CN101076448A - 制作平版印刷印版的方法 - Google Patents
制作平版印刷印版的方法 Download PDFInfo
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- CN101076448A CN101076448A CNA2005800407591A CN200580040759A CN101076448A CN 101076448 A CN101076448 A CN 101076448A CN A2005800407591 A CNA2005800407591 A CN A2005800407591A CN 200580040759 A CN200580040759 A CN 200580040759A CN 101076448 A CN101076448 A CN 101076448A
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1025—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
- B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/04—Intermediate layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/10—Developable by an acidic solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
Abstract
本发明提供了一种制备平版印刷印版的方法,该方法包括提供包含以下的平版印刷印版前体:(i)具有亲水表面或提供有亲水层的载体,(ii)所述载体上的涂层,该涂层包含图像记录层,所述图像记录层含有疏水的热塑性聚合物颗粒和亲水的基料,所述疏水的热塑性聚合物颗粒的平均粒径为40nm至63nm,所述涂层进一步包含颜料,颜料存在于所述图像记录层中或存在于所述涂层的其他层中;使该涂层按图像曝光,从而在图像记录层的曝光区域引起热塑性聚合物颗粒的聚结;对该涂层施用胶溶液,以将图像记录层的未曝光区域从载体上除去,从而使前体显影;和任选烘烤所述显影的前体;其中所述疏水的热塑性聚合物颗粒的平均粒径为40nm至63nm,其中所述图像记录层中疏水的热塑性聚合物颗粒的量相对于该图像记录层高于70%重量且低于85%重量,并且其中所述颜料具有亲水表面,并在按图像曝光和用胶溶液显影后提供可见的图像。以上方法中所用的平版印刷印版前体具有改善的灵敏度,且所得的平版印刷印版显示极好的清除结果,无着色,且印刷运转周期高。
Description
发明领域
本发明涉及制作平版印刷印版的方法,通过该方法,使具有改善的敏感性的印版前体按图像曝光,并用胶溶液显影。
发明背景
平版印刷中,将印版等所谓的印刷底版装在印刷机的滚筒上。底版的表面上带有平版图像,将油墨施加于所述图像,然后将油墨由底版转移至接受材料上,从而得到副本,接受材料一般是纸。在常规的所谓“湿”平版印刷中,将油墨以及水性润版液(也叫润湿液)供给平版图像,平版图像由亲油(或疏水,即接受油墨,排斥水)区和亲水(或疏油,即接受水,排斥油墨)区组成。在所谓“无水胶印”中,平版图像由接受油墨的区域和阻隔油墨(排斥油墨)的区域组成,在无水胶印中,只向底版供给油墨。
印刷底版一般通过所谓的计算机直接制版(CtF)方法获得,其中,例如字体选择、扫描、分色、加网、叠印、版面编排和排版等各种印前步骤通过数字方式完成,用印版记录机将各颜色选择转移至印刷工艺胶片。处理后,可将该胶片用作被称为印版前体的成像材料曝光用的蒙片,印版处理后,得到可用作底版的印版。大约自1995年起,所谓的计算机直接制版(CtF)方法已引起大量关注。该方法也称作“直接制版”方法,省去了胶片的制造,因为该方法通过所谓印版记录机的方式将数字文件直接转移至印版前体。
尤其是对热或红外线敏感的热敏印版,由于其对日光的稳定性而广泛用于计算机直接制版方法。这样的热敏材料可直接暴露于热,例如通过热头(thermal head)的方式暴露于热,但是优选含有将吸收的光转变成热的化合物,因此,这样的热敏材料适合用激光器曝光,尤其是用红外激光二极管曝光。在按图像曝光时产生的热引起(物理-)化学过程,例如烧蚀、聚合、由于聚合物交联而引起的不溶解、分解或热塑性聚合物胶乳的颗粒凝结,在任选的处理之后,得到平版图像。许多热敏印版材料是基于热引起的烧蚀。与烧蚀印版相关的问题是碎片的产生,这些碎片难以除去,并可能妨碍印刷过程,或可能污染印版记录机的曝光光学元件。因此,这样的烧蚀印版需要将碎片从曝光的材料除去的处理步骤。
EP 1 075 941公开了辐射敏感的印版前体,其中加入了光热转化剂,且所述光热转化剂是颗粒状金属氧化物,其中包囊有光热转化有机化合物。
US 4,841,040公开了新的磷酸化、氧化淀粉,该淀粉的分子量为约1500至约40000道尔顿,羧基取代度为0.30至0.96,且磷酸取代度为0.002至约0.005,该淀粉可用于代替平版印刷的胶溶液和润版液中的阿拉伯胶。
US 4,245,031公开了可光敏聚合的组合物,该组合物含有具有多个成盐基团的聚合物,两种特定的烯属不饱和化合物,辐射敏感的自由基生成体系。该组合物提供了具有突出的光感度,并且对氧相对不敏感的可光敏聚合的成分。
EP 770 497公开了一种方法,该方法中的成像材料包括由亲水基料、能够将光转变成热的化合物和疏水的热塑性聚合物颗粒形成的图像记录层,将该材料按图像曝光,从而引起聚合物颗粒的聚结,将图像记录层转变为限定印刷底版印刷区域的疏水相。接着,用清水或水性液体对按图像曝光的前体进行冲洗,使其显影。
