JPH0222095A - Desensitizing treatment of planographic printing plate - Google Patents
Desensitizing treatment of planographic printing plateInfo
- Publication number
- JPH0222095A JPH0222095A JP17077688A JP17077688A JPH0222095A JP H0222095 A JPH0222095 A JP H0222095A JP 17077688 A JP17077688 A JP 17077688A JP 17077688 A JP17077688 A JP 17077688A JP H0222095 A JPH0222095 A JP H0222095A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- printing plate
- plate
- planographic printing
- 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.)
- Pending
Links
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- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229930184652 p-Terphenyl Natural products 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical compound C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Printing Plates And Materials Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電子写真プロセスにより形成された平版印刷
版の不感脂化処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for desensitizing a lithographic printing plate formed by an electrophotographic process.
今日、平版オフセット印刷版としては、ジアゾ化合物と
フェノール樹脂を主成分とするポジ型感光剤やアクリル
系モノマーやポリマーを主成分とするネガ型感光剤を用
いるPS版などが実用化されているが、これらはすべて
低感度のため、あらかじめ画像記録された銀塩写真フィ
ルム原版を密着露光して製版を行っている。一方、コン
ピューター画像処理と大容量データの保存およびデータ
通信技術の進歩によって、近年では、原稿入力、補正、
編集、割り付けから頁組まで一貫してコンピューター操
作され、高速通信網や衛星通信により即時遠隔地の末端
プロッターに出力できる電子編集システムが実用化して
いる。特に、即時性の要求される新聞印刷分野において
電子編集システムの要求度は高い。また、オリジナルが
原版フィルムの形で保存され、これをもとに必要に応じ
て印刷版が複製されている分野においても、光ディスク
などの超大容量記録メディアの発達に伴いオリジナルが
これらの記録メディアにデジタルデータとして保存され
るようになると考えられる。Today, as lithographic offset printing plates, PS plates that use positive-working photosensitizers whose main components are diazo compounds and phenolic resins, and negative-working photosensitizers whose main components are acrylic monomers and polymers are in practical use. Since these all have low sensitivity, plate making is performed by contact exposure of a silver halide photographic film master plate on which an image has been recorded in advance. On the other hand, advances in computer image processing, large-capacity data storage, and data communication technology have enabled manuscript input, correction, and
Electronic editing systems have been put into practical use, in which everything from editing and layout to page assembly is controlled by a computer, and can be immediately output to a terminal plotter in a remote location using high-speed communications networks or satellite communications. In particular, electronic editing systems are in high demand in the field of newspaper printing, which requires immediacy. Furthermore, even in fields where originals are preserved in the form of original film, and printing plates are reproduced as needed based on this, with the development of ultra-high capacity recording media such as optical discs, the originals are being stored on these recording media. It is thought that it will be stored as digital data.
しかしながら、末端プロッターの出力から直接印刷版を
作成する直接型印刷版はほとんど実用化されておらず、
電子編集システムの稼動しているところでも出力は銀塩
写真フィルムにおこなわれこれをもとに間接的にPS版
へ密着露光により印刷版が作成されているのが実状であ
る。これは、出力プロツク−の光源(例えば、He−N
eレーザー、半導体レーザーなど)により実用的な時間
内に印刷版を作成できるだけの高い感度を有する直接型
印刷版の開発が困難であることによる。However, direct printing plates that create printing plates directly from the output of terminal plotters have hardly been put into practical use.
Even in places where electronic editing systems are in operation, the current situation is that output is performed on silver halide photographic film, and based on this, printing plates are indirectly created by contact exposure to PS plates. This is the light source of the output block (e.g. He-N
This is because it is difficult to develop a direct printing plate with a sensitivity high enough to make a printing plate within a practical time using e-lasers, semiconductor lasers, etc.).
直接型印刷版を提供し得る高い光感度を有する感光体と
して電子写真感光体が考えられる。Electrophotographic photoreceptors are considered as photoreceptors with high photosensitivity that can provide direct printing plates.
従来、電子写真を利用した印刷版材料(印刷用原板)と
しては例えば、特公昭47−47610号、特公昭48
−40002号、特公昭48−18325号、特公昭5
1−15766号、特公昭51−25761号公報に記
載の酸化亜鉛−樹脂分散系オフセット印刷版材料が知ら
れており、これは、電子写真法によりトナー画像形成後
その非画像部を不惑脂性とするため不感脂化溶液(例え
ば、フェロシアン塩又はフェリシアン塩を有する酸性水
溶液)で湿潤させた後使用される。このような処理をさ
れたオフセット印刷版は耐剛力が5千枚〜1万枚程度で
あり、これ以上の印刷には適さず1、又不感脂化に適し
た組成にすると静電特性が劣化し、且つ画質が悪化する
などの欠点がある。また、不惑脂化溶液として有害なシ
アン化合物を使用する欠点を有する。Conventionally, as printing plate materials (printing original plates) using electrophotography, for example, Japanese Patent Publication No. 47-47610, Japanese Patent Publication No. 48
-40002, Special Publication No. 18325, Special Publication No. 18325, Special Publication No. 18325
Zinc oxide-resin dispersion offset printing plate materials described in Japanese Patent Publication No. 1-15766 and Japanese Patent Publication No. 51-25761 are known, and after forming a toner image by electrophotography, the non-image area is rendered non-greasy. For this purpose, it is used after wetting with a desensitizing solution (for example, a ferrocyanate or an acidic aqueous solution with a ferricyanate). Offset printing plates treated in this way have a stiffness resistance of approximately 5,000 to 10,000 sheets, making them unsuitable for printing beyond this 1. Also, if the composition is made suitable for desensitization, the electrostatic properties deteriorate. However, there are also drawbacks such as deterioration of image quality. It also has the disadvantage of using harmful cyanide as a fat-freeing solution.
特公昭37−17162号、特公昭38−7758号、
特公昭46−39405号、特公昭52−2437号公
報等に記載される有機光導電体−樹脂系印刷版材料では
、たとえばオキサゾールあるいはオキサジアゾール系化
合物をスチレン−無水マレイン酸共重合体で結着した光
導電性絶縁層を砂目立したアルミニウム板上に設けた電
子写真感光体が用いられており、この感光体上に電子写
真法によりトナー画像形成後アルカリ性有機溶剤で非画
像部を溶解除去(エツチング)して印刷版が形成される
。Special Publication No. 37-17162, Special Publication No. 38-7758,
In the organic photoconductor-resin printing plate materials described in Japanese Patent Publication No. 46-39405 and Japanese Patent Publication No. 52-2437, for example, oxazole or oxadiazole compounds are combined with a styrene-maleic anhydride copolymer. An electrophotographic photoreceptor is used in which a photoconductive insulating layer is formed on a grained aluminum plate, and after a toner image is formed on this photoreceptor by electrophotography, the non-image area is dissolved with an alkaline organic solvent. It is removed (etched) to form a printing plate.
また、特開昭57−147656号にはヒドラゾン化合
物およびバルビッール酸あるいはチオバルビッール酸を
含有する電子写真感光体が開示されている。Further, JP-A-57-147656 discloses an electrophotographic photoreceptor containing a hydrazone compound and barbylic acid or thiobarbylic acid.
その他にも特開昭59−147335号、特開昭59−
152456号、特開昭59=168462号、特開昭
58−145495号等に記載の色素増感された電子写
真感光体が知られている。しかしながら、上記電子写真
感光体を用いて作成した印刷版の非画像部には電子写真
感光層中の物質が吸着し、非画像部を汚染するため、印
刷物の非画像部にインキが付着し、「汚れ」が発生ずる
ため印刷版として使用できなくなるという問題点があっ
た。In addition, JP-A-59-147335, JP-A-59-
Dye-sensitized electrophotographic photoreceptors are known, such as those described in Japanese Patent Application Laid-open No. 152456, Japanese Patent Application Laid-open No. 168462, Japanese Patent Application Laid-Open No. 145495-1987, and the like. However, substances in the electrophotographic photosensitive layer are adsorbed to the non-image areas of printing plates made using the above electrophotographic photoreceptor and contaminate the non-image areas, resulting in ink adhering to the non-image areas of printed matter. There was a problem in that it became unusable as a printing plate due to the occurrence of "stains".
一方、平版印刷版を製版する際、その最終工程(すなわ
ちエツチング後)で版面保護剤(いわゆるガム液)が塗
布される。On the other hand, when making a lithographic printing plate, a plate surface protective agent (so-called gum liquid) is applied in the final step (ie, after etching).
ガム液塗布の目的は非画像領域の親水性を保護するのみ
ならず、画像領域の加筆又は消去等の画像修正、製版後
印刷するまでの期間の保存又は再使用までの保存、印刷
機に取付ける際や取扱い中の指紋、油脂、塵埃等の付着
によって引起される汚れの防止及び傷の発生等からの保
護であり、更に酸化汚れの発生を抑えることである。従
来、平版印刷版用のガム液としては、−船釣にアラビア
ガム、セルロースガム又は分子中にカルボキシル基を有
する水溶性高分子物質の水溶液が使用されていた。しか
しこれらのガム液は有機性汚れ物質が多量に付着した場
合はいずれも不感脂化力が劣り汚れてしまう。The purpose of applying gum liquid is not only to protect the hydrophilicity of non-image areas, but also to modify images such as adding or erasing image areas, to preserve the image after making the plate until it is printed, or to preserve it until it is reused, and to install it in the printing machine. This is to prevent stains caused by the adhesion of fingerprints, oil, fat, dust, etc. during handling and handling, and to protect against scratches, etc., and also to suppress the generation of oxidation stains. Conventionally, gum arabic, cellulose gum, or an aqueous solution of a water-soluble polymeric substance having a carboxyl group in the molecule has been used as a gum solution for lithographic printing plates. However, when a large amount of organic staining substances adhere to these gum liquids, their desensitizing ability is poor and they become stained.
上記原因による汚れが発生した場合には有機性汚れ物質
を取り除く工程が必要となり、これに使用する汚れ除去
液も市販されている(たとえば富士写真フィルム■製の
プレートクリナーCU−3)。When stains occur due to the above causes, a step is required to remove organic stains, and stain removal liquids used for this purpose are also commercially available (for example, Plate Cleaner CU-3 manufactured by Fuji Photo Film ■).
