CN114874673B - 一种耐擦伤免处理ctp版及其制备方法 - Google Patents
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- 229920005989 resin Polymers 0.000 claims abstract description 46
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
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- 238000003756 stirring Methods 0.000 claims description 19
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- 229940079877 pyrogallol Drugs 0.000 description 4
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical group BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
- DZNISTXXJWSWSX-UHFFFAOYSA-L dipotassium;sulfonatooxy sulfate;hydrate Chemical compound O.[K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O DZNISTXXJWSWSX-UHFFFAOYSA-L 0.000 description 2
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- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
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- C09D139/00—Coating compositions based on homopolymers or 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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Abstract
本发明涉及一种耐擦伤免处理CTP版及其制备方法,属于印刷技术领域,免处理CTP版包括铝版基和涂布在所述铝版基上的热敏层,为解决现有技术中存在的问题,本发明中通过对酚醛树脂进行改性,制备出成膜树脂,用于提高成膜的耐溶剂性。成膜树脂填充乳胶粒间隙,形成连续相,起到增稠流平作用以辅助成膜和乳胶粒的双重作用,使成膜更均匀满足印刷需要。乳胶粒属于热塑性材料,其内部包覆有耐磨添加剂,更加稳定,耐磨性更好。耐磨添加剂的比表面积大,存在良好的界面结合力,从而可提高涂层的强度、硬度、耐磨性、耐刮伤性能,极大提高印刷版的印刷次数,提高使用寿命。
Description
技术领域
本发明属于印刷技术领域,具体地,涉及一种耐擦伤免处理CTP版及其制备方法。
背景技术
免处理版材由于其独特的优点将成为热敏成像今后发展的方向,不但适合于脱机直接制版,特别适合于在机直接制版。免处理版材有不需要显影或用较弱碱性显影液显影等几种方式,这样可以避免显影时碱性化学试剂对环境的污染,还可以减少显影环节对成像质量的影响。
版材上含有树脂等高分子材料,高分子及其复合材料在长期使用过程中,受环境因素或外力作用影响,不可避免会产生难以检测的微裂纹或者微损伤。这些缺陷作为应力集中点,在材料使用过程中微裂会不断生长扩大,导致材料的性能大幅下降。印刷版材经常要接触到润版液、洗车水,接触到大量的酯类、聚醚类或者酮类物质,板材使用过程中形成的微裂会影响版材的化学特性,影响板材的使用性能。
发明内容
为了解决背景技术中提到的技术问题,本发明提供一种耐擦伤免处理CTP版及其制备方法。
本发明的目的可以通过以下技术方案实现:
一种耐擦伤免处理CTP版,包括铝版基和涂布在所述铝版基上的热敏层,所述热敏层包括以下重量份的组分:
乳胶粒15-20份、成膜树脂4-6份、阻溶剂1-1.1份、染料0.6-0.8份、产酸剂0.2-0.4份和溶剂80-90份;