EP 514 145公开了辐射敏感的印版,该印版包括含有核-壳颗粒的涂层,该核-壳颗粒具有水不溶性的、可用热软化的核组分,和在水性碱性介质中可溶解或可溶胀的壳组分。辐射导致所选的颗粒至少部分地聚结,形成图像,然后用水性碱性显影剂将未聚结的颗粒选择性地除去。
2004年7月8日提交的,按A 54(3)未公布的EP-A 04 103 245、EP-A 04 103 247和EP-A 04 103 248中,公开了平版印刷印版前体,该前体包括亲水性载体上的涂层,该涂层包括含有疏水的热塑性聚合物颗粒的图像记录层,所述颗粒的平均粒径为45nm至63nm,并且其中热塑性聚合物颗粒的量至少为所述图像记录层的70%重量。曝光后,用碱性显影液除去涂层的非图像区域,使该前体显影。
EP 1 342 568公开了一种方法,该方法中的成像材料包括亲水基料、能够将光转变成热的化合物和疏水的热塑性聚合物颗粒形成的图像记录层,将该材料按图像曝光,从而引起聚合物颗粒的聚结,将图像记录层转变为限定印刷底版印刷区域的疏水相。接着,用胶溶液(gum solution)处理按图像曝光的前体,从而在单一步骤中使印版显影并上胶。在该单一步骤中,用胶溶液将未曝光区域的图像记录层由载体上除去,使载体的亲水表面暴露(该过程也叫“清除”过程),同时用胶保护这些非图像区域的亲水性表面免受污染(指纹、脂、油、灰尘、氧化等)。
2004年5月,有一种印版系统AZURA(AGFA的商标)上市,该印版系统按以上机理工作。与该印版前体相关的问题是低灵敏度,即该印版前体按图像曝光需要更高的能量剂量,以使聚合物颗粒发生足够的聚结,以便可用胶溶液除去未曝光区域,而不影响曝光区域。这意味着该印版需要更长的曝光时间和/或更大功率的激光器,从而造成更低的速度。如果用相对于印版前体的灵敏度而言太低的能量剂量使印版前体曝光,则平版印刷性能质量较差。较差的质量可能导致更低的分辨率,也就是说,灵敏度降低的前体在用低能量剂量曝光并用胶溶液显影后,不能得到高分辨率网屏的精细点。另外,相对于前体灵敏度而言太低的能量剂量可能会减少印版的运转周期,这是由于曝光区域聚合物颗粒的聚结不足造成的。对于高质量印版更重要的是,涂层的疏水-亲水差异足以获得极好的清除效果,也就是使未曝光区域完全从载体上除去,使亲水表面暴露,且不影响曝光区域。清除不足会进一步导致印刷时的着色,即导致非图像区域的油墨接受趋势不合需要的增加。
发明概述
本发明的目的是提供一种制作平版印刷印版的方法,其中所述平版印刷印版前体具有改善的灵敏度,并且印版显示出极好的清除效果,无着色现象,且印刷运转周期长。
根据本发明,通过包含以下步骤的制备平版印刷印版的方法实现该目的:
-提供包含以下的平版印刷印版前体:
(i)具有亲水表面或提供有亲水层的载体,
(ii)所述载体上的涂层,所述涂层包含图像记录层,所述图像记录层含有疏水的热塑性聚合物颗粒和亲水的基料,所述涂层进一步包含颜料,所述颜料存在于所述图像记录层中或存在于所述涂层的其他层中,
-使所述涂层按图像曝光,从而在图像记录层的曝光区域引起热塑性聚合物颗粒的聚结,
-对所述涂层施用胶溶液,以将图像记录层的未曝光区域从载体上除去,从而使前体显影,和
-任选烘烤所述显影的前体,
其中所述疏水的热塑性聚合物颗粒的平均粒径为40nm至63nm,其中所述图像记录层中疏水的热塑性聚合物颗粒的量相对于图像记录层高于70%重量且低于85%重量,并且其中所述颜料具有亲水表面,并在按图像曝光和用胶溶液显影后提供可见的图像。
本发明特定的实施方案在从属权利要求中限定。本发明进一步的优点和实施方案将通过以下描述显而易见。
发明详述
除非特别指明,否则本说明书中所有的化合物浓度以重量百分比表示,此后表示为“重量%”或“%重量”。
本发明方法中所用的平版印刷印版前体是阴图制版的,显影产生的平版图像由曝光区域的疏水区域和未曝光区域的亲水区域组成。疏水区域和亲水区域分别由涂层和载体所限定,所述载体具有亲水表面或提供有亲水层。
所述载体可以是片状材料,例如板,或者可以是圆柱形构件,例如可以绕着印刷机的印刷滚筒滑动的套筒。优选该载体是金属载体,例如铝或不锈钢。
特别优选的平版印刷载体是起纹并阳极化的铝载体。使铝载体起纹和阳极化是已知的。本发明材料中所用的起纹铝载体优选为电化学起纹载体。用于起纹的酸可以是例如硝酸或硫酸。用于起纹的酸优选包括盐酸。也可用例如盐酸和乙酸的混合物。电化学起纹和阳极化参数与所得的平版印刷质量之间的关系是已知的,所述参数例如电极电压、酸性电解质的性质和浓度或者能量消耗;所述平版印刷质量是就Ra和阳极重量(每平方米铝表面上形成的Al2O3的克数)而言。各种制备参数与Ra或阳极重量之间的关系的更多相关细节可参见例如发表于ATB Metallurgie Journal,42卷nr.1-2(2002)第69页的F.R.Mayers的论文“Management of Change in the AluminiumPrinting Industry”(“铝印刷工业中的变化的处理”)。
阳极化的铝载体可接受所谓的阳极后处理,以提高其表面的亲水性。例如,可在例如95℃的高温下用硅酸钠溶液处理铝载体的表面,使铝载体硅酸盐化。或者,可用磷酸盐处理,包括用磷酸盐溶液处理氧化铝表面,所述磷酸盐溶液可进一步含有无机氟化物。而且,可用柠檬酸或柠檬酸盐溶液清洗该氧化铝表面。该处理可在室温下进行,或者可在约30℃至50℃的稍微升高的温度下进行。进一步有意义的处理包括用碳酸氢盐溶液清洗该氧化铝表面。更进一步,可用以下物质处理该氧化铝表面:聚乙烯基膦酸、聚乙烯基甲基基膦酸、聚乙烯醇的磷酸酯、聚乙烯基磺酸、聚乙烯基苯磺酸、聚乙烯醇的硫酸酯和聚乙烯醇与磺化的脂族醛反应形成的缩醛。
