TW202219630A - Photosensitive resin composition, method for producing electronic device, electronic device and method for producing photosensitive resin composition - Google Patents
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本發明係有關一種感光性樹脂組成物、電子裝置之製造方法、電子裝置及感光性樹脂組成物之製造方法。The present invention relates to a photosensitive resin composition, a method for producing an electronic device, an electronic device, and a method for producing the photosensitive resin composition.
在製造電子裝置時,為了形成永久膜(殘留於最終產品中之膜),使用感光性樹脂組成物。具體而言,對用於形成層間膜、表面保護膜、壩材等的永久膜(典型地為硬化膜)之感光性樹脂組成物進行了各種研究。In the manufacture of electronic devices, photosensitive resin compositions are used in order to form permanent films (films that remain in the final product). Specifically, various studies have been conducted on photosensitive resin compositions for forming permanent films (typically, cured films) such as interlayer films, surface protection films, and dam materials.
例如,專利文獻1中記載了一種感光性樹脂組成物,其相對於(A)聚合物(鹼溶性酚樹脂、聚羥基苯乙烯或聚羥基苯乙烯的衍生物)100質量份,含有(B)感光性重氮萘醌化合物1~100質量份、(C)有機溶劑100~1000質量份及(D)接著助劑(含烷氧基矽基的有機化合物)0.1~20質量份。
先前技術文獻
專利文獻
For example,
〔專利文獻1〕日本特開2012-063788號公報[Patent Document 1] Japanese Patent Laid-Open No. 2012-063788
[發明所欲解決之課題][The problem to be solved by the invention]
要求電子裝置中的永久膜具有各種特性。例如,永久膜要求具有良好的拉伸伸長特性,從而不易因外力而破裂。藉由永久膜具有此種特性,可提高電子裝置的產率及可靠性等。Permanent films in electronic devices are required to have various properties. For example, permanent films are required to have good tensile elongation properties so as not to be easily ruptured by external forces. With the permanent film having such characteristics, the productivity and reliability of the electronic device can be improved.
近年來,隨著電子裝置的進一步的升級化、複雜化及微細化等,對永久膜要求之性能日益提高,對拉伸伸長特性亦存在進一步的改良需求。In recent years, with the further upgrading, complication, and miniaturization of electronic devices, the performance required for the permanent film is increasing day by day, and there is also a need for further improvement in the tensile elongation properties.
因此,本發明人等以提供一種可形成具有良好的拉伸伸長特性之永久膜之感光性樹脂組成物為目的之一,對新的感光性樹脂組成物進行了研究。 [解決課題之技術手段] Therefore, the inventors of the present invention have studied a new photosensitive resin composition for one of the purposes of providing a photosensitive resin composition capable of forming a permanent film having favorable tensile elongation properties. [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 have completed the inventions provided below, thereby solving the above-mentioned problems.
依據本發明,提供一種感光性樹脂組成物,其為永久膜形成用的熱固性感光性樹脂組成物,且 含有樹脂和感光劑, 藉由使用波長780nm的光之光散射方式的粒子計數器在流速3g/分時的1分鐘的測量中計數之直徑0.5~20μm的粒子數為100以下。 According to the present invention, there is provided a photosensitive resin composition, which is a thermosetting photosensitive resin composition for forming a permanent film, and Contains resin and sensitizer, The number of particles with a diameter of 0.5 to 20 μm counted by a particle counter using a light scattering method of light having a wavelength of 780 nm in one minute of measurement at a flow rate of 3 g/min was 100 or less.
又,依據本發明,提供一種電子裝置之製造方法,其包括: 製膜步驟,使用上述的感光性樹脂組成物來形成感光性樹脂膜; 曝光步驟,對該感光性樹脂膜進行曝光;及 顯影步驟,對經曝光之該感光性樹脂膜進行顯影。 Also, according to the present invention, a method for manufacturing an electronic device is provided, comprising: In the film-forming step, the above-mentioned photosensitive resin composition is used to form a photosensitive resin film; an exposure step of exposing the photosensitive resin film; and In the developing step, the exposed photosensitive resin film is developed.
又,依據本發明,提供一種電子裝置,其具備永久膜, 該永久膜由上述的感光性樹脂組成物形成。 Further, according to the present invention, there is provided an electronic device including a permanent film, This permanent film is formed from the above-mentioned photosensitive resin composition.
又,依據本發明,提供一種感光性樹脂組成物之製造方法,其為上述的感光性樹脂組成物之製造方法,且包括藉由孔徑0.5μm以下的中空纖維膜過濾器而進行之過濾步驟。 [發明之效果] Further, according to the present invention, there is provided a method for producing a photosensitive resin composition, which is the method for producing the above-mentioned photosensitive resin composition and includes a filtration step by a hollow fiber membrane filter having a pore size of 0.5 μm or less. [Effect of invention]
藉由使用本發明的感光性樹脂組成物,能夠形成具有良好的拉伸伸長特性之永久膜。By using the photosensitive resin composition of the present invention, a permanent film having favorable tensile elongation properties can be formed.
以下,參閱圖式,對本發明的實施形態進行詳細說明。 在圖式中,對相同的構成要素標註相同的符號,並適當省略說明。 為了避免複雜化,在同一圖式內存在複數個相同的構成要素之情況下,有時會僅對一個標註符號,而不會對所有構成要素標註符號。 圖式僅係用於說明者。圖式中的各構件的形狀或尺寸比等,未必與實際物品對應。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same reference numerals are assigned to the same constituent elements, and descriptions thereof are appropriately omitted. In order to avoid complication, when there are a plurality of identical constituent elements in the same drawing, sometimes only one of the constituent elements is marked with a symbol, and all constituent elements are not marked with a symbol. The drawings are for illustrative purposes only. The shapes, size ratios, and the like of each member in the drawings do not necessarily correspond to actual articles.
在本說明書中,若無特別說明,則數值範圍的說明中的表述「X~Y」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」。In this specification, unless otherwise specified, the expression "X to Y" in the description of the numerical range means X or more and Y or less. For example, "1 to 5 mass %" means "1 mass % or more and 5 mass % or less".
在本說明書中的基(原子團)的表述中,未描述取代或未取代之表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)。 本說明書中的表述「(甲基)丙烯酸」表示包括丙烯酸和甲基丙烯酸這兩者之概念。關於「(甲基)丙烯酸酯」等的類似的表述亦相同。 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。 在本說明書中,若無特別說明,則用語「聚醯胺/聚醯亞胺樹脂」包括(i)含有聚醯胺結構但不含聚醯亞胺結構之樹脂、(ii)含有聚醯亞胺結構但不含聚醯胺結構之樹脂及(iii)含有聚醯胺結構和聚醯亞胺結構這兩者之樹脂這三種樹脂。又,在本說明書中,聚醯胺樹脂可以與聚醯胺結構一併含有聚醯亞胺結構,亦可以不含聚醯亞胺結構,聚醯亞胺樹脂可以與聚醯亞胺結構一併含有聚醯胺結構,亦可以不含聚醯胺結構。 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 expression of the group (atomic group) in the present specification, the expression not describing substitution or non-substitution includes both those having no substituent and those having a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). The expression "(meth)acrylic acid" in this specification means a concept including both acrylic acid and methacrylic acid. Similar expressions about "(meth)acrylate" and the like are also the same. 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. In this specification, unless otherwise specified, the term "polyamide/polyimide resin" includes (i) resins containing a polyamide structure but not containing a polyimide structure, (ii) resins containing polyamide These three resins are resins having an amine structure but not containing a polyamide structure and (iii) resins containing both a polyamide structure and a polyimide structure. In addition, in this specification, the polyimide resin may contain the polyimide structure together with the polyimide structure, or may not contain the polyimide structure, and the polyimide resin may contain the polyimide structure together with the polyimide structure. Contains a polyamide structure or may not contain a polyamide structure. 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, used in the meaning of the final product, etc.
<感光性樹脂組成物> 本實施形態的感光性樹脂組成物用於形成永久膜。亦即,本實施形態的感光性樹脂組成物不是暫時用作蝕刻時的遮罩並在使用後去除之光阻劑組成物。使用本實施形態的感光性樹脂組成物形成之永久膜組裝於電子裝置等的最終產品中。 本實施形態的感光性樹脂組成物為熱固性。具體而言,本實施形態的感光性樹脂組成物可以為以下中的某一個:(i)樹脂本身具有熱聚合性、交聯性、(ii)藉由除樹脂(可以為熱固性,亦可以為熱塑性)以外還含有交聯劑/聚合性單體等,組成物整體呈熱固性、(iii)藉由加熱引起閉環反應等的化學反應,藉此不溶性提高。 本實施形態的感光性樹脂組成物至少含有樹脂和感光劑。 當使本實施形態的感光性樹脂組成物通過使用波長780nm的光之光散射方式的粒子計數器時,在流速3g/分時的1分鐘的測量中計數之直徑0.5~20μm的粒子數為100以下。該粒子數較佳為50以下,更佳為20以下。粒子數並無下限,可以為0。從製造成本等的現實觀點考慮,粒子數例如為0.1以上,具體而言為1以上。 <Photosensitive resin composition> The photosensitive resin composition of this embodiment is used for forming a permanent film. That is, the photosensitive resin composition of the present embodiment is not a photoresist composition that is temporarily used as a mask during etching and is removed after use. The permanent film formed using the photosensitive resin composition of the present embodiment is incorporated in a final product such as an electronic device. The photosensitive resin composition of this embodiment is thermosetting. Specifically, the photosensitive resin composition of the present embodiment may be any of the following: (i) the resin itself has thermal polymerizability and crosslinking properties, (ii) by removing the resin (may be thermosetting or In addition to thermoplastic), a crosslinking agent, a polymerizable monomer, etc. are contained, the entire composition is thermosetting, and (iii) a chemical reaction such as a ring-closure reaction is caused by heating, whereby the insolubility is improved. The photosensitive resin composition of the present embodiment contains at least a resin and a photosensitizer. When the photosensitive resin composition of the present embodiment was passed through a particle counter using a light scattering method of light having a wavelength of 780 nm, the number of particles with a diameter of 0.5 to 20 μm counted in the measurement for 1 minute at a flow rate of 3 g/min was 100 or less. . The number of particles is preferably 50 or less, more preferably 20 or less. The number of particles has no lower limit and can be 0. The number of particles is, for example, 0.1 or more, specifically, 1 or more, from the practical viewpoints of production cost and the like.
關於由本實施形態的「粒子少的」感光性樹脂組成物形成之永久膜具有良好的拉伸伸長特性之理由,儘管只是推定,但可如下進行說明。 認為若永久膜中存在粒子,則該粒子所存在之位置會成為破裂的「開端」。因此,推定藉由減少用於形成永久膜之感光性樹脂組成物中的粒子,能夠減少破裂的「開端」,其結果,可獲得良好的拉伸伸長特性。 The reason why the permanent film formed from the photosensitive resin composition with "less particles" of the present embodiment has favorable tensile elongation properties is only an assumption, but it can be explained as follows. It is considered that if particles exist in the permanent film, the position where the particles exist will be the "start" of rupture. Therefore, it is presumed that by reducing the particles in the photosensitive resin composition for forming a permanent film, the "start" of cracks can be reduced, and as a result, favorable tensile elongation characteristics can be obtained.
作為附加效果,藉由減少感光性樹脂組成物的粒子,永久膜(硬化膜)與金屬基板之間的密接性亦趨於變得良好。推定這是因為,藉由減少粒子,會減少「剥離的開端」。As an additional effect, the adhesiveness between a permanent film (cured film) and a metal substrate also tends to become favorable by reducing the particle|grains of the photosensitive resin composition. It is presumed that by reducing the number of particles, the "start of peeling" is reduced.
順帶一提,關於蝕刻時使用之光阻劑組成物,已知若干個減少組成物中的粒子數之嘗試(例如,國際公開第2017/163922號等)。然而,在暫時用作蝕刻時的遮罩並在使用後去除之光阻劑中,通常不會要求「拉伸伸長特性」。為了「提高永久膜的拉伸伸長特性」而減少組成物中的粒子數之技術思想係基於本發明人等的獨自的研究者。Incidentally, regarding the photoresist composition used for etching, several attempts to reduce the number of particles in the composition are known (for example, International Publication No. 2017/163922, etc.). However, in photoresists that are temporarily used as masks during etching and removed after use, "stretch elongation properties" are generally not required. The technical idea of reducing the number of particles in the composition in order to "improve the tensile elongation characteristics of the permanent film" is based on the original researchers of the present inventors.
本實施形態的「粒子少的」感光性樹脂組成物可以藉由使用適當的素材並選擇適當的製造方法、製造條件來製造。例如,在製造感光性樹脂組成物時,藉由進行使用孔徑為0.2μm左右的聚丙烯製的中空纖維膜過濾器之過濾等,能夠製造出本實施形態的感光性樹脂組成物,詳細內容將在實施例等中進行說明。The photosensitive resin composition "with few particles" of the present embodiment can be produced by using appropriate materials and selecting appropriate production methods and production conditions. For example, when the photosensitive resin composition is produced, the photosensitive resin composition of the present embodiment can be produced by performing filtration using a polypropylene hollow fiber membrane filter having a pore diameter of about 0.2 μm. It will be described in Examples and the like.
以下,對本實施形態的感光性樹脂組成物可含有之成分和本實施形態的感光性樹脂組成物的性狀、物性等進行說明。Hereinafter, components which can be contained in the photosensitive resin composition of the present embodiment, and properties, physical properties, and the like of the photosensitive resin composition of the present embodiment will be described.
(樹脂) 鑑於上述的「由於粒子少,因此破裂的「開端」少」之推定機制,認為無論是哪種樹脂系,本實施形態的感光性樹脂組成物皆可獲得良好的拉伸伸長特性。 以下,對從電子裝置製造中的適用的觀點考慮尤其較佳地使用之樹脂亦即環氧樹脂及聚醯胺/聚醯亞胺樹脂進行具體說明。 (resin) In view of the above-mentioned estimation mechanism that "because there are few particles, there are few "starts" of cracking", it is considered that the photosensitive resin composition of the present embodiment can obtain good tensile elongation characteristics regardless of the resin type. Hereinafter, the epoxy resin and the polyimide/polyimide resin, which are particularly preferably used resins from the viewpoint of application in the manufacture of electronic devices, will be specifically described.
·環氧樹脂 作為環氧樹脂,例如可以使用在一個分子中具有兩個以上的環氧基之環氧樹脂。環氧樹脂可以使用單體、低聚物及聚合物全部。環氧樹脂的分子量或分子結構並無特別限定。 ·Epoxy resin As the epoxy resin, for example, an epoxy resin having two or more epoxy groups in one molecule can be used. As the epoxy resin, all monomers, oligomers and polymers can be used. The molecular weight or molecular structure of the epoxy resin is not particularly limited.