所述成膜树脂通过如下步骤制备:
将苯酚、甲醛和氢氧化钡混合,在温度为65℃条件下,反应1h,然后升温至75℃,继续反应1h,然后加入2-羟乙基二硫化物,继续搅拌反应60-70min,将得到的产物在60℃条件下真空除水,得到树脂基体;苯酚、甲醛、2-羟乙基二硫化物和氢氧化钡的用量比为1mol:1.2mol:0.15-0.2mol:5g。
将树脂基体和二甲基乙酰胺混合,然后加入催化剂和甲基丙烯酸异氰基乙酯,在60℃条件下反应3-4h,然后升温至80℃,加入引发剂,继续反应8h,得到成膜树脂。
首先以苯酚、甲醛和2-羟乙基二硫化物为主要原料,制备出树脂基体,在树脂基体的结构中引入双硫键,本发明中利用了双硫键较低的热效应响应条件,实现成膜树脂在常温下的自修复,减少板材使用过程中出现的微裂纹,可以更加有效地配合成膜树脂的中的其他结构,提高热敏层的耐擦伤性。
进一步地,催化剂为二月桂酸二异丁基锡;引发剂选择偶氮二异丁腈。
进一步地,树脂基体、二甲基乙酰胺和甲基丙烯酸异氰基乙酯的用量比为10g:100mL:0.5g;
催化剂的添加量为甲基丙烯酸异氰基乙酯质量的10%;引发剂的添加量为甲基丙烯酸异氰基乙酯质量的10%。
进一步地,乳胶粒通过如下步骤制备:
将2-[十二烷硫基(硫代羰基)硫基]-2-甲基丙酸和去离子水混合,然后加入氢氧化钠调节pH值为7左右,然后加入亚硫酸氢钠搅拌溶解,最后加入混合单体和耐磨添加剂,氮气保护条件下搅拌3h,加入过硫酸钾水溶液,在35℃条件下,搅拌1h,然后升温至70℃,至无回流,停止加热,冷却至室温,用质量分数10%的氯化钠水溶液沉淀,将得到的固体在80℃条件下干燥至室温,得到乳胶粒。2-[十二烷硫基(硫代羰基)硫基]-2-甲基丙酸、去离子水、亚硫酸氢钠、混合单体、耐磨添加剂和过硫酸钾水溶液的用量质量比为0.8:70:0.2:25:4:10;过硫酸钾水溶液为过硫酸钾水和去离子水按照质量比0.2:10混合而成。
进一步地,混合单体为甲基丙烯酸正丁酯、偏二氯乙烯、二乙烯基苯和4-乙烯基吡啶按照质量比10:10:0.5:2组成。
进一步地,阻溶剂为连苯三酚缩二乙烯基苯缩聚树脂的活性醚化物,产酸剂选择三溴甲基苯基砜。
进一步地,染料为背景染料和红外染料等质量混合而成,背景染选择甲基紫,红外染料选择HCD-24。
进一步地,溶剂为二醇单乙醚、丙二醇单乙醚、甲乙酮中的一种。
进一步地,耐磨添加剂通过如下步骤制备:
在60℃条件下,将去离子水和无水乙醇混合,加入二甲氧基甲基乙烯基硅烷搅拌5min,然后加入纳米二氧化硅,搅拌30min,最后将溶液蒸干得到耐磨添加剂。去离子水和无水乙醇的体积比为1:9;二甲氧基甲基乙烯基硅的添加量为纳米二氧化硅质量的10%。无水乙醇和纳米二氧化硅的用量质量比为3:1。利用二甲氧基甲基乙烯基硅烷对纳米二氧化硅进行初级改性,在纳米二氧化硅上引入双键,便于进行后续反应。
一种耐擦伤免处理CTP版的制备方法,包括如下步骤:
步骤一、将铝版进行清洗、中和、电解、氧化、封孔,得到铝版基;
步骤二、按重量份将乳胶粒、成膜树脂、阻溶剂、染料、产酸剂和溶剂混合,用8-12μm、4-6μm、和1-2μm孔径的滤芯进行三级过滤,制得涂布液,将得到的涂布液涂覆在铝版基上,进行烘干,形成热敏层,得到一种耐擦伤免处理CTP版。
进一步地,烘干条件为在120-135℃条件下,烘2-3min。
进一步地,热敏层的重量为1-1.2g/m2。
本发明的有益效果:
为解决现有技术中存在的问题,本发明中通过对酚醛树脂进行改性,制备出成膜树脂,用于提高成膜的耐溶剂性。成膜树脂填充乳胶粒间隙,形成连续相,起到增稠流平作用以辅助成膜和乳胶粒的双重作用,使成膜更均匀满足印刷需要。
酚醛树脂为成膜树脂的主要原料,成膜树脂是由树脂基体在催化剂的作用下通过氨酯键接枝,在树脂基体的结构中引入氨酯链段,然后在引发剂的作用下发生线性聚合,提高成膜树脂的分子量,制成的热敏层能更加抵抗酯类、聚醚类或者酮类物质的侵袭,具有良好的成膜性和耐溶剂性。
乳胶粒属于热塑性材料,其内部包覆有耐磨添加剂,更加稳定,耐磨性更好。耐磨添加剂的比表面积大,存在良好的界面结合力,从而可提高涂层的强度、硬度、耐磨性、耐刮伤性能,极大提高印刷版的印刷次数,提高使用寿命。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
