CN105705525B - 印刷电路板用固化型组合物、使用其的固化涂膜和印刷电路板 - Google Patents
印刷电路板用固化型组合物、使用其的固化涂膜和印刷电路板 Download PDFInfo
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- CN105705525B CN105705525B CN201480060735.1A CN201480060735A CN105705525B CN 105705525 B CN105705525 B CN 105705525B CN 201480060735 A CN201480060735 A CN 201480060735A CN 105705525 B CN105705525 B CN 105705525B
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Classifications
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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- H05K1/0313—Organic insulating material
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Abstract
本发明提供一种印刷电路板用固化型组合物,其耐焊接热性能、铅笔硬度等涂膜的物理强度高,且即使在制成能够应对喷墨印刷法、旋涂法等的低粘度的情况下,也不易在长期保存下引起含有成分的沉降。印刷电路板用固化型组合物的特征在于,包含:(A)比重为3以下的填料、(B)具有羟基的(甲基)丙烯酸酯化合物、和(C)光聚合引发剂。前述(A)比重为3以下的填料优选为无机填料。
Description
技术领域
本发明涉及印刷电路板用的固化型组合物、特别是用于喷墨方式的紫外线固化型的组合物、使用其的保护膜和标记中的至少任一种的印刷电路板用涂膜、以及具有使用其得到的图案的印刷电路板。
背景技术
对于阻焊剂等的印刷电路板用固化型组合物,为了使涂膜的物理强度提高而通常使用添加填料的方法,但在能够应对喷墨法、旋涂法等程度的低粘度的组合物中,长期保存下填料会发生沉降,因此,印刷性的变化、涂膜特性的降低成为问题。
现有技术文献
专利文献
专利文献1:日本特开平5-7079号
专利文献2:日本特开平5-7080号
专利文献3:日本特开平5-7081号
发明内容
发明要解决的问题
然而,在能够应对喷墨法、旋涂法等的极端低粘度的组合物中,填料容易发生沉降,在长期保存下随着填料的沉降而引起印刷性的变化、涂膜特性的降低会成为问题。
本发明是为了解决前述现有技术的问题而作出的,其主要目的在于,提供耐焊接热性能、铅笔硬度等涂膜的物理强度高,且即使在制成能够应对喷墨印刷法、旋涂法等的低粘度的情况下,也不易在长期保存下引起含有成分的沉降。
用于解决问题的方案
发现本发明的上述目的能够通过印刷电路板用固化型组合物而达成,所述印刷电路板用固化型组合物的特征在于,包含:特定的填料、具有羟基的(甲基)丙烯酸酯化合物、和光聚合引发剂。
即,本发明的印刷电路板用固化型组合物的特征在于,包含:(A)比重为3以下的填料、(B)具有羟基的(甲基)丙烯酸酯化合物、和(C)光聚合引发剂。
本发明的印刷电路板用固化型组合物优选前述(A)比重为3以下的填料是无机填料。
此外,本发明的印刷电路板用固化型组合物优选组合物中所含的颗粒的最大粒径为0.1~5μm以下。
此外,本发明的印刷电路板用固化型组合物优选还包含2官能(甲基)丙烯酸酯化合物。
此外,本发明的印刷电路板用固化型组合物优选前述2官能(甲基)丙烯酸酯化合物在25℃下的粘度为5~50mPa·s。
此外,本发明的印刷电路板用固化型组合物优选还包含热固化成分。
此外,本发明的印刷电路板用固化型组合物优选在50℃下的粘度为5~50mPa·s。
本发明的固化涂膜的特征在于,其通过对上述任一项所述的印刷电路板用固化型组合物进行光照射而得到。
本发明的印刷电路板的特征在于,其具有图案固化涂膜,该图案固化涂膜通过将上述任一项所述的印刷电路板用固化型组合物印刷在基板上并对其进行光照射而得到。
本发明的印刷电路板的特征在于,其具有图案固化涂膜,该图案固化涂膜通过利用喷墨印刷法将上述任一项所述的印刷电路板用固化型组合物印刷在基板上并对其进行光照射而得到。
本发明的印刷电路板的特征在于,前述基板为塑料基板。
发明的效果
根据本发明,可以提供一种印刷电路板用固化型组合物,其耐焊接热性能、铅笔硬度等涂膜的物理强度高,且即使在制成能够应对喷墨印刷法、旋涂法等的低粘度的情况下,也不易在长期保存下引起含有成分的沉降。此外,本发明的固化型组合物可以得到对基板等的密合性优异、硬度、耐化学药品性等各特性优异的固化涂膜。进而,本发明的固化型组合物可以适宜用作喷墨用组合物。
具体实施方式
本发明的印刷电路板用固化型组合物(以下,也称为固化型组合物)包含:(A)比重为3以下的填料(成分A)、(B)具有羟基的(甲基)丙烯酸酯化合物(成分B)、和(C)光聚合引发剂(成分C)。
需要说明的是,在本说明书中,(甲基)丙烯酸酯是指,统称丙烯酸酯、甲基丙烯酸酯和它们的混合物的用语,对于其它类似的表述也是同样的。
[(A)比重为3以下的填料]
(A)比重为3以下的填料可以使用公知惯用的填料。作为成分(A)的填料,优选无机填料,也可以为有机填料。
此外,作为成分(A)的填料,优选比重为1~3的填料。
