CN117369212A - 感光性树脂组合物和蚀刻方法 - Google Patents
感光性树脂组合物和蚀刻方法 Download PDFInfo
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- CN117369212A CN117369212A CN202311391186.3A CN202311391186A CN117369212A CN 117369212 A CN117369212 A CN 117369212A CN 202311391186 A CN202311391186 A CN 202311391186A CN 117369212 A CN117369212 A CN 117369212A
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- Prior art keywords
- photosensitive resin
- acid
- compound
- resin composition
- etching
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- 238000005530 etching Methods 0.000 title claims abstract description 51
- 239000011342 resin composition Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 16
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- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 28
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 isocyanate compound Chemical class 0.000 claims abstract description 26
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
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- 229920000647 polyepoxide Polymers 0.000 claims description 27
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 10
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000463 material Substances 0.000 description 3
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- 229920003986 novolac Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
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- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
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- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
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- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- G03F7/32—Liquid compositions therefor, e.g. developers
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- G03F7/26—Processing photosensitive materials; Apparatus therefor
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Landscapes
- Physics & Mathematics (AREA)
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Abstract
本发明的课题在于提供对含有高浓度的氢氟酸或氟化铵的蚀刻液的耐性优异的感光性树脂组合物、和利用该感光性树脂组合物的蚀刻方法。感光性树脂组合物,其是在通过含有氢氟酸或氟化铵的蚀刻液进行蚀刻处理的蚀刻方法中使用的感光性树脂组合物,至少包含(A)酸改性环氧丙烯酸酯、(B)光聚合引发剂、(C)封端异氰酸酯化合物和(D)填料;以及,蚀刻方法,在基材的至少单面上形成含有该感光性树脂组合物的感光性树脂层,对感光性树脂层进行曝光后显影,对感光性树脂层进行加热后,通过含有氢氟酸或氟化铵的蚀刻液进行蚀刻处理。
Description
本申请是申请日为2016年3月16日、申请号为“201680017653.8”、发明名称为“感光性树脂组合物和蚀刻方法”的申请的分案申请。
技术领域
本发明涉及对含有氢氟酸或氟化铵的蚀刻液的耐性优异的感光性树脂组合物、和利用该感光性树脂组合物的蚀刻方法。
背景技术
对玻璃基材、硅基板、钛基板等基材进行蚀刻时,有时使用含有氢氟酸或氟化铵的蚀刻液。例如,作为在玻璃基材上形成图案的方法,在玻璃基材上形成感光性树脂组合物,接着隔着期望图案的光掩模实施曝光,使感光性树脂组合物固化。接着,通过显影除去非曝光部(非固化部),在玻璃基材上形成由感光性树脂组合物形成的抗蚀剂图案。接着,对露出的玻璃基材部吹附含有氢氟酸或氟化铵的蚀刻液从而将玻璃溶解,可以形成图案。
作为在这样的利用含有氢氟酸或氟化铵的蚀刻液进行的蚀刻处理中使用的感光性树脂组合物,一直以来使用负型的感光性树脂组合物。例如,作为难以从玻璃基材剥离的光固化性抗蚀剂材料,公开了含有在侧链上具有烯属不饱和双键的丙烯酸树脂、聚硅烷和光敏剂的抗蚀剂材料(例如参照专利文献1)。此外,作为与玻璃基材的密合性优异的感光性树脂组合物,公开了含有特定的含羧基的粘合剂树脂、光聚合性单体和引发剂、以及特定的有机硅烷化合物的感光性树脂组合物(例如参照专利文献2)。此外,作为玻璃蚀刻用的紫外线固化型抗蚀剂组合物,公开了含有不饱和化合物、含酸基的树脂、光引发剂、烷氧基硅烷化合物、无机微粉末的抗蚀剂组合物(例如参照专利文献3)。然而,仅这些成分的情况下,对含有氢氟酸或氟化铵的蚀刻液的耐久性不充分,浸渍于含有氢氟酸或氟化铵的蚀刻液中时,存在抗蚀剂图案从玻璃基材上剥离的问题。
此外,公开了含有碱可溶性树脂、具有烯属不饱和基团的光聚合性化合物、封端异氰酸酯化合物、填料的感光性树脂组合物(例如参照专利文献4)。然而,在这些成分的组合的情况下,对氢氟酸或氟化铵的浓度为15质量%以上那样的高浓度的蚀刻液的耐性不充分,浸渍于高浓度的蚀刻液中时,有时抗蚀剂图案会从玻璃基材上剥离。
现有技术文献
专利文献
专利文献1:日本特开2005-164877号公报
专利文献2:日本特开2007-316247号公报
专利文献3:日本特开2007-128052号公报
专利文献4:日本特开2013-117682号公报。
发明内容
发明要解决的课题
本发明的课题在于,提供对含有高浓度的氢氟酸或氟化铵的蚀刻液的耐性优异的感光性树脂组合物、和利用该感光性树脂组合物的蚀刻方法。