しかし、このような工程の追加は作業性低下の問題から
好まれない。However, the addition of such a step is not preferred due to the problem of reduced workability.
従って、本発明の目的は電子写真プロセスにより形成さ
れた平版印刷版上より汚れ原因物質を除去すると同時に
更に版面保護をするのに有用な平版印刷版の不感脂化処
理方法を提供することである。Therefore, an object of the present invention is to provide a method for desensitizing a lithographic printing plate, which is useful for removing stain-causing substances from a lithographic printing plate formed by an electrophotographic process and at the same time protecting the plate surface. .
本発明の更なる目的は、特に不感脂化力の優れた版面保
護剤を用いることによる電子写真プロセスにより形成さ
れた平版印刷版用の不感脂化処理方法を提供することに
ある。A further object of the present invention is to provide a desensitization treatment method for lithographic printing plates formed by an electrophotographic process by using a plate surface protective agent having particularly excellent desensitization ability.
一
上記目的は、画像部が導電性基板上に設けられた光導電
体層上に電子写真プロセスにより形成されたトナー像か
らなり、非画像部が導電性基板である平版印刷版を、水
可溶性のカルボキシアルキル化澱粉を含有し、該カルボ
キシアルキル化澱粉のカルボキシアルキル基の導入率が
0.03〜0.5である版面保護剤で処理することを特
徴とする平版印刷版の不感脂化処理方法により達成され
ることが見出された。One of the above objects is to use a water-soluble lithographic printing plate in which the image area consists of a toner image formed by an electrophotographic process on a photoconductor layer provided on a conductive substrate, and the non-image area is a conductive substrate. A desensitizing treatment for a lithographic printing plate, characterized in that it is treated with a plate surface protective agent containing a carboxyalkylated starch and having an introduction rate of carboxyalkyl groups in the carboxyalkylated starch from 0.03 to 0.5. It has been found that this can be achieved by a method.
このカルボキシアルキル化澱粉は澱粉骨格の90重量%
以上がアミロペクチン型であることが好ましい。This carboxyalkylated starch accounts for 90% by weight of the starch skeleton.
It is preferable that the above is an amylopectin type.
本発明に用いられる版面保護剤の主成分であるカルボキ
シアルキル化澱粉の具体例としては、カルボキシメチル
化澱粉、カルボキシエチル化澱粉、カルボキシプロピル
化澱粉等が挙げられる。好ましいものはカルボキシメチ
ル化澱粉である。これらのカルボキシアルキル化澱粉は
一般に、澱粉のアルカリ懸濁液にモノクロル酢酸、モノ
クロルプロピオン酸、モノクロル酪酸のようなモノクロ
ルカルボン酸を作用させることにより合成される。Specific examples of carboxyalkylated starch, which is the main component of the plate surface protectant used in the present invention, include carboxymethylated starch, carboxyethylated starch, carboxypropylated starch, and the like. Preferred is carboxymethylated starch. These carboxyalkylated starches are generally synthesized by reacting an alkaline suspension of starch with a monochlorocarboxylic acid such as monochloroacetic acid, monochloropropionic acid, or monochlorobutyric acid.
カルボキシアルキル基の導入率(澱粉のグルコース単位
1個に対して導入されたカルボキシアルキル基の数)は
澱粉と、モノクロルカルボン酸の仕込比および反応条件
などにより決定されるが、理論的には、澱粉のグルコー
ス残基の3個の水酸基が置換されたもの、すなわち導入
率3まで可能である。尚導入率は予めカルボン酸の形に
しておいてそれを中和滴定することによって求められる
。The introduction rate of carboxyalkyl groups (the number of carboxyalkyl groups introduced per glucose unit of starch) is determined by the charging ratio of starch and monochlorocarboxylic acid, reaction conditions, etc., but theoretically, Three hydroxyl groups of glucose residues in starch are substituted, that is, an introduction rate of up to 3 is possible. The introduction rate can be determined by preparing the carboxylic acid in advance and subjecting it to neutralization titration.
本発明者等は、種々導入率のカルボキシメチル化澱粉の
水溶液を版面保護剤として試験したところ、導入率0.
03〜0.5の範囲で好適な結果が得られることを見出
した。より好ましくは0.05〜0.3の範囲である。The present inventors tested aqueous solutions of carboxymethylated starch with various introduction rates as plate surface protectants, and found that the introduction rate was 0.
It has been found that suitable results can be obtained in the range of 0.03 to 0.5. More preferably, it is in the range of 0.05 to 0.3.
導入率が0.03未満ではその不惑脂化力は、一般の可
溶性澱粉やデキストリンと同程度であり、本発明の目的
を達成することはできない。逆に導入率が0.5を越え
ると高温、高温等の過酷な条件のもとに印刷版を保存し
た場合印刷汚れを生じ易くなる欠点を有する。If the introduction rate is less than 0.03, its fat-unfavorable ability is comparable to that of general soluble starch or dextrin, and the object of the present invention cannot be achieved. On the other hand, if the introduction rate exceeds 0.5, it has the disadvantage that printing stains are likely to occur when the printing plate is stored under harsh conditions such as high temperatures.
一方、澱粉にはグルコース残基が1.4−グルコシド結
合のみで連なる直鎖構造のアミロース型と、1,4−グ
ルコシド結合を主とし、1,6グルコシド結合で枝分れ
構造をとるアミロペクチン型が知られており、一般の澱
粉の組成はアミロース型20重景%、アミロペクチン型
80重量%と言われている。On the other hand, starch has two types: amylose, which has a linear structure in which glucose residues are linked only through 1,4-glucosidic bonds, and amylopectin, which has a branched structure with mainly 1,4-glucosidic bonds and 1,6-glucosidic bonds. is known, and the composition of general starch is said to be 20 weight percent amylose type and 80 weight percent amylopectin type.
本発明者等は、アミロース型とアミロペクチン型のカル
ボキシアルキル化澱粉の種々の比率で版面保護剤として
用いて試験したところアミロペクチン型を90重量%以
上含有するカルボキシメチル化澱粉から得られる版面保
護剤を電子写真プロセスにより形成された平版印刷に用
いることにより優れた親水化力が得られることを見出し
た。より好ましくは、カルボキシメチル化澱粉が全てア
ミロペクチン型からなる場合である。The present inventors conducted tests using various ratios of amylose type and amylopectin type carboxyalkylated starch as a plate surface protective agent, and found that a plate surface protective agent obtained from carboxymethylated starch containing 90% by weight or more of amylopectin type It has been found that excellent hydrophilicity can be obtained by using it in lithographic printing formed by an electrophotographic process. More preferably, the carboxymethylated starch is entirely of the amylopectin type.
本発明において「水可溶性」とは、冷水可溶性の場合の
みならず、熱水可溶性の場合も含むものである。In the present invention, "water soluble" includes not only cold water soluble but also hot water soluble.
本発明に用いられる版面保護剤中のカルボキシアルキル
化澱粉の含有量としては約0.1〜40重量%が好まし
く、より好ましくは、0.5〜25重量%である。The content of carboxyalkylated starch in the plate surface protective agent used in the present invention is preferably about 0.1 to 40% by weight, more preferably 0.5 to 25% by weight.
カルボキシアルキル化澱粉のカルボキシル基は通常ナト
リウム塩やカリウム塩となっており、本発明には、この
ような金属塩が好適に用いられる。The carboxyl group of carboxyalkylated starch is usually a sodium salt or potassium salt, and such metal salts are preferably used in the present invention.
本発明においては、他の水溶性有機高分子化合物を併用
することができる。このような高分子化合物としては例
えば、メチルセルロース、エチルセルロース、ヒドロキ
シエチルセルロース、カルボキシメチルセルロース等の
セルロース誘導体、焙焼澱粉、α化澱粉、デキストリン
、ジアルデヒド澱粉等の澱粉誘導体、アルギン酸塩、ロ
ーカストビーンガム、ストラフクン、ステラビック、プ
ルラン等の天然または半合成高分子化合物が例示できる
。更に、ポリビニルアルコール、ポリビニルピロリドン
、ポリアクリルアミド、ポリビニルメチルエーテル、ポ
リエチレンオキシド、ビニルメチルエーテルと無水マレ
イン酸との共重合体、酢酸ビニルと無水マレイン酸との
共重合体などの合成高分子化合物も併用できる。更にア
ラビアガムを併用した場合、アラビアガムは従来の使用
量よりも著しく少い量で本発明の目的を達成することが
できる。版面保護剤は一般的には酸性領域、即ちpH2
,5〜6の範囲で使用する方が有利である。In the present invention, other water-soluble organic polymer compounds can be used in combination. Examples of such polymer compounds include cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, starch derivatives such as roasted starch, pregelatinized starch, dextrin, and dialdehyde starch, alginates, locust bean gum, and strafukun. Examples include natural or semi-synthetic polymeric compounds such as sterabic, pullulan and the like. Furthermore, synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether, polyethylene oxide, copolymers of vinyl methyl ether and maleic anhydride, and copolymers of vinyl acetate and maleic anhydride are also used. can. Furthermore, when gum arabic is used in combination, the object of the present invention can be achieved with a significantly smaller amount of gum arabic than conventionally used amounts. Plate protective agents are generally used in the acidic region, i.e. pH 2.
, 5 to 6 is more advantageous.
pH値を2.5〜6にするためには一般的には版面保護
剤中に鉱酸、有機酸又は無機塩等を添加する。In order to adjust the pH value to 2.5 to 6, mineral acids, organic acids, or inorganic salts are generally added to the plate surface protectant.
その添加量は通常0.01〜2重量%である。The amount added is usually 0.01 to 2% by weight.
上記有機酸としてはえん酸、酢酸、蓚酸、マロン酸、p
−トルエンスルホン酸、酒石酸、りんご酸、乳酸、レブ
リン酸、有機ホスホン酸などがあり、鉱酸としては硝酸
、硫酸、燐酸等が有用である。The above organic acids include citric acid, acetic acid, oxalic acid, malonic acid, p
-Toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, organic phosphonic acid, etc. are used, and as mineral acids, nitric acid, sulfuric acid, phosphoric acid, etc. are useful.
