TW202307088A - Photosensitive resin composition, resin film, electronic device and method for producing electronic device - Google Patents
Photosensitive resin composition, resin film, electronic device and method for producing electronic device Download PDFInfo
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Abstract
Description
本發明係有關一種感光性樹脂組成物、樹脂膜、電子裝置及電子裝置之製造方法。The invention relates to a photosensitive resin composition, a resin film, an electronic device and a manufacturing method of the electronic device.
在電氣/電子領域中，為了形成絕緣層等硬化膜，有時會使用包含聚醯胺樹脂及/或聚醯亞胺樹脂之感光性樹脂組成物。因此，迄今為止對包含聚醯胺樹脂及/或聚醯亞胺樹脂之感光性樹脂組成物進行了研究。In the electric/electronic field, in order to form a cured film such as an insulating layer, a photosensitive resin composition containing a polyamide resin and/or a polyimide resin may be used. Therefore, studies have been made on photosensitive resin compositions containing polyamide resins and/or polyimide resins.
作為一例，專利文獻1中記載了一種感光性組成物，其包含：至少1種完全醯亞胺化聚醯亞胺聚合物，其具有約20,000道耳頓～約70,000道耳頓範圍的重量平均分子量；至少1種溶解度切換化合物（solubility switching compound）；至少1種光起始劑；及至少1種溶劑，在將環戊酮用作顯影劑之情況下，能夠形成表現出超過約0.15μm/秒的溶解速度之膜。As an example, Patent Document 1 describes a photosensitive composition comprising: at least one fully imidized polyimide polymer having a weight average weight in the range of about 20,000 Daltons to about 70,000 Daltons. Molecular weight; at least 1 solubility switching compound; at least 1 photoinitiator; and at least 1 solvent capable of forming an The film dissolves in seconds.
專利文獻2、3等中亦記載了一種包含聚醯胺樹脂及/或聚醯亞胺樹脂之感光性樹脂組成物。 [先前技術文獻] [專利文獻] Patent Documents 2 and 3 also describe a photosensitive resin composition including polyamide resin and/or polyimide resin. [Prior Art Literature] [Patent Document]
〔專利文獻1〕國際公開第2016/172092號 〔專利文獻2〕國際公開第2007/047384號 〔專利文獻3〕日本特開2018-070829號公報 [Patent Document 1] International Publication No. 2016/172092 [Patent Document 2] International Publication No. 2007/047384 [Patent Document 3] Japanese Patent Laid-Open No. 2018-070829
[發明所欲解決之課題][Problem to be Solved by the Invention]
本發明人進行了研究之結果，明確得知在上述專利文獻1～3中記載的感光性樹脂組成物中，於塗佈了感光性樹脂組成物時的平坦性的方面具有改善的餘地。 又，明確得知在上述專利文獻1～3中記載的感光性樹脂組成物的硬化物中，於耐化學品性及伸長率的方面具有改善的餘地。 As a result of studies conducted by the present inventors, it became clear that in the photosensitive resin compositions described in Patent Documents 1 to 3, there is room for improvement in terms of flatness when the photosensitive resin composition is applied. Moreover, it is clear that there is room for improvement in terms of chemical resistance and elongation in cured products of the photosensitive resin compositions described in Patent Documents 1 to 3 above.
本發明係鑑於該種情況而完成者。本發明的目的在於提供一種塗佈時的平坦性優異，且獲得作為硬化物時的耐化學品性及伸長率的平衡之感光性樹脂組成物。 [解決課題之技術手段] The present invention has been accomplished in view of such circumstances. An object of the present invention is to provide a photosensitive resin composition that is excellent in flatness when applied, and that has a balance between chemical resistance and elongation when it is cured. [Technical means to solve the problem]
本發明人等完成了以下提供之發明，從而解決了上述課題。The inventors of the present invention completed the inventions provided below to solve the above-mentioned problems.
1.一種感光性樹脂組成物，其含有：
耐熱性樹脂（A），其選自在末端或側鏈具有反應性基之聚醯亞胺樹脂及其前驅物、聚苯并㗁唑樹脂及其前驅物或聚醯胺樹脂；
感光劑；以及
交聯劑（B），其在分子內分別具有1個以上含環氧基的基團及（甲基）丙烯醯基。
2.如1.之感光性樹脂組成物，其中，
前述耐熱性樹脂（A）包含閉環聚醯亞胺。
3.如1.或2.之感光性樹脂組成物，其中，
前述耐熱性樹脂（A）包含選自由酸酐基、羧基、胺基、酚性羥基組成之群組中之1種或2種以上作為前述反應性基。
4.如1.至3.中任一項之感光性樹脂組成物，其中，
前述耐熱性樹脂（A）在末端包含酸酐基。
5.如1.至4.中任一項之感光性樹脂組成物，其中，
前述耐熱性樹脂（A）的重量平均分子量為10000以上且100000以下。
6.如1.至5.中任一項之感光性樹脂組成物，其中，
前述耐熱性樹脂（A）包含：含有由下述通式（PI-1）表示之結構單元之聚醯亞胺樹脂，
依本發明，提供一種塗佈時的平坦性優異，且獲得作為硬化物時的耐化學品性及伸長率的平衡之感光性樹脂組成物。According to the present invention, there is provided a photosensitive resin composition which is excellent in flatness at the time of coating, and has a balance of chemical resistance and elongation as a cured product.
在本說明書中，若無特別說明，則數值範圍的說明中的「X～Y」之敘述表示X以上且Y以下。例如，「1～5質量%」表示「1質量%以上且5質量%以下」。 在本說明書中的基（原子團）的敘述中，未記載「取代」或「未取代」之敘述包括「不具有取代基者」和「具有取代基者」這兩者。例如，「烷基」不僅包括不具有取代基之烷基（未取代烷基），而且還包括具有取代基之烷基（取代烷基）。 本說明書中「（甲基）丙烯酸」之敘述表示包括丙烯酸和甲基丙烯酸這兩者之概念。「（甲基）丙烯酸酯」、「（甲基）丙烯醯基」等類似的敘述亦相同。 若無特別說明，則本說明書中的用語「有機基」表示從有機化合物中除去一個以上的氫原子而得之原子團。例如，「1價的有機基」表示從任意的有機化合物中除去一個氫原子而得之原子團。 本說明書中的用語「電子裝置」以包括半導體晶片、半導體元件、印刷配線基板、電路顯示器裝置、資訊通訊終端、發光二極體、物理電池、化學電池等應用電子工學技術之元件、裝置、最終產品等之含義來使用。 In the present specification, unless otherwise specified, the description of "X to Y" in the description of the numerical range means more than X and less than Y. For example, "1 to 5% by mass" means "1 to 5% by mass". In the description of the group (atomic group) in this specification, the description of "substitution" or "unsubstituted" includes both "one without a substituent" and "one with a substituent". For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The description of "(meth)acrylic acid" in this specification shows the concept including both acrylic acid and methacrylic acid. The same applies to similar descriptions such as "(meth)acrylate" and "(meth)acryl". Unless otherwise specified, the term "organic group" in this specification means an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, "monovalent organic group" means an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound. The term "electronic device" in this specification includes semiconductor chips, semiconductor elements, printed wiring boards, circuit display devices, information communication terminals, light-emitting diodes, physical batteries, chemical batteries and other components, devices, The meaning of the final product, etc. to use.
[感光性樹脂組成物] 本實施形態的感光性樹脂組成物含有：耐熱性樹脂（A），其選自在末端或側鏈具有反應性基之聚醯亞胺樹脂及其前驅物、聚苯并㗁唑樹脂及其前驅物或聚醯胺樹脂；感光劑；以及交聯劑（B），其在分子內分別具有1個以上含環氧基的基團及（甲基）丙烯醯基。 [Photosensitive resin composition] The photosensitive resin composition of this embodiment contains: a heat-resistant resin (A) selected from polyimide resins and their precursors, polybenzoxazole resins and their precursors having reactive groups at their terminals or side chains or a polyamide resin; a photosensitizer; and a crosslinking agent (B) each having one or more epoxy group-containing groups and (meth)acryloyl groups in a molecule.
電子裝置中的硬化膜中，要求能夠經受藥液處理之耐化學品性和用於防止龜裂的發生之伸長率，本實施形態的由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性和伸長率良好。 雖詳細內容尚不明確，但認為藉由交聯劑（B）在分子內具有選自含環氧基的基團及（甲基）丙烯醯基之反應性基，使得交聯劑（B）與樹脂組成物中所包含之其他成分反應，或者交聯劑（B）彼此聚合。並且，認為使交聯劑（B）在樹脂組成物的硬化物中緊密地纏結。認為這更進一步提高由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性和伸長率。 In the cured film in electronic devices, chemical resistance that can withstand chemical liquid treatment and elongation to prevent the occurrence of cracks are required. Chemical properties and elongation are good. Although the details are not yet clear, it is considered that the crosslinking agent (B) has a reactive group selected from epoxy group-containing groups and (meth)acryl groups in the molecule, so that the crosslinking agent (B) React with other components contained in the resin composition, or polymerize the crosslinking agent (B) with each other. Furthermore, it is considered that the crosslinking agent (B) is densely entangled in the cured product of the resin composition. This is considered to further improve the chemical resistance and elongation of the resin film formed from the cured product of the photosensitive resin composition.
依據如上所述之內容，本實施形態的感光性樹脂組成物較佳地用於電子裝置中的絕緣層的形成。According to the above-mentioned content, the photosensitive resin composition of this embodiment is preferably used for the formation of the insulating layer in an electronic device.
本實施形態中「含環氧基的基團」係指在結構式中具有作為3員環醚的氧雜環丙烷（環氧乙烷）之取代基。作為其具體例，除了環氧基、環氧丙基、環氧丙醚基以外，可舉出有機基中1個以上的氫原子被環氧基、環氧丙基或環氧丙醚基（從環氧丙醇的OH基除去了氫之基）取代之基，具體而言，可舉出1,2-環氧環己基等。作為有機基，並無特別限定，但例如可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基等烷基；烯丙基、戊烯基、乙烯基等烯基；乙炔基等炔基；亞甲基、亞乙基等亞烷基；苯基、萘基、蒽基等芳基；苄基、苯乙基等芳烷基；甲苯基、二甲苯基等烷芳基（alkaryl）；或金剛烷基、環戊基、環己基、環辛基等環烷基等。The "epoxy group-containing group" in this embodiment refers to a substituent having oxirane (oxirane) which is a 3-membered cyclic ether in the structural formula. As its specific example, in addition to epoxy group, glycidyl group and glycidyl ether group, one or more hydrogen atoms in the organic group can be replaced by epoxy group, glycidyl group or glycidyl ether group ( The group which removed the hydrogen from the OH group of glycidyl alcohol) substitutes, Specifically, 1, 2- epoxy cyclohexyl group etc. are mentioned. The organic group is not particularly limited, but examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neo Alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl and decyl; alkenyl groups such as allyl, pentenyl and vinyl; alkynyl groups such as ethynyl; alkylene groups such as methylene and ethylene Aryl groups such as phenyl, naphthyl, and anthracenyl; Aralkyl groups such as benzyl and phenethyl; Alkaryl groups such as tolyl and xylyl; or adamantyl, cyclopentyl, and cyclohexyl , cyclooctyl and other cycloalkyl groups, etc.
繼續對本實施形態的感光性樹脂組成物所能夠包含之成分、或本實施形態的感光性樹脂組成物的性狀、物性等進行說明。Components that can be contained in the photosensitive resin composition of this embodiment, or the properties, physical properties, and the like of the photosensitive resin composition of this embodiment will be described next.
＜耐熱性樹脂（A）＞ 本實施形態的感光性樹脂組成物含有耐熱性樹脂（A），前述耐熱性樹脂（A）選自在末端或側鏈具有反應性基之聚醯亞胺樹脂及其前驅物、聚苯并㗁唑樹脂及其前驅物或聚醯胺樹脂。 ＜Heat-resistant resin (A)＞ The photosensitive resin composition of this embodiment contains a heat-resistant resin (A), and the heat-resistant resin (A) is selected from polyimide resins having reactive groups at terminals or side chains, precursors thereof, and polybenzoxazoles. Resins and their precursors or polyamide resins.
在此，耐熱性樹脂（A）包含選自由酸酐基、羧基、胺基、酚性羥基構成之群組中之1種或2種以上作為反應性基為較佳，其中，在末端包含酸酐基為進一步較佳。藉由耐熱性樹脂（A）包含上述反應性基，與後述之交聯劑（B）的反應性變得良好，且能夠以高平衡之方式兼具由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性及伸長率。Here, it is preferable that the heat-resistant resin (A) contains one or more reactive groups selected from the group consisting of acid anhydride groups, carboxyl groups, amino groups, and phenolic hydroxyl groups. for further improvement. When the heat-resistant resin (A) contains the above-mentioned reactive group, the reactivity with the crosslinking agent (B) described later becomes good, and it is possible to combine the effects of being formed from the cured product of the photosensitive resin composition in a well-balanced manner. Chemical resistance and elongation of resin film.