可用聚丙烯酸或含有至少30%摩尔丙烯酸单体单元的聚合物(例如GLASCOL D15,一种聚丙烯酸,可购自ALLIED COLLOIDS)的溶液进行另一有用的阳极后处理。
所述载体也可以是柔性载体,可对该柔性载体提供亲水层,后文称作“底层”。该柔性载体例如纸、塑料膜或铝。优选的塑料膜的实例为聚对苯二甲酸乙二醇酯膜、聚萘二甲酸乙二醇酯膜、醋酸纤维素膜、聚苯乙烯膜、聚碳酸酯膜等。该塑料膜载体可以是不透明的或透明的。
所述底层优选是亲水的基料与例如以下的硬化剂交联而成的交联亲水层:甲醛、乙二醛、多异氰酸酯或水解的原硅酸四烷基酯。后者特别优选。亲水底层的厚度可在0.2μm至25μm范围内变化,并优选为1μm至10μm。基底层的优选实施方案更多的实例可参见例如EP-A 1 025 992。
载体上提供的涂层包括含有疏水的热塑性聚合物颗粒的图像记录层。
根据本发明,疏水的聚合物颗粒的数均粒径为40nm至63nm,优选45nm至63nm,更优选45nm至59nm。此处,粒径定义为颗粒直径,由光子相关谱法测定,也叫准弹性方法或动态光散射方法。该方法是测定粒径简便的方法,所测得的粒径值与透射电子显微法(TEM)测得的粒径值很相符,Stanley D.Duke等在2000年5月15日Technical Note-002B中的“Calibration of Spherical Particles by LightScattering(通过光散射测量球形颗粒)”一文(1/3/2000由发表于Particulate Science and Technology 7,第223-228页(1989)中的论文修订)里公开了这一点。如实施例中所述,可用Brookhaven BI-90分析仪测定平均粒径,该仪器可购自Brookhaven Instrument Company,Holtsville,NY,USA。
根据本发明另一实施方案,所述图像记录层中所含疏水的热塑性聚合物颗粒的量大于70%重量并小于85%重量,优选为75%重量至84%重量,更优选77%重量至83%重量。
所述疏水的热塑性聚合物颗粒含有疏水聚合物。适合的疏水聚合物的具体实例为例如聚乙烯、聚(氯乙烯)、聚((甲基)丙烯酸甲酯)、聚((甲基)丙烯酸乙酯)、聚(偏二氯乙烯)、聚(甲基)丙烯腈、聚(乙烯基咔唑)、聚苯乙烯或其共聚物。聚苯乙烯和聚(甲基)丙烯腈或它们的衍生物是非常优选的实施方案。根据这样的优选实施方案,该聚合物含有至少50%重量的聚苯乙烯,更优选含有至少60%重量的聚苯乙烯。为了获得对于有机化学物质(例如印版清洗剂中所用的烃类物质)足够的耐性,该聚合物优选含有至少5%重量,更优选至少30%重量的含氮的单体单元,或对应于(甲基)丙烯腈等以溶解度参数大于20为特征的单体单元。这样的含氮的单体单元的适当的实例公开于EP-A 1 219 416中。根据最优选的实施方案,所述聚合物是基本由苯乙烯单元和丙烯腈单元组成的共聚物,苯乙烯单元和丙烯腈单元的重量比(苯乙烯∶丙烯腈)为1∶1至5∶1,例如2∶1。
该热塑性聚合物颗粒的重均分子量可为5,000g/mol至1,000,000g/mol。
疏水的热塑性聚合物颗粒分散于图像记录层的水性涂层液体中,可以用US 3,476,937中公开的方法制备。另外的特别适合制备热塑性聚合物颗粒水性分散体的方法包括:
-将疏水的热塑性聚合物溶解于于水不混溶的有机溶剂中,
-将所得的溶液分散于水中或水性介质中,和
-通过蒸发除去有机溶剂。
图像记录层进一步包含亲水性基料。亲水性基料的具体实例为乙烯醇、丙烯酰胺、羟甲基丙烯酰胺、羟甲基甲基丙烯酰胺、丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、甲基丙烯酸羟乙酯或马来酸酐/乙烯基甲基醚共聚物的均聚物和共聚物。所用(共)聚合物或(共)聚合物混合物的亲水性优选等同于或高于水解至至少60%重量,优选80%重量程度的聚乙酸乙烯酯的亲水性。
根据本发明另一实施方案,所述图像记录层优选具有的涂层重量为0.45g/m2至0.83g/m2,更优选为0.50g/m2至0.80g/m2,最优选为0.55g/m2至0.75g/m2。
所述涂层除包括图像记录层外,还可包括一层或多层其他层。这样的其他层可以是例如图像记录层和载体之间的粘合改善层;或者是含有一种或多种上述的能将红外线转变成热的化合物的吸光层;或者是在用胶溶液处理过程中除去的覆盖层。
所述图像记录层或其他层进一步含有颜料,该颜料具有亲水表面,并在按图像曝光并用胶溶液显影后提供可见图像。表面的亲水性可以由颜料颗粒表面上亲水基团的存在而产生,所述亲水基团例如阴离子基团或非离子基团。亲水表面可以通过表面处理形成,即通过例如涂布或吸附(adsortion)以下化合物形成:亲水性聚合物、活性物质(例如硅烷偶联剂、环氧化合物、多异氰酸酯等)、表面活性剂(例如阴离子或非离子表面活性剂)或水溶性盐(例如磷酸盐)。典型的亲水性聚合物是具有例如羧酸、磺酸、膦酸、磷酸或其盐等阴离子基团的聚合物或共聚物,或者具有例如聚环氧乙烷等聚环氧烷基团的聚合物或共聚物。着色剂的具体实例如未公布的EP-A 03 103 827中所确定。根据本发明,优选碳的水分散体,例如CAB O JET 200,可购自CABOT,最优选酞菁颜料的水分散体,例如CAB O JET 250,可购自CABOT。
所述图像记录层或其他层也可含有其他成分,例如另外的基料、表面活性剂、显影抑制剂或显影加速剂,尤其是红外线吸收剂。红外线吸收剂是能够将红外线转变成热的化合物。尤其可用的光热转变化合物或红外线吸收剂例如有红外染料、炭黑、金属碳化物、硼化物、氮化物、碳氮化物、青铜结构化的氧化物和导电聚合物分散体,例如聚吡咯分散体、聚苯胺分散体或聚噻吩分散体。
