JP5302848B2 - Thermal lithographic printing plate - Google Patents
Thermal lithographic printing plate Download PDFInfo
- Publication number
- JP5302848B2 JP5302848B2 JP2009244670A JP2009244670A JP5302848B2 JP 5302848 B2 JP5302848 B2 JP 5302848B2 JP 2009244670 A JP2009244670 A JP 2009244670A JP 2009244670 A JP2009244670 A JP 2009244670A JP 5302848 B2 JP5302848 B2 JP 5302848B2
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- Prior art keywords
- water
- forming layer
- image
- image forming
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 2
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- GJIPBTGGOJYQKM-UHFFFAOYSA-N (4-tert-butylphenyl) 3-phenylmethoxynaphthalene-2-carboxylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC2=CC=CC=C2C=C1OCC1=CC=CC=C1 GJIPBTGGOJYQKM-UHFFFAOYSA-N 0.000 description 1
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- JTWBMEAENZGSOQ-UHFFFAOYSA-N 1,2-bis(phenoxymethyl)benzene Chemical compound C=1C=CC=C(COC=2C=CC=CC=2)C=1COC1=CC=CC=C1 JTWBMEAENZGSOQ-UHFFFAOYSA-N 0.000 description 1
- CDEXOTIPVRNXEP-UHFFFAOYSA-N 1,2-bis[(4-octylphenoxy)methyl]benzene Chemical compound C1=CC(CCCCCCCC)=CC=C1OCC1=CC=CC=C1COC1=CC=C(CCCCCCCC)C=C1 CDEXOTIPVRNXEP-UHFFFAOYSA-N 0.000 description 1
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- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Printing Plates And Materials Therefor (AREA)
Description
本発明は、熱により相変換する画像形成層を用いた感熱型平版印刷版に関し、従来のアブレーション方式や機上現像方式等の層除去処理を必要としない、感熱型平版印刷版に関する。 The present invention relates to a heat-sensitive lithographic printing plate using an image forming layer that undergoes phase conversion by heat, and relates to a heat-sensitive lithographic printing plate that does not require a layer removal process such as a conventional ablation method or an on-machine development method.
近年、コンピューター及びその周辺機器の発展により各種デジタルプリンタを用いた平版印刷版の製版方法が各種提案されている。例えば、特開平６−１３８７１９号公報、特開平６−２５０４２４号公報には、乾式電子写真法レーザープリンタにより製版するもの、特開平９−５８１４４号公報には、熱溶融型インクを用いたオンデマンドインクジェットプリンタにより製版するもの、更に、特開昭６３−１６６５９０号公報には熱転写インクリボンを用いたサーマルプリンタにより製版するもの等が知られている。 In recent years, various plate making methods of planographic printing plates using various digital printers have been proposed with the development of computers and peripheral devices. For example, Japanese Patent Application Laid-Open Nos. 6-138719 and 6-250424 disclose plate making using a dry electrophotographic laser printer, and Japanese Patent Application Laid-Open No. 9-58144 includes on-demand using hot-melt ink. A plate making by an ink jet printer, and a plate making by a thermal printer using a thermal transfer ink ribbon are known from JP-A 63-166590.
上記のようなプリンタを用いた製版方法は、従来の可視光レーザー等を用いた光モードタイプとは大別され、取り扱い上において安全光の制約を受けないと言う利点を持つ。また、従来の光モードタイプにおいて通常用いられる露光後の現像処理を必要としない点から、これらの製版方式で製版される印刷版はプロセスレス印刷版と総称されている。 The plate making method using the printer as described above is roughly divided from the conventional optical mode type using a visible light laser or the like, and has an advantage that it is not restricted by safety light in handling. In addition, printing plates made by these plate making methods are collectively referred to as processless printing plates because they do not require post-exposure development processing that is normally used in conventional optical mode types.
しかし上記プロセスレス印刷版は、いずれも保水性付与層が設けられた支持体表面に感脂性（即ち、平版印刷インク着肉性）の記録画像を転写付与することにより印刷版を形成する方式であるため、次のような問題点があった。 However, all of the above processless printing plates are formed by forming a printing plate by transferring and imparting a grease-sensitive (that is, lithographic printing ink inking property) recorded image to the surface of a support provided with a water retention layer. Therefore, there were the following problems.
１）画像を形成する層が親水性であるためトナーやインク等の付着が十分ではなく、例えば転写トナー画像濃度が不足したり、転写画像に白抜けが発生したりするような問題。
２）転写画像の定着が十分ではなく、耐刷性が低下し、特に小ポイント文字の一部や低網点画像に欠落が生じるような問題。
３）非画像部に少量のトナーが不規則に転写されたり、熱転写インクリボンが擦れたりすること等によって、全体的に薄い地汚れが発生する等の問題。
1) Since a layer for forming an image is hydrophilic, adhesion of toner, ink or the like is not sufficient. For example, the transfer toner image density is insufficient, or white spots occur in the transferred image.
2) A problem that the transfer image is not sufficiently fixed, the printing durability is lowered, and a part of a small point character or a low dot image is lost.
3) A problem that a thin background smudge occurs as a result of irregularly transferring a small amount of toner to the non-image area or rubbing the thermal transfer ink ribbon.
一方、支持体上に熱可塑性樹脂あるいは熱溶融性物質を含有する画像形成層を設け、サーマルヘッドや赤外線レーザー等で加熱印字することで親油性の画像部が得られるプロセスレス印刷版等も提案されている。 On the other hand, we propose a processless printing plate that provides an oleophilic image area by providing an image-forming layer containing a thermoplastic resin or a heat-meltable substance on a support and performing thermal printing with a thermal head or infrared laser. Has been.
例えば、特開昭５８−１９９１５３号公報（特許文献１）、あるいは特開昭５９−１７４３９５号公報（特許文献２）には、画像形成層に熱転写リボン等を介さずサーマルヘッド等で直接加熱描画することにより親油性の画像部が得られる感熱型平版印刷版が記載されている。特開２０００−１９０６４９号公報（特許文献３）、特開２０００−３０１８４６号公報（特許文献４）には、赤外線レーザー等で加熱描画することで親油性の画像部が得られる感熱型平版印刷版が記載されている。通常の平版印刷では、上記のように得られた親油性の画像部に水とインキの両方が同時に供給され、該画像部は着色性のインキを受理、他の非画像部は親水性のため水を選択的に受け入れ、該画像上に受理したインキを、例えば、紙等の被印刷体に転写させることによって印刷がなされている。 For example, Japanese Patent Application Laid-Open No. 58-199153 (Patent Document 1) or Japanese Patent Application Laid-Open No. 59-174395 (Patent Document 2) directly draws heat on an image forming layer with a thermal head or the like without using a thermal transfer ribbon or the like. A heat-sensitive lithographic printing plate from which an oleophilic image area can be obtained is described. JP-A-2000-190649 (Patent Document 3) and JP-A-2000-301846 (Patent Document 4) describe a thermosensitive lithographic printing plate in which an oleophilic image portion is obtained by drawing with heat using an infrared laser or the like. Is described. In normal lithographic printing, both water and ink are simultaneously supplied to the oleophilic image area obtained as described above, and the image area accepts colored ink, and the other non-image areas are hydrophilic. Printing is performed by selectively receiving water and transferring the ink received on the image onto a printing medium such as paper.
しかし、これらの感熱型平版印刷版は一般に、画像部と非画像部との親油性／親水性の差が十分でなかったため、鮮明な印刷画像を得難く、耐刷性が不十分であったり、地汚れが発生しやすいという問題を有していた。 However, these heat-sensitive lithographic printing plates generally do not have a sufficient lipophilic / hydrophilic difference between the image area and the non-image area, so that it is difficult to obtain a clear printed image and the printing durability is insufficient. , Had a problem that soiling is likely to occur.
鮮明な高い画像濃度が得られる感熱型平版印刷版として、画像形成層に無機顔料、熱可塑性樹脂及び熱溶融性物質を含有する方法が特開昭６３−６４７４７号公報（特許文献５）で提案されている。また前述の特許文献３、特許文献４に記載される感熱型平版印刷版は、画像部の親油性と非画像部の親水性のバランスを改善するため、親油性を発現する熱溶融性物質を特定の熱伝導率を有する物質でコーティングする方法や、熱によるキレート反応を利用して親水性ポリマーの親水基を疎水化する技術も合わせて開示されている。しかしながら、いずれも反応の制御が難しく、画像部と非画像部との親油性／親水性の差が十分でないため、やはり耐刷性が不十分であったり、地汚れが発生しやすいという問題が残った。 JP-A-63-64747 (Patent Document 5) proposes a method in which an image forming layer contains an inorganic pigment, a thermoplastic resin, and a heat-meltable substance as a heat-sensitive lithographic printing plate capable of obtaining a clear and high image density. Has been. The thermosensitive lithographic printing plates described in Patent Document 3 and Patent Document 4 described above are made of a heat-meltable substance that exhibits lipophilicity in order to improve the balance between the lipophilicity of the image area and the hydrophilicity of the non-image area. A method of coating with a substance having a specific thermal conductivity and a technique of hydrophobizing the hydrophilic group of a hydrophilic polymer using a chelate reaction by heat are also disclosed. However, in both cases, it is difficult to control the reaction, and the difference in lipophilicity / hydrophilicity between the image area and the non-image area is not sufficient. The remaining.
