CN106970502A - 可聚合组合物及其应用 - Google Patents
可聚合组合物及其应用 Download PDFInfo
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- CN106970502A CN106970502A CN201611046760.1A CN201611046760A CN106970502A CN 106970502 A CN106970502 A CN 106970502A CN 201611046760 A CN201611046760 A CN 201611046760A CN 106970502 A CN106970502 A CN 106970502A
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- weight
- polymerizable
- adhesive agent
- compound
- polymerisable compound
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
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Abstract
本发明公开了一种可聚合组合物及其应用。该可聚合组合物包含一红外线吸收剂、一聚合起始剂、一可聚合化合物、以及一聚合物黏着剂,其中该聚合物黏着剂为颗粒状的无规共聚物,并包含衍生自可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的结构单元。该可聚合组合物可用于可成像组件及印刷版的制作。
Description
技术领域
本发明系关于一种可聚合组合物及其应用,尤其系关于一种使用颗粒状的特定无规共聚物作为聚合黏着剂的可聚合组合物,以及该可聚合组合物于制作可成像组件(imageable element)与印刷版的应用。
背景技术
印刷技术系一种将图文透过一印刷版直接或间接转印至待印刷介质表面上的技术,可概分为以下四种:凹版印刷、凸版印刷、网版印刷、及平版印刷。
在平版印刷技术中,主要常见的两种方法为:PS(presensitized plate)版印刷、及CTP(computer to plate)版印刷。近来大多使用CTP版来取代传统PS版,由于CTP版系透过计算机控制热源,因此不需要人工校正印刷版的动作且无需使用黄光室,可在一般室内制版,而且CTP版的制版效率、输出速度与印量相较于PS版皆较为优异。
印刷版一般系透过将一可成像组件进行成像处理以形成所欲的图文而制得。以CTP版为例,一般系透过以下方式制造印刷版:提供一可成像组件,其包括一较佳具有亲水表面的基材及一位于该基材上的可成像层,可成像层上并定义有成像区及非成像区;以可成像层为负型感光层为例,对成像区进行曝光,以形成一潜像(latent image);使该可成像层与显影液接触,以选择性地将非成像区的可成像层自基材表面去除,从而形成图文;接着以润版液润洗该具有图文的可成像组件,以于原可成像层的非成像区处的基材表面形成亲水层,完成印刷版的制作。
在CTP版制程中,需使用热敏性成像胶液来制作印刷版,所述热敏性成像胶液可分为二大类,即正型热敏性成像胶液以及负型热敏性成像胶液。正型热敏性成像胶液的受热区域会溶于显影液,而未受热区域则不溶解。负型热敏性成像胶液的受热区域会形成链结(cross linkage),使结构强度增加,不会溶于显影液,但未受热区域则会溶解于显影液。
另外显影液通常为含水的强碱溶液或含有大量的有机溶剂,后续废液处理必须花费大量成本,且对环境亦不友善,因此目前开发出配合负型热敏性成像胶液的「印刷机上显影(on-press)」技术,其系将可成像组件直接安置于印刷机上,并在初始印刷操作期间将可成像组件与油墨及/或润版液接触而显影,从而制得印刷版。换言之,印刷机上显影技术系直接以润版液处理经曝光处理后的可成像组件,完成显影与润版的操作,并不使用显影液。
发明内容
鉴于此,本发明提供一种可聚合组合物,其可作为负型可成像层材料,具有可透过润版液直接显影、以及所制得的印刷版符合相关显影规范且耐用度高等优点。
本发明之一目的在于提供一种可聚合组合物,其包含:
一红外线吸收剂;
一聚合起始剂;
一可聚合化合物;以及
一聚合物黏着剂,
其中该聚合物黏着剂为颗粒状的无规共聚物,并包含衍生自可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的结构单元。
本发明另一目的在于提供一种负型成像胶液,其包含如上述的可聚合组合物以及溶剂。
本发明另一目的在于提供一种可成像组件,其包含:
一基材;以及
一可成像层,位于该基材上,其中
该可成像层系藉由将上述负型成像胶液涂布于该基材上而形成。
本发明再一目的在于提供一种制造印刷版的方法,其包含以下步骤:
(i)提供一如上所述的可成像组件,于该可成像组件的可成像层上定义成像区及非成像区;
(ii)使成像区的该可成像层暴露于近红外线辐射,以形成一潜像(latentimage);以及
(iii)于步骤(ii)之后,使该可成像层与一润版液接触,从而选择性地将非成像区的该可成像层从该基材去除。
本发明与现有技术相比具有明显的优点和有益效果。本发明提供的可聚合组合物,可用于负型印刷版的制作,其技术特点在于:
1)使用一颗粒状并包含特定单体所衍生的结构单元的无规共聚物作为聚合物黏着剂,在制造可成像组件时具有平滑性与成膜性佳的优点。
2)相较于一般使用接枝共聚物或嵌段共聚物作为聚合物黏着剂的可聚合组合物,本发明具有制程简单、成本较低的优势。
3)本发明的可聚合组合物可作为可成像组件中的可成像层材料,在可成像层经曝光后可直接采用润版液完成显影步骤与润版步骤,且所形成的图文结构可符合相关显影要求,尤其具有溶剂抗性佳、对基材附着力佳、分辨率高、可提升印刷量并降低印刷成本等优点。
为使本发明的上述目的、技术特征及优点能更明显易懂,下文系以部分具体实施态样进行详细说明。
具体实施方式
以下将具体地描述根据本发明的部分具体实施态样;惟,在不背离本发明的精神下,本发明尚可以多种不同形式的态样来实践,不应将本发明保护范围解释为限于说明书所陈述者。此外,除非文中有另外说明,于本说明书中(尤其是在权利要求范围中)所使用的“一”、“该”及类似用语应理解为包含单数及复数形式。且除非文中有另外说明,于本说明书中描述溶液、混合物或组合物中所含的成分时,系以该成分所含的固形份(Non Volatile,NV)计算,即,未纳入溶剂的重量。
可聚合组合物
本发明提供一种可聚合组合物,可用于负型印刷版的制作,其一技术特点在于使用一颗粒状并包含特定单体(可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体)所衍生的结构单元的无规共聚物作为聚合物黏着剂。相较于一般使用接枝共聚物或嵌段共聚物作为聚合物黏着剂的可聚合组合物,本发明具有制程简单、成本较低的优势,而且,本发明可聚合组合物可作为可成像组件中的可成像层材料,在可成像层经曝光后可直接采用润版液完成显影步骤与润版步骤,且所形成的图文结构可符合相关显影规范,尤其具有溶剂抗性佳、对基材附着力佳、分辨率高、可提升印刷量并降低印刷成本等优点。
特定言的,本发明的可聚合组合物系包含一红外线吸收剂、一聚合起始剂、一可聚合化合物、以及一聚合物黏着剂,其中该聚合物黏着剂为颗粒状的无规共聚物,并包含衍生自可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的结构单元,且以该可聚合组合物的固体总重量计,该红外线吸收剂的含量为约0.125重量%至约2.0重量%,该聚合起始剂的含量为约0.25重量%至约12.5重量%,该可聚合化合物的含量为约12.5重量%至约40重量%,且该聚合物黏着剂的含量为约10重量%至约85重量%。
以下就可聚合组合物的各成分分别提供详细说明。
红外线吸收剂
红外线吸收剂系指能够吸收波长在约800纳米至约1200纳米的红外辐射线的吸收剂,其系吸收光辐射线并且将其转化为热量,又可称为“光热转化材料(photothermalconversion material)”。
合适的红外线吸收剂之一态样为颜料。颜料的实例包括例如碳黑、海丽晶绿(Heliogen Green)、尼格洛辛黑(Nigrosine Base)、氧化铁(III)、氧化锰、普鲁士蓝(Prussian Blue)、以及巴黎蓝(Paris blue)。颜料颗粒尺寸较佳系不超过含有该颜料的层厚度,更佳为不超过该层的厚度的一半。
合适的红外线吸收剂的另一态样为具有合适吸收光谱与溶解度的染料,较佳系具有750纳米至1200纳米的高消光系数的染料。染料的实例包括:次甲基(methine)、聚次甲基(polymethine)、芳基次甲基(arylmethine)、花青(cyanine)、半花青(hemicyanine)、链花青(streptocyanine)、方酸菁(squarylium),哌喃鎓(pyrylium)、氧喏(oxonol)、萘醌(naphthoquinone)、蒽醌(anthraquinone)、卟啉(porphyrin)、偶氮(azo)、克酮酸(croconium)、三芳基胺(triarylamine)、噻唑鎓(thiazolium)、吲哚鎓(indolium)、唑鎓(oxazolium)、靛花青(indocyanine)、靛三羰花青(indotricarbocyanine)、三羰花青(oxatricarbocyanine)、酞青素(phthalocyanine)、硫代花青(thiocyanine)、噻三羰花青(thiatricarbocyanine)、部花青(merocyanine)、隐花青(cryptocyanine)、萘酞花青(naphthalocyanine)、聚苯胺(polyaniline)、聚吡咯(polypyrrole)、聚噻吩(polythiophene)、硫属哌喃并亚芳基(chalcogenopyryloarylidene)、双(硫属哌喃并)聚次甲基(bis(chalcogenopyrylo)polymethine)、氧吲(oxyindolizine)、吡唑啉偶氮(pyrazoline azo)、以及类(oxazine)。
于本发明的部分实施态样中,较佳系使用具有亲水性的红外线吸收剂。具有亲水性的红外线吸收剂的实例包括具有一或多个硫酸根基团及/或磺酸根基团的花青染料。于本说明书的实施例中系使用具有亲水性的花青染料作为红外线吸收剂。