根据本发明优选实施方案,所述涂层含有红外线吸收剂,更优选所述图像记录层含有红外线吸收剂,最优选图像记录层含有相对于图像记录层至少6%重量的红外线吸收剂。
例如通过红外激光器或LED使本发明所用的印版前体暴露于热或红外线。优选使用发射波长为约700nm至约1500nm的近红外线的激光器,例如半导体激光二极管、Nd:YAG激光器或Nd:YLF激光器。所需的激光器功率取决于图像记录层的灵敏度、由斑点直径(现代印版记录机在1/e2的最大强度时的典型值:10-25μm)决定的激光束的象素停留时间、扫描速度和曝光装置的分辨率(即每单位直线距离的可寻址的象素数,常以每英寸的点数或dpi表示;典型值:1000-4000dpi)。常用两类激光曝光装置:内滚筒式(ITD)印版记录机和外滚筒式(XTD)印版记录机。用于热敏印版的ITD印版记录机典型的特征为扫描速度很高,高达500米/秒,可能需要几瓦特的激光功率。典型的激光功率为约200mW至约1W的用于热敏印版的XTD印版记录机以更低的扫描速度工作,其扫描速度例如为0.1米/秒至10米/秒。
由于曝光步骤中产生的热,疏水的热塑性聚合物颗粒熔合或凝结,以致形成与印版的印刷区域相对应的疏水相。由热引起的热塑性聚合物颗粒的聚结、软化或熔化可导致凝结(coagulation)。热塑性疏水聚合物颗粒的凝结温度没有明确的上限,但是温度应足以低于该聚合物颗粒的分解温度。优选所述凝结温度比聚合物颗粒发生分解的温度至少低10℃。所述凝结温度优选高于50℃,更优选高于100℃。
显影步骤中,通过提供胶溶液或烤胶溶液(baking gum solution),除去图像记录层未曝光的区域,并且基本不去除曝光区域,也就是说不会对曝光区域产生一定程度的影响,以致使曝光区域的受墨性不能接受。用胶或烤胶显影时可与机械摩擦相结合,例如使用回转刷。例如可通过用浸渍垫擦,通过浸渍、(旋转)涂布、喷雾、倾倒等方法,用手工或用自动的处理装置,将胶或烤胶溶液施用于印版。施用烤胶溶液后,可在烘烤前将印版干燥,或者在本身的烘烤过程中将印版干燥。烘烤过程可在高于热塑性聚合物颗粒凝结温度的温度下进行,例如在100℃至230℃烘烤5到40分钟。例如,可在230℃将曝光并显影的印版烘烤5分钟,在150℃烘烤10分钟,或在120℃烘烤30分钟。烘烤可在常规的热风烘箱中进行或者通过发红外或紫外光的灯照射进行。
胶溶液一般为水性液体,含有一种或多种能够保护印版的平版印刷图像免受污染的表面保护性化合物,所述污染例如氧化、指纹、脂、油或灰尘或者例如印版处理过程中的划擦造成的损坏。这样的化合物适当的实例为成膜的亲水性聚合物或表面活性剂。用胶溶液处理后留在印版上的层优选含有0.1g/m2至20g/m2的表面保护性化合物。
胶溶液通常以浓溶液提供,最后的用户使用前用水将其稀释。本说明书中,胶溶液中所有化合物的浓度以相对于未稀释的胶溶液的重量百分率表示(重量%或%重量),除非另有说明。
用作胶溶液中保护性化合物的优选的聚合物是阿拉伯胶;支链淀粉;纤维素衍生物,如羧甲基纤维素、羧乙基纤维素或甲基纤维素;(环)糊精;聚(乙烯醇);聚(乙烯吡咯烷酮);多糖;丙烯酸、甲基丙烯酸或丙烯酰胺的均聚物和共聚物;乙烯基甲基醚和马来酸酐的共聚物;乙酸乙烯酯和马来酸酐的共聚物;或苯乙烯与马来酸酐的共聚物。非常优选的聚合物是含有羧酸基团、磺酸基团或膦酸基团或其盐的单体的均聚物或共聚物,所述单体例如(甲基)丙烯酸、乙酸乙烯酯、苯乙烯磺酸、乙烯基磺酸、乙烯基膦酸或丙烯酰氨基丙磺酸。
用作表面保护剂的表面活性剂的实例包括阴离子表面活性剂或非离子表面活性剂。胶溶液也可含有一种或多种上述亲水性聚合物作为表面保护剂,另外,还含有一种或多种表面活性剂以改善涂层的表面性质。胶溶液的表面张力优选为40mN/m至50mN/m。
胶溶液优选含有阴离子表面活性剂,更优选含有阴离子基团为磺酸基的阴离子表面活性剂。
阴离子表面活性剂的实例包括脂肪族酸盐(aliphate)、松香酸盐、羟基烷烃磺酸盐、烷烃磺酸盐、二烷基磺基琥珀酸盐、直链烷基苯磺酸盐、支链烷基苯磺酸盐、烷基萘磺酸盐、烷基苯氧基聚氧乙烯丙基磺酸盐、聚氧乙烯烷基磺苯基醚的盐、N-甲基-N-油烯基牛磺酸钠、N-烷基磺基琥珀酸单酰胺二钠、石油磺酸盐、硫酸化蓖麻油、硫酸化牛油、脂族烷基酯的硫酸酯盐、烷基硫酸酯盐、聚氧乙烯烷基醚的硫酸酯、脂族单甘油酯的硫酸酯盐、聚氧乙烯烷基苯基醚的硫酸酯盐、聚氧乙烯苯乙烯基苯基醚的硫酸酯盐、烷基磷酸酯盐、聚氧乙烯烷基醚的磷酸酯盐、聚氧乙烯烷基苯基醚的磷酸酯盐、苯乙烯马来酸酐共聚物部分皂化的化合物、烯烃-马来酸酐共聚物部分皂化的化合物和萘磺酸盐甲醛缩合物。这些阴离子表面活性剂中特别优选的是二烷基磺基琥珀酸盐、烷基硫酸酯盐和烷基萘磺酸盐。
适当的阴离子表面活性剂的具体实例包括十二烷基苯氧基苯二磺酸钠、烷基化的萘磺酸钠盐、亚甲基-二萘-二磺酸二钠、十二烷基苯磺酸钠、磺酸化的烷基二苯醚、全氟烷基磺酸铵或全氟烷基磺酸钾和二辛基磺基琥珀酸钠。
非离子表面活性剂适当的实例包括聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯聚苯乙烯基苯基醚、聚氧乙烯聚氧丙烯烷基醚、聚氧乙烯聚氧丙烯嵌段聚合物、甘油脂族酸的偏酯、脱水山梨糖醇脂族酸的偏酯、季戊四醇脂族酸的偏酯、丙二醇单脂肪酸酯、蔗糖脂肪酸的偏酯、聚氧乙烯脱水山梨糖醇(sorbitan)脂肪酸的偏酯、聚氧乙烯山梨糖醇(sorbitol)脂肪酸的偏酯、聚乙二醇脂肪酸酯、聚甘油脂肪酸的偏酯、聚氧乙烯化的蓖麻油、聚氧乙烯甘油脂肪酸的偏酯、脂肪族二乙醇酰胺、N,N-双-2-羟基烷基胺、聚氧乙烯烷基胺、三乙醇胺脂肪族酯和三烷基胺氧化物。这些非离子表面活性剂中特别优选的是聚氧乙烯烷基苯基醚和聚氧乙烯-聚氧丙烯嵌段共聚物。另外,也可类似地使用含氟和含硅的阴离子表面活性剂和非离子表面活性剂。
