JP2001159813A - Photosensitive resin composition, original plate for printing using same and printing plate - Google Patents
Photosensitive resin composition, original plate for printing using same and printing plateInfo
- Publication number
- JP2001159813A JP2001159813A JP34246299A JP34246299A JP2001159813A JP 2001159813 A JP2001159813 A JP 2001159813A JP 34246299 A JP34246299 A JP 34246299A JP 34246299 A JP34246299 A JP 34246299A JP 2001159813 A JP2001159813 A JP 2001159813A
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- Japan
- Prior art keywords
- photosensitive resin
- resin composition
- absorption peak
- irradiation
- printing
- 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.)
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- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、感光性樹脂組成
物、それを用いた印刷用原版および印刷版に関し、より
詳しくは、特に印刷用レリーフ版の作成に好適な感光性
樹脂組成物、それを用いた印刷用原版および印刷用レリ
ーフ版に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a printing original plate and a printing plate using the same, and more particularly, a photosensitive resin composition suitable for preparing a printing relief plate, The present invention relates to a printing original plate and a printing relief plate using the same.
【０００２】[0002]
【従来の技術】印刷用レリーフ版に用いられる感光性樹
脂組成物は、一般に、可溶性ポリマー、光重合性不飽和
基含有モノマーおよび光重合開始剤を必須成分として含
有し、必要に応じて安定剤、可塑剤等の添加剤が配合さ
れて、当該組成物より感光層が形成される。2. Description of the Related Art A photosensitive resin composition used for a relief plate for printing generally contains a soluble polymer, a monomer containing a photopolymerizable unsaturated group and a photopolymerization initiator as essential components, and if necessary, a stabilizer. An additive such as a plasticizer is blended to form a photosensitive layer from the composition.
【０００３】この感光層に、透明な画像部を有するネガ
フィルム（またはポジフィルム）を通して活性光線を照
射し、露光部の感光層を硬化させた後、非露光部の感光
層を適当な溶剤で溶解除去することによって、印刷目的
のレリーフ版を作成することは広く知られている。The photosensitive layer is irradiated with actinic light through a negative film (or a positive film) having a transparent image area to cure the photosensitive layer in the exposed area, and then the photosensitive layer in the unexposed area is exposed to an appropriate solvent. It is widely known that a relief plate for printing is prepared by dissolving and removing.
【０００４】このレリーフ版作成に用いるネガフィルム
の画像パターンは一定でなく、種々の、線、独立点、活
字、白抜きパターンや網点が混在している場合が多い。
例えば、細い線、小さな独立点、小さな活字や細かい網
点をレリーフ画像にするためには活性光線の露光（照
射）時間を延長して照射量を増やす事が必要である。照
射量が少ないと、非露光部の感光層を適当な溶剤で溶解
除去する（現像）工程中に、露光画像部の硬化が不十分
であるために、当該露光画像部が大膨潤したり、移動や
欠落が発生し、原画に忠実なレリーフ画像が得られな
い。逆に、露光部に囲まれたりあるいは挟まれたする、
細かい非露光画像部の白抜きパターン（例えば白抜き線
や白抜き点）を作成する場合には、照射量が多いと、周
囲の散乱光によって、現像工程での本来の溶剤除去量や
感光層の表面からの深さが減少してしまう。このような
レリーフ版で凸版印刷すると、画像の太りや白抜きパタ
ーンが埋まった画像になり、良好な印刷物が得られな
い。[0004] The image pattern of the negative film used for producing the relief plate is not constant, and various lines, independent points, characters, white patterns, and halftone dots are often mixed.
For example, in order to make a thin line, a small independent point, a small print, or a fine halftone dot into a relief image, it is necessary to extend the exposure (irradiation) time of the active ray and increase the irradiation amount. If the irradiation amount is small, during the step of dissolving and removing the photosensitive layer in the non-exposed area with an appropriate solvent (development), the exposed image area hardly swells due to insufficient curing of the exposed image area, Movement or lack occurs, and a relief image faithful to the original image cannot be obtained. Conversely, it is surrounded or sandwiched by the exposed part,
When creating a fine white pattern (for example, a white line or a white dot) in a fine non-exposed image area, if the irradiation amount is large, the original amount of solvent removed in the developing process and the photosensitive layer due to ambient scattered light The depth from the surface decreases. When letterpress printing is performed with such a relief plate, the image becomes an image in which the thickness of the image or the outline pattern is buried, and a good printed matter cannot be obtained.
【０００５】従って、細い線、小さな独立点、小さな活
字や細かい網点等の露光画像部の形成の場合と、白抜き
パターンの非露光画像部の形成の場合とは、活性光線の
露光（照射）量に関して相反する関係にある。どちらの
場合でも原画を忠実に再現したレリーフ版を作成でき、
良好な印刷物を与えることができるような感光性樹脂組
成物が望まれている。Therefore, the case of forming an exposed image portion such as a thin line, a small independent point, a small type or a small halftone dot, and the case of forming a non-exposed image portion of a white pattern are defined by the exposure (irradiation) of actinic rays. ) There is a conflicting relationship with respect to quantity. In either case, you can create a relief version that faithfully reproduces the original image,
There is a need for a photosensitive resin composition that can provide good printed matter.
【０００６】この問題を解決するために、照射量を多く
しても白抜きパターンの非露光画像部の深さが保てる方
法として、例えば、特開昭５９−１３３５４５８号公報
に記載の、フエノキサジン染料やアクリジニウム染料や
フエノチアジニウム染料等と、活性光線下でのみそれら
の染料を還元する還元剤を併用する方法；ＧＢ−１６０
１２８８号公報やＧＢ−１６００９２５号公報に記載
の、９−ニトロアントラセンおよびビアンスロン類を使
用する方法；特公昭５９−２２２１６号公報に記載の、
１，４−もしくは１，２−ナフトキノンまたはそれらの
誘導体とベンゾインアルキルエーテル類を併用する方
法；特公昭５７−３９４１０号公報に記載の、１，４−
もしくは１，２−ジオキシナフタリンまたはそれらの誘
導体とベンゾインアルキルエーテル類を併用する方法；
特公昭５７−４０４９９号公報に記載の、アミノナフト
キノン類を使用する方法；特公昭６０−２１３７４号公
報に記載の、チオニン系化合物とベンゾインアルキルエ
ーテル類を併用する方法、等が知られている。[0006] In order to solve this problem, as a method of maintaining the depth of the unexposed image portion of the white pattern even if the irradiation amount is increased, for example, a phenoxazine dye described in JP-A-59-13335458 is disclosed. GB-160 in which a dye, an acridinium dye, a phenothiazinium dye, or the like is used in combination with a reducing agent that reduces those dyes only under actinic light;
A method using 9-nitroanthracene and bianthrones described in JP-A-1288 and GB-1600925; a method described in JP-B-59-22216;
A method in which 1,4- or 1,2-naphthoquinone or a derivative thereof is used in combination with a benzoin alkyl ether; 1,4- or 1,2-naphthoquinone described in JP-B-57-39410;
Or a method in which 1,2-dioxynaphthalene or a derivative thereof is used in combination with a benzoin alkyl ether;
A method using aminonaphthoquinones described in JP-B-57-40499; a method using thionin-based compounds and benzoin alkyl ethers described in JP-B-60-21374, and the like are known.