作為環氧樹脂,例如可舉出苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、甲酚萘酚型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基(biphenyl aralkyl)型環氧樹脂、萘骨架型環氧樹脂、雙酚A型環氧樹脂、雙酚A二環氧丙基醚型環氧樹脂、雙酚F型環氧樹脂、雙酚F二環氧丙基醚型環氧樹脂、雙酚S二環氧丙基醚型環氧樹脂、環氧丙基醚型環氧樹脂、芳香族多官能環氧樹脂、脂肪族環氧樹脂、脂肪族多官能環氧樹脂等。 又,還可舉出3,4-環氧環己基甲基(3,4-環氧環己烷)羧酸酯、3,4-環氧-6-甲基環己基甲基(3,4-環氧-6-甲基環己烷)羧酸酯、雙(3,4-環氧-6-甲基環己基甲基)己二酸酯、二環戊二烯氧化物、雙(2,3-環氧環戊基)醚或Daicel Corporation製的CELLOXIDE 2021P、CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085、CELLOXIDE 8000、EPOLEAD GT401等的脂環式環氧樹脂。 進而,還可舉出2,2’-(((((1-(4-(2-(4-(環氧乙-2-基甲氧基)苯基)丙-2-基)苯基)乙-1,1-二基)雙(4,1-伸苯基))雙(伸氧基))雙(亞甲基))雙(環氧乙烷))(例如,Printec Corporation製的Techmore VG3101L)、EPOLIGHT 100MF(kyoeisha Chemical Co.,Ltd.製)、EPIOL TMP(NOF CORPORATION製)等的脂肪族聚環氧丙基醚、1,1,3,3,5,5-六甲基-1,5-雙(3-(環氧乙-2-基甲氧基)丙基)三矽氧烷(例如,DMS-E09(GELEST, INC.製))等。 環氧樹脂可以單獨使用,亦可以組合複數種來使用。 Examples of epoxy resins include phenol novolac epoxy resins, cresol novolac epoxy resins, cresol naphthol epoxy resins, biphenyl epoxy resins, biphenyl aralkyl ) type epoxy resin, naphthalene skeleton type epoxy resin, bisphenol A type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, bisphenol F type epoxy resin, bisphenol F diglycidyl Base ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, glycidyl ether type epoxy resin, aromatic polyfunctional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional ring Oxygen resin etc. Furthermore, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane)carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxycyclohexylmethyl) - Epoxy-6-methylcyclohexane)carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentadiene oxide, bis(2 , 3-epoxycyclopentyl) ether or CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, EPOLEAD GT401 and other alicyclic epoxy resins manufactured by Daicel Corporation. Furthermore, 2,2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl ) ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane)) (for example, manufactured by Printec Corporation Aliphatic polyglycidyl ether such as Techmore VG3101L), EPOLIGHT 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), EPIOL TMP (manufactured by NOF CORPORATION), 1,1,3,3,5,5-hexamethyl -1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (for example, DMS-E09 (manufactured by GELEST, INC.)) and the like. The epoxy resin may be used alone or in combination of a plurality of types.
環氧樹脂可以含有在分子內具有兩個以上的環氧基之固體環氧樹脂。作為固體環氧樹脂,可以使用具有兩個以上的環氧基且在25℃(室溫)為固體者。藉此,能夠提高感光性樹脂組成物的樹脂膜中的機械特性。The epoxy resin may contain a solid epoxy resin having two or more epoxy groups in the molecule. As a solid epoxy resin, what has two or more epoxy groups and is solid at 25 degreeC (room temperature) can be used. Thereby, the mechanical properties in the resin film of the photosensitive resin composition can be improved.
環氧樹脂在分子內含有3官能以上的多官能環氧樹脂(亦即,在一個分子中具有三個以上的環氧基之多官能環氧樹脂)為較佳。藉此,膜充分硬化,例如能夠提高作為永久膜的耐熱性或耐久性。又,耐熱性高是指,即使加熱,永久膜的性狀亦不易發生變化,這使得平坦性進一步提高。It is preferable that the epoxy resin contains a polyfunctional epoxy resin having three or more functions in a molecule (that is, a polyfunctional epoxy resin having three or more epoxy groups in one molecule). Thereby, the film is sufficiently cured, and for example, the heat resistance and durability as a permanent film can be improved. In addition, high heat resistance means that the properties of the permanent film are not easily changed even when heated, which further improves the flatness.
作為3官能以上的多官能環氧樹脂,例如選自由苯酚酚醛(phenol novolac)型環氧樹脂、甲酚酚醛(cresol novolac)型環氧樹脂、三苯基甲烷型環氧樹脂、二環戊二烯型環氧樹脂、雙酚A型環氧樹脂及四甲基雙酚F型環氧樹脂組成之群中的一種以上的環氧樹脂為較佳。其中,三苯基甲烷型環氧樹脂或酚醛型環氧樹脂為更佳。藉此,在提高樹脂膜的耐熱性之同時,能夠實現適當的熱膨脹係數。The trifunctional or higher polyfunctional epoxy resin is, for example, selected from phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene One or more kinds of epoxy resins selected from the group consisting of vinyl-type epoxy resins, bisphenol A-type epoxy resins, and tetramethylbisphenol F-type epoxy resins are preferred. Among them, triphenylmethane type epoxy resin or novolac type epoxy resin is more preferable. Thereby, while improving the heat resistance of a resin film, an appropriate thermal expansion coefficient can be achieved.
環氧樹脂可以含有在分子中具有兩個以上的環氧基之液態環氧樹脂。液態環氧樹脂發揮成膜劑的功能,能夠改善感光性樹脂組成物的樹脂膜的脆性。The epoxy resin may contain a liquid epoxy resin having two or more epoxy groups in the molecule. The liquid epoxy resin functions as a film-forming agent and can improve the brittleness of the resin film of the photosensitive resin composition.
作為液態環氧樹脂,可以使用具有兩個以上的環氧基且在室溫25℃為液態之環氧化合物。液態環氧樹脂在25℃時的黏度例如為1~8000mPa·s,較佳為5~1500mPa·s,更佳為10~1400mPa·s。As a liquid epoxy resin, the epoxy compound which has two or more epoxy groups and is liquid at room temperature 25 degreeC can be used. The viscosity of the liquid epoxy resin at 25° C. is, for example, 1 to 8000 mPa·s, preferably 5 to 1500 mPa·s, and more preferably 10 to 1400 mPa·s.
作為液態環氧樹脂,例如可以含有選自由雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、烷基二環氧丙基醚及脂環式環氧樹脂組成之群中的一種以上。該等可以單獨使用,亦可以組合兩種以上來使用。其中,從顯影後的裂紋減少之觀點考慮,可以使用烷基二環氧丙基醚。The liquid epoxy resin may contain, for example, a group selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, alkyl diglycidyl ether, and alicyclic epoxy resins. of more than one. These may be used alone or in combination of two or more. Among them, alkyl diglycidyl ethers can be used from the viewpoint of reduction of cracks after development.
液態環氧樹脂的環氧當量例如為100~200g/eq,較佳為105~180g/eq,進一步較佳為110~170g/eq。藉此,能夠改善樹脂膜的脆性。The epoxy equivalent of the liquid epoxy resin is, for example, 100 to 200 g/eq, preferably 105 to 180 g/eq, and more preferably 110 to 170 g/eq. Thereby, the brittleness of the resin film can be improved.
液態環氧樹脂的含量的下限值相對於感光性樹脂組成物的所有非揮發成分例如為5質量%以上,較佳為10質量%以上,更佳為15質量%以上。藉此,能夠改善最終得到之硬化膜的脆性。 液態環氧樹脂含量的上限值相對於感光性樹脂組成物的所有非揮發成分例如為40質量%以下,較佳為35質量%以下,更佳為30質量%以下。藉此,能夠實現硬化膜的膜特性的平衡。 The lower limit of the content of the liquid epoxy resin is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, based on all nonvolatile components in the photosensitive resin composition. Thereby, the brittleness of the cured film finally obtained can be improved. The upper limit of the liquid epoxy resin content is, for example, 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less, based on the total nonvolatile content of the photosensitive resin composition. Thereby, the balance of the film characteristics of a cured film can be achieved.
環氧樹脂的含量相對於感光性樹脂組成物的所有非揮發成分例如為40質量%以上,較佳為45質量%以上,更佳為50質量%以上。藉此,能夠提高最終得到之硬化膜的耐熱性或機械強度。 環氧樹脂含量相對於感光性樹脂組成物的所有非揮發成分例如為90質量%以下,較佳為85質量%以下,更佳為80質量%以下。藉此,能夠提高圖案形成性。 The content of the epoxy resin is, for example, 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more with respect to all the nonvolatile components in the photosensitive resin composition. Thereby, the heat resistance and mechanical strength of the cured film finally obtained can be improved. The epoxy resin content is, for example, 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less with respect to all nonvolatile components in the photosensitive resin composition. Thereby, the pattern formability can be improved.
·聚醯胺/聚醯亞胺樹脂 聚醯胺/聚醯亞胺樹脂含有由下述通式(PA-1)表示之結構單元和/或由下述通式(PI-1)表示之結構單元為較佳。 ·Polyamide/polyimide resin The polyamide/polyimide resin preferably contains a structural unit represented by the following general formula (PA-1) and/or a structural unit represented by the following general formula (PI-1).
通式(PA-1)及(PI-1)中, X為2價的有機基, Y為4價的有機基。 In general formulas (PA-1) and (PI-1), X is a divalent organic group, Y is a tetravalent organic group.
在通式(PA-1)及(PI-1)中,X及Y中的至少一個較佳為含氟原子的基。從有機溶劑溶解性的觀點考慮,在通式(PA-1)及(PI-1)中,X及Y皆為含氟原子的基為較佳。In the general formulae (PA-1) and (PI-1), at least one of X and Y is preferably a group containing a fluorine atom. In general formulas (PA-1) and (PI-1), it is preferable that both X and Y are groups containing a fluorine atom from the viewpoint of solubility in organic solvents.
在通式(PA-1)及(PI-1)中,X的2價的有機基和/或Y的4價的有機基含有芳香環結構為較佳,含有苯環結構為更佳。藉此,趨於進一步提高耐熱性。這裡的苯環可以被氟原子、氟化烷基(較佳為三氟甲基)等的含氟原子的基取代,亦可以被其他基取代。 通式(PA-1)及(PI-1)中的X的2價的有機基和/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。作為這裡的2價的連結基,可舉出伸烷基、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)及(PI-1)中,X的2價的有機基的碳數例如為6~30。 在通式(PA-1)及(PI-1)中,Y的4價的有機基的碳數例如為6~20。 通式(PI-1)中的兩個醯亞胺環分別為5員環為較佳。 In the general formulae (PA-1) and (PI-1), the divalent organic group of X and/or the tetravalent organic group of Y preferably contain an aromatic ring structure, and more preferably contain a benzene ring structure. Thereby, the heat resistance tends to be further improved. The benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom, a fluorinated alkyl group (preferably a trifluoromethyl group), or other groups. In the general formulae (PA-1) and (PI-1), the divalent organic group of X and/or the tetravalent organic group of Y have 2 to 6 benzene rings and are bonded via a single bond or a divalent linking group The resulting structure is better. As a divalent linking group here, an alkylene group, a fluorinated alkylene group, an ether group, etc. are mentioned. The alkylene group and the fluorinated alkylene group may be linear or branched. In general formula (PA-1) and (PI-1), the carbon number of the divalent organic group of X is 6-30, for example. In general formula (PA-1) and (PI-1), the carbon number of the tetravalent organic group of Y is 6-20, for example. Preferably, the two imide rings in the general formula (PI-1) are 5-membered rings, respectively.
聚醯胺/聚醯亞胺樹脂含有由下述通式(PA-2)表示之結構單元和/或由下述通式(PI-2)表示之結構單元為更佳。More preferably, the polyamide/polyimide resin contains a structural unit represented by the following general formula (PA-2) and/or a structural unit represented by the following general formula (PI-2).
通式(PA-2)及(PI-2)中, X的含義與通式(PA-1)及(PI-1)中的X的含義相同, Y’表示單鍵、羰基或伸烷基。 In general formula (PA-2) and (PI-2), The meaning of X is the same as that of X in the general formula (PA-1) and (PI-1), Y' represents a single bond, carbonyl or alkylene.
關於X的具體的態樣,含義與通式(PA-1)及(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,較佳為1~4,進一步較佳為1~3。 Regarding the specific aspect of X, the meaning is the same as that described in the general formulae (PA-1) and (PI-1). The alkylene group of Y' may be linear or branched. It is preferable that some or all of the hydrogen atoms of the alkylene group of Y' are substituted with fluorine atoms. The number of carbon atoms in the alkylene group of Y' is, for example, 1-6, preferably 1-4, and more preferably 1-3.
從減小形成硬化膜時的收縮量之觀點等考慮,本實施形態的感光性樹脂組成物含有聚醯亞胺樹脂為較佳,含有具有醯亞胺環結構之聚醯亞胺樹脂為更佳。 將聚醯亞胺樹脂中所含之醯亞胺基的莫耳數設為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(%)表示之醯亞胺化率較佳為90%以上,更佳為95%以上,進一步較佳為98%以上。簡而言之,聚醯亞胺樹脂為不具有或具有少量的開環之醯胺結構且具有大量的閉環之醯亞胺結構之樹脂為較佳。藉由使用此種聚醯亞胺樹脂,能夠進一步抑制加熱導致的收縮(硬化收縮)(這是因為,不會發生由閉環反應引起的脫水)。藉此,能夠實現電子裝置的可靠性的進一步提高或硬化膜的平坦性的進一步提高等。 作為一例,醯亞胺化率可以從NMR譜中的與醯胺基對應的峰的面積或與醯亞胺基對應的峰的面積等得知。作為另一例,醯亞胺化率可以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基對應的峰的面積等得知。 From the viewpoint of reducing the amount of shrinkage at the time of forming the cured film, etc., the photosensitive resin composition of the present embodiment preferably contains a polyimide resin, and more preferably contains a polyimide resin having an imide ring structure . When the number of moles of imide groups contained in the polyimide resin is IM, and the number of moles of imide groups contained in the polyimide resin is AM, the formula is {IM/(IM The imidization rate represented by +AM)}×100(%) is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. In short, it is preferable that the polyimide resin has no or a small amount of ring-opened imide structures and a large amount of ring-closed imide structures. By using such a polyimide resin, shrinkage (hardening shrinkage) due to heating can be further suppressed (this is because dehydration due to ring-closure reaction does not occur). Thereby, the further improvement of the reliability of an electronic device, the further improvement of the flatness of a cured film, etc. can be aimed at. As an example, the imidization rate can be known from the area of the peak corresponding to the imino group in the NMR spectrum, the area of the peak corresponding to the imino group, or the like. As another example, the imidization rate can be known from the area of the peak corresponding to the imino group in the infrared absorption spectrum, the area of the peak corresponding to the imino group, or the like.