制备乳胶粒:
在60℃条件下,将去离子水和无水乙醇混合,加入二甲氧基甲基乙烯基硅烷搅拌5min,然后加入纳米二氧化硅,搅拌30min,最后将溶液蒸干得到耐磨添加剂。去离子水和无水乙醇的体积比为1:9;二甲氧基甲基乙烯基硅的添加量为纳米二氧化硅质量的10%。无水乙醇和纳米二氧化硅的用量质量比为3:1。
将2-[十二烷硫基(硫代羰基)硫基]-2-甲基丙酸和去离子水混合,然后加入氢氧化钠调节pH值为7左右,然后加入亚硫酸氢钠搅拌溶解,最后加入混合单体和耐磨添加剂,氮气保护条件下搅拌3h,加入过硫酸钾水溶液,在35℃条件下,搅拌1h,然后升温至70℃,至无回流,停止加热,冷却至室温,用质量分数10%的氯化钠水溶液沉淀,将得到的固体在80℃条件下干燥至室温,得到乳胶粒。2-[十二烷硫基(硫代羰基)硫基]-2-甲基丙酸、去离子水、亚硫酸氢钠、混合单体、耐磨添加剂和过硫酸钾水溶液的用量质量比为0.8:70:0.2:25:4:10;过硫酸钾水溶液为过硫酸钾水和去离子水按照质量比0.2:10混合而成。混合单体为甲基丙烯酸正丁酯、偏二氯乙烯、二乙烯基苯和4-乙烯基吡啶按照质量比10:10:0.5:2组成。
实施例2
制备成膜树脂:
将苯酚、甲醛和氢氧化钡混合,在温度为65℃条件下,反应1h,然后升温至75℃,继续反应1h,然后加入2-羟乙基二硫化物,继续搅拌反应60min,将得到的产物在60℃条件下真空除水,得到树脂基体;苯酚、甲醛、2-羟乙基二硫化物和氢氧化钡的用量比为1mol:1.2mol:0.15mol:5g。
将树脂基体和二甲基乙酰胺混合,然后加入二月桂酸二异丁基锡和甲基丙烯酸异氰基乙酯,在60℃条件下反应3h,然后升温至80℃,加入偶氮二异丁腈,继续反应8h,得到成膜树脂。树脂基体、二甲基乙酰胺和甲基丙烯酸异氰基乙酯的用量比为10g:100mL:0.5g;二月桂酸二异丁基锡的添加量为甲基丙烯酸异氰基乙酯质量的10%;偶氮二异丁腈的添加量为甲基丙烯酸异氰基乙酯质量的10%。
实施例3
制备成膜树脂:
将苯酚、甲醛和氢氧化钡混合,在温度为65℃条件下,反应1h,然后升温至75℃,继续反应1h,然后加入2-羟乙基二硫化物,继续搅拌反应70min,将得到的产物在60℃条件下真空除水,得到树脂基体;苯酚、甲醛、2-羟乙基二硫化物和氢氧化钡的用量比为1mol:1.2mol:0.2mol:5g。
将树脂基体和二甲基乙酰胺混合,然后加入二月桂酸二异丁基锡和甲基丙烯酸异氰基乙酯,在60℃条件下反应4h,然后升温至80℃,加入偶氮二异丁腈,继续反应8h,得到成膜树脂。树脂基体、二甲基乙酰胺和甲基丙烯酸异氰基乙酯的用量比为10g:100mL:0.5g;二月桂酸二异丁基锡的添加量为甲基丙烯酸异氰基乙酯质量的10%;偶氮二异丁腈的添加量为甲基丙烯酸异氰基乙酯质量的10%。
实施例4
制备一种耐擦伤免处理CTP版:
步骤一、将铝版进行清洗、中和、电解、氧化、封孔,得到铝版基;
步骤二、将按重量份将实施例1制备的乳胶粒、实施例2制备的成膜树脂、阻溶剂、染料、产酸剂、溶剂混合,用8-12μm、4-6μm、和1-2μm孔径的滤芯进行三级过滤,制得涂布液,将得到的涂布液涂覆在铝版基上,在120℃条件下,烘3min,形成重量为1g/m2的热敏层;得到一种耐擦伤免处理CTP版。其中,按重量份计,乳胶粒15份、成膜树脂4份、阻溶剂1份、染料0.6份、产酸剂0.2份和溶剂80份;本实施例中阻溶剂为连苯三酚缩二乙烯基苯缩聚树脂的活性醚化物,产酸剂选择三溴甲基苯基砜。染料为背景染料和红外染料等质量混合而成,背景染选择甲基紫,红外染料选择HCD-24。溶剂为二醇单乙醚。
实施例5
制备一种耐擦伤免处理CTP版:
步骤一、将铝版进行清洗、中和、电解、氧化、封孔,得到铝版基;
步骤二、将按重量份将实施例1制备的乳胶粒、实施例2制备的成膜树脂、阻溶剂、染料、产酸剂、溶剂混合,用8-12μm、4-6μm、和1-2μm孔径的滤芯进行三级过滤,制得涂布液,将得到的涂布液涂覆在铝版基上,在125℃条件下,烘2.5min,形成重量为1.1g/m2的热敏层;得到一种耐擦伤免处理CTP版。其中,按重量份计,乳胶粒18份、成膜树脂5份、阻溶剂1.1份、染料0.7份、产酸剂0.3份和溶剂85份;本实施例中阻溶剂为连苯三酚缩二乙烯基苯缩聚树脂的活性醚化物,产酸剂选择三溴甲基苯基砜。染料为背景染料和红外染料等质量混合而成,背景染选择甲基紫,红外染料选择HCD-24。溶剂为丙二醇单乙醚。
