JPS5922218B2 - Photosensitive materials for printing plates - Google Patents

Description

【発明の詳細な説明】 本発明は新しい電子写真法を利用して印刷原版を作成す
るための感光材料に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive material for producing a printing original plate using a new electrophotographic method.

特に従来広く用いられていた等倍の銀塩リス・フィルム
を介することなく、少い露光量（像露光に関し）で耐刷
性の高い印刷原版を得るための感光材料に関する。反射
原稿とかマイクロ・フィルム化された原稿から印刷原版
一特にオフセット原版一を得る際には高感度の感光系が
必要とされるのでしばしばカメラ・スピード刷版等と呼
称されるが、従来市販乃至提唱されている色々の技術は
少なからず問題点をかゝえている。まず、銀塩の拡散転
写現像を基礎とするものは１枚当りのコストが高く、そ
の割に耐刷力が高くない。In particular, the present invention relates to a photosensitive material for obtaining a printing original plate having high printing durability with a small amount of exposure (in terms of image exposure) without using a silver salt lithium film of the same size that has been widely used in the past. When obtaining a printing original plate, especially an offset original plate, from a reflective original or a micro-filmed original, a highly sensitive photosensitive system is required, so it is often called a camera speed printing plate. The various techniques that have been proposed have quite a few problems. First, those based on silver salt diffusion transfer development have a high cost per sheet and do not have high printing durability.

ＺｎＯ系感光層を利用した電子写真法は感材のコストは
低いが、耐刷力がやはり不充分であり、従来のＰＳ版等
の足もとにも及ばない。又、画質についても充分と云え
なかつた。最近、充電現像法にもとずくＰｙｒｏｆａｘ
なるシステムがスリー・エム社より発表された。Electrophotography using a ZnO-based photosensitive layer has a low cost of photosensitive material, but its printing durability is still insufficient and cannot even come close to the level of conventional PS plates. Also, the image quality could not be said to be sufficient. Recently, Pyrofax based on charge development method
A new system was announced by 3M Corporation.

これは乾式現像を利用し、二度の転写を含むため、耐刷
力はＰＳ刷なみになつたが、トナーのサイズが比較的大
きいため英文の新聞印刷には利用できても漢字をふくむ
日本市場の要求に対しては解像力がたりない。感光性樹
脂類は電子写真や銀塩写真に比して何桁も光感度が低く
、直接カメラ・スピード乃至プロジェクション・スピー
ドを具現することはできない。This uses dry development and involves two transfers, so its printing durability is comparable to that of PS printing.However, because the toner size is relatively large, it can be used for English newspaper printing, but it can be used for Japanese newspapers including Kanji. The resolution is insufficient to meet market demands. Photosensitive resins have many orders of magnitude lower light sensitivity than electrophotography or silver halide photography, and cannot directly achieve camera speeds or projection speeds.

感光性（撮像）は電子写真技術に負担させ、耐刷力乃至
印刷適正はＰＳ版等に持たせるといつた思想は特開昭５
０−１８０１号公報に見られる。即ちＰＳ版の生感材表
面を絶縁性にしておき、これに電子写真的に得たトナー
像を転写、これを全面露光することにより感光性樹脂層
を像状に架橋せしめ、最后に樹脂層を現像することで印
刷原版を得んとするものである。この方法はトナー転写
をふくむため画質に限度があること、通常の電子写真法
ではネガーポジ像を高品質にまとめにくいのでＰＳ版の
感光層のタイプとの組合せに制限を生じ易いこと等の問
題を持つ。The idea that photosensitivity (imaging) should be taken care of by electrophotographic technology, while printing durability and printing suitability should be provided by PS plates, etc., was developed in JP-A No. 5.
0-1801. That is, the surface of the raw photosensitive material of the PS plate is made insulating, a toner image obtained electrophotographically is transferred to this, the entire surface is exposed to crosslink the photosensitive resin layer in an imagewise manner, and finally the resin layer is The purpose is to obtain a printing plate by developing it. This method has problems such as there is a limit to the image quality because it involves toner transfer, and it is difficult to produce high-quality negative-positive images with normal electrophotography, which tends to limit the combination with the type of photosensitive layer of the PS plate. have

本発明は従来の平版版材および感光材料がそのまま使用
でき、従来のオフセツト印刷機の改造も必要とせずに印
刷のできる印刷版の製造法を提供する。The present invention provides a method for manufacturing a printing plate that can use conventional lithographic plate materials and photosensitive materials as they are, and can print without requiring modification of a conventional offset printing machine.

特に、密着焼付の工程を不要とし、従つて高価な銀塩フ
イルムも不要とする印刷版の作製法およぴそれに用いる
感光材料を提供する。本発明の他の目的は上に挙げた如
き各種カメラスピード刷版に伴う問題点を持たないか又
は軽減したカメラ・スピード刷版の作製法を提供するこ
とにある。In particular, the present invention provides a method for producing a printing plate that does not require a contact baking process and therefore does not require an expensive silver salt film, and a photosensitive material used therein. Another object of the present invention is to provide a method for making camera speed printing plates that does not have or reduces the problems associated with the various camera speed printing plates mentioned above.