聚醯胺/聚醯亞胺樹脂含有氟原子為較佳。作為本發明人等的見解,含有氟原子之聚醯胺/聚醯亞胺樹脂相較於不含氟原子者,有機溶劑溶解性趨於良好。因此,藉由使用含有氟原子之聚醯胺/聚醯亞胺樹脂,容易使感光性樹脂組成物的性狀成為清漆狀。 含有氟原子之聚醯胺/聚醯亞胺樹脂中的氟原子的量(質量比率)例如為1~30質量%,較佳為3~28質量%,更佳為5~25質量%。藉由樹脂中含有一定程度大量的氟原子,容易獲得充分的有機溶劑溶解性。另一方面,從與其他性能之間的平衡的觀點考慮,氟原子的量不過多為較佳。 Preferably, the polyimide/polyimide resin contains fluorine atoms. According to the findings of the present inventors, the polyimide/polyimide resin containing fluorine atoms tends to have better solubility in organic solvents than those containing no fluorine atoms. Therefore, by using the polyimide/polyimide resin containing a fluorine atom, the properties of the photosensitive resin composition can be easily made into a varnish-like state. The amount (mass ratio) of fluorine atoms in the fluorine atom-containing polyimide/polyimide resin is, for example, 1 to 30 mass %, preferably 3 to 28 mass %, and more preferably 5 to 25 mass %. Sufficient organic solvent solubility is easily obtained by containing a certain amount of fluorine atoms in the resin. On the other hand, from the viewpoint of balance with other properties, it is preferable that the amount of fluorine atoms is not excessive.
藉由對聚醯胺/聚醯亞胺樹脂的末端進行各種設計,例如能夠進一步提高硬化物的機械物性(拉伸伸長率等)。By variously designing the ends of the polyimide/polyimide resin, for example, the mechanical properties (tensile elongation, etc.) of the cured product can be further improved.
作為一例,聚醯胺/聚醯亞胺樹脂在其末端具有與環氧基反應而可形成鍵之基為較佳。作為此種基,可舉出酸酐基、羥基、胺基、羧基等。As an example, it is preferable that the polyimide/polyimide resin has a group capable of forming a bond by reacting with an epoxy group at the terminal thereof. As such a group, an acid anhydride group, a hydroxyl group, an amino group, a carboxyl group, etc. are mentioned.
較佳為,聚醯胺/聚醯亞胺樹脂在其末端具有酸酐基。在本實施形態的感光性樹脂組成物中,酸酐基和環氧基容易充分地形成鍵。 酸酐基較佳為具有環狀結構的酸酐骨架之基。這裡的「環狀結構」較佳為5員環或6員環,更佳為5員環。 Preferably, the polyimide/polyimide resin has an acid anhydride group at its terminal. In the photosensitive resin composition of this embodiment, an acid anhydride group and an epoxy group are easy to form a bond sufficiently. The acid anhydride group is preferably a group of an acid anhydride skeleton having a cyclic structure. The "ring structure" here is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.
作為對末端結構的補充說明,聚醯胺/聚醯亞胺樹脂在其末端不具有順丁烯二醯亞胺結構為較佳。As a supplementary explanation for the terminal structure, it is preferable that the polyamide/polyimide resin does not have a maleimide structure at its terminal.
聚醯胺樹脂典型地可以藉由使二胺與酸二酐反應(縮聚)來獲得。聚醯亞胺樹脂可以藉由使聚醯胺樹脂醯亞胺化(閉環反應)來獲得。又,亦可以根據需要在聚合物末端導入所希望的官能基。關於具體反應條件,可以參考後述的實施例和國際公開第2016/172092號的實施例的記載等。Polyamide resins can typically be obtained by reacting (polycondensation) a diamine with an acid dianhydride. The polyimide resin can be obtained by imidization (ring closing reaction) of the polyimide resin. Moreover, a desired functional group can also be introduce|transduced into a polymer terminal as needed. Regarding specific reaction conditions, the descriptions of Examples described later and International Publication No. WO 2016/172092, and the like can be referred to.
在最終得到之聚醯胺/聚醯亞胺樹脂中,二胺作為通式(PA-1)或(PI-1)中的2價的有機基X而併入到聚合物中。又,酸二酐作為通式(PA-1)或(PI-1)中的4價的有機基Y而併入到聚合物中。 在聚醯胺/聚醯亞胺樹脂的合成中,可以使用一種或兩種以上的二胺,又,可以使用一種或兩種以上的酸二酐。 In the resulting polyamide/polyimide resin, the diamine is incorporated into the polymer as a divalent organic group X in the general formula (PA-1) or (PI-1). Moreover, the acid dianhydride is incorporated into the polymer as the tetravalent organic group Y in the general formula (PA-1) or (PI-1). In the synthesis of the polyimide/polyimide resin, one or two or more diamines may be used, and one or two or more acid dianhydrides may be used.
作為原料二胺,例如可舉出3,4’-二胺基二苯基醚(3,4’-ODA)、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯(TFMB)、3,3’,5,5’-四甲基聯苯胺、2,3,5,6-四甲基-1,4-苯二胺、3,3’-二胺基二苯基碸、3,3’二甲基聯苯胺、3,3’-雙(三氟甲基)聯苯胺、2,2’-雙(對胺基苯基)六氟丙烷、雙(三氟甲氧基)聯苯胺(TFMOB)、2,2’-雙(五氟乙氧基)聯苯胺(TFEOB)、2,2’-三氟甲基-4,4’-氧基二苯胺(OBABTF)、2-苯基-2-三氟甲基-雙(對胺基苯基)甲烷、2-苯基-2-三氟甲基-雙(間胺基苯基)甲烷、2,2’-雙(2-七氟異丙氧基-四氟乙氧基)聯苯胺(DFPOB)、2,2-雙(間胺基苯基)六氟丙烷(6-FmDA)、2,2-雙(3-胺基-4-甲基苯基)六氟丙烷、3,6-雙(三氟甲基)-1,4-二胺基苯(2TFMPDA)、1-(3,5-二胺基苯基)-2,2-雙(三氟甲基)-3,3,4,4,5,5,5-七氟戊烷、3,5-二胺基三氟甲苯(3,5-DABTF)、3,5-二胺基-5-(五氟乙基)苯、3,5-二胺基-5-(七氟丙基)苯、2,2’-二甲基聯苯胺(DMBZ)、2,2’,6,6’-四甲基聯苯胺(TMBZ)、3,6-二胺基-9,9-雙(三氟甲基)二苯并哌喃(6FCDAM)、3,6-二胺基-9-三氟甲基-9-苯基二苯并哌喃(3FCDAM)、3,6-二胺基-9,9-二苯基二苯并哌喃等。As the raw material diamine, for example, 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl) ) Biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diamine bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, bis( Trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydiphenylamine (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2, 2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2 -Bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5- diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminotrifluorotoluene (3 ,5-DABTF), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethyl Benzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)dibenzopyran ( 6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenyldibenzopyran (3FCDAM), 3,6-diamino-9,9-diphenyldibenzopyran Nan and so on.
作為原料酸二酐,例如可舉出焦蜜石酸二酐(PMDA)、二苯基醚-3,3’,4,4’-四羧酸二酐(ODPA)、二苯甲酮-3,3’,4,4’-四羧酸二酐(BTDA)、聯苯-3,3’,4,4’-四羧酸二酐(BPDA)、二苯基碸-3,3’,4,4’-四羧酸二酐(DSDA)、二苯基甲-3,3’,4,4’-四羧酸二酐、2,2-雙(3,4-酞酸酐)丙烷、2,2-雙(3,4-酞酸酐)-1,1,1,3,3,3-六氟丙烷(6FDA)等。當然,可使用之酸二酐並不僅限定於此。酸二酐可以使用一種或兩種以上。As the raw material acid dianhydride, for example, pyromic acid dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3 ,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenyl-3,3', 4,4'-tetracarboxylic dianhydride (DSDA), diphenylmethyl-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA), etc. Of course, the acid dianhydride that can be used is not limited to this. One or two or more kinds of acid dianhydrides can be used.
以莫耳比計,二胺和酸二酐的使用比率基本上為1:1。但是,為了獲得所希望的末端結構,亦可以過多地使用其中一個。具體而言,藉由過多地使用二胺,聚醯胺/聚醯亞胺樹脂的末端(兩個末端)容易成為胺基。另一方面,藉由過多地使用酸二酐,聚醯胺/聚醯亞胺樹脂的末端(兩個末端)容易成為酸酐基。如上所述,在本實施形態中,聚醯胺/聚醯亞胺樹脂在其末端具有酸酐基為較佳。因此,在本實施形態中,在合成聚醯胺/聚醯亞胺樹脂時,過多地使用酸二酐為較佳。The diamine and dianhydride are used in a substantially 1:1 ratio on a molar basis. However, in order to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using too much diamine, the terminal (both terminals) of the polyimide/polyimide resin is likely to become an amine group. On the other hand, when the acid dianhydride is used too much, the terminal (both terminals) of the polyimide/polyimide resin tends to become an acid anhydride group. As described above, in the present embodiment, the polyamide/polyimide resin preferably has an acid anhydride group at its terminal. Therefore, in this embodiment, when synthesizing a polyimide/polyimide resin, it is preferable to use too much acid dianhydride.
亦可以使某種試劑與藉由縮聚而得之聚醯胺/聚醯亞胺樹脂的末端的胺基和/或酸酐基反應,從而使樹脂末端具有所希望的官能基。The terminal amine group and/or acid anhydride group of the polyimide/polyimide resin obtained by polycondensation can also be reacted with a certain reagent, so that the terminal of the resin has a desired functional group.
聚醯胺/聚醯亞胺樹脂的重量平均分子量例如為5000~100000,較佳為7000~75000,更佳為10000~50000。由於聚醯胺/聚醯亞胺樹脂的重量平均分子量大至一定程度,因此例如能夠獲得硬化膜的充分的耐熱性。又,由於聚醯胺/聚醯亞胺樹脂的重量平均分子量不過大,因此容易使聚醯胺/聚醯亞胺樹脂溶解於有機溶劑。 重量平均分子量通常可以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 weight average molecular weight of the polyamide/polyimide resin is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000. Since the weight average molecular weight of the polyimide/polyimide resin is large to some extent, for example, sufficient heat resistance of the cured film can be obtained. In addition, since the weight average molecular weight of the polyamide/polyimide resin is not too large, it is easy to dissolve the polyamide/polyimide resin in an organic solvent. The weight average molecular weight can usually be determined by a gel permeation chromatography (GPC) method using polystyrene as a standard substance.
順帶一提,在使用聚醯胺/聚醯亞胺樹脂之情況下,與環氧樹脂併用為較佳。環氧樹脂的具體例如上所述。在併用聚醯胺/聚醯亞胺樹脂和環氧樹脂之情況下,其量相對於聚醯胺樹脂和/或聚醯亞胺樹脂100質量份例如為0.5~30質量份,較佳為1~20質量份,進一步較佳為3~15質量份。Incidentally, in the case of using a polyimide/polyimide resin, it is preferable to use it together with an epoxy resin. Specific examples of the epoxy resin are as described above. When using a polyamide/polyimide resin and an epoxy resin together, the amount thereof is, for example, 0.5 to 30 parts by mass, preferably 1, with respect to 100 parts by mass of the polyamide resin and/or the polyimide resin. to 20 parts by mass, more preferably 3 to 15 parts by mass.
(苯氧基樹脂) 本實施形態的感光性樹脂組成物含有苯氧基樹脂為較佳。尤其,在本實施形態的感光性樹脂組成物含有環氧樹脂之情況下,併用環氧樹脂和苯氧基樹脂為較佳。認為藉由使用苯氧基樹脂,例如可提高所形成之膜的可撓性。 「苯氧基樹脂」狹義上是指由雙酚類和環氧氯丙烷合成之聚羥基聚醚,但在本說明書中,使多官能環氧樹脂和多官能酚類複加成反應(polyaddition reaction)而得之高分子(廣義的苯氧基樹脂)亦包括在苯氧基樹脂中。 (phenoxy resin) It is preferable that the photosensitive resin composition of this embodiment contains a phenoxy resin. In particular, when the photosensitive resin composition of the present embodiment contains an epoxy resin, it is preferable to use an epoxy resin and a phenoxy resin in combination. It is considered that by using a phenoxy resin, for example, the flexibility of the formed film can be improved. "Phenoxy resin" refers to a polyhydroxy polyether synthesized from bisphenols and epichlorohydrin in a narrow sense, but in this specification, a polyaddition reaction between a polyfunctional epoxy resin and a polyfunctional phenol is used. ) and the resulting polymer (phenoxy resin in a broad sense) is also included in the phenoxy resin.
作為苯氧基樹脂,例如可舉出雙酚A型苯氧基樹脂、雙酚F型苯氧基樹脂、雙酚A型和雙酚F型的共聚苯氧基樹脂、聯苯型苯氧基樹脂、雙酚S型苯氧基樹脂、聯苯型苯氧基樹脂和雙酚S型苯氧基樹脂的共聚苯氧基樹脂等。其中,雙酚A型苯氧基樹脂或雙酚A型和雙酚F型的共聚苯氧基樹脂為較佳。 苯氧基樹脂可以單獨使用,亦可以併用兩種以上。 Examples of phenoxy resins include bisphenol A-type phenoxy resins, bisphenol F-type phenoxy resins, copolymerized phenoxy resins of bisphenol A-type and bisphenol F-type, and biphenyl-type phenoxy resins. Base resin, bisphenol S type phenoxy resin, biphenyl type phenoxy resin and copolymerized phenoxy resin of bisphenol S type phenoxy resin, etc. Among them, bisphenol A type phenoxy resin or bisphenol A type and bisphenol F type copolymerized phenoxy resin are preferable. The phenoxy resin may be used alone or in combination of two or more.
苯氧基樹脂的重量平均分子量(Mw)較佳為10,000~100,000,更佳為20,000~80,000,進一步較佳為35,000~80,000。 由於苯氧基樹脂的Mw相對較大,因此能夠進一步抑制硬化收縮,並且能夠進一步提高平坦性。儘管該機制的細節尚不明確,但推測:若Mw相對較大,則分子鏈的熱運動受到抑制,其結果,平坦性進一步提高。 另一方面,從溶劑溶解性等的觀點考慮,苯氧基樹脂的Mw為100,000以下為較佳。 重量平均分子量例如作為凝膠滲透層析(GPC)法的聚苯乙烯換算值而被測量。 The weight average molecular weight (Mw) of the phenoxy resin is preferably from 10,000 to 100,000, more preferably from 20,000 to 80,000, and even more preferably from 35,000 to 80,000. Since the Mw of the phenoxy resin is relatively large, the curing shrinkage can be further suppressed, and the flatness can be further improved. Although the details of this mechanism are not clear, it is presumed that when the Mw is relatively large, the thermal motion of the molecular chain is suppressed, and as a result, the flatness is further improved. On the other hand, from the viewpoint of solvent solubility and the like, the Mw of the phenoxy resin is preferably 100,000 or less. The weight-average molecular weight is measured, for example, as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
作為苯氧基樹脂,可以在分子鏈的兩個末端或分子鏈的內部具有環氧基等的反應性基。苯氧基樹脂中的反應性基為能夠與環氧樹脂中的環氧基進行交聯反應者。藉由使用此種苯氧基樹脂,能夠提高樹脂膜中的耐溶劑性或耐熱性。The phenoxy resin may have reactive groups such as epoxy groups at both ends of the molecular chain or inside the molecular chain. The reactive group in the phenoxy resin is one that can undergo a crosslinking reaction with the epoxy group in the epoxy resin. By using such a phenoxy resin, the solvent resistance and heat resistance in a resin film can be improved.