【０００７】これらの諸例のように、上記のような特定
の有機化合物を少量配合することによって、レリーフ形
状を改善することは公知である。しかしながら、これら
の化合物は取扱いに充分な注意が必要な人体に有害なも
のであったり、高価なものであったり、その使用のため
に感度の低下が見られるものであったりする。またその
特有な色のために装置や現像液等の汚染の問題が生じ
る。また、感光性樹脂組成物の構成材料（例えば、可溶
性ポリマーがポリビニルアルコール系やポリアミド系の
場合）や、活性光線の光源（例えばケミカルランプや超
高圧水銀灯の場合）によっては、これらの化合物による
レリーフ形状の改善効果が全く出ない場合があり、必ず
しも万能ではない。As in these examples, it is known to improve the relief shape by adding a small amount of the above-mentioned specific organic compound. However, these compounds are harmful to the human body that requires careful handling, are expensive, or have reduced sensitivity due to their use. In addition, a problem of contamination of the apparatus and the developing solution occurs due to the unique color. In addition, depending on the constituent material of the photosensitive resin composition (for example, when the soluble polymer is a polyvinyl alcohol-based or polyamide-based) or the light source of an actinic ray (for example, a chemical lamp or an ultra-high pressure mercury lamp), relief by these compounds may be used. The effect of improving the shape may not be obtained at all, and is not always versatile.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記の問題
を解決しようとするものであり、その目的は、細い線、
小さな独立点、小さな活字や細かい網点等の露光画像部
の形成と、白抜きパターンの非露光画像部の形成の両方
において、原画を忠実に再現したレリーフ版を作成で
き、良好な印刷物を与えることができる、感光性樹脂組
成物を提供することにある。SUMMARY OF THE INVENTION The present invention seeks to solve the above-mentioned problems, and its object is to provide thin lines,
A relief plate that faithfully reproduces the original image can be created in both the formation of exposed image areas such as small independent points, small prints and fine halftone dots, and the formation of non-exposed image areas of white patterns, giving good printed matter. It is an object of the present invention to provide a photosensitive resin composition.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、細い線、
小さな独立点、小さな活字や細かい網点等の露光画像部
の形成においては、原画の画像パターンに忠実に再現で
き、また、白抜きパターンの非露光画像部の形成におい
ては、画像の太りや白抜きパターンが埋まることのな
い、従って良好な印刷物を形成できる、感光性樹脂組成
物について鋭意検討した結果、本発明を完成するに到っ
た。Means for Solving the Problems We have developed a thin line,
In the formation of exposed image portions such as small independent points, small prints and fine halftone dots, it is possible to faithfully reproduce the original image pattern. As a result of earnestly studying a photosensitive resin composition that does not bury the punched pattern and thus can form a good printed matter, the present invention has been completed.
【００１０】即ち、本発明は以下の通りである。 (1) 可溶性ポリマー、光重合性不飽和基含有モノマーお
よび光重合開始剤を主成分として含有する感光性樹脂組
成物であって、当該組成物の吸収ピークが４００ｎｍ〜
５００ｎｍの波長領域内にあり、かつ活性光線の照射に
よって当該吸収ピークの強度が減少することを特徴とす
る感光性樹脂組成物。 (2) ４００ｎｍ〜５００ｎｍの波長領域内に吸収ピーク
を有し、かつ活性光線の照射によってその吸収ピークの
強度が減少する化合物を含有する、上記(1) に記載の感
光性樹脂組成物。 (3) 感光性樹脂組成物中の成分と反応して４００ｎｍ〜
５００ｎｍの波長領域内に吸収ピークを付与し、かつ活
性光線の照射によってその吸収ピークの強度が減少する
ような化合物を含有する、上記(1) に記載の感光性樹脂
組成物。 (4) 支持体上に、上記(1) 〜(3) のいずれかに記載の感
光性樹脂組成物からなる感光層が形成されてなる印刷用
原版。 (5) 上記(4) に記載の印刷用原版を露光、次いで現像し
てなることを特徴とする印刷版。 (6) レリーフ版である、上記(5) に記載の印刷版。That is, the present invention is as follows. (1) a photosensitive resin composition containing a soluble polymer, a photopolymerizable unsaturated group-containing monomer and a photopolymerization initiator as main components, and the absorption peak of the composition is 400 nm or more.
A photosensitive resin composition having a wavelength within a range of 500 nm, wherein the intensity of the absorption peak is reduced by irradiation with actinic light. (2) The photosensitive resin composition according to the above (1), which contains a compound having an absorption peak in a wavelength region of 400 nm to 500 nm and having a reduced absorption peak intensity upon irradiation with actinic rays. (3) reacting with the components in the photosensitive resin composition to 400 nm
(1) The photosensitive resin composition according to the above (1), which contains a compound that gives an absorption peak in a wavelength region of 500 nm and reduces the intensity of the absorption peak by irradiation with actinic rays. (4) An original printing plate comprising a support and a photosensitive layer comprising the photosensitive resin composition according to any one of the above (1) to (3) formed thereon. (5) A printing plate obtained by exposing and then developing the printing original plate according to (4). (6) The printing plate according to (5), which is a relief plate.
【００１１】吸収ピークが４００ｎｍ〜５００ｎｍの波
長領域内にあり、かつ活性光線の照射によって当該吸収
ピークの強度が減少する本発明の感光性樹脂組成物にお
いては、活性光線に対する感度を保持しつつ、しかも光
源が異なったり、活性光線の露光（照射）量を多くして
も白抜きパターンの非露光画像部が埋まりにくく、画像
の太りがなく、良好な印刷物が得られる。In the photosensitive resin composition of the present invention, in which the absorption peak is in the wavelength region of 400 nm to 500 nm and the intensity of the absorption peak is reduced by irradiation with actinic rays, the sensitivity to actinic rays is maintained while maintaining the sensitivity. Moreover, even if the light source is different or the amount of exposure (irradiation) of the active light beam is increased, the unexposed image portion of the white pattern is hard to be filled, and the image is not thickened, and a good printed matter is obtained.
【００１２】[0012]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明の感光性樹脂組成物は、可溶性ポリマー、光重合
性不飽和基含有モノマーおよび光重合開始剤を主成分と
して含有するものである。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention contains a soluble polymer, a photopolymerizable unsaturated group-containing monomer and a photopolymerization initiator as main components.
【００１３】本発明で使用される可溶性ポリマーとは、
溶剤（現像液）に分散もしくは溶解できるポリマーをい
い、特に、水に分散もしくは溶解できるポリマーが好ま
しい。またその数平均分子量は０．５万以上、特に１万
以上のものが好ましい。例えば、ポリアミド、ポリウレ
タン、ポリエステル、ポリビニルアルコール、ポリビニ
ルエーテル、ポリ（メタ）アクリル酸エステル類、ポリ
ウレア、ポリビニルピロリドン、セルロース誘導体、ポ
リブタジエン共重合体等が挙げられる。また、これらの
ポリマーに光重合性不飽和基を導入したポリマーも使用
可能である。The soluble polymer used in the present invention is:
A polymer that can be dispersed or dissolved in a solvent (developing solution), particularly a polymer that can be dispersed or dissolved in water. The number average molecular weight is preferably at least 50,000, particularly preferably at least 10,000. Examples include polyamide, polyurethane, polyester, polyvinyl alcohol, polyvinyl ether, poly (meth) acrylates, polyurea, polyvinylpyrrolidone, cellulose derivatives, polybutadiene copolymer, and the like. Further, polymers in which a photopolymerizable unsaturated group is introduced into these polymers can also be used.
【００１４】可溶性ポリマーの含有量は、感光性樹脂組
成物中、好ましくは４０〜８０重量％、より好ましくは
５０〜７０重量％である。当該含有量が４０重量％未満
であると、組成物がコールドフローしやすく、また画像
の物性が低下するおそれがある。逆に８０重量％を超え
ると、感度が低下したり、現像時間が長くなるおそれが
ある。また架橋密度が低くなって画像の耐水性や耐溶剤
性が低下するおそれがある。The content of the soluble polymer in the photosensitive resin composition is preferably from 40 to 80% by weight, more preferably from 50 to 70% by weight. If the content is less than 40% by weight, the composition tends to be cold-flowed, and the physical properties of the image may be deteriorated. On the other hand, if it exceeds 80% by weight, the sensitivity may be lowered or the development time may be prolonged. Further, the crosslinking density may be reduced, and the water resistance and solvent resistance of the image may be reduced.