以上の如き諸目的を達成する本発明についてその概要を
材料的に表現すれば、本発明は平版印刷版材基板上に感
光性樹脂層および電気感光性微細粒子を軟化し得る熱可
塑性樹脂中に均一に分散するか、同樹脂の層の表面に層
状に分布させた粒子移動型電子写真感光層をこの順に重
ねて設けた感光材料に関するものであり、印刷版の製法
としては前記の様な複合型の感材を用意し、この粒子移
動型電子写真感光層を利用して粒子の移動にもとづきこ
の感光層の下に設けられた感光性樹脂層の分光応答域の
光に対して充分不透明な画像を形成し、次いで同材料を
全面露光することにより感光性樹脂層を像に応じて架僑
又は解僑せしめ、更に感光性樹脂層を現像する工程をふ
くむことを特徴とする方法に関するもおである。To express the outline of the present invention, which achieves the above-mentioned objects, in terms of materials, the present invention provides a photosensitive resin layer and electrophotosensitive fine particles on a lithographic printing plate substrate in a thermoplastic resin capable of softening. It relates to a photosensitive material in which particle migration type electrophotographic photosensitive layers are layered in this order, either uniformly dispersed or distributed in layers on the surface of a layer of the same resin. A type of photosensitive material is prepared, and this particle migration type electrophotographic photosensitive layer is used to create a layer that is sufficiently opaque to light in the spectral response range of the photosensitive resin layer provided below this photosensitive layer based on the movement of particles. This also relates to a method comprising the steps of forming an image, then exposing the entire surface of the material to light to make the photosensitive resin layer cross-linked or de-thickened depending on the image, and further developing the photosensitive resin layer. It is.

本発明に使用できる平版印刷版材基板は、従来から知ら
れているアルミニウム板、亜鉛板、又は銅−アルミニウ
ム板、銅一ステンレス板、クロム−銅板等のバイメタル
板、又はクロムー銅一アルミニウム板、クロムー銅一鉄
板、クロムー銅−ステンレス板等のトライメタル板等で
ある。The lithographic printing plate material substrate that can be used in the present invention is a conventionally known aluminum plate, zinc plate, or bimetal plate such as a copper-aluminum plate, a copper-stainless steel plate, a chrome-copper plate, or a chrome-copper-aluminum plate. These include tri-metal plates such as chrome-copper-iron plates and chrome-copper-stainless steel plates.

これらは最上層の電子写真感光層の写真処理の際、必要
とされる電導度を充分有しており、この点でも好都合で
ある。これらのものは表面を親水化処理されていてもよ
く、また機械的に研磨されていてもよい〇感光性樹脂層
としてはジアゾニウム塩、アジド化合物、フオトポリマ
ー類、ポリビニルアルコールー重クロム酸塩系、等が代
表的なものである。These materials have sufficient electrical conductivity required during photographic processing of the uppermost electrophotographic light-sensitive layer, and are advantageous in this respect as well. The surface of these materials may be hydrophilized or mechanically polished. The photosensitive resin layer may be a diazonium salt, an azide compound, a photopolymer, or a polyvinyl alcohol-dichromate based resin. , etc. are typical examples.

特に市販されているいわゆるＰＳ版はポジ型もネガ型も
利用できる。粒子移動型電子写真層に関しては少し説明
を要するが、基本的説明は例えば、下記の文献に見出さ
れる：ＷＴＬＬＩＡＭ Ｌ．ＧＯＦＦＥ，Ｐｈｏｔ．Ｓ
ｃｉ．＆ＥｎｇＶ０１．１５．煮４．ｐ３０４〜３０８
（１９７１）：特公昭４３−１０７９６号および同４３
−１３５１３号公報：米国特許第３５２０６８１号明細
書。In particular, commercially available so-called PS plates can be used in both positive and negative types. The particle migration electrophotographic layer requires some explanation, but a basic explanation can be found, for example, in the following document: WTLLIAM L. GOFFE, Photo. S
ci. &EngV01.15. Boiled 4. p304-308
(1971): Special Publication No. 43-10796 and No. 43
-13513 publication: U.S. Patent No. 3520681.

粒子移動型電子写真層の機作を説明すると、基本的には
電気感光性（高電界下−１×１０５■Ａ皿以上程度一光
の作用に応答する）微細粒子を軟化し得る絶縁性媒体（
普通は熱可塑性樹脂）中に均一に分散するか、樹脂層の
表面に層状に分布させた構成を持ち、暗処で帯電露光し
、層を軟化する（熱、溶剤又は両方の作用）と、像に応
じて粒子が基板側へ移行して像を与える。To explain the mechanism of a particle migration type electrophotographic layer, it is basically an insulating medium that can soften electrophotosensitive (responsive to the action of one light of about 1 x 105 ■ A plate or more under high electric field) fine particles. (
It has a structure in which it is uniformly dispersed in a thermoplastic resin (usually a thermoplastic resin) or distributed in layers on the surface of a resin layer, and when it is exposed to charged light in the dark and the layer is softened (by the action of heat, solvent, or both), Particles move toward the substrate in accordance with the image and form an image.

本発明の目的にはは溶剤現像が特に適しているが、その
場合は図にしめす如く（第２図参照）、溶剤は媒体樹脂
をほマ完全に溶解し去り、後にはほとんど裸の粒子が基
板側（ここでは感光性樹脂層上）に残る。光の当つた粒
子が移行する場合はネガ原稿からポジ像が、又はポジ原
稿からネガ像が得られる。この様な例は水添ロジン又は
そのエステル等のエステルやスチレンーヘキシルメタク
リレート共重合体中へセレンの微粒子を分散し、表面を
正に帯電した時に観測される。又、銅フタロシアニン顔
料を水添ロジン中へ均一に分散した層を負に帯電した時
にも観測される。Solvent development is particularly suitable for the purposes of the present invention, in which case the solvent almost completely dissolves the media resin, leaving behind almost bare particles, as shown in the figure (see Figure 2). It remains on the substrate side (here, on the photosensitive resin layer). If particles exposed to light migrate, a positive image can be obtained from a negative original, or a negative image can be obtained from a positive original. Such an example is observed when fine particles of selenium are dispersed in hydrogenated rosin or an ester such as its ester, or a styrene-hexyl methacrylate copolymer, and the surface is positively charged. It is also observed when a layer in which copper phthalocyanine pigment is uniformly dispersed in hydrogenated rosin is negatively charged.