上述表面活性剂中的两种或多种可联合使用。例如,可优选联合使用两种或多种不同的阴离子表面活性剂或联合使用阴离子表面活性剂和非离子表面活性剂。这样的表面活性剂的量没有特别限制,但优选为0.01%重量至20%重量。
胶溶液的pH值优选为3到8,更优选为5到8,最优选为5到7。通常用0.01%重量至2%重量的无机酸、有机酸或无机盐调节胶溶液的pH值。无机酸的实例包括硝酸、硫酸、磷酸和偏磷酸。尤其是用有机酸作为pH控制剂和作为灵敏度降低剂。有机酸的实例包括羧酸、磺酸、膦酸或其盐,例如琥珀酸盐、磷酸盐、膦酸盐、硫酸盐和磺酸盐。有机酸具体的实例包括柠檬酸、乙酸、草酸、丙二酸、对甲苯磺酸、酒石酸、苹果酸、乳酸、乙酰丙酸、植物酸和有机膦酸。
胶溶液还可含有无机盐,优选一碱价磷酸盐或二碱价磷酸盐,更优选碱金属磷酸二氢盐,例如KH2PO4或NaH2PO4。
无机盐的实例包括硝酸镁、磷酸二氢钠、磷酸氢二钠、硫酸镍、六偏磷酸钠和三聚磷酸钠。可用作腐蚀抑制剂的其他无机盐例如硫酸镁或硝酸锌。无机酸、有机酸或无机盐可单独使用或与其中的一种或多种联合使用。
胶溶液还可含有阴离子表面活性剂和无机盐的混合物。该混合物中,所述阴离子表面活性剂优选带有磺酸基的阴离子表面活性剂,更优选单烷基取代或二烷基取代的二苯醚磺酸的碱金属盐;且所述无机盐优选一碱价磷酸盐或二碱价磷酸盐,更优选碱金属的磷酸二氢盐,最优选KH2PO4或NaH2PO4。
除了前面的组分,胶溶液中还可含有润湿剂,例如乙二醇、丙二醇、三乙二醇、丁二醇、己二醇、二乙二醇、二丙二醇、甘油、三羟甲基丙烷和双甘油。所述润湿剂可单独使用或与其中的一种或多种联合使用。一般,上述润湿剂优选用量为1%重量至25%重量。
另外,胶溶液中可含有螯合化合物。稀释用水中所含的钙离子和其他杂质对于印刷有不良影响,因而导致印刷品的污染。可通过向稀释用水中加入螯合化合物解决这一问题。这样的螯合化合物优选的实例包括有机膦酸或膦酰基烷烃三羧酸。具体的实例为乙二胺四乙酸的钾盐或钠盐、二亚乙基三胺五乙酸、三亚乙基四胺六乙酸、羟乙基亚乙基二胺三乙酸、次氮基三乙酸、1-羟基乙烷-1,1-二膦酸和氨基三(亚甲基膦酸)。除了这些螯合剂的这些钠盐或钾盐,还可用有机胺盐。这样的螯合剂优选加入的量相对于稀释状态的胶溶液为0.001%重量至1.0%重量。
另外,所述胶溶液中可含有防腐剂和消泡剂。这样的防腐剂的实例包括酚、酚衍生物、福尔马林、咪唑衍生物、脱氢乙酸钠、4-异噻唑啉-3-酮衍生物、苯并异噻唑啉-3-酮、苯三唑衍生物、脒胍衍生物、季铵盐、吡啶衍生物、喹啉衍生物、胍衍生物、二嗪、三唑衍生物、唑和唑衍生物。这样的防腐剂优选的加入量是能对细菌、真菌、酵母菌等产生稳定效果的量。尽管这样的防腐剂的用量取决于细菌、真菌和酵母菌的种类,但优选用量相对于稀释状态的胶溶液为0.01%重量至4%重量。另外,优选可联合使用两种或多种防腐剂,以便对多种真菌和细菌产生防腐效果。消泡剂优选有机硅消泡剂。这些消泡剂中,可使用乳剂分散型或溶解型消泡剂。这样的消泡剂适当的加入量相对于稀释状态的胶溶液为0.001%重量至1.0%重量。
除了前面的组分,如果需要,胶溶液中可含有吸油墨剂。这样的吸油墨剂的实例包括松节油、二甲苯、甲苯、低庚烷、溶剂石脑油、煤油、溶剂油、烃(例如沸点为约120℃至约250℃的石油馏分)、邻苯二甲酸二酯(例如邻苯二甲酸二丁酯、邻苯二甲酸二庚酯、邻苯二甲酸二正辛酯、邻苯二甲酸二(2-乙基己酯)、邻苯二甲酸二壬酯、邻苯二甲酸二癸酯、邻苯二甲酸二月桂酯、邻苯二甲酸丁基苄酯)、脂族二元酸二酯(例如己二酸二辛酯、己二酸丁基乙二醇酯、壬二酸二辛酯、癸二酸二丁酯、癸二酸二(2-乙基己酯)、癸二酸二辛酯)、环氧化甘油三酯(例如环氧豆油)、磷酸酯(例如磷酸三甲苯酯、磷酸三辛酯、磷酸三氯乙酯)和在一个大气压下凝固点为15℃或更低且沸点为300℃或更高的增塑剂(例如苯甲酸酯(如苯甲酸苄酯))。可与这些溶剂联合使用的其他溶剂的实例包括酮(例如环己酮)、卤代烃(如二氯化乙烯)、乙二醇醚(如乙二醇一甲醚、乙二醇一苯醚、乙二醇一丁醚)、脂族酸(例如己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、十九烷酸、花生酸、山萮酸、木蜡酸、蜡酸、二十七烷酸、褐煤酸、蜂花酸、虫胶蜡酸、异戊酸)和不饱和脂族酸(例如丙烯酸、巴豆酸、异巴豆酸、undecyclic acid、油酸、反油酸、鲸蜡烯酸、芥酸、butecidicacid、山梨酸、亚油酸、亚麻酸、花生四烯酸、丙炔酸、硬脂炔酸、鱼泡酸、塔日酸、里卡利酸)。优选脂族酸在50℃下为液体,更优选脂族酸具有5到25个碳原子,最优选脂族酸具有8到21个碳原子。所述吸油墨剂可以单独使用或与其中的一种或多种联合使用。所述吸油墨剂优选的用量为0.01%重量至10%重量,更优选0.05%重量至5%重量。上述吸油墨剂可以水包油型乳剂存在,或者可在增溶剂的帮助下溶解。
可通过加入增粘化合物,将胶溶液的粘度调至例如1.7cP至5cP,增粘化合物例如聚(环氧乙烷),如分子量为105至107的环氧乙烷。这样的化合物的浓度可为0.01g/l至10g/l。
烤胶具有与上述类似的组成,另外优选在通常的烘烤温度下不蒸发的化合物。适当的烤胶溶液的具体实例描述于例如EP-A 222297、EP-A 1 025 992、DE-A 2 626 473和US 4,786,581。
实施例
平版印刷基材的制备
