CN113025214A - 粘接剂、热敏丝网母版及热敏丝网母版的制造方法 - Google Patents
粘接剂、热敏丝网母版及热敏丝网母版的制造方法 Download PDFInfo
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- CN113025214A CN113025214A CN202011534981.XA CN202011534981A CN113025214A CN 113025214 A CN113025214 A CN 113025214A CN 202011534981 A CN202011534981 A CN 202011534981A CN 113025214 A CN113025214 A CN 113025214A
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
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Abstract
粘接剂、热敏丝网母版及热敏丝网母版的制造方法。一种粘接剂,其含有选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种、多异氰酸酯、聚合性(甲基)丙烯酸酯化合物、和光聚合引发剂。
Description
技术领域
本发明的实施方式涉及粘接剂、热敏丝网母版及热敏丝网母版的制造方法。
背景技术
对于将热塑性树脂薄膜贴合于多孔性支承体而成的热敏孔版母版的热塑性树脂薄膜,利用热头选择性地进行加热而进行熔融穿孔,由此形成对应于图像的穿孔部,而制作丝网印刷等孔版印刷用的版的制版方法被称为热敏制版。作为热敏孔版母版,例如可以利用使用丝网纱作为多孔性支承体的热敏丝网母版等。
日本特开2010-214635号公报记载了使用配混有含有聚氨酯的主剂和含有甲苯二异氰酸酯和聚氨酯树脂的固化剂的粘接剂、将热塑性合成树脂薄膜和丝网印刷用纱体贴合而成的丝网印刷用孔版原纸。
日本特开2018-165002号公报记载了将丝网纱和热塑性树脂薄膜贴合而成的热敏丝网母版,并例示出紫外线固化型粘接剂作为粘接剂。
发明内容
发明要解决的问题
本发明的实施方式的一目的在于,提供粘接强度优异并且可以使用其制造表面的皱折少的物品的粘接剂、以及使用其得到的热敏丝网母版。
用于解决问题的方案
本发明的实施方式涉及一种粘接剂,其含有选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种、多异氰酸酯、聚合性(甲基)丙烯酸酯化合物、和光聚合引发剂。
本发明的其它实施方式涉及一种热敏丝网母版的制造方法,其包括对于依次具备丝网纱、含有上述粘接剂的粘接剂层、和热塑性树脂薄膜的层叠体照射活性能量射线。
本发明的其它实施方式涉及一种热敏丝网母版,其包含丝网纱、使用上述粘接剂形成的层、和热塑性树脂薄膜。
发明的效果
通过本发明的实施方式,可以提供粘接强度优异并且可以使用其制造表面的皱折少的物品的粘接剂、以及使用其得到的热敏丝网母版。
具体实施方式
以下对于本发明的实施方式进行详细说明,但是本发明不被这些实施方式所限定,可以附加各种修正、变更是不言而喻的。
<粘接剂>
实施方式的粘接剂含有选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种(以下也有时称为“成分A”)、多异氰酸酯(以下也有时称为“成分B”)、聚合性(甲基)丙烯酸酯化合物(以下也有时称为“成分C”)、和光聚合引发剂(以下也有时称为“成分D”)。