鉱酸、有機酸又は無機塩等の少な(とも1種もしくは2
種以上を併用しても良い。また本発明の版面保護剤中に
界面活性剤を添加することにより塗膜の面状、等が良化
する。使用できる界面活性剤としてはアニオン界面活性
剤又はノニオン界面活性剤が挙げられる。Mineral acids, organic acids, inorganic salts, etc.
You may use more than one species together. Furthermore, by adding a surfactant to the plate surface protective agent of the present invention, the surface condition of the coating film, etc. can be improved. Surfactants that can be used include anionic surfactants and nonionic surfactants.
アニオン界面活性剤としては脂肪族アルコール硫酸エス
テル塩類、脂肪族アルコール燐酸エステル塩類、二塩基
性脂肪酸エステルのスルホン酸塩類、脂肪酸アミドスル
ホン酸塩類、アルキルアリルスルホン酸塩類、ホルムア
ルデヒド縮合ナフタレンスルホン酸塩類等が用いられる
。Examples of anionic surfactants include aliphatic alcohol sulfate ester salts, aliphatic alcohol phosphate ester salts, dibasic fatty acid ester sulfonate salts, fatty acid amide sulfonate salts, alkylaryl sulfonate salts, formaldehyde condensed naphthalene sulfonate salts, etc. used.
ノニオン界面活性剤としてはポリエチレングリコールア
ルキルエーテル、ポリエチレングリコールアルキルエス
テル、ソルビタンアルキルエステル類、ポリオキシプロ
ピレンポリオキシエチレンエーテル類等が用いられる。As the nonionic surfactant, polyethylene glycol alkyl ether, polyethylene glycol alkyl ester, sorbitan alkyl ester, polyoxypropylene polyoxyethylene ether, etc. are used.
該界面活性剤は二種以上併用することができる。使用量
は特に限定する必要はないが好ましい範囲としては版面
保護剤の0.01〜10重量%である。Two or more kinds of these surfactants can be used in combination. The amount used is not particularly limited, but the preferred range is 0.01 to 10% by weight of the plate surface protectant.
上記成分の他必要により潤滑剤としてグリセリン、エチ
レングリコール、トリエチレングリコール等の低級多価
アルコールも使用することができる。これらの潤滑剤の
含有量は、組成物中に0.1〜5.0重量%、より好ま
しくは0,5〜3.0重量%が適当である。以上の他に
本発明における版面保護剤には、防腐剤などを添加する
ことが出来る。In addition to the above components, lower polyhydric alcohols such as glycerin, ethylene glycol, and triethylene glycol can also be used as lubricants if necessary. The content of these lubricants in the composition is suitably 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight. In addition to the above, preservatives and the like can be added to the plate surface protectant in the present invention.
例えば安息香酸及びその誘導体、フェノール、ホルマリ
ン、デヒドロ酢酸ナトリウム等をO,OO5〜2.0重
量%の範囲で添加できる。For example, benzoic acid and its derivatives, phenol, formalin, sodium dehydroacetate, etc. can be added in an amount of 5 to 2.0% by weight of O, OO.
更に本発明に用いられる版面保護剤の使用方法について
説明する。Furthermore, the method of using the plate surface protective agent used in the present invention will be explained.
後述する電子写真プロセスにより作成されたエツチング
済み平版印刷版に対して本発明に使用する版面保護剤を
版面上に適量注ぎ、これを版全面に塗布するようにスポ
ンジでこずりその後乾燥させる。これを自動化した市販
のガムコーターによっても同様の目的が達せられる。こ
れにより、版面上の汚れ原因物質を除去し、非画像領域
が不惑脂化され更に版面を保護することができる。An appropriate amount of the plate surface protective agent used in the present invention is poured onto the etched lithographic printing plate prepared by the electrophotographic process described below, and rubbed with a sponge so as to coat the entire surface of the plate, followed by drying. A similar purpose can also be achieved by a commercially available gum coater that automates this process. As a result, stain-causing substances on the printing plate are removed, non-image areas are rendered fat-free, and the printing plate can be further protected.
印刷を開始する場合には一般に版面上のガムを水洗して
落しくいわゆるガム落し、)その後通常の手順に従って
印刷を行なってもよいし又、本発明で使用する不惑脂化
液においてはいわゆるガム落しすることなく直ちに印刷
を開始することもできる。更に、印刷時に於いては従来
の様に数多くの不良印刷物を出すことなく、印刷の直後
から充分に満足する鮮明な印刷物を得ることができる。When starting printing, the gum on the printing plate is generally washed with water to remove the so-called gum.) After that, printing may be carried out according to the usual procedure, or the non-fatting liquid used in the present invention may be washed with so-called gum remover. You can also start printing immediately without dropping the printer. Furthermore, during printing, it is possible to obtain satisfactorily clear printed matter immediately after printing, without producing many defective printed matter as in the conventional case.
以下、本発明について更に詳細に説明する。The present invention will be explained in more detail below.
電子写真感光体に用いられる導電性基板としては、導電
性表面を有するプラスチックシートまたは特に溶剤不透
過性および導電性にした紙、アルミニウム板、亜鉛板、
または銅−アルミニウム板、銅−ステンレス板、クロム
−銅板等のバイメタル板、またはクロム−銅−アルミニ
ウム板、クロム鉛−& 板、クロム−銅−ステンレス板
等のトライメタル板等の親水性表面を有する導電性基板
が用いられ、その厚さは、0.1〜3 mmが好ましく
、特に0.1〜0.5肺が好ましい。これらの基板の中
でもアルミニウム板が好適に使用される。本発明におい
て用いられるアルミニウム板はアルミニウムを主成分と
する純アルミニウムや微量の異原子を含むアルミニウム
合金などの板状体であり、その組成が特定されるもので
はなく公知、公用の素材を適宜使用することが出来る。Conductive substrates used in electrophotographic photoreceptors include plastic sheets with conductive surfaces or papers made particularly solvent-impermeable and conductive, aluminum plates, zinc plates,
Or bimetal plates such as copper-aluminum plate, copper-stainless steel plate, chrome-copper plate, etc., or hydrophilic surfaces such as tri-metal plates such as chrome-copper-aluminum plate, chrome-lead plate, chrome-copper-stainless steel plate, etc. The thickness of the conductive substrate is preferably 0.1 to 3 mm, particularly preferably 0.1 to 0.5 mm. Among these substrates, aluminum plates are preferably used. The aluminum plate used in the present invention is a plate-shaped body such as pure aluminum whose main component is aluminum or an aluminum alloy containing a small amount of foreign atoms, and its composition is not specified, and publicly known and publicly used materials are used as appropriate. You can.
このアルミニウム板は公知の方法で砂目立て、陽極酸化
して用いることが出来る。砂目立て処理に先立ってアル
ミニウム板表面の圧延脂を除去するだめに、所望により
界面活性剤またはアルカリ性水溶液による脱脂処理が施
され、砂目立て処理か行われる。砂目立て処理方法には
、機械的に表面を粗面化する方法、電気化学的に表面を
溶解する方法及び化学的に表面を選択溶解させる方法が
ある。機械的に表面を粗面化する方法としては、ボール
研磨法、ブラシ研磨法、ブラスト研磨法、ハフ研磨法等
と称せられる公知の方法を用いることか出来る。また電
気化学的な粗面化法としては塩酸または硝酸電解液中で
交流または直流により、行う方法がある。また、特開昭
54−63902号に開示されている様に両者を組み合
わせた方法も利用できる。This aluminum plate can be used after being grained and anodized using a known method. Prior to the graining treatment, in order to remove rolling fat from the surface of the aluminum plate, degreasing treatment with a surfactant or an alkaline aqueous solution is performed, if desired, and then graining treatment is performed. Graining treatment methods include a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. As a method for mechanically roughening the surface, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a Huff polishing method, etc. can be used. Further, as an electrochemical surface roughening method, there is a method in which alternating current or direct current is used in a hydrochloric acid or nitric acid electrolyte. Furthermore, a method combining both methods can also be used, as disclosed in Japanese Patent Application Laid-Open No. 54-63902.
この様に粗面化されたアルミニウム板は必要に応じてア
ルカリエツチング処理及び中和処理される。The aluminum plate thus roughened is subjected to alkali etching treatment and neutralization treatment as required.
この様に処理されたアルミニウム板は陽極酸化処理され
る。陽極酸化処理に用いられる電解質としては硫酸、燐
酸、修酸、クロム酸、あるいはそれらの混酸が用いられ
、それらの電解質やその濃度は電解質の種類によって適
宜法められる。陽極酸化の処理条件は用いる電解質によ
り種々変わるので、−概に特定し得ないが、−船釣には
電解質の濃度が1〜80重量%溶液、液温は、5〜70
°C1電流密度5〜60A/dポ、電圧1〜100V、
電解時間10秒〜50分の範囲に有れば好適である。陽
極酸化皮膜量は0.1〜10g/rdが好適であるが、
より好ましくは1〜6 g / rdの範囲である。The aluminum plate thus treated is anodized. As the electrolyte used in the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used, and the electrolyte and its concentration are determined as appropriate depending on the type of electrolyte. Since the treatment conditions for anodizing vary depending on the electrolyte used, it cannot be generally specified, but for boat fishing, the electrolyte concentration is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
°C1 current density 5-60A/d, voltage 1-100V,
It is preferable that the electrolysis time is in the range of 10 seconds to 50 minutes. The amount of anodic oxide film is preferably 0.1 to 10 g/rd,
More preferably, it is in the range of 1 to 6 g/rd.
このようにして得られた導電性基板の上に公知の電子写
真感光層(光導電層)を設けて、電子写真感光体を得る
ことが出来る。A known electrophotographic photosensitive layer (photoconductive layer) is provided on the conductive substrate thus obtained to obtain an electrophotographic photoreceptor.