作为(A)比重为3以下的填料的具体例,可举出:氢氧化铝(比重:2.42)、氢氧化镁(比重:2.3~2.4)、滑石(比重:2.7~2.8)、二氧化硅(比重:2.2)、碳酸镁(比重:2.98)、碳酸钙(比重:2.4~2.7)、水滑石(2.03~2.09)、氢氧化钙(2.21)、海泡石(2.0~2.3)、硫酸钙(2.96、酐)、(2.36、2水合物)、高岭土(2.6)、云母(2.8~3.0)、硫酸镁(2.65)、炭黑(1.8~2.1)、飞灰(1.9~2.1)、硅灰石(2.9~3.0)等。通过配混比重为3以下的填料,能够防止印刷电路板用固化型组合物中的沉降的产生,还能够提高耐焊接热性能、铅笔硬度这样的涂膜强度。
从防止沉降产生的观点出发,本发明的固化型组合物中实质上优选不含有比重超过3的填料,但在不损害本发明的固化型组合物的特性、发明的目的的范围内并不排出包含比重超过3的填料。比重超过3的填料也可以使用公知惯用的填料。作为比重超过3的填料的具体例(括号内为比重),可举出:硫酸钡(4.5)、氧化钛(4)、钛酸钡(6.02)、氧化铝(约4)、勃姆石(3.04)、氧化锌(5.6)、氧化镁(3.65)、氧化钙(3.35)、钛酸钾(3.5)、铜(8.74)、铁(7.87)等。
在本发明的固化型组合物100质量份中,(A)比重为3以下的填料的配混量优选为5~30质量份、更优选为10~30质量份。若为5质量份以上,则可以期待物理强度的提高,另一方面,若为30质量份以下,则能够抑制因粘度的上升、触变性的上升而导致的(喷墨)印刷性的降低。
此外,本发明的固化型组合物中所含的颗粒的最大粒径优选为0.1~5μm以下、更优选为0.1~1μm。若最大粒径为0.1μm以上,则颗粒的内聚力不会变得过高,若为5μm以下,则产生喷墨印刷时的喷嘴堵塞等问题的可能性变低,故优选。
组合物中所含的颗粒的最大粒径可以利用粒径分布计测定,将其D100值作为最大粒径。
[(B)具有羟基的(甲基)丙烯酸酯化合物]
(B)具有羟基的(甲基)丙烯酸酯化合物使用单体或低聚物等低分子量的材料,具体而言,使用分子量100~1000的范围、优选分子量110~700的范围的材料。
作为(B)具有羟基的(甲基)丙烯酸酯化合物的具体例,可举出:(甲基)丙烯酸2-羟基-3-丙烯酰氧基丙酯、(甲基)丙烯酸2-羟基-3-苯氧基乙酯、1,4-环己烷二甲醇单(甲基)丙烯酸酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、(甲基)丙烯酸2-羟基丙酯等。作为市售品,有ARONIX M-5700(东亚合成株式会社制造的商品名);4HBA、2HEA、CHDMMA(以上,日本化成株式会社制造的商品名);BHEA、HPA、HEMA、HPMA(以上,日本触媒株式会社制造的商品名);LIGHT ESTER HO、LIGHT ESTER HOP、LIGHT ESTER HOA(以上,共荣社化学株式会社制造的商品名)等。(B)具有羟基的(甲基)丙烯酸酯化合物可以使用1种或组合多种来使用。
其中,特别优选使用丙烯酸2-羟基-3-丙烯酰氧基丙酯、丙烯酸2-羟基-3-苯氧基乙酯、丙烯酸2-羟基乙酯、丙烯酸2-羟基丙酯、丙烯酸4-羟基丁酯、1,4-环己烷二甲醇单丙烯酸酯。此外,从粘度调整的容易性等方面出发,优选使用单官能(甲基)丙烯酸酯化合物。
本发明的固化型组合物100质量份中,(B)具有羟基的(甲基)丙烯酸酯化合物的配混量优选为5~50质量份、更优选为10~30质量份。具有羟基的(甲基)丙烯酸酯的配混量为5质量份以上时,本发明的组合物的特征即密合性变得更良好。另一方面,配混量为50质量份以下时,可以抑制墨的相容性的降低。
本发明的固化型组合物通过组合这样的(A)成分与(B)成分,即使在制成低粘度的情况下,也不易在长期保存下引起含有成分的沉降,且对塑料基板和导体电路金属两者具有优异的密合性,例如作为印刷电路板用的保护墨(resist ink)(抗蚀刻墨(etchingresist ink)、阻焊墨(solder resist ink)、抗镀墨(plating resist Ink)),发挥优异的基板保护性能。此外,即使以低露光量也会发挥优异的固化涂膜特性。
[(C)光聚合引发剂]
作为(C)光聚合引发剂,没有特别限定,例如可以使用光自由基聚合引发剂。作为该光自由基聚合引发剂,只要是利用光、激光、电子束等而产生自由基并引发自由基聚合反应的化合物则均可使用。
作为(C)光聚合引发剂,例如可举出:苯偶姻、苯偶姻甲醚、苯偶姻乙基醚、苯偶姻异丙醚等苯偶姻和苯偶姻烷基醚类;2-羟基-2-甲基-1-苯基-丙烷-1-酮等烷基苯甲酮系;苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮等苯乙酮类;2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-吗啉代苯基)-丁烷-1-酮、N,N-二甲基氨基苯乙酮等氨基苯乙酮类;2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌等蒽醌类;2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2-氯噻吨酮、2,4-二异丙基噻吨酮等噻吨酮类;苯乙酮二甲基缩酮、苯偶酰二甲基缩酮等缩酮类;2,4,5-三芳基咪唑二聚体;核黄素四丁酸酯;2-巯基苯并咪唑、2-巯基苯并噁唑、2-巯基苯并噻唑等硫醇化合物;2,4,6-三均三嗪、2,2,2-三溴乙醇、三溴甲基苯基砜等有机卤素化合物;二苯甲酮、4,4’-双(二乙基氨基)二苯甲酮等二苯甲酮类或呫吨酮类;2,4,6-三甲基苯甲酰基二苯基氧化膦、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦等酰基氧化膦系;双(环戊二烯基)-二-苯基-钛、双(环戊二烯基)-二-氯-钛、双(环戊二烯基)-双(2,3,4,5,6-五氟苯基)钛、双(环戊二烯基)-双(2,6-二氟-3-(吡咯-1-基)苯基)钛等二茂钛类等。
