JP5165197B2 - Planographic printing plate disposal and method for producing the same - Google Patents
Planographic printing plate disposal and method for producing the same Download PDFInfo
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Description
本発明は、平版印刷版用捨版およびその製造方法に関する。 The present invention relates to lithographic printing plate discarding and a method for producing the same.
多色印刷に使用される平版印刷用捨版について、粗面化処理したアルミニウム板上に水溶性樹脂からなる保護膜を設けてなる捨版が開示されている（例えば、特許文献１を参照。）。しかしながら、このような水溶性樹脂のみからなる保護膜が塗布された捨版は、印刷開始時に、不必要に付着したインキを完全に除去するために必要な印刷枚数（損紙枚数）が増大する欠点を有しており、また、高温高湿下で長期保存された場合には、インキを受け付けやすくなり、汚れの原因ともなる。これは、水溶性樹脂である保護膜が厚く塗られたり、あるいは長期保存したために、湿し水への溶解性が劣化するためと考えられる。 A lithographic printing plate used for multicolor printing has been disclosed in which a protective film made of a water-soluble resin is provided on a roughened aluminum plate (see, for example, Patent Document 1). ). However, discarding with such a protective film made of only a water-soluble resin increases the number of printed sheets (number of damaged paper sheets) required to completely remove unnecessary ink at the start of printing. In addition, when stored for a long period of time under high temperature and high humidity, it becomes easier to accept the ink, which also causes stains. This is presumably because the protective film, which is a water-soluble resin, is thickly coated or stored for a long period of time, so that the solubility in dampening water deteriorates.
また、親水性表面を有する金属支持体上に水溶性化合物の下塗層および水不溶性の非感光性樹脂層が設けられた捨版（例えば、特許文献２を参照。）、親水性表面を有する金属支持体上に水溶性化合物の下塗層および表面がマット化された水不溶性の非感光性樹脂層が設けられた捨版（例えば、特許文献３を参照。）が提案されている。しかしながらこのような捨版を作るには、少なくとも２または３回以上の塗布工程を行わなければならない。このため、このような捨版は、製造効率が悪く、安価に製造できない欠点がある。また、印刷時には、非感光性樹脂層を現像液等のアルカリ水溶液で除去しなければならず、現像液の疲労を早める等の問題点を有している。
更に、親水性表面を有する金属支持体上に水溶性樹脂が塗布乾燥された版材を水または水溶液で該水溶性樹脂を溶出させる捨版の製造方法並びに該捨版を用いた平版印刷方法が記載されている（例えば、特許文献４を参照。）。しかしながら、この方法は、溶出処理工程を１つ増やすので手間のかかる方法でもある。
Further, there is provided a method for producing a plate for dissolving a water-soluble resin with water or an aqueous solution and a planographic printing method using the plate for which a water-soluble resin is coated and dried on a metal support having a hydrophilic surface. (For example, see Patent Document 4). However, this method is also a time-consuming method because one elution treatment step is added.
本発明は、たとえ長期保存した場合でも、印刷汚れが発生せず、損紙枚数も大幅に少なく、また、高温高湿下で保存された場合でも表面のタック性が少なく、製版時には水または現像液等の水溶液で溶出処理をしなくても製造できる平版印刷用捨版を提供し、また、合紙なしで積み重ねた場合でも、版同士の接着やキズ等が発生しづらい捨版の積層体を製造する方法を提供することを目的とする。 The present invention does not cause printing stains even when stored for a long period of time, and the number of lost paper sheets is greatly reduced. Further, even when stored under high temperature and high humidity, the surface has little tackiness, and water or development is performed during plate making. Provides a lithographic printing plate that can be produced without an elution treatment with an aqueous solution such as a liquid. Also, even when stacked without interleaving paper, it is difficult to cause adhesion and scratches between plates. An object of the present invention is to provide a method of producing
本発明の１つの側面によると、金属支持体と、支持体の表面上に設けられた保護層であって、アクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α，β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩を含む処理液を塗布、乾燥してなる保護層とのみを備えた平版印刷用捨版が提供され、更に、表面がマット化された平版印刷用捨版が提供される。また、本発明の他の側面によると、金属支持体に、アクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α，β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩を含む処理液を塗布するステップと、該処理液を乾燥させて保護層を得るステップと、さらに前記保護層の表面をマット化させるステップを含む、金属支持体と該金属支持体の表面上に設けられた保護層とのみを備えた平版印刷用捨版の製造方法が提供される。更に、このように製造された平版印刷用捨版を合紙なしで積層した平版印刷用捨版積層体が提供される。 According to one aspect of the present invention, a metal support and a protective layer provided on the surface of the support, the acrylamide being 20 to 90 mol%, acrylonitrile 5 to 60 mol%, α, β-unsaturated carboxylic acid A lithographic printing plate provided only with a protective layer formed by applying and drying a treatment liquid containing an alkali metal salt of a copolymer consisting of 1 to 60 mol% of an acid, and the surface thereof was matted A lithographic printing plate is provided. According to another aspect of the present invention, an alkali of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol% is provided on the metal support. applying a treatment liquid containing a metal salt, a step Ru obtain a protective layer by drying the treatment liquid, comprising the step of further matted surface of the protective layer, of the metal support and the metal support A method for producing a planographic printing plate comprising only a protective layer provided on the surface is provided. Furthermore, a lithographic printing plate stack in which the lithographic printing plates manufactured in this way are stacked without interleaf is provided.