ところが粒子移動法の特徴として、像形成条件を制御一
例えば同一の材料でも帯電符号や帯電強度をかえるーこ
とで簡単にポジ原稿からポジ像を、又はネガ原稿からネ
ガ像を得ることも可能である。例えば銅フタロシアニン
顔料を水添ロジン中へ分散した層を正帯電すれば、ポジ
像が得られ、また負帯電を特に強く行つて強い露光と組
合せるとポジ像が得られる。この様な画像作成方式に関
する自由度は感材全体の設計を大巾に容易にするもので
あり、又各種の原稿を同一感材で撮影することも可能に
する（以下の特許文献参照：特願昭４９−９７４４５号
明細書、ドイツ特許公開第１７７２２７０号明細書；英
国特許第１２３４６５２号および同第１２５７１８９号
明細書）。However, a feature of the particle transfer method is that it is possible to easily obtain a positive image from a positive original, or a negative image from a negative original, by controlling the image forming conditions (for example, by changing the charging sign and charging intensity even for the same material). be. For example, if a layer of copper phthalocyanine pigment dispersed in hydrogenated rosin is positively charged, a positive image can be obtained, and if the layer is particularly strongly negatively charged and combined with strong exposure, a positive image can be obtained. This degree of freedom regarding the image creation method greatly facilitates the design of the entire photosensitive material, and also makes it possible to photograph various manuscripts using the same photosensitive material (see the following patent documents: Application No. 49-97445, German Patent Publication No. 1772270; British Patent Nos. 1234652 and 1257189).

本発明に使用する材料について更に詳しく述べると、感
光性粒子としてはセレン、セレン合金、ＺｎＯ，．Ｔｉ
Ｏ２、ＣｄＳ．ＣｄＳｅ、メタルフリーフタロシアニン
、銅フタロシアニン、キナクリドン、ウオツチングレツ
ド、Ｃ．Ｉ．ピグメントイエロ一１２（Ｃ．Ｉ．２ｌＯ
９Ｏ）、Ｃ．Ｉ．バツトイエロ一１（Ｃ．Ｉ．７Ｏ６Ｏ
Ｏ）、Ｃ．Ｉ．ピグメントレツド８１（Ｃ．Ｉ．４５ｌ
６Ｏ）Ｃ．ｌ．ピグメントレツド１４４、Ｃ．Ｉ．ピグ
メントバイオレツト１９（Ｃ．Ｉ．４６５ＯＯ）および
キナクリドン類、Ｃ．Ｉ．ピグメントブル一１５（Ｃ．
Ｉ．７４ｌ６Ｏ）、Ｃ．Ｉ．ピグメントブル一１６（Ｃ
．Ｉ．７４ｌＯＯ）がある。To explain in more detail the materials used in the present invention, photosensitive particles include selenium, selenium alloys, ZnO, . Ti
O2, CdS. CdSe, metal-free phthalocyanine, copper phthalocyanine, quinacridone, watching red, C.I. I. Pigment Yellow 112 (C.I.2lO
9O), C. I. Battuyero 1 (C.I.7O6O
O), C. I. Pigment Red 81 (C.I.45l
6O)C. l. Pigment Red 144, C. I. Pigment Violet 19 (C.I.465OO) and quinacridones, C.I. I. Pigment Blue 15 (C.
I. 74l6O), C. I. Pigment Blue 16 (C
．． I. 74lOO).

その他にも、多くの有機光導電体が知られており、英国
特許第１１７５４５２号明細書に記載のトリフエノジオ
キサジン類、英国特許第１１５５９７４号明細書に記載
のアントラキノン顔料、英国特許第１１３７８８５号お
よび同１１３７８８６号の明細書に記載のキノンフラン
顔料等を用いることができる。あるいは有機光導電体を
増感剤で増感し、微細化したものを用いる事もできる。
代表的なものはポリビニルカルバゾール、ポリビニルピ
レン等にルイス酸、染料等を加えたものがあげられる。
粒径はサブミクロン〜数ミクロン程度のものがよく、１
μ前後又は０．１μのオーダーのものが特によい。Many other organic photoconductors are known, including triphenodioxazines described in British Patent No. 1175452, anthraquinone pigments described in British Patent No. 1155974, and British Patent No. 1137885. The quinone furan pigments described in the specification of 1137886 and the like can be used. Alternatively, an organic photoconductor that has been sensitized with a sensitizer and made finer can also be used.
Typical examples include polyvinylcarbazole, polyvinylpyrene, etc. to which Lewis acid, dye, etc. are added.
The particle size is preferably from submicron to several microns, and 1
Particularly good is one around μ or on the order of 0.1 μ.

本発明においては、感光性樹脂の分光応答域（一般に紫
外一近紫外一可視域の短波長側）の光に対し充分不透明
であることが顔料には期待され、実際には殆んどのもの
が利用できる。In the present invention, pigments are expected to be sufficiently opaque to light in the spectral response range of photosensitive resins (generally on the short wavelength side of the ultraviolet, near ultraviolet, and visible ranges), and in reality, most pigments are Available.

１種類の顔料のみでは感光性樹脂の分光域の一部分しか
カバーできない時は２種類以上の顔料を併用すればよい
。When only one type of pigment can cover only a part of the spectral range of the photosensitive resin, two or more types of pigments may be used in combination.