于本发明的可聚合组合物中,红外线吸收剂的含量并无特殊限制,只要可提供所欲的光辐射线转化功能即可。一般而言,以可聚合组合物的总重量计,红外线吸收剂的含量可为约0.125重量%至约2.0重量%,例如约0.2重量%、约0.25重量%、约0.3重量%、约0.5重量%、约0.75重量%、约1重量%、约1.25重量%、约1.5重量%或约1.75重量%。
聚合起始剂
聚合起始剂用于在可成像组件成像曝光时,引发可聚合化合物与聚合物黏着剂的聚合反应。一般而言,聚合起始剂在暴露于热或电磁辐射时,会产生自由基从而使聚合反应开始进行,故亦被称为“自由基产生剂(free radical generator)”。可使聚合起始剂产生作用的电磁辐射系包括紫外线、可见光、红外线等,对应于约300纳米至约1,400纳米的光谱范围。于本发明的部分实施态样中,系采用热敏性聚合起始剂,其可透过红外线吸收剂吸收红外线所转化而得的热来产生自由基。热敏性聚合起剂的实例包括:过氧化物,例如过氧化苯甲酰基(benzoyl peroxide);氢过氧化物,例如基氢过氧化物(cumylhydroperoxide);偶氮化合物,例如偶氮双异丁腈(azo bis-isobutyronitrile);2,4,5-三芳基咪唑基二聚体(2,4,5-triaryl imidazolyl dimers)(六芳基双咪唑(hexaarylbisimidazole));三卤代甲基三(trihalomethyl triazine);硼酸盐;鎓盐(onium salt),例如重氮盐(diazonium salt)、碘鎓盐(iodonium salt)、锍鎓盐(sulfonium salt)、鏻盐(phosphonium salt)、及吡啶鎓盐(pyridinium salt);及前述的混合物。于本发明的部分实施态样中,系使用碘鎓盐作为聚合物起始剂。
于本发明的可聚合组合物中,聚合起始剂的含量并无特殊限制,只要可引发可聚合化合物与聚合物黏着剂的聚合反应即可。一般而言,以可聚合组合物的总重量计,聚合起始剂的含量可为约0.25重量%至约12.5重量%,例如约0.5重量%、约1重量%、约2重量%、约2.5重量%、约5重量%、约7重量%、约9重量%、约10重量%、或约12重量%。
可聚合化合物
可聚合化合物与聚合物黏着剂系构成可成像组件的可成像层的主要材料。可聚合化合物意指可藉由聚合物起始剂而聚合或交联的化合物,例如但不限于含烯基的不饱和化合物或异氰酸酯系化合物,并且合适的可聚合化合物通常为多官能的化合物。可聚合化合物的实例包括选自以下群组的化合物:多官能丙烯酸酯系化合物,例如二丙烯酸酯系化合物、三丙烯酸酯系化合物、四丙烯酸酯系化合物、五丙烯酸酯系化合物、六丙烯酸酯系化合物、环氧丙烯酸酯系化合物、聚酯丙烯酸酯系化合物、或聚醚丙烯酸酯系化合物;多异氰酸酯系化合物,例如二异氰酸酯系化合物、三异氰酸酯系化合物、或四异氰酸酯系化合物;多烯丙基系化合物,例如二烯丙基酯系化合物、三烯丙基酯系化合物、或四烯丙基酯系化合物;以及前述的组合。于本发明的部分实施态样中,可聚合化合物系选自以下群组:新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇六丙烯酸酯、及其组合。
于本发明的可聚合组合物中,在曝光成像之后可与聚合物黏着剂共同形成不溶于润版液的成像区的前提下,可聚合化合物的含量可视需要调整。一般而言,以可聚合组合物的总重量计,可聚合化合物的含量可为约12.5重量%至约40重量%,例如约15重量%、约20重量%、约25重量%、约30重量%、或约35重量%。
聚合物黏着剂
聚合物黏着剂可藉由聚合起始剂及曝光程序而发生聚合或交联反应,从而彼此结合或者与可聚合化合物结合。本发明采用的聚合物黏着剂系一无规共聚物,且包含衍生自可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的结构单元。具体言的,该聚合物黏着剂系呈颗粒状的无规共聚物,具有一疏水主链、连接于主链的包含聚氧化烯链段(segment)的侧基、以及连接于主链的非含氮侧基。于不受理论限制下,咸信该聚合物黏着剂同时具有疏水主链以及亲水的含聚氧化烯链段侧基的特点,可有利于可成像组件的显影结果。
聚合物黏着剂的疏水主链可为全碳链,例如聚合物黏着剂系源自烯键式不饱和单体的聚合的情形,或者亦可为包含杂原子的非全碳链,例如聚合物黏着剂系源自单体的缩聚式聚合的情形。
聚合物黏着剂的包含亲水的聚氧化烯链段的侧基系衍生自可聚合的聚氧化烯系单体。举例言的,上述可聚合的聚氧化烯系单体系包含一具下式(1)结构的聚氧化烯链段的烯键式不饱和单体,其中R是C1至C6烷基或是苄基(benzyl group),所述C1至C6烷基例如是甲基、乙基、正丙基、异丙基、正丁基、二级丁基、异丁基等、三级丁基、正戊基、异戊基、新戊基、正己基、异己基、1,1-二甲基-丁基、2,2-二甲基-丁基、环戊基、及环己基;x为1至3的整数;以及y为5至150的整数。较佳地,x为2至3的整数,且y为10至150的整数。
-(O-(CH2)x)y-OR 式(1)
于本发明的部分实施态样中,可聚合的聚氧化烯系单体系具有胺基甲酸酯基团的可聚合的聚氧化烯系单体。上述具有胺基甲酸酯基团的可聚合的聚氧化烯系单体系包含一具下式(2)结构的聚氧化烯链段的烯键式不饱和单体,其中式(2)的R、x、及y具有与式(1)相同的定义。
-NC(=O)-(O-(CH2)x)y-OR 式(2)