氨基甲酸酯系粘接剂通常通过热和湿气等而固化。氨基甲酸酯系粘接剂具有容易得到良好的粘接强度的倾向,但是通常存在直至固化为止的时间比较长的倾向。使用这种粘接剂制造热敏丝网母版等物品时,对于使用粘接剂贴合2层而成的层叠体,在粘接剂固化之前粘接剂的粘度低的状态下在层压装置等制造装置上搬送,由此有可能在所得到的物品表面产生源自层压装置等制造装置的皱折,这有可能成为成品率降低的原因之一。
另外,紫外线固化型粘接剂存在通过照射紫外线而可以在比较短的时间内进行固化的倾向。另一方面,仅使用紫外线固化型粘接剂作为粘接剂的情况下,存在粘接剂过硬、上层与下层的密合性降低而粘接强度降低的情况。
本实施方式的粘接剂含有选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种(成分A)、和多异氰酸酯(成分B),还含有聚合性(甲基)丙烯酸酯化合物(成分C)和光聚合引发剂(成分D)。通过含有成分C和成分D,利用紫外线等活性能量射线,并利用由成分D产生的自由基,可以引发成分C的聚合,可以使成分C固化。因此,在赋予粘接剂之后,首先通过紫外线等活性能量射线照射,使成分C固化而可以提高粘接剂的粘度,由此可以降低层压装置等制造装置上的物品表面的皱折产生。另外,通过该粘接剂含有成分A及B,在热和湿气环境下固化,由此可以得到优异的粘接强度。
对于该粘接剂用途没有特别限定,例如可以优选用作热敏丝网母版用的粘接剂。
粘接剂中,作为成分A,可以含有氨基甲酸酯预聚物、多元醇、或氨基甲酸酯预聚物和多元醇的组合。
作为成分A,可以使用能与成分B相容的成分A。成分A优选在23℃下为液体。
氨基甲酸酯预聚物可以通过多元醇成分和异氰酸酯成分的反应来得到,作为末端官能团,可以含有羟基(-OH)、异氰酸酯基(-NCO)、或它们两者。
氨基甲酸酯预聚物优选不包含(甲基)丙烯酰基。
氨基甲酸酯预聚物优选在23℃下为液体。
对于氨基甲酸酯预聚物的重均分子量没有特别限定,优选为2000~10000、更优选3000~8000。氨基甲酸酯预聚物的重均分子量为在凝胶渗透色谱(GPC)中通过聚苯乙烯换算而得到的值。
氨基甲酸酯预聚物在25℃、剪切速度500/s时的粘度优选为200000mPa·s以下。更优选100000mPa·s以下、特别优选80000mPa·s以下。另外,若状态为液态则对于下限值没有特别限定,氨基甲酸酯预聚物在25℃、剪切速度500/s时的粘度例如可以为5000mPa·s以上。
作为氨基甲酸酯预聚物的市售品,可列举出例如三井化学株式会社制“TakelacA-666”、“TakelacA-695”(都为商品名)等。
氨基甲酸酯预聚物可以单独使用1种或将2种以上组合来使用。
多元醇优选在23℃下为液体。
作为多元醇,若具有2个以上羟基则没有特别限定,优选在两末端具有羟基。
作为多元醇,例如可以使用作为聚氨酯树脂的原材料通常使用的多元醇。
作为多元醇的例子,可列举出聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚缩醛多元醇、聚丙烯酸酯多元醇、聚酯酰胺多元醇、聚硫醚多元醇、聚丁二烯等聚烯烃多元醇等,优选为在两末端具有羟基的聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇等。
多元醇优选不包含(甲基)丙烯酰基。
作为多元醇的市售品,可列举出例如AGC株式会社制“EXCENOL 750ED”(聚醚多元醇)、株式会社ADEKA制“ADEKA NEWACE#50”(聚酯多元醇)、旭化成株式会社制“DURANOLG3452”(聚碳酸酯多元醇)等。
多元醇可以单独使用1种或将2种以上组合来使用。
对于成分A,从粘接强度改善的观点考虑,相对于粘接剂总量优选为5质量%以上、更优选10质量%以上。从粘接强度改善的观点考虑,成分A相对于粘接剂总量例如可以为30质量%以上或50质量%以上。