特に好ましいものは外観が黄色のもの又はシアメ色のも
ので、これ等は組合せても利用される。例を挙げるとピ
グメントブル一１５（Ｃ．Ｉ．７４ｌ６Ｏ）、ピグメン
トブル一１６（Ｃ．Ｉ．７４ｌＯＯ）、ジナフト〔２，
１−２′，３′〕フラン−８，１３−ジオン等がある。
樹脂結合剤は熱可塑性であつて、ある種の無極性溶剤に
迅速に溶解するものが望ましく、代表的には以下のよう
なものが挙げられる：ロジン誘導体：ロジン、不均化ロ
ジン、ロジンのペンタエリスニトールエヌテル、ロジン
のグリセリンエステル、水添ロジン、水添ロジンのグリ
セリンエステル、水添ロジンのペンタエリスリトールエ
ステルリテルペン系樹脂：石油系樹脂；クマロン〜イン
デン樹脂；スチレン共重合体：スチレン一長鎖アルキル
メタクリレート（アルキル基はＣ４以上のものがよい）
共重合体、スチレン一長鎖アルキルアクリレート（アル
キル基はＣ２以上のものがよい）、更に少量（全重量の
５％位まで）の極性モノマーで変性したもの（極性モノ
マーの例：アクリル酸、メタクリル酸、グリシジル（メ
タ）アクリレート、ジアルキルアミノエチル（メタ）ア
クリレート、ヒドロキシアルキル（メタ）アクリレート
、等）。Particularly preferred are those with a yellow or shimmery appearance, and these may also be used in combination. Examples include Pigment Blu 15 (C.I.74l6O), Pigment Blu 16 (C.I.74lOO), Zinaft [2,
1-2',3']furan-8,13-dione and the like.
It is desirable that the resin binder is thermoplastic and quickly dissolves in certain non-polar solvents, and typical examples include the following: Rosin derivatives: rosin, disproportionated rosin, rosin derivatives, etc. Pentaerythritol ester, glycerin ester of rosin, hydrogenated rosin, glycerin ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin Literpene resin: petroleum resin; coumaron-indene resin; styrene copolymer: styrene Long chain alkyl methacrylate (alkyl group preferably has C4 or more)
copolymers, styrene single-chain alkyl acrylates (the alkyl group should be C2 or higher), and those modified with a small amount (up to about 5% of the total weight) of polar monomers (examples of polar monomers: acrylic acid, methacrylate) acids, glycidyl (meth)acrylate, dialkylaminoethyl (meth)acrylate, hydroxyalkyl (meth)acrylate, etc.).

顔料と樹脂の比率は容積比で前者が全体の４〜３０％程
度を占める範囲がよい。本発明の目的を達成するのには
かなりの透過濃度を持つ画像を必要とするので、顔料の
含有率はなるべく高いことが望ましいが、粒子移動法で
は極端に顔料含有率を高めることは却つて像コントラス
トを低下させる傾向もでてくるのでより望しくは６〜２
０％程度である。像コントラストや像濃度は勿論、粒子
移動法電子写真感光層の膜厚にも依存する。この場合も
厚くすればするほど濃度やコントラスト特性がよくなる
ことはなく、一般に最適の範囲が存在し、感光層の組成
や像形成条件により一概には云えないが、表面に顔料層
を設けた型のものでは０．５〜１０μ（特に好ましくは
１〜５μ）、均一分散型のものでは２〜２０μ（特に好
ましくは４〜１０μ）附近膜厚がよく、過度の厚味は却
つて像濃度を低下させる。本発明の目的には均一分散型
のものの方が高い像濃度を得る上に有利であり、一般的
にはサブミクロン径の顔料は膜厚方向に数個含まれるこ
ととなり、このとき１．５程度の透過濃度が比較的容易
に得られる。The ratio of the pigment to the resin is preferably such that the former accounts for about 4 to 30% of the total volume. Achieving the purpose of the present invention requires an image with a considerable transmission density, so it is desirable that the pigment content be as high as possible; however, in the particle transfer method, it is difficult to increase the pigment content extremely. More preferably 6 to 2, as it tends to reduce image contrast.
It is about 0%. It depends not only on the image contrast and image density but also on the film thickness of the particle transfer method electrophotographic photosensitive layer. In this case as well, the thicker the layer, the better the density and contrast characteristics; there is generally an optimal range, and although it cannot be generalized depending on the composition of the photosensitive layer and image forming conditions, A good film thickness is around 0.5 to 10μ (especially preferably 1 to 5μ) for a type of type, and 2 to 20μ (especially preferably 4 to 10μ) for a uniform dispersion type, and an excessive thickness will actually reduce the image density. lower. For the purpose of the present invention, a uniformly dispersed type is more advantageous in obtaining a higher image density, and generally several submicron diameter pigments are included in the film thickness direction, and in this case, 1.5 It is relatively easy to obtain a transmission density of about

一般に顔料は０．０２〜０．１η／ｄ程度の量で塗布さ
れ、これが与える透過濃度は大体０．６−３．２位にな
る。樹脂結合剤の選択にあたつては、感光材料製造時一
粒子移動型電子写真感光層塗布時一下に設けられた感光
性樹脂層を溶解したり、膨潤しにくい溶剤にとけて良好
な塗布適性をしめすことを配慮せねばならない。Generally, the pigment is applied in an amount of about 0.02 to 0.1 η/d, and the transmission density provided by this pigment is about 0.6 to 3.2. When selecting a resin binder, select one that has good coating suitability in a solvent that does not dissolve or swell the underlying photosensitive resin layer when coating a single particle migration type electrophotographic photosensitive layer during the production of photosensitive materials. Consideration must be given to showing the

一般に粒子移動法電子写真では高絶縁性無極性溶剤にと
け易い樹脂がえらばれ、且露光後の現像にもその様な溶
剤が用いられる。一方感光性樹脂層はその溶解に極性溶
剤の存在を必要とするものが多く、上記配慮をするに当
り実際上殆ど制約を課せられることはない。ロジン誘導
体等をアルコール系、ケトン系およびエーテルアルコー
ル系溶剤等にとかして塗布することは多くの場合許され
ない。電子写真感光層の塗布溶剤としては脂肪族炭化水
素、ベンゼン、トルエン、キシレン等の芳香族炭化水素
等が好ましく、これ等は特に多くのジアゾニウム塩系Ｐ
Ｓ感光層を侵さない。Generally, in particle transfer electrophotography, resins that are easily soluble in highly insulating nonpolar solvents are selected, and such solvents are also used for development after exposure. On the other hand, many photosensitive resin layers require the presence of a polar solvent to dissolve them, and there are practically no restrictions on the above considerations. In many cases, it is not permissible to dissolve rosin derivatives and the like in alcohol, ketone, and ether alcohol solvents. As the coating solvent for the electrophotographic photosensitive layer, aliphatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, etc. are preferable, and these are particularly suitable for many diazonium salt-based P.
Does not attack the S photosensitive layer.