【００１５】本発明で使用される光重合性不飽和基含有
モノマーとしては、分子内に光重合可能な不飽和基を１
個以上含有するモノマーであり、従来公知のものが使用
でき、例えば、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（メタ）アクリ
レート、ペンタエリスリトールトリ（メタ）アクリレー
ト、グリセロールジ（メタ）アクリレート；さらには、
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等の多価グリシジ
ルエーテルに、不飽和カルボン酸（アクリル酸、メタク
リル酸等）や不飽和アルコール等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（メタ）アクリレート；グリシジル（メタ）アクリレ
ート等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等が挙げられる。これ
らのモノマーは単独でも２種以上併用してもよい。As the photopolymerizable unsaturated group-containing monomer used in the present invention, one photopolymerizable unsaturated group in the molecule is used.
Monomer or more, and conventionally known ones can be used, for example, acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide, N -Acroylmorpholine, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate;
Polyhydric glycidyl ethers such as ethylene glycol diglycidyl ether and trimethylolpropane triglycidyl ether, and compounds having an ethylenically unsaturated bond and active hydrogen such as unsaturated carboxylic acids (acrylic acid, methacrylic acid, etc.) and unsaturated alcohols Polyhydric (meth) acrylate obtained by addition reaction; addition reaction product of an unsaturated epoxy compound such as glycidyl (meth) acrylate and a compound having active hydrogen such as carboxylic acid and amine; unsaturated polyester; unsaturated polyurethane and the like Is mentioned. These monomers may be used alone or in combination of two or more.
【００１６】光重合性不飽和基含有モノマーの含有量
は、感光性樹脂組成物中、好ましくは５〜６０重量％、
より好ましくは１５〜４０重量％である。当該含有量が
５重量％未満であると、光重合による硬化速度が劣り、
現像後に細い線、小さな独立点、小さな活字や細かい網
点等の露光画像部が残りにくくなり、逆に６０重量％を
超えると、硬化収縮率が大きくなったり、画像の物性が
低下するおそれがあり、好ましくない。The content of the photopolymerizable unsaturated group-containing monomer is preferably 5 to 60% by weight in the photosensitive resin composition.
More preferably, it is 15 to 40% by weight. When the content is less than 5% by weight, the curing speed by photopolymerization is inferior,
After development, exposed image areas such as fine lines, small independent points, small prints and fine halftone dots are unlikely to remain. Conversely, if it exceeds 60% by weight, the cure shrinkage may increase, or the physical properties of the image may deteriorate. Yes, not preferred.
【００１７】本発明で使用される光重合開始剤として
は、従来公知のものが使用でき、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、アントラキノン類、チオキサントン類等が使用
できる。具体的には、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、アントラ
キノン、２−クロロアントラキノン、チオキサントン、
２−クロロチオキサントン等がある。As the photopolymerization initiator used in the present invention, conventionally known photopolymerization initiators can be used, for example, benzophenones, benzoins, acetophenones, benzyls, and the like.
Benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones, thioxanthones and the like can be used. Specifically, benzophenone, benzoin, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzyldimethyl ketal, anthraquinone, 2-chloroanthraquinone, thioxanthone,
2-chlorothioxanthone and the like.
【００１８】光重合開始剤の含有量は、感光性樹脂組成
物中、好ましくは０．０５〜５重量％、より好ましくは
０．１〜２．０重量％である。当該含有量が０．０５重
量％未満であると、光重合が開始しにくく、逆に５重量
％を超えると、当該組成物を使用した感光層の厚み方向
の光重合が悪くなって、細い線、小さな独立点、小さな
活字や細かい網点等の露光画像部が欠けやすくなり、好
ましくない。The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.0% by weight. If the content is less than 0.05% by weight, photopolymerization is unlikely to start, and if it exceeds 5% by weight, photopolymerization in the thickness direction of the photosensitive layer using the composition becomes poor, resulting in a thin film. Exposure image portions such as lines, small independent points, small prints and fine halftone dots are likely to be chipped, which is not preferable.
【００１９】感光性樹脂組成物に安定剤を配合してもよ
く、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、２，６−ジ−ｔ−ブチル−ｐ−クレゾール
等が挙げられる。安定剤の含有量は、感光性樹脂組成物
中、好ましくは０．００１〜５重量％、より好ましくは
０．０１〜１．０重量％である。A stabilizer may be added to the photosensitive resin composition, and examples thereof include hydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyl-p-cresol. The content of the stabilizer in the photosensitive resin composition is preferably 0.001 to 5% by weight, more preferably 0.01 to 1.0% by weight.
【００２０】また、エステルやアミド等の低分子可塑
剤、ポリエステルやポリエーテル、液状ゴム類等のオリ
ゴマー等の可塑剤を感光性樹脂組成物に配合して、光重
合物の物性を変化させることができる。また、公知の染
料や色素を添加して感光性樹脂層を着色し、形成した画
像部を鮮明にすることもできる。In addition, a low-molecular plasticizer such as an ester or an amide, and a plasticizer such as an oligomer such as a polyester or a polyether or a liquid rubber are mixed with the photosensitive resin composition to change the physical properties of the photopolymer. Can be. In addition, a known dye or pigment may be added to color the photosensitive resin layer to sharpen the formed image area.
【００２１】本発明の感光性樹脂組成物は、その吸収ピ
ークが４００ｎｍ〜５００ｎｍの波長領域内にあり、か
つ活性光線の照射によって当該吸収ピークの強度が減少
する。ここで、その吸収ピークが４００ｎｍ未満である
場合、そのような感光性樹脂組成物は活性光線を吸収し
てしまうので、活性光線に対する感度の低下が著しく、
従って光重合が生じにくい。逆に、その吸収ピークが５
００ｎｍを超える場合、そのような感光性樹脂組成物は
色調が鮮明で濃くなり、装置や材料の汚染が目立つ欠点
がある。感光性樹脂組成物の吸収ピークは４２０ｎｍ〜
４９０ｎｍの波長領域内にあることが好ましい。The photosensitive resin composition of the present invention has an absorption peak in a wavelength range of 400 nm to 500 nm, and the intensity of the absorption peak is reduced by irradiation with actinic rays. Here, when the absorption peak is less than 400 nm, since such a photosensitive resin composition absorbs actinic rays, the sensitivity to actinic rays is significantly reduced,
Therefore, photopolymerization hardly occurs. Conversely, the absorption peak is 5
When the thickness is more than 00 nm, such a photosensitive resin composition has a disadvantage that the color tone is clear and dark, and the contamination of the apparatus and the material is conspicuous. The absorption peak of the photosensitive resin composition is from 420 nm to
It is preferably within the wavelength range of 490 nm.
【００２２】また、４００ｎｍ〜５００ｎｍの波長領域
内に吸収ピークを有しても活性光線の照射によってその
吸収ピークの強度が減少しない場合、活性光線の照射量
を多くすると白抜きパターンの非露光画像部が埋まりや
すく、画像太りが見られ、良好な印刷物が得られない。
吸収ピークの強度（画像が得られる最小量の照射で）が
２０％以上、特に３０％以上減少することが好ましい。
吸収ピークの強度の減少率が２０％未満であると、鮮明
な画像が得られにくくなるおそれがある。In the case where the intensity of the absorption peak does not decrease by irradiation with actinic light even if it has an absorption peak in the wavelength region of 400 nm to 500 nm, if the irradiation amount of actinic light is increased, a non-exposed image of a white pattern is obtained. The portion is easily filled, the image is thickened, and good printed matter cannot be obtained.
It is preferred that the intensity of the absorption peak (with the minimum amount of radiation that produces an image) be reduced by 20% or more, especially 30% or more.
If the reduction rate of the intensity of the absorption peak is less than 20%, a clear image may not be easily obtained.
