JP2001042528A - Photosensitive resin composition - Google Patents

Photosensitive resin composition

Info

Publication number
JP2001042528A
JP2001042528A JP11215882A JP21588299A JP2001042528A JP 2001042528 A JP2001042528 A JP 2001042528A JP 11215882 A JP11215882 A JP 11215882A JP 21588299 A JP21588299 A JP 21588299A JP 2001042528 A JP2001042528 A JP 2001042528A
Authority
JP
Japan
Prior art keywords
resin composition
photosensitive resin
weight
polyamide
relief
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP11215882A
Other languages
Japanese (ja)
Other versions
JP3632513B2 (en
Inventor
Akira Tomita
晃 富田
Yuji Taguchi
祐二 田口
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 JP21588299A priority Critical patent/JP3632513B2/en
Publication of JP2001042528A publication Critical patent/JP2001042528A/en
Application granted granted Critical
Publication of JP3632513B2 publication Critical patent/JP3632513B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

PROBLEM TO BE SOLVED: To produce a relief printing plate having satisfactory water resistance and mechanical strength after photo-curing and capable of stably forming a high definition image over a long period of time by incorporating a polyamide comprising specified amounts of three specified compounds, a monomer having a photopolymerizable unsaturated bond and a photopolymerization initiator. SOLUTION: The photosensitive resin composition contains a polyamide comprising 4-60 wt.% compound units of formula I, 30-50 wt.% compound units of formula II and 5-15 wt.% compound units of formula III, a monomer having a photopolymerizable unsaturated bond and a photopolymerization initiator. In the formula I, R1 is >=5C alkylene. In the formula II, R2 is 2-10C hydrocarbon, R3 is 1-4C alkylene or a single bond and R4 is l-4C alkylene. In the formula III, R5 is 2-10C hydrocarbon and R6 and R7 are each methylene or a single bond.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は感光性樹脂組成物に
関し、特に、印刷用レリーフ版に好適な感光性樹脂組成
物に関する。
The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition suitable for a relief plate for printing.

【0002】[0002]

【従来の技術】感光性樹脂組成物は、各種印刷用のレリ
ーフ版やサンドブラスト用レリーフマスク、凸版、凹
版、平版、装飾用図柄、フォトレジスト、ディスプレ
ー、ネームプレート、光接着剤、光硬化性塗料、紫外線
硬化インク、固定化酵素膜などの分野に広く用いられて
いる。
2. Description of the Related Art Photosensitive resin compositions include relief plates for printing and relief masks for sandblasting, relief plates, intaglio plates, planographic plates, decorative patterns, photoresists, displays, nameplates, optical adhesives, and photocurable paints. , UV curable inks, and immobilized enzyme films.

【0003】この種の感光性樹脂組成物は、一般に、合
成高分子化合物(以下、充填ポリマーとも称する)、光
重合性不飽和化合物、および光重合開始剤を基本成分と
して構成されている。基本成分のうちでも、充填ポリマ
ーの特性が、光照射される前および光照射により硬化し
た後の感光性樹脂組成物の物性に大きな影響を与える。
具体的には、感光性樹脂組成物の露光前(光照射前)の
形態保持性や、露光後の光硬化部の堅さや耐磨耗性など
に充填ポリマーの特性が大きく影響する。
[0003] A photosensitive resin composition of this type generally comprises a synthetic polymer compound (hereinafter also referred to as a filling polymer), a photopolymerizable unsaturated compound, and a photopolymerization initiator as basic components. Among the basic components, the properties of the filled polymer greatly affect the physical properties of the photosensitive resin composition before light irradiation and after curing by light irradiation.
Specifically, the properties of the filled polymer greatly affect the shape retention of the photosensitive resin composition before exposure (before light irradiation) and the hardness and abrasion resistance of the photocured portion after exposure.

【0004】感光性樹脂組成物は、活性光線による露光
により、露光された部分は光硬化し、未露光部分は適当
な溶剤で溶解除去されることにより現像される。近年、
取り扱い性やコストの点から溶剤に水を使用する現像が
主流になってきている。感光性樹脂組成物の未露光部分
が水によって除去されるには、充填ポリマーが水溶性
か、若しくは水に分散可能な高い親水性を示すことが必
要である。反面、露光により光硬化した部分は実用時に
水分の吸収量が少ない方が好ましいので、光硬化後はあ
る程度の耐水性が必要となる。
[0004] The photosensitive resin composition is developed by exposure to actinic light, the exposed portions are photocured, and the unexposed portions are dissolved and removed with a suitable solvent. recent years,
Development using water as a solvent has become mainstream in terms of handleability and cost. In order for the unexposed portion of the photosensitive resin composition to be removed by water, the filled polymer needs to be water-soluble or have high hydrophilicity that can be dispersed in water. On the other hand, it is preferable that the portion which has been light-cured by exposure absorbs a small amount of water at the time of practical use.

【0005】特公昭49−43565号公報、特開昭4
9−76602号公報、特公昭53−2082号公報お
よび特公昭54−22229号公報をはじめとして、水
による現像が可能な感光性樹脂組成物は提案されてい
る。しかし、これらは、現像に長時間を要したり、光硬
化後の耐水性が不充分である等、未だ問題を含んでい
る。また、近年、感光性樹脂組成物で作製した印刷用の
レリーフ版における印刷画像の一層の高精細化および耐
刷性能の一層の向上が求められているが、かかる要求を
満足し得る水現像が可能な感光性樹脂組成物は得られて
いないのが実状である。
JP-B-49-43565, JP-A-Showa 4
JP-A-9-76602, JP-B-53-2082 and JP-B-54-22229 have proposed a photosensitive resin composition which can be developed with water. However, these still have problems such as long time required for development and insufficient water resistance after photocuring. Further, in recent years, there has been a demand for higher definition of printed images and further improvement of printing durability in a relief plate for printing made of a photosensitive resin composition, and water development capable of satisfying such demands has been required. In fact, a possible photosensitive resin composition has not been obtained.

【0006】[0006]

【発明が解決しようとする課題】本発明は上記のような
事情に鑑みてなされたものであり、露光時の光散乱が極
めて少なく、水により短時間で現像できると共に光硬化
後は充分な耐水性と機械的強度を示し、特に、高精細画
像を長期にわたって安定に形成できる印刷用レリーフ版
の作成を可能とする感光性樹脂組成物を提供することを
目的とする。
DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, has very little light scattering at the time of exposure, can be developed with water in a short time, and has sufficient water resistance after photocuring. In particular, it is an object of the present invention to provide a photosensitive resin composition which exhibits properties and mechanical strength, and in particular, makes it possible to prepare a printing relief plate capable of stably forming a high-definition image for a long period of time.