また、耐刷性や地汚れといった問題に対しては、特開平１１−９５４１７公報（特許文献６）では、画像形成層にポリビニルアルコール、カルボキシメチルセルロース等の親水性樹脂を架橋して用いることで耐刷性や保水性を改善されることが記載されているが、親水性樹脂自体の相変換を利用するものであるので、画像部の親油化のレベルが低く、親油性／親水性の差が十分ではなかった。特開２０００−７５４７１号公報（特許文献７）では、疎水性発生物質に熱可塑性樹脂、ワックス分散物、撥水剤等を用い、親水性物質にゼラチンやポリビニルアルコール等を用いることで、特に耐水性、印刷再現性等を向上させたとあるが、これも親油性／親水性の差が十分ではなかった。 In addition, with respect to problems such as printing durability and background stains, JP-A-11-95417 (Patent Document 6) is resistant to crosslinking by using a hydrophilic resin such as polyvinyl alcohol or carboxymethyl cellulose in the image forming layer. Although it is described that the printability and water retention are improved, it uses the phase conversion of the hydrophilic resin itself, so the level of lipophilicity in the image area is low and the difference between lipophilicity / hydrophilicity is low. Was not enough. JP-A-2000-75471 (Patent Document 7) uses a thermoplastic resin, a wax dispersion, a water repellent, etc. as a hydrophobic substance and a gelatin, polyvinyl alcohol or the like as a hydrophilic substance. However, the difference in lipophilicity / hydrophilicity was not sufficient.
一方、特開２０００−２３８４５１号公報（特許文献８）では、支持体上に光熱変換物質、熱可塑性樹脂粒子及び樹脂粒子隔離物質を含有する画像形成層を有し、該光熱変換物質の含有比率が膜厚方向に勾配を有することで、耐刷性を高める技術が紹介されているが十分満足できるものではなかった。 On the other hand, JP-A-2000-238451 (Patent Document 8) has an image forming layer containing a photothermal conversion substance, thermoplastic resin particles and resin particle isolating substance on a support, and the content ratio of the photothermal conversion substance. However, although a technique for improving printing durability by introducing a gradient in the film thickness direction has been introduced, it has not been fully satisfactory.
従って、本発明の目的は、十分な耐刷性を保持しながら、且つ保水性（耐汚れ性）が改善された、アブレーション方式や機上現像方式等の層除去処理を必要としない、熱により相変換する画像形成層を用いた感熱型平版印刷版を提供することにある。 Accordingly, the object of the present invention is to maintain sufficient printing durability and improve water retention (dirt resistance), and does not require layer removal processing such as an ablation method or an on-machine development method. It is an object of the present invention to provide a heat-sensitive lithographic printing plate using an image forming layer that undergoes phase conversion.
上記課題は下記の手段によって解決された。
（１）耐水性支持体上に水溶性高分子化合物と熱可塑性樹脂を含有する画像形成層を少なくとも２層有し、耐水性支持体に近い画像形成層（Ａ）の水溶性高分子化合物に対する熱可塑性樹脂の比率が、耐水性支持体から最も離れた画像形成層（Ｂ）の比率よりも高く、且つ該画像形成層（Ｂ）は画像部が形成される層であると共に印刷の際に保水性を有する非画像部として作用する層である事を特徴とする感熱型平版印刷版。
（２）前記画像形成層（Ａ）と画像形成層（Ｂ）の、水溶性高分子化合物に対する熱可塑性樹脂の比率の差が、０．５以上である（１）記載の感熱型平版印刷版。
The above problems have been solved by the following means.
(1) The image forming layer (A) having at least two image-forming layers containing a water-soluble polymer compound and a thermoplastic resin on the water-resistant support, the image-forming layer (A) close to the water-resistant support for the water-soluble polymer compound the ratio of the thermoplastic resin, rather higher than the ratio of the farthest image forming layer of water-resistant support (B), and when printing with the image forming layer (B) is a layer that image portion is formed A heat-sensitive lithographic printing plate characterized by being a layer that acts as a non-image part having water retention .
(2) The thermosensitive lithographic printing plate according to (1), wherein the difference in the ratio of the thermoplastic resin to the water-soluble polymer compound in the image forming layer (A) and the image forming layer (B) is 0.5 or more. .
本発明により、十分な耐刷性を保持しながら、且つ保水性（耐地汚れ性）が改善された感熱型平版印刷版を提供することができる。 According to the present invention, it is possible to provide a heat-sensitive lithographic printing plate with improved water retention (soil resistance) while maintaining sufficient printing durability.
以下、本発明を詳細に説明する。本発明において上記した解決手段によって、良好な耐刷性と耐地汚れ性が得られるという理由については定かではないが、以下のように推測している。 Hereinafter, the present invention will be described in detail. In the present invention, the reason why the above-described solving means can provide good printing durability and stain resistance is not clear, but is presumed as follows.
本発明の感熱型平版印刷版は、耐水性支持体上に熱による相変換を利用し疎水性に変換する画像形成層を有している。ここで疎水性へ変換する層とは、熱が加わるとその層の一部が溶融し疎水性へと変換するもので、熱が与えられない部分は元の層が有する親水性を保持している。より具体的には、熱が加わると画像形成層の一部が溶融し疎水性へと変換する際に、水溶性高分子化合物に埋もれている熱可塑性樹脂が層の表面に滲出することで疎水性が発現する。一方、印字されなかった部分、即ち非画像部の熱可塑性樹脂は水溶性高分子化合物に埋もれたままであるので疎水性を発現しない。このようにして画像部と非画像部の疎水性／親水性の差が生じる感熱型平版印刷版の耐刷性と耐地汚れ性の改善には、印刷中においてもこの差を十分に維持することが重要である。本発明は、耐水性支持体から最も離れた画像形成層（Ｂ）の水溶性高分子化合物に対する熱可塑性樹脂の比率を少なくする事によって、表面の親水性が増し印刷時の保水性の向上が改善されると同時に、これにより低下した親油性を、画像形成層（Ｂ）よりも熱可塑性樹脂の比率が高く、且つ耐水性支持体に近い画像形成層（Ａ）を設けることによって、画像形成時に熱可塑性樹脂を十分に表面に滲出させることが可能となり、高い耐刷性と耐地汚れ性が両立できるものと推測される。 The heat-sensitive lithographic printing plate of the present invention has an image forming layer on a water-resistant support that is converted to hydrophobicity by utilizing phase conversion by heat. Here, the layer to be converted to hydrophobic means that when heat is applied, part of the layer is melted and converted to hydrophobic, and the portion to which heat is not applied retains the hydrophilicity of the original layer. Yes. More specifically, when heat is applied, a part of the image forming layer melts and becomes hydrophobic, so that the thermoplastic resin embedded in the water-soluble polymer compound oozes out on the surface of the layer to make it hydrophobic. Sex is expressed. On the other hand, the non-printed portion, that is, the non-image portion of the thermoplastic resin remains buried in the water-soluble polymer compound and thus does not exhibit hydrophobicity. In this way, the difference between the hydrophobicity / hydrophilicity of the image area and the non-image area is generated. In order to improve the printing durability and background stain resistance of the heat-sensitive lithographic printing plate, this difference is sufficiently maintained even during printing. This is very important. In the present invention, by reducing the ratio of the thermoplastic resin to the water-soluble polymer compound of the image forming layer (B) farthest from the water-resistant support, the hydrophilicity of the surface is increased and the water retention during printing is improved. At the same time, the improved lipophilicity can be achieved by providing an image forming layer (A) having a higher thermoplastic resin ratio than the image forming layer (B) and close to a water-resistant support. In some cases, it is possible to sufficiently allow the thermoplastic resin to exude to the surface, and it is presumed that both high printing durability and soil resistance can be achieved.