本實施形態的感光性樹脂組成物可以僅包含1種耐熱性樹脂（A），亦可以包含2種以上。The photosensitive resin composition of this embodiment may contain only 1 type of heat-resistant resin (A), and may contain 2 or more types.
本實施形態的感光性樹脂組成物中的耐熱性樹脂（A）的含量在感光性樹脂組成物的總固體成分中，1質量%以上為較佳，5質量%以上為更佳，10質量%以上為進一步較佳。藉由使用一定程度多量的耐熱性樹脂（A），容易形成適當厚度的樹脂膜。又，耐熱性樹脂（A）的上限值並無特別限定，但通常為70質量%以下，50質量%以下為較佳。The content of the heat-resistant resin (A) in the photosensitive resin composition of this embodiment is preferably at least 1% by mass, more preferably at least 5% by mass, and 10% by mass in the total solid content of the photosensitive resin composition. The above are further preferred. By using a large amount of heat-resistant resin (A) to some extent, it becomes easy to form a resin film with an appropriate thickness. Also, the upper limit of the heat-resistant resin (A) is not particularly limited, but is usually 70% by mass or less, preferably 50% by mass or less.
本實施形態的感光性樹脂組成物中的耐熱性樹脂（A）的重量平均分子量的下限值係10000以上為較佳，12000以上為更佳，15000以上為進一步較佳。藉由耐熱性樹脂（A）的重量平均分子量為上述下限值以上，除了能夠獲得由感光性樹脂組成物的硬化物形成之樹脂膜的充分的耐化學品性以外，進而還能夠獲得充分的耐熱性。 又，耐熱性樹脂（A）的重量平均分子量的上限值係100000以下為較佳，75000以下為更佳，50000以下為進一步較佳。藉由耐熱性樹脂（A）的重量平均分子量為上述上限值以下，感光性樹脂組成物的流動性得到提高，且塗佈性及塗佈時的平坦性得到提高。 重量平均分子量通常能夠藉由將聚苯乙烯用作標準物質之凝膠滲透層析（GPC）法來求出。 The lower limit of the weight average molecular weight of the heat-resistant resin (A) in the photosensitive resin composition of this embodiment is preferably 10,000 or more, more preferably 12,000 or more, and still more preferably 15,000 or more. When the weight-average molecular weight of the heat-resistant resin (A) is equal to or greater than the above-mentioned lower limit, not only sufficient chemical resistance of the resin film formed of the cured product of the photosensitive resin composition can be obtained, but also sufficient chemical resistance can be obtained. heat resistance. In addition, the upper limit of the weight average molecular weight of the heat-resistant resin (A) is preferably 100,000 or less, more preferably 75,000 or less, and still more preferably 50,000 or less. When the weight average molecular weight of a heat-resistant resin (A) is below the said upper limit, the fluidity|liquidity of a photosensitive resin composition improves, and the flatness at the time of applicability and coating improves. The weight average molecular weight can usually be determined by the gel permeation chromatography (GPC) method using polystyrene as a standard substance.
（聚醯亞胺樹脂） 從能夠抑制由加熱引起之收縮之觀點考慮，本實施形態的感光性樹脂組成物包含聚醯亞胺樹脂作為耐熱性樹脂（A）為較佳，包含閉環聚醯亞胺作為耐熱性樹脂（A）為進一步較佳。又，作為包含閉環聚醯亞胺作為耐熱性樹脂（A）時之優點，與後述之交聯劑（B）的反應性變得良好，且能夠以高平衡之方式兼具由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性及伸長率。 順帶一提，「聚醯亞胺樹脂」通常具有醯亞胺環結構。於此方面，「閉環聚醯亞胺」的表現本來可以簡單地表現為「聚醯亞胺」。但是，本說明書中，尤其為了與聚醯亞胺樹脂前驅物（未形成醯亞胺環）進行區分，有時特意將聚醯亞胺表現為「閉環聚醯亞胺」。本實施形態的感光性樹脂組成物在進行硬化前的階段包含閉環聚醯亞胺為較佳。閉環聚醯亞胺溶解於溶劑為較佳。 (polyimide resin) From the viewpoint of being able to suppress shrinkage caused by heating, it is preferable that the photosensitive resin composition of this embodiment contains polyimide resin as the heat-resistant resin (A), and contains ring-closed polyimide as the heat-resistant resin (A) ) is further preferred. In addition, as an advantage of including ring-closed polyimide as the heat-resistant resin (A), the reactivity with the crosslinking agent (B) described later becomes good, and it is possible to combine the composition of the photosensitive resin with a high balance. The chemical resistance and elongation of the resin film formed by the cured product. Incidentally, "polyimide resin" generally has an imide ring structure. In this respect, the performance of "ring-closed polyimide" could have been simply expressed as "polyimide". However, in this specification, especially in order to distinguish it from a polyimide resin precursor (which does not form an imide ring), polyimide may be intentionally expressed as "ring-closed polyimide". It is preferable that the photosensitive resin composition of this embodiment contains ring-closed polyimide in the stage before hardening. The ring-closed polyimide is preferably dissolved in a solvent.
在使用聚醯亞胺樹脂之情況下，可以僅使用1種聚醯亞胺樹脂，亦可以併用2種以上的聚醯亞胺樹脂。When using a polyimide resin, only 1 type of polyimide resin may be used, and 2 or more types of polyimide resins may be used together.
將聚醯亞胺樹脂中所含之醯亞胺環基的莫耳數設為IM，將聚醯亞胺樹脂中所含之醯胺基的莫耳數設為AM時，由{IM/（IM+AM）}×100（%）表示之醯亞胺環化率係90%以上為較佳，95%以上為更佳，98%以上為進一步較佳。簡言之，聚醯亞胺樹脂係沒有醯胺結構或醯胺結構少且醯亞胺結構多的樹脂為較佳。藉由使用該種聚醯亞胺樹脂，不會發生由閉環反應引起之脫水，因此能夠進一步抑制由加熱引起之收縮（硬化收縮）。藉此，能夠謀求電子裝置的可靠性的進一步提高和由感光性樹脂組成物的硬化物形成之樹脂膜的平坦性的進一步提高等。 作為一例，醯亞胺環化率能夠從NMR譜中的與醯胺基對應的峰的面積或與醯亞胺環基對應的峰的面積等得知。作為另一例，醯亞胺環化率能夠從紅外吸收光譜中的與醯胺基對應的峰的面積或與醯亞胺環基對應的峰的面積等得知。 When the molar number of the imide ring group contained in the polyimide resin is set as IM, and the molar number of the amide group contained in the polyimide resin is set as AM, by {IM/( IM+AM)}×100(%) means that the imide cyclization rate is preferably 90% or more, more preferably 95% or more, and more preferably 98% or more. In short, the polyimide resin has no amide structure or a resin with less amide structure and more amide structure is preferable. By using such a polyimide resin, dehydration due to a ring-closing reaction does not occur, so shrinkage due to heating (hardening shrinkage) can be further suppressed. Thereby, further improvement of the reliability of an electronic device, further improvement of the flatness of the resin film formed from the hardened|cured material of a photosensitive resin composition, etc. can be aimed at. As an example, the imide cyclization rate can be known from the area of a peak corresponding to an amide group or the area of a peak corresponding to an imide ring group in an NMR spectrum. As another example, the imide cyclization rate can be known from the area of the peak corresponding to the amide group or the area of the peak corresponding to the imide ring group in the infrared absorption spectrum.
聚醯亞胺樹脂包含由下述通式（PI-1）表示之結構單元為較佳。The polyimide resin preferably includes a structural unit represented by the following general formula (PI-1).
通式（PI-1）中， X為2價的有機基， Y為4價的有機基， X及Y中的至少一個為含氟原子之基。 In the general formula (PI-1), X is a divalent organic group, Y is a tetravalent organic group, At least one of X and Y is a group containing a fluorine atom.
X的2價的有機基及/或Y的4價的有機基包含芳香環結構為較佳，包含苯環結構為更佳。藉此，耐熱性趨於進一步提高。 從有機溶劑溶解性的觀點考慮，X及Y這兩個係含氟原子之基為較佳。 X的2價的有機基及/或Y的4價的有機基具有2～6個苯環經由單鍵或2價的連結基鍵結而成之結構為較佳。作為此處的2價的連結基，能夠舉出伸烷基、氟化伸烷基、醚基等。伸烷基及氟化伸烷基可以為直鏈狀，亦可以為支鏈狀。 X的2價的有機基的碳數例如為6～30。 Y的4價的有機基的碳數例如為6～20。 通式（PI-1）中的2個醯亞胺環分別為5員環為較佳。 The divalent organic group of X and/or the tetravalent organic group of Y preferably include an aromatic ring structure, more preferably include a benzene ring structure. Thereby, heat resistance tends to be further improved. From the viewpoint of solubility in organic solvents, X and Y are preferably groups containing fluorine atoms. The divalent organic group of X and/or the tetravalent organic group of Y preferably have a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. The alkylene group and the fluorinated alkylene group may be linear or branched. The carbon number of the divalent organic group of X is 6-30, for example. The carbon number of the tetravalent organic group of Y is 6-20, for example. The two imide rings in the general formula (PI-1) are preferably 5-membered rings.
聚醯亞胺樹脂包含由下述通式（PI-2）表示之結構單元為更佳。The polyimide resin preferably includes a structural unit represented by the following general formula (PI-2).
通式（PI-2）中， X與通式（PI-1）中的X的含義相同， Y’表示單鍵或伸烷基。 In the general formula (PI-2), X has the same meaning as X in the general formula (PI-1), Y' represents a single bond or an alkylene group.
關於X的具體的態樣，與通式（PI-1）中說明者相同。 Y’的伸烷基可以為直鏈狀，亦可以為支鏈狀。Y’的伸烷基的氫原子的一部分或全部被氟原子取代為較佳。Y’的伸烷基的碳數例如為1～6，1～4為較佳，1～3為進一步較佳。 The specific aspects of X are the same as those described in the general formula (PI-1). The alkylene group of Y' may be linear or branched. Part or all of the hydrogen atoms in the alkylene group of Y' are preferably substituted by fluorine atoms. The carbon number of the alkylene group of Y' is, for example, 1-6, preferably 1-4, and more preferably 1-3.
聚醯亞胺樹脂能夠藉由使聚醯亞胺樹脂前驅物進行閉環反應而獲得。作為聚醯亞胺樹脂前驅物，能夠使用聚醯胺樹脂。The polyimide resin can be obtained by subjecting a polyimide resin precursor to a ring-closing reaction. As the polyimide resin precursor, a polyamide resin can be used.
（聚苯并㗁唑樹脂） 聚苯并㗁唑樹脂包含由下述式（PB01）表示之結構單元為較佳。 (polybenzoxazole resin) The polybenzoxazole resin preferably includes a structural unit represented by the following formula (PB01).
在使用聚苯并㗁唑樹脂之情況下，可以僅使用1種聚苯并㗁唑樹脂，亦可以併用2種以上的聚苯并㗁唑樹脂。When using a polybenzoxazole resin, only 1 type of polybenzoxazole resin may be used, and 2 or more types of polybenzoxazole resin may be used together.
聚苯并㗁唑樹脂能夠藉由使聚苯并㗁唑樹脂前驅物進行閉環反應而獲得。作為聚苯并㗁唑樹脂前驅物，能夠使用聚醯胺樹脂。The polybenzoxazole resin can be obtained by subjecting a polybenzoxazole resin precursor to a ring-closing reaction. A polyamide resin can be used as the polybenzoxazole resin precursor.
（聚醯胺樹脂） 聚醯胺樹脂包含由下述通式（PA-1）表示之結構單元為較佳。 (polyamide resin) The polyamide resin preferably includes a structural unit represented by the following general formula (PA-1).
在使用聚醯胺樹脂之情況下，可以僅使用1種聚醯胺樹脂，亦可以併用2種以上的聚醯胺樹脂。When using a polyamide resin, only 1 type of polyamide resin may be used, and 2 or more types of polyamide resins may be used together.
通式（PA-1）中，X為2價的有機基，Y為4價的有機基，X及Y中的至少一個係含氟原子之基為較佳。從有機溶劑溶解性的觀點考慮，在通式（PA-1）中，X及Y這兩個係含氟原子之基為較佳。In the general formula (PA-1), X is a divalent organic group, Y is a tetravalent organic group, and at least one of X and Y is preferably a group containing a fluorine atom. From the viewpoint of solubility in organic solvents, in the general formula (PA-1), X and Y are preferably groups containing fluorine atoms.