于60℃下将0.30mm厚的铝箔在含有40g/l氢氧化钠的水溶液中浸8秒钟,并用软化水冲洗2秒钟,使其脱脂。然后在含有12g/l盐酸和38g/l硫酸铝(18水合物)的水溶液中,用交流电,在15秒内,用电化学的方法使该铝箔产生粒纹,该过程的温度为33℃,电流密度为130A/dm2。用软化水冲洗2秒钟后,再用含155g/l硫酸的水溶液在70℃下将该铝箔酸蚀4秒钟,去除污垢,并在25℃下用软化水冲洗2秒钟。接着在45℃,以22A/dm2的电流密度,在含有155g/l硫酸的水溶液中,对该铝箔进行阳极氧化13秒,然后用软化水清洗2秒,在40℃下用含有4g/l聚乙烯基膦酸的溶液进行10秒钟后处理,在20℃下用软化水冲洗2秒钟,然后干燥。
从而得到表面粗糙度Ra为0.21μm,且Al2O3阳极重量为4g/m2的载体。
印版前体1-2的制备
将涂料溶液涂布于上述平版印刷基材上,制得印版前体1和2。涂层的组成如表1中限定。用购自Brookhaven Instrument Company,Holtsville,NY,USA的Brookhaven BI-90分析仪测定苯乙烯/丙烯腈共聚物的平均粒径,结果见表2。由水性涂料溶液涂布该涂层,得到重0.8g/m2的干燥涂层。
表1:干燥涂层的组成(%重量)
成分 | %重量 |
聚合物颗粒(1) | 77 |
IR-2(2) | 10 |
聚丙烯酸基料(3) | 10 |
Cab O Jet 200(4) | 3 |
(1)聚合物颗粒是苯乙烯/丙烯腈的共聚物,苯乙烯与丙烯腈的重量比为60/40,用阴离子润湿剂稳定化;平均粒径见表2;
(2)具有以下结构的红外吸收染料IR-2:
(3)ALLIED COLLOIDS的Glascol D15,Mw=2.7×107g/mol;
(4)CABOT的碳水分散体。
印版前体1-2的成像和处理
用Creo Trendsetter 2344T(40W)(印版记录机,CREO的商标,Burnaby,Canada)使印版前体1和2曝光,以150rpm和最高达330mJ/cm2的变化的能量密度进行操作。
成像后,在上胶装置中使印版前体显影,使用Agfa RC520(AGFA的商标)作为上胶溶液。RC520溶液是含有浓度为39.3g/l的表面活性剂DOWFAX 3B2(可购自DOW CHEMICAL)、浓度为9.8g/l的柠檬酸一水合物和浓度为32.6g/l的柠檬酸三钠二水合物的水溶液,RC520溶液的pH值约为5。
印刷结果
将印版装在GTO46印刷机上(购自Heidelberger DruckmaschinenAG),用K+E Novavit 800 Skinnex油墨(BASF Drucksysteme GmbH的商标)和3%FS101(AGFA的商标)的10%异丙醇溶液作为润版液,开始印刷工作。
通过未曝光区域清除结果的目视检查和印刷时未曝光区域中着色现象的出现,并通过运转周期耐性(run-length resistance)(表2),确定印版的平版印刷性能。良好的运转周期耐性(+)是指100,000次印刷后,印刷时仍能再现200lpi网屏的2%亮部(highlight)。不足的运转周期耐性(-)是指1,000次印刷后,200lpi网屏的亮部出现下降。
表2:运转周期和灵敏度结果
实施例号 | 印版前体 | 平均粒径nm | 灵敏度(*)(mJ/cm2) | 曝光能量(mJ/cm2) | 运行周期(**) |
本发明实施例 | 前体1 | 51 | 215 | 215260330 | +++ |
对比实施例 | 前体2 | 65 | 330 | 215260330 | --+ |
(*):在印刷副本上清楚再现200lpi网屏的2%点所需的能量;
(**):见上文。
本发明实施例1和对比实施例1都显示极好的清除效果,并且没有着色。表2中的结果证明,含有平均粒径为51nm的胶乳的前体1具有改善的灵敏度和良好的运转周期。对比实施例1中,含有平均粒径为65nm的胶乳的前体2仅在高曝光能量下显示高运转周期,并且灵敏度降低。
印版前体3-6的制备
将涂料溶液涂布于上述平版印刷基材上,制得印版前体3至6。涂层的组成如表3中限定。用购自Brookhaven Instrument Company,Holtsivlle,NY,USA的Brookhaven BI-90分析仪测定苯乙烯/丙烯腈共聚物的平均粒径,结果见表4。由水性涂料溶液涂布该涂层,得到重0.6g/cm2的干燥涂层。
表3:干燥涂层的组成(%重量)
成分 | %重量 |
聚合物颗粒(1) | 77 |
IR-2(2) | 10 |
聚丙烯酸基料(3) | 10 |
Cab O Jet 200(4) | 3 |
(1)聚合物颗粒是苯乙烯/丙烯腈的共聚物,苯乙烯与丙烯腈的重量比为60/40,用阴离子润湿剂稳定化;平均粒径见表4;
(2)如表1中确定的IR-2;
(3)ALLIED COLLOIDS的Glascol D15;
(4)CABOT的碳水分散体。
印版前体3-6的成像和处理
用Creo Trendsetter 2344T(40W)(印版记录机,CREO的商标,Burnaby,Canada)使印版前体3-6曝光,以150rpm和最高330mJ/cm2的变化的能量密度进行操作。
成像后,在上胶装置中使印版前体显影,使用Agfa RC520(AGFA的商标)作为上胶溶液。
印刷结果
将印版装在GTO46印刷机上(可购自HeidelbergerDruckmaschinen AG),用K+E Novavit 800 Skinnex油墨(BASFDrucksysteme GmbH的商标)和3%FS101(AGFA的商标)的10%异丙醇溶液作为润版液,开始印刷工作。