【００２３】感光性樹脂組成物が４００ｎｍ〜５００ｎ
ｍの波長領域内に吸収ピークを有することは、分光光度
計を用いて、感光性樹脂組成物の吸収スペクトル曲線を
測定し、４００ｎｍ〜５００ｎｍの波長領域内に吸収ピ
ークが存在することで確認できる。また、活性光線の照
射によってその吸収ピークの強度が減少するかどうか
は、活性光線の照射前後の感光性樹脂組成物の吸収スペ
クトル曲線の測定し、その吸収ピークの強度の変化によ
り確認できる。When the photosensitive resin composition has a thickness of 400 nm to 500 n
Having an absorption peak in the wavelength region of m can be confirmed by measuring the absorption spectrum curve of the photosensitive resin composition using a spectrophotometer and confirming that the absorption peak exists in the wavelength region of 400 nm to 500 nm. . Whether or not the intensity of the absorption peak is reduced by irradiation with actinic light can be confirmed by measuring the absorption spectrum curve of the photosensitive resin composition before and after irradiation with the actinic light and changing the intensity of the absorption peak.
【００２４】本発明の感光性樹脂組成物においては、
その吸収ピークが４００ｎｍ〜５００ｎｍの波長領域内
にあるので、活性光線をある程度吸収し、感度が少し低
いが、光重合開始剤の存在下、活性光線の照射によっ
て当該吸収ピークの強度が減少して、照射中に照射部の
感度が高くなる、というものである。従って、活性光線
に対する感度を保持しつつ、しかも光源が異なったり、
活性光線の露光（照射）量を多くしても白抜きパターン
の非露光画像部が埋まりにくく、画像の太りがなく、良
好な印刷物が得られる。In the photosensitive resin composition of the present invention,
Since the absorption peak is in the wavelength region of 400 nm to 500 nm, the active light is absorbed to some extent and the sensitivity is slightly low. However, in the presence of the photopolymerization initiator, the intensity of the absorption peak decreases due to the irradiation of the active light. That is, the sensitivity of the irradiation unit increases during irradiation. Therefore, while maintaining sensitivity to actinic rays, and the light source is different,
Even if the amount of exposure (irradiation) of the actinic ray is increased, the non-exposed image portion of the white pattern is hard to be filled, and the image is not thickened and a good printed matter is obtained.
【００２５】吸収ピークが４００ｎｍ〜５００ｎｍの波
長領域内にあり、かつ活性光線の照射によってその吸収
ピークの強度が減少するような感光性樹脂組成物は、４
００ｎｍ〜５００ｎｍの波長領域内に吸収ピークを有
し、かつ光重合開始剤の存在下、活性光線の照射によっ
てその吸収ピークの強度が減少する化合物を、通常の感
光性樹脂組成物に配合することにより調製することがで
きる。A photosensitive resin composition having an absorption peak in the wavelength region of 400 to 500 nm and whose intensity of the absorption peak is reduced by irradiation with actinic rays is 4
Compounding a compound having an absorption peak in the wavelength region of 00 nm to 500 nm and having a reduced absorption peak intensity by irradiation with actinic light in the presence of a photopolymerization initiator, in a usual photosensitive resin composition. Can be prepared.
【００２６】４００ｎｍより短波長に吸収ピークを有す
る化合物は、活性光線を吸収してしまうので感度の低下
が著しく、逆に、５００ｎｍより長波長に吸収ピークを
有する化合物は、色調が鮮明で濃くなり、装置や材料の
汚染が目立つ欠点がある。当該化合物は４２０ｎｍ〜４
９０ｎｍの波長領域内に吸収ピークを有することが好ま
しい。また、４００ｎｍ〜５００ｎｍの波長領域内に吸
収ピークを有するが、活性光線の照射によってその吸収
ピークの強度が減少しないような化合物を配合しても、
活性光線の照射量を多くすると白抜きパターンの非露光
画像部が埋まりやすく、良好な印刷物が得られない。A compound having an absorption peak at a wavelength shorter than 400 nm absorbs actinic light, so that the sensitivity is significantly reduced. Conversely, a compound having an absorption peak at a wavelength longer than 500 nm has a clear and deep color tone. However, there is a disadvantage that contamination of the apparatus and the material is conspicuous. The compound is from 420 nm to 4
It preferably has an absorption peak in a wavelength region of 90 nm. Further, even if a compound having an absorption peak in a wavelength region of 400 nm to 500 nm but not reducing the intensity of the absorption peak by irradiation with actinic rays,
If the irradiation amount of the actinic ray is increased, the unexposed image portion of the white pattern is easily filled, and a good printed matter cannot be obtained.
【００２７】４００ｎｍ〜５００ｎｍの波長領域内に吸
収ピークを有し、かつ活性光線の照射によってその吸収
ピークの強度が減少するような化合物としては、特に限
定されないが、例えば、クリソイジン（２，４−ジアミ
ノアゾベンゼン）やその塩酸塩であるクリソイジンＧ、
オレンジＧ、オイルエローＡＢ、メルレッド、メチルオ
レンジ、Ｎ−シクロヘキシルアミノ−１，４−ナフトキ
ノン等が挙げられる。これらは単独で使用しても２種以
上併用してもよい。The compound having an absorption peak in the wavelength region of 400 nm to 500 nm and whose intensity of the absorption peak is reduced by irradiation with actinic rays is not particularly limited. For example, chrysoidin (2,4- Diaminoazobenzene) and its hydrochloride chrysoidin G,
Orange G, oil yellow AB, Melred, methyl orange, N-cyclohexylamino-1,4-naphthoquinone, and the like. These may be used alone or in combination of two or more.
【００２８】上記の化合物の配合量は、感光性樹脂組成
物中、好ましくは０．００１〜１．０重量％、より好ま
しくは０．０１〜０．０５重量％である。当該配合量が
０．００１重量％未満の場合、上記化合物による効果が
得られず、逆に１．０重量％を超える場合、感度が低下
して硬化不良となり、また着色が激しくなり、好ましく
ない。The compounding amount of the above compound is preferably 0.001 to 1.0% by weight, more preferably 0.01 to 0.05% by weight in the photosensitive resin composition. If the compounding amount is less than 0.001% by weight, the effect of the above compound cannot be obtained, and if it exceeds 1.0% by weight, sensitivity is lowered to cause poor curing and coloring is intensified, which is not preferable. .
【００２９】あるいは、感光性樹脂組成物に配合した時
に、組成物中の他の構成成分と反応して、結果として４
００ｎｍ〜５００ｎｍの波長領域内に吸収ピークを与
え、かつ光重合開始剤の存在下、活性光線の照射によっ
てその吸収ピークの強度が減少するような化合物を、配
合することによっても本発明の感光性樹脂組成物を調製
することができる。このような化合物としては、例えば
１，４−ナフトキノンが挙げられ、当該化合物は、感光
性樹脂組成物中のアミン化合物と反応して４５０ｎｍに
吸収ピークが与えられ、その吸収ピークの強度は活性光
線の照射によって減少する。Alternatively, when blended in the photosensitive resin composition, it reacts with other components in the composition, resulting in 4
The photosensitivity of the present invention can also be obtained by blending a compound which gives an absorption peak in the wavelength region of from 00 nm to 500 nm and whose absorption peak intensity is reduced by irradiation with actinic light in the presence of a photopolymerization initiator. A resin composition can be prepared. Examples of such a compound include 1,4-naphthoquinone, and the compound reacts with an amine compound in the photosensitive resin composition to give an absorption peak at 450 nm, and the intensity of the absorption peak is determined by actinic light. By irradiation.
【００３０】上記の化合物の配合量は、反応する組成物
中の他の構成成分の量にもよるが、と反応感光性樹脂組
成物中、好ましくは０．００５〜０．５重量％、より好
ましくは０．０１〜０．２重量％である。当該配合量が
０．００５重量％未満の場合、上記化合物による効果が
得られず、逆に０．５重量％を超える場合、感度の低下
して硬化不良となり、また着色が激しくなり、好ましく
ない。The amount of the above compound depends on the amount of other components in the composition to be reacted, but is preferably 0.005 to 0.5% by weight in the reaction photosensitive resin composition. Preferably it is 0.01 to 0.2% by weight. When the amount is less than 0.005% by weight, the effect of the above compound cannot be obtained. On the other hand, when the amount exceeds 0.5% by weight, the sensitivity is lowered to cause poor curing, and the coloring becomes intense. .