在通式（PA-1）中，X的2價的有機基及/或Y的4價的有機基包含芳香環結構為較佳，包含苯環結構為更佳。藉此，耐熱性趨於進一步提高。此處的苯環可以被氟原子、氟化烷基（三氟甲基為較佳）等含氟原子之基取代，亦可以被其他基取代。 通式（PA-1）中的X的2價的有機基及/或Y的4價的有機基具有2～6個苯環經由單鍵或2價的連結基鍵結而成之結構為較佳。作為此處的2價的連結基，能夠舉出伸烷基、氟化伸烷基、醚基等。伸烷基及氟化伸烷基可以為直鏈狀，亦可以為支鏈狀。 在通式（PA-1）中，X的2價的有機基的碳數例如為6～30。 在通式（PA-1）中，Y的4價的有機基的碳數例如為6～20。 In the general formula (PA-1), the divalent organic group of X and/or the tetravalent organic group of Y preferably include an aromatic ring structure, more preferably include a benzene ring structure. Thereby, heat resistance tends to be further improved. The benzene ring here may be substituted by fluorine atoms, fluorinated alkyl groups (preferably trifluoromethyl) and other groups containing fluorine atoms, or may be substituted by other groups. In the general formula (PA-1), the divalent organic group of X and/or the tetravalent organic group of Y have a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. good. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. The alkylene group and the fluorinated alkylene group may be linear or branched. In general formula (PA-1), the carbon number of the divalent organic group of X is 6-30, for example. In general formula (PA-1), the carbon number of the tetravalent organic group of Y is 6-20, for example.
聚醯胺樹脂包含由下述通式（PA-2）表示之結構單元為更佳。The polyamide resin preferably includes a structural unit represented by the following general formula (PA-2).
通式（PA-2）中， X與通式（PA-1）中的X的含義相同， Y’表示單鍵或伸烷基。 In general formula (PA-2), X has the same meaning as X in the general formula (PA-1), Y' represents a single bond or an alkylene group.
如前所述，聚醯胺樹脂亦能夠用作聚醯亞胺樹脂前驅物或聚苯并㗁唑樹脂前驅物。As mentioned above, the polyamide resin can also be used as a polyimide resin precursor or a polybenzoxazole resin precursor.
耐熱性樹脂（A）可以具有酚性羥基等鹼可溶性基，亦可以不具有。 在使用鹼性顯影液之微影術製程中適用本實施形態的感光性樹脂組成物之情況下，耐熱性樹脂（A）具有鹼可溶性基為較佳。 另一方面，在使用以有機溶劑為主成分的顯影液（成分的95質量%以上為有機溶劑的顯影液）之微影術製程中適用本實施形態的感光性樹脂組成物之情況下，耐熱性樹脂（A）實質上可以不具有鹼可溶性基。具體而言，耐熱性樹脂（A）的總結構單元中，具有酚性羥基等鹼可溶性基之結構單元的比率係0～10mol%為較佳，0～5mol%為更佳，0～3mol%為進一步較佳。 The heat-resistant resin (A) may or may not have alkali-soluble groups such as phenolic hydroxyl groups. When applying the photosensitive resin composition of this embodiment to the lithography process using an alkaline developer, it is preferable that the heat-resistant resin (A) has an alkali-soluble group. On the other hand, when the photosensitive resin composition of this embodiment is applied to a lithography process using a developer mainly composed of an organic solvent (a developer whose composition is 95% by mass or more of an organic solvent), the heat-resistant The permanent resin (A) does not have to have an alkali-soluble group substantially. Specifically, in the total structural units of the heat-resistant resin (A), the ratio of structural units having alkali-soluble groups such as phenolic hydroxyl groups is preferably 0-10 mol%, more preferably 0-5 mol%, and 0-3 mol% for further improvement.
＜感光劑＞ 本實施形態的感光性樹脂組成物含有感光劑。 感光劑只要為藉由光產生活性物種而能夠使感光性樹脂組成物硬化者，則並無特別限定。 ＜Sensitizer＞ The photosensitive resin composition of this embodiment contains a photosensitizer. The photosensitive agent is not particularly limited as long as it can harden the photosensitive resin composition by generating active species with light.
感光劑包含光自由基產生劑為較佳。光自由基產生劑尤其在使多官能（甲基）丙烯酸酯化合物聚合時有效。It is preferable that the photosensitizer contains a photoradical generator. A photoradical generator is effective especially when polymerizing a polyfunctional (meth)acrylate compound.
能夠使用之光自由基產生劑並無特別限定，能夠適當使用公知者。
例如能夠舉出：2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1-羥基環己基苯酮、2-羥基-2-甲基-1-苯丙-1-酮、1-〔4-（2-羥基乙氧基）苯基〕-2-羥基-2-甲基-1-丙-1-酮、2-羥基-1-{4-〔4-（2-羥基-2-甲基丙醯基）苄基〕苯基}-2-甲基丙-1-酮、2-甲基-1-（4-甲基苯硫基）-2-
在使用感光劑之情況下，可以僅使用1種感光劑，亦可以使用2種以上的感光劑。 感光劑的含量相對於耐熱性樹脂（A）100質量份，例如為1～30質量份，5～20質量份為較佳。 In the case of using a photosensitizer, only one kind of photosensitizer may be used, or two or more kinds of photosensitizers may be used. Content of a photosensitive agent is 1-30 mass parts with respect to 100 mass parts of heat-resistant resin (A), for example, Preferably it is 5-20 mass parts.
＜交聯劑（B）＞ 本實施形態的感光性樹脂組成物含有在分子內分別具有1個以上含環氧基的基團及（甲基）丙烯醯基之交聯劑（B）。 ＜Crosslinking agent (B)＞ The photosensitive resin composition of the present embodiment contains a crosslinking agent (B) each having one or more epoxy group-containing groups and (meth)acryloyl groups in the molecule.
認為藉由交聯劑（B）在分子中分別具有1個以上含環氧基的基團及（甲基）丙烯醯基，使得交聯劑（B）與樹脂組成物中所包含之其他成分反應，或者交聯劑（B）彼此聚合。並且，認為使交聯劑（B）在樹脂組成物的硬化物中緊密地纏結。認為這提高由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性及伸長率。It is considered that the crosslinking agent (B) has one or more epoxy group-containing groups and (meth)acryl groups in the molecule, so that the crosslinking agent (B) and other components contained in the resin composition react, or the crosslinkers (B) polymerize with each other. Furthermore, it is considered that the crosslinking agent (B) is densely entangled in the cured product of the resin composition. This is considered to improve the chemical resistance and elongation of the resin film formed from the cured product of the photosensitive resin composition.
交聯劑（B）在分子內的一個末端和另一個末端分別各具有1個含環氧基的基團和（甲基）丙烯醯基為較佳。藉由具備該結構，減少未反應的官能基，作為結果，由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性得到提高。The crosslinking agent (B) preferably has an epoxy group-containing group and a (meth)acryl group at one terminal and the other terminal in the molecule, respectively. By having this structure, unreacted functional groups are reduced, and as a result, the chemical resistance of the resin film formed of the cured product of the photosensitive resin composition is improved.
交聯劑（B）包含由通式（1）表示之化合物為較佳。The crosslinking agent (B) preferably contains a compound represented by the general formula (1).
通式（1）中， X 1表示（甲基）丙烯醯基。X 2作為含環氧基的基團表示環氧丙基、環氧丙醚基、環氧基或3,4-環氧環己基。又，n表示1～10的整數。 In the general formula (1), X 1 represents a (meth)acryl group. X2 as an epoxy group-containing group represents a glycidyl group, a glycidyl ether group, an epoxy group or a 3,4-epoxycyclohexyl group. Moreover, n represents the integer of 1-10.
藉由X 2選自上述官能基，從而交聯劑（B）與樹脂組成物中所包含之其他成分或交聯劑（B）彼此的反應性變得良好，且由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性得到提高，因此較佳。 When X2 is selected from the above-mentioned functional groups, the reactivity between the crosslinking agent (B) and other components contained in the resin composition or the crosslinking agent (B) becomes good, and the photosensitive resin composition Since the chemical resistance of the resin film formed of a hardened|cured material improves, it is preferable.
又，藉由n在1～10的範圍內，由感光性樹脂組成物的硬化物形成之樹脂膜的伸長率變得更適合，因此較佳。Moreover, when n exists in the range of 1-10, since the elongation rate of the resin film formed from the hardened|cured material of a photosensitive resin composition will become more suitable, it is preferable.
交聯劑（B）中，作為滿足上述通式（1）之化合物，包含選自以下化學式（2）～（4）中的任一化合物之1種或2種以上為較佳。藉由包含選自以下化學式（2）～（4）中的任一化合物之1種或2種以上，能夠以高平衡之方式兼具由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性及伸長率。The crosslinking agent (B) preferably contains one or two or more compounds selected from any one of the following chemical formulas (2) to (4) as a compound satisfying the above general formula (1). By including one or more compounds selected from any one of the following chemical formulas (2) to (4), the resistance of the resin film formed of the cured photosensitive resin composition can be combined in a well-balanced manner. Chemical properties and elongation.
交聯劑（B）的含量相對於耐熱性樹脂（A）100質量份，例如為0.1質量份以上，0.5質量份以上為較佳，1質量份以上為更佳。藉由交聯劑（B）的含量為0.1質量份以上，感光性樹脂組成物的硬化物能夠具有高耐化學品性。 又，交聯劑（B）的含量相對於耐熱性樹脂（A）100質量份，例如為30質量份以下，20質量份以下為較佳，10質量份以下為更佳。藉由交聯劑（B）的含量為30質量份以下，除了感光性樹脂組成物中的耐熱性樹脂（A）的比率得以維持，且感光性樹脂組成物的硬化物的伸長率變得良好以外，充分地提高感光性樹脂組成物與基材的密接性。 The content of the crosslinking agent (B) is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the heat-resistant resin (A). When the content of the crosslinking agent (B) is 0.1 parts by mass or more, the cured product of the photosensitive resin composition can have high chemical resistance. Moreover, content of a crosslinking agent (B) is 30 mass parts or less with respect to 100 mass parts of heat-resistant resins (A), for example, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less. When the content of the crosslinking agent (B) is 30 parts by mass or less, the ratio of the heat-resistant resin (A) in the photosensitive resin composition is maintained, and the elongation of the cured product of the photosensitive resin composition becomes favorable In addition, the adhesiveness between the photosensitive resin composition and the substrate is sufficiently improved.
本實施形態的感光性樹脂組成物可以僅包含1種交聯劑（B），亦可以包含2種以上。The photosensitive resin composition of this embodiment may contain only 1 type of crosslinking agent (B), and may contain 2 or more types.
＜其他添加劑＞ 本實施形態的感光性樹脂組成物能夠任意含有除了上述之耐熱性樹脂（A）、感光劑及交聯劑（B）以外的添加劑。 ＜Other additives＞ The photosensitive resin composition of the present embodiment can optionally contain additives other than the above-mentioned heat-resistant resin (A), photosensitizer, and crosslinking agent (B).
（多官能（甲基）丙烯酸化合物） 本實施形態的感光性樹脂組成物包含官能基數為3官能以上的多官能（甲基）丙烯酸化合物為較佳。 3官能以上的多官能（甲基）丙烯酸化合物係指（甲基）丙烯醯基的個數為3以上的樹脂。認為多官能（甲基）丙烯酸化合物藉由與交聯劑（B）的丙烯醯基鍵結，在與耐熱性樹脂（A）及交聯劑（B）之間形成網狀結構。推測藉由形成該種複雜地纏結之結構，樹脂膜的耐化學品性變得良好。 (polyfunctional (meth)acrylic compound) It is preferable that the photosensitive resin composition of this embodiment contains the polyfunctional (meth)acrylic compound whose functional group number is 3 or more functional. The trifunctional or more polyfunctional (meth)acrylic compound refers to a resin having three or more (meth)acryloyl groups. It is considered that the multifunctional (meth)acrylic compound forms a network structure with the heat-resistant resin (A) and the crosslinking agent (B) by bonding with the acryl group of the crosslinking agent (B). It is presumed that the chemical resistance of the resin film becomes favorable by forming such a complicated entangled structure.
此時，多官能（甲基）丙烯酸化合物的官能基數係4官能以上為更佳，5官能以上為進一步較佳。藉由多官能（甲基）丙烯酸化合物為上述官能基數以上，由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性變得更適合。 又，多官能（甲基）丙烯酸化合物的官能基數係15官能以下為較佳，13官能以下為更佳，11官能以下為進一步較佳。藉由多官能（甲基）丙烯酸化合物為上述官能基數以下，由感光性樹脂組成物的硬化物形成之樹脂膜的伸長率變得良好。 In this case, the number of functional groups of the polyfunctional (meth)acrylic compound is more preferably tetrafunctional or higher, and more preferably pentafunctional or higher. When the polyfunctional (meth)acrylic compound has more than the said number of functional groups, the chemical resistance of the resin film formed from the hardened|cured material of a photosensitive resin composition becomes more suitable. Also, the number of functional groups of the polyfunctional (meth)acrylic compound is preferably 15 or less, more preferably 13 or less, and still more preferably 11 or less. When the polyfunctional (meth)acrylic compound has the said number of functional groups or less, the elongation rate of the resin film formed from the hardened|cured material of a photosensitive resin composition will become favorable.