本発明の平版印刷用捨版は、アクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α,β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩を含有する処理液が塗布されており、塗膜中にアクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α,β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩に由来する化合物が存在している。アクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α,β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩は、金属支持体、特にアルミニウム板の表面の保護膜として働き、表面の酸化を防止する役目を有する。更に、高温高湿下で長期保存された場合でも、表面のタック性（表面のベト付き）が非常に少なく、合紙が無い場合でも版同士が付着するようなことなく、又、作用は明確でないが、長期保存して後で印刷機にかけても、湿し水を受け付けやすく、印刷時の汚れが発生しない。 The lithographic printing plate of the present invention is a treatment containing an alkali metal salt of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol%. The solution is applied and is derived from an alkali metal salt of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol% in the coating film. The compound is present. An alkali metal salt of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol% is a protective film on the surface of a metal support, particularly an aluminum plate. And has the role of preventing surface oxidation. Furthermore, even when stored for a long time under high temperature and high humidity, the surface tackiness (with surface stickiness) is very small, and even if there is no interleaf, the plates do not adhere to each other, and the action is clear However, even if it is stored for a long time and applied to a printing machine later, it is easy to receive dampening water, and stains during printing do not occur.
また、本発明の平版印刷用捨版は、単なる１層のみ、あるいは２回塗布であるので、製造効率が良く、塗布された膜について水または現像液等の水溶液で溶出処理等の工程を行ってもよいが、行わなくても印刷機にセットすることができるので、印刷に使用するＰＳ版と同じ作業で捨版を製造することが出来る等の長所を有している。
また、積層体として積み重ね、長期保存された場合や高温、高湿下で保管された場合でも、版同士の接着等が発生しづらく、印刷時での地汚れや損紙枚数も少ない等の長所を有している。
Further, since the lithographic printing plate of the present invention is applied only by one layer or twice, the production efficiency is good, and the applied film is subjected to a process such as elution treatment with an aqueous solution such as water or a developer. However, since it can be set in a printing machine without performing it, it has the advantage that a discarded plate can be produced by the same operation as the PS plate used for printing.
In addition, even when stacked as a laminate and stored for a long time or stored under high temperature and high humidity, adhesion between plates is difficult to occur, and there are advantages such as less soiling and the number of damaged paper during printing. have.
以下に詳細に説明するように、本発明によれば、水または現像液等の水溶液で溶出処理することなく、そのまま印刷機にセット可能で、初期印刷時の損紙枚数が少なく、また、版を直接積み重ねて高温、多湿雰囲気中に長期保存した場合でも、版同士の付着もなく、単層あるいは２回塗布だけでの平版印刷用捨版、並びに当該捨版を合紙なしで積層した積層体を得ることができる。 As will be described in detail below, according to the present invention, it can be set in a printing machine as it is without elution treatment with an aqueous solution such as water or a developer, and the number of lost paper sheets at the time of initial printing is small. Even when stored directly in a high-temperature and high-humidity atmosphere, the plates are not adhered to each other, and the plates for lithographic printing with a single layer or only two coatings are laminated, and the plates are laminated without interleaf. You can get a body.
以下に、本発明の実施の形態を説明する。もっとも、以下に説明する実施の形態は本発明を限定するものではない。本発明の平版印刷用捨版は、金属支持体上にアクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α,β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩含む処理液を塗布、乾燥してなる保護層、場合によっては更に表面がマット化されたものである。 Hereinafter, embodiments of the present invention will be described. However, the embodiments described below do not limit the present invention. The lithographic printing plate of the present invention is an alkali metal of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol% on a metal support. A protective layer obtained by applying and drying a treatment solution containing salt, and in some cases, the surface is further matted.
上記金属支持体は、金属からなる支持体の他、プラスチックフィルム等の非金属の表面に金属からなる層が設けられたものであってもよい。特に、金属支持体は、金属としてアルミニウムまたはアルミニウム合金を用いたもの（本明細書にあっては、アルミニウム支持体とも記す。）であることが好ましい。具体的には、アルミニウム支持体として、純アルミニウム板、またはアルミニウムを主成分とし、微量の異元素を含む合金板を用いることができ、更にアルミニウムがラミネートもしくは蒸着されたプラスチックフィルムを用いることもできる。このように本発明に適用される金属支持体は、その組成が特定されるものでなく、従来公知公用の素材のアルミニウム板等の金属支持体を適宜に利用することができる。本発明で用いられる金属支持体の厚みは、好ましくはおおよそ０．１〜０．５ｍｍ、より好ましくは０．１５〜０．３ｍｍである。 In addition to the metal support, the metal support may be a nonmetal surface such as a plastic film provided with a metal layer. In particular, the metal support is preferably one using aluminum or an aluminum alloy as a metal (also referred to as an aluminum support in this specification). Specifically, a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements can be used as the aluminum support, and a plastic film on which aluminum is laminated or vapor-deposited can also be used. . As described above, the composition of the metal support applied to the present invention is not specified, and a metal support such as an aluminum plate made of a conventionally known and publicly used material can be appropriately used. The thickness of the metal support used in the present invention is preferably about 0.1 to 0.5 mm, more preferably 0.15 to 0.3 mm.
金属支持体を粗面処理するに先立ち、表面の圧延油を除去するために、金属支持体には、例えば、界面活性剤、又はアルカリ性水溶液等による脱脂処理が施されることが好ましい。 Prior to roughening the metal support, the metal support is preferably subjected to a degreasing treatment with, for example, a surfactant or an alkaline aqueous solution in order to remove the rolling oil on the surface.