【0007】[0007]

【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意研究した結果、ω−アミノ酸および/
またはラクタムと、ピペラジン環を有するジアミンのジ
カルボン酸塩と、シクロヘキサン環を有するジアミンの
ジカルボン酸塩とを、特定の重量比で重縮合して得られ
たポリアミド樹脂を充填ポリマーに用いることにより、
感光性樹脂組成物へ活性光線が少ない散乱で深く浸透
し、しかも、短時間の水現像で未露光部を速やかに除去
でき、さらに光硬化部は極めて強靱に硬化し得るという
知見を得、該知見に基づいて本発明を完成させた。即
ち、本発明は以下の特徴を有している。
Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that ω-amino acids and / or
Or by using a polyamide resin obtained by polycondensation of a lactam and a dicarboxylate of a diamine having a piperazine ring with a dicarboxylate of a diamine having a cyclohexane ring at a specific weight ratio, as a filling polymer,
The active light penetrates deeply into the photosensitive resin composition with little scattering, and furthermore, it has been found that the unexposed portion can be quickly removed by short-time water development, and that the photocured portion can be cured very strongly. The present invention has been completed based on the findings. That is, the present invention has the following features.

【0008】(1)下記一般式(I)で示される単位4
0〜60重量%と、下記一般式(II)で示される単位
30〜50重量%と、下記一般式(III)で示される
単位5〜15重量%とからなるポリアミド、光重合可能
な不飽和結合を有する単量体および光重合開始剤を含有
することを特徴とする感光性樹脂組成物。
(1) Unit 4 represented by the following general formula (I)
Polyamide comprising 0 to 60% by weight, 30 to 50% by weight of a unit represented by the following general formula (II), and 5 to 15% by weight of a unit represented by the following general formula (III); A photosensitive resin composition comprising a monomer having a bond and a photopolymerization initiator.

【化4】 (式中、R1 は炭素数が5以上のアルキレン基)Embedded image (Wherein, R 1 is an alkylene group having 5 or more carbon atoms)

【化5】 (式中、R2 は炭素数が2〜10の炭化水素基、R3
炭素数が1〜4のアルキレン基または単結合、R4 は炭
素数が1〜4のアルキレン基)
Embedded image (Wherein, R 2 is a hydrocarbon group having 2 to 10 carbon atoms, R 3 is an alkylene group or a single bond having 1 to 4 carbon atoms, and R 4 is an alkylene group having 1 to 4 carbon atoms)

【化6】 (式中、R5 は炭素数が2〜10の炭化水素基、R6
7 はメチレン基または単結合)
Embedded image (Wherein, R 5 is a hydrocarbon group having 2 to 10 carbon atoms, R 6 ,
R 7 is a methylene group or a single bond)

【0009】(2)光重合可能な不飽和結合を有する単
量体および光重合開始剤の合計含有量が30〜60重量
%である上記(1)記載の感光性樹脂組成物。
(2) The photosensitive resin composition according to the above (1), wherein the total content of the photopolymerizable monomer having an unsaturated bond and the photopolymerization initiator is 30 to 60% by weight.

【0010】(3)さらに安定剤および/または可塑剤
を含有し、該安定剤および/または可塑剤、光重合可能
な不飽和結合を有する単量体および光重合開始剤の合計
含有量が30〜60重量%である上記(1)記載の感光
性樹脂組成物。
(3) It further contains a stabilizer and / or a plasticizer, and the total content of the stabilizer and / or the plasticizer, the monomer having a photopolymerizable unsaturated bond and the photopolymerization initiator is 30. The photosensitive resin composition according to the above (1), wherein the amount is from 60 to 60% by weight.

【0011】(4)波長360nmの光の散乱率が10
%以下である上記(1)〜(3)のいずれかに記載の感
光性樹脂組成物。
(4) The scattering rate of light having a wavelength of 360 nm is 10
% Of the photosensitive resin composition according to any one of the above (1) to (3).

【0012】[0012]

【発明の実施の形態】本発明の感光性樹脂組成物は、前
記の一般式(I)(II)(III)で示される3つの
構造単位が特定の重量比で共重合されたポリアミド樹脂
を充填ポリマーに用い、該充填ポリマーの他、光重合可
能な不飽和結合を有する単量体(以下、光重合性不飽和
単量体と称す)および光重合開始剤を必須とし、必要に
応じて安定剤や可塑剤などの添加剤が含有されて、なる
ものである。
BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises a polyamide resin obtained by copolymerizing the above-mentioned three structural units represented by the general formulas (I), (II) and (III) at a specific weight ratio. A monomer having a photopolymerizable unsaturated bond (hereinafter, referred to as a photopolymerizable unsaturated monomer) and a photopolymerization initiator, which are used as the filling polymer, are required as necessary. It contains additives such as stabilizers and plasticizers.

【0013】一般式(I)の構造単位は、炭素数が5以
上のアルキレン基のω−アミノ酸の縮合残基であり、該
ω−アミノ酸としてはたとえばアミノカプロン酸、アミ
ノへプタン酸、アミノカプリル酸、アミノラウリル酸な
どを挙げることができる。これらのω−アミノ酸またそ
のラクタムを共重合成分として使用することにより、こ
れらの構造単位をポリアミドに導入することができる
が、特に、ε−カプロラクタムが好適である。
The structural unit of the general formula (I) is a condensed residue of an ω-amino acid having an alkylene group having 5 or more carbon atoms. Examples of the ω-amino acid include aminocaproic acid, aminoheptanoic acid and aminocaprylic acid. , Aminolauric acid and the like. By using these ω-amino acids or their lactams as copolymerization components, these structural units can be introduced into polyamides, but ε-caprolactam is particularly preferred.

【0014】一般式(II)の構造単位は、ピペラジン
環を有するジアミンのジカルボン酸塩の縮合残基であ
る。R2 は炭素数が2〜10の炭化水素基で、−CO〜
CO−は脂肪族、芳香族または脂環族ジカルボン酸の残
基である。該脂肪族、芳香族または脂環族ジカルボン酸
としては、例えば、コハク酸、アジピン酸、グルタル
酸、アゼライン酸、セバシン酸、デカンジカルボン酸、
テレフタル酸、イソフタル酸、シクロヘキサンジカルボ
ン酸を挙げることができるが、特に、アジピン酸が好ま
しい。また、R3 は炭素数が1〜4のアルキレン基また
は単結合、R4 は炭素数が1〜4のアルキレン基で、−
NH〜NH−はピペラジン環を有するジアミンの残基で
ある。該ピペラジン環を有するジアミンとしては、N,
N’−ビス(アミノメチル)−ピペラジン、N,N’−
ビス(アミノエチル)−ピペラジン、N,N’−ビス
(γ−アミノプロピル)ピペラジン、N,N’−ジ(ア
ミノペンチル)ピペラジンなどを挙げることができる。
The structural unit of the general formula (II) is a condensed residue of a dicarboxylic acid salt of a diamine having a piperazine ring. R 2 is a hydrocarbon group having 2 to 10 carbon atoms,
CO- is the residue of an aliphatic, aromatic or alicyclic dicarboxylic acid. As the aliphatic, aromatic or alicyclic dicarboxylic acid, for example, succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, decanedicarboxylic acid,
Although terephthalic acid, isophthalic acid, and cyclohexanedicarboxylic acid can be mentioned, adipic acid is particularly preferable. R 3 is an alkylene group having 1 to 4 carbon atoms or a single bond; R 4 is an alkylene group having 1 to 4 carbon atoms;
NH to NH- are residues of a diamine having a piperazine ring. Examples of the diamine having a piperazine ring include N,
N'-bis (aminomethyl) -piperazine, N, N'-
Bis (aminoethyl) -piperazine, N, N′-bis (γ-aminopropyl) piperazine, N, N′-di (aminopentyl) piperazine and the like can be mentioned.