作為多官能（甲基）丙烯酸化合物，作為一例，能夠使用由以下通式（5）表示之多官能（甲基）丙烯酸化合物。在以下通式（5）中，R’為氫原子或甲基，n為0～3，R為氫原子或（甲基）丙烯醯基。As a polyfunctional (meth)acrylic compound, the polyfunctional (meth)acrylic compound represented by following general formula (5) can be used as an example. In the following general formula (5), R' is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group.
作為多官能（甲基）丙烯酸化合物的具體例，能夠舉出乙二醇二（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、二三羥甲基丙烷四（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯等多元醇聚丙烯酸酯類、雙酚A二環氧丙基醚的二（甲基）丙烯酸酯、己二醇二環氧丙基醚的二（甲基）丙烯酸酯等環氧丙烯酸酯類、藉由聚異氰酸酯與（甲基）丙烯酸羥乙酯等含羥基的（甲基）丙烯酸酯的反應而得之胺酯（甲基）丙烯酸酯等。當然，多官能（甲基）丙烯酸化合物並不僅限定於該些。Specific examples of polyfunctional (meth)acrylic compounds include ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetrakis(meth)acrylate, ) acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate ) Polyol polyacrylates such as acrylate, di(meth)acrylate of bisphenol A diglycidyl ether, di(meth)acrylate of hexanediol diglycidyl ether, etc. Epoxy acrylic acid Esters, amine (meth)acrylates obtained by reacting polyisocyanate with hydroxyl-containing (meth)acrylates such as hydroxyethyl (meth)acrylate. Of course, the polyfunctional (meth)acrylic compound is not limited to these.
又，作為多官能（甲基）丙烯酸化合物的市售品，能夠舉出ARONIX M-400、ARONIX M-460、ARONIX M-402、ARONIX M-510、ARONIX M-520（TOAGOSEI CO., LTD.製）、KAYARAD T-1420、KAYARAD DPHA、KAYARAD DPCA20、KAYARAD DPCA30、KAYARAD DPCA60、KAYARAD DPCA120（Nippon Kayaku Co.,Ltd.製）、Viscoat#230、Viscoat#300、Viscoat#802、Viscoat#2500、Viscoat#1000、Viscoat#1080（OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製）、NK ESTETR A-BPE-10、NK ESTETR A-GLY-9E、NK ESTETR A-9550、NK ESTETR A-DPH（SHIN-NAKAMURA CHEMICAL CO, LTD.製）等。當然，多官能（甲基）丙烯酸化合物的市售品並不僅限定於該些。In addition, commercially available polyfunctional (meth)acrylic compounds include ARONIX M-400, ARONIX M-460, ARONIX M-402, ARONIX M-510, ARONIX M-520 (TOAGOSEI CO., LTD. ), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat#230, Viscoat#300, Viscoat#802, Viscoat#2500, Viscoat #1000, Viscoat#1080 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), NK ESTETRA A-BPE-10, NK ESTETRA A-GLY-9E, NK ESTETRA A-9550, NK ESTETRA A-DPH (SHIN-NAKAMURA CHEMICAL CO, LTD.), etc. Of course, commercially available polyfunctional (meth)acrylic compounds are not limited to these.
在使用多官能（甲基）丙烯酸酯化合物之情況下，相對於聚醯亞胺樹脂等耐熱性樹脂（A）100質量份的多官能（甲基）丙烯酸酯化合物的量係30～130質量份為較佳，50～130質量份為更佳，85～125質量份為進一步較佳。When using a polyfunctional (meth)acrylate compound, the amount of the polyfunctional (meth)acrylate compound is 30 to 130 parts by mass relative to 100 parts by mass of a heat-resistant resin (A) such as a polyimide resin More preferably, it is 50-130 mass parts, and it is still more preferable that it is 85-125 mass parts.
如前所述，認為在本實施形態的感光性樹脂組成物中，藉由硬化形成聚醯胺樹脂及/或聚醯亞胺樹脂與多官能（甲基）丙烯酸酯的「纏結結構」，並且認為藉由適當地調整相對於聚醯胺樹脂及/或聚醯亞胺樹脂的多官能（甲基）丙烯酸酯化合物的使用量，聚醯胺樹脂及/或聚醯亞胺樹脂與多官能（甲基）丙烯酸酯化合物適當地纏結，又，不參與纏結之多餘的成分變少。作為結果，由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性及伸長率變得更適合。As mentioned above, it is considered that in the photosensitive resin composition of this embodiment, polyamide resin and/or "entanglement structure" of polyimide resin and polyfunctional (meth)acrylate is formed by curing, And it is considered that by appropriately adjusting the usage amount of the multifunctional (meth)acrylate compound relative to the polyamide resin and/or polyimide resin, the polyamide resin and/or polyimide resin and the multifunctional The (meth)acrylate compound is properly entangled, and the unnecessary components that do not participate in the entanglement are reduced. As a result, the chemical resistance and elongation of the resin film formed from the cured product of the photosensitive resin composition become more suitable.
在感光性樹脂組成物包含多官能（甲基）丙烯酸化合物之情況下，可以僅包含1種多官能（甲基）丙烯酸酯化合物，亦可以包含2種以上的多官能（甲基）丙烯酸酯化合物。在後者之情況下，併用官能基數不同的多官能（甲基）丙烯酸酯化合物為較佳。認為藉由併用官能基數不同的多官能（甲基）丙烯酸酯化合物，能夠形成更複雜的「纏結結構」，且由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性及伸長率變得更適合。 順帶一提，市售的多官能（甲基）丙烯酸酯化合物中，亦存在官能基數不同的多官能（甲基）丙烯酸酯化合物的混合物。 When the photosensitive resin composition contains a polyfunctional (meth)acrylic compound, it may contain only one type of polyfunctional (meth)acrylate compound, or may contain two or more types of polyfunctional (meth)acrylate compounds . In the latter case, it is preferable to use polyfunctional (meth)acrylate compounds having different numbers of functional groups in combination. It is believed that by using multifunctional (meth)acrylate compounds with different functional groups together, a more complex "entangled structure" can be formed, and the chemical resistance and elongation of the resin film formed from the cured product of the photosensitive resin composition rate becomes more appropriate. Incidentally, among commercially available polyfunctional (meth)acrylate compounds, there are also mixtures of polyfunctional (meth)acrylate compounds having different numbers of functional groups.
又，在併用聚醯亞胺樹脂與多官能（甲基）丙烯酸化合物之情況下，作為硬化機制，能夠採用多官能（甲基）丙烯酸化合物的聚合反應。該聚合反應在原理上不伴隨脫水，因此於由加熱引起之收縮小的方面，併用聚醯亞胺樹脂與多官能（甲基）丙烯酸化合物亦有利。Moreover, when using a polyimide resin and a polyfunctional (meth)acrylic compound together, as a hardening mechanism, the polymerization reaction of a polyfunctional (meth)acrylic compound can be used. In principle, this polymerization reaction is not accompanied by dehydration, so it is also advantageous to use a polyimide resin and a polyfunctional (meth)acrylic compound in combination because the shrinkage caused by heating is small.
（熱自由基起始劑） 本實施形態的感光性樹脂組成物可以包含熱自由基起始劑。 在感光性樹脂組成物含有多官能（甲基）丙烯酸化合物作為添加劑之情況下，藉由使用熱自由基起始劑，促進多官能（甲基）丙烯酸化合物的聚合反應。作為結果，能夠提高由感光性樹脂組成物的硬化物形成之樹脂膜的耐化學品性（對有機溶劑等的耐性）。 (Thermal Radical Initiator) The photosensitive resin composition of this embodiment may contain a thermal radical initiator. In the case where the photosensitive resin composition contains a polyfunctional (meth)acrylic compound as an additive, the polymerization reaction of the polyfunctional (meth)acrylic compound is accelerated by using a thermal radical initiator. As a result, the chemical resistance (resistance to organic solvents, etc.) of the resin film formed from the cured product of the photosensitive resin composition can be improved.
熱自由基起始劑包含有機過氧化物為較佳。作為有機過氧化物，能夠舉出辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化物、1,1,3,3-四甲基丁基過氧2-乙基己酸酯、草酸過氧化物、2,5-二甲基-2,5-二（2-乙基己醯基過氧）己烷、1-環己基-1-甲基乙基過氧2-乙基己酸酯、三級己基過氧2-乙基己酸酯、三級丁基過氧2-乙基己酸酯、間甲苯甲醯基過氧化物、苯甲醯基過氧化物、甲基乙基酮過氧化物、乙醯基過氧化物、三級丁基氫過氧化物、二-三級丁基過氧化物、異丙苯氫過氧化物、二異丙苯基過氧化物、三級丁基過苯甲酸酯、對氯苯甲醯基過氧化物、環己酮過氧化物等。Preferably, the thermal radical initiator comprises an organic peroxide. Examples of organic peroxides include octyl peroxide, lauryl peroxide, stearyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoic acid ester, oxalate peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethyl Ethylhexanoate, tertiary hexylperoxy 2-ethylhexanoate, tertiary butylperoxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, formazan Ethyl ethyl ketone peroxide, acetyl peroxide, tertiary butyl hydroperoxide, di-tertiary butyl peroxide, cumene hydroperoxide, dicumyl peroxide , Tertiary butyl perbenzoate, p-chlorobenzoyl peroxide, cyclohexanone peroxide, etc.
在使用熱自由基起始劑之情況下，可以僅使用1種熱自由基起始劑，亦可以使用2種以上的熱自由基起始劑。 在使用熱自由基起始劑之情況下，其量相對於多官能（甲基）丙烯酸化合物100質量份，0.1～30質量份為較佳，1～20質量份為更佳。 When using a thermal radical initiator, only 1 type of thermal radical initiator may be used, and 2 or more types of thermal radical initiators may be used. When using a thermal radical initiator, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylic compound.
（環氧樹脂） 本實施形態的感光性樹脂組成物可以包含除了交聯劑（B）以外的環氧樹脂。認為環氧樹脂與聚醯亞胺樹脂形成鍵，藉由如此形成之鍵，能夠提高由感光性樹脂組成物的硬化物形成之樹脂膜的機械物性（拉伸伸長率等）。 (epoxy resin) The photosensitive resin composition of this embodiment may contain epoxy resins other than a crosslinking agent (B). It is considered that the epoxy resin and the polyimide resin form a bond, and the mechanical properties (such as tensile elongation) of the resin film formed from the cured product of the photosensitive resin composition can be improved by the bond formed in this way.
作為環氧樹脂的具體例，能夠舉出以下。當然，環氧樹脂並不僅限定於該些。 雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚M型環氧樹脂（4,4’-（1,3-伸苯基二亞異丙基）雙酚型環氧樹脂（4,4’-（1,3-phenylene diisopropylidene）bisphenol type epoxy resin））、雙酚P型環氧樹脂（4,4’-（1,4-伸苯基二亞異丙基）雙酚型環氧樹脂）、雙酚Z型環氧樹脂（4,4’-環亞己基雙酚型環氧樹脂）、四甲基雙酚F型環氧樹脂等雙酚型環氧樹脂；苯酚酚醛清漆型環氧樹脂、溴化苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、四苯酚基乙烷型酚醛清漆型環氧樹脂、具有縮環芳香族烴結構之酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；聯苯型環氧樹脂；伸茬基型環氧樹脂、聯苯芳烷基（biphenyl aralkyl）型環氧樹脂等芳烷基型環氧樹脂；伸萘基醚型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、萘二醇型環氧樹脂、2～4官能環氧型萘樹脂、聯萘型環氧樹脂、萘芳烷基型環氧樹脂等具有萘骨架之環氧樹脂；蒽型環氧樹脂；苯氧基型環氧樹脂；二環戊二烯型環氧樹脂；降莰烯型環氧樹脂；金剛烷型環氧樹脂；茀型環氧樹脂、含磷環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、雙酚A酚醛清漆型環氧樹脂、聯二甲酚型環氧樹脂、三羥基苯基甲烷型環氧樹脂、芪型環氧樹脂、四苯酚基乙烷型環氧樹脂、三聚異氰酸三環氧丙酯等雜環式環氧樹脂；N,N,N’,N’-四環氧丙基間二甲苯二胺、N,N,N’,N’-四環氧丙基雙胺基甲基環己烷、N,N-二環氧丙基苯胺等環氧丙基胺類、或（甲基）丙烯酸環氧丙酯與具有乙烯性不飽和雙鍵之化合物的共聚物；具有丁二烯結構之環氧樹脂；雙酚的二環氧丙基醚化物；萘二醇的二環氧丙基醚化物；酚類的環氧丙基醚化物等。 Specific examples of epoxy resins include the following. Of course, epoxy resins are not limited to these. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4 ,4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin (4,4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin)), bisphenol P-type ring Oxygen resin (4,4'-(1,4-phenylene diisopropylidene) bisphenol-type epoxy resin), bisphenol Z-type epoxy resin (4,4'-cyclohexylene bisphenol-type ring Oxygen resin), tetramethylbisphenol F-type epoxy resin and other bisphenol-type epoxy resins; phenol novolak-type epoxy resin, brominated phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, four Phenol-based ethane-type novolak-type epoxy resin, novolac-type epoxy resin with condensed ring aromatic hydrocarbon structure and other novolac-type epoxy resins; biphenyl-type epoxy resin; stubble-based epoxy resin, biphenyl Aralkyl type epoxy resins such as biphenyl aralkyl type epoxy resins; naphthyl ether type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, naphthalene diol type epoxy resins , 2-4 functional epoxy naphthalene resins, binaphthyl epoxy resins, naphthalene aralkyl epoxy resins and other epoxy resins with a naphthalene skeleton; anthracene epoxy resins; phenoxy epoxy resins; Cyclopentadiene-type epoxy resin; norcamphene-type epoxy resin; adamantane-type epoxy resin; fennel-type epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin , bisphenol A novolac epoxy resin, bixylenol epoxy resin, trihydroxyphenylmethane epoxy resin, stilbene epoxy resin, tetraphenylphenol ethane epoxy resin, trimeric isocyanide Heterocyclic epoxy resins such as triglycidyl acid; N,N,N',N'-tetraepoxypropyl m-xylylenediamine, N,N,N',N'-tetraepoxypropyl Copolymers of glycidylamines such as bisaminomethylcyclohexane, N,N-diglycidylaniline, or glycidyl (meth)acrylate and compounds with ethylenically unsaturated double bonds Epoxy resins with butadiene structure; Diglycidyl ethers of bisphenols; Diglycidyl ethers of naphthalene diol; Glycidyl ethers of phenols, etc.