作為苯氧基樹脂,較佳地使用在25℃為固體者。具體而言,較佳地使用非揮發成分為90質量%以上的苯氧基樹脂。藉由使用此種苯氧基樹脂,能夠使硬化物的機械特性良好。As a phenoxy resin, what is solid at 25 degreeC is used preferably. Specifically, a phenoxy resin having a nonvolatile content of 90% by mass or more is preferably used. By using such a phenoxy resin, the mechanical properties of the cured product can be improved.
苯氧基樹脂含量的下限值相對於環氧樹脂或聚醯胺/聚醯亞胺樹脂100質量份較佳為20質量份以上,更佳為25質量份以上,進一步較佳為30質量份以上。藉此,能夠獲得充分的可撓性。又,認為可充分獲得作為推定機制而既述之抑制過度的熱硬化或藉由流動等使膜表面平坦化之效果。 苯氧基樹脂含量的上限值相對於環氧樹脂或聚醯胺/聚醯亞胺樹脂100質量份較佳為60質量份以下,更佳為55質量份以下,進一步較佳為50質量份以下。藉此,苯氧基樹脂容易充分溶解於後述的溶劑,從而能夠獲得塗佈性優異的感光性樹脂組成物。 The lower limit of the phenoxy resin content is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass relative to 100 parts by mass of the epoxy resin or polyamide/polyimide resin above. Thereby, sufficient flexibility can be obtained. In addition, it is considered that the effects of suppressing excessive thermal hardening and flattening the film surface by flow, etc., which are estimated mechanisms, can be sufficiently obtained. The upper limit of the phenoxy resin content is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and further preferably 50 parts by mass relative to 100 parts by mass of the epoxy resin or polyamide/polyimide resin the following. Thereby, the phenoxy resin can be easily and fully dissolved in the solvent mentioned later, and the photosensitive resin composition excellent in coatability can be obtained.
本實施形態的感光性樹脂組成物可以含有苯氧基樹脂以外的其他熱塑性樹脂。作為此種熱塑性樹脂,可舉出聚乙烯縮醛樹脂、(甲基)丙烯酸系樹脂、聚醯胺系樹脂(例如,尼龍等)、熱塑性胺酯系樹脂、聚烯烴系樹脂(例如,聚乙烯、聚丙烯等)、聚碳酸酯、聚酯系樹脂(例如,聚對酞酸乙二酯、聚對酞酸丁二酯等)、聚縮醛、聚伸苯硫醚、聚醚醚酮、液晶聚合物、氟樹脂(例如,聚四氟乙烯、聚偏二氟乙烯等)、改質聚苯醚(modified polyphenylene ether)、聚碸、聚醚碸、聚芳酯(polyarylate)、聚醯胺醯亞胺、聚醚醯亞胺、熱塑性聚醯亞胺等。 在使用其他熱塑性樹脂之情況下,可以單獨使用,亦可以併用兩種以上。 The photosensitive resin composition of the present embodiment may contain other thermoplastic resins other than the phenoxy resin. Examples of such thermoplastic resins include polyvinyl acetal resins, (meth)acrylic resins, polyamide-based resins (for example, nylon, etc.), thermoplastic urethane-based resins, and polyolefin-based resins (for example, polyethylene resins). , polypropylene, etc.), polycarbonate, polyester resins (for example, polyethylene terephthalate, polybutylene terephthalate, etc.), polyacetal, polyphenylene sulfide, polyether ether ketone, Liquid crystal polymer, fluororesin (for example, polytetrafluoroethylene, polyvinylidene fluoride, etc.), modified polyphenylene ether, polysulfone, polyethersulfone, polyarylate, polyamide Imide, polyether imide, thermoplastic polyimide, etc. When other thermoplastic resins are used, they may be used alone or in combination of two or more.
(感光劑) 本實施形態的感光性樹脂組成物含有感光劑。作為感光劑,可以使用藉由光的作用改變感光性樹脂組成物對顯影液的溶解性和/或使感光性組成物硬化之任意的感光劑。 (photosensitive agent) The photosensitive resin composition of this embodiment contains a photosensitizer. As the photosensitizer, any photosensitizer that changes the solubility of the photosensitive resin composition in the developing solution and/or hardens the photosensitive composition by the action of light can be used.
作為一例,感光劑含有光陽離子聚合起始劑為較佳。尤其,光陽離子聚合起始劑在樹脂含有環氧樹脂時較佳地使用。由光陽離子聚合起始劑產生之活性物種藉由所謂的化學增幅的機制使環氧樹脂中的環氧基以連鎖反應的方式聚合。又,會引起對顯影液的溶解性的變化/硬化。As an example, it is preferable that the photosensitive agent contains a photocationic polymerization initiator. In particular, the photocationic polymerization initiator is preferably used when the resin contains an epoxy resin. The active species generated by the photocationic polymerization initiators polymerize the epoxy groups in the epoxy resin in a chain reaction manner by the mechanism of so-called chemical amplification. In addition, a change in solubility in a developer and hardening are caused.
作為光陽離子聚合起始劑的具體例,可舉出鎓鹽化合物。更具體而言,可舉出重氮鹽、二芳基錪鹽等的錪鹽、三芳基鋶鹽之類的鋶鹽、三芳基吡喃鎓(pyrylium)鹽、苄基吡啶鎓硫氰酸酯(benzyl pyridinium thiocyanate)、二烷基苯甲醯甲基鋶鹽、二烷基羥基苯基鏻鹽等的光酸產生劑或陽離子型光聚合起始劑。 其中,從圖案形成性的觀點考慮,使用三芳基鋶鹽為較佳。 As a specific example of a photocationic polymerization initiator, an onium salt compound is mentioned. More specifically, diazonium salts, iodonium salts such as diaryl iodonium salts, periconium salts such as triaryl periconium salts, triaryl pyrylium salts, and benzylpyridinium thiocyanate can be mentioned. Photoacid generators or cationic photopolymerization initiators such as benzyl pyridinium thiocyanate, dialkylbenzylmethyl sulfamate, and dialkylhydroxyphenylphosphonium salts. Among them, it is preferable to use a triaryl perionium salt from the viewpoint of pattern forming properties.
作為鎓鹽化合物的相對陰離子(counter anions),可舉出硼酸根陰離子、磺酸根陰離子、沒食子酸根陰離子、磷系陰離子、銻系陰離子等。更具體而言,可舉出磺酸根陰離子、二磺醯亞胺酸根陰離子、六氟磷酸根陰離子、氟銻酸根陰離子、四氟硼酸根陰離子、四(五氟苯基)硼酸根陰離子等。Examples of counter anions of the onium salt compound include borate anions, sulfonate anions, gallate anions, phosphorus-based anions, antimony-based anions, and the like. More specifically, a sulfonate anion, a disulfoimidate anion, a hexafluorophosphate anion, a fluoroantimonate anion, a tetrafluoroborate anion, a tetrakis(pentafluorophenyl)borate anion, etc. are mentioned.
作為另一例,感光劑含有光自由基聚合起始劑為較佳。 尤其,在感光性樹脂組成物含有後述的多官能(甲基)丙烯酸酯化合物之情況下,光自由基產生劑可有效地使其聚合。 As another example, it is preferable that the photosensitizer contains a photoradical polymerization initiator. In particular, when the photosensitive resin composition contains the polyfunctional (meth)acrylate compound described later, the photoradical generator can effectively polymerize it.
可使用之光自由基產生劑並無特別限定,可以適當使用公知者。 例如可舉出: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-啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1、2-(二甲基胺基)-2-〔(4-甲基苯基)甲基〕-1-〔4-(4-啉基)苯基〕-1-丁酮等的烷基苯酮系化合物;二苯甲酮、4,4’-雙(二甲基胺基)二苯甲酮、2-羧基二苯甲酮等的二苯甲酮系化合物;安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚等的安息香系化合物;9-氧硫𠮿、2-乙基-9-氧硫𠮿、2-異丙基-9-氧硫𠮿、2-氯-9-氧硫𠮿、2,4-二甲基-9-氧硫𠮿、2,4-二乙基-9-氧硫𠮿等的9-氧硫𠮿系化合物;2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-對稱三、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-對稱三、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)-對稱三、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)-對稱三等的鹵甲基化三系化合物;2-三氯甲基-5-(2’-苯并呋喃基)-1,3,4-二唑、2-三氯甲基-5-〔β-(2’-苯并呋喃基)乙烯基〕-1,3,4-二唑、4-二唑、2-三氯甲基-5-呋喃基-1,3,4-二唑等的鹵甲基化二唑系化合物;2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑等的聯咪唑系化合物;1,2-辛二酮,1-〔4-(苯基硫基)苯基〕-2-(鄰苯甲醯基肟)、乙酮,1-〔9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基〕-,1-(鄰乙醯基肟)等的肟酯系化合物;雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等的環戊二烯鈦系化合物;p-二甲基胺基安息香酸、p-二乙基胺基安息香酸等的安息香酸酯系化合物;9-苯基吖啶等的吖啶系化合物;等。其中,尤其可以較佳地使用肟酯系化合物。 The photo-radical generator that can be used is not particularly limited, and known ones can be appropriately used. For example: 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenone, 2-hydroxy-2-methyl -1-Phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[4-(2-Hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylphenylthio) base) -2- Linoprop-1-one, 2-benzyl-2-dimethylamino-1-(4- Linophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Alkyl phenone-based compounds such as olinyl)phenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone Benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. benzoin-based compounds; 9-oxythiocyanate , 2-ethyl-9-oxothio , 2-isopropyl-9-oxothio , 2-chloro-9-oxysulfur , 2,4-dimethyl-9-oxothio , 2,4-diethyl-9-oxothio etc. 9-oxosulfur 𠮿 Series compound; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric tri , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-symmetric three halomethylated tris Series compound; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)ethenyl]-1,3,4- oxadiazole, 4- oxadiazole, 2-trichloromethyl-5-furyl-1,3,4- Halomethylation of oxadiazoles etc. oxadiazole compounds; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2, 4-Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole-based compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]- 2-(O-benzyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(o- Acetyl oxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) Cyclopentadiene titanium-based compounds such as phenyl) titanium; benzoic acid ester-based compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, etc.; 9-phenylacridine, etc. Acridine series compounds; etc. Among them, oxime ester-based compounds can be preferably used in particular.
在感光性樹脂組成物含有感光劑之情況下,可以僅含有一種感光劑,亦可以含有兩種以上的感光劑。 感光劑的含量相對於感光性樹脂組成物的全部固體成分例如為0.3~5.0質量%,較佳為0.5~4.5質量%,更佳為1.0~4.0質量%。藉由設為0.3質量%以上,能夠提高圖案形成性。又,藉由設為5.0質量%以下,能夠減少膜中的離子成分,並且能夠提高最終的膜的絕緣性或可靠性。 When the photosensitive resin composition contains a sensitizer, only one sensitizer may be contained, or two or more sensitizers may be contained. The content of the photosensitizer is, for example, 0.3 to 5.0 mass %, preferably 0.5 to 4.5 mass %, and more preferably 1.0 to 4.0 mass % with respect to the total solid content of the photosensitive resin composition. By making it 0.3 mass % or more, pattern formability can be improved. Moreover, by setting it as 5.0 mass % or less, the ion component in a film can be reduced, and the insulating property and reliability of a final film can be improved.
(多官能(甲基)丙烯酸酯化合物) 本實施形態的感光性樹脂組成物可以含有多官能(甲基)丙烯酸酯化合物。作為多官能(甲基)丙烯酸酯化合物,可無特別限制地舉出在一個分子中具有兩個以上的(甲基)丙烯醯基者。 (Multifunctional (meth)acrylate compound) The photosensitive resin composition of this embodiment may contain a polyfunctional (meth)acrylate compound. As a polyfunctional (meth)acrylate compound, what has two or more (meth)acryloyl groups in one molecule is mentioned without a restriction|limiting in particular.
作為本發明人等的見解,多官能(甲基)丙烯酸酯化合物與聚醯胺/聚醯亞胺樹脂一併使用為較佳。儘管細節尚不明確,但認為在多官能(甲基)丙烯酸酯化合物硬化(聚合)時會形成與聚醯胺樹脂和/或聚醯亞胺樹脂複雜地「纏結」之結構。尤其,推測多官能(甲基)丙烯酸酯化合物藉由聚合而形成「包裹」具有醯亞胺環等的環狀骨架之聚醯亞胺樹脂或聚醯胺結構的至少一部分因熱而閉環從而可具有環狀骨架之聚醯胺樹脂的環狀骨架之網狀結構。推測藉由形成此種複雜地纏結之結構,硬化膜的性能變得良好。According to the findings of the present inventors, it is preferable to use a polyfunctional (meth)acrylate compound together with a polyimide/polyimide resin. Although the details are not clear, it is believed that when the polyfunctional (meth)acrylate compound hardens (polymerizes) it forms a structure that is complexly "entangled" with the polyimide resin and/or polyimide resin. In particular, it is presumed that the polyfunctional (meth)acrylate compound is polymerized to form a polyimide resin having a cyclic skeleton such as an imide ring, or that at least a part of the polyimide structure is ring-closed due to heat. A network structure of a cyclic skeleton of a polyamide resin having a cyclic skeleton. It is presumed that the performance of the cured film becomes good by forming such a complex entangled structure.
從實現如上所述的纏結之結構之觀點或獲得耐久性高且耐化學品性良好的硬化膜之觀點考慮,多官能(甲基)丙烯酸酯化合物為3官能以上為較佳。多官能(甲基)丙烯酸酯化合物的官能基數並無上限,從原料的易獲取性等觀點考慮,官能基數的上限例如為11官能。 作為粗略的趨勢,在使用官能基((甲基)丙烯醯基)的數量多的多官能(甲基)丙烯酸酯化合物之情況下,硬化膜的耐化學品性趨於提高。另一方面,在使用官能基((甲基)丙烯醯基)的數量少的多官能(甲基)丙烯酸酯化合物之情況下,硬化膜的拉伸伸長率等的機械物性趨於變得良好。 The polyfunctional (meth)acrylate compound is preferably trifunctional or more from the viewpoint of realizing the above-mentioned entangled structure or obtaining a cured film having high durability and good chemical resistance. There is no upper limit on the number of functional groups of the polyfunctional (meth)acrylate compound, but the upper limit of the number of functional groups is, for example, 11 functional groups from the viewpoints of easy availability of raw materials and the like. As a rough trend, when a polyfunctional (meth)acrylate compound having a large number of functional groups ((meth)acryloyl groups) is used, the chemical resistance of the cured film tends to improve. On the other hand, when a polyfunctional (meth)acrylate compound having a small number of functional groups ((meth)acryloyl groups) is used, mechanical properties such as tensile elongation of the cured film tend to be favorable. .
作為一例,多官能(甲基)丙烯酸酯化合物含有7官能以上的(甲基)丙烯酸酯化合物為較佳。 作為一例,多官能(甲基)丙烯酸酯化合物含有5~6官能以上的(甲基)丙烯酸酯化合物為較佳。 作為一例,多官能(甲基)丙烯酸酯化合物含有3~4官能以上的(甲基)丙烯酸酯化合物為較佳。 As an example, it is preferable that the polyfunctional (meth)acrylate compound contains a (meth)acrylate compound having 7 or more functions. As an example, it is preferable that the polyfunctional (meth)acrylate compound contains a (meth)acrylate compound having 5 to 6 functions or more. As an example, it is preferable that the polyfunctional (meth)acrylate compound contains a (meth)acrylate compound having 3 to 4 functions or more.