【0015】一般式(III)の構造単位は、シクロヘ
キサン環を有するジアミンのジカルボン酸塩の縮合残基
である。R5 は炭素数が2〜10の炭化水素基で、−C
O〜CO−は上記一般式(II)のそれと同義である。
また、R6 、R7 はメチレン基または単結合で、−NH
〜NH−はシクロヘキサン環を有するジアミンの残基で
ある。該シクロヘキサン環を有するジアミンとしては、
例えば、1,3−ジアミノシクロヘキサン、1,3−ビ
スアミノメチルシクロヘキサン、1,4−ジアミノシク
ロヘキサン、1,4−ビスアミノメチルシクロヘキサン
などを挙げることができる。
The structural unit of the general formula (III) is a condensed residue of a dicarboxylic acid salt of a diamine having a cyclohexane ring. R 5 is a hydrocarbon group having 2 to 10 carbon atoms,
O to CO- have the same meanings as those in formula (II).
R 6 and R 7 are each a methylene group or a single bond, and —NH
-NH- is a residue of a diamine having a cyclohexane ring. As the diamine having a cyclohexane ring,
For example, 1,3-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1,4-diaminocyclohexane, 1,4-bisaminomethylcyclohexane and the like can be mentioned.

【0016】本発明に用いるポリアミドは、重合体中の
一般式(I)(II)(III)の単位の重量比が40
〜60:30〜50:5〜15となるように、ω−アミ
ノ酸および/またはそのラクタム、ピペラジン環を有す
るジアミンのジカルボン酸塩、およびシクロヘキサン環
を有するジアミンのジカルボン酸塩からなる3種の原料
を仕込み、重縮合することにより得ることができる。
The polyamide used in the present invention has a weight ratio of units of the general formulas (I), (II) and (III) in the polymer of 40.
-60- to 50: 5 to 15, three kinds of raw materials comprising an ω-amino acid and / or a lactam thereof, a dicarboxylate of a diamine having a piperazine ring, and a dicarboxylate of a diamine having a cyclohexane ring And then polycondensed.

【0017】本発明におけるポリアミドは、ω−アミノ
酸および/またはラクタムの縮合残基(一般式(I)の
単位)の含有量を40〜60重量%、好ましくは50〜
60重量%の範囲、ピペラジン環を有するジアミンのジ
カルボン酸塩の縮合残基(一般式(II)の単位)の含
有量を30〜50重量%の範囲、シクロヘキサン環を有
するジアミンのジカルボン酸塩の縮合残基(一般式(I
II)の単位)の含有量を5〜15重量%の範囲にする
ことが重要であり、かかるポリマー構成とすることで、
感光性樹脂組成物に極めて良好な物性を与える充填ポリ
マーと成り得る。
The polyamide in the present invention has a content of condensed residue of ω-amino acid and / or lactam (unit of the general formula (I)) of 40 to 60% by weight, preferably 50 to 60% by weight.
The content of the condensed residue (unit of the general formula (II)) of the dicarboxylate of the diamine having a piperazine ring is in the range of 30 to 50 wt%, the content of the dicarboxylate of the diamine having a cyclohexane ring is 60 wt%. The condensed residue (general formula (I
It is important that the content of unit (II)) is in the range of 5 to 15% by weight.
It can be a filled polymer that gives the photosensitive resin composition extremely good physical properties.

【0018】ω−アミノ酸またそのラクタムの縮合残基
(一般式(I)の単位)が40重量%未満ではポリマー
の結晶性が低下し、樹脂組成物の成形性に支障をきた
し、また、光硬化部の機械的強度が十分に高められなく
なる。また、60重量%より多い場合はポリマーの親水
性が低下して水現像性が低下する。また、ピペラジン環
を有するジアミンのジカルボン酸塩の縮合残基(一般式
(II)の単位)が30重量%未満ではポリマーの親水
性が低下して水現像性に支障をきたし、50重量%より
多い場合はポリマーの親水性が高くなり過ぎ、現像後の
光硬化部の機械的強度が十分に高められなくなる。ま
た、シクロヘキサン環を有するジアミンのジカルボン酸
塩の縮合残基(一般式(III)の単位)が5重量未満
では露光時の光散乱を十分に低減し得なくなり、また、
レリーフ抜け深さを十分に増大し得なくなり、15重量
%より多い場合はポリマーの結晶性や親水性の低下が起
こる。
When the condensed residue of the ω-amino acid or its lactam (unit of the general formula (I)) is less than 40% by weight, the crystallinity of the polymer is lowered, and the moldability of the resin composition is hindered. The mechanical strength of the hardened part cannot be sufficiently increased. On the other hand, when the content is more than 60% by weight, the hydrophilicity of the polymer decreases, and the water developability decreases. If the condensed residue (unit of the general formula (II)) of the dicarboxylic acid salt of a diamine having a piperazine ring is less than 30% by weight, the hydrophilicity of the polymer is reduced and water developability is hindered. If the amount is too large, the hydrophilicity of the polymer becomes too high, and the mechanical strength of the photocured portion after development cannot be sufficiently increased. If the condensed residue of the dicarboxylic acid salt of diamine having a cyclohexane ring (unit of the general formula (III)) is less than 5%, light scattering at the time of exposure cannot be sufficiently reduced, and
If the depth of relief relief cannot be sufficiently increased, and if it exceeds 15% by weight, the crystallinity and hydrophilicity of the polymer will decrease.

【0019】本発明で用いるポリアミドは、前記の特定
の共重合体組成を有し、室温以上の結晶化温度を有する
ので、成形体(生版)の形状安定性がよく、保存中に流
動が生じ形状が変化するような問題は生じない。それに
もかかわらず、感光性樹脂組成物は熱変性や熱分解を起
こさない比較的低い温度で容易に熱溶融成形を行うこと
ができる。また、本発明で用いるポリアミドは感光性樹
脂組成物中で適度の結晶性を有するので、生版の形状安
定性が良好であるにもかかわらず、光透過性に優れ、照
射光の散乱を抑制できるので、原画に忠実な鮮明な画像
が得られる。本発明の感光性樹脂組成物から得られた生
版は、露光時の活性光線の散乱が極めて少なく活性光線
が深く浸透し得、しかも、露光感度および水現像性とも
に極めて良好となり、短時間の現像作業で、解像度が高
く、かつ、深いレリーフ深度のレリーフ版を作成するこ
とができる。具体的には、300μmスリット幅のレリ
ーフ抜け深さが90μm以上の従来のこの種の感光性樹
脂組成物では得られなかったレリーフ像を得ることがで
きる。さらに、特筆すべき点は、光硬化した部分が十分
な耐水性および傑出した強靭性を示し、従来よりも耐刷
性が大幅に向上する点である。
Since the polyamide used in the present invention has the above-mentioned specific copolymer composition and has a crystallization temperature of room temperature or higher, the molded article (raw plate) has good shape stability and has a good flow during storage. There is no problem that the resulting shape changes. Nevertheless, the photosensitive resin composition can be easily subjected to hot melt molding at a relatively low temperature that does not cause thermal denaturation or thermal decomposition. In addition, since the polyamide used in the present invention has a moderate crystallinity in the photosensitive resin composition, it has excellent light transmittance and suppresses the scattering of irradiation light despite good shape stability of the raw plate. As a result, a clear image faithful to the original image can be obtained. The raw plate obtained from the photosensitive resin composition of the present invention has a very small amount of active light scattering at the time of exposure, and the active light can penetrate deeply.Moreover, both the exposure sensitivity and the water developability are extremely good. In the developing operation, a relief plate having a high resolution and a high relief depth can be created. Specifically, a relief image having a slit width of 300 μm and a depth of relief relief of 90 μm or more, which cannot be obtained with a conventional photosensitive resin composition of this type, can be obtained. Furthermore, it should be noted that the photocured portion shows sufficient water resistance and outstanding toughness, and the printing durability is significantly improved as compared with the related art.