光導電層に用いる光導電性材料としては従来から知られ
ている数多くの有機または無機の化合物を用いることが
できる。例えば、公知の分散可能な光導電性材料として
は、セレン、セレン−テルル、硫化カドミウム、酸化亜
鉛等の無機光導電材料を挙げることが出来る。また、有
機光導電性化合物としては、
1) 米国特許第3112197号明細書などに記載さ
れているトリアゾール誘導体、
2)米国特許第3189447号明細書などに記載され
ているオキサジアゾール誘導体、
3)特公昭37−16096号公報などに記載されてい
るイミダゾール誘導体、
4)米国特許第3615402号、同3820989号
、同3542544号、特公昭45−555号、同51
−10983号、特開昭51−93224号、同55−
108667号、同55156953号、同56−36
656号明細書、公報などに記載のポリアリールアルカ
ン誘導体、
5) 米国特許第3180729号、同4278746
号、特開昭55−88064号、同55−88065号
、同49−105537号、同55−51086号、同
56−80051号、同56−88141号、同57−
45545号、同54−112637号、同55−74
546号明細書、公報などに記載されているビラプリン
誘導体及びピラゾロン誘導体、
6) 米国特許第3615404号、特公昭51−10
105号、同46−3712号、同47−28336号
、特開昭54−83435号、同54−110836号
、同54−119925号明細書、公報などに記載され
ているフェニレンジアミン誘導体、
7)米国特許第3567450号、同3180703号
、同3240597号、同3658520号、同423
2103号、同4175961号、同4012376号
、西独国特許(DSA)1110518号、特公昭49
−35702号、同39−27577号、特開昭55−
144250号、同56−119132号、同56−2
2437号明細書、公報などに記載されているアリール
アミン誘導体、
8) 米国特許第3526501号明細書記載のアミノ
置換カルコン誘導体、
9) 米国特許第3542546号明細書などに記載の
N。As the photoconductive material used in the photoconductive layer, many conventionally known organic or inorganic compounds can be used. For example, known dispersible photoconductive materials include inorganic photoconductive materials such as selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the like. In addition, as organic photoconductive compounds, 1) triazole derivatives described in US Pat. No. 3,112,197, etc., 2) oxadiazole derivatives, described in US Pat. No. 3,189,447, etc., 3) Imidazole derivatives described in Japanese Patent Publication No. 37-16096, etc., 4) U.S. Pat.
-10983, JP-A-51-93224, JP-A-55-
No. 108667, No. 55156953, No. 56-36
Polyarylalkane derivatives described in 656 specification, publications, etc. 5) U.S. Pat. No. 3,180,729, U.S. Pat. No. 4,278,746
No. 55-88064, 55-88065, 49-105537, 55-51086, 56-80051, 56-88141, 57-
No. 45545, No. 54-112637, No. 55-74
Virapurin derivatives and pyrazolone derivatives described in No. 546 specification, gazette, etc. 6) U.S. Patent No. 3,615,404, Japanese Patent Publication No. 51-10
105, 46-3712, 47-28336, JP-A-54-83435, JP-A-54-110836, JP-A-54-119925 specifications, publications, etc.; 7) U.S. Patent Nos. 3,567,450, 3,180,703, 3,240,597, 3,658,520, and 423
No. 2103, No. 4175961, No. 4012376, West German Patent (DSA) No. 1110518, Special Publication No. 1977
No.-35702, No. 39-27577, JP-A-55-
No. 144250, No. 56-119132, No. 56-2
8) Amino-substituted chalcone derivatives as described in US Pat. No. 3,526,501; 9) N as described in US Pat. No. 3,542,546.
N−ビラプリン誘導体、
10)米国特許第3257203号明細書などに記載の
オキサゾール誘導体、
11)特開昭56−46234号公報などに記載のスチ
リルアントラセン誘導体、
12)特開昭54−110837号公報等に記載されて
いるフルオレノン誘導体、
13)米国特許第3717462号、特開昭54−59
143号(米国特許第4150987号に対応)、同5
5−52063号、同55−52064号、同55−4
6760号、同55−85495号、同57−1135
0号、同57−148749号、同57104144号
明細書、公報などに記載されているヒドラゾン誘導体、
14)米国特許第4047948号、同4047949
号、同4265990号、同4273846号、同42
99897号、同4306008号明細書などに記載の
ベンジジン誘導体、
15)特開昭58−190953号、同59−9554
0号、同5997148号、同59−195658号、
同62−36674号公報などに記載されているスチル
ヘン誘導体等がある。N-virapurine derivatives, 10) Oxazole derivatives described in US Pat. No. 3,257,203, etc., 11) Styryl anthracene derivatives described in JP-A-56-46234, etc., 12) JP-A-54-110837, etc. Fluorenone derivatives described in 13) U.S. Pat. No. 3,717,462, JP-A-54-59
No. 143 (corresponding to U.S. Pat. No. 4,150,987), No. 5
No. 5-52063, No. 55-52064, No. 55-4
No. 6760, No. 55-85495, No. 57-1135
0, US Pat. No. 57-148749, US Pat. No. 57104144, publications, etc.; 14) US Pat.
No. 4265990, No. 4273846, No. 42
Benzidine derivatives described in JP-A-58-190953 and JP-A-59-9554, etc.
No. 0, No. 5997148, No. 59-195658,
Examples include stilhen derivatives described in JP-A No. 62-36674 and the like.
また、上記のような低分子光導電性化合物の他に、次の
ような高分子化合物も使用することが出来る。Further, in addition to the above-mentioned low-molecular photoconductive compounds, the following high-molecular compounds can also be used.
16)特公昭34−10966号公報記載のポリビニル
カルバゾール及びその誘導体、
17)特公昭43−18674号、同43−19192
号公報記載のポリビニルピレン、ポリビニルアントラセ
ン、ポリ−2−ビニル−4−(4′−ジメチルアミノフ
ェニル)−5−フェニルオキサゾール、ポリ3−ビニル
−N−エチルカルバゾール等のビニル重合体、
18)特公昭43−19193号公報記載のポリアセナ
フチレン、ポリインデン、アセナフチレンとスチレンの
共重合体等の重合体、
19)特公昭56−13940号公報などに記載のピレ
ンホルムアルデヒド樹脂、フロムピレン−ホルムアルデ
ヒド樹脂、エチルカルバゾール−ホルムアルデヒド樹脂
等の縮合樹脂、
20)特開昭56−90883号、同56−16155
0号公報に記載された各種のトリフェニルメタンポリマ
ー、また、光導電体の感度の向上、望みの感光波長域を
持たせるため等の目的のために、各種の顔料、染料等を
使用することが出来る。これらの例としては、
1)米国特許第4436800号、同4439506号
、特開昭47−37543号、同58−123541号
、同58−192042号、同58−219263号、
同59−78356号、同60179746号、同61
−148453号、同61−238063号、特公昭6
0−5941号、同60−45664号等に記載された
モノアゾ、ビスアゾ、トリスアゾ顔料2)米国特許第3
397086号、同4666802号等に記載の金属フ
タロシアニンあるいは無金属フタロシアニン等のフタロ
シアニン顔料
3) 米国特許第3371884号等に記載のペリレン
系顔料
4) 英国特許第2237680号等に記載のインジゴ
、チオインジゴ誘導体
5)英国特許第2237679号等に記載のキナクリド
ン系顔料
6) 英国特許第2237678号、特開昭59−18
4348号、同62−28738号等に記載の多環キノ
ン系顔料7)特開昭47−30331号等に記載のビス
ベンズイミダゾール系顔料
8) 米国特許第4396610号、同4644082
号等に記載のスクアリウム塩基顔料
9)特開昭第59−53850号、同61−21254
2号等に記載のアズレニウム塩系顔料
また、増感染料としては、「増感剤」125頁(講談社
81987) r電子写真J 12 9 (197
3)「有機合成化学J 24 No、111010
(1966)等に記載の公知の化合物を使用することが
出来る。例えば、10)米国特許第3141770号、
同4283475号、特公昭節48−25658号、特
開昭62−71965号等に記載のピリリウム系染料
11) へpplied 0ptics 5up
ple+nent 3 50 (1969)、特開
昭50−39548号等に記載のトリアリールメタン系
染料
12)米国特許第3597196号等に記載のシアニン
系染料
13)特開昭60−163047号、同59−1645
88号、同60252517号等に記載のスチリル系染
料これらの有機光導電性材料は1種または2種以上を併
用して用いても良い。16) Polyvinylcarbazole and derivatives thereof described in Japanese Patent Publication No. 34-10966, 17) Japanese Patent Publication No. 43-18674 and Japanese Patent Publication No. 43-19192
18) Vinyl polymers such as polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4-(4'-dimethylaminophenyl)-5-phenyloxazole, and poly3-vinyl-N-ethylcarbazole described in the publication No. 18) Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 19193-1970, 19) Pyrene formaldehyde resins, frompyrene-formaldehyde resins, and ethyl resins described in Japanese Patent Publication No. 13940-1983. Condensation resins such as carbazole-formaldehyde resins, 20) JP-A-56-90883, JP-A-56-16155
In addition to the various triphenylmethane polymers described in Publication No. 0, various pigments, dyes, etc. can be used for purposes such as improving the sensitivity of the photoconductor and giving it a desired photosensitive wavelength range. I can do it. Examples of these include: 1) U.S. Pat. No. 4,436,800, U.S. Pat.
No. 59-78356, No. 60179746, No. 61
-148453, No. 61-238063, Special Publication No. 6
Monoazo, bisazo, and trisazo pigments described in No. 0-5941, No. 60-45664, etc. 2) U.S. Patent No. 3
Phthalocyanine pigments such as metal phthalocyanine or metal-free phthalocyanine described in No. 397086 and No. 4666802, etc. 3) Perylene pigments described in U.S. Pat. No. 3,371,884, etc. 4) Indigo and thioindigo derivatives described in British Patent No. 2,237,680, etc. ) Quinacridone pigments described in British Patent No. 2237679, etc. 6) British Patent No. 2237678, Japanese Patent Application Laid-open No. 59-18
7) Bisbenzimidazole pigments described in JP-A No. 47-30331, etc. 8) U.S. Pat. Nos. 4,396,610 and 4,644,082.
Squarium base pigments described in JP-A No. 59-53850 and JP-A No. 61-21254.
The azulenium salt pigment described in No. 2, etc. Also, as a sensitizing dye, see "Sensitizer" p. 125 (Kodansha 81987) r Electrophotography J 12 9 (197
3) “Organic Synthetic Chemistry J 24 No. 111010
(1966) and the like can be used. For example, 10) U.S. Pat. No. 3,141,770;
Pyrylium dyes described in Japanese Patent Publication No. 4283475, Japanese Patent Publication No. 48-25658, Japanese Patent Application Laid-Open No. 62-71965, etc. 11) pplied 0ptics 5up
ple+nent 3 50 (1969), JP-A-50-39548, etc. 12) Cyanine-based dyes, described in U.S. Pat. No. 3,597,196, etc. 13) JP-A-60-163,047, JP-A-59- 1645
Styryl dyes described in No. 88, No. 60252517, etc. These organic photoconductive materials may be used alone or in combination of two or more.