用于解决课题的手段
上述课题可以通过下述手段来解决。
(1)感光性树脂组合物,其是在通过含有氢氟酸或氟化铵的蚀刻液进行蚀刻处理的蚀刻方法中使用的感光性树脂组合物,其特征在于,至少包含(A)酸改性环氧丙烯酸酯、(B)光聚合引发剂、(C)封端异氰酸酯化合物和(D)填料。
(2)根据上述(1)所述的感光性树脂组合物,其中,(A)酸改性环氧丙烯酸酯为至少使环氧树脂(a1)、选自丙烯酸和甲基丙烯酸中的至少1种化合物(a2)、与选自含羧酸化合物和含羧酸化合物的酸酐中的至少1种化合物(a3)反应而成的化合物,环氧树脂(a1)为双酚A型环氧树脂。
(3)根据上述(1)或(2)所述的感光性树脂组合物,其中,(A)酸改性环氧丙烯酸酯为至少使环氧树脂(a1)、选自丙烯酸和甲基丙烯酸中的至少1种化合物(a2)、与选自含羧酸化合物和含羧酸化合物的酸酐中的至少1种化合物(a3)反应而成的化合物,化合物(a3)为选自琥珀酸和琥珀酸酐中的至少1种。
(4)根据上述(1)~(3)中任一项所述的感光性树脂组合物,其中,(C)封端异氰酸酯化合物为通过甲乙酮肟封端的1,6-六亚甲基二异氰酸酯。
(5)根据上述(1)~(4)中任一项所述的感光性树脂组合物,其中,(D)填料为滑石。
(6)蚀刻方法,其特征在于,在基材的至少单面形成含有上述(1)~(5)中任一项所述的感光性树脂组合物的感光性树脂层,对感光性树脂层进行曝光后显影,加热感光性树脂层后,通过含有氢氟酸或氟化铵的蚀刻液进行蚀刻处理。
发明的效果
本发明的感光性树脂组合物由于含有(A)酸改性环氧丙烯酸酯(以下有时表示为“成分(A)”)和(B)光聚合引发剂(以下有时表示为“成分(B)”),因此通过曝光而以图案状形成固化膜。通过在实施碱显影并形成抗蚀剂图案之后进行加热处理,通过由(C)封端异氰酸酯化合物(以下有时表示为“成分(C)”)中的封端异氰酸酯基产生的异氰酸酯基与成分(A)中的羧基和羟基的热交联而形成强固的结合,对含有氢氟酸或氟化铵的蚀刻液的耐性大幅提高。(D)填料(以下有时表示为“成分(D)”)使膜强固,抑制含有氢氟酸或氟化铵的蚀刻液的浸透。
并且,本发明的感光性树脂组合物通过含有成分(A)~(D),对含有氢氟酸或氟化铵的蚀刻液的耐性优异,即使在通过氢氟酸或氟化铵的浓度为15质量%以上那样的高浓度的蚀刻液进行蚀刻时,也能够实现难以从基材上剥离的效果。
具体实施方式
以下,针对本发明进行详细说明。
本发明的感光性树脂组合物至少包含(A)酸改性环氧丙烯酸酯、(B)光聚合引发剂、(C)封端异氰酸酯化合物和(D)填料。
作为成分(A),可以举出至少使环氧树脂(a1)、选自丙烯酸和甲基丙烯酸中的至少1种化合物(a2)、与选自含羧酸化合物和含羧酸化合物的酸酐中的至少1种化合物(a3)反应而成的化合物。该化合物可以通过例如对环氧树脂(a1)施予选自丙烯酸和甲基丙烯酸中的至少1种化合物(a2)、进一步施予化合物(a3)来合成。
作为环氧树脂(a1),可以举出苯酚酚醛清漆型、甲酚酚醛清漆型、双酚A型、双酚F型、三苯酚型、四苯酚型、苯酚-亚二甲苯基型、缩水甘油醚型或者它们的卤化环氧树脂。
作为化合物(a3)的含羧酸化合物,可以使用马来酸(Maleic Acid)、琥珀酸(Succinic Acid)、衣康酸(Itaconic Acid)、邻苯二甲酸(Phthalic Acid)、四氢邻苯二甲酸(Tetrahydrophthalic Acid)、六氢邻苯二甲酸(Hexahydrophthalic Acid)、内亚甲基四氢邻苯二甲酸(Endomethylenetetrahydrophthalic Acid)、甲基内亚甲基四氢邻苯二甲酸(Methylendomethylenetetrahydrophthalic Acid)、氯菌酸(Chlorendic Acid)、甲基四氢邻苯二甲酸(Methyltetrahydrophthalic Acid)、偏苯三甲酸(Trimellitic Acid)、均苯四甲酸(Pyromellitic Acid)、二苯甲酮四甲酸(Benzophenonetetracarboxylic Acid)等。作为含羧酸化合物的酸酐,可以举出上述的含羧酸化合物的酸酐。