本発明の耐水性支持体に近い画像形成層（Ａ）の水溶性高分子化合物に対する熱可塑性樹脂の比率が、耐水性支持体から最も離れた画像形成層（Ｂ）の比率よりも高い事を特徴とする感熱型平版印刷版を作製する方法に制限はないが、例えば、画像形成層（Ａ）を塗布し、次に画像形成層（Ｂ）を順次塗布して重ねていく方法や、スライドホッパー方式で多層を同時に塗布する方法等がある。 The ratio of the thermoplastic resin to the water-soluble polymer compound in the image forming layer (A) close to the water-resistant support of the present invention is higher than the ratio of the image forming layer (B) farthest from the water-resistant support. There is no limitation on the method of producing the featured thermal lithographic printing plate. For example, a method of applying the image forming layer (A) and then applying the image forming layer (B) in sequence and stacking them, or a slide There is a method of simultaneously applying multiple layers by a hopper method.
本発明において耐水性支持体に近い画像形成層（Ａ）の水溶性高分子化合物に対する熱可塑性樹脂の比率が、耐水性支持体から最も離れた画像形成層（Ｂ）の比率よりも高くなるように構成すればどのような比率でも良いが、画像形成層（Ａ）の比率と画像形成層（Ｂ）の比率との差が０．５以上であることが好ましい。 In the present invention, the ratio of the thermoplastic resin to the water-soluble polymer compound in the image forming layer (A) close to the water-resistant support is higher than the ratio of the image forming layer (B) farthest from the water-resistant support. However, it is preferable that the difference between the ratio of the image forming layer (A) and the ratio of the image forming layer (B) is 0.5 or more.
本発明において画像形成層を３層設ける場合、画像形成層（Ａ）と画像形成層（Ｂ）の間に位置する画像形成層（Ｃ）の水溶性高分子化合物に対する熱可塑性樹脂の比率は、耐水性支持体から最も離れた画像形成層（Ｂ）よりも高くても低くても良いが、耐水性支持体に近い画像形成層（Ａ）の比率よりも低く、画像形成層（Ｂ）の比率よりも高いことが好ましい。 When three image forming layers are provided in the present invention, the ratio of the thermoplastic resin to the water-soluble polymer compound in the image forming layer (C) located between the image forming layer (A) and the image forming layer (B) is: Although it may be higher or lower than the image forming layer (B) furthest from the water-resistant support, it is lower than the ratio of the image forming layer (A) close to the water-resistant support, and the image forming layer (B) It is preferable that the ratio is higher.
耐水性支持体から最も離れた画像形成層（Ｂ）の水溶性高分子化合物に対する熱可塑性樹脂の比率（熱可塑性樹脂の質量／水溶性高分子化合物の質量）には好ましい範囲があり、０．０１〜１０であることが好ましく、更に好ましくは０．１〜３である。また耐水性支持体に近い画像形成層（Ａ）における比率にも好ましい範囲があり、０．１〜５０であることが好ましく、更に好ましくは１〜２０である。 There is a preferred range in the ratio of the thermoplastic resin to the water-soluble polymer compound (mass of thermoplastic resin / mass of water-soluble polymer compound) of the image forming layer (B) farthest from the water-resistant support. It is preferable that it is 01-10, More preferably, it is 0.1-3. Further, the ratio in the image forming layer (A) close to the water-resistant support also has a preferable range, preferably from 0.1 to 50, and more preferably from 1 to 20.
本発明の感熱型平版印刷版の画像形成層には、熱可塑性樹脂を含有する。かかる熱可塑性樹脂としては、鎖状ポリマーからなり加熱によって可塑性を示す固体状の有機高分子化合物であって、有機高分子化合物の水分散体を指す。代表例はスチレンブタジエン共重合体、アクリロニトリルブタジエン共重合体、メチルメタクリレートブタジエン共重合体、スチレンアクリロニトリルブタジエン共重合体、スチレンメチルメタクリレートブタジエン共重合体等の、その変性物を含めた合成ゴムラテックスが好ましく用いられるが、スチレン無水マレイン酸共重合体、メチルビニルエーテル無水マレイン酸共重合体、ポリアクリル酸共重合体、ポリスチレン、スチレン／アクリル酸エステル共重合体、ポリアクリル酸エステル、ポリメタクリル酸エステル、アクリル酸エステル／アクリル酸エステル共重合体、及び低融点ポリアミド樹脂等の水分散体も使用可能である。これら熱可塑性樹脂は単独もしくは２種以上併用して用いることができる。印刷インクのビヒクル（バインダー成分）との親和性から、かかる熱可塑性樹脂としては合成ゴムラテックスが好ましく、特にスチレンブタジエン共重合体とその変性物が望ましい。好ましい熱可塑性樹脂の配合量としては、全ての画像形成層の固形分量に対して５〜５０質量％とすることが好ましい。 The image forming layer of the heat-sensitive lithographic printing plate of the present invention contains a thermoplastic resin. Such a thermoplastic resin is a solid organic polymer compound made of a chain polymer and exhibiting plasticity by heating, and refers to an aqueous dispersion of the organic polymer compound. Representative examples are synthetic rubber latex including modified products such as styrene butadiene copolymer, acrylonitrile butadiene copolymer, methyl methacrylate butadiene copolymer, styrene acrylonitrile butadiene copolymer, styrene methyl methacrylate butadiene copolymer. Styrene maleic anhydride copolymer, methyl vinyl ether maleic anhydride copolymer, polyacrylic acid copolymer, polystyrene, styrene / acrylic acid ester copolymer, polyacrylic acid ester, polymethacrylic acid ester, acrylic Aqueous dispersions such as acid ester / acrylic acid ester copolymers and low melting point polyamide resins can also be used. These thermoplastic resins can be used alone or in combination of two or more. In view of the affinity with the vehicle (binder component) of the printing ink, the thermoplastic resin is preferably a synthetic rubber latex, and particularly preferably a styrene butadiene copolymer and a modified product thereof. A preferable blending amount of the thermoplastic resin is preferably 5 to 50% by mass with respect to the solid content of all the image forming layers.
また熱による溶融、融着効果を発現しやすくするためには、熱可塑性樹脂のガラス転移温度は５０〜１５０℃、更に好ましくは５５〜１２０℃のものを使用するのが良い。ガラス転移温度が５０℃未満では製造工程中に液状に相変化を起こし、非画像部にも親油性が発現するため印刷地汚れの原因となる場合がある。また１５０℃を超える場合はポリマーの熱溶融が起こりにくく、比較的小出力のレーザーや小型サーマルプリンタでは強固な画像を形成するのが困難となる場合がある。 Moreover, in order to make it easy to express the effect of melting and fusing by heat, it is preferable to use a thermoplastic resin having a glass transition temperature of 50 to 150 ° C, more preferably 55 to 120 ° C. If the glass transition temperature is less than 50 ° C., a phase change occurs in a liquid state during the production process, and oleophilicity appears in the non-image area, which may cause printing stains. When the temperature exceeds 150 ° C., the polymer is hardly melted by heat, and it may be difficult to form a strong image with a relatively small output laser or a small thermal printer.
本発明の感熱型平版印刷版の画像形成層には、水溶性高分子化合物を含有する。かかる水溶性高分子化合物としては、例えば、ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アセトアセチル基変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、澱粉及びその誘導体、ゼラチン、カゼイン、アルギン酸ソーダ、ポリビニルピロリドン、スチレン・マレイン酸共重合体塩、スチレン・アクリル酸共重合体塩等が挙げられる。これらの水溶性高分子化合物は単独使用でも２種類以上の併用でも良く、特に皮膜形成に富むゼラチンやポリビニルアルコールとその変性物が非画像部の親水性保持に好ましく選択される。かかる水溶性高分子化合物の配合量は画像形成層の全固形分量に対して０．５〜５０質量％が好ましい。 The image forming layer of the heat-sensitive lithographic printing plate of the present invention contains a water-soluble polymer compound. Examples of such water-soluble polymer compounds include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, starch and derivatives thereof, gelatin, casein, and sodium alginate. , Polyvinylpyrrolidone, styrene / maleic acid copolymer salt, styrene / acrylic acid copolymer salt, and the like. These water-soluble polymer compounds may be used alone or in combination of two or more, and gelatin, polyvinyl alcohol and modified products thereof, which are particularly rich in film formation, are preferably selected for maintaining the hydrophilicity of the non-image area. The amount of the water-soluble polymer compound is preferably 0.5 to 50% by mass with respect to the total solid content of the image forming layer.