另一方面,成分A相对于粘接剂总量优选为80质量%以下、更优选60质量%以下、进一步优选40质量%以下、进一步优选30质量%以下。
成分A例如相对于粘接剂总量优选为5~80质量%、更优选5~60质量%、进一步优选10~40质量%、进一步优选10~30质量%。
粘接剂含有后述的溶剂的情况下,成分A的量例如可以相对于粘接剂的总量处于上述数值范围内,例如也可以相对于从粘接剂的总质量排除溶剂的质量之外的质量,处于上述数值范围内。
对于成分A,从粘接强度改善的观点考虑,相对于成分A和成分B的总量,优选为5质量%以上、更优选10质量%以上。从粘接强度改善的观点考虑,成分A相对于成分A和成分B的总量例如可以为40质量%以上或60质量%以上。
粘接剂可以含有多异氰酸酯作为成分B。
作为多异氰酸酯,若具有2个以上异氰酸酯基则没有特别限定,优选在末端具有异氰酸酯基。作为多异氰酸酯,可以使用能与成分A相容的多异氰酸酯。多异氰酸酯优选在23℃下为液体。
作为多异氰酸酯,可以为脂肪族多异氰酸酯、脂环族多异氰酸酯、芳香族多异氰酸酯等中的任意一种。
作为多异氰酸酯的具体例,可列举出例如六亚甲基二异氰酸酯(1,6-二异氰酸酯己烷)(HDI)、1,3-双(异氰酸根合甲基)苯、1,3-双(异氰酸根合甲基)环己烷、1,5-萘二异氰酸酯、二苯基甲烷-4,4-二异氰酸酯、间二甲苯二异氰酸酯、4,4’-亚甲基双(亚苯基异氰酸酯)(MDI)、甲苯二异氰酸酯(TDI)等二异氰酸酯;1-甲基苯-2,4,6-三基三异氰酸酯、1,6,11-三异氰酸根合十一烷等三异氰酸酯;聚亚甲基聚苯基多异氰酸酯等,进而也可列举出这些多异氰酸酯的改性体等。
例如若使用主溶剂为挥发性有机溶剂的溶剂油墨(溶剂系油墨)进行印刷,则将所制版的母版用于印刷后,残留于印刷后的母版的溶剂油墨的溶剂蒸发,固体成分容易成为结块而残留。将这种固化物用溶剂擦去时,存在将热塑性树脂薄膜和丝网纱粘接的粘接剂溶解于溶剂而热塑性树脂薄膜从丝网纱剥离的情况。为了反复使用所制版的母版,期望粘接剂不易溶解于擦去中使用的溶剂。因此,从粘接剂的耐溶剂性改善的观点考虑,作为多异氰酸酯,更优选为多异氰酸酯的改性体。作为多异氰酸酯的改性体,可列举出例如多异氰酸酯的异氰脲酸酯改性体、缩二脲改性体、脲基甲酸酯改性体、噁二嗪三酮改性体等。从耐溶剂性改善的观点考虑,优选为多异氰酸酯的异氰脲酸酯改性体、多异氰酸酯的缩二脲改性体,更优选多异氰酸酯的异氰脲酸酯改性体。
多异氰酸酯的异氰脲酸酯改性体由于N-C键的旋转的自由度低、容易生成硬的涂膜,因此溶剂不易侵入。
作为多异氰酸酯的改性体,从耐溶剂性改善的观点考虑,优选为脂肪族多异氰酸酯的改性体、更优选脂肪族二异氰酸酯的改性体、进一步优选六亚甲基二异氰酸酯的改性体。例如优选为六亚甲基二异氰酸酯的异氰脲酸酯改性体、六亚甲基二异氰酸酯的缩二脲改性体,从耐溶剂性改善的观点考虑,更优选为六亚甲基二异氰酸酯的异氰脲酸酯改性体。
作为多异氰酸酯的市售品,可列举出旭化成株式会社制“Duranate TPA-100”(六亚甲基二异氰酸酯的异氰脲酸酯改性体)、“Duranate 24A-100”(六亚甲基二异氰酸酯的缩二脲改性体)、BASF INOAC Polyurethanes Ltd.制“Lupranate MI”(4,4’-亚甲基双(亚苯基异氰酸酯))、“Lupranate TDI”(甲苯二异氰酸酯)等。
多异氰酸酯可以单独使用1种或将2种以上组合来使用。
从提高通过异氰酸酯基彼此的反应实现的交联密度,由此改善耐溶剂性的观点考虑和/或从通过提高成分B和成分C的相容性,在紫外线照射时可以有效地提高粘接剂粘度,由此进一步降低使用粘接剂得到的物品表面的皱折产生的观点考虑,成分B相对于粘接剂总量优选为10质量%以上、更优选30质量%以上、更优选40质量%以上、进一步优选50质量%以上、进一步优选60质量%以上。