成分(A)中,环氧树脂(a1)为双酚A型时、化合物(a3)为选自琥珀酸和琥珀酸酐中的至少1种时,对含有氢氟酸或氟化铵的蚀刻液的耐性进一步提高。
成分(A)的酸值影响碱显影速度、抗蚀剂剥离速度、感光性树脂层的柔软性等。酸值优选为40~120mgKOH/g。该酸值低于40mgKOH/g的情况下,存在碱显影时间变长的倾向,另一方面,如果该酸值大于120mgKOH/g,则有时对作为被处理体的基材的粘贴性变差。
此外,成分(A)的质均分子量优选为3,000~15,000。质均分子量低于3,000的情况下,有时难以将固化前的感光性树脂组合物形成为覆膜状态。另一方面,如果大于15,000,则存在对碱显影液的溶解性恶化的倾向。
作为成分(B),可以举出二苯甲酮、N,N'-四甲基-4,4'-二氨基二苯甲酮(米蚩酮)、N,N'-四乙基-4,4'-二氨基二苯甲酮、4-甲氧基-4'-二甲基氨基二苯甲酮、2-苯甲基-2-二甲基氨基-1-(4-吗啉代苯基)-丁酮-1、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代-丙酮-1等芳族酮;2-乙基蒽醌、菲醌、2-叔丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2-甲基-1,4-萘醌、2,3-二甲基蒽醌等醌类;苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻苯基醚等苯偶姻醚化合物;苯偶姻、甲基苯偶姻、乙基苯偶姻等苯偶姻化合物;安息香双甲醚等偶苯酰衍生物;2-(邻氯苯基)-4,5-二苯基咪唑二聚体、2-(邻氯苯基)-4,5-二(甲氧基苯基)咪唑二聚体、2-(邻氟苯基)-4,5-二苯基咪唑二聚体、2-(邻甲氧基苯基)-4,5-二苯基咪唑二聚体、2-(对甲氧基苯基)-4,5-二苯基咪唑二聚体等2,4,5-三芳基咪唑二聚体;9-苯基吖啶、1,7-双(9,9'-吖啶基)庚烷等吖啶衍生物;N-苯基甘氨酸、N-苯基甘氨酸衍生物、香豆素系化合物等。上述2,4,5-三芳基咪唑二聚体中的2个2,4,5-三芳基咪唑的芳基的取代基可以相同而给出对称的化合物,也可以不同而给出非对称的化合物。此外,也可以如二乙基噻吨酮与二甲基氨基苯甲酸的组合那样组合噻吨酮系化合物与叔胺化合物。这些可以单独使用或者组合使用2种以上。
成分(C)是指异氰酸酯基被封端剂保护的化合物,可以通过使异氰酸酯化合物的异氰酸酯基与封端剂反应而得到。封端异氰酸酯化合物是在常温下稳定、但在某些一定的条件下进行加热时封端剂会裂解从而产生异氰酸酯基的化合物。
作为封端剂,有苯酚、甲酚、对乙基苯酚、对叔丁基苯酚等酚系;乙醇、丁醇、乙二醇、甲基溶纤剂、苯甲基醇等醇系;丙二酸二乙酯、乙酰乙酸乙酯等活性亚甲基系;乙酰苯胺、乙酰胺等酰胺系;其他酰亚胺系;胺系;咪唑系;吡唑系;脲系;氨基甲酸系;亚胺系;甲醛肟、乙醛肟、丙酮肟、甲乙酮肟、二乙酰一肟、环己酮肟等肟系;硫醇系;亚硫酸氢钠、亚硫酸氢钾等亚硫酸盐系;内酰胺系等。从常温保存性、交联性出发,作为封端剂,优选为甲乙酮肟(Methyl Ethyl Ketoxime)。
作为异氰酸酯化合物,可以举出2,6-甲苯二异氰酸酯、2,4-甲苯二异氰酸酯、亚二甲苯基二异氰酸酯、1,6-六亚甲基二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、4,4'-亚甲基双(环己基异氰酸酯)、三甲基己烷亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、萘二异氰酸酯、联甲苯胺二异氰酸酯、赖氨酸二异氰酸酯、甲基环己烷-2,4-二异氰酸酯、甲基环己烷-2,6-二异氰酸酯、1,3-(异氰酸甲酯基)环己烷、二聚酸二异氰酸酯和它们的加合体、缩二脲体、异氰脲酸酯体等预聚物。从感光性树脂组合物层与基材的密合性和显影性的观点出发,作为异氰酸酯化合物,优选为1,6-六亚甲基二异氰酸酯。