在將環氧樹脂用作添加劑之情況下，其量相對於聚醯亞胺樹脂等耐熱性樹脂（A）100質量份，例如為0.5～100質量份，1～50質量份為較佳，3～20質量份為進一步較佳。When an epoxy resin is used as an additive, the amount thereof is, for example, 0.5 to 100 parts by mass, preferably 1 to 50 parts by mass, relative to 100 parts by mass of a heat-resistant resin (A) such as a polyimide resin, and 3 -20 mass parts is still more preferable.
在將環氧樹脂用作添加劑之情況下，可以僅使用1種環氧樹脂，亦可以併用2種以上的環氧樹脂。When using an epoxy resin as an additive, only 1 type of epoxy resin may be used, and 2 or more types of epoxy resins may be used together.
（硬化觸媒） 本實施形態的感光性樹脂組成物可以包含硬化觸媒。 在感光性樹脂組成物含有含環氧基的基團的化合物之情況下，有時藉由使用硬化觸媒，會促進環氧樹脂的反應。 (hardening catalyst) The photosensitive resin composition of this embodiment may contain a hardening catalyst. When the photosensitive resin composition contains an epoxy group-containing compound, the reaction of the epoxy resin may be accelerated by using a curing catalyst.
作為硬化觸媒，能夠舉出環氧樹脂的技術領域中已知的硬化觸媒（通常，亦稱為硬化促進劑）。例如，可舉出：1,8-二吖雙環[5,4,0]十一烯-7（1,8-diazabicyclo[5.4.0]-undecene-7）等二吖雙環烯烴及其衍生物；三丁胺、苄基二甲胺等胺系化合物；2-甲基咪唑等咪唑化合物；三苯膦、甲基二苯膦等有機膦類；四苯基硼酸四苯鏻（tetraphenylphosphonium tetraphenylborate）、四苯甲酸硼酸四苯鏻、四萘甲酸硼酸四苯鏻、四萘甲醯氧基硼酸四苯鏻（tetraphenylphosphonium tetranaphthoic acid borate）、四萘氧基硼酸四苯鏻（tetraphenylphosphonium tetranaphthyloxyborate）、4,4’-磺醯基二酚四苯鏻（tetraphenylphosphonium 4,4’-sulfonyl diphenolate）等四取代鏻鹽；加成有苯醌之三苯膦等。其中，可較佳地舉出有機膦類。Examples of the curing catalyst include those known in the technical field of epoxy resins (generally, also referred to as curing accelerators). Examples include: 1,8-diazabicyclo[5,4,0]undecene-7 (1,8-diazabicyclo[5.4.0]-undecene-7) and other diazabicycloalkenes and their derivatives Amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; tetraphenylphosphonium tetraphenylborate, Tetraphenylphosphonium tetrabenzoic acid borate, tetraphenylphosphonium tetranaphthoic acid borate, tetraphenylphosphonium tetranaphthoic acid borate, tetraphenylphosphonium tetranaphthyloxyborate, 4,4' -Tetraphenylphosphonium 4,4'-sulfonyl diphenol and other tetrasubstituted phosphonium salts; triphenylphosphine added with benzoquinone, etc. Among them, organic phosphines are preferably used.
在使用硬化觸媒之情況下，其量相對於含環氧基的基團的化合物100質量份，例如為1～80質量份，5～50質量份為較佳，5～30質量份為更佳。In the case of using a curing catalyst, the amount thereof is, for example, 1 to 80 parts by mass, preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the compound containing an epoxy group. good.
（矽烷偶合劑） 本實施形態的感光性樹脂組成物可以包含矽烷偶合劑。 藉由使用矽烷偶合劑，能夠更加提高由感光性樹脂組成物形成之樹脂膜與基材的密接性。 (silane coupling agent) The photosensitive resin composition of this embodiment may contain a silane coupling agent. By using a silane coupling agent, the adhesiveness of the resin film formed from the photosensitive resin composition and a base material can be improved more.
作為矽烷偶合劑，例如能夠使用含胺基之矽烷偶合劑、含環氧基的基團之矽烷偶合劑、含（甲基）丙烯醯基之矽烷偶合劑、含巰基之矽烷偶合劑、含乙烯基之矽烷偶合劑、含脲基之矽烷偶合劑、含硫醚基之矽烷偶合劑、具有環狀酸酐結構之矽烷偶合劑等矽烷偶合劑。As the silane coupling agent, for example, an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth)acryl group-containing silane coupling agent, a mercapto-containing silane coupling agent, a vinyl-containing Silane coupling agents such as silane coupling agents containing urea groups, silane coupling agents containing thioether groups, and silane coupling agents with cyclic anhydride structures.
在本實施形態中，作為耐熱性樹脂（A）使用聚醯亞胺樹脂之情況下，可較佳地使用具有環狀酸酐結構之矽烷偶合劑。儘管詳細內容尚不明確，但推測環狀酸酐結構容易與聚醯亞胺的主鏈、側鏈及/或末端反應，因此可獲得尤為良好的密接性提高效果。In this embodiment, when using a polyimide resin as a heat-resistant resin (A), it is preferable to use the silane coupling agent which has a cyclic acid anhydride structure. Although the details are unclear, it is presumed that the cyclic acid anhydride structure easily reacts with the main chain, side chain, and/or terminal of the polyimide, so that a particularly good adhesion-improving effect can be obtained.
在使用矽烷偶合劑之情況下，可以單獨使用，亦可以併用2種以上的矽烷偶合劑。When using a silane coupling agent, it may use individually, and may use 2 or more types of silane coupling agents together.
在使用矽烷偶合劑之情況下，將聚醯亞胺樹脂等耐熱性樹脂（A）的使用量設為100質量份時，其使用量例如為0.1～20質量份，0.3～15質量份為較佳，0.4～12質量份為更佳，0.5～10質量份為進一步較佳。In the case of using a silane coupling agent, when the amount of heat-resistant resin (A) such as polyimide resin is set to 100 parts by mass, the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass. Preferably, 0.4-12 mass parts is more preferable, 0.5-10 mass parts is still more preferable.
（界面活性劑） 本實施形態的感光性樹脂組成物可以包含界面活性劑。 藉由包含界面活性劑，能夠進一步提高感光性樹脂組成物的塗佈性或由感光性樹脂組成物形成之樹脂膜的平坦性。 作為界面活性劑，可舉出氟系界面活性劑、聚矽氧系界面活性劑、烷基系界面活性劑、丙烯酸系界面活性劑等。 作為另一觀點，界面活性劑為非離子性為較佳。例如從抑制與組成物中的其他成分的意外反應來提高組成物的保存穩定性之觀點考慮，使用非離子性的界面活性劑為較佳。 (surfactant) The photosensitive resin composition of this embodiment may contain a surfactant. By including a surfactant, the applicability of the photosensitive resin composition or the flatness of a resin film formed from the photosensitive resin composition can be further improved. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, acrylic-based surfactants, and the like. From another viewpoint, it is preferable that the surfactant is nonionic. For example, it is preferable to use a nonionic surfactant from the viewpoint of suppressing unexpected reactions with other components in the composition and improving the storage stability of the composition.
界面活性劑包含含有氟原子及矽原子中的至少任一者之界面活性劑為較佳。藉此，不僅有助於獲得均勻的樹脂膜（提高塗佈性）或提高顯影性，而且還有助於提高接著強度。作為該種界面活性劑，例如係含有氟原子及矽原子中的至少任一者之非離子系界面活性劑為較佳。作為可用作界面活性劑之市售品，例如可舉出DIC Corporation製的「Megafac（註冊商標）」系列的F-251、F-253、F-281、F-430、F-477、F-551、F-552、F-553、F-554、F-555、F-556、F-557、F-558、F-559、F-560、F-561、F-562、F-563、F-565、F-568、F-569、F-570、F-572、F-574、F-575、F-576、R-40、R-40-LM、R-41、R-94等含氟之低聚物結構的界面活性劑、NEOS COMPANY LIMITED製的Ftergent250、Ftergent251等含氟之非離子系界面活性劑、Wacker Chemie AG製SILFOAM（註冊商標）系列（例如，SD 100 TS、SD 670、SD 850、SD 860、SD 882）等聚矽氧系界面活性劑。 又，作為較佳的界面活性劑，還能夠舉出3M公司製的FC4430或FC4432等。 It is preferable that the surfactant contains a surfactant containing at least any one of a fluorine atom and a silicon atom. This contributes not only to obtaining a uniform resin film (improving coatability) or improving developability, but also to improving adhesive strength. As such a surfactant, for example, a nonionic surfactant containing at least any one of a fluorine atom and a silicon atom is preferable. Examples of commercially available products that can be used as surfactants include F-251, F-253, F-281, F-430, F-477, F -551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563 , F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94 Fluorine-containing oligomer structure surfactants, fluorine-containing non-ionic surfactants such as Ftergent250 and Ftergent251 manufactured by NEOS COMPANY LIMITED, SILFOAM (registered trademark) series manufactured by Wacker Chemie AG (for example, SD 100 TS, SD 670, SD 850, SD 860, SD 882) and other polysiloxane surfactants. Moreover, FC4430, FC4432 etc. by 3M company can also be mentioned as a preferable surfactant.
在使用界面活性劑之情況下，可以單獨使用，亦可以併用2種以上的界面活性劑。When using a surfactant, it may be used individually, and may use 2 or more types of surfactant together.
在本實施形態的感光性樹脂組成物包含界面活性劑之情況下，將耐熱性樹脂（A）的含量設為100質量份時，其量例如為0.001～1質量份，0.005～0.5質量份為較佳。When the photosensitive resin composition of this embodiment contains a surfactant, when the content of the heat-resistant resin (A) is 100 parts by mass, the amount is, for example, 0.001 to 1 part by mass, and 0.005 to 0.5 parts by mass. better.
（溶劑/組成物的性狀） 本實施形態的感光性樹脂組成物包含溶劑為較佳。藉此，能夠藉由塗佈法對基材（尤其，具有階差之基材）容易形成感光性樹脂膜。 溶劑通常包含有機溶劑。只要能夠溶解或分散上述各成分且實質上不與各構成成分進行化學反應者，則有機溶劑並無特別限定。 (properties of solvent/composition) It is preferable that the photosensitive resin composition of this embodiment contains a solvent. Thereby, a photosensitive resin film can be easily formed on a base material (especially, a base material with a step) by a coating method. Solvents generally include organic solvents. The organic solvent is not particularly limited as long as it can dissolve or disperse the above-mentioned components and does not substantially chemically react with the components.
作為有機溶劑，例如可舉出丙酮、甲基乙基酮、甲苯、丙二醇甲基乙基醚、丙二醇二甲基醚、丙二醇1-單甲基醚2-乙酸酯、二乙二醇乙基甲基醚、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、苄醇、碳酸丙烯酯、乙二醇二乙酸酯、丙二醇二乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇甲基-正丙醚、乙酸丁酯、γ-丁內酯、乳酸甲酯、乳酸乙酯、乳酸丁酯等。該些可以單獨使用，亦可以組合複數個而使用。Examples of organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl Methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol Monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate, etc. These may be used individually or in combination of several.