于本发明的部分实施态样中,可聚合的聚氧化烯系单体系一具下式(3)结构的聚氧化烯链段的烯键式不饱和单体,其中t为0或1,z为1至20的整数,G为-C(=O)-O-、-O-、或-CH2-,且Y具有式(2)结构。
(CH2=CHt(CH3)1-t))-G-(CH2)z-Y 式(3)
聚合物黏着剂的非含氮侧基系衍生自可聚合的非聚氧化烯系非含氮单体。于本发明的部分实施态样中,可聚合的非聚氧化烯系非含氮单体系烯键式不饱和的非聚氧化烯系非含氮单体。该烯键式不饱和的非聚氧化烯系非含氮单体的实例包括:苯乙烯类单体、烷基乙烯基醚、烷基乙烯基酯、以及前述的组合。于本发明的部分实施态样中,可聚合的非聚氧化烯系非含氮单体系苯乙烯类单体。
用语“苯乙烯类单体”系指苯乙烯及其衍生物。苯乙烯类单体的实例可选自以下群组:苯乙烯、4-氯-α-甲基苯乙烯(4-chloro-α-methylstyrene)、α-甲基苯乙烯、4-甲基苯乙烯、α-乙基苯乙烯、4-乙基苯乙烯、3-甲基苯乙烯、4-丙基苯乙烯、4-环己基苯乙烯、二乙烯基苯、氟苯乙烯、溴苯乙烯、氯苯乙烯、氯甲基苯乙烯、4-甲氧基苯乙烯、4-乙氧基苯乙烯、羟基苯乙烯(hydroxystyrene)、乙酰氧基苯乙烯(acetoxystyrene)、1-乙烯基萘(1-vinylnaphthalene)、2-乙烯基萘(2-vinylnaphthalene)、4-十二烷基苯乙烯、2-乙基-4-苯甲基苯乙烯、4-(苯基丁基)苯乙烯、及其组合。较佳系使用选自以下群组的苯乙烯类单体:苯乙烯、α-甲基苯乙烯、4-甲基苯乙烯、α-乙基苯乙烯、4-乙基苯乙烯、3-甲基苯乙烯、4-丙基苯乙烯,4-十二烷基苯乙烯、4-甲氧基苯乙烯、4-乙氧基苯乙烯、或其组合。于本说明书的实施例中系使用苯乙烯。
烷基乙烯醚的实例可选自以下群组:直链烷基乙烯醚、分支链烷基乙烯醚、环烷基乙烯醚、羟基烷基乙烯醚、及其组合,较佳地,所述烷基乙烯醚中的烷基系C1至C18烷基,具体实例包括甲基乙烯基醚、乙基乙烯基醚(ethyl vinyl ether,EVE)、及烯丙基乙烯基醚,但不限于此。
烷基乙烯酯的实例可选自以下群组:直链烷基乙烯酯、分支链烷基乙烯酯、环烷基乙烯酯、羟基烷基乙烯酯、及其组合。较佳地,烷基乙烯酯中的烷基系C1至C18烷基,具体实例包括甲基乙烯基酯、乙基乙烯基酯、烯丙基乙烯基酯、第三碳酸乙烯酯、及醋酸乙烯酯(vinyl Acetate,Vac),但不限于此。
于本发明的部分实施态样中,合成聚合物黏着剂的可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的比例为,以可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的总重计,可聚合的聚氧化烯系单体的比例系约5重量%至约40重量%。惟本发明亦不排除以其他比例合成聚合物黏着剂的情形。
本发明所涉的聚合物黏着剂系呈颗粒形式的无规共聚物,所述颗粒系指在一般物理性加工条件下不会聚结或结合形成连续膜的离散颗粒型态。颗粒的数量平均直径可为约100纳米至约500纳米,较佳为约150纳米至约250纳米。此外,聚合物黏着剂的重量平均分子量(Mw)通常为约20,000至约200,000,较佳为约50,000至约100,000。于不受理论限制下,咸信(离散)颗粒形式的聚合物黏着剂可进一步提升成像组件的显影效果;特别是使用纳米级颗粒的聚合物黏着剂可改善可成像组件的平滑性与印刷版分辨率。
于本发明的可聚合组合物中,可单独使用一种符合所述条件的聚合物黏着剂,亦可合并使用多种符合所述条件的聚合物黏着剂。另外,在曝光成像之后可与可聚合化合物共同形成所需图文结构的前提下,聚合物黏着剂的含量可视需要调整。一般而言,以可聚合组合物的总重量计,聚合物黏着剂的含量可为约10重量%至约85重量%,例如约15重量%至约75重量%、约30重量%至约75重量%、约35重量%至约75重量%、或约35重量%至约60重量%。当聚合物黏着剂的含量小于10重量%时,可聚合组合物的成膜性不佳,且所制得印刷版的上墨性与耐磨性不佳;而当聚合物黏着剂的含量大于85重量%时,所制得印刷版的显影性下降,无法有效显影。
本发明可聚合组合物可视需要加入一或多种此技术领域具有通常知识者所熟知的添加剂,包含但不限于共-黏着剂(co-binder)、或无机填料。
共-黏着剂通常为水溶性或水分散性聚合物,例如纤维素衍生物,如羧甲基纤维素、甲基纤维素、羟丙基甲基纤维素、羟丙基纤维素、羟乙基纤维素;聚乙烯醇;聚丙烯酸;聚甲基丙烯酸;聚乙烯基吡咯烷酮;聚乳酸;聚乙烯基磷酸;合成共聚物,例如烷氧基聚乙二醇丙烯酸酯或甲基丙烯酸酯,如甲氧基聚乙二醇丙烯酸酯或甲基丙烯酸酯、与如甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸丁酯、或甲基丙烯酸烯丙酯的单体的共聚物;以及其混合物。共-黏着剂可提供一可交联位点,例如,一烯基不饱和位点。