作为成分(D),可以举出二氧化硅、滑石、石英、氧化铝、硫酸钡、钛酸钡、粘土、碳酸镁、碳酸钙、氧化铝、氢氧化铝、氧化钛、云母等。它们的通过激光衍射法得到的平均粒径D50优选为0.01μm~20μm、更优选为0.1μm~10μm。在小于0.01μm的粒径情况下,难以粉碎填料,价格变高。此外,在大于20μm的粒径的情况下,容易发生抗蚀剂图案的不稳定。从对含有氢氟酸或氟化铵的蚀刻液的耐性的观点出发,作为成分(D),优选为滑石。
本发明的感光性树脂组合物中,根据需要,可以含有除上述成分(A)~(D)以外的成分。作为这样的成分,可以举出交联性单体、增感剂、热聚合抑制剂、增塑剂、着色剂(染料、颜料)、光发色剂、热发色抑制剂、消泡剂、阻燃剂、稳定剂、密合性赋予剂、流平剂、剥离促进剂、抗氧化剂、香料、热固化剂、拒水剂和拒油剂等,可以分别含有0.01~20质量%左右。这些成分可以单独使用1种或组合使用2种以上。
本发明的感光性树脂组合物根据需要,可以含有甲醇、乙醇、正丙醇、2-丁醇、正己醇等醇类;丙酮、2-丁酮等酮类;乙酸乙酯、乙酸丁酯、乙酸正戊基酯、硫酸甲酯、丙酸乙酯、邻苯二甲酸二甲酯、苯甲酸乙酯等酯类;甲苯、二甲苯、苯、乙基苯等芳族烃类;四氢呋喃、二乙基醚、乙二醇单甲基醚、乙二醇单乙基醚、1-甲氧基-2-丙醇等醚类;N,N-二甲基甲酰胺、二甲基亚砜等溶剂或它们的混合溶剂。
本发明的感光性树脂组合物中,成分(A)的配合量相对于成分(A)、(B)、(C)和(D)的总量优选为35~55质量%、更优选为40~50质量%。成分(A)的配合量小于35质量%的情况下,有时覆膜性变差。如果成分(A)的配合量大于55质量%,则有时对含有氢氟酸或氟化铵的蚀刻液的耐性降低。
成分(B)的配合量相对于成分(A)、(B)、(C)和(D)的总量优选为0.1~10质量%、更优选为0.2~5质量%。成分(B)的配合量小于0.1质量%的情况下,存在光聚合性变得不充分的倾向。另一方面,如果大于10质量%,则曝光时在感光性树脂层的表面处吸收增大,存在感光性树脂层内部的光交联变得不充分的倾向。
成分(C)的配合量相对于成分(A)、(B)、(C)和(D)的总量优选为5~25质量%、更优选为10~20质量%。成分(C)的配合量小于5质量%的情况中,有时加热后的对含有氢氟酸或氟化铵的蚀刻液的耐性变得不充分。另一方面,如果大于25质量%,则存在光固化变得不充分、分辨性变得不充分的倾向。
成分(D)的配合量相对于成分(A)、(B)、(C)和(D)的总量优选为20~45质量%、更优选为25~40质量%。成分(D)的配合量小于20质量%的情况下,将感光性树脂组合物制成干膜时,有时容易发生边缘融合。另一方面,如果大于45质量%,则有时抗蚀剂剥离后(D)成分残留于基材上,形成残渣缺陷。
本发明的蚀刻方法中,首先在基材上涂布感光性树脂组合物并干燥,从而形成含有感光性树脂组合物的感光性树脂层。可以使预先在载体膜上形成有感光性树脂层的感光性膜(干膜)贴合于基材上。接着,实施图案的曝光,使曝光部固化。接着,实施碱显影,除去作为抗蚀剂图案而不需要的部分(非曝光部),形成仅由固化的感光性树脂层形成的抗蚀剂图案。作为碱显影液,可以使用例如碳酸碱金属盐的水溶液。对碱显影后的抗蚀剂图案实施加热(烘烤)处理。接着,用含有氢氟酸或氟化铵的蚀刻液实施蚀刻处理。其后,可以实施抗蚀剂剥离。
作为基材,可以举出玻璃、陶瓷、氧化银、硅、锗、钽、半导体基板、石英、钛等。