作為一例,多官能(甲基)丙烯酸酯化合物可以含有由以下通式表示的化合物。在以下通式中,R’為氫原子或甲基,n為0~3,R為氫原子或(甲基)丙烯醯基。複數個R’可以相同,亦可以不同。As an example, the polyfunctional (meth)acrylate compound may contain a compound represented by the following general formula. In the following general formula, 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. The plurality of R's may be the same or different.
作為多官能(甲基)丙烯酸酯化合物的具體例,可舉出以下。當然,多官能(甲基)丙烯酸酯化合物並不僅限定於此。Specific examples of the polyfunctional (meth)acrylate compound include the following. Of course, the polyfunctional (meth)acrylate compound is not limited to this.
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)丙烯酸酯等的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)丙烯酸酯等的環氧丙烯酸酯類、藉由聚異氰酸酯與(甲基)丙烯酸羥乙酯等的含羥基的(甲基)丙烯酸酯的反應而得之胺酯(甲基)丙烯酸酯等。Ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, neotaerythritol tri(meth)acrylate , polyol polyacrylates such as neopentaerythritol tetra (meth)acrylate, dipeoerythritol penta (meth)acrylate, dipivalerythritol hexa (meth)acrylate, bisphenol A Epoxy acrylates such as di(meth)acrylate of diglycidyl ether, di(meth)acrylate of hexanediol diglycidyl ether, etc., by polyisocyanate and (meth)acrylic The amine ester (meth)acrylate etc. obtained by the reaction of the hydroxyl group-containing (meth)acrylate, such as hydroxyethyl ester.
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)等的市售品。ARONIX M-400, ARONIX M-460, ARONIX M-402, ARONIX M-510, ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60 , KAYARAD DPCA120 (made by Nippon Kayaku Co., Ltd.), Viscoat#230, Viscoat#300, Viscoat#802, Viscoat#2500, Viscoat#1000, Viscoat#1080 (made by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), NK ESTETR A -Commercial products such as BPE-10, NK ESTETR A-GLY-9E, NK ESTETR A-9550, and NK ESTETR A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.).
在感光性樹脂組成物含有多官能(甲基)丙烯酸酯化合物之情況下,可以僅含有一種多官能(甲基)丙烯酸酯化合物,亦可以含有兩種以上的多官能(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,可形成更複雜的「纏結結構」,從而硬化膜的特性進一步提高。 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(甲基)丙烯酸酯的混合物。 When the photosensitive resin composition contains a polyfunctional (meth)acrylate compound, only one type of polyfunctional (meth)acrylate compound may be contained, or two or more types of polyfunctional (meth)acrylate compounds may be contained . In the latter case, it is preferable to use together a polyfunctional (meth)acrylate compound having a different number of functional groups. It is considered that a more complicated "entanglement structure" can be formed by using a polyfunctional (meth)acrylate compound having a different number of functional groups in combination, thereby further improving the properties of the cured film. Incidentally, in commercially available polyfunctional (meth)acrylate compounds, mixtures of (meth)acrylates having different numbers of functional groups exist.
在使用多官能(甲基)丙烯酸酯化合物之情況下,多官能(甲基)丙烯酸酯化合物相對於環氧樹脂和/或聚醯胺/聚醯亞胺樹脂100質量份之量較佳為50~200質量份,更佳為60~150質量份。 多官能(甲基)丙烯酸酯化合物的使用量並無特別限定,但藉由如上所述適當地調整使用量,能夠進一步提高各性能中的一種或兩種以上。如上所述,在本實施形態的感光性樹脂組成物中,認為藉由硬化可形成聚醯胺/聚醯亞胺樹脂與多官能(甲基)丙烯酸酯的「纏結結構」,且認為藉由適當地調整多官能(甲基)丙烯酸酯化合物相對於聚醯胺/聚醯亞胺樹脂之使用量,聚醯胺/聚醯亞胺樹脂和多官能(甲基)丙烯酸酯化合物會適當地纏結,又,與纏結無關的額外的成分會減少。又,認為性能會變得進一步良好。 In the case of using a polyfunctional (meth)acrylate compound, the amount of the polyfunctional (meth)acrylate compound relative to 100 parts by mass of the epoxy resin and/or polyimide/polyimide resin is preferably 50 to 200 parts by mass, more preferably 60 to 150 parts by mass. The usage-amount of a polyfunctional (meth)acrylate compound is not specifically limited, By adjusting the usage-amount suitably as mentioned above, one or two or more of each performance can be improved further. As described above, in the photosensitive resin composition of the present embodiment, it is considered that the "entanglement structure" of the polyimide/polyimide resin and the polyfunctional (meth)acrylate can be formed by curing, and it is considered that the By appropriately adjusting the amount of the polyfunctional (meth)acrylate compound to be used relative to the polyamide/polyimide resin, the polyamide/polyimide resin and the polyfunctional (meth)acrylate compound will be appropriately The tangles, again, are reduced in extra components not related to the tangles. In addition, it is considered that the performance will be further improved.
(熱自由基起始劑) 本實施形態的感光性樹脂組成物可以含有熱自由基起始劑。認為藉由使用熱自由基起始劑,例如可進一步促進上述的多官能(甲基)丙烯酸酯化合物的聚合反應。 (thermal free radical initiator) The photosensitive resin composition of this embodiment may contain a thermal radical initiator. It is considered that the polymerization reaction of the above-mentioned polyfunctional (meth)acrylate compound can be further accelerated by using a thermal radical initiator, for example.
熱自由基起始劑含有有機過氧化物為較佳。作為有機過氧化物,可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、三級丁基過氧化氫、二-三級丁基過氧化物、異丙苯基過氧化氫、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。The thermal radical initiator preferably contains an organic peroxide. Examples of the organic peroxide include octyl peroxide, lauryl peroxide, stearyl peroxide, 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoic acid Esters, oxalic acid peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethyl 2-ethylhexanoate, tertiary hexyl peroxy 2-ethyl hexanoate, tertiary butyl peroxy 2-ethyl hexanoate, m-toluol peroxide, benzyl peroxide, methyl Ethyl ethyl ketone peroxide, acetyl peroxide, tertiary butyl hydroperoxide, di-tertiary butyl peroxide, cumyl hydroperoxide, dicumyl peroxide, Tertiary butyl perbenzoate, p-chlorobenzyl peroxide, cyclohexanone peroxide, etc.
在使用熱自由基起始劑之情況下,可以僅使用一種熱自由基起始劑,亦可以使用兩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)丙烯酸酯化合物100質量份例如較佳為0.1~30質量份,更佳為1~20質量份。 In the case of using a thermal radical initiator, only one thermal radical initiator may be used, or two or more thermal radical initiators may be used. In the case of using a thermal radical initiator, the amount thereof is, for example, preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polyfunctional (meth)acrylate compound.
(硬化觸媒) 本實施形態的感光性樹脂組成物可以含有硬化觸媒。硬化觸媒具有促進環氧樹脂的反應之作用。藉由使用硬化觸媒,能夠使使用環氧樹脂之反應充分進行,從而例如進一步提高硬化膜的拉伸伸長率。 (hardening catalyst) The photosensitive resin composition of the present embodiment may contain a curing catalyst. The hardening catalyst has the function of promoting the reaction of the epoxy resin. By using a hardening catalyst, the reaction using an epoxy resin can fully progress, for example, the tensile elongation of a cured film can be further improved.
作為硬化觸媒,可舉出作為環氧樹脂的硬化觸媒(通常,亦稱為硬化促進劑)已知的化合物。例如,可舉出:1,8-二吖雙環[5,4,0]十一烯-7等的二吖雙環烯烴及其衍生物;三丁胺、苄基二甲胺等的胺系化合物;2-甲基咪唑等的咪唑化合物;三苯膦、甲基二苯膦等的有機膦類;四苯基硼酸四苯鏻、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、四萘氧基硼酸四苯鏻、4,4’-磺醯基二酚四苯鏻等的四取代鏻鹽;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 compounds known as curing catalysts for epoxy resins (usually, also referred to as curing accelerators). For example, diazbicycloolefins such as 1,8-diazbicyclo[5,4,0]undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine can be mentioned. ; Imidazole compounds such as 2-methylimidazole; Organophosphines such as triphenylphosphine, methyldiphenylphosphine, etc.; Tetraphenylphosphonium tetranaphthyloxyborate, tetraphenylphosphonium tetranaphthyloxyborate, tetraphenylphosphonium tetranaphthyloxyborate, 4,4'-sulfonyldiphenol tetraphenylphosphonium, etc.; triphenylphosphine, etc. with benzoquinone added . Among them, organic phosphines are preferably mentioned.
在使用硬化觸媒之情況下,其量相對於環氧樹脂100質量份例如為1~80質量份,較佳為5~50質量份。 順帶一提,在將本實施形態的感光性樹脂組成物設為化學增幅型,並藉由利用光照射產生之活性物種引起連鎖的化學反應來進行硬化之情況下,本實施形態的感光性樹脂組成物通常不含硬化觸媒。 In the case of using a curing catalyst, the amount thereof is, for example, 1 to 80 parts by mass, or preferably 5 to 50 parts by mass, with respect to 100 parts by mass of the epoxy resin. Incidentally, in the case where the photosensitive resin composition of the present embodiment is chemically amplified and cured by a chain chemical reaction caused by an active species generated by light irradiation, the photosensitive resin of the present embodiment is The composition usually does not contain a hardening catalyst.
(密接助劑) 本實施形態的感光性樹脂組成物含有密接助劑為較佳。藉此,例如能夠進一步提高與基板之間的密接性。 (Adhesion Auxiliary) It is preferable that the photosensitive resin composition of this embodiment contains an adhesion adjuvant. Thereby, the adhesiveness with a board|substrate can be improved further, for example.
密接助劑並無特別限定。例如,可以使用含胺基的矽烷偶合劑、含環氧基的矽烷偶合劑、含(甲基)丙烯醯基的矽烷偶合劑、含巰基的矽烷偶合劑、含乙烯基的矽烷偶合劑、含脲基的矽烷偶合劑、含硫醚基的矽烷偶合劑等的矽烷偶合劑。 在使用矽烷偶合劑之情況下,可以單獨使用一種,亦可以併用兩種以上。 The adhesion adjuvant is not particularly limited. For example, an amine group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth)acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a Silane coupling agents such as urea group-containing silane coupling agents and thioether group-containing silane coupling agents. In the case of using a silane coupling agent, one type may be used alone, or two or more types may be used in combination.
作為含胺基的矽烷偶合劑,例如可舉出雙(2-羥乙基)-3-胺基丙基三乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三乙氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二乙氧基矽烷、N-苯基-γ-胺基-丙基三甲氧基矽烷等。 作為含環氧基的矽烷偶合劑,例如可舉出γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-環氧丙基丙基三甲氧基矽烷等。 作為含(甲基)丙烯醯基的矽烷偶合劑,例如可舉出γ-((甲基)丙烯醯氧基丙基)三甲氧基矽烷、γ-((甲基)丙烯醯氧基丙基)甲基二甲氧基矽烷、γ-((甲基)丙烯醯氧基丙基)甲基二乙氧基矽烷等。 作為含巰基的矽烷偶合劑,例如可舉出3-巰基丙基三甲氧基矽烷等。 作為含乙烯基的矽烷偶合劑,例如可舉出乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷等。 作為含脲基的矽烷偶合劑,例如可舉出3-脲基丙基三乙氧基矽烷等。 作為含硫醚基的矽烷偶合劑,例如可舉出雙(3-(三乙氧基矽基)丙基)二硫化物、雙(3-(三乙氧基矽基)丙基)四硫化物等。 作為含酸酐的矽烷偶合劑,例如可舉出3-三甲氧基矽基丙基琥珀酸酐、3-三乙氧基矽基丙基琥珀酸酐、3-二甲基甲氧基矽基丙基琥珀酸酐等。 Examples of the amino group-containing silane coupling agent include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltriethoxysilane. Propyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyl Trimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N -β(aminoethyl)γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, etc. Examples of the epoxy group-containing silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-epoxypropyl propyl trimethoxy silane, etc. Examples of the (meth)acryloyl group-containing silane coupling agent include γ-((meth)acryloyloxypropyl)trimethoxysilane, γ-((meth)acryloyloxypropyl) ) Methyldimethoxysilane, γ-((meth)acryloyloxypropyl)methyldiethoxysilane, etc. As a mercapto group-containing silane coupling agent, 3-mercaptopropyl trimethoxysilane etc. are mentioned, for example. Examples of the vinyl group-containing silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like. As a ureido group-containing silane coupling agent, 3-ureidopropyl triethoxysilane etc. are mentioned, for example. Examples of the sulfide group-containing silane coupling agent include bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide things etc. Examples of the acid anhydride-containing silane coupling agent include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-dimethylmethoxysilylpropyl succinic anhydride. acid anhydride, etc.
又,作為密接助劑,不僅可舉出矽烷偶合劑,還可舉出鈦偶合劑或鋯偶合劑等。Moreover, as an adhesion auxiliary agent, not only a silane coupling agent, but a titanium coupling agent, a zirconium coupling agent, etc. can be mentioned.
在使用密接助劑之情況下,可以單獨使用,亦可以併用兩種以上的密接助劑。 在使用密接助劑之情況下,其使用量以感光性樹脂組成物的非揮發性成分的總量為基準較佳為0.3~5質量%,更佳為0.4~4質量%,進一步較佳為0.5~3質量%。 When an adhesion adjuvant is used, it may be used alone, or two or more adhering adjuvants may be used in combination. In the case of using an adhesion adjuvant, the amount used is preferably 0.3 to 5% by mass, more preferably 0.4 to 4% by mass, and still more preferably 0.3 to 5% by mass based on the total amount of the nonvolatile components of the photosensitive resin composition. 0.5 to 3 mass %.
(界面活性劑) 本實施形態的感光性樹脂組成物含有界面活性劑為較佳。藉此,能夠進一步提高感光性樹脂組成物的塗佈性或膜的平坦性。 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。 (surfactant) It is preferable that the photosensitive resin composition of this embodiment contains a surfactant. Thereby, the coatability of the photosensitive resin composition and the flatness of the film can be further improved. As the surfactant, a fluorine-based surfactant, a polysiloxane-based surfactant, an alkyl-based surfactant, an acrylic-based surfactant, and the like can be mentioned.
界面活性劑包含含有氟原子及矽原子中的至少一種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。 作為另一觀點,界面活性劑為非離子性為較佳。使用非離子性的界面活性劑例如從抑制與組成物中的其他成分之間的非預期的反應來提高組成物的保存穩定性之觀點考慮為較佳。 It is preferable that the surfactant contains at least 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 contributing to an improvement in adhesive strength. From another viewpoint, it is preferable that the surfactant is nonionic. The use of a nonionic surfactant is preferable, for example, from the viewpoint of improving the storage stability of the composition by suppressing unintended reactions with other components in the composition.