また非画像部の耐水性及び機械的強度を向上させるため、画像形成層は前記水溶性高分子化合物の種類に応じて硬膜剤（耐水化剤）を含有することが好ましい。硬膜剤としては、メラミン樹脂、エポキシ樹脂、ポリイソシアネート化合物、アルデヒド化合物、シラン化合物、クロム明礬、ジビニルスルホン等、樹脂の架橋を促すことによって耐水性を付与するものを用いることができるが、特に好ましい硬膜剤はゼラチンの場合ジビニルスルホンが、ポリビニルアルコールの場合グリオキザールが好ましく用いられる。硬膜剤の配合量は全画像形成層が含有する水溶性高分子化合物の固形分量に対して、０．０１〜３０質量％とすることが好ましく、より好ましくは５〜３０質量％である。 In order to improve the water resistance and mechanical strength of the non-image area, the image forming layer preferably contains a hardening agent (waterproofing agent) according to the type of the water-soluble polymer compound. As the hardener, melamine resin, epoxy resin, polyisocyanate compound, aldehyde compound, silane compound, chromium alum, divinyl sulfone, etc., which can impart water resistance by promoting the crosslinking of the resin can be used. A preferable hardening agent is preferably divinyl sulfone in the case of gelatin, and glyoxal in the case of polyvinyl alcohol. The blending amount of the hardener is preferably 0.01 to 30% by mass, more preferably 5 to 30% by mass, based on the solid content of the water-soluble polymer compound contained in the entire image forming layer.
本発明の画像形成層には熱溶融性物質を含有することができ、耐刷性の観点からより、好ましい形態の１つである。含有する熱溶融性物質としては、融点が５０〜１５０℃の有機化合物であることが好ましく、熱溶融性物質の融点が５０℃未満では製造工程中に溶融してしまい印刷物の地汚れの原因となる場合があり、一方１５０℃を超えるとサーマルヘッド等の熱印加で溶融しにくく、親油性の発現が乏しい場合がある。好ましく使用される熱溶融性物質としては、例えば、カルナバワックス、マイクロクリスタリンワックス、パラフィンワックス、ポリエチレンワックスなどのワックス類、ラウリン酸、ステアリン酸、オレイン酸、パルミチン酸、ベヘン酸、モンタン酸などの脂肪酸、及びそのエステル、アミド類が挙げられ、その他、１−（１−ナフトキシ）−２−フェノキシエタン、１−（２−ナフトキシ）−４−フェノキシブタン、１−（２−イソプロピルフェノキシ）−２−（２−ナフトキシ）エタン、１−（４−メチルフェノキシ）−３−（２−ナフトキシ）プロパン、１−（２−メチルフェノキシ）−２−（２−ナフトキシ）エタン、１−（３−メチルフェノキシ）−２−（２−ナフトキシ）エタン、１−（２−ナフトキシ）−２−フェノキシエタン、１−（２−ナフトキシ）−６−フェノキシヘキサン、１−フェノキシ−２−（２−フェニルフェノキシ）エタン、１−（２−メチルフェノキシ）−２−（４−フェニルフェノキシ）エタン、１，４−ジフェノキシブタン、１，４−ビス（４−メチルフェノキシ）ブタン、１，２−ジ（３，４−ジメチルフェノキシ）エタン、１−フェノキシ−３−（４−フェニルフェノキシ）プロパン、１−（４−tert−ブチルフェノキシ）−２−フェノキシエタン、１，２−ジフェノキシエタン、１−（４−メチルフェノキシ）−２−フェノキシエタン、１−（２，３−ジメチルフェノキシ）−２−フェノキシエタン、１−（３，４−ジメチルフェノキシ）−２−フェノキシエタン、１−（４−エチルフェノキシ）−２−フェノキシエタン、１−（４−イソプロピルフェノキシ）−２−フェノキシエタン、１，２−ビス（２−メチルフェノキシ）エタン、１−（２−メチルフェノキシ）−２−（４−メチルフェノキシ）エタン、１−（４−tert−ブチルフェノキシ）−２−（２−メチルフェノキシ）エタン、１，２−ビス（３−メチルフェノキシ）エタン、１−（３−メチルフェノキシ）−２−（４−メチルフェノキシ）エタン、１−（４−エチルフェノキシ）−２−（３−メチルフェノキシ）エタン、１，２−ビス（４−メチルフェノキシ）エタン、１−（２，３−ジメチルフェノキシ）−２−（４−メチルフェノキシ）エタン、１−（２，５−ジメチルフェノキシ）−２−（４−メチルフェノキシ）エタン、フェノキシ酢酸−２−ナフチル、２−ナフトキシ酢酸−４−メチルフェニル、２−ナフトキシ酢酸−３−メチルフェニル、１−ベンジルオキシナフタレン、２−ベンジルオキシナフタレン、２−ｐ−クロロベンジルオキシナフタレン、２−ｐ−イソプロピルベンジルオキシナフタレン、２−ドデシルオキシナフタレン、２−デカノイルオキシナフタレン、２−ミリストイルオキシナフタレン、２−ｐ−tert−ブチルベンゾイルオキシナフタレン、２−ベンゾイルオキシナフタレン、２−ベンジルオキシ−３−Ｎ−（３−ドデシルオキシプロピル）カルバモイルナフタレン、２−ベンジルオキシ−３−Ｎ−オクチルカルバモイルナフタレン、２−ベンジルオキシ−３−ドデシルオキシカルボニルナフタレン、２−ベンジルオキシ−３−ｐ−tert−ブチルフェノキシカルボニルナフタレン、シュウ酸ジベンジル、シュウ酸ジ（ｐ−メチルベンジル）、シュウ酸ジ（ｐ−クロロベンジル）、シュウ酸ジ（ｍ−メチルベンジル）、シュウ酸ジ（ｐ−エチルベンジル）、シュウ酸ジ（ｐ−メトキシベンジル）、シュウ酸ビス（２−フェノキシエチル）、シュウ酸ビス（２−ｏ−クロロフェノキシエチル）、シュウ酸ビス（２−ｐ−クロロフェノキシエチル）、シュウ酸ビス（２−ｐ−エチルフェノキシエチル）、シュウ酸ビス（２−ｍ−メトキシフェノキシエチル）、シュウ酸ビス（２−ｐ−メトキシフェノキシエチル）、シュウ酸ビス（４−フェノキシブチル）、１，２−ジフェノキシメチルベンゼン、１，３−ジフェノキシメチルベンゼン、１，４−ジ（２−メチルフェノキシメチル）ベンゼン、１，４−ジ（３−メチルフェノキシメチル）ベンゼン、１，３−ジ（４−メチルフェノキシメチル）ベンゼン、１，３−ジ（２，４−ジメチルフェノキシメチル）ベンゼン、１，３−ジ（２，６−ジメチルフェノキシメチル）ベンゼン、１，４−ジ（２−クロロフェノキシメチル）ベンゼン、１，２−ジ（４−クロロフェノキシメチル）ベンゼン、１，３−ジ（４−クロロフェノキシメチル）ベンゼン、１，２−ジ（４−オクチルフェノキシメチル）ベンゼン、１，３−ジ（４−オクチルフェノキシメチル）ベンゼン、１，３−ジ（４−イソプロピルフェニルフェノキシメチル）ベンゼン、１，４−ジ（４−イソプロピルフェニルフェノキシメチル）ベンゼン等が挙げられる。これらは単独でも２種以上を併用して用いても良い。 The image forming layer of the present invention can contain a heat-meltable substance, which is one of preferred forms from the viewpoint of printing durability. The heat-melting substance to be contained is preferably an organic compound having a melting point of 50 to 150 ° C. If the melting point of the hot-melting substance is less than 50 ° C., it will melt during the production process and cause print stains. On the other hand, when the temperature exceeds 150 ° C., it is difficult to melt by applying heat from a thermal head or the like, and the expression of lipophilicity may be poor. Examples of the heat-meltable substance preferably used include waxes such as carnauba wax, microcrystalline wax, paraffin wax and polyethylene wax, and fatty acids such as lauric acid, stearic acid, oleic acid, palmitic acid, behenic acid, and montanic acid. , And esters and amides thereof, 1- (1-naphthoxy) -2-phenoxyethane, 1- (2-naphthoxy) -4-phenoxybutane, 1- (2-isopropylphenoxy) -2- (2-naphthoxy) ethane, 1- (4-methylphenoxy) -3- (2-naphthoxy) propane, 1- (2-methylphenoxy) -2- (2-naphthoxy) ethane, 1- (3-methylphenoxy) ) -2- (2-naphthoxy) ethane, 1- (2-naphthoxy) -2-phenoxye 1- (2-naphthoxy) -6-phenoxyhexane, 1-phenoxy-2- (2-phenylphenoxy) ethane, 1- (2-methylphenoxy) -2- (4-phenylphenoxy) ethane, 1, 4-diphenoxybutane, 1,4-bis (4-methylphenoxy) butane, 1,2-di (3,4-dimethylphenoxy) ethane, 1-phenoxy-3- (4-phenylphenoxy) propane, 1- (4-tert-Butylphenoxy) -2-phenoxyethane, 1,2-diphenoxyethane, 1- (4-methylphenoxy) -2-phenoxyethane, 1- (2,3-dimethylphenoxy) -2-phenoxy Ethane, 1- (3,4-dimethylphenoxy) -2-phenoxyethane, 1- (4-ethylphenoxy) -2-phenoxyethane, 1- (4- Sopropylphenoxy) -2-phenoxyethane, 1,2-bis (2-methylphenoxy) ethane, 1- (2-methylphenoxy) -2- (4-methylphenoxy) ethane, 1- (4-tert-butyl) Phenoxy) -2- (2-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 1- (3-methylphenoxy) -2- (4-methylphenoxy) ethane, 1- (4- Ethylphenoxy) -2- (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1- (2,3-dimethylphenoxy) -2- (4-methylphenoxy) ethane, 1- (2,5-dimethylphenoxy) -2- (4-methylphenoxy) ethane, phenoxyacetic acid-2-naphthyl, 2-naphthoxyacetic acid-4-methylphenyl, 2- Futoxyacetic acid-3-methylphenyl, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 2-p-chlorobenzyloxynaphthalene, 2-p-isopropylbenzyloxynaphthalene, 2-dodecyloxynaphthalene, 2-decanoyloxynaphthalene 2-myristoyloxynaphthalene, 2-p-tert-butylbenzoyloxynaphthalene, 2-benzoyloxynaphthalene, 2-benzyloxy-3-N- (3-dodecyloxypropyl) carbamoylnaphthalene, 2-benzyloxy-3- N-octylcarbamoylnaphthalene, 