抗蚀剂图案的加热(烘烤)处理出于提高感光性树脂层与基材的密合、提高对含有氢氟酸或氟化铵的蚀刻液的耐性等目的而实施。加热温度优选为所使用的封端剂的裂解温度以上。优选为90~250℃、进一步优选为110~200℃。如果小于90℃,则交联反应的进行慢,如果大于250℃,则有可能发生其他成分的分解。加热时间优选为10~90分钟。
作为载体膜,优选为使紫外线透过的透明膜。例如可以使用聚丙烯、聚乙烯、聚酯、聚乙烯醇等。其中,特别是在使用聚对苯二甲酸乙二醇酯膜时,对层压适应性、剥离适应性、光透过性、折射率有利,此外,从廉价、不会变脆、耐溶剂性优异、具备高拉伸强度等优点出发,是非常容易利用的。载体膜的厚度优选为1~100μm。
作为在基材或载体膜上涂布感光性树脂组合物并干燥从而形成感光性树脂层的方法,可以通过辊涂机、逗点涂布机、凹槽辊涂布机、气刀、口模式涂机布、刮条涂布机等方法来进行。感光性树脂层的厚度优选为3~150μm。如果小于3μm,则有时难以涂布在感光性树脂层的基材上、难以从载体膜转印至基材,如果大于150μm,则有时抗蚀剂图案的分辨性变差。
实施例
以下,通过实施例进一步详细地说明本发明,但本发明不限定于该实施例。
(实施例1~13、比较例1~3)
混合表1~表3所示的各成分,得到感光性树脂组合物。应予说明,表1~表3中的各成分配混量的单位表示质量份。将所得涂布液使用线棒涂布于聚对苯二甲酸乙二醇酯(PET)膜(商品名:R310,25μm厚,三菱树脂公司制)上,在100℃下干燥8分钟,除去溶剂成分,在PET膜的单面上得到由实施例1~13、比较例1~3的感光性树脂组合物形成的感光性树脂层(干燥膜厚:60μm)。
[表1]
[表2]
[表3]
表1~表3中,各成分如下所示。
<成分(A)>
(A-1)酸改性环氧丙烯酸酯KAYARAD(注册商标)UXE-3024(商品名,日本化药公司制,浓度65质量%,环氧树脂(a1):复合型)
(A-2)酸改性环氧丙烯酸酯KAYARAD(注册商标)CCR-1235(商品名,日本化药公司制,浓度62质量%,环氧树脂(a1):甲酚酚醛清漆型环氧树脂)
(A-3)酸改性环氧丙烯酸酯KAYARAD(注册商标)ZAR-1035(商品名,日本化药公司制,浓度65质量%,环氧树脂(a1):双酚A型环氧树脂)
(A-4)酸改性环氧丙烯酸酯KAYARAD(注册商标)ZFR-1401H(商品名,日本化药公司制,浓度62质量%,环氧树脂(a1):双酚F型环氧树脂)
(A-5)环氧树脂(a1)为双酚A型环氧树脂(商品名:JER828、三菱化学公司制)、化合物(a3)为琥珀酸、且以环氧树脂(a1):化合物(a3):丙烯酸的摩尔比为1:2:2进行反应而得到的酸改性环氧丙烯酸酯
(A-6)环氧树脂(a1)为双酚A型环氧化合物(商品名:JER828、三菱化学公司制)、化合物(a3)为邻苯二甲酸、且以环氧树脂(a1):化合物(a3):丙烯酸的摩尔比为1:2:2进行反应而得到的酸改性环氧丙烯酸酯
<成分(B)>
(B-1)2-(2'-氯苯基)-4,5-二苯基咪唑二聚体(B-2)4,4'-双(二乙基氨基)二苯甲酮
<成分(C)>
(C-1)スミジュール(SUMIDUR、注册商标)BL3175(商品名,住化コベストロウレタン公司制,基质:1,6-六亚甲基二异氰酸酯,封端剂:甲乙酮肟,浓度75质量%)
(C-2)デスモジュール(DESMODUR、注册商标)BL1100(商品名,住化コベストロウレタン公司制,基质:2,6-甲苯二异氰酸酯,封端剂:ε-己内酰胺)
(C-3)ディスモサーム(DESMOTHERM、注册商标)2170(商品名,住化コベストロウレタン公司制,基质:4,4'-二苯基甲烷二异氰酸酯,封端剂:活性亚甲基,浓度70质量%)
<成分(D)>
(D-1)沉降性硫酸钡#100(堺化学工业公司制)
(D-2)滑石(商品名:LMS-200,富士タルク工业公司制,平均粒径5μm)
(D-3)二氧化硅(商品名:FB-3SDC,电气化学工业公司制)
(D-4)滑石(商品名:SG95,日本タルク公司制,平均粒径2.5μm)