作為可較佳地用作界面活性劑之市售品,例如可舉出DIC Corporation製「Megafac」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等的含氟的低聚物結構的界面活性劑、NEOS COMPANY LIMITED製Ftergent250、Ftergent251等的含氟的非離子系界面活性劑、wacker asahikasei silicone co.,ltd.製SILFOAM(註冊商標)系列(例如,SD 100 TS、SD 670、SD 850、SD 860、SD 882)等的聚矽氧系界面活性劑。 又,作為較佳的界面活性劑,還可舉出3M公司製的FC4430或FC4432等。 Examples of commercially available products that can be preferably used as surfactants include F-251, F-253, F-281, F-430, F-477, and F-551 of the "Megafac" series manufactured by DIC Corporation. , 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, etc. Fluorine-containing oligomer structure surfactant, fluorine-containing nonionic surfactants such as Ftergent250 and Ftergent251 manufactured by NEOS COMPANY LIMITED, SILFOAM (registered trademark) series (for example, SD 100 TS, SD 670, SD 850, SD 860, SD 882) and other polysiloxane-based surfactants. Moreover, as a preferable surfactant, FC4430, FC4432 by 3M company, etc. are mentioned.
在使用界面活性劑之情況下,其使用量以感光性樹脂組成物的非揮發性成分的總量為基準例如為0.001~1質量%,較佳為0.005~0.5質量%。When using a surfactant, the usage-amount is 0.001-1 mass % based on the total amount of the nonvolatile component of the photosensitive resin composition, for example, Preferably it is 0.005-0.5 mass %.
(水) 本實施形態的感光性樹脂組成物可以含有水。由於水的存在,例如容易進行矽烷偶合劑的水解反應,基板與硬化膜之間的密接性趨於進一步提高。 (water) The photosensitive resin composition of this embodiment may contain water. Due to the presence of water, for example, the hydrolysis reaction of the silane coupling agent tends to proceed, and the adhesiveness between the substrate and the cured film tends to be further improved.
在本實施形態的感光性樹脂組成物含有水之情況下,其量相對於感光性樹脂組成物的全部固體成分(非揮發成分)100質量份較佳為0.1~5質量份,更佳為0.2~3質量份,進一步較佳為0.5~2質量份。 感光性樹脂組成物的水分量可以藉由Karl Fischer法進行定量。 When the photosensitive resin composition of the present embodiment contains water, the amount thereof is preferably 0.1 to 5 parts by mass, and more preferably 0.2 parts by mass relative to 100 parts by mass of the total solid content (non-volatile content) of the photosensitive resin composition. to 3 parts by mass, more preferably 0.5 to 2 parts by mass. The moisture content of the photosensitive resin composition can be quantified by the Karl Fischer method.
(溶劑/組成物的性狀) 本實施形態的感光性樹脂組成物含有溶劑為較佳。藉此,能夠藉由塗佈法對基板容易形成感光性樹脂膜。 溶劑通常含有有機溶劑。 只要是能夠溶解或分散上述的各成分且實質上不與各構成成分進行化學反應者,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, the photosensitive resin film can be easily formed on the board|substrate by the coating method. The solvent usually contains an organic solvent. The 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.
作為溶劑的具體例,例如可舉出N-甲基-2-吡咯啶酮、γ-丁內酯、N,N-二甲基乙醯胺、二甲基亞碸、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、丙二醇單甲基醚、二丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、1,3-丁二醇乙酸甲酯、1,3-丁二醇-3-單甲基醚、丙酮酸甲酯、丙酮酸乙酯及3-甲氧基丙酸甲酯等。溶劑可以單獨使用,亦可以組合複數種來使用。Specific examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, and diethylene glycol dimethylide. Ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate , butyl lactate,
在本實施形態的感光性樹脂組成物含有溶劑之情況下,本實施形態的感光性樹脂組成物通常為清漆狀。更具體而言,本實施形態的感光性樹脂組成物較佳為樹脂和感光劑溶解於溶劑中而成之清漆狀的組成物。 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,由於樹脂「溶解」於溶劑,因此能夠獲得均質的硬化膜。 When the photosensitive resin composition of this embodiment contains a solvent, the photosensitive resin composition of this embodiment is usually varnish-like. More specifically, the photosensitive resin composition of the present embodiment is preferably a varnish-like composition in which a resin and a photosensitizer are dissolved in a solvent. 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, since resin "dissolves" in a solvent, a homogeneous cured film can be obtained.
在使用溶劑之情況下,以感光性樹脂組成物中的全部固體成分(非揮發成分)的濃度較佳為成為10~50質量%,更佳為成為20~45質量%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。此外,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 whole solid content (nonvolatile matter) in a photosensitive resin composition may become 10-50 mass %, and it is more preferable to use it as 20-45 mass %. By setting it as this range, each component can be melt|dissolved or dispersed sufficiently. Moreover, favorable coatability can be ensured, and the flatness at the time of spin coating can also be improved. Moreover, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the nonvolatile components.
(其他成分) 除上述的成分以外,本實施形態的感光性樹脂組成物還可以根據需要含有其他成分。作為此種成分,例如可舉出抗氧化劑、二氧化矽等的填料粒子、敏化劑、成膜化劑等。 但是,考慮到拉伸伸長性能,本實施形態的感光性樹脂組成物不含填料粒子為較佳。 (other ingredients) In addition to the above-mentioned components, the photosensitive resin composition of the present embodiment may contain other components as necessary. As such a component, filler particles, such as an antioxidant and silica, a sensitizer, a film-forming agent, etc. are mentioned, for example. However, in consideration of tensile elongation performance, it is preferable that the photosensitive resin composition of the present embodiment does not contain filler particles.
(補充事項) 本實施形態的感光性樹脂組成物較佳為負型(亦即,因曝光而引起硬化(交聯)反應等導致對顯影液的溶解性降低者)。認為藉由減少負型的感光性樹脂組成物中的粒子數,可進一步減少粒子的存在阻礙硬化(交聯)反應之情況。亦即,認為粒子數的減少所產生之效果「良好的拉伸伸長特性」尤其能夠在負型的感光性樹脂組成物中獲得。 (Supplementary Matters) The photosensitive resin composition of the present embodiment is preferably a negative type (that is, one whose solubility in a developing solution is lowered due to a curing (crosslinking) reaction or the like due to exposure). By reducing the number of particles in the negative-type photosensitive resin composition, it is considered that the presence of particles inhibits the curing (crosslinking) reaction further. That is, it is considered that the effect "good tensile elongation characteristics" by the reduction in the number of particles can be obtained especially in a negative-type photosensitive resin composition.
本實施形態的感光性樹脂組成物較佳為化學增幅型(亦即,對顯影液的溶解性因由感光劑產生之活性化學物種引起連鎖反應而發生變化(在負型之情況下,對顯影液的溶解性降低)者)。認為藉由減少化學增幅型的感光性樹脂組成物中的粒子數,會變得難以阻礙連鎖反應。其結果,認為得到之永久膜的拉伸伸長特性變得進一步良好。The photosensitive resin composition of the present embodiment is preferably of a chemically amplified type (that is, the solubility to the developer is changed by the chain reaction caused by the active chemical species generated by the photosensitive agent (in the case of the negative type, the solubility to the developer is changed) of reduced solubility)). It is considered that it becomes difficult to inhibit the chain reaction by reducing the number of particles in the chemically amplified photosensitive resin composition. As a result, it is considered that the tensile elongation characteristics of the obtained permanent film became more favorable.
<感光性樹脂組成物之製造方法> 本實施形態的感光性樹脂組成物可以藉由選擇適當的製造方法、製造條件來製造。 具體而言,本實施形態的感光性樹脂組成物可以藉由歷經由孔徑0.5μm以下的中空纖維膜過濾器進行之過濾步驟等來製造。亦即,可以藉由利用孔徑0.5μm以下的中空纖維膜過濾器過濾混合上述的各成分(樹脂、感光劑、溶劑等)而得之感光性樹脂組成物來製造在流速3g/分時的1分鐘的測量中計數之直徑0.5~20μm的粒子數為100以下的感光性樹脂組成物。 作為本發明人等的見解,中空纖維膜過濾器相較於膜過濾器等的其他過濾器,捕獲由永久膜形成用的感光性樹脂組成物產生之粒子之能力高。 <Manufacturing method of photosensitive resin composition> The photosensitive resin composition of this embodiment can be manufactured by selecting an appropriate manufacturing method and manufacturing conditions. Specifically, the photosensitive resin composition of the present embodiment can be produced by going through a filtration step or the like through a hollow fiber membrane filter having a pore diameter of 0.5 μm or less. That is, a photosensitive resin composition at a flow rate of 3 g/min can be produced by filtering and mixing a photosensitive resin composition obtained by mixing the above-mentioned components (resin, photosensitizer, solvent, etc.) with a hollow fiber membrane filter having a pore diameter of 0.5 μm or less. The photosensitive resin composition in which the number of particles with a diameter of 0.5 to 20 μm counted in the minute measurement is 100 or less. According to the findings of the present inventors, the hollow fiber membrane filter has a higher capability of capturing particles generated from the photosensitive resin composition for permanent membrane formation than other filters such as membrane filters.
中空纖維膜過濾器的孔徑較佳為0.05μm以上且0.5μm以下,更佳為0.05μm以上且0.3μm以下。 儘管亦受到所過濾之感光性樹脂組成物的總量和流速之影響,但從減少堵塞之觀點考慮,中空纖維膜過濾器的膜面積例如為5000cm 2以上,較佳為10000cm 2以上,進一步較佳為15000cm 2以上。膜面積並無上限,但從成本等的觀點考慮,上限例如為50000cm 2,具體而言為40000cm 2,更具體而言為30000cm 2。 中空纖維膜過濾器的材質較佳為聚烯烴,更佳為聚丙烯。 與中空纖維膜過濾器相關的各種資訊通常記載於型錄或規格書中。 The pore diameter of the hollow fiber membrane filter is preferably 0.05 μm or more and 0.5 μm or less, and more preferably 0.05 μm or more and 0.3 μm or less. Although it is also affected by the total amount and flow rate of the photosensitive resin composition to be filtered, from the viewpoint of reducing clogging, the membrane area of the hollow fiber membrane filter is, for example, 5000 cm 2 or more, preferably 10000 cm 2 or more, and more Preferably, it is 15000cm 2 or more. There is no upper limit on the film area, but from the viewpoint of cost and the like, the upper limit is, for example, 50,000 cm 2 , specifically 40,000 cm 2 , and more specifically 30,000 cm 2 . The material of the hollow fiber membrane filter is preferably polyolefin, more preferably polypropylene. Various information related to hollow fiber membrane filters are usually recorded in catalogs or specifications.
過濾步驟可以僅進行1次,亦可以進行複數次。進行複數次過濾步驟時的具體的態樣可以為循環過濾。 又,過濾步驟亦可以為包括使用孔徑相對較大的過濾器之預過濾步驟和使用孔徑相對較小的過濾器之主過濾步驟之多階段過濾步驟。在該情況下,至少在主過濾中使用孔徑0.5μm以下的中空纖維膜過濾器。作為預過濾中的過濾器,通常選擇孔徑大於主過濾中使用之過濾器者。預過濾中使用之過濾器可以為中空纖維膜過濾器,亦可以為不是膜過濾器等的中空纖維膜過濾器的過濾器。 The filtering step may be performed only once or a plurality of times. A specific aspect when performing a plurality of filtering steps may be cyclic filtering. Also, the filtering step may be a multi-stage filtering step including a pre-filtering step using a filter with a relatively large pore size and a main filtering step using a filter with a relatively small pore size. In this case, a hollow fiber membrane filter having a pore diameter of 0.5 μm or less is used at least in the main filtration. As a filter in the pre-filtration, a filter with a pore size larger than that used in the main filtration is usually selected. The filter used for prefiltration may be a hollow fiber membrane filter or a filter other than a hollow fiber membrane filter such as a membrane filter.
過濾的流速並無特別限定。例如,考慮感光性樹脂組成物的黏度和非揮發成分濃度、過濾器的孔徑和膜面積、製造效率等,在10~1000g/分左右的範圍內適當設定即可。順帶一提,在上述的多階段過濾步驟之情況下,可以在預過濾步驟與主過濾步驟之間改變流速。在該情況下,通常使預過濾步驟中的流速大於主過濾步驟中的流速。The flow rate of filtration is not particularly limited. For example, the viscosity and nonvolatile content concentration of the photosensitive resin composition, the pore diameter and membrane area of the filter, the production efficiency, etc. may be appropriately set within the range of about 10 to 1000 g/min. Incidentally, in the case of the above-described multi-stage filtration step, the flow rate may be changed between the pre-filtration step and the main filtration step. In this case, the flow rate in the pre-filtration step is usually made larger than the flow rate in the main filtration step.
中空纖維膜過濾器例如可以從KITZ MICRO FILTER CORPORATION獲取。Hollow fiber membrane filters are available, for example, from KITZ MICRO FILTER CORPORATION.
<電子裝置之製造方法、電子裝置> 可以使用本實施形態的感光性樹脂組成物來製造電子裝置(具備由感光性樹脂組成物形成之膜之電子裝置)。 例如,可以藉由如下電子裝置之製造方法來製造電子裝置,該電子裝置之製造方法包括:(i)製膜步驟,在表面具有段差之基板的該表面,使用本實施形態的感光性樹脂組成物形成感光性樹脂膜;(ii)曝光步驟,對感光性樹脂膜進行曝光;及(iii)顯影步驟,對經曝光之感光性樹脂膜進行顯影。 <Manufacturing method of electronic device, electronic device> An electronic device (an electronic device including a film formed of the photosensitive resin composition) can be produced using the photosensitive resin composition of the present embodiment. For example, an electronic device can be manufactured by a manufacturing method of an electronic device including: (i) a film forming step, in which the surface of the substrate having a level difference on the surface is composed of the photosensitive resin of the present embodiment (ii) exposure step, exposing the photosensitive resin film; and (iii) developing step, developing the exposed photosensitive resin film.
參閱圖1A~圖1D,對電子裝置之製造方法之一例更具體地進行說明。藉由這裡說明之電子裝置之製造方法,能夠以與銅配線等的金屬構件接觸之形式設置永久膜。Referring to FIGS. 1A to 1D , an example of a method of manufacturing an electronic device will be described in more detail. According to the manufacturing method of the electronic device demonstrated here, a permanent film can be provided so that it may contact metal members, such as copper wiring.