【0020】本発明の感光性樹脂組成物の露光時におけ
る光散乱が極めて少ないのは、充填ポリマーとして特定
のポリアミドを使用することに併せて、感光性樹脂組成
物中における光重合性不飽和単量体および光重合開始剤
の合計含有量、または、後述する安定剤や可塑剤などの
添加剤を更に配合する場合の光重合性不飽和単量体、光
重合開始剤および添加剤の合計含有量を30〜60重量
%、好ましくは35〜55重量%、より好ましくは40
〜50重量%とすることによるものである。例えば、日
立製作所(株)製、U−3210型自記分光光度計と1
50φ積分球付属装置(150−0901)を用いて測
定した360nmの波長光の散乱率=〔散乱透過量/
(直進透過量+散乱透過量)〕を、従来では成し得なか
った10%以下(好ましくは7.0%以下)まで減少さ
せることができる。
The light scattering at the time of exposure of the photosensitive resin composition of the present invention is extremely small because, in addition to the use of a specific polyamide as the filling polymer, the photopolymerizable unsaturated monomer in the photosensitive resin composition is used. The total content of the monomer and the photopolymerization initiator, or the total content of the photopolymerizable unsaturated monomer, the photopolymerization initiator and the additive when further adding an additive such as a stabilizer or a plasticizer described below. The amount is 30-60% by weight, preferably 35-55% by weight, more preferably 40% by weight.
5050% by weight. For example, U-3210 self-recording spectrophotometer manufactured by Hitachi, Ltd.
Scattering factor of light having a wavelength of 360 nm measured using a 50φ integrating sphere attachment device (150-0901) = [scattering transmission amount /
(Straight transmission amount + scattering transmission amount)] can be reduced to 10% or less (preferably 7.0% or less), which could not be achieved conventionally.

【0021】本発明で用いる光重合性不飽和単量体とし
ては、分子内に光重合可能な不飽和基を1個以上含有す
る化合物であり、公知のものが使用できる。このような
化合物としては、たとえば、アクリル酸、メタクリル
酸、イタコン酸、2−ヒドロキシエチルアクリレート、
2−ヒドロキシプロピルアクリレート、アクリルアミ
ド、メタクリルアミド、N−メチロールアクリルアミ
ド、N−アクロイルモルホリン、ペンタエリスリトール
ジアクリレート、ペンタエリスリトールトリアクリレー
ト、グリセロールジメタクリレート、エチレングリコー
ルジグリシジルエーテル、トリメチロールプロパントリ
グリシジルエーテルなどの多価グリシジルエーテルに不
飽和カルボン酸や不飽和アルコールなどのエチレン性不
飽和結合と活性水素を持つ化合物を付加反応させて得ら
れる多価アクリレートやメタアクリレート、グリシジル
アクリレートなどの不飽和エポキシ化合物とカルボン酸
やアミンのような活性水素を有する化合物の付加反応
物、不飽和ポリエステル、不飽和ポリウレタンなどであ
る。これらの単量体は単独あるいは2種以上混合して使
用することがきる。これらの光重合性不飽和単量体の感
光性樹脂組成物中の含有率は5〜50重量%の範囲から
適宜選択するのが好ましい。5重量%以下では樹脂組成
物の光硬化性に支障をきたし、50重量%より多くなる
と露光前の樹脂組成物(生版)の形状保持性に支障をき
たす。
The photopolymerizable unsaturated monomer used in the present invention is a compound containing at least one photopolymerizable unsaturated group in the molecule, and known compounds can be used. Such compounds include, for example, acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide, N-acryloylmorpholine, pentaerythritol diacrylate, pentaerythritol triacrylate, glycerol dimethacrylate, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and the like Unsaturated epoxy compounds, such as polyhydric acrylates, methacrylates, and glycidyl acrylates, obtained by the addition reaction of polyhydric glycidyl ether with a compound having an active hydrogen and an ethylenically unsaturated bond such as an unsaturated carboxylic acid or unsaturated alcohol Examples include addition products of compounds having active hydrogen such as acids and amines, unsaturated polyesters and unsaturated polyurethanes. These monomers can be used alone or in combination of two or more. It is preferable that the content of the photopolymerizable unsaturated monomer in the photosensitive resin composition is appropriately selected from the range of 5 to 50% by weight. When the amount is less than 5% by weight, the photocurability of the resin composition is impaired. When the amount is more than 50% by weight, the shape retention of the resin composition (raw plate) before exposure is impaired.

【0022】光重合開始剤としては公知のものが使用可
能であり、具体的には、例えば、ベンゾフェノン類、ベ
ンゾイン類、アセトフェノン類、ベンジル類、ベンゾイ
ンアルキルエーテル類、ベンジルアルキルケタール類、
アンスラキノン類、チオキサントン類などが使用でき
る。好適な具体例としては、ベンゾフェノン、ベンゾイ
ン、アセトフェノン、ベンゾインメチルエーテル、ベン
ゾインエチルエーテル、ベンジルジメチルケタール、ア
ンスラキノン、2−クロロアンスラキノン、チオキサン
トン、2−クロロチオキサントンなどが挙げられる。こ
れらは感光性樹脂組成物中に0.05〜5重量%含有さ
せるのが好ましい。0.05重量%より少ないと光重合
開始能力に支障をきたし、5重量%より多いと印刷用レ
リーフを作成する場合の生版の厚み方向の光硬化性が低
下し、画像の欠けが起こりやすくなる。
As the photopolymerization initiator, known photopolymerization initiators can be used. Specifically, for example, benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals,
Anthraquinones, thioxanthones and the like can be used. Preferred specific examples include benzophenone, benzoin, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzyldimethyl ketal, anthraquinone, 2-chloroanthraquinone, thioxanthone, 2-chlorothioxanthone, and the like. These are preferably contained in the photosensitive resin composition in an amount of 0.05 to 5% by weight. When the amount is less than 0.05% by weight, the photopolymerization initiation ability is hindered. When the amount is more than 5% by weight, the photocurability in the thickness direction of the raw plate in producing a relief for printing is reduced, and the image is likely to be chipped. Become.