另一方面,成分B相对于粘接剂总量优选为90质量%以下、更优选85质量%以下。
成分B例如相对于粘接剂总量优选为10~90质量%、更优选30~90质量%、进一步优选40~90质量%、进一步优选50~85质量%、进一步优选60~85质量%。
粘接剂含有后述的溶剂的情况下,成分B的量例如可以相对于粘接剂总量处于上述的数值范围内,例如也可以相对于从粘接剂的总质量排除溶剂的质量之外的质量,处于上述数值范围内。
从改善耐溶剂性的观点考虑、和/或从进一步降低皱折产生的观点考虑,成分B相对于成分A和成分B的总量优选为10质量%以上、更优选30质量%以上、进一步优选65质量%以上、进一步优选70质量%以上。
若增加成分B相对于成分A和成分B的总量的比率则成分B和成分C由于相容性高,在紫外线照射时可以有效地提高粘接剂粘度,由此存在可以更有效地降低皱折产生的倾向。若降低成分C的量则可以增加成分A和成分B的量,由此能够进一步改善粘接强度和耐溶剂性。
成分A和成分B优选质量比(A:B)为90:10~5:95,从改善耐溶剂性的观点考虑、和/或从进一步降低使用粘接剂得到的物品表面的皱折产生的观点考虑,更优选70:30~5:95、进一步优选35:65~5:95、进一步优选30:70~10:90。成分A和成分B例如可以为80:20~36:64、或80:20~40:60。
粘接剂可以含有聚合性(甲基)丙烯酸酯化合物作为成分C。
作为聚合性(甲基)丙烯酸酯化合物,可以使用具有1个以上(甲基)丙烯酰基的聚合性(甲基)丙烯酸酯化合物。作为聚合性(甲基)丙烯酸酯化合物,优选为1分子中具有2个以上(甲基)丙烯酰基的多官能化合物。
作为聚合性(甲基)丙烯酸酯化合物,例如可以使用(甲基)丙烯酸酯单体、(甲基)丙烯酸酯低聚物、或这两者等。(甲基)丙烯酸酯指的是甲基丙烯酸酯、丙烯酸酯或这两者。(甲基)丙烯酰基指的是丙烯酰基、甲基丙烯酰基、或这两者。
作为单官能的(甲基)丙烯酸酯单体的例子,可列举出丙烯酸2-羟基丙酯、苯酚EO改性丙烯酸酯(“EO改性”指的是环氧乙烷改性)、丙烯酸二环戊烯氧基乙基酯、丙烯酸异冰片酯、苯酚环氧乙烷改性丙烯酸酯、芴二丙烯酸酯等。作为多官能(甲基)丙烯酸酯单体的例子,可列举出聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、双酚A二缩水甘油基醚二丙烯酸酯、四乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、N-丙烯酰氧基乙基六氢酞酰亚胺、二羟甲基二环戊烷二丙烯酸酯、异氰脲酸EO改性二丙烯酸酯等。
作为(甲基)丙烯酸酯单体的市售品,可列举出例如共荣社化学株式会社制“Lightester HOP-A(N)”(商品名)、东亚合成株式会社制“ARONIX M-102”、“ARONIX M-350”(都为商品名)、新中村化学工业株式会社制“Nk Ester A-200”、“Nk Ester A-DPH”(都为商品名)等。
作为(甲基)丙烯酸酯低聚物的例子,可列举出氨基甲酸酯(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯等。
氨基甲酸酯(甲基)丙烯酸酯含有(甲基)丙烯酰基和氨基甲酸酯键。
作为氨基甲酸酯(甲基)丙烯酸酯的例子,可列举出苯基缩水甘油基醚丙烯酸酯六亚甲基二异氰酸酯氨基甲酸酯预聚物、季戊四醇三丙烯酸酯六亚甲基二异氰酸酯氨基甲酸酯预聚物、季戊四醇三丙烯酸酯甲苯二异氰酸酯氨基甲酸酯预聚物、季戊四醇三丙烯酸酯异佛尔酮二异氰酸酯氨基甲酸酯预聚物、二季戊四醇五丙烯酸酯六亚甲基二异氰酸酯氨基甲酸酯预聚物等。