2-benzyloxy-3-dodecyloxycarbonylnaphthalene, 2-benzyloxy-3-p-tert-butylphenoxycarbonylnaphthalene, dibenzyl oxalate, di-oxalate (p-me Tilbenzyl), di (p-chlorobenzyl) oxalate, di (m-methylbenzyl) oxalate, di (p-ethylbenzyl) oxalate, di (p-methoxybenzyl) oxalate, bis (2-phenoxy oxalate) Ethyl), bis (2-o-chlorophenoxyethyl) oxalate, bis (2-p-chlorophenoxyethyl) oxalate, bis (2-p-ethylphenoxyethyl) oxalate, bis (2-m- Methoxyphenoxyethyl), bis (2-p-methoxyphenoxyethyl) oxalate, bis (4-phenoxybutyl) oxalate, 1,2-diphenoxymethylbenzene, 1,3-diphenoxymethylbenzene, 1,4- Di (2-methylphenoxymethyl) benzene, 1,4-di (3-methylphenoxymethyl) benzene, 1,3-di (4-methyl) Phenoxymethyl) benzene, 1,3-di (2,4-dimethylphenoxymethyl) benzene, 1,3-di (2,6-dimethylphenoxymethyl) benzene, 1,4-di (2-chlorophenoxymethyl) benzene 1,2-di (4-chlorophenoxymethyl) benzene, 1,3-di (4-chlorophenoxymethyl) benzene, 1,2-di (4-octylphenoxymethyl) benzene, 1,3-di (4 -Octylphenoxymethyl) benzene, 1,3-di (4-isopropylphenylphenoxymethyl) benzene, 1,4-di (4-isopropylphenylphenoxymethyl) benzene and the like. These may be used alone or in combination of two or more.
これらの熱溶融性物質は、常温で固体の物質であるが、熱による反応性を高めるために、微分散処理を行って使用されることが好ましい。微分散処理の方法は、一般に塗料製造時に用いられる湿式分散法であるロールミル、コロイドミル、ボールミル、アトライター、サンドミル等のビーズミル等を使用することができる。ビーズミルでは、ジルコニア、チタニア、アルミナ等のセラミックビーズや、クロム、スチール等の金属ビーズ、ガラスビーズ等が使用できる。分散粒径はメジアン径で０．１〜１．２μｍが望ましく、特に好ましくは０．３〜０．８μｍである。なお、メジアン径とは、粒子体の一つの集団の全体積を１００％として累積曲線を求めた時、累積曲線が５０％となる点の粒子径（累積平均径）であり、粒度分布を評価するパラメータの一つとしてレーザー回折／散乱式粒度分布測定装置ＬＡ９２０（（株）堀場製作所製）等を用いて測定することができる。 These heat-meltable substances are substances that are solid at normal temperature, but are preferably used after being subjected to fine dispersion treatment in order to increase the reactivity due to heat. As a fine dispersion treatment method, a bead mill such as a roll mill, a colloid mill, a ball mill, an attritor or a sand mill, which is a wet dispersion method generally used at the time of producing a paint, can be used. In the bead mill, ceramic beads such as zirconia, titania and alumina, metal beads such as chrome and steel, glass beads and the like can be used. The dispersed particle diameter is preferably from 0.1 to 1.2 μm in median diameter, particularly preferably from 0.3 to 0.8 μm. The median diameter is the particle diameter (cumulative average diameter) at which the cumulative curve becomes 50% when the total curve of one population of particles is 100%, and the particle size distribution is evaluated. As one of the parameters to be measured, it can be measured using a laser diffraction / scattering particle size distribution measuring apparatus LA920 (manufactured by Horiba, Ltd.) or the like.
本発明の感熱型平版印刷版では、視認性確保のため一般的な感熱記録紙、感圧記録紙に使用されるフェノール誘導体や芳香族カルボン酸誘導体等の顕色剤や発色剤（電子供与性染料前駆体）を含有させることができる。 In the heat-sensitive lithographic printing plate of the present invention, a developer or a color former (electron donating property) such as a phenol derivative or an aromatic carboxylic acid derivative used for general heat-sensitive recording paper and pressure-sensitive recording paper for ensuring visibility. Dye precursor).
顕色剤の具体的な例としては、４−クミルフェノール、ヒドロキノンモノベンジルエーテル、４，４′−イソプロピリデンジフェノール、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、４，４′−ジヒドロキシジフェニル−２，２−ブタン、４，４′−ジヒドロキシジフェニルメタン、２，２−ビス（４−ヒドロキシフェニル）−４−メチルペンタン、２，２−ビス（４−ヒドロキシフェニル）ヘプタン、ビス（４−ヒドロキシフェニルチオエトキシ）メタン、１，５−ジ（４−ヒドロキシフェニルチオ）−３−オキサペンタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１，４−ビス〔α−メチル−α−（４′−ヒドロキシフェニル）エチル〕ベンゼン、１，３−ビス〔α−メチル−α−（４′−ヒドロキシフェニル）エチル〕ベンゼン、４，４′−ジヒドロキシジフェニルスルフィド、ジ（４−ヒドロキシ−３−メチルフェニル）スルフィン、４−ヒドロキシ−４′−メチルジフェニルスルホン、４−ヒドロキシ−４′−イソプロポキシジフェニルスルホン、２，４′−ジヒドロキシジフェニルスルホン、４，４′−ジヒドロキシジフェニルスルホン、ビス（３−アリル−４−ヒドロキシフェニル）スルホン、４−ヒドロキシフェニル−４′−ベンジルオキシフェニルスルホン、４−ヒドロキシ−３′，４′−テトラメチレンビフェニルスルホン、３，４−ジヒドロキシフェニル−ｐ−トリルスルホン、４，４′−ジヒドロキシベンゾフェノン、４−ヒドロキシ安息香酸ベンジル、Ｎ，Ｎ′−ジ−ｍ−クロロフェニルチオ尿素、Ｎ−（フェノキシエチル）−４−ヒドロキシフェニルスルホンアミド等のフェノール性化合物、４−〔３−（ｐ−トリルスルホニル）プロピルオキシ〕サリチル酸亜鉛、４−〔２−（ｐ−メトキシフェノキシ）エチルオキシ〕サリチル酸亜鉛、５−〔ｐ−（２−ｐ−メトキシフェノキシエトキシ）クミル〕サリチル酸亜鉛、ｐ−クロロ安息香酸亜鉛等の芳香族カルボン酸の亜鉛塩、更にはチオシアン酸亜鉛のアンチピリン錯体等の有機酸性物質等が例示される。 Specific examples of the developer include 4-cumylphenol, hydroquinone monobenzyl ether, 4,4'-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'- Dihydroxydiphenyl-2,2-butane, 4,4′-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) heptane, bis (4 -Hydroxyphenylthioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [α -Methyl-α- (4'-hydroxyphenyl) ethyl] benzene, 1,3-bis [α-methyl-α- (4'-hydro Cyphenyl) ethyl] benzene, 4,4'-dihydroxydiphenyl sulfide, di (4-hydroxy-3-methylphenyl) sulfine, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone 2,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-hydroxy-3 ', 4'-tetramethylenebiphenylsulfone, 3,4-dihydroxyphenyl-p-tolylsulfone, 4,4'-dihydroxybenzophenone, benzyl 4-hydroxybenzoate, N, N'-di-m-chlorophenylthiourea, N- (phenoxy Phenolic compounds such as (ciethyl) -4-hydroxyphenylsulfonamide, zinc 4- [3- (p-tolylsulfonyl) propyloxy] salicylate, 4- [2- (p-methoxyphenoxy) ethyloxy] zinc salicylate, 5- [P- (2-p-methoxyphenoxyethoxy) cumyl] Zinc salts of aromatic carboxylic acids such as zinc salicylate and zinc p-chlorobenzoate, and organic acidic substances such as antipyrine complexes of zinc thiocyanate The