また、金属支持体には、粗面化処理が施されることが好ましい。金属支持体の表面の粗面化処理は、種々の方法により行うことができる。例えば、機械的に粗面化する方法、電気化学的に表面を粗面化する方法または化学的に表面を選択溶解させる方法により行われる。機械的方法としては、ブラシ研磨、ボール研磨、ブラスト研磨、バフ研磨法等の公知の方法を用いることができる。また、電気化学的な粗面化方法としては、塩酸又は硝酸電解液中で交流又は直流により行う方法がある。また、特開昭５３−１２３２０４号公報に開示されている機械的方法と電気化学的な方法を組み合わせた方法も利用することができる。 The metal support is preferably subjected to a roughening treatment. The surface roughening treatment of the metal support can be performed by various methods. For example, it is carried out by a mechanical surface roughening method, an electrochemical surface roughening method or a chemical surface selective dissolution method. As the mechanical method, a known method such as brush polishing, ball polishing, blast polishing, or buffing can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, a method combining a mechanical method and an electrochemical method disclosed in JP-A-53-123204 can also be used.
このように粗面化された金属支持体には、必要に応じてアルカリエッチング処理及び中和処理された後、所望により表面の保水性や耐摩耗性を高めるために陽極酸化処理が施されることが好ましい。金属支持体の陽極酸化処理に用いられる電解質として、一般的に硫酸、リン酸、蓚酸、クロム酸またはそれらの混酸が用いることができる。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一概に特定し得ないが、一般的には電解質の濃度が１〜６０質量％溶液、液温は５〜６０℃、電流密度２〜５０Ａ／ｄｍ2、電圧１〜１００Ｖ、電解時間５秒〜３分の範囲であれば適当である。陽極酸化皮膜の量は０．５〜４．０ｇ／ｍ2が適当で、０．５ｇ／ｍ2未満であると耐摩耗性が悪くなる場合があり、４．０ｇ／ｍ2を超えると、製造コストがかかり、また、印刷時にインキがカラミ易くなるので好ましくない場合がある。 The roughened metal support is subjected to an alkali etching treatment and neutralization treatment as necessary, and then anodized to enhance the surface water retention and wear resistance as desired. It is preferable. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof can be used as an electrolyte used for anodizing treatment of a metal support. The treatment conditions for anodization vary depending on the electrolyte used and thus cannot be specified in general. In general, however, the electrolyte concentration is 1 to 60% by mass solution, the liquid temperature is 5 to 60 ° C., and the current density is 2 to 50 A / day. dm 2 , voltage 1 to 100 V, and electrolysis time 5 seconds to 3 minutes are suitable. If the amount of anodic oxide film is 0.5 to 4.0 g / m 2 is appropriate, may wear resistance is poor is less than 0.5 g / m 2, when it exceeds 4.0 g / m 2, The manufacturing cost is high, and the ink tends to be damaged at the time of printing.
陽極酸化を施された後、アクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α,β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩を含有する処理液を塗布するが、その前に、陽極酸化された金属支持体は、さらに、例えばアルカリ金属ケイ酸塩、リン酸ナトリウム、弗化ナトリウム、弗化ジルコニウム、アルキルチタネート、トリヒドロキシ安息香酸等の単独あるいは混合液による化成処理や、熱水溶液への浸漬もしくは水蒸気浴等による封孔処理や、特開平１０−２９７１３０号に記載の表面処理や、または酢酸ストロンチウム、酢酸亜鉛、酢酸マグネシウム、もしくは安息香酸カルシウム等の水溶液による被覆処理等をすることができる。 After anodizing, a treatment liquid containing an alkali metal salt of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol% Before being applied, the anodized metal support may further comprise, for example, alkali metal silicate, sodium phosphate, sodium fluoride, zirconium fluoride, alkyl titanate, trihydroxybenzoic acid or the like alone or in combination. Chemical conversion treatment with liquid, sealing treatment with a hot aqueous solution or sealing with a steam bath, surface treatment described in JP-A-10-297130, or strontium acetate, zinc acetate, magnesium acetate, calcium benzoate, etc. A coating treatment with an aqueous solution can be performed.
本発明に用いられるアクリルアミド／アクリロニトリル／α,β−不飽和カルボン酸共重合体のアルカリ金属塩は、好ましくはアクリルアミドを２０〜９０モル％、より好ましくは３５〜８５モル％、アクリロニトリルを５〜６０モル％、より好ましくは１０〜５０モル％、α,β−不飽和カルボン酸を１〜６０モル％、より好ましくは２〜５０モル％の割合で共重合させ、苛性ソーダや苛性カリ等で中和して取り出すことができる。 The alkali metal salt of the acrylamide / acrylonitrile / α, β-unsaturated carboxylic acid copolymer used in the present invention is preferably 20 to 90 mol% of acrylamide, more preferably 35 to 85 mol%, and 5 to 60 of acrylonitrile. Mol%, more preferably 10 to 50 mol%, α, β-unsaturated carboxylic acid is copolymerized at a ratio of 1 to 60 mol%, more preferably 2 to 50 mol%, and neutralized with caustic soda or caustic potash. Can be taken out.
上記共重合体中、アクリルアミドが２０モル％未満の場合には、水に溶けづらくなり、水溶液として作製しづらくなる場合があり、９０モル％を超える場合には、水に過剰に溶けやすくなり、塗布した時に水分を吸収しやすくなるので好ましくない場合がある。 In the above copolymer, when acrylamide is less than 20 mol%, it is difficult to dissolve in water, and it may be difficult to prepare as an aqueous solution, and when it exceeds 90 mol%, it tends to be excessively soluble in water, Since it becomes easy to absorb a water | moisture content when apply | coating, it may be unpreferable.
上記共重合体中、アクリロニトリルが５モル％未満の場合には、塗膜にした時に、ベタ付きやすくなる場合があり、６０モル％を超える場合には、水または印刷時の湿し水に溶解しづらくなる場合がある。 In the above copolymer, if acrylonitrile is less than 5 mol%, it may become sticky when coated, and if it exceeds 60 mol%, it will dissolve in water or dampening water during printing. It may be difficult.