在本實施形態的感光性樹脂組成物包含溶劑之情況下，本實施形態的感光性樹脂組成物通常為清漆狀。由於本實施形態的感光性樹脂組成物為清漆狀，因此能夠藉由塗佈形成均勻的膜。又，本實施形態的感光性樹脂組成物為清漆狀並且至少耐熱性樹脂（A）溶解於溶劑為較佳。When the photosensitive resin composition of this embodiment contains a solvent, the photosensitive resin composition of this embodiment is normally a varnish shape. Since the photosensitive resin composition of the present embodiment is in the form of a varnish, a uniform film can be formed by coating. Moreover, it is preferable that the photosensitive resin composition of this embodiment is varnish-like, and at least heat-resistant resin (A) is dissolved in a solvent.
在使用溶劑之情況下，以感光性樹脂組成物中的總固體成分（非揮發成分）的濃度成為10～50質量%為較佳，成為20～45質量%為更佳的方式使用。藉由設為該範圍，能夠使各成分充分地溶解或分散。又，能夠確保良好的塗佈性，進而還使旋塗時的平坦性變得良好。進而，藉由調整非揮發成分的含量，能夠適當地控制感光性樹脂組成物的黏度。When using a solvent, it is preferable to use it so that the density|concentration of the total solid content (non-volatile matter) in a photosensitive resin composition may become 10-50 mass %, and it is more preferable that it shall be 20-45 mass %. By setting it as this range, each component can be fully dissolved or disperse|distributed. In addition, good applicability can be ensured, and the flatness at the time of spin coating can also be made good. Furthermore, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the non-volatile components.
除了上述成分以外，本實施形態的感光性樹脂組成物根據需要還可以包含上述成分以外的成分。作為該種成分，例如可舉出抗氧化劑、二氧化矽（silica）等填充劑、敏化劑、膜化劑等。 順帶一提，本實施形態的感光性樹脂組成物不包含（甲基）丙烯醯胺系化合物（具有（甲基）丙烯醯胺結構之化合物），或者即使包含亦為組成物的總非揮發成分中的1質量%以下為較佳。 In addition to the above-mentioned components, the photosensitive resin composition of this embodiment may contain components other than the above-mentioned components as needed. Such components include, for example, antioxidants, fillers such as silica (silica), sensitizers, film-forming agents, and the like. Incidentally, the photosensitive resin composition of this embodiment does not contain a (meth)acrylamide-based compound (a compound having a (meth)acrylamide structure), or even if it contains it, it is the total non-volatile component of the composition 1% by mass or less is preferable.
[樹脂膜] 本實施形態的一實施形態中，樹脂膜由上述感光性樹脂組成物的硬化物構成為較佳。 [resin film] In one embodiment of the present embodiment, it is preferable that the resin film is constituted by a cured product of the above-mentioned photosensitive resin composition.
例如，在電子裝置的基材上塗佈上述感光性樹脂組成物並使其硬化，從而能夠形成樹脂膜。For example, a resin film can be formed by applying and curing the above-mentioned photosensitive resin composition on a base material of an electronic device.
[電子裝置] 本實施形態中，電子裝置具備上述樹脂膜為較佳。 [electronic device] In this embodiment, it is preferable that the electronic device includes the above-mentioned resin film.
本實施形態的電子裝置能夠藉由下述製造步驟來製造。The electronic device of this embodiment can be manufactured through the following manufacturing steps.
本實施形態的電子裝置之製造方法包括： 膜形成步驟，其使用上述感光性樹脂組成物在基材上形成感光性樹脂膜； 曝光步驟，其對感光性樹脂膜進行曝光；及 顯影步驟，其對經曝光之感光性樹脂膜進行顯影。 又，本實施形態的電子裝置之製造方法在上述顯影步驟之後包括對經曝光之感光性樹脂膜進行加熱而使其硬化之熱硬化步驟為較佳。藉此，能夠獲得由耐化學品性及伸長率優異的感光性樹脂組成物的硬化物形成之樹脂膜。 The manufacturing method of the electronic device of this embodiment includes: a film forming step of forming a photosensitive resin film on a substrate using the above photosensitive resin composition; an exposing step of exposing the photosensitive resin film; and A developing step, which develops the exposed photosensitive resin film. Furthermore, the method of manufacturing an electronic device according to this embodiment preferably includes a thermosetting step of heating and curing the exposed photosensitive resin film after the above-mentioned developing step. Thereby, the resin film which consists of the hardened|cured material of the photosensitive resin composition excellent in chemical resistance and elongation can be obtained.
膜形成步驟通常藉由在基材上塗佈感光性樹脂組成物來進行。膜形成步驟能夠使用旋塗機、棒塗機、噴霧裝置、噴墨裝置等來進行。 在接下來的曝光步驟之前，以使所塗佈之感光性樹脂組成物中的溶劑乾燥等為目的進行適當的加熱為較佳。此時的加熱例如藉由以80～150℃的溫度加熱1～60分鐘來進行。 乾燥後的感光性樹脂膜的厚度根據最終要得到之電子裝置的結構而適當發生變化，例如為1～100μm左右，具體而言為1～50μm左右。 The film forming step is usually performed by coating a photosensitive resin composition on a substrate. The film forming step can be performed using a spin coater, a bar coater, a spray device, an inkjet device, or the like. Before the next exposure process, it is preferable to heat appropriately for the purpose of drying the solvent in the applied photosensitive resin composition, etc. The heating at this time is performed, for example, by heating at a temperature of 80 to 150° C. for 1 to 60 minutes. The thickness of the photosensitive resin film after drying varies appropriately depending on the structure of the electronic device to be finally obtained, and is, for example, about 1 to 100 μm, specifically about 1 to 50 μm.
曝光步驟中的曝光量並無特別限定。100～2000mJ/cm 2為較佳，200～1000mJ/cm 2為更佳。 曝光中使用之光源並無特別限定，只要發出感光性樹脂組成物中的感光劑進行反應之波長的光（例如，g射線或i射線）之光源即可。典型地使用高壓水銀燈。 根據需要，可以實施曝光後烘烤。曝光後烘烤的溫度並無特別限定。50～150℃為較佳，50～130℃為更佳，55～120℃為進一步較佳，60～110℃尤為佳。又，曝光後烘烤的時間係1～30分鐘為較佳，1～20分鐘為更佳，1～15分鐘為進一步較佳。 在曝光步驟中，能夠使用光罩。藉此，能夠使用感光性樹脂組成物來形成所期望的「圖案」。 The exposure amount in the exposure step is not particularly limited. 100-2000mJ/cm 2 is preferable, and 200-1000mJ/cm 2 is more preferable. The light source used for exposure is not particularly limited, as long as it emits light of a wavelength (for example, g-ray or i-ray) at which the photosensitive agent in the photosensitive resin composition reacts. Typically high pressure mercury lamps are used. A post-exposure bake may be performed as needed. The temperature of the post-exposure baking is not particularly limited. 50-150°C is more preferable, 50-130°C is more preferable, 55-120°C is still more preferable, and 60-110°C is particularly preferable. Moreover, the post-exposure baking time is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, and still more preferably 1 to 15 minutes. In the exposure step, a photomask can be used. Thereby, a desired "pattern" can be formed using a photosensitive resin composition.
作為顯影步驟中的顯影液，例如可舉出有機系顯影液、水溶性顯影液等。在本實施形態中，顯影液含有有機溶劑為較佳。更具體而言，顯影液係以有機溶劑為主成分之顯影液（成分的95質量%以上為有機溶劑之顯影液）為較佳。 藉由利用含有有機溶劑之顯影液進行顯影，與利用鹼性顯影液（水系）進行顯影之情況相比，能夠抑制由顯影液引起之圖案膨潤等。亦即，容易獲得更精細的圖案。 As a developing solution in an image development process, an organic type developing solution, a water-soluble developing solution, etc. are mentioned, for example. In this embodiment, it is preferable that the developing solution contains an organic solvent. More specifically, it is preferable that the developer is a developer mainly composed of an organic solvent (95% by mass or more of the component is an organic solvent). By performing development with a developing solution containing an organic solvent, it is possible to suppress swelling of the pattern due to the developing solution, etc., compared to the case of performing development with an alkaline developing solution (aqueous system). That is, finer patterns are easily obtained.
作為可使用於顯影液之有機溶劑，具體而言，可舉出環戊酮等酮系溶劑、丙二醇單甲醚乙酸酯（PGMEA）或乙酸丁酯等酯系溶劑、丙二醇單甲醚等醚系溶劑等。 作為顯影液，可以使用僅由有機溶劑構成且僅包含不可避免地包含之雜質之有機溶劑顯影液。作為不可避免地包含之雜質，有金屬元素和水分，但從防止電子裝置污染等的觀點考慮，不可避免地包含之雜質越少越好。 Specific examples of organic solvents that can be used in the developer include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ethers such as propylene glycol monomethyl ether. Department of solvents, etc. As the developer, an organic solvent developer consisting only of an organic solvent and containing only unavoidable impurities can be used. Examples of unavoidable impurities include metal elements and moisture, but from the viewpoint of preventing contamination of electronic devices, the less unavoidable impurities are better.
使顯影液與感光性樹脂膜接觸之方法並無特別限定。能夠適當適用通常已知的浸漬法、旋覆浸沒法（puddle method）、噴霧法等。The method of bringing the developing solution into contact with the photosensitive resin film is not particularly limited. A generally known dipping method, a puddle method, a spray method, and the like can be appropriately applied.
顯影步驟的時間通常為5～300秒左右，在10～120秒左右的範圍內，根據樹脂膜的膜厚或所形成之圖案的形狀等適當調整為較佳。The time of the developing step is usually about 5 to 300 seconds, preferably within the range of about 10 to 120 seconds, and is appropriately adjusted according to the film thickness of the resin film, the shape of the pattern to be formed, and the like.
熱硬化步驟的條件並無特別限定，例如能夠以160～250℃左右的加熱溫度加熱30～240分鐘左右。The conditions of the thermosetting step are not particularly limited, and for example, heating can be performed at a heating temperature of about 160 to 250° C. for about 30 to 240 minutes.
以上，對本發明的實施形態進行了描述，但該些為本發明的示例，能夠採用上述以外的各種結構。又，本發明並不限定於上述實施形態，能夠達成本發明的目的之範圍內的變形、改進等包括在本發明中。 [實施例] As mentioned above, although embodiment of this invention was described, these are examples of this invention, and various structures other than the above-mentioned can be employ|adopted. In addition, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the range that can achieve the object of the present invention are included in the present invention. [Example]
根據實施例及比較例，對本發明的實施態樣進行詳細說明。為了慎重起見而事先說明，本發明並不僅限定於實施例。Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It is explained in advance for the sake of caution, but the present invention is not limited only to the Examples.
[各原料的合成] ＜耐熱性樹脂（A-1）的合成＞ 在具備攪拌機及冷卻管之5L的可分離式燒瓶中，添加2,2’-雙（三氟甲基）聯苯胺304.2g（0.95莫耳）、4,4’-（六氟亞異丙基）二酞酸酐355.39g（0.80莫耳）、4,4’-氧基二酞酸二酐（4,4’-oxydiphthalic dianhydride）62.04g（0.20莫耳）及GBL1684g，在氮環境下並在室溫進行了16小時的聚合反應。接著，在油浴中使反應液溫度上升至180℃並進行了3小時反應之後，冷卻至室溫而製作了聚醯亞胺樹脂溶液。 接著，將反應液一邊攪拌一邊滴加到異丙醇/水=4/7的混合溶液中，從而使樹脂固體析出。對所獲得之固體進行粗過濾之後，進一步用異丙醇/水=4/7進行清洗而獲得了聚醯亞胺的白色固體。藉由在200℃對所獲得之白色固體進行真空乾燥，從而獲得了在末端具有酸酐基之聚醯亞胺樹脂（A-1）。 藉由GPC測量而測出之聚醯亞胺樹脂（A-1）的重量平均分子量（Mw）為49,000。 [Synthesis of Raw Materials] ＜Synthesis of heat-resistant resin (A-1)＞ In a 5L separable flask equipped with a stirrer and a cooling tube, add 304.2 g (0.95 moles) of 2,2'-bis(trifluoromethyl)benzidine, 4,4'-(hexafluoroisopropylidene ) diphthalic anhydride 355.39g (0.80 mole), 4,4'-oxydiphthalic dianhydride (4,4'-oxydiphthalic dianhydride) 62.04g (0.20 mole) and GBL1684g, under nitrogen environment and in room The polymerization reaction was carried out at room temperature for 16 hours. Next, the temperature of the reaction liquid was raised to 180° C. in an oil bath to react for 3 hours, and then cooled to room temperature to prepare a polyimide resin solution. Next, the reaction solution was added dropwise to a mixed solution of isopropanol/water=4/7, stirring, to precipitate a resin solid. The obtained solid was roughly filtered, and then washed with isopropanol/water=4/7 to obtain a white solid of polyimide. The polyimide resin (A-1) which has an acid anhydride group at the terminal was obtained by vacuum-drying the obtained white solid at 200 degreeC. The weight average molecular weight (Mw) of the polyimide resin (A-1) measured by GPC was 49,000.