【0023】感光性樹脂組成物には充填ポリマー、光重
合性不飽和単量体および光重合性開始剤以外に安定剤や
可塑剤などの添加剤を必要に応じて含有させることがで
きる。安定剤としては、例えば、ハイドロキノン、ハイ
ドロキノンモノメチルエーテルや2、6−ジ−t−ブチ
ル−p−クレゾールなどが挙げられ、これらは組成物中
に0.001〜5重量%程度含有させるのが好ましい。
可塑剤は光硬化物の物性変化を目的に添加され、例え
ば、エステルやアミドなどの低分子可塑剤、ポリエステ
ルやポリエーテル、液状ゴム類などのオリゴマーが挙げ
られる。該可塑剤は組成物中に0.1〜20重量%、好
ましくは5〜15重量%含有させるのが好ましい。ま
た、露光、現像後に得られる製品用途に応じて、公知の
染料や色素を添加して感光性樹脂組成物を着色すること
もできる。
The photosensitive resin composition can contain additives such as a stabilizer and a plasticizer, if necessary, in addition to the filler polymer, the photopolymerizable unsaturated monomer and the photopolymerizable initiator. Examples of the stabilizer include hydroquinone, hydroquinone monomethyl ether and 2,6-di-t-butyl-p-cresol, and these are preferably contained in the composition at about 0.001 to 5% by weight. .
The plasticizer is added for the purpose of changing the physical properties of the photocured product, and examples thereof include low-molecular plasticizers such as esters and amides, and oligomers such as polyesters, polyethers, and liquid rubbers. The plasticizer is contained in the composition in an amount of 0.1 to 20% by weight, preferably 5 to 15% by weight. In addition, according to the product use obtained after exposure and development, a known dye or pigment may be added to color the photosensitive resin composition.

【0024】本発明の感光性樹脂組成物は、印刷用レリ
ーフ版を得る場合の溶融成形法の他、例えは、熱プレ
ス、注型、或いは、溶融押出し、溶液キャストなど公知
の任意の方法により目的の製品に応じた所望の形状物に
成形できる。
The photosensitive resin composition of the present invention can be prepared by any known method such as hot pressing, casting, melt extrusion, or solution casting, in addition to the melt molding method for obtaining a relief plate for printing. It can be formed into a desired shape according to the target product.

【0025】印刷用レリーフ版を得る場合はシート状に
成形した成形物(生版)を公知の接着剤を介して、或い
は、介さずに支持体に積層して使用することができる。
支持体としてはスチール、アルミニウム、ガラス、ポリ
エステルフィルムなどのプラスチックフィルム、金属蒸
着したフィルムなど任意のものが使用できる。シート状
成形物(生版)を支持体上に積層した積層体にして供給
する場合にはシート状成形物(生版)に接して保護層が
さらに積層される。保護層はフイルム状のプラスチッ
ク、例えば、ポリエステルの125μm厚みのフイルム
に粘着性のない透明で現像液に分散又は溶解する高分子
を1〜3μmの厚みで塗布したものが用いられる。この
薄い高分子の皮膜を有する保護層をシート状成形物(生
版)に接することによって、シート状成形物(生版)の
表面粘着性が強い場合であっても次の露光操作時に行う
保護層の剥離を容易に行うことができる。
When a relief plate for printing is obtained, a molded product (raw plate) formed into a sheet can be used by laminating it on a support with or without a known adhesive.
As the support, any material such as steel, aluminum, glass, a plastic film such as a polyester film, and a metal-deposited film can be used. When the sheet-like molded product (raw plate) is supplied as a laminate laminated on a support, a protective layer is further laminated in contact with the sheet-shaped molded product (raw plate). As the protective layer, a film-like plastic, for example, a polyester film having a thickness of 1 to 3 μm coated with a 125-μm-thick polyester film having a non-adhesive and transparent and dispersible or soluble in a developing solution is used. By contacting the protective layer having the thin polymer film with the sheet-shaped molded product (raw plate), even if the surface adhesiveness of the sheet-shaped molded product (raw plate) is strong, the protection performed at the next exposure operation is performed. The layer can be easily peeled off.

【0026】このような組成物からなる層単独、もしく
はこの層と支持体とからなる感光性原版は、感光性層に
透明画像部を有するネガフィルムまたはポジフィルムを
密着して重ね合せ、その上方から活性光線を照射して露
光をおこなうと、露光部のみが不溶化ならびに硬化す
る。活性光線は通常300〜450nmの波長を中心と
する高圧水銀灯、超高圧水銀灯、メタルハライドラン
プ、キセノン灯、ケミカルランプなどの光源を用いる。
A layer of such a composition alone, or a photosensitive original plate comprising this layer and a support, is laminated on a negative layer or a positive film having a transparent image portion on a photosensitive layer in close contact with each other. When exposure is carried out by irradiating with actinic rays from above, only the exposed portions are insolubilized and cured. As the actinic ray, a light source such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp having a wavelength of usually 300 to 450 nm is used.

【0027】次いで、適当な溶剤、特に本発明では中性
の水により非露光部分を溶解除去することによって、鮮
明な画像部を有する凸版を得る。このためには、スプレ
ー式現像装置、ブラシ式現像装置などを用いる。
Next, the unexposed portion is dissolved and removed with an appropriate solvent, particularly in the present invention, neutral water to obtain a relief plate having a clear image area. For this purpose, a spray developing device, a brush developing device, or the like is used.

【0028】以下、実施例および比較例により本発明を
さらに詳しく説明する。以下の実施例および比較例中の
部数は重量部のことである。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The number of parts in the following Examples and Comparative Examples is parts by weight.

【0029】(実施例1)ε−カプロラクタム52.5
部、N,N’−ビス(γ−アミノプロピル)ピペラジン
アジペート40.0部、1,3−ビスアミノメチルシク
ロヘキサンアジペート7.5部と水100部を反応器に
加え、充分な窒素置換を行った後に、密閉して徐々に加
熱し、内圧が10kg/cm2 に達した時点から反応器
内の水を徐々に留出させて約1時間で常圧に戻し、その
後0.5時間常圧で反応させた。最高重合温度は210
℃で、融点140℃、比粘度1.83の透明淡黄色のポ
リアミド−1を得た。
Example 1 ε-caprolactam 52.5
Parts, N, N'-bis (γ-aminopropyl) piperazine adipate (40.0 parts), 1,3-bisaminomethylcyclohexane adipate (7.5 parts) and water (100 parts) were added to the reactor, and the mixture was sufficiently purged with nitrogen. After the internal pressure reached 10 kg / cm 2 , the water in the reactor was gradually distilled off and returned to normal pressure in about 1 hour, and then normal pressure for 0.5 hour Was reacted. Maximum polymerization temperature is 210
A clear pale yellow polyamide-1 having a melting point of 140 ° C. and a specific viscosity of 1.83 at ℃ was obtained.