粒子移動型感光層の現像は、上にも述べた様に感光性樹
脂層を溶解したり、悪い影響を及ぼさない溶剤で行うの
が最もよい。As mentioned above, it is best to develop the particle migration type photosensitive layer with a solvent that does not dissolve or adversely affect the photosensitive resin layer.

実際には、ケロシンシクロヘキサン、リグロイン、石油
エーテル、ベンゼン、トルエン、キシレン、イソパラフ
イン系炭化水素、ジメチルポリシロキサン、四塩化炭素
等が用いられる。現像後の画像はほゾ裸の顔料よりなり
（第２図ｃ参照）、このま＼では強くこすれば顔料粒子
は落ちてしまう。Actually, kerosene cyclohexane, ligroin, petroleum ether, benzene, toluene, xylene, isoparaffinic hydrocarbons, dimethylpolysiloxane, carbon tetrachloride, etc. are used. The developed image consists of bare pigment (see Figure 2c), and if you rub it too hard, the pigment particles will fall off.

ここで像を破壊しない様に一様露光を行つてもよく、あ
るいは一旦軽く定着（具体的には、うすくラツカ一をか
ける等の処理をする）してもよい。最後に感光性樹脂層
を現像する。図ではＮ−Ｐ型電子写真層とＮ−Ｐ型感光
性樹脂層ｌの組合せを示したが、電子写真法としてはＰ
−Ｐ型のものも可能であり、又感光性樹脂層もＰ−Ｐ特
性のものも多くあるので、Ｐ−Ｐ型の組合せでもよい。
最終刷版をポジと決めた時、次の４つの組合せが考えら
れる〇重要なことは、粒子移動層による画像は本質的に
エツジ強調性がなく、像質の再現性、安全性に関しても
従来の電子写真に比してはるかに向上しているため、刷
版のように高品質の要求される分野では特にこの特徴が
発揮されることである。Here, uniform exposure may be performed so as not to destroy the image, or light fixing may be performed (specifically, processing such as applying a light glaze) may be performed. Finally, the photosensitive resin layer is developed. The figure shows a combination of an N-P type electrophotographic layer and an N-P type photosensitive resin layer l, but as an electrophotographic method, P
A -P type is also possible, and since there are many photosensitive resin layers with P-P characteristics, a P-P type combination may also be used.
When it is decided that the final printing plate is positive, the following four combinations are possible. The important thing is that the image created by the particle movement layer essentially has no edge enhancement, and the reproducibility and safety of the image quality are This feature is particularly useful in fields where high quality is required, such as printing plates, as it is much improved compared to electrophotography.

又、注意すべきことは、従来の電子写真法は広い面積の
一様な現像を苦手としていたので前記の組合せの表の中
で良好な像（特に感光性樹脂層に対するマスター像とし
て）を与える組合せはポジ−ポジ（１）及びネガ−ポジ
偵の２例のみで、Ｉ，ｌｌｌの二つの場合はどうしても
修正作業や長時間の現像操作を必要とした。粒子移動現
像法は階調制御の自由度も高く、Ｎ一Ｐ型、Ｐ−Ｐ型い
ずれでも硬調な像をきわめて短い現像時間（精々５秒、
一般には１〜２秒）で与えうるので、前記徂合せ１，ｎ
，およびのいずれの場合も利用することができる〇特に
、ＰＳ版に用いられている感光層の電子写真的影響を考
えると、Ｎ−Ｐ型のＰＳ版はきわめて薄い感光層を持ち
、電気的には何の影響も及ぼさない。Also, it should be noted that the conventional electrophotographic method is not good at developing uniformly over a wide area, so the above combination table provides a good image (especially as a master image for the photosensitive resin layer). There were only two combinations, positive-positive (1) and negative-positive, and the two cases I and Ill inevitably required correction work and long-time developing operations. Particle transfer development has a high degree of freedom in gradation control, and both N-P type and P-P type can produce high-contrast images in an extremely short development time (5 seconds at most).
In general, it can be given in 1 to 2 seconds), so the above combination 1, n
, and 〇In particular, when considering the electrophotographic influence of the photosensitive layer used in PS plates, the NP type PS plate has an extremely thin photosensitive layer and is electrically sensitive. has no effect on.

即ち電子写真層は直接基板に設けられているにひとしく
、電子写真的処理には何等特別の配慮をする必要はない
。一方ポジ−ポジのＰＳ感光層は光で分子結合が切れる
タイプの樹脂を用いるため、一般に膜厚も大きく、層自
身も絶縁性で電荷保持能力が高い。しかし、実験の結果
、この感光層の上に設けた粒子移動層の実技には殆ど悪
い影響のないことが判明した。That is, the electrophotographic layer is equivalent to being provided directly on the substrate, and there is no need to take any special consideration in electrophotographic processing. On the other hand, since a positive-positive PS photosensitive layer uses a type of resin whose molecular bonds can be broken by light, the film thickness is generally large, and the layer itself is insulating and has a high charge retention ability. However, as a result of experiments, it was found that the particle migration layer provided on the photosensitive layer had almost no adverse effect on practical performance.