作为氨基甲酸酯(甲基)丙烯酸酯的市售品的例子,可列举出共荣社化学株式会社制“AH-600”、“UA-306H”、“UA-306T”、“UA-306I”、“UA-510H”(都为商品名)等。
作为环氧(甲基)丙烯酸酯,可以使用包含丙烯酸或甲基丙烯酸的羧基和具有环氧基的化合物的环氧基反应而得到的结构的化合物。
作为环氧(甲基)丙烯酸酯的市售品的例子,可列举出例如共荣社化学株式会社制“EPOXY ESTER 80MFA”(商品名)等。
作为聚酯(甲基)丙烯酸酯的市售品的例子,可列举出例如东亚合成株式会社制“ARONIX M-7100”、“ARONIX M-6100”(都为商品名)等。
这些聚合性(甲基)丙烯酸酯化合物可以单独使用1种或将2种以上组合来使用。
从进一步降低使用粘接剂得到的物品表面的皱折产生的观点考虑、和/或从提高通过成分C的固化实现的粘接剂的粘度、降低夹着粘接剂的上层和下层的粘接部位的偏移产生、由此进一步改善粘接强度的观点考虑,成分C相对于粘接剂总量优选为1质量%以上、更优选3质量%以上、进一步优选6质量%以上。
另一方面,从粘接强度进一步改善的观点考虑,成分C相对于粘接剂总量优选为40质量%以下、优选30质量%以下、进一步优选15质量%以下。
成分C的量例如相对于粘接剂总量优选为1~40质量%、更优选1~30质量%、进一步优选3~30质量%、进一步优选6~30质量%、进一步优选6~15质量%。
粘接剂可以含有光聚合引发剂作为成分D。
作为光聚合引发剂,若通过紫外线等活性能量射线的照射而产生自由基并引发成分C的聚合反应则没有特别限定。
作为光聚合引发剂,可列举出例如酰基氧化膦系化合物、噻吨酮系化合物、苯乙酮系化合物和二苯甲酮系化合物等。
作为酰基氧化膦系化合物,可列举出例如双(2,4,6-三甲基苯甲酰基)-苯基氧化膦、2,4,6-三甲基苯甲酰基-二苯基-氧化膦、乙基(2,4,6-三甲基苯甲酰基)苯基次膦酸酯和双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦等。
作为噻吨酮系化合物,可列举出例如噻吨酮、2-氯噻吨酮、2,4-二乙基噻吨酮、异丙基噻吨酮、1-氯-4-丙基噻吨酮、3-[3,4-二甲基-9-氧代-9H-噻吨酮-2-基-氧基]-2-羟基丙基-N,N,N-三甲基氯化铵和氟噻吨酮等。
作为苯乙酮系化合物,可列举出例如2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羟基乙氧基)苯基]-2-羟基-2-甲基-1-丙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代基丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-吗啉代基苯基)丁烷-1-酮、二乙氧基苯乙酮、低聚{2-羟基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮}、2-羟基-1-{4-[4-(2-羟基-2-甲基丙酰基)苄基]苯基}-2-甲基丙烷-1-酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-吗啉基)苯基]1-丁酮等。
作为二苯甲酮系化合物,可列举出例如二苯甲酮、4-苯基二苯甲酮、甲基-邻苯甲酰基苯甲酸酯、2,4,6-三甲基二苯甲酮、4-苯甲酰基-4’-甲基二苯基硫醚和1-[4-(4-苯甲酰基苯基)硫基]苯基]-2-甲基-2-[(4-甲基苯基)磺酰基]-1-丙酮等。
这些光聚合引发剂可以单独使用1种或将2种以上组合来使用。
成分D相对于成分C和成分D的总量优选为0.1质量%以上、优选1质量%以上。另一方面,成分D相对于成分C和成分D的总量优选为10质量%以下、更优选5质量%以下。成分D相对于成分C和成分D的总量例如优选为0.1~10质量%、更优选1~5质量%。