【0030】ポリアミド−1を55.0部、N−メチル
トルエンスルホン酸アミドを7.7部、1,4−ナフト
キノンを0.02部、メタノール50.0部と水10部
を攪拌機付き加熱溶解釜中で60℃、2時間混合してポ
リマーを完全に溶解してから、トリメチロールプロパン
トリグリシジルエーテルのアクリル酸付加物を30.1
部、メタクリル酸を3.1部、ハイドロキノンモノメチ
ルエーテルを0.1部、亜硫酸アンモニウム0.3部と
ベンジルジメチルケタールを1.0部を混ぜて30分間
溶解した。次に徐々に昇温してメタノールと水を留出さ
せて、釜内の温度が110℃になるまで濃縮した。この
段階で、流動性のある粘稠な感光性樹脂組成物が得られ
た。
55.0 parts of polyamide-1, 7.7 parts of N-methyltoluenesulfonic acid amide, 0.02 parts of 1,4-naphthoquinone, 50.0 parts of methanol and 10 parts of water are heated and melted with a stirrer. After mixing in a kettle at 60 ° C. for 2 hours to completely dissolve the polymer, an acrylic acid adduct of trimethylolpropane triglycidyl ether was added in an amount of 30.1.
Parts, 3.1 parts of methacrylic acid, 0.1 part of hydroquinone monomethyl ether, 0.3 part of ammonium sulfite and 1.0 part of benzyldimethyl ketal were mixed and dissolved for 30 minutes. Next, the temperature was gradually raised to distill off methanol and water, and concentrated until the temperature in the kettle reached 110 ° C. At this stage, a viscous photosensitive resin composition having fluidity was obtained.

【0031】この感光性樹脂組成物を125μm厚みの
ポリエステルフイルム上にとり、同様のポリエステルフ
イルムを重ね、ラミネーターで全厚みが1050μmの
シートを作成し、室温で24時間放置後に85℃で3分
間加熱した。ポリエステルフイルムを剥離した感光性樹
脂組成物のシートにおける光散乱性を、日立製作所
(株)製、U−3210型自記分光光度計と150φ積
分球付属装置(150−0901)を用いて360nm
での光散乱率を測定したところ、光散乱率は7.0%で
あった。
This photosensitive resin composition was placed on a polyester film having a thickness of 125 μm, and the same polyester film was laminated thereon. A sheet having a total thickness of 1050 μm was formed with a laminator, left at room temperature for 24 hours and heated at 85 ° C. for 3 minutes. . The light scattering property of the photosensitive resin composition sheet from which the polyester film was peeled was measured at 360 nm using a U-3210 type self-recording spectrophotometer manufactured by Hitachi, Ltd. and a 150φ integrating sphere attachment device (150-0901).
Was measured, the light scattering rate was 7.0%.

【0032】共重合ポリエステル(バイロンRV−30
SS、東洋紡(株)製)と多官能イソシアネート(コロ
ネートL、日本ポリウレタン(株)製)と褐色染料の反
応物を厚み15μmの被膜でコートした厚み180μm
のポリエステルフイルムを支持体として被膜に接して上
記の感光性樹脂組成物を流延する。厚み2μmのポリビ
ニルアルコール(AH−24、日本合成化学(株)製)
の被膜をコートした厚み125μmのポリエステルフイ
ルムを被膜側を感光性樹脂組成物に接するようにして、
ラミネーターを用いて全厚みが1080μmのシート状
の積層体を成形した。このシートは室温下で堅い板状に
固化した。24時間後にこのシートを85℃で3分間加
熱して生版を得た。
Copolyester (Vylon RV-30)
SS, manufactured by Toyobo Co., Ltd.) and a reaction product of a polyfunctional isocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) and a brown dye coated with a 15 μm-thick film to a thickness of 180 μm
The above photosensitive resin composition is cast by contacting the film with the polyester film as a support. 2 μm thick polyvinyl alcohol (AH-24, manufactured by Nippon Synthetic Chemical Co., Ltd.)
A 125 μm-thick polyester film coated with a film of the above was coated so that the film side was in contact with the photosensitive resin composition,
Using a laminator, a sheet-like laminate having a total thickness of 1080 μm was formed. This sheet solidified into a hard plate at room temperature. After 24 hours, the sheet was heated at 85 ° C. for 3 minutes to obtain a raw plate.

【0033】生版を7日間以上保管した後に、125μ
mのポリエステルフイルムを剥離してテストネガフイル
ム(感度測定用グレイスケールネガフイルムと画像再現
性評価用画像のネガフイルム)を真空密着させ、超高圧
水銀灯で40秒間露光した。次にブラシ式ウォッシャー
(100μmφナイロンブラシ、日本電子精機(株)制
作JW−A2−PD型)で水道水を現像液にして、23
℃で2分間現像してレリーフ画像を得ることができた。
更に60℃で5分間、温風乾燥した後に超高圧水銀灯で
30秒間後露光して得られたレリーフを評価した結果、
グレイスケールは17段、画像部は2%網点、100μ
m独立点、30μm細線が再現されていた。また、30
0μmスリット幅のレリーフ抜け深さは90μmであっ
た。このレリーフで印刷テストを行った結果、画像の太
りがなくシャープな刷り上がりの鮮明画像の印刷物が得
られた。また、30万部の印刷を行ったが、レリーフの
とびやクラックの発生はなく、極めて良好な耐刷性を示
した。
After storing the raw plate for 7 days or more,
Then, the test negative film (the gray scale negative film for sensitivity measurement and the negative film of the image for evaluating image reproducibility) was brought into close contact with each other under vacuum, and exposed to an ultrahigh pressure mercury lamp for 40 seconds. Next, tap water was used as a developer with a brush type washer (100 μmφ nylon brush, JW-A2-PD manufactured by JEOL Ltd.),
Development at 2 ° C. for 2 minutes gave a relief image.
After further drying at 60 ° C. for 5 minutes with hot air, the relief obtained by post-exposure with an ultra-high pressure mercury lamp for 30 seconds was evaluated.
Gray scale: 17 steps, image area: 2% halftone, 100μ
m independent points and 30 μm thin lines were reproduced. Also, 30
The depth of relief relief at a slit width of 0 μm was 90 μm. As a result of performing a printing test with this relief, a printed matter of a sharp image without sharpening of the image was obtained. Further, 300,000 copies were printed, but no relief jumps or cracks were generated, and extremely good printing durability was exhibited.

【0034】(比較例1)ε−カプロラクタム55.0
部、N,N’−ビス(γ−アミノプロピル)ピペラジン
アジペート45.0部を原料に、他は実施例1と同様の
操作でポリアミド−2を合成した。得られた重合体は融
点150℃、比粘度2.02の透明淡黄色であった。該
ポリアミド−2を用いて実施例1と同様に感光性樹脂組
成物を調製し、生版を作成したが、水現像時間が10分
間以上になったので、生版の熱処理温度を100℃、3
分間に変更し、現像時間が3分間で行えるようにした。
生版の光散乱率を実施例1と同様にして測定したところ
11.4%であった。また、画像再現性評価を実施例1
と同様にして行ったところ、グレイスケールは16段、
画像部は5%網点、200μm独立点、30μm細線が
再現し、300μmスリット幅のレリーフ抜け深さは4
5μmであった。また、30万部の印刷を行ったが、レ
リーフ表面ににひび割れの発生が認められた。
Comparative Example 1 ε-caprolactam 55.0
Part, N, N′-bis (γ-aminopropyl) piperazine adipate was used as a starting material, and polyamide-2 was synthesized in the same manner as in Example 1 except for the above. The obtained polymer was transparent and pale yellow with a melting point of 150 ° C. and a specific viscosity of 2.02. Using the polyamide-2, a photosensitive resin composition was prepared in the same manner as in Example 1 to prepare a raw plate. However, since the water development time became 10 minutes or more, the heat treatment temperature of the raw plate was set to 100 ° C. 3
Minutes, so that the development time could be 3 minutes.
When the light scattering rate of the raw plate was measured in the same manner as in Example 1, it was 11.4%. The image reproducibility was evaluated in Example 1.
When I went in the same way as above, the gray scale was 16 steps,
The image area reproduces 5% halftone dots, 200 μm independent points, and 30 μm fine lines, and the relief depth of 300 μm slit width is 4
It was 5 μm. Further, 300,000 copies were printed, but cracks were found on the relief surface.