为提升显影速度,本发明可聚合组合物可视需要添加一或多种无机填料,适用于本发明的无机填料系为本发明所属技术领域中具有通常知识者所熟知者,其实例包括但不限于:二氧化硅、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、石墨、煅烧高岭土、白岭土、云母、水滑石、中空二氧化硅、玻璃珠、陶瓷晶须、纳米碳管、及前述的组合。较佳实例为氧化锌、二氧化硅、氧化锆、二氧化钛、或其混合物。此外,上述无机填料的比表面积范围较佳为约100平方米/克至约250平方米/克,更佳为约150平方米/克至约200平方米/克。添加无机填料可进一步提升所制得可成像组件的机上显影速度,一般而言,以可聚合组合物的总重量计,其含量系约0.1重量%至约10重量%的间,较佳系约0.5重量%至约5重量%。
负型成像胶液
本发明的可聚合组合物可用于制作印刷版用的可成像组件的负型成像胶液。因此,本发明亦提供一种负型成像胶液,其系包含可聚合组合物与溶剂,溶剂系用于将负型成像胶液的黏度调整至适合操作的范围。溶剂可在调配可聚合组合物各成分时添加,亦可在最终欲进行涂布时添加。根据本发明之一实施态样,溶剂宜在调配可聚合组合物各成分时适当添加,并在最终依实际的条件及需求而进行调整黏度时,进一步添加溶剂,使固形份在约5重量%至约30重量%的范围。上述溶剂的种类并无特殊限制,可为任何可溶解或分散可聚合组合物各成分、但不与该等成分反应且对聚合反应无不利影响的惰性有机溶剂。举例言的,合适的溶剂可选自以下群组:水、酯类、酮类、醇类、醚类、内酰胺类或其组合。水溶剂的非限制性实例包括纯水或去离子水;酯类溶剂的非限制性实例包括乙酸乙酯、或乙酸丁酯;酮类溶剂的非限制性实例包括甲乙酮、甲基异丁基酮、甲基丙基酮、或丙酮;醇类溶剂的非限制性实例包括甲醇、乙醇、正丙醇、异丙醇、或丁醇;醚类溶剂的非限制性实例包括丙醚、丁醚、乙二醇甲醚或丙二醇甲醚;内酰胺类溶剂的非限制性实例包括N-甲基吡咯烷酮、N-乙基吡咯烷酮。于本发明的部分实施态样中,该溶剂系为去离子水、正丙醇、甲乙酮(MEK)、丙二醇甲醚(PM)、以及前述的混合物。上述的负型成像胶液可藉由熟习此项技术人士所熟知的任何一种方式制备。举例言的,可将本发明的可聚合组合物以搅拌器均匀混合,随后溶解或分散于适合的溶剂中而制成负型成像胶液。
可成像组件
本发明的负型成像胶液可用于制作印刷版用的可成像组件。因此,本发明亦提供一种可成像组件,其包含一基材以及一位于该基材上的可成像层,其中该可成像层系藉由将包含如上述的可聚合组合物之一负型成像胶液涂布于该基材上而形成。于本发明的可成像组件中,合适的基材可为任何现有技术中用于制备平版印刷版的基材,且通常具有坚固、稳定且具弹性等特性。举例言的,可采用聚合物基材、陶瓷基材、金属基材(如铝基材、锌基材、钛基材、及前述金属的合金基材)、或纸基材,并且所述基材可为一体成形结构或层压结构。另外,基材通常具有亲水表面,以使得显影后润版液可附着于基材表面;该亲水表面可透过物理磨版(graining)、电化学磨版、化学磨版、阳极氧化以及封孔等常见表面处理技术来提供。于本发明之一较佳实施态样中,该基材系一亲水铝基材。
上述可成像层可藉由本领域的常规涂布方法而形成,例如,可藉由旋转涂布法、棒涂法(bar cotaing method)、凹版涂布法、狭缝涂布法(slot coating method)、辊涂法(rolloer coating method)、或铸模涂布法(die coating method)等方法将包含本发明可聚合组合物的负型成像胶液涂布至基材表面;接着进行适度干燥以形成可成像层。干燥方式包括但不限于烘箱、空气干燥、及鼓风干燥。
于本发明的部分实施态样中,基材与可成像层的间可更包含一功能性涂层,例如,可更包含一显影性改良层以改良显影效果,或包含一热绝缘层以提供成像曝光区域热绝缘效果的。于本发明的另一部分实施态样中,可成像层上亦可更包含一功能性涂层,例如是可在可成像组件储存时防止氧气渗透到可成像层中的保护层(cover layer)。类此涂层的使用乃所属领域具有通常知识者观得本案说明书内容后可基于其所具备的通常知识而完成者,于此不予赘述。
制造印刷版的方法
本发明的可成像组件可用于制作印刷版。因此,本发明另提供一种制造印刷版的方法,该方法包含:(i)提供一如上述的可成像组件,于该可成像组件的可成像层上定义成像区及非成像区;(ii)使成像区的可成像层暴露于近红外线辐射,以形成一潜像(latentimage);以及(iii)于步骤(ii)之后,使可成像层与一润版液接触,从而选择性地将非成像区的可成像层从基材去除。
于步骤(i)中,系根据欲印刷的图案,将可成像层定义出一成像区及一非成像区。举例言的,可利用一由待印刷图案所制得的屏蔽,置于可成像层上以区分成像区与非成像区;或者,可透过计算机设定待印刷图案,并由此控制步骤(ii)中近红外线辐射的照射区域。
于步骤(ii)中,可使用任何可发射近红外线辐射的装置,例如红外线发光二极管(LED)激光器。当近红外线辐射照射至成像区后,引发可成像层的聚合或交联反应,从而形成一含有待印刷图文的潜像。
于步骤(iii)中,系利用润版液去除非成像区的可成像层,所使用的润版液可为本领域常用的润版液,并无特殊限制。一般而言,润版液为一种水性混合物,其可含有减感剂、pH值调节剂、缓冲剂、杀菌剂、防霉剂、润湿剂,溶剂等成分,所述溶剂例如水、醇类(如异丙醇或乙醇)、醚类(如二乙醚或乙二醇单甲醚)、及前述的混合物。
本发明可聚合组合物形成的成像层在未经步骤(ii)的近红外线辐射曝光的非成像区可容易地被润版液去除,显影结果可符合相关显影规范,而经步骤(ii)的近红外线辐射曝光的成像区所形成的图文结构具有溶剂抗性佳、对基材附着力佳、分辨率高等优点,可以抵抗润版液的侵蚀,且可提升印刷量,降低印刷成本。