成分D相对于粘接剂总量例如优选为0.05~5质量%、更优选0.1~2质量%。
粘接剂例如可以含有溶剂作为稀释剂。作为溶剂,优选为有机溶剂。
粘接剂根据需要可以含有抗静电剂、润滑剂、增粘剂、填充剂、流平剂、着色剂等添加剂。
粘接剂例如可以为1组分型、2组分型或3组分型等的粘接剂。例如可以将成分A和成分B分别保管、将成分A和成分B在使用时混合。此时,成分A和成分B以外的其它成分可以与成分A和/或成分B一起保管。另外,例如也可以将成分A、成分B、和成分C及D分别保管,将它们在使用时混合。此时,成分A、成分B、成分C及成分D以外的其它成分可以与它们中的任意一者一起保管。
<热敏丝网母版>
实施方式的热敏丝网母版包含丝网纱、使用上述粘接剂形成的层、和热塑性树脂薄膜。
热敏丝网母版优选为使用上述粘接剂将丝网纱和热塑性树脂薄膜贴合而成的。热敏丝网母版例如优选依次具备丝网纱、使用粘接剂形成的层、和热塑性树脂薄膜。优选在热敏丝网母版中,丝网纱与使用粘接剂形成的层互相连接,并且使用粘接剂形成的层与热塑性树脂薄膜互相连接。
作为丝网纱,只要不会由于热头的加热而实质上发生穿孔而在印刷中可以通过油墨即可,例如可以使用由聚酯、尼龙、人造丝、不锈钢、丝绸、棉等纤维制作的纱。
丝网纱的厚度通常为40~270μm、优选50~150μm。
丝网纱的网眼数(每1英寸的纤维的根数)通常为40~500、优选50~350网眼。纵向和横向的网眼数只要处于上述网眼数的范围内则可以相同或不同。
作为热塑性树脂薄膜,例如可以使用聚乙烯系树脂薄膜、聚丙烯系树脂薄膜、聚酯系树脂薄膜、聚酰胺系树脂薄膜、聚氯乙烯系树脂薄膜、聚偏二氯乙烯系树脂薄膜等。它们之中,可以优选使用聚酯系树脂薄膜等。作为聚酯系树脂,可列举出例如聚对苯二甲酸乙二醇酯、聚2,6-萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、对苯二甲酸乙二醇酯/间苯二甲酸乙二醇酯共聚物、对苯二甲酸丁二醇酯/对苯二甲酸乙二醇酯共聚物、对苯二甲酸丁二醇酯/对苯二甲酸六亚甲基酯共聚物、对苯二甲酸六亚甲基酯/对苯二甲酸1,4-环己烷二亚甲基酯共聚物、对苯二甲酸乙二醇酯/2,6-萘二甲酸乙二醇酯共聚物等。热塑性树脂薄膜根据需要可以含有颜料、粘度调整剂、分散剂、染色剂、润滑剂、交联剂、增塑剂等各种添加剂。
热塑性树脂薄膜的厚度若为能够进行热敏数字丝网制版的厚度即可,通常为0.5~10μm、优选1~5μm。
热塑性树脂薄膜优选具备适于通过热敏数字丝网制版而容易地发生熔融穿孔的收缩性,可以适当经过单轴拉伸或双轴拉伸。
热敏丝网母版可以包含其它层。例如在热塑性树脂薄膜的与热头接触的一侧,为了防止热塑性树脂薄膜对热头的热粘、或降低热头和热塑性树脂薄膜的摩擦等而可以设置保护涂层。
对于热敏丝网母版的制造方法没有特别限定。
热敏丝网母版例如可以通过包括对于依次具备丝网纱、含有上述粘接剂的粘接剂层、热塑性树脂薄膜的层叠体(以下也有时称为层叠体L)照射活性能量射线(以下也有时称为“活性能量射线照射工序”)的方法而制造。
层叠体L中包含的粘接剂层为含有上述粘接剂的层,可以使用上述粘接剂得到。例如通过在丝网纱和热塑性树脂薄膜之间赋予粘接剂,可以形成粘接剂层。
层叠体L例如可以通过包括在丝网纱和热塑性树脂薄膜之间赋予粘接剂的工序的方法而制造。通过在丝网纱和热塑性树脂薄膜之间赋予粘接剂的工序,可以依次配置丝网纱、含有粘接剂的粘接剂层、热塑性树脂薄膜。层叠体L可以含有其它层。
粘接剂可以预先混合各成分,也可以在即将使用之前混合各成分。
对于在丝网纱和热塑性树脂薄膜之间赋予粘接剂的方法没有特别限定。具体而言,例如可以使用辊涂机等赋予粘接剂并将丝网纱和热塑性树脂薄膜贴合。