这些公知惯用的光聚合引发剂可以单独使用或以2种以上的混合物的形式使用,还可以加入N,N-二甲基氨基苯甲酸乙酯、N,N-二甲基氨基苯甲酸异戊酯、4-二甲基氨基苯甲酸戊酯、三乙胺、三乙醇胺等叔胺类等光引发助剂。
作为市售品,可举出:IRGACURE 261、184、369、651、500、819、907、784、2959、DAROCUR1116、1173、CGI1700、CGI1750、CGI1850、CG-24-61、LUCIRIN TPO、CGI-784(以上,BASF JAPAN LTD.制造的商品名)、DAICATII(Daicel Chemical Industries,Ltd.制造的商品名)、RHODORSIL PHOTOINITIATOR2074(Rhodia Corporation制造的商品名)、UbecrylP36(UCB Corporation制造的商品名)、Esacure KIP150、KIP65LT、KIP100F、KT37、KT55、KTO46、KIP75/B、ONE(Fratelli Lamberti Corporation制造的商品名)等。
本发明的固化型组合物100质量份中,(C)光聚合引发剂的配混比例优选为0.5~10质量份的范围。
(2官能(甲基)丙烯酸酯化合物)
本发明的印刷电路板用固化型组合物优选还包含2官能(甲基)丙烯酸酯化合物(不具有羟基)。通过添加2官能(甲基)丙烯酸酯化合物(不具有羟基),能够进一步提高印刷电路板用固化型组合物中的各成分的相容性。
作为2官能(甲基)丙烯酸酯(不具有羟基)的具体例子,可举出:1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯等二元醇的二丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、使新戊二醇与环氧乙烷和环氧丙烷中至少任一种加成而得到的二元醇的二丙烯酸酯、己内酯改性羟基特戊酸新戊二醇二丙烯酸酯等二醇的二丙烯酸酯、双酚A EO加成物二丙烯酸酯、双酚A PO加成物二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、氢化二环戊二烯基二丙烯酸酯、环己基二丙烯酸酯等具有环状结构的二丙烯酸酯等。
作为市售品,可列举出LIGHT ACRYLATE 1,6HX-A、1,9ND-A、3EG-A、4EG-A(共荣社化学株式会社制造的商品名)、HDDA、1,9-NDA、DPGDA、TPGDA(Daicel-Cytec Company Ltd.制造的商品名)、Viscoat#195、#230、#230D、#260、#310HP、#335HP、#700HV(大阪有机化学工业株式会社制造的商品名)、ARONIX M-208、M-211B、M-220、M-225、M-240、M-270(东亚合成株式会社制造的商品名)等。
其中,从粘度和相容性的观点出发,优选具有碳原子数4~12的烷基链的二元醇的二丙烯酸酯,特别优选1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯。
这些2官能丙烯酸酯化合物的配混量在本发明的固化型组合物100质量份中优选为20~80质量份、更优选为40~70质量份。2官能(甲基)丙烯酸酯的配混量为20质量份以上时,墨的相容性变得良好。另一方面,配混量为80质量份以下时,墨的密合性变得良好。
2官能(甲基)丙烯酸酯化合物在25℃下的粘度优选为5~50mPa·s、特别优选为5~30mPa·s。在该粘度范围内,作为2官能(甲基)丙烯酸酯化合物的稀释剂的处理性变得良好,能够将各成分均匀混合。其结果,可以期待涂膜的整面对基板均匀地密合。
(热固化成分)
本发明的固化型组合物中可以加入热固化成分。通过加入热固化成分,能够期待密合性、耐热性提高。作为本发明中使用的热固化成分,可以使用三聚氰胺树脂、苯并胍胺树脂、三聚氰胺衍生物、苯并胍胺衍生物等氨基树脂、封端异氰酸酯化合物、环碳酸酯化合物、具有环状(硫)醚基的热固化成分、双马来酰亚胺、碳二亚胺树脂等公知的热固化性树脂。从保存稳定性优异的观点出发,特别优选的是封端异氰酸酯化合物。
上述分子中具有多个环状(硫)醚基的热固化成分为分子中具有多个3、4或5元环的环状(硫)醚基中任一者或两种基团的化合物,例如可列举出分子内具有多个环氧基的化合物、即多官能环氧化合物;分子内具有多个氧杂环丁基的化合物、即多官能氧杂环丁烷化合物;分子内具有多个硫醚基的化合物、即环硫树脂等。
作为上述多官能环氧化合物,可举出:ADEKA株式会社制造的Adekacizer O-130P、Adekacizer O-180A、Adekacizer D-32、Adekacizer D-55等环氧化植物油;三菱化学株式会社制造的jER828、jER834、jER1001、jER1004、Daicel Chemical Industries,Ltd.制造的EHPE3150、DIC株式会社制造的EPICLON840、EPICLON850、EPICLON1050、EPICLON2055、东都化成株式会社制造的EPOTOHTO YD-011、YD-013、YD-127、YD-128、陶氏化学制造的D.