 2-
anthraquinones such as chloranthraquinone,
benzophenone, p-aminobenzophenone, p
- Benzophenones such as chlorbenzophenone, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, and benzyls. The amount of the photosensitizer to be used is 0.01 to 5% relative to the total amount of the polyamide, the compound represented by the general formula (), and the monomer having a photopolymerizable unsaturated bond.
It is preferably 0.1 to 2% by weight, especially 0.1 to 2% by weight. Thermal polymerization inhibitors prevent thermal polymerization of monomers having photopolymerizable unsaturated groups due to heating during preparation, molding, and processing of photosensitive resin compositions, or dark reactions during storage of the photosensitive resin compositions. Add to.
As such a thermal polymerization inhibitor, conventionally known ones can be used. For example, hydroquinones such as hydroquinone, mono-t-butylhydroquinone, benzoquinone, 2,5-di-p-
Examples include benzoquinones such as benzoquinone, catechols such as catechol and pt-butylcatechol, and picric acids. The amount of thermal polymerization inhibitor used is 0.001 to 2% by weight, especially 0.05% by weight, based on the total amount of the polyamide, the compound represented by formula (), and the monomer having a photopolymerizable unsaturated bond.
~0.5% by weight is preferred. As described above, the photosensitive resin composition of the present invention contains a compound represented by the general formula (), a polyamide having basic nitrogen, a monomer having a photopolymerizable unsaturated bond, a photosensitizer, and a thermal polymerization inhibitor. The compound can be easily obtained by dissolving it in a solvent such as water, methanol, ethanol, carbon tetrachloride, toluene, or xylene, evaporating only the solvent from this solution, and mixing uniformly. The photosensitive resin composition of the present invention is usually formed into a sheet-like material and used as a photosensitive resin original plate. That is, a mixture having the above-mentioned composition is formed into a sheet-like product such as a plate, film, or foil having a desired thickness by a method such as hot pressing, casting, or melt extrusion. Further, this sheet-like material is laminated on a support with or without an adhesive. Any material such as steel, aluminum, glass, or plastic film can be used as the support. When the obtained photosensitive resin original plate is closely stacked with a negative film or a positive film having a transparent image area on the photosensitive layer and active light is irradiated from above, only the exposed area becomes insolubilized and hardened. As a light source that emits such actinic rays, various mercury lamps, carbon arc lamps, xenon lamps, ultraviolet rays, fluorescent lamps, etc. can be used. After irradiation with light, the non-exposed areas are dissolved and removed using a suitable solvent to obtain a relief plate with clear image areas. In the present invention, since an ammonium salt-type polyamide having a nitrogen atom, which is produced by the reaction of a compound represented by the general formula () with a polyamide having a basic nitrogen, is used as the base material, it can be easily and quickly treated with just water. It can be developed easily. Of course, development can also be carried out using various acid aqueous solutions, mixtures of water and alcohol, lower aliphatic alcohols, lower paper aliphatic alcohols, and solvents that can solubilize the polyamide binder, such as calcium chloride or zinc chloride. Since the relief plate of the present invention obtained in this way has extremely short exposure and development times, the resulting image has very sharp edges. Moreover, the letterpress is extremely flexible due to the effect of the compound represented by the formula (), and the ink is transferred neatly even to paper with a rough surface such as high-quality paper, and the ink does not smear even when printed at high speed with a rotary printing press. It is very clear. The present invention will be explained in detail below with reference to Examples. In addition, in the examples, all parts simply indicate parts by weight. Reference Example 1 40 parts of N,N-bis(γ-aminopropyl)piperazine adipate and 60 parts of ε-caprolactam were added to a reaction vessel, and after sufficient nitrogen purging, the vessel was sealed and gradually heated. From the time the internal pressure reached 10Kg/ m2 , water was distilled out until the pressure could no longer be maintained, and the pressure returned to normal pressure in about 1 hour.
The reaction was carried out at normal pressure for a period of time. The resulting polymer has a specific viscosity of
1.59, is a milky white polyamide with a softening point of 110℃,
It was virtually insoluble in neutral water. Example 1 34 parts of a compound represented by the following formula (), Reference Example 1
100 parts of the polyamide obtained above, 30 parts of a 1:2 condensate of ethylene glycol diglycidyl ether and acrylic acid, 2 parts of benzophenone and 0.2 parts of hydroquinone were added to 300 parts of methanol and dissolved by heating. When this solution is cast onto a glass plate and left under reduced pressure to completely remove methanol, the thickness becomes 0.6 mm.
A transparent film-like photosensitive resin composition with a diameter of 1.0 mm was obtained. This composition was easily dissolved in water at room temperature. The obtained film was adhered onto a 0.25 mm thick polyester film to obtain a photosensitive original plate. A 133-line mesh-resolved photographic image negative film was brought into close contact with the photosensitive layer of this original plate, and exposed for 4 minutes using an exposure machine P-113-D manufactured by Dainippon Screen. After exposure, the film was developed for 2 minutes using Dainippon Screen's Printite Washer BR-A3, dried, and then post-exposed.
The resulting letterpress faithfully reproduced the original image. Next, when this letterpress was attached to a letterpress rotary printing machine BF-201 manufactured by Ukita Kogyo and printed, very good prints were obtained, with no fading in the shadow areas and no thickening in the highlight areas. . Also, 20 of the above letterpress
The hardness at 65% RH was 28° (Shore D) and it was quite flexible. Example 2 63 parts of the compound represented by the following formula (2), 100 parts of the polyamide obtained in Reference Example 1, 1:2 condensate of ethylene glycol diglycidyl ether and acrylic acid
30 parts, 2 parts of benzophenone, 0.2 parts of hydroquinone
1 part was added to 300 parts of methanol and heated to dissolve.
A photosensitive original plate was obtained from this solution in the same manner as in Example 1, and subjected to exposure, development, drying, and post-exposure. The obtained letterpress reproduced the original image, and a good printed matter was obtained. In addition, the hardness was 30° (Shore D). Example 3 29 parts of the compound represented by the following formula (3), 100 parts of the polyamide obtained in Reference Example 1, 30 parts of a 1:2 condensate of ethylene glycol diglycidyl ether and acrylic acid
1 part, 2 parts of benzophenone, and 0.2 parts of hydroquinone were added to 300 parts of methanol and dissolved by heating. A photosensitive original plate was obtained from this solution in the same manner as in Example 1, and subjected to exposure, development, drying, and post-exposure. The resulting letterpress reproduced the original image. When this relief was printed in the same manner as in Example 1, very good printed matter was obtained. The hardness of the letterpress was 33°. Comparative Example 1 10 parts of methacrylic acid, 100 parts of the polyamide obtained in Reference Example 1, 30 parts of a 1:2 condensate of ethylene glycol diglycidyl ether and acrylic acid, 2 parts of benzophenone, and 0.2 parts of hydroquinone were added to 300 parts of methanol and heated. and dissolved. A photosensitive original plate was obtained from this solution in the same manner as in Example 1, exposed to light,
Development, drying, and post-exposure were performed. When printing was performed using the obtained letterpress in the same manner as in Example 1,
Fading occurred in the shadow areas, and the printed matter was not good. Furthermore, the hardness of the letterpress was 50° (Shore D) and lacked flexibility. Example 4 21 parts of the compound represented by the following formula (4), 100 parts of the polyamide obtained in Reference Example 1, 30 parts of a 1:2 condensate of ethylene glycol diglycidyl ether and acrylic acid
1 part, 2 parts of benzophenone, and 0.2 parts of hydroquinone were added to 300 parts of methanol and dissolved by heating. A photosensitive original plate was obtained from this solution in the same manner as in Example 1, and subjected to exposure, development, drying, and post-exposure. The resulting letterpress reproduced the original image. When this relief was printed in the same manner as in Example 1, very good printed matter was obtained. The hardness of the letterpress was 33°.