粘接剂的赋予量通常处于0.05~10.0g/m2的范围内。从粘接强度的观点考虑,赋予量优选为0.05g/m2以上。从油墨通过性、良好的穿孔的观点考虑,涂布量优选为10.0g/m2以下。
对于层叠体L照射活性能量射线的方法没有特别限定。
作为活性能量射线,可列举出紫外线、X射线、电子束、可见光等,其中优选为紫外线。
照射活性能量射线的工序中,例如可以使用照射紫外线的光源将紫外线照射到层叠体L。作为照射紫外线的光源,可列举出:发射出紫外线的UV-LED、高压汞灯、卤化金属灯、氙灯等。
活性能量射线例如可以由层叠体L的丝网纱侧照射、也可以由热塑性树脂薄膜侧照射。
热敏丝网母版的制造方法中,除了活性能量射线照射工序之外可以还包括其它工序。
热敏丝网母版的制造方法中,在活性能量射线照射工序之前可以包括制造层叠体L的工序。
热敏丝网母版的制造方法例如优选在活性能量射线照射工序之后,包括将所得到的层叠体以卷状卷取的工序。
热敏丝网母版的制造方法例如优选在活性能量射线照射工序之后包括将所得到的层叠体干燥的干燥工序。作为干燥工序中的干燥温度,优选为30℃~60℃(例如50℃)。作为干燥时间,优选为1~5天(例如3天)。可以调整湿度、可以将湿度设为70~90%(例如RH80%)
干燥可以改变条件以多阶段进行。例如可以在温度40~70℃(例如60℃)下进行第一阶段的干燥,然后例如在多湿状态(例如RH70~90%)下进行第二阶段的干燥。多湿状态时,温度可以为25~35℃程度。对于第一阶段的干燥和第二阶段的干燥时间没有特别限定,可以分别为1~2天程度。
热敏丝网母版的制造方法例如在活性能量射线照射工序之后,可以依次包括将所得到的层叠体以卷状卷取的工序、和干燥工序。
该热敏丝网母版可以利用使用了热头的热敏制版装置等制版而作为孔版印刷用的版使用。
可以使用将该热敏丝网母版制版而得到的版进行孔版印刷。作为印刷中使用的油墨,例如可以使用能用于丝网印刷等孔版印刷的油墨。上述油墨可以为油性油墨、溶剂油墨、水性油墨、油包水(W/O)型乳液油墨、水包油(O/W)型乳液油墨、塑料溶胶油墨中的任意一种。
[实施例]
以下对于本发明基于实施例和比较例进行详细说明,但是本发明不仅限于这些实施例。只要没有特别说明则“%”为“质量%”。表中的各材料的配混量也以“质量%”表示。
1.粘接剂
表1及2示出各实施例和比较例的粘接剂的组成。表1及2中的各成分的配混量以质量%表示。各实施例和比较例的粘接剂是将表1及2所示的材料以表1及2所示的比率混合来使用的。
表1及2中记载的各材料的详细说明如下所示。
Takelac A-666:氨基甲酸酯预聚物(三井化学株式会社制)
EXCENOL 750ED:聚醚多元醇(AGC株式会社制)
Duranate TPA-100:六亚甲基二异氰酸酯(HDI)的异氰脲酸酯改性体(旭化成株式会社制)(表1和表2中为“TPA-100”)
UA-306H:氨基甲酸酯(甲基)丙烯酸酯(季戊四醇三丙烯酸酯六亚甲基二异氰酸酯氨基甲酸酯预聚物)(共荣社化学株式会社制)
EPOXY ESTER 80MFA:环氧(甲基)丙烯酸酯(Epolight 80MF(甘油二缩水甘油基醚)丙烯酸加成物)(共荣社化学株式会社制)
Omnirad907:光聚合引发剂(2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代基丙烷-1-酮)(IGM Resin公司)
2.热敏丝网母版的制作
使用层压装置,利用上述粘接剂将厚度73μm的聚酯制丝网纱(网眼数#200、线径48μm)(日本特殊织物株式会社制“79/200-48”)、和厚度2μm的双轴拉伸聚酯薄膜贴合而得到层叠体。粘接剂使用辊涂机以赋予量3.0g/m2进行赋予。