兹以下列具体实施态样进一步例示说明本发明,其中,所采用的量测仪器及方法分别如下:
可成像组件外观判断
首先,以目视方式确认可成像组件表面是否有不规则凸起或凹陷,若有不规则凸起或凹陷即判定为表面粗糙。之后,藉由SCREEN 8600曝光机对可成像组件进行曝光,由于曝光机对于版面平整度订有业界的标准要求,因此若是可以正常进版、曝光、退版,表示版面平整度符合业界标准要求,称为表面平整;相反地,若是在曝光过程中出现无法正常进退版、或无法正常曝光的现象,则判定为表面不平整。
曝光反差测试
使用SCREEN 8600曝光机,将可成像组件在150毫焦耳/平方厘米(mJ/cm2)的条件下曝光后,以HunterLab ColorQuest XE的分光谱仪分别量测非曝光区(0%网点区)与曝光区(100%网点区)的L、a*、b*值,各区域取10点测量并记录数值后取平均,并计算出ΔE=(ΔL2+Δa*2+Δb*2)^(1/2),若ΔE≥1.5则可称为有“可视反差”。
低化学显影测试
将1千克的低化学显影剂“长显-500S”(购自长兴材料工业股份有限公司)加水配制成40千克的显影液并置于PS88BF显影机中,将显影温度控制在23℃且控制显影时间为30秒,将曝光后的印刷版放入显影机中进行显影并检视显影结果。若成像清晰且非成像区没有可成像层材料残留则为纪录为“ok”,若是成像区的图文破损但非成像区没有可成像层材料残留则记录为“图文破损”,若是成像不清晰且非成像区有可成像层材料残留则记录为“Δ”,而若是非成像区的可成像层材料完全无法被移除则记录为“X”。
机上显影测试
将经过曝光的可成像组件藉由新开元47XIII快速印刷机进行机上显影。显影步骤为:挂印刷版、将水墨辊同时靠上印刷版、靠上后运转5秒。观察印刷版是否完全显影并以此判断显影速度,若是显影不完全可以再延长时间至1分钟。之后,开始走纸印刷并计算张数,印至第50张后停止走纸,取出第50张纸,根据纸的成像清晰度与非成像区的洁净度来判断印刷结果。若成像清晰且非成像区没有油墨残留则记录为“ok”,若是成像破损但非成像区没有油墨残留则记录为“图文破损”,若是成像不清晰且非成像区有油墨残留则记录为“Δ”,而若是纸面完全沾满油墨则记录为“X”。
耐20重量%异丙醇测试
将经过曝光的可成像组件以低化学显影方式进行显影,以制得印刷版。以20重量%异丙醇沾湿药用纱布,随后将纱布固定在一往复式磨耗机的测试头上,并将印刷版固定于往复式磨耗机上,其中往复式磨耗机系以60赫(Hz)的运作频率搭配500克的负重在100%网点区进行磨耗测试,来回摩擦1000次后观察网点是否减薄来判断测试结果。若网点没有减薄则记录为“ok”,若网点有减薄则记录为“Δ”,而若已经露出印刷版底则记录为“X”。
成像区上墨性测试
依一般机上显影的方式对经过曝光的可成像组件进行显影,以制得印刷版。以该印刷版印刷样品并观察印刷样品在1%、2%、3%、4%、5%、6%、7%、10%网点的墨色浓度来判断测试结果。若是全区的墨色浓度都可以被肉眼辨识则记录为“ok”,若是只有2%至10%可以被辨识则记录为“Δ”,而若是3%以上才能被辨识则记录为“X”。
印刷量测试
将4张可成像组件经分色曝光后以Komori Lithrone S26进行机上显影,所使用的润版液为5重量%的异丙醇水溶液,油墨为一般大豆油墨,且纸张为模造纸。以每分钟15,000张的印刷速度来进行印量测试,以每5,000张的间隔取下引刷样品,即,取第1张、第5,000张、第10,000张、第15,000张,以此类推,一直到第100,000张的印刷样品,并以网点机量测印刷样品上的网点值变化。当印刷样品的网点与第1张印刷样品的网点差异超过0.5%时就停止印刷,并记录停止时的印刷量。
实施例
亲水单体HM-400的制备
在一四口烧瓶中加入400克的甲氧基聚乙二醇(methoxypolyethylene glycol)(Mw=1,000至8,000)、0.04克的氢醌单甲醚(monomethyl ether of hydroquinone,MEHQ)、与0.04克的二月桂酸二丁基锡(dibutyltin dilaurate),并将四口分别接上机械搅拌器、温度探针与温度计、冷凝管、以及加料漏斗与干燥空气通气管,并在加料漏斗中加入140克的2-异氰酸基丙烯酸乙酯(2-isocyanatoethyl acrylate)(结构:;型号:KarenzAOI,购自Showa Denko)。将反应温度升至60℃后,历时3小时将2-异氰酸基丙烯酸乙酯缓缓滴入反应瓶中,完成后将温度控制在60℃并持续搅拌3小时,随后以红外线光谱仪确认2270cm-1讯号消失以判断反应是否完成,之后将产物倒入聚丙烯(PP)瓶中封盖保存。
聚合物黏着剂的制备
本发明的聚合物黏着剂制备过程可视需要利用溶剂调整至适合操作的范围,一般而言固形份比例占聚合物黏着剂重量的约10重量%至约50重量%。合宜的溶剂可选自以下群组:水、酯类、酮类、醇类、醚类、内酰胺类或其组合。于以下聚合物黏着剂的制备例中,系以固形份25重量%为例。
制备例1:聚合物黏着剂SU-1000