本発明の光導電層には、感度向上などの目的としては、
例えば、トリニトロフルオレノン、クロラニル、テトラ
シアノエチレン等の電子吸引性化合物、特開昭58−6
5439号、同58−102239号、同5B−129
439号、同62−71965号等に記載の化合物等を
挙げることが出来る。In the photoconductive layer of the present invention, for purposes such as improving sensitivity,
For example, electron-withdrawing compounds such as trinitrofluorenone, chloranil, and tetracyanoethylene, JP-A-58-6
No. 5439, No. 58-102239, No. 5B-129
Examples include compounds described in No. 439 and No. 62-71965.
電子写真製版用感光体においては、光導電性化合物自体
が皮膜性を有する場合があるが、光導電性化合物が皮膜
性を有さない場合は結合樹脂を用いることが出来る。結
合樹脂としては、電子写真の分野で公知の樹脂を使用す
ることが出来る。電子写真製版用感光体を用いて印刷版
を作成するには、最終的に非画像部の光導電層を除去す
る必要があるが、このプロセスは、光導電層のエツチン
グ液に対する溶解性あるいはトナー像のエツチング液に
対するレジスト性などの相対的な関係によって決まるた
め、−概に言うことば出来ない。結合樹脂としては、後
述のエツチング液に可溶または分散可能な高分子化合物
が好ましい。In a photoreceptor for electrophotographic engraving, the photoconductive compound itself may have film properties, but if the photoconductive compound does not have film properties, a binding resin can be used. As the binding resin, resins known in the field of electrophotography can be used. In order to create a printing plate using a photoreceptor for electrophotographic engraving, it is necessary to finally remove the photoconductive layer in the non-image area, but this process is difficult due to the solubility of the photoconductive layer in the etching solution or the It is difficult to generalize because it depends on the relative relationship of the image to the etching solution, such as its resistivity. The binding resin is preferably a polymer compound that is soluble or dispersible in the etching solution described below.
具体的には、例えば、スチレンと無水マレイン酸の共重
合体、スチレンと無水マレイン酸モノアルキルエステル
の共重合体、メタクリル酸/メタクリル酸エステル共重
合体、スチレン/メタクリル酸/メタクリル酸エステル
共重合体、アクリル酸/メタクリル酸エステル共重合体
、スチレン/アクリル酸/メタクリル酸エステル共重合
体、酢酸ビニル/クロトン酸共重合体、酢酸ビニル/ク
ロトン酸/メタクリル酸エステル共重合体等のアクリル
酸エステル、メタクリル酸エステル、スチレン、酢酸ビ
ニルなどとアクリル酸、メタクリル酸、イタコン酸、ク
ロトン酸、マレイン酸、無水マレイン酸、フマル酸など
のカルボン酸含有モノマーあるいは酸無水物基含有モノ
マーとの共重合体やメタクリル酸アミド、ビニルピロリ
ドン、フェノール性水酸基、スルホン酸基、スルホンア
ミド基、スルホンイミド基をもつ単量体を含有する共重
合体、フェノール樹脂、部分ケン化酢酸ビニル樹脂、キ
シレン樹脂、ポリビニルブチラール等のビニルアセクー
ル樹脂をあげることができる。Specifically, for example, a copolymer of styrene and maleic anhydride, a copolymer of styrene and monoalkyl maleic anhydride, a methacrylic acid/methacrylic ester copolymer, a styrene/methacrylic acid/methacrylic ester copolymer Acrylic acid esters such as acrylic acid/methacrylic acid ester copolymer, styrene/acrylic acid/methacrylic acid ester copolymer, vinyl acetate/crotonic acid copolymer, vinyl acetate/crotonic acid/methacrylic acid ester copolymer, etc. Copolymers of , methacrylic acid esters, styrene, vinyl acetate, etc. and carboxylic acid-containing monomers or acid anhydride group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, etc. and methacrylic acid amide, vinylpyrrolidone, copolymers containing monomers with phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, and sulfonimide groups, phenolic resins, partially saponified vinyl acetate resins, xylene resins, polyvinyl butyral Examples include vinyl acecool resins such as
酸無水物基、またはカルボン酸基を有するモノマーを共
重合成分として含有する共重合体、およびフェノール樹
脂は、電子写真製版用感光体としたときの光導電層の電
荷保持力が高く、好結果をもって使用することができる
。A copolymer containing a monomer having an acid anhydride group or a carboxylic acid group as a copolymerization component, and a phenol resin have a high charge retention ability of the photoconductive layer when used as a photoreceptor for electrophotographic engraving, resulting in good results. It can be used with.
酸無水物基を有するモノマーを共重合成分として含有す
る共重合体としては、スチレンと無水マレイン酸の共重
合体が好ましい。また、この共重合体のハーフエステル
も使用することができる。As the copolymer containing a monomer having an acid anhydride group as a copolymerization component, a copolymer of styrene and maleic anhydride is preferable. Half esters of this copolymer can also be used.
カルボン酸基を有するモノマーを共重合成分として含有
する共重合体としては、アクリル酸もしくはメタクリル
酸と、アクリル酸もしくはメタクリル酸のアルキルエス
テル、アリールエステルモジくはアラルキルエステルと
の2元以上の共重合体が好ましい。また、酢酸ビニルと
クロトン酸共重合体、酢酸ビニルと炭素数2〜18のカ
ルボン酸のビニルエステルとクロトン酸との3元共重合
体も好ましい例である。フェノール樹脂の中で特に好ま
しいものとしては、フェノール、0−クレゾール、m−
クレゾール、またはp−クレゾールとホルムアルデヒド
またはアセトアルデヒドとを酸性条件下で縮合させて得
られるノボラック樹脂をあげることができる。結合樹脂
は単独で、あるいは2種以上混合して用いても良い。Copolymers containing a monomer having a carboxylic acid group as a copolymerization component include two or more copolymers of acrylic acid or methacrylic acid and an alkyl ester, aryl ester module, or aralkyl ester of acrylic acid or methacrylic acid. Combination is preferred. Further, preferable examples include a copolymer of vinyl acetate and crotonic acid, and a terpolymer of vinyl acetate, a vinyl ester of a carboxylic acid having 2 to 18 carbon atoms, and crotonic acid. Among the phenolic resins, phenol, 0-cresol, m-
Examples include novolac resins obtained by condensing cresol or p-cresol with formaldehyde or acetaldehyde under acidic conditions. The binding resin may be used alone or in combination of two or more.
光導電性化合物と結合樹脂を用いる場合は、光導電性化
合物の含有量が少ないと感度が低下するため、結合樹脂
1重量部に対して光導電性化合物は、0.05重量部以
上、より好ましくは0.1重量部以上の範囲で使用する
ことが出来る。また光導電層の膜厚は、薄すぎると現像
に必要な電荷が帯電できず、厚すぎるとエツチングの際
にサイドエッチと称する平面方向のエツチングを起こし
て良好な画像を得られず、0.1〜30μ、より好まし
くは0.5〜10μで使用できる。When using a photoconductive compound and a binding resin, the sensitivity decreases if the content of the photoconductive compound is small, so the amount of the photoconductive compound should be 0.05 part by weight or more per 1 part by weight of the binding resin. Preferably, it can be used in an amount of 0.1 part by weight or more. Furthermore, if the photoconductive layer is too thin, it will not be able to charge the charge necessary for development, and if it is too thick, etching in the plane direction called side etching will occur, making it impossible to obtain a good image. It can be used in a range of 1 to 30μ, more preferably 0.5 to 10μ.
本発明の電子写真製版用印刷版は常法に従って光導電層
を導電性基板上に塗布することによって得られる。光導
電層の作成に当たっては、光導電層を構成する成分を同
一層中に含有させる方法、あるいは二層以上の層に分離
して含有させる方法、例えば電荷担体発生物質と電荷担
体輸送物質を異なる層に分離して用いる方法等が知られ
ており、いずれの方法にても作成することができる。塗
布液は、光導電層を構成する各成分を適当な溶媒に溶解
し、作成するが、顔料などの溶媒に不溶な成分を用いる
ときは、ボールミル、ペイントシェーカー、ダイノミル
、アトライター等の分散機により粒径5μ〜0.1μに
分散して用いる。光導電層に使用する結合樹脂、その他
の添加剤は顔料などの分散時、あるいは分散後に添加す
ることが出来る。この様にして作成した塗布液を回転塗
布、ブレード塗布、ナイフ塗布、リバースロール塗布、
ティップ塗布、ロッドバー塗布、スプレー塗布の様な公
知の方法で基体上に塗布乾燥して電子写真製版用印刷版
を得ることが出来る。塗布液を作成する溶媒としては、
ジクロロメタン、ジクロロエタン、クロロフォルム等の
ハロゲン化炭化水素類、メタノール、エタノール等のア
ルコール頚、アセトン、メチルエチルケトン、シクロヘ
キサノン等のケトン類、エチレングリコールモノメチル
エーテル、2−メトキシエチルアセテート等のグリコー
ルエーテル類、テトラヒドロフラン、ジオキサン等のエ
ーテル類、酢酸エチル、酢酸ブチル等のエステル類等が
挙げられる。The electrophotographic printing plate of the present invention can be obtained by coating a photoconductive layer on a conductive substrate according to a conventional method. When creating a photoconductive layer, the components constituting the photoconductive layer can be contained in the same layer, or they can be contained separately in two or more layers, for example, by using different charge carrier generating substances and charge carrier transporting substances. There are known methods for separating the layer into layers, and it can be produced by any of these methods. The coating solution is prepared by dissolving each component constituting the photoconductive layer in an appropriate solvent, but when using components that are insoluble in solvents such as pigments, a dispersing machine such as a ball mill, paint shaker, Dyno Mill, or Attritor is used. It is used after being dispersed to a particle size of 5 μm to 0.1 μm. The binding resin and other additives used in the photoconductive layer can be added during or after dispersing the pigment. The coating liquid prepared in this way can be applied by spin coating, blade coating, knife coating, reverse roll coating,
A printing plate for electrophotolithography can be obtained by coating and drying on a substrate by a known method such as tip coating, rod bar coating, or spray coating. As a solvent for creating a coating solution,
Halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, alcohols such as methanol and ethanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, glycol ethers such as ethylene glycol monomethyl ether and 2-methoxyethyl acetate, tetrahydrofuran, and dioxane. and esters such as ethyl acetate and butyl acetate.