对该层叠体照射紫外线,将所得到的层叠体卷取,利用60℃的恒温器干燥1天后,利用30℃80%RH的恒温器干燥1天,制作热敏丝网母版。
3.评价
使用如上所述得到的各实施例及比较例的粘接剂或热敏丝网母版,如下所述进行皱折产生数、粘接强度和耐溶剂性的评价。结果如表1和表2所示。
<皱折产生数>
对于各实施例及比较例的热敏丝网母版的1m×100m的范围内的皱折的产生数进行计数,按照下述评价基准评价。
S:1m×100m的范围内的皱折的产生数0个
A:1m×100m的范围内的皱折的产生数1~4个
B:1m×100m的范围内的皱折的产生数5~10个
C:1m×100m的范围内的皱折的产生数超过10个
<粘接强度>
使用各实施例及比较例的热敏丝网母版评价粘接强度。具体而言,在热敏丝网母版的热塑性树脂薄膜侧粘贴粘胶带,将端部的丝网纱和热塑性树脂薄膜剥离后,利用株式会社东洋精机制作所制“Strograph VGS05-D”测定层压剥离强度,对于所得到的结果基于下述评价基准进行评价。
S:120gf/25mm以上
A:100gf/25mm以上且不足120gf/25mm
B:60gf/25mm以上且不足100gf/25mm
C:不足60gf/25mm
<耐溶剂性>
使用各实施例及比较例的粘接剂评价耐溶剂性。具体而言,利用涂布厚度5μm的棒涂机将上述粘接剂涂布于厚度125μm的PET薄膜上,利用60℃的恒温器干燥1天后、利用30℃80%RH的恒温器干燥1天。
将所得到的涂膜浸渍于甲苯15分钟,测定甲苯浸渍前后的涂膜的重量变化率,对于其绝对值基于下述评价基准进行评价。
S:0.5%以下
A:超过0.5%且为2.0%以下
B:超过2.0%且为5.0%以下
C:超过5.0%
[表1]
[表2]
如表所示那样,实施例1~7得到皱折产生数和粘接强度都优异的结果。
与此相对地,粘接剂中都不含有成分C和成分D的比较例1及2中,皱折产生数都多。粘接剂中都不含有成分A和成分B的比较例3中,粘接强度变差。
Claims (5)
1.一种粘接剂,其含有选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种、多异氰酸酯、聚合性(甲基)丙烯酸酯化合物、和光聚合引发剂。
2.根据权利要求1所述的粘接剂,其中,所述选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种与所述多异氰酸酯的质量比为90:10~5:95。
3.根据权利要求2所述的粘接剂,其中,所述选自由氨基甲酸酯预聚物和多元醇组成的组中的至少一种与所述多异氰酸酯的质量比为35:65~5:95。
4.一种热敏丝网母版的制造方法,其包括对于依次具备丝网纱、含有权利要求1~3中任一项所述的粘接剂的粘接剂层、和热塑性树脂薄膜的层叠体照射活性能量射线。
5.一种热敏丝网母版,其包含丝网纱、使用权利要求1~3中任一项所述的粘接剂形成的层、和热塑性树脂薄膜。
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JP2002030261A (ja) * | 2000-07-17 | 2002-01-31 | Toagosei Co Ltd | 紫外線硬化型接着剤組成物及び感熱孔版印刷原紙 |
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CN114633543A (zh) * | 2022-02-25 | 2022-06-17 | 河南亿思达数码材料有限公司 | 一种用于数码热熔制版的丝印网膜及其制备方法 |
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