＜耐熱性樹脂（A-2）的合成＞ 在2L的可分離式燒瓶中，加入γ-丁內酯428g、4,4’-氧基二酞酸二酐155.11g及甲基丙烯酸2-羥乙酯130.14g，在室溫攪拌燒瓶內的成分而使其完全溶解。接著，在室溫一邊攪拌一邊添加吡啶79.1g，進一步在室溫攪拌了16小時。 ＜Synthesis of heat-resistant resin (A-2)＞ In a 2L separable flask, add 428g of γ-butyrolactone, 155.11g of 4,4'-oxydiphthalic dianhydride, and 130.14g of 2-hydroxyethyl methacrylate, and stir the contents of the flask at room temperature. ingredients to dissolve completely. Next, 79.1 g of pyridine was added with stirring at room temperature, and further stirred at room temperature for 16 hours.
一邊在冰冷下對如上所述獲得之溶液進行冷卻攪拌，一邊經30分鐘在該溶液中添加了將二（環己亞胺）甲烷（dicyclohexyl carbodiimide）206.3g溶解於γ-丁內酯206g中而得到之溶液。接著，添加4,4’-二胺基二苯醚120.1g及γ-丁內酯240g，進一步在室溫繼續攪拌了2小時。 反應結束之後，添加乙醇30g攪拌了1小時。之後，添加γ-丁內酯400g進一步進行攪拌，藉由過濾除去了所生成之沉澱物。藉此獲得了聚醯胺酸酯的反應液。 在室溫，將所獲得之反應液一邊攪拌一邊滴加到大量的30質量%甲醇水溶液中，使樹脂沉澱。濾取所獲得之沉澱物並進行真空乾燥，藉此獲得了在末端具有胺基之聚醯胺樹脂（A-2）。 藉由GPC測量而測出之聚醯胺樹脂（A-2）的重量平均分子量（Mw）為30,000。 While cooling and stirring the solution obtained above under ice cooling, 206.3 g of dicyclohexyl carbodiimide was dissolved in 206 g of γ-butyrolactone was added to the solution over 30 minutes. The resulting solution. Next, 120.1 g of 4,4'-diaminodiphenyl ether and 240 g of γ-butyrolactone were added, and stirring was continued at room temperature for 2 hours. After completion of the reaction, 30 g of ethanol was added and stirred for 1 hour. Thereafter, 400 g of γ-butyrolactone was added and stirred, and the generated precipitate was removed by filtration. In this way, a reaction solution of polyamide ester was obtained. The obtained reaction liquid was dripped at room temperature into a large amount of 30 mass % methanol aqueous solution, stirring, and resin was precipitated. The obtained precipitate was collected by filtration and vacuum-dried to obtain a polyamide resin (A-2) having an amino group at the terminal. The weight average molecular weight (Mw) of the polyamide resin (A-2) measured by GPC measurement was 30,000.
＜耐熱性樹脂（A-3）的合成＞ 在具備攪拌機及冷卻管之5L的可分離式燒瓶中，添加2,2’-雙（三氟甲基）聯苯胺317.04g（0.99莫耳）、4,4’-（六氟亞異丙基）二酞酸酐355.39g（0.80莫耳）、4,4’-氧基二酞酸二酐62.04g（0.20莫耳）及GBL1714g，在氮環境下並在室溫進行了16小時的聚合反應。接著，在油浴中使反應液溫度上升至180℃並進行了3小時反應之後，冷卻至室溫而製作了聚醯亞胺樹脂溶液。 接著，將反應液一邊攪拌一邊滴加到異丙醇/水=4/7的混合溶液中，從而使樹脂固體析出。對所獲得之固體進行粗過濾之後，進一步用異丙醇/水=4/7進行清洗而獲得了聚醯亞胺的白色固體。藉由在200℃對所獲得之白色固體進行真空乾燥，從而獲得了在末端具有酸酐基之聚醯亞胺樹脂（A-3）。 藉由GPC測量而測出之聚醯亞胺樹脂（A-3）的重量平均分子量（Mw）為110,000。 ＜Synthesis of heat-resistant resin (A-3)＞ In a 5L separable flask equipped with a stirrer and a cooling tube, add 317.04 g (0.99 moles) of 2,2'-bis(trifluoromethyl)benzidine, 4,4'-(hexafluoroisopropylidene ) 355.39 g (0.80 mol) of diphthalic anhydride, 62.04 g (0.20 mol) of 4,4'-oxydiphthalic dianhydride, and 1714 g of GBL were polymerized at room temperature for 16 hours under a nitrogen atmosphere. Next, the temperature of the reaction liquid was raised to 180° C. in an oil bath to react for 3 hours, and then cooled to room temperature to prepare a polyimide resin solution. Next, the reaction solution was added dropwise to a mixed solution of isopropanol/water=4/7, stirring, to precipitate a resin solid. The obtained solid was roughly filtered, and then washed with isopropanol/water=4/7 to obtain a white solid of polyimide. The polyimide resin (A-3) which has an acid anhydride group at the terminal was obtained by vacuum-drying the obtained white solid at 200 degreeC. The weight average molecular weight (Mw) of the polyimide resin (A-3) measured by GPC measurement was 110,000.
＜硬化觸媒（F-1）的合成＞ 在帶攪拌裝置的可分離式燒瓶中，裝入4,4’-雙酚S37.5g（0.15mol）、甲醇100mL，並在室溫進行攪拌溶解，進而一邊攪拌一邊添加了預先在50mL的甲醇中溶解氫氧化鈉4.0g（0.1mol）而得到之溶液。接著，添加了預先在150mL的甲醇中溶解四苯基溴化鏻41.9g（0.1mol）而得到之溶液。繼續攪拌片刻，追加了300mL的甲醇之後，將燒瓶內的溶液一邊攪拌一邊滴加到大量的水中，從而獲得了白色沉澱。將沉澱進行過濾、乾燥而獲得了白色結晶的硬化觸媒（F-1）。 ＜Synthesis of hardening catalyst (F-1)＞ In a separable flask equipped with a stirring device, 37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 mL of methanol were charged, and stirred and dissolved at room temperature, and then 50 mL of methanol in advance was added while stirring. A solution obtained by dissolving 4.0 g (0.1 mol) of sodium hydroxide in Next, a solution obtained by dissolving 41.9 g (0.1 mol) of tetraphenylphosphonium bromide in advance in 150 mL of methanol was added. Stirring was continued for a while, and after adding 300 mL of methanol, the solution in the flask was added dropwise to a large amount of water while stirring to obtain a white precipitate. The precipitate was filtered and dried to obtain a hardened catalyst (F-1) of white crystals.
＜感光性樹脂組成物的製備＞ 根據後述表1摻合各原料，並在室溫攪拌至原料完全溶解，從而獲得了溶液。之後，用孔徑0.2μm的聚丙烯製過濾器過濾了該溶液。如此，獲得了清漆狀感光性樹脂組成物。 ＜Preparation of photosensitive resin composition＞ Each raw material was blended according to Table 1 described below, and stirred at room temperature until the raw materials were completely dissolved to obtain a solution. Thereafter, the solution was filtered through a polypropylene filter with a pore diameter of 0.2 μm. In this way, a varnish-like photosensitive resin composition was obtained.
表1中的各成分的原料的詳細內容如下所述。The details of the raw materials of each component in Table 1 are as follows.
＜耐熱性樹脂（A）＞ （A-1）上述中合成之耐熱性樹脂（聚醯亞胺樹脂） （A-2）上述中合成之耐熱性樹脂（聚醯胺樹脂） （A-3）上述中合成之耐熱性樹脂（聚醯亞胺樹脂） 順帶一提，（A-1）及（A-3）具有由上述通式（PI-1）表示之結構單元及由通式（PI-2）表示之結構單元。 又，（A-1）及（A-3）只要基於原料單體的結構，則實質上不具有酚性羥基等鹼可溶性基。 ＜Heat-resistant resin (A)＞ (A-1) Heat-resistant resin (polyimide resin) synthesized above (A-2) Heat-resistant resin (polyamide resin) synthesized above (A-3) Heat-resistant resin (polyimide resin) synthesized above Incidentally, (A-1) and (A-3) have a structural unit represented by the above general formula (PI-1) and a structural unit represented by general formula (PI-2). Moreover, (A-1) and (A-3) do not substantially have alkali-soluble groups, such as a phenolic hydroxyl group, as long as they are based on the structure of a raw material monomer.
＜具有含環氧基的基團和（甲基）丙烯醯基之交聯劑（B）＞ （B-1）甲基丙烯酸環氧丙酯 （B-2）4-羥基丁基丙烯酸酯環氧丙基醚 （B-3）3,4-環氧環己基甲基丙烯酸甲酯 （B-4）丙烯酸環氧丙酯 <Crosslinking agent (B) having an epoxy group-containing group and a (meth)acryl group> (B-1) Glycidyl methacrylate (B-2) 4-Hydroxybutyl acrylate glycidyl ether (B-3) 3,4-epoxycyclohexyl methyl methacrylate (B-4) Glycidyl acrylate
＜多官能（甲基）丙烯酸化合物＞ （C-1）Viscoat#802（OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製、三新戊四醇丙烯酸酯、單新戊四醇丙烯酸酯及二新戊四醇丙烯酸酯的混合物；前述通式（5）的化合物） （C-2）A-9550（SHIN-NAKAMURA CHEMICAL CO, LTD.製、5-6官能（烷氧基化）二新戊四醇丙烯酸酯） （C-3）Viscoat#300（OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製、單新戊四醇丙烯酸酯） （C-4）Viscoat#230（OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製、1,6-己二醇二丙烯酸酯） ＜Multifunctional (meth)acrylic compounds＞ (C-1) Viscoat#802 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., a mixture of tri-neopentyl acrylate, mono-neopentyl acrylate, and dipentyl acrylate; the compound of the aforementioned general formula (5) compound) (C-2) A-9550 (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., 5-6 functional (alkoxylated) diperythritol acrylate) (C-3) Viscoat #300 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., mono-neopentylthritol acrylate) (C-4) Viscoat #230 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., 1,6-hexanediol diacrylate)
＜感光劑＞ （D-1）Irgacure OXE01（BASF公司製、肟酯型光自由基產生劑） ＜Sensitizer＞ (D-1) Irgacure OXE01 (manufactured by BASF Corporation, oxime ester type photoradical generator)
（熱自由基起始劑） （E-1）Parka Dox BC（KAYAKU NOURYON CORPORATION製、二異丙苯基過氧化物） (Thermal Radical Initiator) (E-1) Parka Dox BC (manufactured by KAYAKU NOURYON CORPORATION, dicumyl peroxide)
＜硬化觸媒＞ （F-1）上述中合成之硬化觸媒（鏻鹽） ＜Hardening catalyst＞ (F-1) Hardening catalyst (phosphonium salt) synthesized above
＜矽烷偶合劑＞ （G-1）X-12-967C（Shin-Etsu Chemical Co., Ltd.製、具有環狀酸酐結構之矽烷偶合劑） （G-2）KBM-403（Shin-Etsu Chemical Co., Ltd.製、含環氧基的基團的矽烷偶合劑） ＜Silane coupling agent＞ (G-1) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent having a cyclic anhydride structure) (G-2) KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., epoxy group-containing silane coupling agent)
＜界面活性劑＞ （H-1）FC4432（3M公司製、氟系界面活性劑） ＜Surfactant＞ (H-1) FC4432 (manufactured by 3M Company, fluorine-based surfactant)
＜溶劑＞ （J-1）乳酸乙酯（EL） （J-2）γ-丁內酯（GBL） <Solvent> (J-1) Ethyl Lactate (EL) (J-2) Gamma-butyrolactone (GBL)
＜拉伸伸長率＞ （拉伸伸長率測量用試驗片的製作） 在12吋的矽晶圓上利用旋塗以乾燥後的膜厚成為10μm之方式塗佈各實施例及各比較例的感光性樹脂組成物，接著藉由以120℃進行3分鐘的加熱而獲得了感光性樹脂膜。對所獲得之塗佈膜利用i射線步進器以曝光寬度5mm、長度50mm的範圍之方式經由光罩進行了300mJ/cm 2的曝光。之後，利用噴霧顯影機並使用環戊酮及丙二醇單甲醚乙酸酯對經曝光之樹脂膜連同矽晶圓一起進行顯影，進而利用旋轉乾燥進行風乾後，以140℃在加熱板上進行了2分鐘的乾燥。進而，之後在氮環境下，以170℃進行90分鐘的熱處理，從而獲得了樹脂膜。 藉由將所獲得之樹脂膜浸漬於2質量%氫氟酸水溶液中而從基板剝離，並進行水洗之後，以60℃乾燥10小時，從而獲得了測量用試驗片（50mm×5mm×10μm厚）。 <Tensile elongation> (Preparation of test pieces for measuring tensile elongation) The photosensitive materials of Examples and Comparative Examples were coated on a 12-inch silicon wafer by spin coating so that the film thickness after drying became 10 μm. The photosensitive resin composition was obtained by heating at 120° C. for 3 minutes, and a photosensitive resin film was obtained. The obtained coating film was exposed to 300 mJ/cm 2 through a photomask so as to expose a range of 5 mm in width and 50 mm in length using an i-ray stepper. Afterwards, the exposed resin film was developed together with the silicon wafer using a spray developer using cyclopentanone and propylene glycol monomethyl ether acetate, and then air-dried by spin drying, and then processed on a hot plate at 140°C. 2 minutes dry. Furthermore, it heat-processed for 90 minutes at 170 degreeC in nitrogen atmosphere after that, and obtained the resin film. The obtained resin film was peeled off from the substrate by immersing it in a 2% by mass hydrofluoric acid aqueous solution, washed with water, and dried at 60°C for 10 hours to obtain a test piece for measurement (50mm×5mm×10μm thick) .