また、発色剤（電子供与性染料前駆体）の具体的な例としては、（１）トリアリールメタン系化合物として３，３′−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド（クリスタル・バイオレット・ラクトン）、３，３′−ビス（ｐ−ジメチルアミノフェニル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（１，２−ジメチルインドール−３−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（２−メチルインドール−３−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（２−フェニルインドール−３−イル）フタリド、３，３−ビス（１，２−ジメチルインドール−３−イル）−５−ジメチルアミノフタリド、３，３−ビス（１，２−ジメチルインドール−３−イル）−６−ジメチルアミノフタリド、３，３−ビス（９−エチルカルバゾール−３−イル）−５−ジメチルアミノフタリド、３，３−ビス（２−フェニルインドール−３−イル）−５−ジメチルアミノフタリド、３−ｐ−ジメチルアミノフェニル−３−（１−メチルピロール−２−イル）−６−ジメチル−アミノフタリド等：（２）ジフェニルメタン系化合物として、４，４′−ビス−ジメチルアミノベンズヒドリンベンジルエーテル、Ｎ−ハロフェニルロイコオーラミン、Ｎ−２，４，５−トリクロロフェニルロイコオーラミン等：（３）キサンテン系化合物として、ローダミンＢ−アニリノラクタム、ローダミンＢ−ｐ−ニトロアニリノラクタム、ローダミンＢ−ｐ−クロロアニリノラクタム、３−ジエチルアミノ−７−ジベンジルアミノフルオラン、３−ジエチルアミノ−７−オクチルアミノフルオラン、３−ジエチルアミノ−７−フェニルフルオラン、３−ジエチルアミノ−７−（３，４−ジクロロアニリノ）フルオラン、３−ジエチルアミノ−７−（２−クロロアニリノ）フルオラン、３−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−ピペリジノ−６−メチル−７−アニリノフルオラン、３−エチル−トリルアミノ−６−メチル−７−アニリノフルオラン、３−エチル−トリルアミノ−６−メチル−７−フェニチルフルオラン、３−ジエチルアミノ−７−（４−ニトロアニリノ）フルオラン等：（４）チアジン系化合物として、ベンゾイルロイコメチレンブルー、ｐ−ニトロベンゾイルロイコメチレンブルー等：（５）スピロ系化合物として、３−メチル−スピロ−ジナフトピラン、３−エチル−スピロ−ジナフトピラン、３，３′−ジクロロ−スピロ−ジナフトピラン、３−ベンジル−スピロ−ジナフトピラン、３−メチルナフト−（３−メトキシ−ベンゾ）−スピロピラン、３−プロピル−スピロ−ジベンゾピラン等が挙げられる。また、これらは単独でも２種以上を併用して用いても良い。 Specific examples of color formers (electron-donating dye precursors) include (1) 3,3′-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (1) as a triarylmethane compound ( Crystal violet lactone), 3,3′-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (P-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3- Bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethyl Ruaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3- p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like: (2) 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N -Halophenyl leucooramine, N-2,4,5-trichlorophenyl leucooramine, etc .: (3) As xanthene compounds, rhodamine B-anilinolactam, rhodamine Bp-nitroanilinolactam, rhodamine B- p-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, -Diethylamino-7-octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3-diethylamino-7- (3,4-dichloroanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-ethyl- Tolylamino-6-methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilino) fluorane, etc .: (4) thiazine compounds As benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue Etc .: (5) Examples of spiro compounds include 3-methyl-spiro-dinaphthopyrans, 3-ethyl-spiro-dinaphthopyrans, 3,3′-dichloro-spiro-dinaphthopyrans, 3-benzyl-spiro-dinaphthopyrans, 3-methylnaphtho- ( 3-methoxy-benzo) -spiropyran, 3-propyl-spiro-dibenzopyran and the like. These may be used alone or in combination of two or more.
更に、本発明では光熱変換物質を配合することもできる。光熱変換剤を用いることで、サーマルヘッドだけでなく赤外線レーザー等の活性光による書き込みも可能となる。光熱変換物質の例としては、効率よく光を吸収し熱に変換する材料が好ましく、使用する光源によって異なるが、例えば近赤外光を放出する半導体レーザーを光源として使用する場合には、近赤外に吸収帯を有する近赤外光吸収剤が好ましく、例えば、カーボンブラック、シアニン系色素、ポリメチン系色素、アズレニウム系色素、スクワリウム系色素、チオピリリウム系色素、ナフトキノン系色素、アントラキノン系色素等の有機化合物や、フタロシアニン系、アゾ系、チオアミド系の有機金属錯体、鉄粉、黒鉛粉末、酸化鉄粉、酸化鉛、酸化銀、酸化クロム、硫化鉄、硫化クロム等の金属化合物類等が挙げられる。 Furthermore, in the present invention, a photothermal conversion substance can be blended. By using a photothermal conversion agent, writing with active light such as an infrared laser as well as a thermal head is possible. As an example of the photothermal conversion substance, a material that efficiently absorbs light and converts it into heat is preferable. Depending on the light source used, for example, when a semiconductor laser emitting near infrared light is used as the light source, Near-infrared light absorbers having an absorption band outside are preferable, for example, organic materials such as carbon black, cyanine dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes Examples thereof include metal compounds such as compounds, phthalocyanine-based, azo-based, and thioamide-based organometallic complexes, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide.
本発明の感熱型平版印刷版が有する画像形成層は、画像部の耐刷性、非画像部の耐水性及び機械的強度の観点から、乾燥固形分として０．５〜３０ｇ／ｍ２であることが好ましい。 The image-forming layer of the heat-sensitive lithographic printing plate of the present invention has a dry solid content of 0.5 to 30 g / m 2 from the viewpoints of printing durability of image areas, water resistance of non-image areas and mechanical strength. It is preferable.
本発明の感熱型平版印刷版に用いる耐水性支持体としては、プラスチックフィルム、樹脂被覆紙、耐水紙等が使用できる。具体的にはポリエチレン、ポリプロピレン等のポリオレフィン、ポリエーテルサルフォン、ポリエステル、ポリ（メタ）アクリレート、ポリカーボネート、ポリアミド及びポリ塩化ビニル等のプラスチックフィルムとこれらプラスチックを表面にラミネートやコーティングした樹脂被覆紙、メラミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、エポキシ化ポリアミド樹脂等の湿潤紙力剤によって耐水化された紙を好適に用いることができる。 As the water-resistant support used in the heat-sensitive lithographic printing plate of the present invention, a plastic film, resin-coated paper, water-resistant paper and the like can be used. Specifically, plastic films such as polyolefins such as polyethylene and polypropylene, polyethersulfone, polyester, poly (meth) acrylate, polycarbonate, polyamide, and polyvinyl chloride, and resin-coated paper with these plastics laminated or coated on the surface, melamine Paper that has been water-resistant with a wet paper strength agent such as formaldehyde resin, urea formaldehyde resin, or epoxidized polyamide resin can be suitably used.
次に、上述した本発明の感熱型平版印刷版を用いた製版方法について説明する。本発明の感熱型平版印刷版は、感熱型の画像形成層を有するため、画像形成層中に光熱変換物質を配合することにより例えば７６０ｎｍから１２００ｎｍの赤外光を含む光を照射することで画像部を形成することが可能であり、更に赤外線を放射する固体レーザー及び半導体レーザーにより画像部を形成することが好ましい。特にレーザー露光によれば、コンピューターのデジタル情報から直接所望の画像様の記録が可能となる。またサーマルヘッドやヒートブロック等により画像形成層を直接熱により描画し画像部を形成することも可能であるが、サーマルヘッドによればコンピューターのデジタル情報から直接所望の画像様の記録が可能となる。 Next, a plate making method using the above-described heat-sensitive lithographic printing plate of the present invention will be described. Since the heat-sensitive lithographic printing plate of the present invention has a heat-sensitive image-forming layer, an image is formed by irradiating light containing infrared light of, for example, 760 nm to 1200 nm by blending a photothermal conversion substance in the image-forming layer. The image portion can be formed by a solid-state laser and a semiconductor laser emitting infrared rays. In particular, laser exposure enables desired image-like recording directly from digital information of a computer. It is also possible to draw an image forming layer directly by heat with a thermal head or a heat block to form an image portion. However, the thermal head enables recording of a desired image directly from digital information of a computer. .