如本发明实施例1中所述确定这些前体的灵敏度、清除效果和着色,并总结于表4中。
表4:印版灵敏度和非成像区着色情况的结果
实施例号 | 印版前体 | 平均粒径nm | 灵敏度(*)(mJ/cm2) | 可清除性(**) | 着色性(***) |
对比实施例2 | 前体3 | 36 | - | - | - |
本发明实施例2 | 前体4 | 45 | 110 | + | + |
本发明实施例3 | 前体5 | 50 | 150 | + | + |
本发明实施例4 | 前体6 | 61 | 170 | + | + |
(*):在印刷副本上清楚再现200lpi网屏的2%点所需的能量;
(**):+表示极好的清除;
-表示不足的清除;
(***):+表示无着色;
-表示着色。
表4的结果表明,含有平均粒径≥45nm的胶乳的前体显示极好的清除结果,无着色,且灵敏度高。对比实施例2中,含有粒径为36nm的胶乳的前体3显示不足的清除结果,并且有着色。
印版前体7-12的制备
将涂料溶液涂布于上述平版印刷基材上,制得印版前体7至12。涂层的组成如表5中限定。由水性涂料溶液涂布该涂层,得到重0.6g/cm2的干燥涂层。
表5:干燥涂层的组成(%重量)
印版前体 | 聚合物颗粒(1) | IR-2(2) | 基料(3) | Cab O Jet 250(4) |
前体7 | 65% | 6% | 26% | 3% |
前体8 | 75% | 6% | 16% | 3% |
前体9 | 79% | 8% | 6% | 7% |
前体10 | 81% | 8% | 6% | 5% |
前体11 | 83% | 8% | 6% | 3% |
前体12 | 85% | 6% | 6% | 3% |
(1)聚合物颗粒是苯乙烯/丙烯腈的共聚物,苯乙烯与丙烯腈的重量比为60/40,用阴离子润湿剂稳定化;平均粒径为51nm,由可购自Brookhaven Instrument Company,Holtsville,NY,USA的BrookhavenBI-90分析仪测得;
(2)如表1中确定的IR-2;
(3)ALLIED COLLOIDS的Glascol D15;
(4)CABOT的Cu-酞菁水分散体。
印版前体7-12的成像和处理
用Creo Trendsetter 2344T(40W)(印版记录机,CREO的商标,Burnaby,Canada)使印版前体7-12曝光,以150rpm和最高330mJ/cm2的变化的能量密度进行操作。
成像后,在上胶装置中使印版前体显影,使用Agfa RC520(AGFA的商标)作为上胶溶液。
印刷结果
将印版装在GTO46印刷机上(可购自HeidelbergerDruckmaschinen AG),用K+E Novavit 800 Skinnex油墨(BASFDrucksysteme GmbH的商标)和3%FS101(AGFA的商标)的10%异丙醇溶液作为润版液,开始印刷工作。
如本发明实施例1中所述确定这些前体的灵敏度、清除效果和着色,并总结于表6中。
表6:印版灵敏度和非成像区着色情况的结果
实施例号 | 印版前体 | 灵敏度(*)(mJ/cm2) | 可清除性(**) | 着色性(***) |
对比实施例3 | 前体7 | 330 | + | + |
本发明实施例5 | 前体8 | 190 | + | + |
本发明实施例6 | 前体9 | 190 | + | + |
本发明实施例7 | 前体10 | 190 | + | + |
本发明实施例8 | 前体11 | 190 | + | + |
对比实施例4 | 前体12 | - | - | - |
(*):在印刷副本上清楚再现200lpi网屏的2%点所需的能量;
(**):+表示极好的清除;
-表示不足的清除;
(***):+表示无着色;
-表示着色。
表6的结果表明,含有<85%重量的51nm胶乳的前体显示极好的清除结果,且无着色,但只有当胶乳的量>65%重量时,获得高灵敏度,即对于含有65%重量胶乳的前体7,得到330mJ/m2的灵敏度。
印版前体13-16的制备
以与印版前体7至12同样的方法制备印版前体13至16,不同之处在于用等量的Cap O Jet 200代替Cab O Jet 250。前体13至16的涂层的组成如表7中限定。由水性涂料溶液将该涂层涂布于上述平版印刷基材上,得到重0.6g/cm2的干燥涂层。
表7:干燥涂层的组成(%重量)
印版前体 | 聚合物颗粒(1) | IR-2(2) | 基料(3) | Cab O Jet 200(4) |
前体13 | 65% | 6% | 26% | 3% |
前体14 | 75% | 6% | 16% | 3% |
前体15 | 83% | 8% | 6% | 3% |
前体16 | 85% | 6% | 6% | 3% |
(1)聚合物颗粒是苯乙烯/丙烯腈的共聚物,苯乙烯与丙烯腈的重量比为60/40,用阴离子润湿剂稳定化;平均粒径为51nm,由可购自Brookhaven Instrument Company,Holtsville,NY,USA的BrookhavenBI-90分析仪测得;
(2)由表1中确定的IR-2;
(3)ALLIED COLLOIDS的Glascol D15;
(4)CABOT的碳水分散体。
印版前体13-16的成像和处理
用与上述前体7-12相同的方法对印版前体13-16进行曝光和处理。
印刷结果
将印版装在GTO46印刷机上(可购自HeidelbergerDruckmaschinen AG),用K+E Novavit 800 Skinnex油墨(BASFDrucksysteme GmbH的商标)和3%FS101(AGFA的商标)的10%异丙醇溶液作为润版液,开始印刷工作。