【００３１】本発明の感光性樹脂組成物は、例えば、熱
プレス、注型または溶融押出し、溶液キャスト等の公知
の任意の方法により所望の厚さのシート状物とすること
ができる。また、このシート状物を感光層として、公知
の接着剤を介してまたは介さずに支持体に積層すること
もできる。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等のプラスチックフィル
ム、金属蒸着したフィルム等任意のものが使用できる。The photosensitive resin composition of the present invention can be formed into a sheet having a desired thickness by any known method such as hot pressing, casting or melt extrusion, and solution casting. Further, this sheet-like material can be laminated as a photosensitive layer on a support with or without a known adhesive. As the support, any material such as a plastic film such as steel, aluminum, glass, and polyester film, and a metal-deposited film can be used.
【００３２】感光層と支持体とからなる感光性樹脂印刷
用原版（生版）の場合には、感光層上に保護層が積層さ
れてもよい。この保護層には、フィルム状のプラスチッ
ク（例えばポリエステルの１２５μｍ厚みのフィルム）
に、粘着性のない透明で現像液に分散または溶解し得る
高分子からなる薄膜（厚さ１〜３μｍ）を有する保護材
が用いられる。この薄膜が感光層と接するように、当該
保護材を感光層上に積層する。そして、露光操作前にこ
の積層体から当該保護材のフィルム状のプラスチックの
みを剥離し露光する。感光層表面の粘着性が強い場合で
あっても、保護材の薄膜は粘着性がないので、薄膜から
フィルム状のプラスチックを容易に剥離することができ
る。In the case of a photosensitive resin printing original plate (raw plate) comprising a photosensitive layer and a support, a protective layer may be laminated on the photosensitive layer. For this protective layer, a film-like plastic (for example, a polyester film having a thickness of 125 μm)
In addition, a protective material having a thin film (thickness of 1 to 3 μm) made of a polymer which is transparent and has no tackiness and can be dispersed or dissolved in a developer is used. The protective material is laminated on the photosensitive layer so that the thin film contacts the photosensitive layer. Then, before the exposure operation, only the film-like plastic of the protective material is peeled off from the laminate and exposed. Even when the surface of the photosensitive layer has strong adhesiveness, the thin film of the protective material has no adhesiveness, so that the film-like plastic can be easily peeled from the thin film.
【００３３】上記の感光性樹脂組成物からなるシート状
物、または感光性樹脂組成物からなる層が支持体上に形
成された積層体の感光性樹脂印刷用原版（生版）は、シ
ート状物上または感光層上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３００ｎ
ｍ〜４００ｎｍ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
ランプ等の光源を用いる。The photosensitive resin printing original plate (raw plate) of the above-mentioned sheet-like material made of the above-mentioned photosensitive resin composition or a laminate in which a layer made of the above-mentioned photosensitive resin composition is formed on a support is a sheet-like material. When a negative film or a positive film having a transparent image portion is closely adhered to an object or a photosensitive layer and superposed, and exposed to actinic rays from above, and exposed, only the exposed portion is insolubilized and cured. Actinic light is usually 300n
A light source such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or a chemical lamp having a wavelength of m to 400 nm is used.
【００３４】次いで適当な溶剤、特に中性水により非露
光部分を溶解除去することによって、鮮明な画像部を有
する感光性樹脂印刷版を得る。溶解除去にはスプレー式
現像装置またはブラシ式現像装置を用いる。Next, the photosensitive resin printing plate having a clear image area is obtained by dissolving and removing the non-exposed portion with a suitable solvent, especially neutral water. A spray-type developing device or a brush-type developing device is used for dissolution and removal.
【００３５】以下に実施例で本発明をさらに詳しく説明
する。実施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. Parts in the examples are parts by weight.
【００３６】実施例１ ε−カプロラクタム６２部、Ｎ−（２−アミノエチル）
ピペラジンとアジピン酸とのナイロン塩３８部および水
１００部をステンレス製オートクレーブに入れ、内部の
空気を窒素ガスで５回置換した後、１８０℃で１時間加
熱した。次に反応温度を２４０℃まで４５分間で上昇さ
せながら、徐々に留出水分を除き、更に窒素ガスを２０
ｍｌ／分の流量で流しながら２時間加熱してポリアミド
（１）を得た。 Example 1 62 parts of ε-caprolactam, N- (2-aminoethyl)
38 parts of a nylon salt of piperazine and adipic acid and 100 parts of water were placed in a stainless steel autoclave, the inside air was replaced with nitrogen gas five times, and then heated at 180 ° C. for 1 hour. Then, while raising the reaction temperature to 240 ° C. in 45 minutes, the distillate water was gradually removed, and nitrogen gas was further added for 20 minutes.
The mixture was heated for 2 hours while flowing at a flow rate of ml / min to obtain a polyamide (1).
【００３７】ポリアミド（１）５５．０部、Ｎ−エチル
トルエンスルホン酸アミド７．７部、１，４−ナフトキ
ノン０．０２部、クリソイジンＧ（２，４−ジアミノア
ゾベンゼン・塩酸塩）０．０３部、メタノール５０．０
部および水１０部を、攪拌付き加熱解釜中に添加し、６
０℃で２時間混合してポリマーを完全に溶解した。次い
で、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３０．１部、メタクリル酸３．１部、
イタコン酸０．１部、ハイドロキノンモノメチルエーテ
ル０．１部、亜硫酸アンモニウム０．３部およびベンジ
ルジメチルケタール１．０部を添加し、３０分間混合し
て溶解した。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を得
た。55.0 parts of polyamide (1), 7.7 parts of N-ethyltoluenesulfonic acid amide, 0.02 parts of 1,4-naphthoquinone, 0.03 parts of chrysoidin G (2,4-diaminoazobenzene hydrochloride) Parts, methanol 50.0
Parts and 10 parts of water are added into a stirrer with stirring.
Mixing for 2 hours at 0 ° C. completely dissolved the polymer. Then, 30.1 parts of an acrylic acid adduct of trimethylolpropane triglycidyl ether, 3.1 parts of methacrylic acid,
0.1 part of itaconic acid, 0.1 part of hydroquinone monomethyl ether, 0.3 part of ammonium sulfite and 1.0 part of benzyldimethyl ketal were added, 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.
【００３８】この感光性樹脂組成物を１２５μｍ厚みの
ポリエステルフィルム上にとり、もう１枚の同様のポリ
エステルフィルムをその上に重ね、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１０３℃で３分間加熱した。２枚のポリエステル
フィルムを剥離した感光性樹脂組成物シートを、日立製
作所（株）製、３２０型自記分光光度計を用いて３６０
ｎｍから６００ｎｍ迄の吸収スペクトル曲線を測定した
結果、４６０ｎｍに吸収ピークを有し、その透過率は
２．２％であった。この感光性樹脂組成物シートを超高
圧水銀灯（ＯＲＣ社製、Polymer Printer 3000型）で４
０秒間露光してから上記と同様に吸収スペクトル曲線を
測定したところ、４６０ｎｍの吸収ピークが減少してそ
の透過率は１０．９％であり、吸収ピーク強度の減少率
は５８％であった。This photosensitive resin composition was placed on a polyester film having a thickness of 125 μm, another sheet of the same polyester film was placed thereon, and a sheet having a total thickness of 1050 μm was formed with a laminator. Heated at 103 ° C. for 3 minutes. The photosensitive resin composition sheet from which the two polyester films were peeled off was subjected to 360-degree recording using a 320-type self-recording spectrophotometer manufactured by Hitachi, Ltd.
As a result of measuring an absorption spectrum curve from nm to 600 nm, it had an absorption peak at 460 nm, and its transmittance was 2.2%. This photosensitive resin composition sheet is applied to an ultra-high pressure mercury lamp (ORC, Polymer Printer 3000 type).