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664、住友化学工业株式会社制造的SUMI-EPOXYESA-011、ESA-014、ELA-115、ELA-128、旭化成工业株式会社制造的A.E.R.330、A.E.R.331、A.E.R.661、A.E.R.664等(均为商品名)双酚A型环氧树脂;YDC-1312、氢醌型环氧树脂、YSLV-80XY双酚型环氧树脂、YSLV-120TE硫醚型环氧树脂(均为东都化成株式会社制造);三菱化学株式会社制造的jERYL903、DIC株式会社制造的EPICLON152、EPICLON165、东都化成株式会社制造的EPOTOHTO YDB-400、YDB-500、陶氏化学制造的D.E.R.542、住友化学工业株式会社制造的SUMI-EPOXY ESB-400、ESB-700、旭化成工业株式会社制造的A.E.R.711、A.E.R.714等(均为商品名)溴化环氧树脂;三菱化学株式会社制造的jER152、jER154、陶氏化学制造的D.E.N.431、D.E.N.438、DIC株式会社制造的EPICLONN-730、EPICLONN-770、EPICLONN-865、东都化成株式会社制造的EPOTOHTO YDCN-701、YDCN-704、日本化药株式会社制造的EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306、住友化学工业株式会社制造的SUMI-EPOXY ESCN-195X、ESCN-220、旭化成工业株式会社制造的A.E.R.ECN-235、ECN-299等(均为商品名)酚醛清漆型环氧树脂;日本化药株式会社制造的NC-3000、NC-3100等联苯酚酚醛清漆型环氧树脂;DIC株式会社制造的EPICLON830、三菱化学株式会社制造的jER807、东都化成株式会社制造的EPOTOHTO YDF-170、YDF-175、YDF-2004等(均为商品名)双酚F型环氧树脂;东都化成株式会社制造的EPOTOHTO ST-2004、ST-2007、ST-3000(商品名)等氢化双酚A型环氧树脂;三菱化学株式会社制造的jER604、东都化成株式会社制造的EPOTOHTO YH-434、住友化学工业株式会社制造的SUMI-EPOXY ELM-120等(均为商品名)缩水甘油胺型环氧树脂;乙内酰脲型环氧树脂;Daicel Chemical Industries,Ltd.制造的CELLOXIDE 2021等(均为商品名)脂环式环氧树脂;三菱化学株式会社制造的YL-933、陶氏化学制造的T.E.N.、EPPN-501、EPPN-502等(均为商品名)三羟基苯基甲烷型环氧树脂;三菱化学株式会社制造的YL-6056、YX-4000、YL-6121(均为商品名)等联二甲苯酚型或联苯酚型环氧树脂或它们的混合物;日本化药株式会社制造的EBPS-200、ADEKA株式会社制造的EPX-30、DIC株式会社制造的EXA-1514(商品名)等双酚S型环氧树脂;三菱化学株式会社制造的jER157S(商品名)等双酚A酚醛清漆型环氧树脂;三菱化学株式会社制造的jERYL-931等(均为商品名)四羟苯基乙烷型环氧树脂;日产化学工业株式会社制造的TEPIC等(均为商品名)杂环式环氧树脂;日本油脂株式会社制造的BLENMER DGT等邻苯二甲酸二缩水甘油酯树脂;东都化成株式会社制造的ZX-1063等四缩水甘油基二甲苯酰基乙烷树脂(tetraglycidylxylenoyl ethane resin);新日铁化学株式会社制造的ESN-190、ESN-360、DIC株式会社制造的HP-4032、EXA-4750、EXA-4700等含萘基环氧树脂;DIC株式会社制造的HP-7200、HP-7200H等具有双环戊二烯骨架的环氧树脂;日本油脂株式会社制造的CP-50S、CP-50M等甲基丙烯酸缩水甘油酯共聚系环氧树脂;进而环己基马来酰亚胺与甲基丙烯酸缩水甘油酯的共聚环氧树脂;环氧改性的聚丁二烯橡胶衍生物(例如Daicel ChemicalIndustries,Ltd.制造的PB-3600等)、CTBN改性环氧树脂(例如东都化成株式会社制造的YR-102、YR-450等)等,但并不限定于这些。这些环氧树脂可以单独使用或组合2种以上使用。其中,特别优选酚醛清漆型环氧树脂、联二甲苯酚型环氧树脂、联苯酚型环氧树脂、联苯酚酚醛清漆型环氧树脂、萘型环氧树脂或它们的混合物。
作为多官能氧杂环丁烷化合物,例如可举出:双[(3-甲基-3-氧杂环丁基甲氧基)甲基]醚、双[(3-乙基-3-氧杂环丁基甲氧基)甲基]醚、1,4-双[(3-甲基-3-氧杂环丁基甲氧基)甲基]苯、1,4-双[(3-乙基-3-氧杂环丁基甲氧基)甲基]苯、丙烯酸(3-甲基-3-氧杂环丁基)甲酯、丙烯酸(3-乙基-3-氧杂环丁基)甲酯、甲基丙烯酸(3-甲基-3-氧杂环丁基)甲酯、甲基丙烯酸(3-乙基-3-氧杂环丁基)甲酯、它们的低聚物或共聚物等多官能氧杂环丁烷类、以及氧杂环丁醇与酚醛清漆树脂、聚(对羟基苯乙烯)、Cardo型双酚类、杯芳烃类、间苯二酚杯芳烃类、或倍半硅氧烷等具有羟基的树脂的醚化物等。此外,还可列举出具有氧杂环丁烷环的不饱和单体与(甲基)丙烯酸烷基酯的共聚物等。
作为分子中具有多个环状硫醚基的化合物,例如可列举出三菱化学株式会社制造的双酚A型环硫树脂YL7000等。此外,也可以使用采用同样的合成方法、将酚醛清漆型环氧树脂的环氧基的氧原子替换为硫原子而成的环硫树脂等。
作为三聚氰胺衍生物、苯并胍胺衍生物等氨基树脂,例如有羟甲基三聚氰胺化合物、羟甲基苯并胍胺化合物、羟甲基甘脲化合物和羟甲基尿素化合物等。进而,烷氧基甲基化三聚氰胺化合物、烷氧基甲基化苯并胍胺化合物、烷氧基甲基化甘脲化合物和烷氧基甲基化尿素化合物分别通过将羟甲基三聚氰胺化合物、羟甲基苯并胍胺化合物、羟甲基甘脲化合物和羟甲基尿素化合物的羟甲基替换为烷氧基甲基而得到。对于该烷氧基甲基的种类没有特别限定,例如可以为甲氧基甲基、乙氧基甲基、丙氧基甲基、丁氧基甲基等。特别优选对人体、环境友好的福尔马林浓度为0.2%以下的三聚氰胺衍生物。