上記共重合体中、α,β−不飽和カルボン酸が１モル％未満の場合には、水に溶けづらくなる場合があり、６０モル％を超える場合には、逆に水に過剰に溶けやすくなり、塗膜にした時に水分を吸着してベトつく場合があるので好ましくない。 In the above copolymer, when the α, β-unsaturated carboxylic acid is less than 1 mol%, it may be difficult to dissolve in water, and when it exceeds 60 mol%, it tends to be excessively soluble in water. It is not preferable because when the coating film is formed, moisture may be adsorbed and sticky.
上記反応は過硫酸カリウム等を、モノマー全体の０．０１〜１質量％、触媒として使用し、反応温度は、通常１０〜９０℃の範囲で行う。 In the above reaction, potassium persulfate or the like is used as a catalyst in an amount of 0.01 to 1% by mass of the whole monomer, and the reaction temperature is usually in the range of 10 to 90 ° C.
本発明に用いられる上記アクリルミド／アクリロニトリル／α,β−不飽和カルボン酸共重合体の平均重量分子量は３，０００〜５０，０００の範囲が好ましく、平均重量分子量３，０００未満の場合には、水に過剰に溶けやすくなり、湿気によりベタ付く傾向になり、５０，０００を超える場合には、水に溶けづらくなり、印刷時に汚れの要因になるので好ましくない。 The average weight molecular weight of the acrylimide / acrylonitrile / α, β-unsaturated carboxylic acid copolymer used in the present invention is preferably in the range of 3,000 to 50,000, and when the average weight molecular weight is less than 3,000. , It tends to be excessively soluble in water and tends to become sticky due to moisture. If it exceeds 50,000, it becomes difficult to dissolve in water and causes stains during printing.
本発明における共重合体は、効果を損なわない範囲において、上記３成分の他に従来公知の他のモノマー成分を導入して多元共重合体としてもよい。 The copolymer in the present invention may be a multi-component copolymer by introducing other conventionally known monomer components in addition to the above three components within a range not impairing the effect.
処理液を塗布することで保護層を設ける際の、処理液中のアクリルアミド／アクリロニトリル／α,β−不飽和カルボン酸共重合体のアルカリ金属塩の濃度は、好ましくは処理液の０．１〜３０質量％、より好ましくは０．２〜１０質量％である。０．１質量％未満では好ましい塗布被覆量を得るのが難しい場合があり、３０質量％を超えると、厚く塗布されやすく、例えば塗布量が１．０ｇ／ｍ2を越えると、印刷時の湿し水での溶解が遅れ、インキ離れ性が悪くなる場合があるため、損紙が多くなるという問題が出やすい。さらに、高湿下で、合紙なしで長期保存された場合に、版同士が接着し易くなり、搬送不良等のトラブルを引き起こす場合がある。また、一旦溶解したものがゲル化する等して好ましくない場合がある。 When the protective layer is provided by applying the treatment liquid, the concentration of the alkali metal salt of the acrylamide / acrylonitrile / α, β-unsaturated carboxylic acid copolymer in the treatment liquid is preferably 0.1 to 0.1% of the treatment liquid. 30% by mass, more preferably 0.2 to 10% by mass. If it is less than 0.1% by mass, it may be difficult to obtain a preferable coating amount. If it exceeds 30% by mass, it is easy to apply a thick coating. For example, if the coating amount exceeds 1.0 g / m 2 , the moisture during printing Since the dissolution with water is delayed and the ink releasability may deteriorate, the problem of increased waste paper tends to occur. Furthermore, when stored for a long time without interleaving paper under high humidity, the plates can easily adhere to each other, which can cause problems such as poor conveyance. In addition, once dissolved, it may be undesirable because it gels.
本発明の処理液には、性能を損なわない限りにおいて、例えば水溶性樹脂、界面活性剤、有機溶剤、染料および必要に応じ防腐剤、防黴剤、消泡剤並びにキレート剤等を添加することができる。 In the treatment liquid of the present invention, for example, a water-soluble resin, a surfactant, an organic solvent, a dye and, if necessary, an antiseptic, an antifungal agent, an antifoaming agent, a chelating agent, etc. are added as long as the performance is not impaired. Can do.
水溶性樹脂としては、例えばアラビアガム、デキストリン、ゼラチン、例えばアルギン酸ナトリウムのようなアルギン酸塩、例えばカルボキシメチルセルロース、ヒドロキシエチルセルロースのような水溶性セルロース、ポリビニルアルコール及びその誘導体、ポリビニルピロリドン、ポリアクリル酸類、ポリメタクリル酸類等を挙げることができる。これらの水溶性樹脂は、必要に応じて２種以上組み合わせて使用することができる。 Examples of the water-soluble resin include gum arabic, dextrin, gelatin, alginate such as sodium alginate, water-soluble cellulose such as carboxymethyl cellulose and hydroxyethyl cellulose, polyvinyl alcohol and derivatives thereof, polyvinyl pyrrolidone, polyacrylic acids, poly And methacrylic acid. These water-soluble resins can be used in combination of two or more as required.