在一四口烧瓶中加入80克的亲水单体HM-400、120克的苯乙烯、5克的偶氮双异丁腈(azobisisobutyronitrile,AIBN)、500克的正丙醇、与100克的去离子水(DI-water),并于四口分别接上机械搅拌器、温度探针与温度计、冷凝管、以及加料漏斗与干燥氮气通气管。将反应温度升至80℃后持续搅拌8小时,以气相层析仪确认产物中是否还有未反应的苯乙烯残留,若有则延长反应时间3小时后再测量单体残留量。待反应完成后,将温度降至室温,获得颗粒状的聚合物黏着剂SU-1000,将聚合物黏着剂SU-1000倒出至PP瓶中封盖保存。经凝胶渗透层析仪(gel permeation chromatography,GPC)测得聚合物黏着剂SU-1000的分子量主峰为63,000。
制备例2:聚合物黏着剂SU-1001
以与制备例1相同的方式制备聚合物黏着剂SU-1001,惟调整亲水单体HM-400的用量为50克,以及调整苯乙烯的用量为150克。经GPC测得聚合物黏着剂SU-1001的分子量主峰为68,000。
制备例3:聚合物黏着剂SU-1002
以与制备例1相同的方式制备聚合物黏着剂SU-1002,惟调整亲水单体HM-400的用量为30克,以及调整苯乙烯的用量为170克。经GPC测得聚合物黏着剂SU-1002的分子量主峰为71,000。
制备例4:聚合物黏着剂SU-1003
以与制备例1相同的方式制备聚合物黏着剂SU-1003,惟调整亲水单体HM-400的用量为10克,以及调整苯乙烯的用量为190克。经GPC测得聚合物黏着剂SU-1003的分子量主峰为80,000。
比较制备例1:比较聚合物黏着剂SU-2000
在一四口烧瓶中加入80克的亲水单体HM-400、60克的苯乙烯、60克的丙烯腈、5克的AIBN、500克的正丙醇、与100克的去离子水,并于四口分别接上机械搅拌器、温度探针与温度计、冷凝管、以及加料漏斗与干燥氮气通气管。将反应温度升至80℃后持续搅拌8小时,以气相层析仪确认产物中是否还有未反应的苯乙烯残留,若有则延长反应时间3小时后再测量单体残留量。待反应完成后,将温度降至室温,获得颗粒状的比较聚合物黏着剂SU-2000,将比较聚合物黏着剂SU-2000倒出至PP瓶中封盖保存。经GPC测得比较聚合物黏着剂SU-2000的分子量主峰为66,000。
比较制备例2:比较聚合物黏着剂SU-3300
以与比较制备例1相同的方式制备比较聚合物黏着剂SU-3300,惟以600克的N-乙基吡咯烷酮取代正丙醇与水。经GPC测得比较聚合物黏着剂SU-3300的分子量主峰为86,000。
比较制备例3:比较聚合物黏着剂PU-0615树脂
在一四口烧瓶中加入47.7克的双酚A双(2-羟乙基)醚(bisphenol A bis(2-hydroxyethyl)ether)、2.5克的二羟甲基丙酸(dimethylolpropionic acid)、1.6克的二丁锡二月桂酸酯、45.6克的异佛酮二异氰酸酯(isophorone diisocyanate,IPDI)、3.8克的3,5-二甲基吡唑(3,5-dimethylpyrazole)、与235克的乙酸乙酯,并于四口分别接上机械搅拌器、温度探针与温度计、冷凝管、以及加料漏斗与干燥氮气通气管。将温度升至70℃后搅拌1小时,随后将温度升至80℃并持温搅拌12小时,以红外线光谱仪确认2270cm-1信号消失来判断反应是否完成。待反应完成后,将温度降至室温,接着加入0.8克的氢氧化钠与8.2克的去离子水,并将所得产物倒入PP瓶中。于冰浴下将该PP瓶以高速均质机在15,000rpm的转速搅拌3分钟,接着静置冰浴中冷却1分钟,重复前述均质步骤4次,以获得乳液型态的比较聚合物黏着剂PU-0615树脂。最后以回旋浓缩仪将乙酸乙酯移除,获得到稳定的比较聚合物黏着剂PU-0615树脂。经GPC测得比较聚合物黏着剂PU-0615树脂的分子量主峰为37,000。
负型成像胶液的制备
实施例1
于PM与MEK混合溶剂(PM:MEK=1:1,其中PM为丙二醇甲醚且MEK为甲乙酮)中,加入具亲水性的花青染料(型号:S-0306,购自FEW Chemicals)作为红外线吸收剂、(购自强力化工)作为聚合起始剂、二新戊四醇五丙烯酸酯(型号:SR-399,购自Sartomer)作为可聚合化合物、以及聚合物黏着剂SU-1000,并搅拌均匀以制得具有225.18克的PM与MEK混合溶剂的负型成像胶液1,各成分的重量如表1所示。
实施例2
以与实施例1相同的方式制备负型成像胶液2,惟另添加0.36重量%的二氧化硅微球粒子(型号:1030,购自EVONIK),并调整溶剂的用量,如表1所示。
实施例3
以与实施例1相同的方式制备负型成像胶液3,惟以聚合物黏着剂SU-1001取代聚合物黏着剂SU-1000,如表1所示。
实施例4
以与实施例1相同的方式制备负型成像胶液4,惟以聚合物黏着剂SU-1002取代聚合物黏着剂SU-1000,如表1所示。
实施例5
以与实施例1相同的方式制备负型成像胶液5,惟以聚合物黏着剂SU-1003取代聚合物黏着剂SU-1000,如表1所示。
实施例6
以与实施例1相同的方式制备负型成像胶液6,惟以新戊四醇三丙烯酸酯(型号:SR-444,购自Sartomer)取代二新戊四醇五丙烯酸酯作为可聚合化合物,如表1所示。
实施例7
以与实施例4相同的方式制备可聚合组合物7,惟调整聚合物黏着剂的重量,如表1所示。
实施例8
以与实施例4相同的方式制备可聚合组合物8,惟调整聚合物黏着剂的重量,如表1所示。
比较实施例1
以与实施例1相同的方式制备比较负型成像胶液1,惟不添加可聚合化合物(二新戊四醇五丙烯酸酯),如表1所示。