<(E)碱可溶性树脂>
(E-1)成分;甲基丙烯酸甲酯/丙烯酸正丁酯/甲基丙烯酸以质量比58/15/27进行共聚而得到的共聚树脂(质均分子量70000)
<(F)具有烯属不饱和基团的光聚合性化合物>
(F-1)2,2'-双-(4-甲基丙烯酰氧基五乙氧基苯基)丙烷(商品名:BPE-500,新中村化学工业公司制)
(F-2)三羟甲基丙烷三丙烯酸酯(商品名:TMP-A,共荣社化学公司制)
接着,在厚度为2mm的玻璃基材上,将上述所得的含有实施例1~13和比较例1~3的感光性树脂组合物的感光性树脂层在100℃下进行热压接。接着,隔着光掩模(线/间隙=500μm/500μm),通过超高压汞灯进行曝光。曝光后,在室温下放置10分钟,接着,剥掉PET膜,在感光性树脂层的表面上,在30℃以0.1MPa的喷洒压力喷洒1质量%的碳酸钠水溶液,除去非曝光部,进行显影。其后,在20℃下,以0.1MPa的喷洒压力进行水洗,干燥。其后,实施150℃、30分钟的烘烤处理。
接着,将上述制作的形成抗蚀剂图案后的玻璃基材在高浓度的20质量%氢氟酸水溶液(25℃)中浸渍40分钟。实施例1~13的感光性树脂组合物中,未发生感光性树脂层的剥离,能够实现50μm以上深度的蚀刻。另一方面,比较例1~3的感光性树脂组合物中,发生感光性树脂层的剥离,无法实现良好的蚀刻。
将实施例1~4进行对比,成分(A)包含使用双酚A型环氧树脂作为环氧树脂(a1)而得到的酸改性环氧丙烯酸酯(A-3)、成分(C)为被甲乙酮肟封端的1,6-六亚甲基二异氰酸酯(C-1)、且成分(D)为滑石(D-2)的实施例2和4中,即使进一步延长浸渍时间蚀刻至100μm以上的深度,也未发生感光性树脂层的剥离。
将实施例2、4、5和6进行对比,成分(A)包含使用双酚A型环氧树脂作为环氧树脂(a1)而得到的酸改性环氧丙烯酸酯(A-3)的实施例2和4中,即使进一步延长浸渍时间蚀刻至100μm以上的深度,也未发生感光性树脂层的剥离。
将实施例7、8和9进行对比,成分(C)为被甲乙酮肟封端的1,6-六亚甲基二异氰酸酯(C-1)的实施例7中,即使进一步延长浸渍时间蚀刻至100μm以上的深度,也未发生感光性树脂层的剥离。
将实施例7和10进行对比,成分(A)为使用琥珀酸作为化合物(a3)而得到的酸改性环氧丙烯酸酯(A-5)的实施例7中,即使进一步延长浸渍时间蚀刻至100μm以上的深度,也未发生感光性树脂层的剥离。
将实施例7、11、12和13进行对比,成分(D)为滑石(D-4)的实施例7和成分(D)为滑石(D-2)的实施例12中,即使进一步延长浸渍时间蚀刻至100μm以上的深度,也未发生感光性树脂层的剥离。
工业实用性
本发明的感光性树脂组合物能够用作使用含有氢氟酸或氟化铵的蚀刻液进行加工时的抗蚀剂。
Claims (3)
1.蚀刻方法,其特征在于,在基材的至少单面上形成含有感光性树脂组合物的感光性树脂层,对感光性树脂层进行曝光后显影,加热感光性树脂层后,通过含有氢氟酸或氟化铵的蚀刻液进行蚀刻处理,
感光性树脂组合物至少包含(A)酸改性环氧丙烯酸酯、(B)光聚合引发剂、(C)封端异氰酸酯化合物和(D)填料,
(A)酸改性环氧丙烯酸酯为至少使环氧树脂(a1)、选自丙烯酸和甲基丙烯酸中的至少1种化合物(a2)、与选自含羧酸化合物和含羧酸化合物的酸酐中的至少1种化合物(a3)反应而成的化合物,
环氧树脂(a1)为双酚A型环氧树脂,
化合物(a3)为选自琥珀酸和琥珀酸酐中的至少1种,
(C)封端异氰酸酯化合物为封端的1,6-六亚甲基二异氰酸酯,
前述蚀刻液中的氢氟酸或氟化铵的浓度为15质量%以上。
2.根据权利要求1所述的蚀刻方法,其中,(C)封端异氰酸酯化合物为通过甲乙酮肟封端的1,6-六亚甲基二异氰酸酯。
3.根据权利要求1或2所述的蚀刻方法,其中,(D)填料为滑石。
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