界面活性剤としては、例えばポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー等のノニオン界面活性剤、例えば脂肪酸塩類、アルキル硫酸エステル塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル燐酸エステル塩類、ナフタレンスルホン酸ホルマリン縮合物等のアニオン界面活性剤、例えばベタイン型、グリシン型、アラニン型、スルホベタイン型の両性界面活性剤及びシリコーン系並びにフッ素系界面活性剤等が挙げられる。界面活性剤は、処理適性の改善や水への溶出性改善のために用いられるが、泡発生等の弊害も出るため、処理液の処方に準じて添加量を調整する必要がある。 Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene polyoxypropylene block polymer, such as fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyls. Anionic surfactants such as naphthalene sulfonates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, such as betaine-type, glycine-type, alanine-type, sulfobetaine-type amphoteric surfactants and silicone-based and fluorine-based surfactants Etc. Surfactants are used to improve processing suitability and water elution, but they also cause adverse effects such as foaming, so it is necessary to adjust the addition amount according to the prescription of the processing liquid.
有機溶剤としては、例えばメタノール、エタノール、n-プロピルアルコール、イソプロピルアルコール等の低級アルコールが好ましく挙げられる。有機溶剤の添加は、被覆膜のレベリング性や乾燥性を向上させるとともに、処理液の消泡効果をもたらすので好ましいが、それに反して、環境汚染の原因ともなるので、必要最小限の添加に心がけることに越したことはない。 Preferred examples of the organic solvent include lower alcohols such as methanol, ethanol, n-propyl alcohol, and isopropyl alcohol. The addition of an organic solvent is preferable because it improves the leveling and drying properties of the coating film and also provides a defoaming effect for the treatment liquid. On the other hand, it also causes environmental pollution. There has never been more to keep in mind.
染料としては、メチレンブルー、ビクトリアブルー、クリスタルバイオレット、ローダミンＢ等の塩基性染料、エオシン、エリスロシン、ローズベンガル等の酸性染料、オイルブルー６１３（オリエント化学工業製）等の油溶性染料、および食用赤色１０６号等の染料が挙げられる。染料は、本発明の平版印刷用捨版の着色を目的として添加するためであると共に処理塗布液の濃度管理や塗布状態の確認のために使用する。従って、少量の添加で着色力の大きい染料が好ましく、蛍光増白染料等のように無着色でありながら、紫外線を照射すると蛍光を発するような染料も使用できる。それら染料の使用や添加量に制限はないが、処理液がアルマイト層に接触するので、アルマイト層に浸透し着色したり、ムラ、汚染並びに感脂化等の原因となり印刷に弊害を及ぼすような染料の選択や添加は好ましくない。 Examples of the dye include basic dyes such as methylene blue, Victoria blue, crystal violet and rhodamine B, acidic dyes such as eosin, erythrosin and rose bengal, oil-soluble dyes such as oil blue 613 (manufactured by Orient Chemical Industries), and food red 106 And dyes such as No. The dye is added for the purpose of coloring the lithographic printing plate of the present invention, and is used for concentration control of the treatment coating solution and confirmation of the coating state. Therefore, a dye having a large coloring power with a small amount of addition is preferable, and a dye that emits fluorescence when irradiated with ultraviolet rays while being uncolored, such as a fluorescent whitening dye, can be used. There are no restrictions on the use or addition amount of these dyes, but since the processing solution comes into contact with the anodized layer, it may penetrate into the anodized layer and become colored, causing unevenness, contamination, and oil sensitization. The selection or addition of dyes is not preferred.
本発明において、保護層を塗布した後、さらに表面をマット化する場合がある。表面をマット化する方法としては、本発明明の処理液にマット剤等を添加する方法、保護層表面に水溶液樹脂あるいは水溶性樹脂とマット剤等を溶解、分散させた溶液をスプレー塗布する方法等がある。マット剤としては、例えば二酸化珪素、酸化亜鉛、酸化チタン、アルミナ粉末、澱粉、コンスターチ、重合体粒子（例えばポリアクリル酸、ポリスチレン等の粒子）等が挙げられる。 In the present invention, after the protective layer is applied, the surface may be further matted. As a method for matting the surface, a method of adding a matting agent or the like to the treatment liquid of the present invention, a method of spray-coating a solution in which an aqueous resin or a water-soluble resin and a matting agent are dissolved and dispersed on the surface of the protective layer Etc. Examples of the matting agent include silicon dioxide, zinc oxide, titanium oxide, alumina powder, starch, starch, polymer particles (for example, particles such as polyacrylic acid and polystyrene), and the like.
本発明の処理液を塗布する方法としては、種々の方法を用いることができ、例えば、回転塗布、押し出し塗布、バーコーター塗布、ロール塗布、エアーナイフ塗布、ディップ塗布、カーテン塗布等を挙げることができる。塗布量は、乾燥後の保護層の重量に換算して、好ましくは０．０１〜１．０ｇ／ｍ2、より好ましくは０．０２〜０．８ｇ／ｍ2であることが好ましい。保護層の重量が０．０１ｇ／ｍ2未満であると、保護膜としての機能が損なわれ、表面が酸化される等して汚れやすくなる場合がある。保護層の重量が１．０ｇ／ｍ2を超えると、印刷時の湿し水での溶解が遅れ、インキ離れ性が悪くなる場合があるため、損紙が多くなるという問題が出やすい。さらには高湿下で、合紙なしで長期保存された場合に、版同士が接着し易くなり、搬送不良等のトラブルを引き起こす場合がある。 Various methods can be used as a method for applying the treatment liquid of the present invention, such as spin coating, extrusion coating, bar coater coating, roll coating, air knife coating, dip coating, curtain coating and the like. it can. The coating amount, in terms of the weight of the protective layer after drying is preferably preferably 0.01 to 1.0 g / m 2, more preferably from 0.02~0.8g / m 2. If the weight of the protective layer is less than 0.01 g / m 2 , the function as a protective film may be impaired, and the surface may be oxidized and become easily contaminated. When the weight of the protective layer exceeds 1.0 g / m 2 , dissolution with dampening water during printing is delayed, and ink releasability may be deteriorated, so that the problem of increased waste paper tends to occur. In addition, when stored for a long time without interleaving paper under high humidity, the plates are likely to adhere to each other, which may cause trouble such as conveyance failure.