作为这些的市售品,例如可举出:Cymel300、Cymel301、Cymel303、Cymel370、Cymel325、Cymel327、Cymel701、Cymel266、Cymel267、Cymel238、Cymel1141、Cymel272、Cymel202、Cymel1156、Cymel1158、Cymel1123、Cymel1170、Cymel1174、Cymel UFR65、Cymel300(均为Mitsui-Cyanamid Ltd.制造)、NIKALAC Mx-750、NIKALAC Mx-032、NIKALACMx-270、NIKALAC Mx-280、NIKALAC Mx-290、NIKALAC Mx-706、NIKALAC Mx-708、NIKALACMx-40、NIKALAC Mx-31、NIKALAC Ms-11、NIKALAC Mw-30、NIKALAC Mw-30HM、NIKALAC Mw-390、NIKALAC Mw-100LM、NIKALAC Mw-750LM(均为三和化学株式会社制造)等。这种热固化成分可以单独使用1种,也可以组合使用2种以上。
异氰酸酯化合物、封端异氰酸酯化合物为1分子内具有多个异氰酸酯基或封端化异氰酸酯基的化合物。作为这种1分子内具有多个异氰酸酯基或封端化异氰酸酯基的化合物,可列举出多异氰酸酯化合物、或封端异氰酸酯化合物等。需要说明的是,封端化异氰酸酯基是指异氰酸酯基利用与封端剂的反应被保护而暂时钝化了的基团,加热至规定温度时该封端剂解离而生成异氰酸酯基。通过加入上述多异氰酸酯化合物、或封端异氰酸酯化合物,确认到固化性和所得固化物的强韧性得到提高。
作为这种多异氰酸酯化合物,例如可使用芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环式多异氰酸酯。
作为芳香族多异氰酸酯的具体例子,例如可举出:4,4’-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、萘-1,5-二异氰酸酯、邻苯二亚甲基二异氰酸酯、间苯二亚甲基二异氰酸酯和2,4-甲苯二异氰酸酯二聚体等。
作为脂肪族多异氰酸酯的具体例子,可举出:四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、4,4-亚甲基双(环己基异氰酸酯)和异佛尔酮二异氰酸酯等。
作为脂环式多异氰酸酯的具体例子,可举出:双环庚烷三异氰酸酯。此外,还可列举出前文所列举的异氰酸酯化合物的加合体、缩二脲体和异氰脲酸酯体等。
作为封端异氰酸酯化合物,可以使用异氰酸酯化合物与异氰酸酯封端剂的加成反应产物。作为可与封端剂反应的异氰酸酯化合物,例如可列举出上述多异氰酸酯化合物等。
作为异氰酸酯封端剂,例如可列举出苯酚、甲酚、二甲苯酚、氯苯酚和乙基苯酚等酚系封端剂;ε-己内酰胺、δ-戊内酰胺、γ-丁内酰胺和β-丙内酰胺等内酰胺系封端剂;乙酰乙酸乙酯和乙酰丙酮等活性亚甲基系封端剂;甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、二乙二醇单甲醚、丙二醇单甲醚、苯甲醚、乙醇酸甲酯、乙醇酸丁酯、二丙酮醇、乳酸甲酯和乳酸乙酯等醇系封端剂;甲醛肟、乙醛肟、丙酮肟、甲乙酮肟、二乙酰基单肟、环己酮肟等肟系封端剂;丁硫醇、己硫醇、叔丁硫醇、苯硫酚、甲基苯硫酚、乙基苯硫酚等硫醇系封端剂;乙酰胺、苯甲酰胺等酸酰胺系封端剂;丁二酰亚胺和马来酰亚胺等酰亚胺系封端剂;二甲苯胺、苯胺、丁胺、二丁胺等胺系封端剂;咪唑、2-乙基咪唑等咪唑系封端剂;亚甲基亚胺和亚丙基亚胺等亚胺系封端剂等。
封端异氰酸酯化合物可以为市售品,例如可列举出Sumidule BL-3175、BL-4165、BL-1100、BL-1265、DESMODUR TPLS-2957、TPLS-2062、TPLS-2078、TPLS-2117、DESMOSOME2170、DESMOSOME2265(均为Sumitomo Bayer Urethane Co.,Ltd.制造)、CORONATE2512、CORONATE2513、CORONATE2520(均为Nippon Polyurethane Industry Co.,Ltd.制造)、B-830、B-815、B-846、B-870、B-874、B-882(均为三井武田化学株式会社制造)、TPA-B80E、17B-60PX、E402-B80T(均为旭化成化学株式会社制造)等。需要说明的是,Sumidule BL-3175、BL-4265是使用甲乙肟作为封端剂而得到的。这种1分子内具有多个异氰酸酯基或封端化异氰酸酯基的化合物可以单独使用1种,也可以组合2种以上使用。
这种热固化成分的配混量在本发明的固化型组合物100质量份中优选为1~30质量份。配混量为1质量份以上时,可得到充分的涂膜的强韧性、耐热性。另一方面,为30质量份以下时,能够抑制保存稳定性降低。
本发明的印刷电路板用固化型组合物中,除上述成分之外,还可以根据需要配混表面张力调整剂、表面活性剂、消光剂、用于调整膜物性的聚酯系树脂、聚氨酯系树脂、乙烯基系树脂、丙烯酸类树脂、橡胶系树脂、蜡类、酞菁蓝、酞菁绿、碘绿、双偶氮黄、结晶紫、氧化钛、炭黑、萘黑等公知惯用的着色剂、有机硅系、氟系、高分子系等的消泡剂和流平剂中的至少1种、咪唑系、噻唑系、三唑系、硅烷偶联剂等密合性赋予剂那样的公知惯用的添加剂类。
进而,本发明的印刷电路板用固化型组合物中,除上述成分之外还可以在不损害特性的范围内配混树脂。作为树脂,可以使用公知惯用的树脂,优选具有多烯骨架的(甲基)丙烯酸酯化合物。前述多烯骨架例如优选使用聚丁二烯或异戊二烯、或这两者的聚合而形成,特别优选由通式(I)所示的重复单元构成。
(式中,n表示10~300。)
由于这种重复单元的烯属双键,对印刷电路板用固化型保护剂组合物赋予柔软性,对基材的追随性增加,可得到良好的密合性。