After the exposure for 0 second, the absorption spectrum curve was measured in the same manner as described above. As a result, the absorption peak at 460 nm was reduced, the transmittance was 10.9%, and the reduction rate of the absorption peak intensity was 58%.
【００３９】これとは別に、共重合ポリエステル（バイ
ロンＲＶ−３０ＳＳ 東洋紡績（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１８０μｍのポリエス
テルフィルム上に、厚み１５μｍとなるようにコートし
て被膜を形成し、当該フィルムを支持体とし、この上に
上記の感光性樹脂組成物を流延した。ポリビニルアルコ
ール（ＡＨ−２４ 日本合成化学（株）製）被膜（厚み
２μｍ）を有する、厚み１２５μｍのポリエステルフィ
ルムを、その被膜が感光性樹脂組成物と接するように、
感光性樹脂組成物上に載せ、ラミネーターを用い、全厚
みが１０８０μｍの積層体を得た。この積層体は室温下
で堅い板状に固化した。２４時間後、この積層体を１０
３℃で３分間加熱して感光性樹脂印刷用原版（生版）を
得た。Separately, a copolyester (Vylon RV-30SS manufactured by Toyobo Co., Ltd.) and a polyfunctional isocyanate (Coronate L Nippon Polyurethane Co., Ltd.)
Product) and a reaction product of a brown dye were coated on a 180 μm-thick polyester film so as to have a thickness of 15 μm to form a film. The film was used as a support, and the above-mentioned photosensitive resin composition was coated thereon. Cast. A polyester film having a thickness of 125 μm having a polyvinyl alcohol (AH-24 manufactured by Nippon Synthetic Chemical Co., Ltd.) coating (thickness: 2 μm) is contacted with the photosensitive resin composition so that the coating is in contact with the photosensitive resin composition.
A laminate having a total thickness of 1080 μm was obtained on a photosensitive resin composition using a laminator. This laminate solidified into a hard plate at room temperature. After 24 hours, the laminate was
The mixture was heated at 3 ° C. for 3 minutes to obtain a photosensitive resin printing original plate (raw plate).
【００４０】感光性樹脂印刷用原版を７日間以上保管し
た後、１２５μｍのポリエステルフィルムを剥離し、次
いでテストネガフィルム（感度測定用グレイスケールネ
ガフィルムと画像再現性評価用画像のネガフィルム）を
真空密着させ、超高圧水銀灯（ＯＲＣ社製、Polymer Pr
inter 3000型）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）製 ＪＷ−Ａ２−ＰＤ型）を用い、水道水を現像
液として、２３℃で２分間現像し、レリーフ画像を得
た。更に６０℃で５分間、温風乾燥した後に超高圧水銀
灯（ＯＲＣ社製、Polymer Printer 3000型）で３０秒間
露光して得られたレリーフ版を評価した結果、グレイス
ケールは１６段、画像部は２％網点、１００μｍ独立点
および３０μｍ細線が再現されていた。また、３００μ
ｍスリット幅のレリーフ抜け深さは９８μｍであった。
高感度で画像の再現性の優れている事が確認された。こ
のレリーフ版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印刷物が得られた。After storing the photosensitive resin printing plate for 7 days or more, the 125 μm polyester film was peeled off, and then the test negative film (a gray scale negative film for sensitivity measurement and a negative film for image for evaluating image reproducibility) were vacuumed. Adhering to an ultra-high pressure mercury lamp (ORC, Polymer Pr
(inter 3000 type). Next, using a brush type washer (100 μmφ nylon brush, JW-A2-PD type manufactured by JEOL Ltd.), developing was performed at 23 ° C. for 2 minutes using tap water as a developer to obtain a relief image. After further drying with hot air at 60 ° C. for 5 minutes and exposing with a super-high pressure mercury lamp (ORC, Polymer Printer 3000) for 30 seconds, the resulting relief plate was evaluated. 2% halftone dots, 100 μm independent points and 30 μm fine lines were reproduced. Also, 300μ
The relief penetration depth of m slit width was 98 μm.
It was confirmed that the image had high sensitivity and excellent image reproducibility. As a result of performing a printing test using this relief plate, a printed matter having a sharp print without thickening of the image was obtained.
【００４１】比較例１ 実施例１において、１，４−ナフトキノンとクリソイジ
ンＧを使用しなかったこと以外は、実施例１と同様の方
法により、感光性樹脂組成物シートおよび感光性樹脂印
刷用原版（生版）を作成し、これらを実施例１と同様の
方法により評価した。感光性樹脂組成物シートの吸収ス
ペクトル曲線から、４００ｎｍ〜５００ｎｍの波長領域
内に吸収ピークが認められなかった。感光性樹脂印刷用
原版を用い、実施例１と同様の方法により露光、現像し
て得られたレリーフ版を評価した結果、グレイスケール
は２０段で画像が明瞭に再現されなかったので、２０秒
間の露光後、実施例１と同様の方法により現像して得ら
れたレリーフ版を評価した結果、グレイスケールは１６
段、画像部は１００μｍ独立点、３０μｍ細線は再現さ
れていたが、２％網点が埋まり、また３００μｍスリッ
ト幅のレリーフ抜け深さは１５μｍであり、画像の太り
が大きくシャープな刷り上がりの印刷物は得られなかっ
た。 Comparative Example 1 A photosensitive resin composition sheet and a photosensitive resin printing plate were prepared in the same manner as in Example 1 except that 1,4-naphthoquinone and chrysoidin G were not used. (Raw plates) were prepared and evaluated by the same method as in Example 1. From the absorption spectrum curve of the photosensitive resin composition sheet, no absorption peak was observed in the wavelength region of 400 nm to 500 nm. Using a photosensitive resin printing original plate, the relief plate obtained by exposing and developing by the same method as in Example 1 was evaluated. As a result, the image was not clearly reproduced at 20 steps in the gray scale. After the exposure, the relief plate obtained by developing in the same manner as in Example 1 was evaluated.
The column and the image area were 100 μm independent points and 30 μm thin lines were reproduced, but 2% halftone dots were buried, and the relief depth of the 300 μm slit width was 15 μm. Could not be obtained.
【００４２】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
７．５部および水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た。内圧が１
０ｋｇ／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℃であった。得
られた重合体は融点１４０℃、比粘度１．８３の透明淡
黄色のポリアミド（２）を得た。 Example 2 55.0 parts of ε-caprolactam, N, N′-bis (γ-
Aminopropyl) piperazine adipate 40.0 parts,
7.5 parts of 1,3-bisaminomethylcyclohexane adipate and 100 parts of water were added to the reactor, and after sufficient nitrogen replacement, the vessel was sealed and gradually heated. Internal pressure is 1
When the pressure reached 0 kg / cm 2 , water in the reactor was gradually distilled off, returned to normal pressure in about 1 hour, and then reacted at normal pressure for 0.5 hour. The maximum polymerization temperature was 210 ° C. The obtained polymer was a transparent pale yellow polyamide (2) having a melting point of 140 ° C. and a specific viscosity of 1.83.
【００４３】ポリアミド（２）５５．０部、Ｎ−エチル
トルエンスルホン酸アミド５．０部、１，４−ナフトキ
ノン０．０３部、メタノール５０．０部および水１０部
を、攪拌付き加熱解釜中に添加し、６０℃で２時間混合
してポリマーを完全に溶解した。次いで、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
３４．７部、メタクリル酸２．９部、グリシジルメタク
リレート１．０部、ハイドロキノンモノメチルエーテル
０．１部、亜硫酸アンモニウム０．３部、シュウ酸０．
１部およびベンジルジメチルケタール１．０部を添加
し、実施例１と同様の方法により、感光性樹脂組成物を
得、次いで、実施例１と同様の方法により、感光性樹脂
組成物シートと感光性樹脂印刷用原版（生版）を作成し
た。55.0 parts of polyamide (2), 5.0 parts of N-ethyltoluenesulfonic acid amide, 0.03 part of 1,4-naphthoquinone, 50.0 parts of methanol and 10 parts of water were stirred in a heating furnace with stirring. And mixed at 60 ° C. for 2 hours to completely dissolve the polymer. Then, 34.7 parts of an acrylic acid adduct of trimethylolpropane triglycidyl ether, 2.9 parts of methacrylic acid, 1.0 part of glycidyl methacrylate, 0.1 part of hydroquinone monomethyl ether, 0.3 part of ammonium sulfite, 0 parts of oxalic acid .