比较实施例2
以与实施例1相同的方式制备比较负型成像胶液2,惟以Hybridur 580黏着剂(购自Air Products)取代聚合物黏着剂SU-1000,如表1所示。
比较实施例3
以与实施例1相同的方式制备比较负型成像胶液3,惟以比较聚合物黏着剂PU-0615树脂取代聚合物黏着剂SU-1000,如表1所示。
比较实施例4
以与实施例2相同的方式制备比较负型成像胶液4,惟以比较聚合物黏着剂SU-2000取代聚合物黏着剂SU-1000,如表1所示。
比较实施例5
以与实施例1相同的方式制备比较负型成像胶液5,惟以比较聚合物黏着剂SU-3300取代聚合物黏着剂SU-1000,并调整溶剂的用量,如表1所示。
表1
*:此聚合物黏着剂数值为扣除溶剂后的固形份重量
可成像组件的制备
准备一经过脱脂、电化学粗化、阳极化、及封孔处理而获得的亲水铝基材,使用铸模涂布机将负型成像胶液1至8及比较负型成像胶液1至5分别涂布于一亲水铝基材上,并干燥后,制得可成像组件1至8及比较可成像组件1至5。
观察可成像组件1至8及比较可成像组件1至5的涂布外观,并对可成像组件1至8及比较可成像组件1至5分别实施曝光反差测试、低化学显影测试、机上显影测试、耐20重量%异丙醇测试、成像区上墨性测试、及印刷量测试,结果纪录于表2中。
表2
如表2所示,利用本发明可聚合组合物所制得的可成像组件1至8,皆符合显影规范(如曝光反差、低化学显影、机上显影、成像区上墨性等)、具有良好的耐溶剂性、且可提供较高的印刷量,印刷版的耐用性大幅提升。尤其,与实施例1相比,实施例2额外添加的无机填料(二氧化硅微球粒子)可进一步提升所制得可成像组件的机上显影速度。此外,由实施例1及实施例3至5可知,以不同比例的可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体制备的聚合物黏着剂均有提供本发明诉求的功效。另外,由实施例4及实施例7至8可知,以不同用量的聚合物黏着剂均有提供本发明诉求的功效。相对地,如比较实施例1所示,当负型成像胶液中不包含可聚合化合物时,所制得的可成像组件无法符合各显影规范;如比较实施例2及3所示,若所使用的聚合物黏着剂并非本发明所指定的无规共聚物,例如改以胺甲酸乙酯/丙烯酸混合黏着剂(实施例2)或PU黏着剂(实施例3)替代时,所制得的可成像组件明显在涂布外观、部分显影规范、及印刷量上表现较差;以及如比较实施例4及5所示,当聚合物黏着剂含有氰基时,所制得的可成像组件亦在部分显影规范及印刷量上表现较差。
上述实施例仅为例示性说明本发明的原理及其功效,并阐述本发明的技术特征,而非用于限制本发明的保护范畴。任何熟悉本技术者在不违背本发明的技术原理及精神下,可轻易完成的改变或安排,均属本发明所主张的范围。因此,本发明的权利保护范围系如权利要求范围所列。
Claims (10)
1.一种可聚合组合物,其特征在于,其包含:
一红外线吸收剂;
一聚合起始剂;
一可聚合化合物;以及
一聚合物黏着剂,其中该聚合物黏着剂为颗粒状的无规共聚物,并包含衍生自可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的结构单元。
2.如权利要求1所述的可聚合组合物,其特征在于,该可聚合的聚氧化烯系单体系包含一具下式(1)结构的聚氧化烯链段:
-(O-(CH2)x)y-OR 式(1),
其中x是1至3的整数,y是5至200的整数,且R系C1至C6烷基或苄基。
3.如权利要求1所述的可聚合组合物,其特征在于,该可聚合的聚氧化烯系单体系具有胺基甲酸酯基团的可聚合的聚氧化烯系单体。
4.如权利要求1所述的可聚合组合物,其特征在于,该可聚合的非聚氧化烯系非含氮单体系选自以下群组:苯乙烯类单体、烷基乙烯基醚、烷基乙烯基酯、及其组合。
5.如权利要求1所述的可聚合组合物,其特征在于,以可聚合的聚氧化烯系单体与可聚合的非聚氧化烯系非含氮单体的总重计,可聚合的聚氧化烯系单体的比例系为约5重量%至约40重量%。
6.如权利要求1所述的可聚合组合物,其特征在于,以该可聚合组合物的总重量计,该红外线吸收剂的含量为约0.125重量%至约2.0重量%,该聚合起始剂的含量为约0.25重量%至约12.5重量%,该可聚合化合物的含量为约12.5重量%至约40重量%,且该聚合物黏着剂的含量为约10重量%至约85重量%。
7.如权利要求6所述的可聚合组合物,其特征在于,以该可聚合组合物的总重量计,该聚合物黏着剂的含量为约35重量%至约75重量%。
8.一种负型成像胶液,其特征在于,其包含如权利要求1至7中任一项所述的可聚合组合物以及溶剂。
9.一种可成像组件,其特征在于,其包含:
一基材;以及
一可成像层,位于该基材上,
其中该可成像层系藉由将如权利要求8所述的负型成像胶液涂布于该基材上而形成。
10.一种制造印刷版的方法,其特征在于,该方法包含以下步骤:
(i)提供一如权利要求9的所述的可成像组件,于该可成像组件的可成像层上定义成像区及非成像区;
(ii)使成像区的该可成像层暴露于近红外线辐射,以形成一潜像;以及
(iii)于步骤(ii)之后,使该可成像层与一润版液接触,从而选择性地将非成像区的该可成像层从该基材去除。
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