サーマルヘッドを使用する場合は、厚膜または薄膜のラインヘッドを用いたラインプリンタや薄膜のシリアルヘッドを用いたシリアルプリンタ等が使用できる。記録エネルギー密度は、１０〜１００ｍＪ／ｍｍ２であることが好ましく、また比較的高品質な出力画像を得るためにはヘッドの画像記録密度が３００ｄｐｉ以上であることが好ましい。 When a thermal head is used, a line printer using a thick film or thin film line head, a serial printer using a thin film serial head, or the like can be used. The recording energy density is preferably 10 to 100 mJ / mm 2 , and the head image recording density is preferably 300 dpi or more in order to obtain a relatively high quality output image.
本発明の感熱型平版印刷版は、従来の平版印刷版で好適に用いられてきた任意公知の表面処理剤でインキ受容性に変換ないしは受容性を改善させることも可能である。印刷方法、あるいは使用する不感脂化液、給湿液等は普通に良く知られた方法により施すこともできる。 The heat-sensitive lithographic printing plate of the present invention can be converted into ink receptivity or improved receptivity with any known surface treatment agent that has been suitably used in conventional lithographic printing plates. The printing method, or the desensitizing liquid and the moisturizing liquid to be used can be applied by a generally well-known method.
以下、実施例を用いて本発明を説明するが、無論この記述により本発明が限定されるものではない。なお、以下の記述中、％や部は特に示さない限り質量比を示すものである。 EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited by this description. In the following description, “%” and “part” indicate mass ratio unless otherwise specified.
（実施例１）
両面にラミネート加工が施された厚さ約１８０μｍのポリエチレン被覆紙の片面に、下記画像形成層塗工液ａ処方で表１の如く１層目（画像形成層（Ａ））、２層目（画像形成層（Ｂ））の塗工液を作製し、スライドホッパーコーティング法により湿分塗布量１層目３０ｇ／ｍ２、２層目１０ｇ／ｍ２となるように同時塗布した後、乾燥し画像形成層を作製し、サンプルＮｏ．１〜１３の感熱型平版印刷版を得た。
＜画像形成層塗工液ａ＞
水溶性高分子化合物
ゼラチン Ｘ ｋｇ
熱可塑性物質
カルボキシル化ＳＢＲ樹脂：ラックスター７１３２Ｃ 固形分として Ｙ ｋｇ
（ＤＩＣ（株）製、固形分４５％水分散体）
界面活性剤
ＮＩＫＫＯＬ ＯＴＰ−７５ 固形分として ０．２５ｇ
（日光ケミカルズ（株）製）
硬膜剤
１，３−ビス（ビニルスルホニル）−２−プロパノール 固形分として ０．１５ｋｇ
発色剤混合スラリー 固形分として ２．１ｋｇ
水で全量を５０ｋｇに調製した。
Example 1
As shown in Table 1, the first layer (image forming layer (A)) and the second layer (as shown in Table 1) are coated on one side of a polyethylene-coated paper having a thickness of about 180 μm and laminated on both sides. to prepare a coating liquid of the image forming layer (B)), were simultaneously coated to a wet coating weight first layer 30 g / m 2, 2-layer 10 g / m 2 by a slide hopper coating method, dried An image forming layer was prepared and sample no. 1 to 13 thermosensitive lithographic printing plates were obtained.
<Image forming layer coating solution a>
Water-soluble polymer compound Gelatin X kg
Thermoplastic material Carboxylated SBR resin: Luck Star 7132C Y kg as solid content
(DIC Corporation, 45% solid content aqueous dispersion)
Surfactant NIKKOL OTP-75 0.25 g as solid content
(Nikko Chemicals Co., Ltd.)
Hardener 1,3-bis (vinylsulfonyl) -2-propanol 0.15 kg as solid content
Coloring agent mixed slurry 2.1kg as solid content
The total amount was adjusted to 50 kg with water.
上記画像形成層塗工液に用いる発色剤混合スラリーは予め下記構成により調製した。
＜発色剤混合スラリーの調製＞
材料ａ：１，２−ビス（３−メチルフェノキシ）エタン
（三光（株）製：ＫＳ−２３２）
材料ｂ：４−ヒドロキシ−４′−イソプロポキシジフェニルスルホン
（日本曹達（株）製：Ｄ−８）
材料ｃ：３−ジブチルアミノ−６−メチル−７−アニリノフルオラン
（山本化成（株）製：ＯＤＢ２）
The color former mixed slurry used for the image forming layer coating solution was prepared in advance with the following constitution.
<Preparation of color former mixed slurry>
Material a: 1,2-bis (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS-232)
Material b: 4-hydroxy-4'-isopropoxy diphenyl sulfone (Nippon Soda Co., Ltd. product: D-8)
Material c: 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd .: ODB2)
材料ａ、ｂ、ｃを予め、個々に小型ダイノーミル（ビーズミル）でジルコニアビーズを用いて任意の粒径まで微分散処理を施し、固形分濃度約３０％に調製された分散液をそれぞれ作製し、分散液ａ、分散液ｂ、分散液ｃとした。分散液ａ、ｂ各々３部に対し、分散液ｃ１部を常温下で混合することで発色剤混合スラリーを調製した。 The materials a, b, and c are each preliminarily dispersed in a small dyno mill (bead mill) using a zirconia bead to an arbitrary particle size, thereby preparing dispersions each having a solid content concentration of about 30%, Dispersion a, dispersion b, and dispersion c were used. A color former mixed slurry was prepared by mixing 1 part of the dispersion c at room temperature with 3 parts of each of the dispersions a and b.
また比較として、両面にラミネート加工が施された厚さ約１８０μｍのポリエチレン被覆紙の片面に、下記画像形成層塗工液ｂ処方の如く作製した塗工液を、スライドホッパーコーティング法により湿分塗布量６０ｇ／ｍ２で塗布し乾燥して、サンプルＮｏ．１４の感熱型平版印刷版を得た。 Also, as a comparison, a coating liquid prepared as shown in the following image forming layer coating liquid b formulation was applied to one side of a polyethylene-coated paper with a thickness of about 180 μm and laminated on both sides by the slide hopper coating method. The sample was applied in an amount of 60 g / m 2 and dried. 14 heat-sensitive lithographic printing plates were obtained.
＜画像形成層塗工液ｂ＞
水溶性高分子化合物
ゼラチン １．２５ｋｇ
熱可塑性物質
カルボキシル化ＳＢＲ樹脂：ラックスター７１３２Ｃ 固形分として １．８ｋｇ
（ＤＩＣ（株）製、固形分４５％水分散体）
界面活性剤
ＮＩＫＫＯＬ ＯＴＰ−７５ 固形分として ０．２５ｇ
（日光ケミカルズ（株）製）
硬膜剤
１，３−ビス（ビニルスルホニル）−２−プロパノール 固形分として ０．１５ｋｇ
発色剤混合スラリー 固形分として ２．１ｋｇ
水で全量を５０ｋｇに調製した。
<Image forming layer coating solution b>
Water-soluble polymer compound gelatin 1.25kg
Thermoplastic substance Carboxylated SBR resin: Luck Star 7132C 1.8kg as solid content
(DIC Corporation, 45% solid content aqueous dispersion)
Surfactant NIKKOL OTP-75 0.25 g as solid content
(Nikko Chemicals Co., Ltd.)
Hardener 1,3-bis (vinylsulfonyl) -2-propanol 0.15 kg as solid content
Coloring agent mixed slurry 2.1kg as solid content
The total amount was adjusted to 50 kg with water.
このように作製した感熱型平版印刷版に、ダイレクトサーマルプリンタ（東芝テック（株）製バーコードプリンタＢ−４３３：ライン型サーマルヘッド３００ｄｐｉ）のテスト印字モード（印刷速度２インチ／ｓｅｃ、印加エネルギー１８．６ｍＪ／ｍｍ２）で画像を記録し、印刷版を作製した。 A test printing mode (printing speed 2 inches / sec, applied energy 18) of a direct thermal printer (barcode printer B-433 manufactured by TOSHIBA TEC CO., LTD .: line type thermal head 300 dpi) is applied to the heat-sensitive lithographic printing plate thus prepared. .6 mJ / mm 2 ), an image was recorded, and a printing plate was produced.