1 part and 1.0 part of benzyldimethyl ketal were added, and a photosensitive resin composition was obtained in the same manner as in Example 1. Then, the photosensitive resin composition sheet was exposed to light in the same manner as in Example 1. An original plate for raw resin printing (raw plate) was prepared.
【００４４】この感光性樹脂組成物シートをケミカルラ
ンプ（三菱電機（株）製、ネオルミスーパＦＬ２０ＳＢ
Ｌ−３６０型、波長範囲：３５０〜４００ｎｍ）で３分
間照射して、実施例１と同様の方法により照射前後の吸
収スペクトル曲線を測定した結果、４５５ｎｍに吸収ピ
ークが認められ、照射前で透過率が３８．０％、照射後
で透過率が５７．７％であり、吸収ピーク強度の減少率
は４６％であった。This photosensitive resin composition sheet was treated with a chemical lamp (manufactured by Mitsubishi Electric Corporation, NEOL MISUPER FL20SB).
(L-360 type, wavelength range: 350 to 400 nm) for 3 minutes, and an absorption spectrum curve before and after irradiation was measured in the same manner as in Example 1. As a result, an absorption peak was observed at 455 nm, and transmission before irradiation was performed. The transmittance was 38.0%, the transmittance after irradiation was 57.7%, and the reduction rate of the absorption peak intensity was 46%.
【００４５】感光性樹脂印刷用原版を、実施例１と同様
のテストネガフィルムを用いてケミカルランプ（三菱電
機（株）製、ネオルミスーパＦＬ２０ＳＢＬ−３６０
型、波長範囲：３５０〜４００ｎｍ）で３分間照射後、
実施例１と同様の方法により現像してレリーフ版を作成
した結果、クレイスケールは１５段、画像部は２％網
点、１００μｍ独立点および３０μｍ細線が再現されて
いた。また、３００μｍスリット幅のレリーフ抜け深さ
は８０μｍであった。高感度で画像の再現性の優れてい
る事が確認された。このレリーフで印刷テストを行った
結果、鮮明な印刷物が得られた。Using a test negative film similar to that of Example 1, a photosensitive resin printing original plate was used as a chemical lamp (manufactured by Mitsubishi Electric Corporation, NEOL MISUPER FL20SBL-360).
Mold, wavelength range: 350 to 400 nm) for 3 minutes,
As a result of developing a relief plate by developing in the same manner as in Example 1, 15 steps of clay scale, 2% halftone dot, 100 μm independent point and 30 μm fine line were reproduced in the image area. Further, the depth of the relief with a slit width of 300 μm was 80 μm. It was confirmed that the image had high sensitivity and excellent image reproducibility. As a result of a printing test using this relief, a clear printed matter was obtained.
【００４６】比較例２ 実施例２において、１，４−ナフトキノンの代わりにチ
タンエローを０．０２５部添加したこと以外は、実施例
２と同様の方法により、感光性樹脂組成物シートと感光
性樹脂印刷用原版（生版）を作成した。ケミカルランプ
（三菱電機（株）製、ネオルミスーパＦＬ２０ＳＢＬ−
３６０型、波長範囲：３５０〜４００ｎｍ）で３分間照
射して、実施例１と同様の方法により照射前後の吸収ス
ペクトル曲線を測定した結果、感光性樹脂組成物シート
の吸収スペクトル曲線から４１０ｎｍに吸収ピークが認
められたが、ケミカルランプで３分間照射してもその吸
収ピークの透過率は変動しなかった。また、感光性樹脂
印刷用原版を、実施例１と同様のテストネガフィルムを
用いてケミカルランプで３分間照射後、実施例１と同様
の方法により現像してレリーフ版を作成した結果、グレ
イスケールは１６段、画像部は１００μｍ独立点および
３０μｍ細線は再現されていたが、２％網点が埋まり、
３００μｍスリット幅のレリーフ抜け深さは３０μｍで
あり、画像の太りが大きくシャープな刷り上がりの印刷
物は得られなかった。 Comparative Example 2 A photosensitive resin composition sheet and a photosensitive resin were prepared in the same manner as in Example 2 except that 0.025 part of titanium yellow was added instead of 1,4-naphthoquinone. An original plate for printing (raw version) was created. Chemical lamp (manufactured by Mitsubishi Electric Corporation, NEOL MISUPER FL20SBL-
(Type 360, wavelength range: 350 to 400 nm) for 3 minutes, and the absorption spectrum curves before and after the irradiation were measured in the same manner as in Example 1. As a result, the absorption was observed at 410 nm from the absorption spectrum curve of the photosensitive resin composition sheet. Although a peak was observed, the transmittance of the absorption peak did not change even after irradiation with a chemical lamp for 3 minutes. The photosensitive resin printing original plate was irradiated with a chemical lamp for 3 minutes using the same test negative film as in Example 1, and then developed in the same manner as in Example 1 to produce a relief plate. Was 16 steps, the image part was 100 μm independent points and 30 μm fine lines were reproduced, but 2% halftone dots were filled,
The depth of relief relief with a slit width of 300 μm was 30 μm, and a thick printed image with a large thickness was not obtained.
【００４７】実施例３ 部分鹸化ポリビニルアルコール（クラレ（株）ＬＭ−１
０ＨＤ）６０部、ジエチレングリコールジメタクリレー
ト１０部、エポキシエステル７０−ＰＡ（共栄社化学
（株））２６．７部、ハイドロキノンモノメチルエーテ
ル０．１部、ジメチルベンジルケタール１．２部、ジエ
チレングリコール２部、クリソイジン０．０２部および
メタノール５０部を、６０℃で２時間混合し溶解した
後、樹脂温度が１１０℃になる迄、加熱濃縮し、実施例
１と同様の方法より、感光性樹脂組成物を得、次いで、
実施例１と同様の方法より、感光性樹脂組成物シートと
感光性樹脂印刷用原版（生版）を作成した。 Example 3 Partially saponified polyvinyl alcohol (Kuraray LM-1)
0HD) 60 parts, diethylene glycol dimethacrylate 10 parts, epoxy ester 70-PA (Kyoeisha Chemical Co., Ltd.) 26.7 parts, hydroquinone monomethyl ether 0.1 part, dimethylbenzyl ketal 1.2 parts, diethylene glycol 2 parts, chrysoidin 0 After mixing and dissolving 0.02 parts and 50 parts of methanol at 60 ° C. for 2 hours, the mixture was heated and concentrated until the resin temperature reached 110 ° C., and a photosensitive resin composition was obtained in the same manner as in Example 1. Then
In the same manner as in Example 1, a photosensitive resin composition sheet and a photosensitive resin printing original plate (raw plate) were prepared.
【００４８】感光性樹脂組成物シートをフィリップス社
（株）製のＴＬ−Ｋ１０ランプ（波長範囲：３５０〜４
００ｎｍ）で２分間照射して、実施例１と同様の方法に
より照射前後の吸収スペクトル曲線を測定した結果、４
５５ｎｍに吸収ピークが認められ、照射前で透過率が１
２．９％、照射後で透過率が５０．５％であり、吸収ピ
ーク強度の減少率は３２％であった。また、感光性樹脂
印刷用原版を、実施例１と同様のテストネガフィルムを
用いてフィリップス社（株）製のＴＬ−Ｋ１０ランプで
２分間照射後、現像液を４重量％のラウリルベンゼンス
ルホン酸ナトリウム水溶液を用いて現像して得られたレ
リーフ版は、グレイスケールは１５段、画像部は２％網
点、１００μｍ独立点および３０μｍ細線が再現されて
いた。また、３００μｍスリット幅のレリーフ抜け深さ
は１０２μｍであった。高感度で画像の再現性の優れて
いる事が確認された。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印刷
物が得られた。The photosensitive resin composition sheet was used as a TL-K10 lamp (wavelength range: 350 to 4) manufactured by Philips Corporation.