しかしながら、きわめて低湿度の雰囲気では、粒子移動
層にか＼る電界が弱まる傾向が明かにみとめられ、その
様な場合には電子写真感光層２と感光性樹脂層３との間
にコロイダルアルミナの如き親水性コロイドやポリビニ
ルベンジルトリメチルアンモニウムクロライド等の導電
性樹脂層あるいはこれらの混合物層４を薄く設ければよ
い（第３図参照）。一般に粒子移動記録法では移動粒子
を受取る先の基板表面は適度の粗さを持つ方が像質が高
い場合が多く、従つて基板の表面を粗面とするか、ある
いは感光性樹脂層または、導電性樹脂層を粗面化してお
くのがよい。粗さの程度は１〜数μの微粒子を少量の結
合剤で連結した様な膜の表面がよく、上記コロイダルア
ルミナはこの要請を満足する面を与えるので特に好まし
い。導電性樹脂の好ましい例は以下の特許明細書に記載
がある。米国特許第３０１１９１８号、同第３２９３１
１５号、及び同第３４７９２１５号明細書、特公昭４３
−２７５８６号、特公昭４４１５５６４号、及び特公昭
４８−３２３７６号公報、特開昭４９−５０９３９号公
報。これらには四級アンモニア塩型ポリマーが記載され
ているが、これらのポリマーはコロイダル・アルミナと
混合使用できるので特に粒子移動型記録層の下塗に好適
である。下塗を粒子移動型層の下に設ける時は下塗層の
４０ｗｔ％以上がコロイダル・アルミナでｌイ当り０．
１〜５ｆ１塗布されていることが望ましい。However, in an extremely low-humidity atmosphere, there is a clear tendency for the electric field applied to the particle movement layer to weaken, and in such cases, colloidal alumina is used between the electrophotographic photosensitive layer 2 and the photosensitive resin layer 3. A thin layer 4 of a hydrophilic colloid, a conductive resin layer such as polyvinylbenzyltrimethylammonium chloride, or a mixture thereof may be provided (see FIG. 3). In general, in the particle migration recording method, the image quality is often higher if the surface of the substrate that receives the moving particles has a moderate roughness. It is preferable to roughen the surface of the conductive resin layer. The surface roughness of the film is preferably such that fine particles of 1 to several microns are connected with a small amount of binder, and the colloidal alumina described above is particularly preferable because it provides a surface that satisfies this requirement. Preferred examples of the conductive resin are described in the following patent specifications. U.S. Patent No. 3011918, U.S. Patent No. 32931
No. 15 and Specification No. 3479215, Special Publication No. 1979
-27586, Japanese Patent Publication No. 4415564, Japanese Patent Publication No. 48-32376, and Japanese Patent Publication No. 49-50939. Quaternary ammonia salt type polymers are described in these documents, and these polymers can be used in combination with colloidal alumina, so they are particularly suitable as an undercoat for a particle migration type recording layer. When an undercoat is provided under the particle migration type layer, 40 wt% or more of the undercoat layer is colloidal alumina and 0.5 wt% per liter of colloidal alumina.
It is desirable that 1 to 5 f1 be coated.

更に、粒子移動法による像は樹脂等を背景部にも残さな
いのでそれ等による紫外線吸収もなく、一様露光の際の
ロスが少い。以下の実施例によつて本発明を更に具体的
に説明する。Furthermore, since the image formed by the particle movement method does not leave any resin or the like in the background, there is no ultraviolet absorption caused by them, and there is little loss during uniform exposure. The present invention will be explained in more detail with reference to the following examples.

これらの実施例においては、本発明の感光材料を用いて
印刷原版を作成する実技も明らかにしてある。実施例
１ 黄色セーフライト下の暗室で富士写真フイルム製感光性
アルミプレートタイプＳＫ（ネガタイプＰＳ版）の一面
に、次の様にして得た分散液を乾燥後の膜厚が５μとな
る様に塗布した。In these examples, practical techniques for creating printing original plates using the photosensitive material of the present invention are also clarified. Example
1 In a dark room under a yellow safelight, the dispersion obtained as follows was applied to one side of a photosensitive aluminum plate type SK (negative type PS plate) manufactured by Fuji Photo Film so that the film thickness after drying was 5μ. .

水添ロジン（ハーキユレス社製、ステイベライトレジン
）の４０％トルエン溶液２５重量部にβ型銅フタロシア
ニン（Ｃ．Ｉ．ピグメントブル一１５）１重量部を添加
し、サンドミルで分散后、更に磁性ボールミルで１０時
間混練して青色の懸濁液を得た。1 part by weight of β-type copper phthalocyanine (C.I. Pigment Blue 15) was added to 25 parts by weight of a 40% toluene solution of hydrogenated rosin (manufactured by Hercules Co., Ltd., Stabelite Resin), and after being dispersed in a sand mill, the mixture was further magnetized. The mixture was kneaded in a ball mill for 10 hours to obtain a blue suspension.

乾燥后、粒子移動型感光層を−５００ボルトにコロナ帯
電し、ポジ原稿を投影露光した。After drying, the particle migration type photosensitive layer was corona charged to -500 volts, and a positive original was exposed by projection.

明部での露光は約２００００ルツクス・秒であつた。こ
れをキシレンに５秒間浸漬し、更にケロシンですすいで
とりだすと高コントラストのネガ像が得られた。飽和像
濃度は１．３であつた（透過濃度）。これに紫外〜近紫
外光を一様照射し、現像し、アラビアゴムを塗布して非
感脂処理を施し刷版が完成した。実施例 ２ 砂目立てしたアルミニウム板の上にポリビニルアルコー
ル／重クロム酸塩感光液をホワーラ一で塗布し、乾燥し
た。The light exposure was approximately 20,000 lux·sec. When this was immersed in xylene for 5 seconds and rinsed with kerosene, a high contrast negative image was obtained. The saturated image density was 1.3 (transmission density). This was uniformly irradiated with ultraviolet to near ultraviolet light, developed, and coated with gum arabic for non-liposensitizing treatment to complete the printing plate. Example 2 A polyvinyl alcohol/dichromate photosensitive solution was applied with a whirlpool onto a grained aluminum plate and dried.