上述(甲基)丙烯酸酯化合物的多烯骨架中,上述通式(I)所示的重复单元优选为50%以上、更优选为80%以上。
进而,(甲基)丙烯酸酯化合物的多烯骨架还可以包含下述通式(II)所示的单元。
作为具体例子,优选使用以下的材料。即,将(甲基)丙烯酸2-羟基乙酯介由2,4-甲苯二异氰酸酯与液态聚丁二烯的羟基进行氨基甲酸酯加成反应而得到的液态聚丁二烯氨基甲酸酯(甲基)丙烯酸酯、使加成了马来酸酐的马来化聚丁二烯与2-羟基丙烯酸酯进行酯化反应而得到的液态聚丁二烯丙烯酸酯、由马来化聚丁二烯的羧基与(甲基)丙烯酸缩水甘油酯的环氧酯化反应而得到的液态聚丁二烯(甲基)丙烯酸酯、使环氧化剂作用于液态聚丁二烯而得到的环氧化聚丁二烯与(甲基)丙烯酸的酯化反应而得到的液态聚丁二烯(甲基)丙烯酸酯、由具有羟基的液态聚丁二烯与(甲基)丙烯酰氯的脱氯反应而得到的液态聚丁二烯(甲基)丙烯酸酯、使将分子两末端具有羟基的液态聚丁二烯的不饱和双键氢化而成的液态氢化1,2聚丁二烯二醇经氨基甲酸酯(甲基)丙烯酸酯改性所得到的液态氢化1,2聚丁二烯(甲基)丙烯酸酯等。
作为市售品的例子,可举出:NISSO PB TE-2000、NISSO PB TEA-1000、NISSO PBTE-3000、NISSO PB TEAI-1000(以上均为日本曹达株式会社制造)、CN301、CN303、CN307(SARTOMER Corporation制造)、BAC-15(大阪有机化学工业株式会社制造)、BAC-45(大阪有机化学工业株式会社制造)、EY RESIN BR-45UAS(Light Chemical Industries Co.,Ltd.制造)等。
具有多烯骨架的(甲基)丙烯酸酯可以使用1种或组合多种使用。
此外,本发明的印刷电路板用固化型组合物可以为了调整组合物的粘度而配混稀释剂。
作为稀释剂,可举出:稀释溶剂、光反应性稀释剂、热反应性稀释剂等。这些稀释剂当中优选光反应性稀释剂。
作为光反应性稀释剂,可列举出(甲基)丙烯酸酯类、乙烯基醚类、亚乙基衍生物、苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯、马来酸酐、双环戊二烯、N-乙烯基吡咯烷酮、N-乙烯基甲酰胺、苯二亚甲基二氧杂环丁烷、氧杂环丁醇、3-乙基-3-(苯氧基甲基)氧杂环丁烷、间苯二酚二缩水甘油醚等具有不饱和双键、氧杂环丁基、环氧基的化合物。
这些当中优选(甲基)丙烯酸酯类、进一步优选单官能(甲基)丙烯酸酯类是优选的。作为单官能(甲基)丙烯酸酯类,例如可列举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸羟基丙酯、(甲基)丙烯酸羟基丁酯、甲基丙烯酸缩水甘油酯等(甲基)丙烯酸酯类、丙烯酰吗啉等。
这些稀释剂的配混量在本发明的固化型组合物100质量份中优选为1~30质量份。
此外,本发明的印刷电路板用固化型组合物可以为了提高组合物的UV固化后的粘着性而配混3官能以上的(甲基)丙烯酸酯化合物(不具有羟基)。
作为3官能以上的(甲基)丙烯酸酯化合物,可列举出以三羟甲基丙烷三丙烯酸酯、三羟甲基甲烷三丙烯酸酯、环氧乙烷改性三羟甲基丙烷三丙烯酸酯、环氧丙烷改性三羟甲基丙烷三丙烯酸酯、环氧氯丙烷改性三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、四羟甲基甲烷四丙烯酸酯、环氧乙烷改性磷酸三丙烯酸酯、环氧丙烷改性磷酸三丙烯酸酯、环氧氯丙烷改性甘油三丙烯酸酯、二季戊四醇六丙烯酸酯、二三羟甲基丙烷四丙烯酸酯、或它们的倍半硅氧烷改性物等为代表的多官能丙烯酸酯;或者与它们相对应的甲基丙烯酸酯单体、ε己内酯改性三丙烯酰氧基乙基异氰脲酸酯。该3官能以上的多官能(甲基)丙烯酸酯化合物的配混量在本发明的组合物100质量份中优选为1~40质量份。
具有上述各成分的本发明的印刷电路板用固化型组合物可以用于丝网印刷法、喷墨法、浸涂法、流涂法、辊涂法、棒涂法、帘涂法等印刷方法。特别是将本发明的印刷电路板用固化型组合物用于喷墨法时,本发明的印刷电路板用固化型组合物在50℃下的粘度优选为5~50mPa·s、更优选为5~20mPa·s。由此,顺利的印刷成为可能,而不会对喷墨打印机造成不必要的负担。
本发明中,粘度是指根据JIS K2283在常温(25℃)或50℃下测定的粘度。在常温下为150mPa·s以下、或50℃下的粘度为5~50mPa·s时,可以利用喷墨印刷法进行印刷。
进而,本发明的印刷电路板用固化型组合物根据上述组成而制成喷墨方式用的墨来应用时,能够对柔性电路板进行辊对辊方式的印刷。此时,在通过喷墨打印机后安装后述光照射用光源,从而能够高速地形成图案固化涂膜。
光照射可以利用紫外线或活性能量的照射而进行,优选紫外线。作为光照射的光源,低压汞灯、中压汞灯、高压汞灯、超高压汞灯、氙灯、金属卤化物灯等是适当的。此外,也可以利用电子束、α射线、β射线、γ射线、X射线、中子射线等。
进而根据需要在光照射后通过加热而进行固化。此处,加热温度例如为80~200℃。通过设为上述加热温度范围,能够充分固化。加热时间例如为10~100分钟。
进而,本发明的印刷电路板用固化型组合物对于包含以聚亚胺等为主要成分的塑料基板、和设置于其上的导体电路的印刷电路板密合性优异、且能够形成耐焊接热性能、耐化学药品性、耐溶剂性、铅笔硬度、耐化学镀金性、弯曲性等各特性优异的图案固化涂膜。
实施例
以下,示出实施例具体说明本发明,但本发明不仅限定于这些实施例。需要说明的是,以下,在没有特别说明的情况下,“份”是指质量份。
(实施例1~5和比较例1~2)
将表1中示出的成分按照表1中示出的比例(单位:份)配混,用搅拌机预混合,制备固化型组合物。
对于如上所述制作的固化型组合物、及其固化涂膜评价以下的性质。
1.静置1个月后的沉降