なお、塗布された処理液の乾燥は、種々の方法で行うことができ、特に限定されるものでない。具体的には、エアードライヤー、熱風ドライヤー、赤外線ヒーター、遠赤外線ヒーター等で乾燥させる。 The applied treatment liquid can be dried by various methods and is not particularly limited. Specifically, it is dried with an air dryer, hot air dryer, infrared heater, far-infrared heater or the like.
また、本発明の側面によると、上記平版印刷版用捨版を、水及び／又は水溶液で処理することなく印刷機にセットして印刷する平版印刷版用捨版を用いた印刷方法が提供される。本発明にかかる印刷方法は、上記平版印刷版用捨版を用いる他は、従来と同様にすることができるため、詳細な説明は省略する。なお、上記文献２、４等に、平版印刷版用捨版を用いた印刷方法について詳述されている。なお、上記したように、本発明にかかる平版印刷版用捨版を用いた印刷方法にあたっては、水及び／又は水溶液で処理する必要がない。これは、本発明の捨版の表面が長期に亘っても親水性を保持しており、そのまま印刷機に掛けても印刷機上の湿し水を受け付け、インキを弾く性質を有しており、印刷汚れが生じないためである。これは多分にも本発明の保護膜中アクリルアミド／アクリロニトリル／α,β−不飽和カルボン酸共重合体のアルカリ金属塩を使用した場合の特異的効果のためであると考えられる。他方、上記文献２、４に記載されている捨版は、このまま印刷機に掛けるとインキが付着し、汚れになるので、水または現像液等で表面の樹脂を一旦溶解除去し、再度グラビアガム等を塗布して不感脂化した後に使用される捨版である。 Further, according to an aspect of the present invention, there is provided a printing method using a planographic printing plate discarding, in which the planographic printing plate discarding is set in a printing machine without printing with water and / or an aqueous solution. The Since the printing method according to the present invention can be the same as that of the prior art except that the lithographic printing plate is used, detailed description thereof is omitted. In addition, the above-mentioned documents 2, 4 and the like detail the printing method using the planographic printing plate discarding. As described above, in the printing method using the planographic printing plate disposal according to the present invention, it is not necessary to treat with water and / or an aqueous solution. This is because the surface of the plate of the present invention retains hydrophilicity even for a long period of time, and has the property of accepting dampening water on the printing machine and repelling the ink even if it is applied to the printing machine as it is. This is because printing stains do not occur. This is probably due to the specific effect when the alkali metal salt of acrylamide / acrylonitrile / α, β-unsaturated carboxylic acid copolymer is used in the protective film of the present invention. On the other hand, the discards described in the above-mentioned documents 2 and 4 cause ink to adhere and become dirty when they are applied to a printing machine as they are, so the resin on the surface is once dissolved and removed with water or a developer, and then again gravure gum. It is a discarded plate used after desensitizing by applying etc.
本発明の捨版は、表面が親水性表面を有しており、折り曲げ部を付けてそのまま印刷機にセットし、湿し水ローラー、インキローラーを備えた通常のオフセット印刷機で印刷可能である。また、本発明の捨版は、従来使われている感光性平版印刷版（ＰＳ版）用現像液或いはコンピュータートゥープレート（ＣＴＰ）用現像液及びガム液で処理した後に印刷機にセットして印刷しても、汚れ等が発生せず、捨版としての機能を充分に発揮する。従って、本発明の捨版は、製版方法として、従来のＰＳ版用自動現像機、プレヒート有り又は無しのＣＴＰ用自動現像機等を通過させた後で、捨版として使用しても、何ら問題は発生しない。 The discard plate of the present invention has a hydrophilic surface, and can be printed on a normal offset printing press equipped with a fountain solution roller and an ink roller, with the folded portion attached, and set in a printing machine as it is. . In addition, the disposal of the present invention can be performed by using a conventional photosensitive lithographic printing plate (PS plate) developer or computer-to-plate (CTP) developer and gum solution, and then setting it in a printing machine for printing. Even if it does not occur, the function as a discarded plate is fully exhibited. Accordingly, the discarding of the present invention is not a problem even if it is used as a discarding plate after passing through a conventional PS plate automatic developing machine, a CTP automatic developing machine with or without preheating, etc. as a plate making method. Does not occur.
以下に、本発明を実施例によりさらに具体的に示すが、本実施例は本発明を限定するものでない。
［アクリルアミド／アクリロニトリル／α,β−不飽和カルボン酸共重合体のアルカリ金属塩の合成例］
攪拌機、温度計、滴下ロート、還流冷却器及び窒素導入管を備えた１Ｌ四つ口フラスコに脱イオン水６３ｇ、アクリルアミド５０ｇ（４６．９モル％）、アクリロニトリル２０ｇ（２２．２モル％）、アクリル酸３０ｇ（２７．９モル％）、開始剤として過硫酸カリウム１ｇを仕込み、窒素ガスを通じながら加熱して７０℃で２時間反応して重合を完結した。４０℃以下に冷却後、２５質量％苛性ソーダで中和する。次いで脱イオン水で希釈し、ｐＨ６．５、濃度１５質量％、２５℃での粘度が１０，０００ｍＰａ・ｓの淡黄色透明の共重合体水溶液（１）を得た。
The present invention will be described more specifically with reference to the following examples. However, the present examples do not limit the present invention.