光導電層には光導電性化合物、結合樹脂の他に光導電層
の柔軟性、塗布面状などの膜物性を改良する目的で、必
要に応じて、可塑剤、界面活性剤、その他の添加剤を加
えることが出来る。可塑剤としては、ビフェニル、塩化
ビフェニル、0−テルフェニル、p−テルフェニル、ジ
ブチルフタレート、ジメチルグリコールフタレート、ジ
オクチルフタレート、トリフェニル燐酸等が挙げられる
。In addition to the photoconductive compound and the binding resin, the photoconductive layer may contain plasticizers, surfactants, and other additives as necessary to improve the film properties such as flexibility and coating surface condition of the photoconductive layer. agent can be added. Examples of the plasticizer include biphenyl, chlorinated biphenyl, 0-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, and the like.
本発明において使用する電子写真製版印刷版は前述の電
子写真感光体を用いて公知のプロセスによって作成する
ことができる。即ち、暗所で実質的に一様に帯電し、画
像露光により静電潜像を形成する。露光方法としては、
半導体レーザ、HeNeレーザ等による走査露光あるい
はキセノンランプ、タングステンランプ、蛍光灯等を光
源として反射画像露光、透明陽画フィルムを通した密着
露光などが挙げられる。次に上記静電潜像をトナーによ
って現像する。現像法としては従来公知の方法、例えば
、カスケード現像、磁気ブラシ現像、パウダークラウド
現像、液体現像などの各種の方法を用いることが出来る
。なかでも液体現像は微細な画像を形成することが可能
であり、印刷版を作成するために好適である。形成され
たトナー画像は公知の定着法、例えば、加熱定着、圧力
定着、溶剤定着等により定着することが出来る。The electrophotographic printing plate used in the present invention can be produced by a known process using the above-mentioned electrophotographic photoreceptor. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. As for the exposure method,
Examples include scanning exposure using a semiconductor laser, HeNe laser, etc., reflection image exposure using a xenon lamp, tungsten lamp, fluorescent lamp, etc. as a light source, and contact exposure using a transparent positive film. Next, the electrostatic latent image is developed with toner. As the developing method, various conventionally known methods such as cascade development, magnetic brush development, powder cloud development, and liquid development can be used. Among these, liquid development is capable of forming fine images and is suitable for creating printing plates. The formed toner image can be fixed by a known fixing method, such as heat fixing, pressure fixing, solvent fixing, or the like.
この様に形成したトナー画像をレジストとして作用させ
、非画像部の光導電層をエツチング液により除去するこ
とにより印刷版が作成できる。A printing plate can be prepared by allowing the toner image thus formed to act as a resist and removing the photoconductive layer in non-image areas with an etching solution.
トナー画像形成後の非画像部の光導電性絶縁層を除去す
るエツチング液としては、光導電性絶縁層を除去できる
ものなら任意の溶剤が使用可能であり、特に限定される
ものではないが、好ましくは、アルカリ性溶剤が使用さ
れる。ここで言う、アルカリ性溶剤とは、アルカリ性化
合物を含有する水溶液もしくは、アルカリ性化合物を含
有する有機溶剤もしくは、アルカリ性化合物を含有する
水溶液と有機溶剤との混合物である。アルカリ性化合物
としては、水酸化ナトリウム、水酸化カリウム、炭酸ナ
トリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケ
イ酸ナトリウム、メクケイ酸カリウム、リン酸ナトリウ
ム、リン酸カリウム、アンモニア、およびモノエタノー
ルアミン、ジェタノールアミン、トリエタノールアミン
等のアミノアルコール類等などの有機および無機の任意
のアルカリ性の化合物を挙げることが出来る。エツチン
グ液の溶媒としては前述のように、水もしくは多くの有
機溶剤を使用することが出来るが、臭気、公害性の点か
ら水を主体としたエツチング液が好ましく使用される。As the etching solution for removing the photoconductive insulating layer in the non-image area after toner image formation, any solvent can be used as long as it can remove the photoconductive insulating layer, and is not particularly limited. Preferably, alkaline solvents are used. The alkaline solvent referred to here is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent. Alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium mekusilicate, sodium phosphate, potassium phosphate, ammonia, and monoethanolamine and jetanolamine. , amino alcohols such as triethanolamine, and any organic and inorganic alkaline compounds. As mentioned above, water or many organic solvents can be used as the solvent for the etching solution, but from the viewpoint of odor and pollution, an etching solution mainly composed of water is preferably used.
水を主体としたエツチング液には、必要に応じて、各種
の有機溶剤を添加することも出来る。好ましい有機溶剤
としては、メタノール、エタノール、プロパツール、ブ
タノール、ヘンシルアルコール、フェネチルアルコール
等の低級アルコールや芳香族アルコールおよびエチレン
グリコール、ジエチレングリコール、トリエチレングリ
コール、ポリエチレングリコール、セルソルブ類、およ
びモノエタノールアミン、ジェタノールアミン、トリエ
タノールアミン等のアミノアルコール類等を挙げること
が出来る。また、エツチング液には界面活性剤、消泡剤
、その他必要に応じて各種の添加剤を含有したものが使
用される。If necessary, various organic solvents can be added to the etching solution mainly composed of water. Preferred organic solvents include lower alcohols and aromatic alcohols such as methanol, ethanol, propatool, butanol, hensyl alcohol, and phenethyl alcohol, as well as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and monoethanolamine. Amino alcohols such as jetanolamine and triethanolamine can be mentioned. Further, the etching solution used contains a surfactant, an antifoaming agent, and various other additives as necessary.
画像部を形成するトナーは前記エツチング液に対してレ
ジスト性を有する樹脂成分を含有していることが好まし
い。樹脂成分としては例えば、メタクリル酸、メタクリ
ル酸エステルなどを用いたアクリル樹脂、酢酸ビニル樹
脂、酢酸ビニルとエチレン又は塩化ビニルなどの共重合
体、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリビニル
ブチラールのようなビニルアセクール樹脂、ポリスチレ
ン、スチレンとブタジェン、メタクリル酸エステルなど
の共重合物、ポリエチレン、ポリプロピ゛レン及びその
塩素化物、ポリエステル樹脂(例、ポリエチレンテレフ
タレート、ポリエチレンイソフタレート、ビスフェノー
ルAのポリカルボネー1〜)、ポリアミド樹脂(例、ポ
リカプラミド、ポリへキサメチレンアジボアミド、ポリ
へギサメチレンセハカミド)、フェノール樹脂、キシレ
ン樹脂、アルキッド樹脂、ビニル変性アルキッド樹脂、
ゼラチン、カルボキシメチルセルロースなどのセルロー
スエステル誘導体又、ワックス、ポリオレフィン、ろう
などがある。It is preferable that the toner forming the image area contains a resin component having resist properties to the etching solution. Examples of resin components include acrylic resins using methacrylic acid, methacrylic acid esters, etc., vinyl acetate resins, copolymers of vinyl acetate and ethylene or vinyl chloride, vinyl chloride resins, vinylidene chloride resins, and vinyls such as polyvinyl butyral. Acecool resin, polystyrene, copolymers of styrene and butadiene, methacrylic acid esters, etc., polyethylene, polypropylene and its chlorinated products, polyester resins (e.g., polyethylene terephthalate, polyethylene isophthalate, polycarbonate of bisphenol A 1-), polyamide Resins (e.g., polycapramide, polyhexamethyleneaziboamide, polyhexamethylene sehakamide), phenolic resins, xylene resins, alkyd resins, vinyl-modified alkyd resins,
Examples include gelatin, cellulose ester derivatives such as carboxymethyl cellulose, wax, polyolefin, and wax.
本発明に使用する電子写真製版用感光体においては、前
記導電性基板と光導電層の間に必要によりカゼイン、ポ
リビニルアルコール、エチルセルロース、フェノール樹
脂、スチレン−無水マレイン酸共重合体、ポリアクリル
酸、モノエタノールアミン、ジェタノールアミン、トリ
メタノールアミン、トリプロパツールアミン、トリエタ
ノールアミン及びそれらの塩酸塩、修酸塩、燐酸塩、ア
ミノ酢酸、アラニン等のモノアミノモノカルボン酸;例
えばセリン、スレオニン、ジヒドロキシエチルグリシン
等のオキシアミノ酸;例えばシスティン、シスチン等の
硫黄を含むアミノ酸;例えばアスパラギン酸、グルタミ
ン酸等のモノアミノジカルボン酸;例えばりシン等のジ
アミノモノカルボン酸;例えばp−ヒドロキシフェニル
グリシン、フェニルアラニン、アントラニル酸等の芳香
族核を持つアミノ酸;例えばトリプトファン、プロリン
等の複素環をもつアミノ酸;例えばスルファミン酸、シ
クロヘキシルスルファミン酸等の脂肪族アミノスルホン
酸;例えばエチレンジアミン四酢酸、ニトリロ三酢酸、
イミノニ酢酸、ヒドロキシエチルイミノニ酢酸、ヒドロ
キシエチルエチレンジアミン三酢酸、エチレンジアミン
ニ酢酸、シクロヘキサンジアミン四酢酸、ジエチレント
リアミン五酢酸、グリコールエーテルジアミン四酢酸等
の(ポリ)アミノポリ酢酸;およびこれらの化合物の酸
基の1部又は全部がナトリウム塩、カリウム塩、アンモ
ニウム塩などからなる中間層を前記基板と光導電層との
接着性、光導電層の静電特性、溶出性および/又は印刷
特性を改良する目的で設けることができる。In the electrophotographic photoreceptor used in the present invention, if necessary, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride copolymer, polyacrylic acid, Monoaminomonocarboxylic acids such as monoethanolamine, jetanolamine, trimethanolamine, tripropaturamine, triethanolamine and their hydrochlorides, oxalates, phosphates, aminoacetic acid, alanine; for example, serine, threonine, oxyamino acids such as dihydroxyethylglycine; sulfur-containing amino acids such as cysteine and cystine; monoaminodicarboxylic acids such as aspartic acid and glutamic acid; diaminomonocarboxylic acids such as ricin; e.g. p-hydroxyphenylglycine, phenylalanine, Amino acids with an aromatic nucleus such as anthranilic acid; Amino acids with a heterocyclic ring such as tryptophan and proline; Aliphatic aminosulfonic acids such as sulfamic acid and cyclohexylsulfamic acid; For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
(Poly)aminopolyacetic acids such as iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminediacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid; and one of the acid groups of these compounds An intermediate layer partially or entirely composed of a sodium salt, potassium salt, ammonium salt, etc. is provided for the purpose of improving the adhesion between the substrate and the photoconductive layer, the electrostatic properties, dissolution properties, and/or printing properties of the photoconductive layer. be able to.