如本发明实施例1中所述确定这些前体的灵敏度、清除效果和着色,并总结于表8中。
表8:印版灵敏度和非成像区着色情况的结果
实施例号 | 印版前体 | 灵敏度(*)(mJ/cm2) | 可清除性(**) | 着色性(***) |
对比实施例5 | 前体13 | 330 | + | + |
本发明实施例9 | 前体14 | 210 | + | + |
本发明实施例10 | 前体15 | 190 | + | + |
对比实施例6 | 前体16 | - | - | - |
(*):在印刷副本上清楚再现200lpi网屏的2%点所需的能量;
(**):+表示极好的清除;
-表示不足的清除;
(***):+表示无着色;
-表示着色。
表8的结果表明,含有<85%重量的51nm胶乳的前体显示极好的清除结果,且无着色,但只有当胶乳的量>65%重量时,获得高灵敏度,即对于含有65%重量胶乳的前体13,得到330mJ/m2的灵敏度。
Claims (17)
1.一种制作平版印刷印版的方法,所述方法包括以下步骤:
-提供包含以下的平版印刷印版前体:
(i)具有亲水表面或提供有亲水层的载体,
(ii)所述载体上的涂层,所述涂层包含图像记录层,所述层含有疏水的热塑性聚合物颗粒和亲水的基料,所述涂层进一步包含颜料,所述颜料存在于所述图像记录层中或存在于所述涂层的其他层中,
-使所述涂层按图像曝光,从而在图像记录层的曝光区域引起热塑性聚合物颗粒的聚结,
-对所述涂层施用胶溶液,将图像记录层的未曝光区域从载体上除去,从而使前体显影,和
-任选烘烤所述显影的前体,
其中所述疏水的热塑性聚合物颗粒的平均粒径为40nm至63nm,其中所述疏水的热塑性聚合物颗粒的量相对于图像记录层高于70%重量且低于85%重量,并且其中所述颜料具有亲水表面,并在按图像曝光和用胶溶液显影后提供可见的图像。
2.权利要求1的方法,其中所述颗粒的平均粒径为45nm至63nm。
3.权利要求1的方法,其中所述颗粒的平均粒径为45nm至59nm。
4.上述权利要求中任一项的方法,其中所述疏水的热塑性聚合物颗粒的量相对于所述图像记录层为75%重量至84%重量。
5.上述权利要求中任一项的方法,其中所述疏水的热塑性聚合物颗粒的量相对于所述图像记录层为77%重量至83%重量。
6.上述权利要求中任一项的方法,其中所述图像记录层的涂层重量为0.45g/m2至0.85g/m2。
7.上述权利要求中任一项的方法,其中所述图像记录层的涂层重量为0.50g/m2至0.80g/m2。
8.上述权利要求中任一项的方法,其中所述图像记录层的涂层重量为0.55g/m2至0.75g/m2。
9.上述权利要求中任一项的方法,其中所述疏水的热塑性聚合物颗粒包括苯乙烯和丙烯腈或甲基丙烯腈的共聚物。
10.上述权利要求中任一项的方法,其中所述涂层进一步包含红外线吸收剂。
11.权利要求10的方法,其中所述红外线吸收剂在所述图像记录层中的量相对于所述图像记录层至少为6%重量。
12.上述权利要求中任一项的方法,其中所述颜料表面上有亲水基团。
13.权利要求12的方法,其中所述亲水基团是阴离子基团或非离子基团。
14.上述权利要求中任一项的方法,其中所述胶溶液含有亲水性的成膜聚合物和/或表面活性剂,且其中所述胶溶液的pH值为3至8。
15.上述权利要求中任一项的方法,其中所述显影在上胶装置中进行,所述上胶装置具有至少一个辊,用于在显影过程中摩擦和/或刷涂该涂层。
16.权利要求15的方法,其中所述按图像曝光的步骤在印版记录机中进行,所述印版记录机通过传送工具与所述上胶装置机械地连接。
17.权利要求15或16的方法,其中所述任选的烘烤步骤在烘烤装置中进行,所述烘烤装置通过传送工具与所述上胶装置机械地连接。
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US60/617,694 | 2004-10-12 | ||
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EP (1) | EP1817166B1 (zh) |
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CN (1) | CN101076448B (zh) |
AT (1) | ATE455647T1 (zh) |
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US8419923B2 (en) | 2006-08-03 | 2013-04-16 | Agfa Graphics Nv | Lithographic printing plate support |
CN102193309A (zh) * | 2010-03-18 | 2011-09-21 | 富士胶片株式会社 | 平版印刷版的制版方法及平版印刷版 |
CN102193309B (zh) * | 2010-03-18 | 2015-12-09 | 富士胶片株式会社 | 平版印刷版的制版方法及平版印刷版 |
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WO2006037716A1 (en) | 2006-04-13 |
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EP1817166A1 (en) | 2007-08-15 |
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