[Synthesis example of alkali metal salt of acrylamide / acrylonitrile / α, β-unsaturated carboxylic acid copolymer]
In a 1 L four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen introduction tube, 63 g of deionized water, 50 g of acrylamide (46.9 mol%), 20 g of acrylonitrile (22.2 mol%), acrylic 30 g (27.9 mol%) of acid and 1 g of potassium persulfate as an initiator were charged, heated while passing through nitrogen gas, and reacted at 70 ° C. for 2 hours to complete the polymerization. After cooling to 40 ° C. or lower, neutralize with 25% by mass sodium hydroxide. Subsequently, it was diluted with deionized water to obtain a pale yellow transparent copolymer aqueous solution (1) having a pH of 6.5, a concentration of 15% by mass, and a viscosity at 25 ° C. of 10,000 mPa · s.
［支持体の作製］
厚さ０．３０ｍｍのアルミニウム板（材質１０５０）をアルカリ脱脂した後、パーミストンの水懸濁液をかけながらナイロンブラシで表面を研磨し、よく水洗した。次いで、７０℃、１５質量％水酸化ナトリウム水溶液を５秒間かけ流し、表面を３ｇ／ｍ2エッチングした後、さらに水洗を行い、１Ｎ塩酸浴中で２００クーロン／ｄｍ2で電解粗面化処理を行った。引き続き水洗した後、１５質量％水酸化ナトリウム水溶液で表面を再度エッチングし、水洗を行った後、２０質量％の硝酸水溶液に浸漬して、デスマットした。次いで、１５質量％硫酸水溶液中で陽極酸化処理を行って、２．０ｇ／ｍ2の酸化皮膜を形成した。この支持体を水洗後、７５℃の珪酸ナトリウムの５％水溶液に１０秒間浸漬処理し、水洗、乾燥して、支持体１を作製した。
[Production of support]
An aluminum plate (material 1050) having a thickness of 0.30 mm was degreased with alkali, then the surface was polished with a nylon brush while applying a water suspension of palmiston, and washed thoroughly with water. Next, after pouring a 15 mass% sodium hydroxide aqueous solution at 70 ° C. for 5 seconds and etching the surface by 3 g / m 2 , the surface is further washed with water and subjected to electrolytic surface roughening treatment at 200 coulomb / dm 2 in a 1N hydrochloric acid bath. went. Subsequently, the surface was etched again with a 15% by mass aqueous sodium hydroxide solution, washed with water, and then immersed in a 20% by mass nitric acid aqueous solution for desmutting. Subsequently, an anodizing treatment was performed in a 15% by mass sulfuric acid aqueous solution to form a 2.0 g / m 2 oxide film. After washing this support with water, it was immersed in a 5% aqueous solution of sodium silicate at 75 ° C. for 10 seconds, washed with water and dried to produce Support 1.
［実施例１〜３、比較例１］
この後、下記表１の組成処理液を、乾燥後の被覆量が０．２ｇ／ｍ2になるようにロール塗布して、各平版印刷用捨版を作製した。
[Examples 1 to 3, Comparative Example 1]
Thereafter, the composition treatment liquid shown in Table 1 below was roll-coated so that the coating amount after drying was 0.2 g / m 2 , thereby preparing each planographic printing plate.
［実施例４］
上記支持体１と同じようにアルミニウム表面を研磨、粗面化し、陽極酸化処理したのち、珪酸ナトリウムの処理をせずに水洗、乾燥して、支持体２を作製し、この支持体上に実施例１と同じ組成処理液１を、乾燥後の被覆量が０．２ｇ／ｍ2になるようにロール塗布して、平版印刷用捨版を作製した。
[Example 4]
The aluminum surface is polished, roughened and anodized in the same manner as the above support 1, and then washed with water and dried without treatment with sodium silicate to produce a support 2, which is then carried out on this support. The same composition treatment liquid 1 as in Example 1 was roll-coated so that the coating amount after drying was 0.2 g / m 2 to prepare a planographic printing plate.
［比較例２］
上記支持体１をそのまま平版捨版板として使用し性能比較した。
[Comparative Example 2]
The support 1 was used as a lithographic plate as it was, and the performance was compared.
［平版印刷用捨版の性能評価］
上記のように作製した実施例１〜４、比較例１〜２の平版印刷用捨版について、下記の性能評価を行った。
[Performance evaluation of lithographic printing plates]
The following performance evaluation was performed on the lithographic printing plates of Examples 1 to 4 and Comparative Examples 1 and 2 produced as described above.
［損紙枚数評価］
得られた各平版印刷用捨版をそのままオフセット輪転印刷機にかけ、東洋インキ株式会社のＴＫ両面機エコー墨インキと、湿し水は真水（水道水）を用いて毎時１０万枚のスピードで印刷開始し、全面ベタ汚れから湿し水ローラーを落とした後、汚れが消えるまでの枚数を比較した。結果を下記表２に示す。
[Evaluation of number of waste paper]
Each lithographic printing plate obtained is directly applied to an offset rotary printing press, and printed at a speed of 100,000 sheets per hour using Toyo Ink's TK double-sided echo ink and fresh water (tap water). The number of sheets until the dirt disappeared after the dampening water roller was dropped from the whole solid dirt was compared. The results are shown in Table 2 below.
［保存性能評価］
得られた各平版印刷用捨版を３５℃、８５％の高温、多湿雰囲気中に１０日間放置後、上記の印刷条件にて印刷し、汚れの発生状態を目視評価した。結果を下記表２に示す。
評価基準；○印刷紙面に汚れが見られず。△僅かに小点状の汚れが発生する。×印刷紙面全体に薄い汚れが発生し、５０００部印刷しても汚れが残る。
[Storage performance evaluation]
Each lithographic printing plate obtained was allowed to stand in a high-temperature, high humidity of 35 ° C. and 85% for 10 days, then printed under the above printing conditions, and the state of occurrence of stains was visually evaluated. The results are shown in Table 2 below.