【0035】(実施例2)ε−カプロラクタム55.0
部、N,N’−ビス(γ−アミノプロピル)ピペラジン
アジペート40.0部、1,3−ビスアミノメチルシク
ロヘキサンアジペート5.0部を原料に、他は実施例1
と同様にしてポリアミド−3を得た。得られた重合体は
融点145℃、比粘度1.88の透明淡黄色であった。
このポリアミド−3を用いて実施例1と同様に感光性樹
脂組成物を調製し、生版を作成した。なお、熱処理は9
5℃、3分間で行った。生版の光散乱率を実施例1と同
様にして測定したところ5.3%であった。また、画像
再現性評価を実施例1と同様にして行ったところ、グレ
イスケールは17段、2%網点、200μm独立点、3
0μm細線が再現し、300μmスリット幅のレリーフ
抜け深さは95μmで良好であった。また、30万部の
印刷を行ったが、レリーフのとびやクラックの発生はな
く、極めて良好な耐刷性を示した。
Example 2 ε-caprolactam 55.0
Parts, N, N'-bis (γ-aminopropyl) piperazine adipate 40.0 parts, 1,3-bisaminomethylcyclohexane adipate 5.0 parts
In the same manner as in the above, polyamide-3 was obtained. The obtained polymer was transparent and pale yellow with a melting point of 145 ° C. and a specific viscosity of 1.88.
Using this polyamide-3, a photosensitive resin composition was prepared in the same manner as in Example 1 to prepare a raw plate. The heat treatment is 9
Performed at 5 ° C. for 3 minutes. The light scattering rate of the raw plate was measured in the same manner as in Example 1, and it was 5.3%. When the image reproducibility was evaluated in the same manner as in Example 1, the gray scale was 17 steps, 2% halftone dot, 200 μm independent point,
The fine line of 0 μm was reproduced, and the depth of relief with a slit width of 300 μm was 95 μm, which was good. Further, 300,000 copies were printed, but no relief jumps or cracks were generated, and extremely good printing durability was exhibited.

【0036】(比較例2)ε−カプロラクタム52.5
部、N,N’−ビス(γ−アミノプロピル)ピペラジン
アジペート37.5部と1,6−ヘキサメチレンジアミ
ンアジペート10.0部を原料に、他は実施例1と同様
の操作にしてポリアミド−4を合成した。得られた重合
体は融点145℃、比粘度1.89の透明淡黄色であっ
た。このポリアミド−4を用いて実施例1と同様に感光
性樹脂組成物を調製し、生版を作成した。生版の光散乱
率を実施例1と同様にして測定したところ15.2%で
あった。また、画像再現性評価を実施例1と同様にして
行ったところ、グレイスケールは17段、2%網点、2
00μm独立点、30μm細線が再現したが300μm
スリット幅のレリーフ抜け深さが35μmであり、鮮明
画像が得られなかった。
Comparative Example 2 ε-caprolactam 52.5
Parts, N, N'-bis (γ-aminopropyl) piperazine adipate (37.5 parts) and 1,6-hexamethylenediamine adipate (10.0 parts) as raw materials, and the same procedure as in Example 1 was repeated, except that the polyamide- 4 was synthesized. The obtained polymer was transparent and pale yellow with a melting point of 145 ° C. and a specific viscosity of 1.89. Using this polyamide-4, a photosensitive resin composition was prepared in the same manner as in Example 1 to prepare a raw plate. The light scattering rate of the raw plate was measured in the same manner as in Example 1 and found to be 15.2%. When the image reproducibility was evaluated in the same manner as in Example 1, the gray scale was 17 steps, 2% halftone dots,
00μm independent point, 30μm fine line reproduced but 300μm
The relief depth of the slit width was 35 μm, and a clear image could not be obtained.

【0037】(実施例3)ε−カプロラクタム52.5
部、N,N’−ビス(γ−アミノプロピル)ピペラジン
アジペート37.5部、1,3−ビスアミノメチルシク
ロヘキサンアジペート10.0部を原料に、他は実施例
1と同様の操作でポリアミド−5を合成した。得られた
重合体は融点145℃、比粘度2.00の透明淡黄色で
あった。このポリアミド−5を用いて実施例1と同様に
感光性樹脂組成物を調製し、生版を作成した。生版の光
散乱率を実施例1と同様にして測定したところ5.1%
であった。また、画像再現性評価を実施例1と同様にし
て行ったところ、グレイスケールは17段、2%網点、
200μm独立点、30μm細線が再現した。300μ
mスリット幅のレリーフ抜け深さが105μmあり、鮮
明な画像が得られた。また、30万部の印刷を行った
が、レリーフのとびやクラックの発生はなく、極めて良
好な耐刷性を示した。
Example 3 ε-caprolactam 52.5
Parts, N, N'-bis (γ-aminopropyl) piperazine adipate (37.5 parts), 1,3-bisaminomethylcyclohexane adipate (10.0 parts) as raw materials, and the same procedure as in Example 1 except for polyamide- 5 was synthesized. The obtained polymer was transparent and pale yellow with a melting point of 145 ° C. and a specific viscosity of 2.00. Using this polyamide-5, a photosensitive resin composition was prepared in the same manner as in Example 1 to prepare a raw plate. When the light scattering rate of the raw plate was measured in the same manner as in Example 1, it was 5.1%.
Met. When the image reproducibility was evaluated in the same manner as in Example 1, the gray scale was 17 steps, 2% halftone dots,
A 200 μm independent point and a 30 μm thin line were reproduced. 300μ
The depth of relief relief of m slit width was 105 μm, and a clear image was obtained. Further, 300,000 copies were printed, but no relief jumps or cracks were generated, and extremely good printing durability was exhibited.

【0038】(比較例3)ε−カプロラクタム37.5
部、N,N’−ビス(γ−アミノプロピル)ピペラジン
アジペート42.5部、1,3−ビスアミノメチルシク
ロヘキサンアジペート20.0部を原料に、他は実施例
1と同様の操作にしてポリアミド−6を合成した。得ら
れた重合体は融点135℃、比粘度1.80の透明淡黄
色であった。このポリアミド−6を用いて実施例1と同
様に感光性樹脂組成物を調製し、ポリエステルフイルム
をラミネートし、積層シートを作成したが感光性樹脂組
成物層が固化せずに粘着性の強い生版しか得られなかっ
たので、性能評価を中断した。
Comparative Example 3 ε-caprolactam 37.5
Parts, N, N'-bis (γ-aminopropyl) piperazine adipate (42.5 parts), 1,3-bisaminomethylcyclohexane adipate (20.0 parts) as raw materials, and operating as in Example 1, polyamide -6 was synthesized. The obtained polymer was transparent and pale yellow with a melting point of 135 ° C. and a specific viscosity of 1.80. Using this polyamide-6, a photosensitive resin composition was prepared in the same manner as in Example 1, and a polyester film was laminated to form a laminated sheet. However, the photosensitive resin composition layer was not solidified and had a strong adhesive property. Since only the version was obtained, the performance evaluation was interrupted.