实施例6
制备一种耐擦伤免处理CTP版:
步骤一、将铝版进行清洗、中和、电解、氧化、封孔,得到铝版基;
步骤二、将按重量份将实施例1制备的乳胶粒、实施例2制备的成膜树脂、阻溶剂、染料、产酸剂、溶剂混合,用8-12μm、4-6μm、和1-2μm孔径的滤芯进行三级过滤,制得涂布液,将得到的涂布液涂覆在铝版基上,在135℃条件下,烘2min,形成重量为1.2g/m2的热敏层;得到一种耐擦伤免处理CTP版。其中,按重量份计,乳胶粒20份、成膜树脂6份、阻溶剂1.1份、染料0.8份、产酸剂0.4份和溶剂90份;本实施例中阻溶剂为连苯三酚缩二乙烯基苯缩聚树脂的活性醚化物,产酸剂选择三溴甲基苯基砜。染料为背景染料和红外染料等质量混合而成,背景染选择甲基紫,红外染料选择HCD-24。溶剂为甲乙酮。
对比例1
与实施例1相比,不添加耐磨添加剂,其余原料及制备过程保持不变,制备出乳胶粒a,然后将制备的乳胶粒a替换实施例6中的乳胶粒,其余原料及制备过程保持不变。
对比例2
将实施例6中的成膜树脂换成市场购买的对甲酚树脂,其余原料及制备过程保持不变。
对实施例4-6和对比例1-2制备的样品进行测试;
耐印力评价:将样版置于景德镇J4104D印刷机上正常印刷,考察其耐印力。采用手术刀在样品表面切出宽约20um左右的裂纹,在室温自然光线下放置24小时后,利用超显微系统观察裂纹变化情况。
测试结果如下表1所示:
表1
实施例4 | 实施例5 | 实施例6 | 对比例1 | 对比例2 | |
印刷力(万) | >10 | >10 | >10 | 8 | >10 |
是否修复 | 是 | 是 | 是 | 是 | 否 |
从上表1可知本发明制备的耐擦伤免处理CTP版具有良好的耐刮伤性。
在说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (6)
1.一种耐擦伤免处理CTP版,包括铝版基和涂布在所述铝版基上的热敏层,其特征在于,所述热敏层包括以下重量份的组分:乳胶粒15-20份、成膜树脂4-6份、阻溶剂1-1.1份、染料0.6-0.8份、产酸剂0.2-0.4份和溶剂80-90份;
所述成膜树脂通过如下步骤制备:
将苯酚、甲醛和氢氧化钡混合,在温度为65℃条件下,反应1h,然后升温至75℃,继续反应1h,然后加入2-羟乙基二硫化物,继续搅拌反应60-70min,得到树脂基体;
将树脂基体和二甲基乙酰胺混合,然后加入催化剂和甲基丙烯酸异氰基乙酯,在60℃条件下反应3-4h,然后升温至80℃,加入引发剂,继续反应8h,得到成膜树脂;
所述乳胶粒通过如下步骤制备:
将2-[十二烷硫基(硫代羰基)硫基]-2-甲基丙酸和去离子水混合,然后调节pH,然后加入亚硫酸氢钠搅拌溶解,最后加入混合单体和耐磨添加剂,氮气保护条件下搅拌3h,加入过硫酸钾水溶液,在35℃条件下,搅拌1h,然后升温至70℃,至无回流,停止加热,得到乳胶粒;所述混合单体为甲基丙烯酸正丁酯、偏二氯乙烯、二乙烯基苯和4-乙烯基吡啶按照质量比10:10:0.5:2组成;
所述耐磨添加剂通过如下步骤制备:
在60℃条件下,将去离子水和无水乙醇混合,加入二甲氧基甲基乙烯基硅烷搅拌5min,然后加入纳米二氧化硅,搅拌30min,最后将溶液蒸干得到耐磨添加剂。
2.根据权利要求1所述的一种耐擦伤免处理CTP版,其特征在于,染料为背景染料和红外染料等质量混合而成。
3.根据权利要求1所述的一种耐擦伤免处理CTP版,其特征在于,溶剂为二醇单乙醚、丙二醇单乙醚、甲乙酮中的一种。
4.根据权利要求1所述的一种耐擦伤免处理CTP版的制备方法,其特征在于,包括如下步骤:
步骤一、将铝版进行清洗、中和、电解、氧化、封孔,得到铝版基;
步骤二、按重量份将乳胶粒、成膜树脂、阻溶剂、染料、产酸剂和溶剂混合,用8-12μm、4-6μm、和1-2μm孔径的滤芯进行三级过滤,制得涂布液,将得到的涂布液涂覆在铝版基上,进行烘干,形成热敏层,得到一种耐擦伤免处理CTP版。
5.根据权利要求4所述的一种耐擦伤免处理CTP版的制备方法,其特征在于,烘干条件为在120-135℃条件下,烘2-3min。
6.根据权利要求4所述的一种耐擦伤免处理CTP版的制备方法,其特征在于,热敏层的重量为1-1.2g/m2。
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