膜厚は約３μであつた。次にこの上にコロイダルアルミ
ナ（日産化学製、アルミナゾル３００）をメタノールで
稀釈して１．５９／Ｔｒｌの割合で塗布した。ついで実
施例１の銅フタロシアニンを黄色のジナフト〔２，１−
２′，３′〕フラン−８，１３−ジオンにかえた以外は
同じ操作で黄色の感光性塗液を調製し、同様に塗布した
。The film thickness was about 3μ. Next, colloidal alumina (manufactured by Nissan Chemical, Alumina Sol 300) diluted with methanol was applied on top of this at a ratio of 1.59/Trl. Next, the copper phthalocyanine of Example 1 was converted into yellow dinaphtho[2,1-
A yellow photosensitive coating liquid was prepared in the same manner except that 2',3']furan-8,13-dione was used and coated in the same manner.

乾燥后、＋５００ボルトに帯電し、最明部で約２０００
ルツクス秒の露光が与えられる様にポジへ原稿像を投影
した。After drying, it is charged to +500 volts, and about 2000 volts at the brightest part.
The original image was projected onto a positive so that an exposure of lux seconds was given.

５秒間トルエンに浸漬して現像し、更にエツソ社のアイ
ソパ一Ｇにてすすいだところ鮮明なポジ像を得た。The film was developed by immersing it in toluene for 5 seconds, and was further rinsed with Etsuo's Isopa G to obtain a clear positive image.

これの４００ｍμ附近の濃度は約１．５であつた。全面
紫外光露光しすすぎの浴が乾いた後（温風を数分間当て
ればよい）、水を用いてポリビニルアルコール層を現像
した。この時、粒子からなる像も当然脱落してしまう。
次に塩酸で浅くアレミ版露出面を腐蝕し、ゴム止めし、
ラツカーチンクタ一を塗布した腐蝕部にラツカ一を詰め
た。The concentration near 400 mμ was about 1.5. After the entire surface was exposed to UV light and the rinsing bath was dry (warm air could be applied for a few minutes), the polyvinyl alcohol layer was developed using water. At this time, the image made of particles naturally falls off.
Next, lightly corrode the exposed surface of the aluminum plate with hydrochloric acid, and seal it with rubber.
The corroded areas that had been coated with Ratsuka Tinkuta were filled with Ratsuka Tinkuta.

次に反転剥離処理により光硬化した感光性樹脂層を除去
し、こうして露出した版面にアラビアゴムを塗布、非感
脂処理をして平凹版を得た。実施例 ３ チバ・カーキー社製の（ＣＲＯＭＯＰＨＴＡＬＹＥＬＬ
ＯＷクロモフタル・イエロ− Ａ２Ｒ（フラバンスロン
、Ｃ．Ｉ．７Ｏ６ＯＯ、バツト１２重量部と水添ロジン
のペンタエリスリトールエステルの４０％トルエン溶液
２５０部を充分混練して塗液を用意した。Next, the photocured photosensitive resin layer was removed by a reverse peeling process, and the thus exposed plate surface was coated with gum arabic and subjected to a non-greasy process to obtain a flat intaglio plate. Example 3 (CROMOPHTALYELL manufactured by Ciba Kirkey)
A coating liquid was prepared by sufficiently kneading 12 parts by weight of OW Chromophthal Yellow A2R (Flavanceron, C.I.7O6OO, butt) and 250 parts of a 40% toluene solution of pentaerythritol ester of hydrogenated rosin.

富士写真フイルム社製ポジタイプＰＳ版（ＧＡＰ）これ
は砂目立て後陽極酸化したアルミニウム板にポジ型感光
層を設けたもの一のポジ型感光層上に上記塗液を塗布し
、黄色の電子写真層の厚味が６μとなる様にした。Positive type PS plate (GAP) manufactured by Fuji Photo Film Co., Ltd. This is a positive type photosensitive layer provided on an aluminum plate that has been grained and then anodized.The above coating liquid is applied on the positive type photosensitive layer, and a yellow electrophotographic layer The thickness was set to 6μ.

乾燥后、正コロナにさらして表面電位を６４０ボルトと
した。After drying, it was exposed to positive corona to give a surface potential of 640 volts.

明部での露光量が１２００ルツクス・秒となる様に像露
光（ポジ原稿、マイクロフイルム）し、（露光后１５０
ボルト程度の残留電位が観測された）キシレン現像した
処鮮鋭なポジ像を得た。更に、一様露光でＰＳ感光層を
像状に解橋、所定の現像液で処理、ガム引きして刷版を
完成した〇実施例 ４実施例３の電子写真感光層をネガ
タイプＰＳ版（富士写真フイルム社製ＧＫＮ）へ同様に
塗布し、ネガ原稿を用いて粒子移動法によりネガ像を得
た〇飽和濃度は１．６であつた。Image exposure (positive original, microfilm) was performed so that the exposure amount in bright areas was 1200 lux/sec, and (after exposure 150 lux/second)
A sharp positive image was obtained by xylene development. Furthermore, the PS photosensitive layer was imagewise delinked by uniform exposure, treated with a prescribed developer, and gummed to complete the printing plate. GKN (manufactured by Photo Film Co., Ltd.) was coated in the same manner, and a negative image was obtained by the particle transfer method using a negative original. The saturation density was 1.6.

一様露光でＰＳ層を減感処理後、ラツカ一盛り、ガム引
きして刷版を得た。実施例 ５ 実施例３において、電子写真層を設ける前にＧＡＰ感光
層表面に、コロイダルアルミナ５０部とポリビニルベン
ジルトリメチルアンモニウムクロライド２０部よりなる
層を水で塗布量２９／イとなる様に塗布、乾燥后、実施
例３と同様電子写真層を設け、同様の実技をした。After desensitizing the PS layer by uniform exposure, it was coated with a glaze and gummed to obtain a printing plate. Example 5 In Example 3, before providing the electrophotographic layer, a layer consisting of 50 parts of colloidal alumina and 20 parts of polyvinylbenzyltrimethylammonium chloride was applied to the surface of the GAP photosensitive layer with water at a coating amount of 29/I, After drying, an electrophotographic layer was provided in the same manner as in Example 3, and the same practical technique was performed.