在透明的玻璃瓶的容器中适量添加按照表1中的实施例1~5和比较例1~2的配方制备而得到的印刷电路板用固化型组合物并进行密闭后,在25℃下放置1个月后,通过目视确认沉淀物的有无,以如下评价基准进行评价。
○:未确认到沉淀物且均匀。
×:确认到沉淀物。
-:(因未配混填料)未产生沉淀物。
将测定结果示于表2。
2.UV固化后的指触干燥性
使用30μm的涂膜器(ERICHSEN COMPANY制),将1.中使用的静置1个月后的实施例1~5和比较例1~2的各印刷电路板用固化型组合物涂布到聚酰亚胺基材(UPILEX 25S)上,利用高压汞灯(ORC CORPORATION制的HMW-713)以150mJ/cm2进行固化,评价涂膜的表面的指触干燥性。
○:无粘性
×:未固化且液状保持不变
将测定结果示于表2。
3.与聚酰亚胺的密合性
使用30μm的涂膜器(ERICHSEN COMPANY制),将1.中使用的静置1个月后的实施例1~5和比较例1~2的各印刷电路板用固化型组合物涂布到聚酰亚胺基材(UPILEX 25S)上,利用高压汞灯(ORC CORPORATION制的HMW-713)以150mJ/cm2进行固化。然后,在150℃的热风循环式干燥炉中进行60分钟加热处理。对于制作的样品实施划格胶带剥离试验(JISK5600)。
○:无剥离
×:有剥离
将测定结果示于表2。
4.与FR-4的密合性
使用30μm的涂膜器(ERICHSEN COMPANY制),将1.中使用的静置1个月后的实施例1~5和比较例1~2的各印刷电路板用固化型组合物涂布到FR-4基材上,利用高压汞灯(ORCCORPORATION制的HMW-713)以150mJ/cm2进行固化。然后,在150℃的热风循环式干燥炉中进行60分钟加热处理。对于制作的样品实施划格胶带剥离试验(JIS K5600)。
○:无剥离
×:有剥离
将测定结果示于表2。
5.与铜的密合性
使用30μm的涂膜器(ERICHSEN COMPANY制),将1.中使用的静置1个月后的实施例1~5和比较例1~2的各印刷电路板用固化型组合物涂布到铜箔上,利用高压汞灯(ORCCORPORATION制的HMW-713)以150mJ/cm2进行固化。然后,在150℃的热风循环式干燥炉中进行60分钟加热处理。对于制作的样品实施划格胶带剥离试验。
○:无剥离
×:有剥离
将测定结果示于表2。
6.铅笔硬度(表面硬度)评价
使用5.中得到的固化涂膜,对于表面的铅笔硬度根据JIS K 5600-5-4进行测定。
7.耐弯曲性
准备利用厚度25μm的聚亚胺薄膜和由厚度12μm的铜箔形成的梳形的铜布线(布线图案)而构成的柔性覆铜层叠板(长度110mm、宽度60mm、铜布线宽度/铜布线间隔=200μm/200μm)。使用压电型喷墨打印机利用喷墨印刷在该柔性覆铜层叠板的基板上以膜厚为15μm的方式进行涂布。此时,在刚刚印刷后利用喷墨头所附带的高压汞灯进行UV暂时固化。然后通过在150℃下加热1小时而进行固化,得到试验片。对于固化后的试验片,使用MIT(Massachusetts Institute of Technology)试验机在下述条件下以保护膜为内侧重复实施弯曲,求出变得无法导通的循环数。每1次评价中对33个试验片实施试验,计算变得无法导通的平均值。试验条件和判定基准如以下所示。
耐MIT试验条件
载荷:500gf
角度:角对向135°
速度:175次/分钟
前端:R0.38mm圆筒
评价基准
○:50次以上
×:低于50次
8.耐溶剂性
通过目视观察5.中得到的固化涂膜在丙酮中浸渍30分钟后的涂膜状态,按照以下的基准进行评价。
评价基准
○:完全未观察到变化。
×:观察到涂膜的溶胀或剥离。
9.耐化学药品性
通过目视观察5.中得到的固化涂膜在5wt%的硫酸水溶液中浸渍10分钟后的涂膜状态,按照以下的基准进行观察。
评价基准
○:完全未观察到变化。
×:观察到涂膜的溶胀或剥离。
10.耐焊接热性能
按照JIS C-5012的方法,将5.中得到的固化涂膜在260℃的焊料槽中浸渍10秒后,通过目视观察进行利用透明胶带的剥离试验后的涂膜状态,按照以下的基准进行评价。
评价基准
○:涂膜未发生变化。
△:涂膜发生变化。
×:涂膜剥离。
11.耐化学镀金性
使用市售的化学镀镍浴和化学镀金浴,以镍0.5μm、金0.03μm的条件在5.中得到的固化涂膜上进行镀覆,进行固化涂膜表面状态的观察。判定基准如下所述。
评价基准
○:完全未观察到变化。
×:明显产生白化或发雾。
[表1]
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | |
2官能丙烯酸酯单体※1 | 35 | 35 | 35 | 35 | 35 | 35 | 35 |
含羟基丙烯酸酯单体※2 | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
3官能丙烯酸酯单体※3 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
3官能甲基丙烯酸酯单体※4 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
引发剂※5 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
引发剂※6 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
引发剂※7 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
热固化成分※8 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
湿润分散剂※9 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