また、光導電層上に必要により光導電層の静電特性、ト
ナー現像時の現像特性、あるいは画像特性を改良する目
的で光導電層除去時に溶解し得るオーバーコート層を設
けることができる。このオーバーコート層は、機械的に
マット化されたもの、あるいはマット剤が含有される樹
脂層であってもよい。マット剤としては二酸化珪素、酸
化亜鉛、酸化チタン、酸化ジルコニウム、ガラス粒子、
アルミナ、澱粉、重合体粒子(たとえばポリメチルメタ
アクリレート、ポリスチレン、フェノール樹脂などの粒
子)及び米国特許第2710245号明細書、米国特許
第2992101号明細書に記載されているマット剤が
含まれる。これらは二種以上併用することができる。マ
ット剤を含有する樹脂層に使用される樹脂は使用される
エツチング液との組み合わせにより、適宜選択される。Further, an overcoat layer that can be dissolved when the photoconductive layer is removed can be provided on the photoconductive layer, if necessary, for the purpose of improving the electrostatic properties of the photoconductive layer, the development properties during toner development, or the image properties. This overcoat layer may be mechanically matted or a resin layer containing a matting agent. As matting agents, silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles,
Included are alumina, starch, polymer particles (eg particles of polymethyl methacrylate, polystyrene, phenolic resins, etc.) and matting agents as described in US Pat. No. 2,710,245 and US Pat. No. 2,992,101. Two or more of these can be used in combination. The resin used in the resin layer containing the matting agent is appropriately selected depending on the combination with the etching solution used.
具体的には例えばアラビアゴム、ニカワ、ゼラチン、カ
ゼイン、セルローズ類(たとえばビスコース、メチルセ
ルローズ、エチルセルローズ、ヒドロキシエチルセルロ
ーズ、ヒドロキシプロピルメチルセルローズ、カルボキ
シメチルセルローズ等)、澱粉類(例えば可溶性澱粉、
変性澱粉等)、ポリビニルアルコール、ポリエチレンオ
キシド、ポリアクリル酸、ポリアクリルアミド、ポリビ
ニルメチルエーテル、エポキシ樹脂、フェノール樹脂(
特にノボラック型フェノール樹脂が好ましい)、ポリア
ミド、ポリビニルブチラール等がある。これらは二種以
上併用することができる。Specifically, for example, gum arabic, glue, gelatin, casein, celluloses (e.g., viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, etc.), starches (e.g., soluble starch,
modified starch, etc.), polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl methyl ether, epoxy resin, phenolic resin (
Particularly preferred are novolac type phenolic resins), polyamides, polyvinyl butyral, and the like. Two or more of these can be used in combination.
本発明を実施例により更に具体的に説明するが、本発明
はその主旨を越えない限り以下の実施例に=34
限定されるものではない。なお、実施例において部又は
%は特に指定のない限りすべて重量部又は重量%を示す
。The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, in the examples, all parts or % indicate parts by weight or % by weight unless otherwise specified.
実施例1〜12及び比較例1〜3
表−1に示した種々の構造および組成のカルボキシメチ
ル化澱粉100重量部を純水740重量部に溶解した。Examples 1 to 12 and Comparative Examples 1 to 3 100 parts by weight of carboxymethylated starches having various structures and compositions shown in Table 1 were dissolved in 740 parts by weight of pure water.
比較例としてアラビアガム、焙焼デキストリン(商品名
クリームデキストリン#5 松谷化学■製)、酵素分解
デキストリン(商品名アミコール6H日数化学■製)各
100重量部を別別に740重量部の純水に溶解した。As a comparative example, 100 parts by weight each of gum arabic, roasted dextrin (trade name: Cream Dextrin #5, manufactured by Matsutani Kagaku ■), and enzymatically decomposed dextrin (trade name: Amicol 6H, manufactured by Hikaku Kagaku ■) were separately dissolved in 740 parts by weight of pure water. did.
これらの水溶液のそれぞれに、アニオン界面活性剤であ
るイソプロビルナフクレンスルホン酸ナトリウムの35
%水溶液5重量部、デヒドロ酢酸ナトリウム0.3重量
部を溶解し、更に燐酸(85%)を用いてpHを3.5
に調整し、版面保護剤試料とした。Each of these aqueous solutions contained 35% of the anionic surfactant sodium isoprobylnafucrene sulfonate.
% aqueous solution and 0.3 parts by weight of sodium dehydroacetate, and further adjusted the pH to 3.5 using phosphoric acid (85%).
This was used as a plate protection agent sample.
次にJIS 1050アルミニウムシートをパミスー水
懸濁液を研磨剤として、回転ナイロンブラシで表面を砂
目立てした。この時の表面粗さ(中心線平均粗さ)は0
.5μであった。水洗後、70°Cの10%苛性ソーダ
水溶液に浸漬しアルミニウムの溶解量が6g/n?にな
るようにエツチングした。水洗後、30%硝酸水溶液に
1分間浸漬することにより中和し、十分水洗した。その
後、0.7%硝酸水溶液中で、陽極時電圧13ポル1〜
、陰極時電圧6ボルトの矩形波交番波形を用いて(特公
昭55−1.9191号に記載)20秒間電電解面化を
行い、20%硝酸の50°C溶液中に浸漬して表面を洗
浄した後、水洗した。更に、20%硫酸水溶液中で陽極
酸化皮膜重量が3.0g/rnとなるように陽極酸化処
理を施して、水洗、乾燥したのち、更にβアラニンを2
8mg / rrTとなるように塗布、乾燥することに
より、基板を作成した。Next, the surface of the JIS 1050 aluminum sheet was grained using a rotating nylon brush using a pumice water suspension as an abrasive. At this time, the surface roughness (center line average roughness) is 0
.. It was 5μ. After washing with water, it was immersed in a 10% caustic soda aqueous solution at 70°C, and the amount of dissolved aluminum was 6 g/n? I etched it to make it look like this. After washing with water, it was neutralized by immersing it in a 30% nitric acid aqueous solution for 1 minute, and was thoroughly washed with water. Then, in a 0.7% nitric acid aqueous solution, the voltage at the anode was 13 pols 1 to 1.
Electrolytic surface treatment was carried out for 20 seconds using a rectangular alternating waveform with a cathode voltage of 6 volts (described in Japanese Patent Publication No. 55-1.9191), and the surface was immersed in a 50°C solution of 20% nitric acid. After washing, it was washed with water. Furthermore, after anodizing in a 20% sulfuric acid aqueous solution so that the weight of the anodic oxide film was 3.0 g/rn, washing with water and drying, β-alanine was further added to 2.
A substrate was prepared by coating and drying at a concentration of 8 mg/rrT.
この基板上に下記の光導電層用塗布液をパーコーターで
塗布、120°C110分間乾燥し電子写真製版用感光
体を作成した。The following photoconductive layer coating solution was applied onto this substrate using a Percoater and dried at 120° C. for 110 minutes to prepare a photoreceptor for electrophotographic engraving.
(光導電層用塗布液)
下記に示すヒドラゾン
化合物 25部ベンジルメタ
クリレートと
メタクリル酸の共重合体
(メタクリル酸3.0モル%) 75部下記のチオ
ピリリウム塩化合物 1.18部メチレンクロライド
510部メチルセルソルブアセテート 150
部このようにして作成した電子写真製版用感光体の乾燥
膜厚は4μであった。(Coating liquid for photoconductive layer) Hydrazone compound shown below 25 parts Copolymer of benzyl methacrylate and methacrylic acid (methacrylic acid 3.0 mol%) 75 parts Thiopyrylium salt compound shown below 1.18 parts Methylene chloride
510 parts Methyl cell solve acetate 150
The dry film thickness of the electrophotographic photoreceptor thus prepared was 4 μm.
次に、この試料を暗所でコロナ帯電機により表面電位+
400■に帯電した後タングステン光で露光し、液体現
像剤リコーMRP(IJコー■)で現像することにより
、鮮明なポジ画像を得る事が出来た。更に、作成した画
像を120°Cで2分間加熱し、トナー画像を定着した
。Next, this sample was charged with a surface potential of ++ using a corona charger in a dark place.
After being charged to 400 cm, it was exposed to tungsten light and developed with a liquid developer Ricoh MRP (IJ Co.), making it possible to obtain a clear positive image. Furthermore, the created image was heated at 120° C. for 2 minutes to fix the toner image.
この非画像部をケイ酸カリウム40部、水酸化カリウム
10部、エタノール100部を水800部に希釈したエ
ツチング液によって除去し、十分水洗した。This non-image area was removed with an etching solution prepared by diluting 40 parts of potassium silicate, 10 parts of potassium hydroxide, and 100 parts of ethanol in 800 parts of water, and the film was thoroughly washed with water.
このように作成した平版印刷版の表面に前述の版面保護
剤試料を各々スポンジにふくませて、塗布し、余剰分を
布で拭き取り、印刷用試料とした。Each of the above-mentioned plate surface protective agent samples was applied to the surface of the lithographic printing plate thus prepared using a sponge, and the excess was wiped off with a cloth to prepare a printing sample.