この時は表面電位４５０ボルト程度でよかつた。以上の
記述から明らかなように、本発明に特に次の様なａ）〜
ｃ）の構成においてその特色を最大限に発揮する。At this time, a surface potential of about 450 volts was sufficient. As is clear from the above description, the present invention particularly includes the following a) to
Its features are maximized in the configuration c).

ａ）粒子移動で得られる像の形成される面が粗面を形成
している場合：粗度は略々次の範囲にはいつていればよ
い。a) When the surface on which the image obtained by particle movement is formed is a rough surface: The roughness may be approximately within the following range.

即ち、凹凸の振巾は０．５〜７μ、その周期は１５μ〜
数１００μ、特に望ましくは振巾１〜４μ、周期１５〜
７０μである。その時粒子移動による像は損矢が少く、
コントラストが最も大きいことが経験的にたしかめられ
ている。この様な粗さは前にものべた様に基板を粗面化
しておいてもよく、または感光性樹脂層をマツト化して
おいてもよい。更に中間層４（第３図参照）をコロイダ
ルアルミナ、コロイダルシリカ等でマツト化しておいて
もよい。しかしながらマツト化した時粒子移動による像
質がよくなる理由はまだ明らかでない。ｂ）感光性樹脂
層がそれ自身電荷を保持し得ない様なネガタイブのもの
で、その上に直接電子写真層を設け、これにネガ像を得
る組合せ：マスタ一像をネガで得ると背景の修正が容易
で実用上望ましい。That is, the amplitude of the unevenness is 0.5 to 7μ, and the period is 15μ to
Several 100μ, particularly preferably a width of 1 to 4μ, a period of 15 to
It is 70μ. At that time, the image due to particle movement has fewer arrow losses,
It has been empirically confirmed that the contrast is the greatest. Such roughness may be achieved by roughening the substrate as described above, or by matting the photosensitive resin layer. Furthermore, the intermediate layer 4 (see FIG. 3) may be matted with colloidal alumina, colloidal silica, or the like. However, it is not yet clear why the image quality improves due to particle movement when matted. b) A combination in which the photosensitive resin layer itself is of a negative type and cannot hold an electric charge, and an electrophotographic layer is provided directly on it to obtain a negative image: When one master image is obtained as a negative, the background It is easy to modify and is desirable in practice.

又層構成を簡単になる。ｃ）粒子移動型感光層が黄色お
よび又はシアンの顔料をふくみ、実技前の感光層の透過
光学濃度が３５００λ附近の波長の光に対し、１．５以
上のもの。It also simplifies the layer structure. c) The particle migration type photosensitive layer contains yellow and/or cyan pigments, and the transmitted optical density of the photosensitive layer before practical training is 1.5 or more for light with a wavelength around 3500λ.

以上本発明を詳細に説明したが、本発明による感光材料
を用いる印刷原版作成の態様を述べると次の通りである
。Although the present invention has been described in detail above, the mode of producing a printing original plate using the photosensitive material according to the present invention will be described as follows.

特許請求範囲に記載の感光材料の粒子移動型電子写真感
光層を利用して粒子移動に基く画像を形成し、得られた
画像は感光性樹脂層の分光応答域の光に対し充分不透明
であり、次いで、全面露光することにより感光性樹脂層
を像に応じて架橋又は解僑せしめ、更に感光性樹脂層を
現像する工程をふくむことを特徴とする印刷原版の作製
法。An image based on particle movement is formed using a particle movement type electrophotographic photosensitive layer of a photosensitive material according to the claims, and the obtained image is sufficiently opaque to light in the spectral response range of the photosensitive resin layer. 1. A method for producing a printing original plate, which comprises the steps of: next, exposing the entire surface to light to crosslink or de-thicken the photosensitive resin layer according to the image; and further developing the photosensitive resin layer.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明の感光材料の模式的断面図であり、第２
図は本発明による印刷版の作製工程を図解したものであ
つてそれぞれａ）一様帯電、ｂ）像露光、ｃ）現像、ｄ
）一様露光およびｅ）感光性樹脂層の現像の諸工程を示
しており、第３図は本発明の感光材料の層構造の他の態
様を示したものである。 図において、１：印刷版基板、２：感光性樹脂層（２１
：未硬化部分、２２：硬化部分）、３：粒子移動型電子
写真感光層および４：中間層であり、ｃはコロナ帯電器
そしてｏは原稿を示す。FIG. 1 is a schematic cross-sectional view of the photosensitive material of the present invention, and FIG.
The figures illustrate the steps for producing a printing plate according to the present invention, including a) uniform charging, b) image exposure, c) development, and d.
) uniform exposure and e) development of the photosensitive resin layer, and FIG. 3 shows another embodiment of the layer structure of the photosensitive material of the present invention. In the figure, 1: printing plate substrate, 2: photosensitive resin layer (21
: uncured portion, 22: cured portion), 3: particle migration type electrophotographic photosensitive layer, and 4: intermediate layer, c indicates a corona charger, and o indicates an original.

Claims (1)

【特許請求の範囲】[Claims] １ 平版印刷版材基板上に感光性樹脂層および電気感光
性微細粒子を軟化し得る熱可塑性樹脂中に均一に分散す
るか、軟化し得る熱可塑性樹脂層の表面に層状に分布さ
せた粒子移動型電子写真感光層をこの順に重ねて設けた
ことを特徴とする印刷原版用感光材料。1 Particle movement in which a photosensitive resin layer and electrophotosensitive fine particles are uniformly dispersed in a softenable thermoplastic resin on a lithographic printing plate substrate, or distributed in a layered manner on the surface of a softenable thermoplastic resin layer. A photosensitive material for a printing original plate, characterized in that electrophotographic photosensitive layers are stacked in this order.