表面张力调整剂※10 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
二氧化硅※11 | 10 | 20 | 30 | ||||
氢氧化铝※12 | 20 | ||||||
滑石※13 | 20 | ||||||
硫酸钡※14 | 20 | ||||||
∑ | 118.1 | 128.1 | 138.1 | 108.1 | 108.1 | 108.1 | 107.6 |
填料配混量(%) | 8.47 | 15.6 | 21.7 | 18.5 | 18.5 | 0.0 | 0.0 |
表1中的产品名和简写如下所示。
※1:DPGDA、二丙二醇二丙烯酸酯(BASF JAPANLTD.制)
※2:4HBA、丙烯酸4-羟基丁酯(日本化成株式会社制)
※3:Laromer LR8863:EO改性三羟甲基丙烷三丙烯酸酯(BASF JAPAN LTD.制)
※4:EBECRYL 168(DAICEL-ALLNEX LTD.制)
※5:DAROCUR 1173、2-羟基-2-甲基-1-苯基-丙烷-1-酮(BASF JAPAN LTD.制)
※6:2-乙基AQ、2-乙基蒽醌(BASF JAPAN LTD.制)
※7:IRGACURE 819、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(BASF JAPAN LTD.制)
※8:BI7982、封端异氰酸酯(Baxenden Company制)
※9:disperbyk-111、湿润分散剂(BYK Japan KK.制)
※10:BYK-307、有机硅系添加剂(BYK Japan KK.制)
※11:Nipsil SS-70、比重2.2(Tosoh Silica Corporation制)
※12:HIGILITE H43、比重2.5(Showa Denko K.K.制)
※13:LMP-100、比重2.7(FUJI TALC INDUSTRIAL CO.,LTD.制)
※14:B-30、比重4.5(Sakai Chemical Industry Co.,Ltd.制)
[表2]
如表2所示,本发明的实施例1~5的印刷电路板用固化型组合物在静置1个月后沉降、UV固化后的指触干燥性、与聚酰亚胺的密合性、与铜的密合性、铅笔硬度、弯曲性、耐溶剂性、耐化学药品性、耐焊接热性能、耐化学镀金性的各方面均显示出良好的结果。
确认到:特别是在将成分A的配混量相对于组合物100质量份设为5~30质量份的实施例2~5中,铅笔硬度极其优异。
另一方面,在使用比重超过3的填料代替本发明的成分A的比较例1中,静置1个月后确认到沉降。此外,确认到:在比较例1、缺少本发明的成分A的比较例2中,铅笔硬度、耐溶剂性、耐化学药品性、耐焊接热性能和耐化学镀金性均差,无法获得充分的特性。
产业上的可利用性
如以上说明的那样,本发明的印刷电路板用固化型组合物能够形成作为阻焊层所要求的耐焊接热性能、耐化学药品性、铅笔硬度、耐化学镀金性等各特性优异的精细图案。此外,以喷墨方式喷射时,为了能够进行喷射而必须设为低粘度。通常认为低粘度的光固化型组合物的密合性/耐热性等特性低,但本组合物即使为低粘度也能够适用于印刷电路板的基于喷墨方式的阻焊图案形成。因此,可以用于例如UV成形品材料、光造型用材料、3D喷墨用材料等用途。此外,本发明的印刷电路板用光固化型组合物也可用于除阻焊剂以外的保护墨、例如抗蚀刻墨、阻焊墨和抗镀墨、以及标记墨。
Claims (12)
1.一种印刷电路板用固化型组合物,其特征在于,包含:
(A)比重为3以下的填料、
(B)具有羟基的(甲基)丙烯酸酯化合物、和
(C)光聚合引发剂,
且相对于固化型组合物100质量份,(A)比重为3以下的填料的配混量为10~30质量份。
2.根据权利要求1所述的印刷电路板用固化型组合物,其特征在于,所述(A)比重为3以下的填料是无机填料。
3.根据权利要求1所述的印刷电路板用固化型组合物,其特征在于,组合物中所含的颗粒的最大粒径为0.1~5μm以下。
4.根据权利要求1所述的印刷电路板用固化型组合物,其特征在于,还包含2官能(甲基)丙烯酸酯化合物。
5.根据权利要求4所述的印刷电路板用固化型组合物,其特征在于,所述2官能(甲基)丙烯酸酯化合物在25℃下的粘度为5~50mPa·s。
6.根据权利要求1所述的印刷电路板用固化型组合物,其特征在于,还包含热固化成分。
7.根据权利要求1所述的印刷电路板用固化型组合物,其特征在于,在50℃下的粘度为5~50mPa·s。
8.一种固化涂膜,其特征在于,其通过对权利要求1~7中任一项所述的印刷电路板用固化型组合物进行光照射而得到。
9.一种印刷电路板,其特征在于,其具有图案固化涂膜,所述图案固化涂膜通过将权利要求1~7中任一项所述的印刷电路板用固化型组合物印刷在基板上并对其进行光照射而得到。
10.一种印刷电路板,其特征在于,其具有图案固化涂膜,所述图案固化涂膜通过利用喷墨印刷法将权利要求1~7中任一项所述的印刷电路板用固化型组合物印刷在基板上并对其进行光照射而得到。
11.根据权利要求9所述的印刷电路板,其特征在于,所述基板为塑料基板。
12.根据权利要求10所述的印刷电路板,其特征在于,所述基板为塑料基板。
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KR20220108288A (ko) * | 2021-01-26 | 2022-08-03 | 삼성디스플레이 주식회사 | 조성물, 이를 이용하여 폴리머를 제조하는 방법 및 이로부터 제조된 폴리머 |
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