【0039】[0039]

【発明の効果】以上の説明により明らかなように、本発
明の感光性樹脂組成物によれば、水現像が可能で、高感
度で、光硬化後は充分な耐水性と機械的強度を示す感光
性樹脂組成物を得ることができる。特に、短時間の熱処
理による溶融成形で生版を作成でき、しかも、短時間の
水現像で、従来にない高精細な印刷画像が長期間安定に
形成される印刷用レリーフ版を作製できるという極めて
有益な効果が得られる。
As is apparent from the above description, the photosensitive resin composition of the present invention can be developed with water, has high sensitivity, and exhibits sufficient water resistance and mechanical strength after photocuring. A photosensitive resin composition can be obtained. In particular, a raw plate can be prepared by melt molding by a short-time heat treatment, and a relief plate for printing can be produced in which a high-definition print image can be stably formed for a long period of time by a short time of water development. A beneficial effect is obtained.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C08K 5/092 C08K 5/092 5/10 5/10 5/13 5/13 5/20 5/20 5/45 5/45 C08L 77/00 C08L 77/00 G03F 7/00 502 G03F 7/00 502 7/004 501 7/004 501 502 502 7/027 502 7/027 502 7/028 7/028 Fターム(参考) 2H025 AA00 AA13 AB02 AC01 AD01 BC13 BC31 BJ00 CA00 CB24 CB41 CC01 CC05 FA17 FA42 2H096 AA02 BA05 EA02 GA08 4J001 DA01 DB02 DB04 DC13 DC25 EA06 EA14 EA15 EA17 EB06 EB07 EB08 EB09 EB14 EB36 EB37 EC14 EC29 FA03 FB03 FC06 GA03 GA12 GB02 GB03 GB05 GB06 JA20 JB06 JB34 JB42 JC01 4J002 CL051 EE037 EE047 EE057 EF046 EH009 EH076 EJ028 EP009 EP016 FD029 FD038 FD207 GP03 4J011 AA05 PA30 PA33 PA37 PA96 PB23 PB24 PC02 PC08 QA02 QA03 QA06 QA17 QA23 QA34 QA39 QB13 QB19 QB23 SA02 SA12 SA22 SA32 SA34 SA38 SA41 SA54 SA58 SA63 SA64 UA01 VA01 WA01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C08K 5/092 C08K 5/092 5/10 5/10 5/13 5/13 5/20 5/20 5 / 45 5/45 C08L 77/00 C08L 77/00 G03F 7/00 502 G03F 7/00 502 7/004 501 7/004 501 502 502 7/027 502 7/027 502 7/028 7/028 F term ( Reference) 2H025 AA00 AA13 AB02 AC01 AD01 BC13 BC31 BJ00 CA00 CB24 CB41 CC01 CC05 FA17 FA42 2H096 AA02 BA05 EA02 GA08 4J001 DA01 DB02 DB04 DC13 DC25 EA06 EA14 EA15 EA17 EB06 EB07 EB08 GB03 EB09 GB03 GB06 JA20 JB06 JB34 JB42 JC01 4J002 CL051 EE037 EE047 EE057 EF046 EH009 EH076 EJ028 EP009 EP016 FD029 FD038 FD207 GP03 4J011 AA05 PA30 PA33 PA37 PA96 PB23 PB24 PC02 PC08 QA02 QA03 QA03 QA03 QAQ3 QB19 QB23 SA02 SA12 SA22 SA32 SA34 SA38 SA41 SA54 SA58 SA63 SA64 UA01 VA01 WA01

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 下記一般式(I)で示される単位40〜
60重量%と、下記一般式(II)で示される単位30
〜50重量%と、下記一般式(III)で示される単位
5〜15重量%とからなるポリアミド、光重合可能な不
飽和結合を有する単量体および光重合開始剤を含有する
ことを特徴とする感光性樹脂組成物。 【化1】 (式中、R1 は炭素数が5以上のアルキレン基) 【化2】 (式中、R2 は炭素数が2〜10の炭化水素基、R3
炭素数が1〜4のアルキレン基または単結合、R4 は炭
素数が1〜4のアルキレン基) 【化3】 (式中、R5 は炭素数が2〜10の炭化水素基、R6
7 はメチレン基または単結合)
1. A unit represented by the following general formula (I):
60% by weight and a unit 30 represented by the following general formula (II)
Characterized by containing a polyamide comprising 50 to 50% by weight and 5 to 15% by weight of a unit represented by the following general formula (III), a photopolymerizable monomer having an unsaturated bond, and a photopolymerization initiator. Photosensitive resin composition. Embedded image (Wherein, R 1 is an alkylene group having 5 or more carbon atoms) Wherein R 2 is a hydrocarbon group having 2 to 10 carbon atoms, R 3 is an alkylene group or a single bond having 1 to 4 carbon atoms, and R 4 is an alkylene group having 1 to 4 carbon atoms. ] (Wherein, R 5 is a hydrocarbon group having 2 to 10 carbon atoms, R 6 ,
R 7 is a methylene group or a single bond)
【請求項2】 光重合可能な不飽和結合を有する単量体
および光重合開始剤の合計含有量が30〜60重量%で
ある請求項1記載の感光性樹脂組成物。
2. The photosensitive resin composition according to claim 1, wherein the total content of the monomer having a photopolymerizable unsaturated bond and the photopolymerization initiator is 30 to 60% by weight.
【請求項3】 さらに安定剤および/または可塑剤を含
有し、該安定剤および/または可塑剤、光重合可能な不
飽和結合を有する単量体および光重合開始剤の合計含有
量が30〜60重量%である請求項1記載の感光性樹脂
組成物。
3. The composition further contains a stabilizer and / or a plasticizer, and the total content of the stabilizer and / or the plasticizer, the monomer having a photopolymerizable unsaturated bond and the photopolymerization initiator is 30 to The photosensitive resin composition according to claim 1, which is 60% by weight.
【請求項4】 波長360nmの光の散乱率が10%以
下である請求項1〜3のいずれかに記載の感光性樹脂組
成物。
4. The photosensitive resin composition according to claim 1, wherein a scattering rate of light having a wavelength of 360 nm is 10% or less.
JP21588299A 1999-07-29 1999-07-29 Photosensitive resin composition Expired - Lifetime JP3632513B2 (en)

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Application Number Priority Date Filing Date Title
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JP3632513B2 JP3632513B2 (en) 2005-03-23

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016071044A (en) * 2014-09-29 2016-05-09 東洋紡株式会社 Photosensitive resin composition for relief printing and photosensitive resin relief printing plate precursor obtained from the composition
WO2017169572A1 (en) 2016-03-29 2017-10-05 東洋紡株式会社 Relief printing original plate for rotary letterpress printing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016071044A (en) * 2014-09-29 2016-05-09 東洋紡株式会社 Photosensitive resin composition for relief printing and photosensitive resin relief printing plate precursor obtained from the composition
WO2017169572A1 (en) 2016-03-29 2017-10-05 東洋紡株式会社 Relief printing original plate for rotary letterpress printing

Also Published As

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