これらの印刷用試料の不感脂化力を評価するために予め
試料を35°C85%の条件下に3日間放置した。それ
らの試料を印刷機ハフダスター900CD−Xオフセツ
ト印刷機に取り付は通常の方法に従って1000枚印刷
した後、湿し水と印刷用紙の供給を停止し、印刷版試料
全面にインキを付着させてから再び通常の印刷条件に戻
して印刷した。この評価法によればアラビアガムのよう
に不感脂化力の強い版面保護剤を用いた印刷版試料では
非画像部上のインキは直ちに払えて(すなわち除去され
て)良好な印刷物が得られた。しかし、比較例2.3で
は非画線部上のインキがなかなか払えず良好な印刷物が
得られるまでに25枚の印刷を要した。表1に示すよう
にカルボキシメチル化澱粉を用いた版面保護剤のうち、
カルボキシメチル基導入率0.03〜0.5の範囲が良
好であり、更にアミロペクチン型が90%以上でアラビ
アガムと同等の不感脂化力を有することが認められた。In order to evaluate the desensitizing power of these printing samples, the samples were left for 3 days at 35° C. and 85%. Attach the samples to the Huff Duster 900CD-X offset printer according to the normal method, after printing 1000 sheets, stop supplying dampening water and printing paper, and apply ink to the entire surface of the printing plate sample. Printing was performed again under normal printing conditions. According to this evaluation method, for printing plate samples using a plate surface protectant with strong desensitizing power such as gum arabic, the ink on the non-image areas was immediately wiped off (that is, removed) and good prints were obtained. . However, in Comparative Examples 2 and 3, the ink on the non-image areas was difficult to brush off, and it took 25 prints to obtain a good printed product. As shown in Table 1, among the plate surface protectants using carboxymethylated starch,
It was found that a carboxymethyl group introduction rate in the range of 0.03 to 0.5 was good, and that the amylopectin type had desensitizing power equivalent to that of gum arabic at 90% or more.
(以下余白) 非常にすぐれている。(Margin below) Very good.
劣っている。Inferior.
○すぐれている。○Excellent.
×非常に劣っている。×Very poor.
実施例13
カルボキシメチル化澱粉(カルボキシメチル基導入率約
0.3はv ioo%アミロペクチン型で5%水溶液の
粘度が15cps(25°C)のもの)150重量部、
アルキルジフェニルエーテルジスルホン酸ナトリウムの
40%水溶液5.0重量部、pオキシ安息香酸エーテル
0.2重量部、くえん酸2.0重量部、第2燐酸アンモ
ニウム2.0重量部を純水790.8重量部に溶解し版
面保護剤を調製した一方実施例1における基板に下記の
光導電層用分散液をバーコーターにより塗布し、電子写
真製版用感光体を作成した。Example 13 150 parts by weight of carboxymethylated starch (carboxymethyl group introduction rate of about 0.3 is of the vioo% amylopectin type and the viscosity of a 5% aqueous solution is 15 cps (25°C)),
5.0 parts by weight of a 40% aqueous solution of sodium alkyl diphenyl ether disulfonate, 0.2 parts by weight of p-oxybenzoic acid ether, 2.0 parts by weight of citric acid, 2.0 parts by weight of dibasic ammonium phosphate, and 790.8 parts by weight of pure water. On the other hand, the following photoconductive layer dispersion was applied to the substrate of Example 1 using a bar coater to prepare a photoreceptor for electrophotographic engraving.
光導電層用分散液
トリスアゾ化合物 1.0部酢酸ビニルと
クロトン酸の共重合体
(RESYN No、28−1310カネボウ・ニスニ
スシー株式会社製) 10部テ
トラヒドロフラン 100部を500
mlのガラス製容器にガラスピーズと共にいれ、ペイン
トシェーカー(東洋精機製作所■)で60分間分散し、
光導電層用分散液を作成した。Dispersion liquid for photoconductive layer Trisazo compound 1.0 parts Copolymer of vinyl acetate and crotonic acid (RESYN No. 28-1310 manufactured by Kanebo Nisniscy Co., Ltd.) 10 parts Tetrahydrofuran 100 parts to 500 parts
ml glass container with glass peas, disperse for 60 minutes with a paint shaker (Toyo Seiki Seisakusho ■),
A dispersion liquid for a photoconductive layer was prepared.
この光導電層の厚みは約4μであった。これを実施例1
と同様な方法で、トナー現像、エツチングした。The thickness of this photoconductive layer was about 4 microns. Example 1
Toner development and etching were performed in the same manner as above.
上記の印刷版を2分割し、一方には上記の版面保護剤試
料を、他方には比較例−1のアラビアガムからなる版面
保護剤試料を塗布した。The above printing plate was divided into two parts, and one side was coated with the above plate surface protection agent sample, and the other side was coated with the plate surface protection agent sample made of gum arabic of Comparative Example-1.
2つの試料を温度45°C1湿度85%の恒温恒湿槽で
7日間保管した後、ハイデルベルグKOR−D印刷機で
通常の方法に従い印刷を行った。The two samples were stored in a constant temperature and humidity chamber at a temperature of 45° C. and a humidity of 85% for 7 days, and then printed using a Heidelberg KOR-D printing machine according to the usual method.
その結果両者とも、全く汚れることなく10万枚の印刷
物を与え、本発明による版面保護剤を用いた試料は、ア
ラビアガムからなる版面保護剤と同等の不感脂化力をも
っていることがわかった。As a result, both samples produced 100,000 prints without any staining, and it was found that the sample using the plate protectant according to the present invention had desensitizing power equivalent to that of the plate protectant made of gum arabic.
実施例14
カルボキシメチル化澱粉(アミロペクチン型でカルボキ
シメチル基導入率0.25.5%水溶液の粘度が300
cps (25°C)のもの)50重量部と酵素分解デ
キストリン(商品名アミコールIB日澱化学■製)15
0重量部、アルキルジフェニルエーテルジスルホン酸ナ
トリウムの40%水溶液5.0重量部、p−オキシ安息
香酸エーテル0.2重量部、くえん酸2.0重量部、第
2燐酸アンモニウム2.0重量部を純水790.8重量
部に溶解して版面保護剤試料を作成した。Example 14 Carboxymethylated starch (amylopectin type, carboxymethyl group introduction rate 0.25.5% aqueous solution viscosity 300
cps (at 25°C)) and 15 parts by weight of enzymatically decomposed dextrin (trade name: Amicol IB manufactured by Nippon Depot Chemical Co., Ltd.)
0 parts by weight, 5.0 parts by weight of a 40% aqueous solution of sodium alkyl diphenyl ether disulfonate, 0.2 parts by weight of p-oxybenzoic acid ether, 2.0 parts by weight of citric acid, and 2.0 parts by weight of diammonium phosphate. A plate surface protectant sample was prepared by dissolving it in 790.8 parts by weight of water.
次に上記試料においてカルボキシメチル化澱粉を除去し
、水溶性樹脂として酵素分解デキストリン(アミコール
IB)のみ200重量部を使用して版面保護剤試料を作
成した。Next, carboxymethylated starch was removed from the above sample, and a plate protectant sample was prepared using only 200 parts by weight of enzymatically decomposed dextrin (Amicol IB) as a water-soluble resin.
実施例1と同様に作成した印刷版に上記試料をガムコー
ターG−800(富士写真フィルム■製)を用いて塗布
、乾燥し、印刷用試料とした。The above sample was coated on a printing plate prepared in the same manner as in Example 1 using Gum Coater G-800 (manufactured by Fuji Photo Film ■) and dried to obtain a printing sample.
これらの試料を温度45°C湿度85%の恒温恒湿槽で
3日間保管した後、ハイデルベルグKOR−D印刷機で
、実施例1と同様の方法でインキ払いテストを行った。After storing these samples in a constant temperature and humidity chamber at a temperature of 45° C. and a humidity of 85% for 3 days, an ink removal test was performed using a Heidelberg KOR-D printing machine in the same manner as in Example 1.
その結果、カルボキシメチル化澱粉を含有する版面保護
剤を用いた試料では12枚でインキが払えて良好な印刷
物が得られたのに対して、酵素分解デキストリンのみの
試料では良好な印刷物を得るのに25枚の印刷を要した
。As a result, the sample using a plate protectant containing carboxymethylated starch was able to remove the ink and produce good prints after 12 sheets, whereas the sample using only enzymatically decomposed dextrin did not produce good prints. It took 25 pages to print.
本発明に従い版面保護剤を電子写真プロセスによる平版
印刷版に適用すると、アラビアガムと同等のすぐれた不
惑脂化力が得られる。When the plate surface protective agent of the present invention is applied to a lithographic printing plate produced by an electrophotographic process, an excellent anti-greasing power equivalent to that of gum arabic can be obtained.
Claims (1)
写真プロセスにより形成されたトナー像からなり、非画
像部が導電性基板である平版印刷版を、水可溶性のカル
ボキシアルキル化澱粉を含有し、該カルボキシアルキル
化澱粉のカルボキシアルキル基の導入率が0.03〜0
.5である版面保護剤で処理することを特徴とする平版
印刷版の不感脂化処理方法。A lithographic printing plate in which the image area consists of a toner image formed by an electrophotographic process on a photoconductor layer provided on a conductive substrate and the non-image area is a conductive substrate is coated with water-soluble carboxyalkylated starch. and the carboxyalkylated starch has a carboxyalkyl group introduction rate of 0.03 to 0.
.. 5. A method for desensitizing a lithographic printing plate, comprising treating it with a plate surface protectant according to item 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17077688A JPH0222095A (en) | 1988-07-11 | 1988-07-11 | Desensitizing treatment of planographic printing plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17077688A JPH0222095A (en) | 1988-07-11 | 1988-07-11 | Desensitizing treatment of planographic printing plate |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0222095A true JPH0222095A (en) | 1990-01-24 |
Family
ID=15911166
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17077688A Pending JPH0222095A (en) | 1988-07-11 | 1988-07-11 | Desensitizing treatment of planographic printing plate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0222095A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008027904A (en) * | 2006-06-26 | 2008-02-07 | Commissariat A L'energie Atomique | Aqueous dispersing element with starch and lithium-titanium mixed oxide base for lithium storage battery electrode |
-
1988
- 1988-07-11 JP JP17077688A patent/JPH0222095A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008027904A (en) * | 2006-06-26 | 2008-02-07 | Commissariat A L'energie Atomique | Aqueous dispersing element with starch and lithium-titanium mixed oxide base for lithium storage battery electrode |
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