Evaluation criteria: ○ There is no stain on the printed paper. ΔSlightly dotted spots are generated. X A thin stain occurs on the entire surface of the printing paper, and the stain remains even after printing 5000 copies.
［実施例５］
厚さ０．３ｍｍ、幅８５０ｍｍのコイル状アルミニウム板を支持体１と同様なる処理をし、次いで実施例１と同様に、上記処理液１を塗布・乾燥した後、ポリアクリル酸１０質量％水溶液をスプレー塗布して表面をマット化した。マットの高さは平均８μｍ、大きさは平均２０μｍ、塗布量は１００ｍｇ／ｍ2であった。かくして得られたコイル状アルミニウム板を幅４００ｍｍとなるように合紙を重ねることなく、スリッター装置にて裁断したのち、カット長１１００ｍｍのシートに切断し、合紙がないまま連続的に自動集積し、５００枚積み重ねて大量包装した。このように作製、集積された版を、版さばきのための水平エアーブローおよび吸盤ゴムで１枚毎に版材を自動給版する装置で給版したところ、２枚もち上がりやキズ等の発生はなかった。長期（６ヶ月）保管および３５℃、湿度８５％７日間保管後においても、版同士の接着も発生せず、また、印刷では損紙枚数１００枚程度で問題なかった。
[Example 5]
A coiled aluminum plate having a thickness of 0.3 mm and a width of 850 mm was treated in the same manner as the support 1, and then the treatment solution 1 was applied and dried in the same manner as in Example 1, followed by a 10% by weight polyacrylic acid aqueous solution. Was spray coated to make the surface matte. The average mat height was 8 μm, the average size was 20 μm, and the coating amount was 100 mg / m 2 . The coiled aluminum plate thus obtained was cut with a slitter device without overlapping the interleaving paper so that the width was 400 mm, then cut into a sheet having a cut length of 1100 mm, and continuously collected without any interleaving paper. , 500 sheets were stacked and packaged in large quantities. When the plates prepared and accumulated in this way are fed by a device that automatically feeds the plate material one by one with a horizontal air blow and sucker rubber for spreading the plate, two sheets are raised and scratches are generated. There was no. Even after long-term storage (6 months) and storage at 35 ° C. and humidity 85% for 7 days, the plates did not adhere to each other.
［比較例３］
実施例５において上記比較例１で用いた処理液４を塗布乾燥後、実施例５と同様の裁断、集積を行った。３５℃、湿度８５％７日間保管後では、版同士の接着しているものがあった。
[Comparative Example 3]
In Example 5, the treatment liquid 4 used in Comparative Example 1 was coated and dried, and then the same cutting and accumulation as in Example 5 were performed. After storage at 35 ° C. and humidity of 85% for 7 days, there were some plates adhered to each other.
表２から明らかなように、本発明の平版印刷用捨版は、水または現像液のような水溶液で溶出処理することなく、そのまま印刷機にセットでき、初期印刷時の損紙枚数が少なく、また、高温、多湿雰囲気中に長期保存した場合でも、印刷汚れが発生しない平版印刷用捨版であることが分かった。 As is clear from Table 2, the planographic printing plate of the present invention can be set as it is in a printing machine without elution treatment with an aqueous solution such as water or a developer, and the number of lost paper during initial printing is small. Further, it was found that the lithographic printing plate was free from printing stain even when stored in a high temperature and high humidity atmosphere for a long time.
Claims (4)
前記保護層が、アクリルアミド２０〜９０モル％、アクリロニトリル５〜６０モル％、α，β−不飽和カルボン酸１〜６０モル％からなる共重合体のアルカリ金属塩からなる平版印刷用捨版。 A lithographic printing plate comprising only a metal support and a protective layer provided on the surface of the metal support,
A lithographic printing plate wherein the protective layer comprises an alkali metal salt of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol%.
該処理液を乾燥して保護層を得るステップと、
さらに前記保護層の表面をマット化するステップと
を含む、金属支持体と該金属支持体の表面上に設けられた保護層とのみを備えた平版印刷用捨版の製造方法。 Applying a treatment liquid containing an alkali metal salt of a copolymer comprising acrylamide 20 to 90 mol%, acrylonitrile 5 to 60 mol%, and α, β-unsaturated carboxylic acid 1 to 60 mol% on a metal support; ,
A step Ru obtain a protective layer and drying the treatment liquid,
And a step of matting the surface of the protective layer . A method for producing a lithographic printing plate comprising only a metal support and a protective layer provided on the surface of the metal support .
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| JP2005357311A JP5165197B2 (en) | 2005-12-12 | 2005-12-12 | Planographic printing plate disposal and method for producing the same |
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| JP5538197B2 (en) * | 2010-03-26 | 2014-07-02 | 富士フイルム株式会社 | Removable plate precursor for lithographic printing plate, discarded plate precursor assembly for lithographic printing plate, and plate making method for lithographic printing plate |
| JP5680390B2 (en) * | 2010-12-03 | 2015-03-04 | 富士フイルム株式会社 | Removable plate precursor for lithographic printing plate, discarded plate precursor assembly for lithographic printing plate, and plate making method for lithographic printing plate |
| JP6546939B2 (en) * | 2016-01-29 | 2019-07-17 | 富士フイルム株式会社 | Planographic printing plate dummy plate, printing method using planographic printing plate dummy plate, and plate making method of planographic printing plate dummy plate |
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