Claims (1)

【特蚱請求の範囲】  塩基性窒玠を有するポリアミド、光重合可胜
な䞍飜和結合を有する単量䜓および光重合開始剀
からなる感光性暹脂組成物においお、光重合可胜
な䞍飜和結合を有する単量䜓の党郚たたは䞀郚ず
しお䞋蚘䞀般匏(1)で衚わされる化合物を含有する
こずを特城ずする感光性暹脂組成物。 匏䞭、は炭玠原子数〜24の二䟡の炭化氎玠
基たたは分子䞭に、――、―COO―、―
NHCO―を有する炭玠原子数〜24の二䟡の炭
化氎玠基、は―SO3H、【匏】 【匏】を瀺し、は炭玠原子数〜10のアル キル基たたはプニル基を瀺す。
[Scope of Claims] 1. In a photosensitive resin composition comprising a polyamide having basic nitrogen, a monomer having a photopolymerizable unsaturated bond, and a photopolymerization initiator, a monomer having a photopolymerizable unsaturated bond 1. A photosensitive resin composition comprising a compound represented by the following general formula (1) as all or part of the polymer. In the formula, X is a divalent hydrocarbon group having 1 to 24 carbon atoms or -O-, -COO-, -
A divalent hydrocarbon group having 1 to 24 carbon atoms and having NHCO-, Y is -SO 3 H, [Formula] [Formula], and R is an alkyl group or phenyl group having 1 to 10 carbon atoms. .
JP7831681A 1981-05-22 1981-05-22 Photosensitive resin composition Granted JPS57192461A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7831681A JPS57192461A (en) 1981-05-22 1981-05-22 Photosensitive resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7831681A JPS57192461A (en) 1981-05-22 1981-05-22 Photosensitive resin composition

Publications (2)

Publication Number Publication Date
JPS57192461A JPS57192461A (en) 1982-11-26
JPS6367176B2 true JPS6367176B2 (en) 1988-12-23

Family

ID=13658526

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7831681A Granted JPS57192461A (en) 1981-05-22 1981-05-22 Photosensitive resin composition

Country Status (1)

Country Link
JP (1) JPS57192461A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ215095A (en) * 1985-02-12 1989-04-26 Napp Systems Inc Photosensitive resin compositions
JPS6392618A (en) * 1986-10-07 1988-04-23 Sumitomo Chem Co Ltd Photocurable composition containing phosphoric ester
JP2639728B2 (en) * 1989-04-27 1997-08-13 富士写真フむルム株匏䌚瀟 Photosensitive lithographic printing plate
JP4217341B2 (en) * 1999-05-24 2009-01-28 日本化薬株匏䌚瀟 Aromatic polyamide resin composition
JP2001253916A (en) * 2000-03-10 2001-09-18 Nippon Chem Ind Co Ltd Fluoroalkyl group-containing phosphonic acid oligomers, method of producing the same and their use

Also Published As

Publication number Publication date
JPS57192461A (en) 1982-11-26

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