印刷評価として耐刷性については、印刷機はＨＡＭＡＤＡＨ２３４Ｃ（ハマダ印刷機（株）製オフセット印刷機の商標）を使用し、インキはニューチャンピオンＦグロス墨Ｎ（ＤＩＣ（株）製の商標）、給湿液はＳＬＭ−ＯＤ（三菱製紙（株）製給湿液の商標）の１２％水溶液を使用し、印刷開始前に給湿液にて版面をくまなく拭き与えた後、強制条件で評価をするために、版胴と版の間に０．１ｍｍのゲージフィルムを挟み、印圧を上げた状態で印刷を開始した。印刷物の画像に欠落を生じ印刷できなくなった枚数を下記評価基準で評価した。
＜耐刷性＞
◎：５，０００枚以上
○：３，０００〜５，０００枚未満
△：１，０００〜３，０００枚未満
×：１，０００枚未満
結果を表２に示す。
As for printing durability, as for printing durability, HAMADAH234C (trademark of offset printing machine manufactured by Hamada Printing Co., Ltd.) is used as a printing machine, and ink is New Champion F Gloss Sumi N (trademark manufactured by DIC Corporation), supply. The dampening solution uses a 12% aqueous solution of SLM-OD (trademark of dampening solution manufactured by Mitsubishi Paper Industries Co., Ltd.). Before starting printing, wipe the plate surface thoroughly with dampening solution, and then evaluate under forced conditions. In order to achieve this, printing was started with a 0.1 mm gauge film sandwiched between the plate cylinder and the plate and the printing pressure increased. The number of printed images that were missing and could not be printed was evaluated according to the following evaluation criteria.
<Print durability>
A: 5,000 or more B: 3,000 to less than 5,000 B: 1,000 to less than 3,000 x: Less than 1,000 results are shown in Table 2.
保水性（地汚れ性）についての印刷評価は、印刷機はＲｙｏｂｉ３２００ＣＤ（リョービイマジクス（株）製の商標）を使用し、インキはニューチャンピオン紫６８Ｎ（ＤＩＣ（株）製の商標）、給湿液はＳＬＭ−ＯＤ（三菱製紙（株）製給湿液の商標）２％水溶液を使用し印刷開始前に給湿液にて版面をくまなく拭き与えた後印刷を開始した。印刷物の非画像部に汚れ（地汚れ）が発生した枚数を下記評価基準で評価した。
＜地汚れ性＞
◎：２，０００枚以上
○：１，５００〜２，０００枚未満
△：１，０００〜１，５００枚未満
×：１，０００枚未満
結果を表２に示す。
For printing evaluation of water retention (soil stain), the printing press uses Ryobi 3200CD (trademark made by Ryobi Imagics Co., Ltd.), the ink is New Champion Purple 68N (trademark made by DIC Co., Ltd.), humidification The liquid used was a 2% aqueous solution of SLM-OD (trademark of humidifying liquid manufactured by Mitsubishi Paper Industries Co., Ltd.), and printing was started after wiping the entire plate surface with the humidifying liquid before starting printing. The number of stains (background stains) generated on the non-image area of the printed material was evaluated according to the following evaluation criteria.
<Soil dirt>
A: More than 2,000 sheets O: 1,500 to less than 2,000 sheets Δ: 1,000 to less than 1,500 sheets ×: Less than 1,000 sheets The results are shown in Table 2.
表２に示す結果から判るように、本発明は比較例と比べて十分な耐刷性を保持しながら、且つ保水性が改善された感熱型平版印刷版であることが判る。 As can be seen from the results shown in Table 2, it can be seen that the present invention is a heat-sensitive lithographic printing plate with improved water retention while maintaining sufficient printing durability as compared with the comparative example.
（実施例２）
両面にラミネート加工が施された厚さ約１８０μｍのポリエチレン被覆紙の片面に、下記画像形成層塗工液ｃ処方で表３の如く１層目の塗工液を作製し、スライドホッパーコーティング法により湿分塗布量２０ｇ／ｍ２で塗布し乾燥後、更に画像形成層塗工液ｃ処方で表３の如く２層目の塗工液を作製し、スライドホッパーコーティング法により湿分塗布量２０ｇ／ｍ２で塗布、乾燥し、更に画像形成層塗工液ｃ処方で表３の如く３層目の塗工液を作製し、スライドホッパーコーティング法により湿分塗布量２０ｇ／ｍ２で塗布、乾燥して画像形成層を作製し、サンプルＮｏ．１５〜１８の感熱型平版印刷版を得た。このとき使用した発色剤混合スラリーは、前記したサンプルＮｏ．１のものと同じものを使用した。比較として、前記サンプルＮｏ．１４の感熱型平版印刷版を使用した。このように作製した感熱型平版印刷版を、実施例１と同様にして印刷・評価を行った。結果を表４に示す。
＜画像形成層塗工液ｃ＞
水溶性高分子化合物
ゼラチン Ｘ ｋｇ
熱可塑性物質
カルボキシル化ＳＢＲ樹脂：ラックスター７１３２Ｃ 固形分として Ｙ ｋｇ
（ＤＩＣ（株）製、固形分４５％水分散体）
熱溶融物質
モンタン酸エステルワックス：ハイドリンＪ−５３７ 固形分として ０．４５ｋｇ
（中京油脂(株)製、固形分３０％水分散体）
界面活性剤
ＮＩＫＫＯＬ ＯＴＰ−７５ 固形分として ０．２５ｇ
（日光ケミカルズ（株）製
硬膜剤
１，３−ビス（ビニルスルホニル）−２−プロパノール 固形分として ０．１５ｋｇ
発色剤混合スラリー 固形分として ２．１ｋｇ
水で全量を５０ｋｇに調製した。
(Example 2)
On one side of a polyethylene-coated paper with a thickness of about 180 μm that has been laminated on both sides, the first layer coating solution is prepared as shown in Table 3 with the following image-forming layer coating solution c formulation, and the slide hopper coating method is used. After applying and drying at a moisture application amount of 20 g / m 2 , a coating solution for the second layer as shown in Table 3 was prepared according to the image forming layer coating solution c formulation, and the moisture application amount was 20 g / m by the slide hopper coating method. Apply and dry at m 2 , and then prepare the third layer coating liquid as shown in Table 3 with the image forming layer coating liquid c formulation, and apply and dry at a moisture application amount of 20 g / m 2 by the slide hopper coating method. As a result, an image forming layer was prepared. 15-18 thermosensitive lithographic printing plates were obtained. The color former mixed slurry used at this time was the sample No. described above. The same one was used. For comparison, the sample No. Fourteen thermosensitive lithographic printing plates were used. The thus produced thermosensitive lithographic printing plate was printed and evaluated in the same manner as in Example 1. The results are shown in Table 4.
<Image forming layer coating solution c>
Water-soluble polymer compound Gelatin X kg
Thermoplastic material Carboxylated SBR resin: Luck Star 7132C Y kg as solid content
(DIC Corporation, 45% solid content aqueous dispersion)
Hot melted material Montanate wax: Hydrin J-537 0.45kg as solid content
(Manufactured by Chukyo Yushi Co., Ltd., 30% solid dispersion in water)
Surfactant NIKKOL OTP-75 0.25 g as solid content
(Hardener 1,3-bis (vinylsulfonyl) -2-propanol manufactured by Nikko Chemicals Co., Ltd. 0.15 kg as solid content
Coloring agent mixed slurry 2.1kg as solid content
The total amount was adjusted to 50 kg with water.
表４に示す結果から判るように、本発明は比較例と比べて十分な耐刷性を保持しながら、且つ保水性が改善された感熱型平版印刷版であることが判る。 As can be seen from the results shown in Table 4, it can be seen that the present invention is a heat-sensitive lithographic printing plate having a sufficient printing durability and improved water retention as compared with the comparative example.
Claims (2)
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| JP2009244670A JP5302848B2 (en) | 2009-10-23 | 2009-10-23 | Thermal lithographic printing plate |
| PCT/JP2010/066753 WO2011048912A1 (en) | 2009-10-23 | 2010-09-28 | Heat-sensitive lithographic printing plate and printing method thereof |
| CN201080047759.5A CN102712202B (en) | 2009-10-23 | 2010-09-28 | Thermosensitive type lithographic plate and printing process thereof |
| DE112010004234.9T DE112010004234B4 (en) | 2009-10-23 | 2010-09-28 | Thermosensitive lithographic printing plate and its printing process |
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