(製膜步驟:圖1A)
在製膜步驟中,在具有段差10之基板1的具有段差之表面側,使用本實施形態的感光性樹脂組成物形成感光性樹脂膜3。
基板1並無特別限定。作為基板1,例如可舉出矽晶圓、陶瓷基板、鋁基板、SiC晶圓及GaN晶圓等。
段差10例如為Cu再配線。當然,段差10亦可以為Cu再配線以外的段差。段差10的高度例如為1~10μm,較佳為1~5μm。
感光性樹脂膜3的厚度(沒有段差10之部分的厚度)例如為1~15μm,較佳為1~10μm。該厚度大於段差10的高度即可。
(Film production step: Figure 1A)
In the film forming step, the
作為形成感光性樹脂膜3之方法,可舉出藉由旋塗法、噴塗法、浸漬法、印刷法、輥塗法、噴墨法等將液體狀的感光性樹脂組成物提供至基板上之方法。典型地,形成樹脂膜之方法為旋塗。
藉由變更膜形成條件或調整感光性樹脂組成物的黏度,能夠調整感光性樹脂膜3的厚度。
As a method of forming the
在製膜步驟之後且在曝光步驟之前,對感光性樹脂膜3進行加熱乾燥為較佳。有時將該加熱乾燥稱為「預烘烤(pre bake)」。
加熱乾燥的溫度通常為50~180℃,較佳為60~150℃。又,加熱乾燥時間通常為30~600秒,較佳為30~300秒左右。藉由該加熱乾燥,能夠充分去除感光性樹脂組成物中的溶劑。典型地,加熱係藉由加熱板或烘箱等來進行。
It is preferable to heat-dry the
(曝光步驟:圖1B)
在曝光步驟中,經由光罩20曝光感光性樹脂膜3。作為曝光用活性光線,例如為X射線、電子束、紫外線、可見光等。就波長而言,200~500nm的活性光線為較佳。從圖案解析度或裝置易操作性的觀點考慮,光源為汞燈的g射線、h射線或i射線為較佳。又,可以混合使用兩種以上的光線。
作為曝光裝置,接觸對準器、鏡面投影或步進器為較佳。
曝光步驟中的曝光量通常在40~1500mJ/cm
2(較佳為80~1000mJ/cm
2)之間,可根據感光性樹脂組成物的靈敏度、樹脂膜的膜厚、所欲得到之圖案形狀等適當調整。
(Exposure Step: FIG. 1B ) In the exposure step, the
在曝光步驟與顯影步驟之間,對樹脂膜進行加熱(曝光後加熱)為較佳。藉此,因曝光而開裂、分解等之物質(感光劑等)進行反應,能夠期待圖案形狀變得良好等。曝光後加熱的溫度、時間例如為50~200℃、10~600秒左右。It is preferable to heat the resin film (post-exposure heating) between the exposure step and the development step. Thereby, a substance (photosensitive agent, etc.) that is cracked, decomposed, etc. by exposure reacts, and it can be expected that the pattern shape becomes favorable. The temperature and time of heating after exposure are, for example, about 50 to 200° C. for 10 to 600 seconds.
(顯影步驟:圖1C)
在顯影步驟中,使用顯影液對曝光步驟中曝光之感光性樹脂膜進行顯影。藉此,能夠去除感光性樹脂膜3的一部分,從而得到設置有開口5之樹脂膜3A。本實施形態的感光性樹脂組成物通常為負型。因此,開口5設置於與光罩20的遮光部對應之部分。
顯影步驟例如可以藉由浸漬法、覆液法、旋轉噴塗法等方法來進行。
(Development step: Figure 1C)
In the development step, the photosensitive resin film exposed in the exposure step is developed using a developer. Thereby, a part of the
在本實施形態中,顯影液含有有機溶劑為較佳。更具體而言,顯影液為以有機溶劑為主要成分之顯影液(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,更容易獲得清晰的圖案。In this embodiment, it is preferable that the developer contains an organic solvent. More specifically, it is preferable that the developer is a developer containing an organic solvent as a main component (95% by mass or more of the components is an organic solvent). By developing with a developing solution containing an organic solvent, compared with the case of developing with an alkaline developing solution (aqueous), pattern swelling and the like caused by the developing solution can be suppressed. That is, it is easier to obtain a clear pattern.
作為可使用於顯影液之有機溶劑,具體而言,可舉出環戊酮等的酮系溶劑、丙二醇單甲醚乙酸酯(PGMEA)或乙酸丁酯等的酯系溶劑、丙二醇單甲醚等的醚系溶劑等。 作為顯影液,可以使用僅由有機溶劑構成且僅含有不可避免地含有之雜質之有機溶劑顯影液。另外,作為不可避免地含有之雜質,有金屬元素,但從防止電子裝置污染等的觀點考慮,不可避免地含有之雜質越少越好。 Specific examples of the organic solvent usable in the developer include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and propylene glycol monomethyl ether. and other ether-based solvents, etc. As the developer, an organic solvent developer composed of only an organic solvent and containing only impurities that are inevitably contained can be used. In addition, there are metal elements as impurities that are inevitably contained, but from the viewpoint of preventing contamination of electronic devices, the less impurities that are inevitably contained, the better.
顯影步驟的時間通常為5~300秒左右,較佳為在10~120秒左右的範圍內,可根據樹脂膜的膜厚或所形成之圖案的形狀等適當調整。The time of the developing step is usually about 5 to 300 seconds, preferably about 10 to 120 seconds, and can be appropriately adjusted according to the thickness of the resin film, the shape of the pattern to be formed, and the like.
在顯影步驟與後續步驟之間,例如可以具有使樹脂膜3A硬化之硬化步驟。硬化例如可以在150~250℃、藉由30~240分鐘的加熱處理來進行。Between the development step and the subsequent step, for example, there may be a hardening step of hardening the
(追加再配線步驟:圖1D)
可以在顯影步驟中設置之開口5的部分設置與段差10(例如,Cu再配線)不同之Cu再配線11。藉由改善樹脂膜3A的上表面的平坦性,能夠精確地設置微細的Cu再配線11。
(Additional rewiring step: Figure 1D)
A portion of the
以上,對本發明的實施形態進行了描述,但該等僅為本發明的示例,亦可以採用上述以外的各種構成。又,本發明並不限定於上述的實施形態,能夠實現本發明目的之範圍內的變形、改進等皆包括在本發明中。 〔實施例〕 The embodiments of the present invention have been described above, but these are merely examples of the present invention, and various configurations other than those described above may be employed. In addition, this invention is not limited to the above-mentioned embodiment, The deformation|transformation, improvement, etc. within the range which can achieve the objective of this invention are all included in this 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. The present invention is not limited only to the Examples, which are explained beforehand for the sake of prudence.
<使用環氧樹脂之實施例> (感光性樹脂組成物的製造) 首先,得到以下的表1所示之組成的均勻的混合物。 <Example using epoxy resin> (Manufacture of photosensitive resin composition) First, a homogeneous mixture of the composition shown in Table 1 below was obtained.
[表1]
環氧樹脂EPPN-201為Nippon Kayaku Co.,Ltd.製的由以下化學式表示之化合物。 環氧樹脂LX-01為OSAKA SODA CO., LTD.製的由以下的化學式表示之化合物。 苯氧基樹脂PKHA為Gabriel Phenoxies公司製的由以下化學式表示之化合物。 感光劑(光陽離子聚合起始劑)CPI-310B為San-Apro Ltd.製的光酸產生劑,陽離子結構:三芳基(苯基)锍、陰離子結構:B(C 6F 5) 4。 界面活性劑FC4432為3M公司製的非離子性氟系界面活性劑。 密接助劑X-12-967C為Shin-Etsu Chemical Co., Ltd.製的3-三甲氧基矽基丙基琥珀酸酐。 The epoxy resin EPPN-201 is a compound represented by the following chemical formula manufactured by Nippon Kayaku Co., Ltd.. The epoxy resin LX-01 is a compound represented by the following chemical formula, manufactured by OSAKA SODA CO., LTD. The phenoxy resin PKHA is a compound represented by the following chemical formula manufactured by Gabriel Phenoxies. Sensitizer (photocationic polymerization initiator) CPI-310B is a photoacid generator manufactured by San-Apro Ltd., cationic structure: triaryl (phenyl) sulfonium, anionic structure: B(C 6 F 5 ) 4 . The surfactant FC4432 is a nonionic fluorine-based surfactant manufactured by 3M. The adhesion adjuvant X-12-967C is 3-trimethoxysilylpropyl succinic anhydride manufactured by Shin-Etsu Chemical Co., Ltd.
在以下實施例1-1~1-3、比較例1-1~1-2中的某一條件下過濾了上述混合物。其後,製造了感光性樹脂組成物。The above-mentioned mixture was filtered under any of the following conditions of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2. Then, the photosensitive resin composition was manufactured.
·實施例1-1 使混合物以100g/分的流速通過KITZ MICRO FILTER CORPORATION的中空纖維膜過濾器(型號:F70SC12F-L8、孔徑:0.2μm、材質:聚丙烯、膜面積:20000cm 2)而進行了過濾。 ·實施例1-2 首先,使混合物以100g/分的流速通過Entegris公司的膜過濾器(型號:PIAA01P01、孔徑:1.0μm、材質:聚乙烯、膜面積:8000cm 2)而進行過濾之後,接著使其以100g/分的流速通過KITZ MICRO FILTER CORPORATION的中空纖維膜過濾器(型號:F70SC12F-L8、孔徑:0.2μm、材質:聚丙烯、膜面積:20000cm 2)而進行了過濾。 ·實施例1-3 首先,使用Entegris公司的膜過濾器(型號:PIAH01P01、孔徑:0.5μm、材質:聚乙烯、膜面積:8000cm 2)以1000g/分的流速對混合物進行了3次循環過濾。使進行該循環過濾之後的混合物以500g/分的流速通過KITZ MICRO FILTER CORPORATION的中空纖維膜過濾器(型號:F70SC12F-L8、孔徑:0.2μm、材質:聚丙烯、膜面積:20000cm 2)而進行了過濾。 Example 1-1 The mixture was passed through a hollow fiber membrane filter (model: F70SC12F-L8, pore size: 0.2 μm, material: polypropylene, membrane area: 20000 cm 2 ) of KITZ MICRO FILTER CORPORATION at a flow rate of 100 g/min. filtered. Example 1-2 First, the mixture was filtered through a membrane filter (Model: PIAA01P01, pore size: 1.0 μm, material: polyethylene, membrane area: 8000 cm 2 ) of Entegris Corporation at a flow rate of 100 g/min, and then This was filtered through a hollow fiber membrane filter (Model: F70SC12F-L8, pore diameter: 0.2 μm, material: polypropylene, membrane area: 20000 cm 2 ) of KITZ MICRO FILTER CORPORATION at a flow rate of 100 g/min. Example 1-3 First, the mixture was filtered three times at a flow rate of 1000 g/min using a membrane filter (model: PIAH01P01, pore size: 0.5 μm, material: polyethylene, membrane area: 8000 cm 2 ) from Entegris. . The mixture after the circulating filtration was passed through a hollow fiber membrane filter (Model: F70SC12F-L8, pore diameter: 0.2 μm, material: polypropylene, membrane area: 20000 cm 2 ) of KITZ MICRO FILTER CORPORATION at a flow rate of 500 g/min. filtered.
·比較例1-1 使混合物以100g/分的流速通過Entegris公司的膜過濾器(型號:PIAG01P01、孔徑:0.2μm、材質:超高分子量聚乙烯、膜面積:8800cm 2)而進行了過濾。 ·比較例1-2 首先,使混合物以100g/分的流速通過Entegris公司的膜過濾器(型號:PIAA01P01、孔徑:1.0μm、材質:聚乙烯、膜面積:8000cm 2)而進行過濾之後,接著使其以100g/分的流速通過Entegris公司的膜過濾器(型號:PIAG01P01、孔徑:0.2μm、材質:超高分子量聚乙烯、膜面積:8800cm 2)而進行了過濾。 Comparative Example 1-1 The mixture was filtered at a flow rate of 100 g/min through a membrane filter (model: PIAG01P01, pore diameter: 0.2 μm, material: ultra-high molecular weight polyethylene, membrane area: 8800 cm 2 ) manufactured by Entegris. Comparative Example 1-2 First, the mixture was filtered at a flow rate of 100 g/min through a membrane filter (Model: PIAA01P01, pore size: 1.0 μm, material: polyethylene, membrane area: 8000 cm 2 ) manufactured by Entegris, and then This was filtered through a membrane filter (model: PIAG01P01, pore diameter: 0.2 μm, material: ultra-high molecular weight polyethylene, membrane area: 8800 cm 2 ) manufactured by Entegris at a flow rate of 100 g/min.
(粒子數的測量) 使各感光性樹脂組成物以流速3g/分流過使用波長780nm的光之光散射方式的粒子計數器內,對在1分鐘的測量中計數之直徑0.5~20μm的粒子數進行了計數。 作為粒子計數器,使用了RION Co., Ltd.「KS-42改」。 (measurement of particle number) Each photosensitive resin composition was flowed through a particle counter using a light scattering method of light having a wavelength of 780 nm at a flow rate of 3 g/min, and the number of particles with a diameter of 0.5 to 20 μm counted in 1 minute of measurement was counted. As a particle counter, RION Co., Ltd. "KS-42 Kai" was used.
(拉伸伸長特性的評價) 將各感光性樹脂組成物塗佈於Si晶圓上,使溶劑乾燥,從而形成了膜厚10μm的樹脂膜。在170℃、2小時的條件下,使該樹脂膜硬化,得到硬化膜。冷卻至室溫之後,將整個晶圓切成5mm×20mm,進而利用氫氟酸水溶液從晶圓剥離了硬化膜。將剥離出之硬化膜設置於萬能試驗機,在室溫下,以5mm/分的速度進行了拉伸試驗。其後,對破裂點拉伸率進行了測量。 針對各實施例、比較例各進行了10次測量。在後述的表中記載了藉由10次測量得到之破裂點拉伸率的平均值。 (Evaluation of tensile elongation properties) Each photosensitive resin composition was applied on a Si wafer, and the solvent was dried to form a resin film having a thickness of 10 μm. The resin film was cured under the conditions of 170° C. and 2 hours to obtain a cured film. After cooling to room temperature, the entire wafer was cut into 5 mm×20 mm, and the cured film was peeled off from the wafer with an aqueous hydrofluoric acid solution. The peeled cured film was placed in a universal testing machine, and a tensile test was performed at room temperature at a speed of 5 mm/min. Thereafter, the elongation at break point was measured. The measurement was performed 10 times for each of the Examples and Comparative Examples. The average value of the elongation at break point obtained by 10 measurements is described in the table below.
(與金屬之間的密接性的評價) 藉由如下製程製作了評價樣品。 將各感光性樹脂組成物塗佈於Cu製晶圓上,使溶劑乾燥,從而形成了膜厚5μm的樹脂膜。其後,藉由曝光、顯影在感光性樹脂膜上形成通孔,在170℃、2小時的條件下,使其硬化,得到硬化膜。接著,利用O 2電漿去除了殘留於樹脂膜之浮渣。接著,藉由濺射在該基板上形成作為密接層的Ti層(厚度50nm)、Cu層(300nm)之後,形成阻劑(TMMR(註冊商標)P-W1000T PM TOKYO OHKA KOGYO CO., LTD.製),其後進行銅電鍍,用鍍銅填充通孔,利用阻劑剥離液(ST-120 TOKYO OHKA KOGYO CO., LTD.製)剥離阻劑,得到評價樣品。 (Evaluation of Adhesion with Metal) An evaluation sample was produced by the following process. Each photosensitive resin composition was applied on a Cu wafer, and the solvent was dried to form a resin film having a thickness of 5 μm. Then, through-holes were formed in the photosensitive resin film by exposure and image development, and it was made to harden on the conditions of 170 degreeC and 2 hours, and the cured film was obtained. Next, the scum remaining on the resin film was removed by O 2 plasma. Next, a Ti layer (thickness: 50 nm) and a Cu layer (300 nm) were formed on the substrate by sputtering, and then a resist (TMMR (registered trademark) P-W1000T PM TOKYO OHKA KOGYO CO., LTD. made), then copper plating was performed, the through holes were filled with copper plating, and the resist was stripped with a resist stripping solution (manufactured by ST-120 TOKYO OHKA KOGYO CO., LTD.) to obtain an evaluation sample.