(200 nm) for 2 minutes, and the absorption spectrum curves before and after irradiation were measured in the same manner as in Example 1. As a result, 4
An absorption peak was observed at 55 nm, and the transmittance was 1 before irradiation.
2.9%, the transmittance after irradiation was 50.5%, and the reduction rate of the absorption peak intensity was 32%. The photosensitive resin printing plate was irradiated with a TL-K10 lamp (manufactured by Philips) for 2 minutes using the same test negative film as in Example 1, and then the developing solution was diluted with 4% by weight of laurylbenzenesulfonic acid. The relief plate obtained by developing with a sodium aqueous solution had 15 steps of gray scale, 2% halftone dot, 100 μm independent point, and 30 μm fine line in the image area. Also, the depth of relief relief with a slit width of 300 μm was 102 μm. It was confirmed that the image had high sensitivity and excellent image reproducibility. As a result of performing a printing test with this relief, a printed matter having a sharp print without an image thickening was obtained.
【００４９】[0049]
【発明の効果】以上の説明で明らかなように、本発明の
感光性樹脂組成物によれば、細い線、小さな独立点、小
さな活字や細かい網点等の露光画像部の形成の場合と、
白抜きパターンの非露光画像部の形成の場合のどちらの
場合でも原画を忠実に再現したレリーフ版を作成でき、
良好な印刷物を与える高感度で、鮮明な画像再現性を有
するレリーフ版が得られる。また、本発明の感光性樹脂
組成物においては、照射部分は未照射部分に比較して退
色するので、現像工程前にも画像の判別が容易である。
さらに、本発明の感光性樹脂組成物は黄色や淡黄赤色で
あるので、装置等の汚染が目立たない。As is clear from the above description, according to the photosensitive resin composition of the present invention, the case of forming an exposed image portion such as a thin line, a small independent point, a small type or a fine halftone dot,
In either case of forming a non-exposed image part of a white pattern, it is possible to create a relief plate that faithfully reproduces the original image,
A relief plate having high sensitivity and clear image reproducibility that gives good printed matter can be obtained. Further, in the photosensitive resin composition of the present invention, since the irradiated portion fades in color compared with the unirradiated portion, it is easy to determine the image even before the developing step.
Furthermore, since the photosensitive resin composition of the present invention is yellow or pale yellow-red, contamination of equipment and the like is not noticeable.
───────────────────────────────────────────────────── 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） Ｇ０３Ｆ 7/00 ５０２ Ｇ０３Ｆ 7/00 ５０２ (72)発明者 本井 慶一 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 小木 浩二 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 南村 公子 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 富田 晃 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 Ｆターム(参考） 2H025 AA01 AA02 AA04 AB02 AC01 AD01 BC13 BC31 CA00 CB00 CC11 CC13 FA17 2H096 AA02 BA05 EA02 GA08 4J011 PA53 PA67 PA69 PA74 PA76 PA88 PA95 PA96 PC02 QA02 QA03 QA06 QA17 QA34 QA37 QA39 QB12 QB19 QB23 RA02 RA03 RA05 RA06 RA07 RA09 RA10 RA15 SA01 SA02 SA21 SA22 SA31 SA32 SA34 SA41 SA51 SA54 SA63 SA64 TA01 UA01 VA01 WA01 4J026 AA02 AA30 AA31 AA45 AA61 AA68 AB01 AB02 AB07 AB28 AC22 AC35 BA25 BA28 BA29 BA30 BA32 BA40 BA50 BB01 BB02 DB26 DB36 GA07 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G03F 7/00 502 G03F 7/00 502 (72) Inventor Keiichi Motoi 2-1-1 Katata, Otsu City, Shiga Prefecture No. 1 Toyobo Co., Ltd. Research Institute (72) Koji Ogi 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Kimiko Minamimura 2-1-1 Katata, Otsu-shi, Shiga Prefecture No. 1 Toyobo Co., Ltd. Research Laboratory (72) Inventor Akira Tomita 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Laboratory F-term (reference) 2H025 AA01 AA02 AA04 AB02 AC01 AD01 BC13 BC31 CA00 CB00 CC11 CC13 FA17 2H096 AA02 BA05 EA02 GA08 4J011 PA53 PA67 PA69 PA74 PA76 PA88 PA95 PA96 PC02 QA02 QA03 QA06 QA17 QA34 QA37 QA39 QB12 QB19 QB2 3 RA02 RA03 RA05 RA06 RA07 RA09 RA10 RA15 SA01 SA02 SA21 SA22 SA31 SA32 SA34 SA41 SA51 SA54 SA63 SA64 TA01 UA01 VA01 WA01 4J026 AA02 AA30 AA31 AA45 AA61 AA68 AB01 AB02 AB07 AB28 AC22 AC35 BA25 BA28 BA29 BA30 BA32 BA40 BA50
Claims (6)
モノマーおよび光重合開始剤を主成分として含有する感
光性樹脂組成物であって、当該組成物の吸収ピークが４
００ｎｍ〜５００ｎｍの波長領域内にあり、かつ活性光
線の照射によって当該吸収ピークの強度が減少すること
を特徴とする感光性樹脂組成物。1. A photosensitive resin composition containing a soluble polymer, a photopolymerizable unsaturated group-containing monomer and a photopolymerization initiator as main components, wherein the composition has an absorption peak of 4
A photosensitive resin composition having a wavelength within the range of from 00 nm to 500 nm, wherein the intensity of the absorption peak is reduced by irradiation with actinic light.
吸収ピークを有し、かつ活性光線の照射によってその吸
収ピークの強度が減少する化合物を含有する、請求項１
に記載の感光性樹脂組成物。2. A compound having an absorption peak in a wavelength region of 400 nm to 500 nm, the intensity of which is reduced by irradiation with actinic light.
3. The photosensitive resin composition according to item 1.
００ｎｍ〜５００ｎｍの波長領域内に吸収ピークを付与
し、かつ活性光線の照射によってその吸収ピークの強度
が減少するような化合物を含有する、請求項１に記載の
感光性樹脂組成物。3. A reaction with a component in the photosensitive resin composition to obtain 4
2. The photosensitive resin composition according to claim 1, comprising a compound that gives an absorption peak in a wavelength range of from 00 nm to 500 nm and reduces the intensity of the absorption peak upon irradiation with actinic light.
記載の感光性樹脂組成物からなる感光層が形成されてな
る印刷用原版。4. An original printing plate comprising a support and a photosensitive layer comprising the photosensitive resin composition according to claim 1 formed on a support.
いで現像してなることを特徴とする印刷版。5. A printing plate, wherein the printing plate precursor according to claim 4 is exposed and then developed.
刷版。6. The printing plate according to claim 5, which is a relief plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34246299A JP4379988B2 (en) | 1999-12-01 | 1999-12-01 | Photosensitive resin composition, printing original plate and printing plate using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34246299A JP4379988B2 (en) | 1999-12-01 | 1999-12-01 | Photosensitive resin composition, printing original plate and printing plate using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001159813A true JP2001159813A (en) | 2001-06-12 |
| JP4379988B2 JP4379988B2 (en) | 2009-12-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34246299A Expired - Fee Related JP4379988B2 (en) | 1999-12-01 | 1999-12-01 | Photosensitive resin composition, printing original plate and printing plate using the same |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015163216A1 (en) * | 2014-04-25 | 2015-10-29 | 株式会社ダイセル | Curable composition and cured product of same |
-
1999
- 1999-12-01 JP JP34246299A patent/JP4379988B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015163216A1 (en) * | 2014-04-25 | 2015-10-29 | 株式会社ダイセル | Curable composition and cured product of same |
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| Publication number | Publication date |
|---|---|
| JP4379988B2 (en) | 2009-12-09 |
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