（拉伸伸長率的測量） 使用拉伸試驗機（ORIENTEC CORPORATION製、TENSILON RTC-1210A），在23℃環境下，以基於JIS K 7161之方法對藉由前述的（拉伸伸長率測量用試驗片的製作）獲得之測量用試驗片實施拉伸試驗，測量了試驗片的拉伸伸長率。拉伸試驗中的拉伸速度設為5mm/分。拉伸伸長率的單位為%。 (measurement of tensile elongation) Using a tensile testing machine (manufactured by ORIENTEC CORPORATION, TENSILON RTC-1210A), the measurement obtained by the above (production of test piece for measuring tensile elongation) was carried out by the method based on JIS K 7161 in an environment of 23°C. A tensile test was performed on the test piece, and the tensile elongation of the test piece was measured. The tensile speed in the tensile test was set at 5 mm/min. The unit of tensile elongation is %.
＜耐化學品性＞ （耐化學品性評價用基板的製作） 在12吋的矽晶圓上利用旋塗以乾燥後的膜厚成為5μm之方式塗佈各實施例及各比較例的感光性樹脂組成物，接著藉由以120℃進行3分鐘的加熱而獲得了感光性樹脂膜。對所獲得之塗佈膜，利用i射線步進器不經由光罩而進行了300mJ/cm 2的曝光。之後，利用噴霧顯影機並使用環戊酮及丙二醇單甲醚乙酸酯進行顯影，進而利用旋轉乾燥進行風乾後，以140℃在加熱板上進行了2分鐘的乾燥。進而之後，在氮環境下，以170℃進行90分鐘的熱處理，從而獲得了帶樹脂膜的矽晶圓（評價用基板）。 <Chemical Resistance> (Preparation of substrates for chemical resistance evaluation) The photosensitivity of each example and each comparative example was coated on a 12-inch silicon wafer by spin coating so that the film thickness after drying became 5 μm. The resin composition obtained the photosensitive resin film by heating at 120 degreeC for 3 minutes next. The obtained coating film was exposed to 300 mJ/cm 2 using an i-ray stepper without passing through a photomask. After that, it developed with a spray developing machine using cyclopentanone and propylene glycol monomethyl ether acetate, and after air-drying by spin drying, it dried on the hot plate at 140 degreeC for 2 minutes. Further, heat treatment was performed at 170° C. for 90 minutes in a nitrogen atmosphere to obtain a silicon wafer with a resin film (substrate for evaluation).
（耐化學品性的評價） 對藉由前述的（耐化學品性評價用基板的製作）獲得之評價用基板上的樹脂膜的膜厚進行了測量（膜厚A）。接著，將該評價用基板在50℃的阻劑剥離液（二甲基亞碸/四甲基氫化銨=96wt%/4wt%）中浸漬10分鐘，之後用異丙醇清洗之後利用旋轉乾燥進行了乾燥。進而將基板在150℃的加熱板上進行乾燥後對樹脂膜的膜厚進行了測量（膜厚B）。依據膜厚A及膜厚B由下述式計算出膜厚變化率。將膜厚變化率小於5%者設為優，將小於10%者設為良，將超過10%者設為不合格而進行了耐化學品性的評價。 膜厚變化率（%）=（膜厚A-膜厚B）/膜厚A×100 (Evaluation of chemical resistance) The film thickness (film thickness A) of the resin film on the evaluation substrate obtained in the aforementioned (production of chemical resistance evaluation substrate) was measured. Next, the substrate for evaluation was immersed in a resist stripping solution (dimethylsulfide/tetramethylammonium hydride = 96wt%/4wt%) at 50°C for 10 minutes, washed with isopropyl alcohol, and then spin-dried. up dry. Furthermore, after drying the board|substrate on the hot plate of 150 degreeC, the film thickness of the resin film was measured (film thickness B). From the film thickness A and the film thickness B, the film thickness change rate was calculated from the following formula. The film thickness change rate was less than 5% as excellent, less than 10% as good, and more than 10% as unacceptable, and the chemical resistance was evaluated. Film thickness change rate (%) = (film thickness A-film thickness B)/film thickness A×100
＜塗佈時的平坦性的評價（階差埋入平坦性）＞ 製作了在帶氧化膜的矽晶圓上形成有寬度5μm/間距5μm、高度5μm的Cu配線之Cu配線基板。藉由旋塗在該Cu配線基板上以乾燥後的膜厚成為10μm之方式塗佈各實施例及各比較例的感光性樹脂組成物，並以120℃乾燥3分鐘，從而形成了感光性樹脂膜。 利用高壓水銀燈對所獲得之感光性樹脂膜進行了300mJ/cm 2的曝光。之後，在環戊酮中浸漬了30秒。進而之後，在氮環境下，以170℃進行90分鐘的熱處理，從而在基板上形成了樹脂膜。 切開所獲得之帶樹脂膜的基板，並對其剖面進行研磨，藉由剖面SEM觀察，評價了感光性樹脂膜的表面的凹凸。將表面的凹凸為1μm以下者評價為優（良好），將表面的凹凸為1～3μm者評價為良（能夠使用之級別），將超過3μm者評價為不合格（無法使用之級別）。 <Evaluation of flatness during coating (level difference embedding flatness)> A Cu wiring board in which Cu wirings with a width of 5 μm/pitch of 5 μm and a height of 5 μm were formed on a silicon wafer with an oxide film was produced. The photosensitive resin composition of each example and each comparative example was applied by spin coating on this Cu wiring board so that the film thickness after drying became 10 micrometers, and it dried at 120 degreeC for 3 minutes, and the photosensitive resin was formed. membrane. The obtained photosensitive resin film was exposed to 300 mJ/cm 2 using a high-pressure mercury lamp. Thereafter, it was immersed in cyclopentanone for 30 seconds. Further, heat treatment was performed at 170° C. for 90 minutes in a nitrogen atmosphere to form a resin film on the substrate. The obtained board|substrate with a resin film was cut|disconnected, the cross-section was polished, and the roughness of the surface of the photosensitive resin film was evaluated by SEM observation of a cross-section. Surface irregularities of 1 μm or less were rated as excellent (good), those with surface irregularities of 1 to 3 μm were rated as good (level for use), and those exceeding 3 μm were rated as unacceptable (level for use).
＜常溫黏度變化率＞ 利用E型黏度計（TVE-25L）對剛摻合後的各實施例及各比較例的感光性樹脂組成物的黏度進行了測量。將此時的黏度設為A。之後，將各實施例及各比較例的感光性樹脂組成物的清漆在23℃保管7天，並再次測量了黏度。將此時的黏度設為B。 將黏度A及黏度B代入下述式，計算出黏度變化率。將黏度變化率為5%以下者評價為優，將超過5%且10%以下者評價為良，將超過10%者評價為不合格。為了獲得穩定之膜厚，黏度變化率低為較佳。 黏度變化率[%]={（黏度A-黏度B）/黏度A}×100 ＜Rate of Viscosity Change at Normal Temperature＞ The viscosity of the photosensitive resin composition of each Example and each comparative example immediately after blending was measured with the E-type viscometer (TVE-25L). Let the viscosity at this time be A. After that, the varnish of the photosensitive resin composition of each Example and each comparative example was stored at 23° C. for 7 days, and the viscosity was measured again. Let the viscosity at this time be B. Substitute viscosity A and viscosity B into the following formula to calculate the viscosity change rate. A viscosity change rate of 5% or less was evaluated as excellent, a viscosity change rate of more than 5% and 10% or less was evaluated as good, and a viscosity change rate of more than 10% was evaluated as unacceptable. In order to obtain a stable film thickness, a low viscosity change rate is better. Viscosity change rate [%]={(viscosity A-viscosity B)/viscosity A}×100
＜玻璃轉移溫度（Tg）＞ 對於利用與前述的（拉伸伸長率測量用試驗片的製作）相同的方法獲得之試驗片，使用熱機械分析裝置（Seiko Instruments Inc.製、TMA/SS6000），以10℃/分鐘的升溫速度加熱至300℃，並測量了所獲得之試驗片的熱膨脹率。 接著，依據所獲得之測量結果，由熱膨脹率的反曲點計算出硬化物的玻璃轉移溫度（Tg）。Tg的單位為℃。 ＜Glass transition temperature (Tg)＞ For the test piece obtained by the same method as above (preparation of test piece for measuring tensile elongation), use a thermomechanical analysis device (manufactured by Seiko Instruments Inc., TMA/SS6000) at a heating rate of 10°C/min. It was heated to 300° C., and the coefficient of thermal expansion of the obtained test piece was measured. Then, based on the obtained measurement results, the glass transition temperature (Tg) of the cured product was calculated from the inflection point of the thermal expansion coefficient. The unit of Tg is °C.
＜圖案形成性＞ 在表面具有3000Å的鍍銅層之12吋矽晶圓上，以乾燥後的膜厚成為5μm之方式旋塗各實施例及各比較例的感光性樹脂組成物，利用加熱板以120℃乾燥3分鐘，從而獲得了感光性樹脂膜。對該感光性樹脂膜，通過TOPPAN INC.製遮罩（測試圖No.1：描繪有寬度0.5～50μm的殘留圖案及沖孔圖案），使用i射線步進器（Canon Inc.製、FPA-5500iX），一邊改變曝光量，一邊照射了i射線。 對曝光後的膜，利用噴霧顯影機並使用環戊酮以2500轉顯影30秒，接著使用丙二醇單甲醚乙酸酯以2500轉顯影10秒，進而利用旋轉乾燥以2500轉風乾10秒之後，在加熱板上以120℃進行了4分鐘的乾燥。進而之後，在氮環境下，以170℃進行90分鐘的熱處理，從而獲得了帶圖案的樹脂膜。 對所獲得之圖案進行觀察，將開有小於5μmΦ的通孔者評價為優，將開有5μmΦ以上且小於10μmΦ的通孔者評價為良，將開有10μmΦ以上的通孔者評價為不合格。 ＜Pattern Formability＞ On a 12-inch silicon wafer with a copper-plated layer of 3000 Å on the surface, the photosensitive resin composition of each example and each comparative example was spin-coated so that the film thickness after drying became 5 μm, and dried at 120° C. for 3 hours using a hot plate. Minutes to obtain a photosensitive resin film. The photosensitive resin film was passed through a mask made by TOPPAN INC. (test pattern No. 1: a residual pattern and a punched hole pattern with a width of 0.5 to 50 μm were drawn), and an i-ray stepper (manufactured by Canon Inc., FPA- 5500iX), i-rays were irradiated while changing the exposure. The exposed film was developed with a spray developer at 2500 rpm for 30 seconds using cyclopentanone, then developed with propylene glycol monomethyl ether acetate at 2500 rpm for 10 seconds, and then air-dried at 2500 rpm for 10 seconds using spin drying. Drying was performed at 120° C. for 4 minutes on a hot plate. Furthermore, it heat-processed for 90 minutes at 170 degreeC in nitrogen atmosphere, and obtained the resin film with a pattern. Observation of the obtained patterns, the ones with the through holes of less than 5 μmΦ were evaluated as excellent, the ones with the through holes of 5 μmΦ or more and less than 10 μmΦ were evaluated as good, and the ones with the through holes of 10 μmΦ or more were evaluated as unacceptable .
【表1】
如表1所示，實施例1～8的感光性樹脂組成物與比較例1相比，拉伸伸長率及耐化學品性的結果均優異。又，實施例1～8的感光性樹脂組成物與比較例2相比，階差埋入平坦性的結果優異。As shown in Table 1, compared with Comparative Example 1, the photosensitive resin compositions of Examples 1 to 8 were excellent in both tensile elongation and chemical resistance. Moreover, the photosensitive resin composition of Examples 1-8 was excellent in the result of level difference embedding flatness compared with the comparative example 2.
本申請主張基於2021年6月7日申請之日本專利申請第2021-095212號的優先權，並將其公開的全部內容援用於此。This application claims priority based on Japanese Patent Application No. 2021-095212 for which it applied on June 7, 2021, and uses the entire disclosure content here.
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