接著,藉由如下評價方法對與金屬之間的密接性進行了評價。 對評價樣品進行了簡單的回焊處理。利用260℃的熱板加熱5秒鐘之後,從熱板取出,冷却至室溫。加熱、冷却的操作實施了10次。與金屬之間的密接狀態的確認係藉由FIB-SEM來實施。對用鍍銅填充之通孔部進行FIB加工,利用SEM觀察剖面,確認了樹脂膜與Cu的界面有無剥離。 Next, the adhesiveness with the metal was evaluated by the following evaluation method. A simple reflow process was performed on the evaluation samples. After heating on a 260°C hot plate for 5 seconds, it was taken out from the hot plate and cooled to room temperature. The operation of heating and cooling was performed 10 times. The confirmation of the adhesion state with the metal was implemented by FIB-SEM. The through-hole portion filled with copper plating was subjected to FIB processing, and the cross section was observed by SEM to confirm whether or not the interface between the resin film and Cu was peeled off.
匯總粒子數的測量結果、拉伸伸長特性的評價結果及與金屬之間的密接性的評價結果,示於下表。The measurement results of the particle number, the evaluation results of the tensile elongation properties, and the evaluation results of the adhesion with metals are summarized in the following table.
[表2]
如上表所示,由粒子數少的感光性樹脂組成物形成之硬化膜(永久膜)的拉伸伸長特性比由粒子數多的感光性樹脂組成物形成者良好。又,由粒子數少的感光性樹脂組成物形成之硬化膜(永久膜)表現出了與金屬之間的良好的密接性。As shown in the above table, the cured film (permanent film) formed from the photosensitive resin composition having a small number of particles has better tensile elongation properties than those formed from the photosensitive resin composition having a large particle number. Moreover, the cured film (permanent film) formed from the photosensitive resin composition with a small particle number shows favorable adhesiveness with a metal.
(圖案形成性的評價) 為了慎重起見,如下確認了使用上述的環氧樹脂之感光性樹脂組成物具有作為「感光性樹脂組成物」的圖案形成性。 (Evaluation of Pattern Formability) For the sake of prudence, the photosensitive resin composition using the above-mentioned epoxy resin was confirmed to have pattern formability as a "photosensitive resin composition" as follows.
使用旋塗機在8吋矽晶圓上塗佈了實施例1-1的感光性樹脂組成物。塗佈之後,在大氣中,利用加熱板在120℃預烘烤3分鐘,得到膜厚約為9μm的樹脂膜。 經由TOPPAN INC.製遮罩(描繪有寬度1.0~100μm的殘留圖案及沖孔圖案)對該樹脂膜照射了i射線。照射中使用了i射線步進器(Nikon Corporation製、NSR-4425i)。 曝光之後,將晶圓放置於加熱板上,在大氣中進行了70℃、5分鐘的烘烤處理。 其後,將丙二醇單甲基醚乙酸酯用作顯影液,進行30秒鐘噴霧顯影,藉此溶解去除了未曝光部。 藉由以上步驟,得到僅選擇性地去除了膜中的未曝光部之圖案。亦即,確認到藉由使用光罩之曝光,能夠形成「圖案」。 The photosensitive resin composition of Example 1-1 was coated on an 8-inch silicon wafer using a spin coater. After the coating, in the atmosphere, a hot plate was used for prebaking at 120° C. for 3 minutes to obtain a resin film having a film thickness of about 9 μm. The resin film was irradiated with i-rays through a mask made by TOPPAN INC. (with a residual pattern and a punching pattern having a width of 1.0 to 100 μm drawn). For the irradiation, an i-ray stepper (manufactured by Nikon Corporation, NSR-4425i) was used. After exposure, the wafer was placed on a hot plate and baked at 70° C. for 5 minutes in the atmosphere. Then, the unexposed part was melt|dissolved and removed by performing spray image development for 30 second using propylene glycol monomethyl ether acetate as a developer. Through the above steps, a pattern in which only the unexposed portion in the film is selectively removed is obtained. That is, it was confirmed that a "pattern" can be formed by exposure using a mask.
又,代替實施例1-1的感光性樹脂組成物,使用實施例1-2及1-3的感光性樹脂組成物,亦同樣地得到圖案。Moreover, the pattern was obtained similarly using the photosensitive resin composition of Example 1-2 and 1-3 instead of the photosensitive resin composition of Example 1-1.
<使用聚醯胺/聚醯亞胺樹脂之實施例> (聚合物(A-1)的合成) 首先,將2,2’-雙(三氟甲基)-4,4’-二胺基聯苯(以下,亦稱為TFMB)64.1g(0.20莫耳)和二苯甲酮-3,3’,4,4’-四羧酸二酐(以下,亦稱為BTDA)70.9g(0.22莫耳)放入具備攪拌機及冷却管之適當的尺寸的反應容器中。其後,進而在反應容器中添加了GBL500g。 通入10分鐘氮氣之後,一邊攪拌,一邊將溫度提升至60℃,進行了1.5小時反應。其後,進而在180℃進行3小時反應,藉此使二胺和酸二酐聚合,製成了聚醯亞胺溶液。 將得到之聚醯亞胺溶液用丙酮進行稀釋,製作出稀釋液,接著,將稀釋液滴加於水/甲醇=3/1的混合溶液中,使白色固體析出。回收得到之白色固體,以120℃的溫度進行了真空乾燥。藉由以上步驟,得到在末端具有酸酐之聚醯亞胺粉末亦即聚合物(A-1)。 藉由GPC測量測出之聚合物(A-1)的重量平均分子量(Mw)為25,000。 又,對聚合物(A-1)進行 1H-NMR測量,根據聚醯亞胺的醯胺峰相對於芳香環的峰之定量值計算出了醯亞胺化率(定義如前述)。醯亞胺化率為99%以上。 <Example using polyimide/polyimide resin> (Synthesis of polymer (A-1)) First, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl (hereinafter, also referred to as TFMB) 64.1g (0.20 mol) and benzophenone-3,3',4,4'-tetracarboxylic dianhydride (hereinafter, also referred to as BTDA) 70.9g (0.22 moles) into an appropriately sized reaction vessel with a stirrer and cooling tubes. Then, GBL500g was added to the reaction container further. After nitrogen gas was introduced for 10 minutes, the temperature was raised to 60°C while stirring, and the reaction was performed for 1.5 hours. Then, the reaction was further performed at 180° C. for 3 hours to polymerize the diamine and the acid dianhydride to prepare a polyimide solution. The obtained polyimide solution was diluted with acetone to prepare a diluted solution, and the diluted solution was then added dropwise to a mixed solution of water/methanol=3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 120°C. Through the above steps, a polyimide powder having an acid anhydride at the terminal, that is, a polymer (A-1) was obtained. The weight average molecular weight (Mw) of the polymer (A-1) measured by GPC measurement was 25,000. Furthermore, the polymer (A-1) was subjected to 1 H-NMR measurement, and the imidization ratio (defined as above) was calculated from the quantitative value of the polyimide amide peak relative to the aromatic ring peak. The imidization rate is over 99%.
以下示出聚合物(A-1)的化學式。The chemical formula of the polymer (A-1) is shown below.
(感光性樹脂組成物的製造) 首先,均勻地混合以下的各素材,得到混合物。 ·樹脂 上述(A-1) 100質量份 ·多官能(甲基)丙烯酸酯化合物 Viscoat#802(OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製、由以下化學式表示之結構) 80質量份 (Manufacture of photosensitive resin composition) First, each of the following materials is uniformly mixed to obtain a mixture. ·Resin 100 parts by mass of the above (A-1) ·Multifunctional (meth)acrylate compound Viscoat #802 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., a structure represented by the following chemical formula) 80 parts by mass
·感光劑
Irugacure OXE02(BASF公司製、肟酯型光自由基產生劑) 10質量份
·熱自由基產生劑
PERKADOX BC(Nouryon公司製、有機過氧化物、異丙苯基(cumyl)過氧化物) 10質量份
·環氧樹脂
TECHMORE VG3101L(Printec Corporation製) 7質量份
CELLOXIDE 2021P(Daicel Corporation製) 3質量份
·硬化觸媒
4,4’-磺醯基二酚四苯鏻 3質量份
上述硬化觸媒的合成方法如下。
將4,4’-雙酚S 37.5g(0.15mol)、甲醇100mL放入附攪拌裝置的可分離式燒瓶中,在室溫下進行攪拌溶解,進而一邊進行攪拌,一邊添加了預先將氫氧化鈉4.0g(0.1mol)溶解於50mL的甲醇中而得之溶液。接著,添加了預先將四苯基溴化膦41.9g(0.1mol)溶解於150mL的甲醇中而得之溶液。持續攪拌一段時間,並追加300mL的甲醇之後,將燒瓶內的溶液一邊進行攪拌一邊滴加到大量的水中,得到白色沉澱。過濾沉澱,並進行了乾燥。藉由以上步驟,得到白色結晶的目標產物。
·密接助劑(矽烷偶合劑)
KBM-503(Shin-Etsu Chemical Co., Ltd.製、3-甲基丙烯醯氧基丙基三甲氧基矽烷) 5質量份
X-12-967C(Shin-Etsu Chemical Co., Ltd.製、結構如上所述) 2質量份
·界面活性劑
FC4432(3M公司製、氟系) 0.1質量份
·水 2質量份
·溶劑(有機溶劑)
乳酸乙酯(EL) 259質量份
γ-丁內酯(GBL) 259質量份
·Photosensitive agent
Irugacure OXE02 (manufactured by BASF, oxime ester type photoradical generator) 10 parts by mass
· Thermal free radical generator
PERKADOX BC (manufactured by Nouryon, organic peroxide, cumyl peroxide) 10 parts by mass
·Epoxy resin
TECHMORE VG3101L (manufactured by Printec Corporation) 7 parts by mass
CELLOXIDE 2021P (manufactured by Daicel Corporation) 3 parts by mass
· Hardening catalyst
4,4'-
在以下實施例2-1或比較例2-1中的某一條件下過濾了上述混合物。其後,製造了感光性樹脂組成物。 ·實施例2-1 使混合物以50g/分的流速通過KITZ MICRO FILTER CORPORATION的中空纖維膜過濾器(型號:F50C12T-L2、孔徑:0.2μm、材質:聚丙烯、膜面積:20000cm 2)而進行了過濾。 ·比較例2-1 使混合物以50g/分的流速通過Entegris公司的膜過濾器(型號:CWUG0S1S3、孔徑:0.2μm、材質:超高分子量聚乙烯、膜面積:8800cm 2)而進行了過濾。 The above mixture was filtered under one of the following conditions in Example 2-1 or Comparative Example 2-1. Then, the photosensitive resin composition was manufactured. Example 2-1 The mixture was passed through a hollow fiber membrane filter of KITZ MICRO FILTER CORPORATION (model: F50C12T-L2, pore size: 0.2 μm, material: polypropylene, membrane area: 20000 cm 2 ) at a flow rate of 50 g/min. filtered. Comparative Example 2-1 The mixture was filtered at a flow rate of 50 g/min through a membrane filter (model: CWUGOS1S3, pore diameter: 0.2 μm, material: ultra-high molecular weight polyethylene, membrane area: 8800 cm 2 ) manufactured by Entegris.
(粒子數的測量) 以與使用環氧樹脂之實施例相同的方式進行了測量。 (measurement of particle number) Measurements were carried out in the same manner as in the examples using epoxy resins.
(拉伸伸長特性的評價) 將各感光性樹脂組成物塗佈於Si晶圓上,使溶劑乾燥,從而形成了膜厚7μm的樹脂膜。在200℃、2小時、氮氣環境下(氧濃度1000ppm以下)的條件下,使該樹脂膜硬化,得到硬化膜。冷卻至室溫之後,將整個晶圓切成5mm×20mm,進而利用氫氟酸水溶液從晶圓剥離了硬化膜。將剥離出之硬化膜設置於萬能試驗機,在室溫下,以5mm/分的速度進行了拉伸試驗。其後,對破裂點拉伸率進行了測量。 針對各實施例、比較例各進行了10次測量。在後述的表中記載了藉由10次測量得到之破裂點拉伸率的平均值。 (Evaluation of tensile elongation properties) Each photosensitive resin composition was applied on a Si wafer, and the solvent was dried to form a resin film having a thickness of 7 μm. This resin film was hardened under the conditions of 200 degreeC, 2 hours, and nitrogen atmosphere (oxygen concentration 1000 ppm or less), and the cured film was obtained. After cooling to room temperature, the entire wafer was cut into 5 mm×20 mm, and the cured film was peeled off from the wafer with an aqueous hydrofluoric acid solution. The peeled cured film was placed in a universal testing machine, and a tensile test was performed at room temperature at a speed of 5 mm/min. Thereafter, the elongation at break point was measured. The measurement was performed 10 times for each of the Examples and Comparative Examples. The average value of the elongation at break point obtained by 10 measurements is described in the table below.
匯總粒子數的測量結果及拉伸伸長特性的評價結果,示於下表。The measurement results of the particle number and the evaluation results of the tensile elongation characteristics are summarized in the following table.
[表3]
如上表所示,在聚醯胺/聚醯亞胺樹脂系中,由粒子數少的感光性樹脂組成物形成之硬化膜(永久膜)的拉伸伸長特性亦比由粒子數多的感光性樹脂組成物形成者良好。 由該結果及前述的環氧樹脂系的結果可知,與樹脂的種類無關地,永久膜(硬化膜)的拉伸伸長特性會因感光性樹脂組成物中的粒子數少而變得良好。 As shown in the above table, in the polyimide/polyimide resin system, the cured film (permanent film) formed of the photosensitive resin composition with a small number of particles has a higher tensile elongation property than a photosensitive resin composition with a large number of particles. Resin composition formers are good. From this result and the result of the above-mentioned epoxy resin system, it turns out that the tensile elongation characteristic of a permanent film (cured film) becomes favorable because the number of particles in the photosensitive resin composition is small, regardless of the type of resin.
(圖案形成性的評價) 為了慎重起見,如下確認了使用上述的聚醯胺/聚醯亞胺樹脂之感光性樹脂組成物具有作為「感光性樹脂組成物」的圖案形成性。 (Evaluation of Pattern Formability) For the sake of prudence, the photosensitive resin composition using the above-mentioned polyimide/polyimide resin was confirmed to have pattern formability as a "photosensitive resin composition".
使用旋塗機在8吋矽晶圓上將使用上述的聚醯胺/聚醯亞胺樹脂之感光性樹脂組成物塗佈成乾燥後的膜厚成為5μm。其後,利用熱板在100℃進行3分鐘乾燥,得到感光性樹脂膜。 使用i射線步進器(Nikon Corporation製、NSR-4425i)一邊改變曝光量,一邊經由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)對該感光性樹脂膜照射了i射線。 其後,將環戊酮用作顯影液,進行30秒鐘顯影,並以2500轉進行10秒鐘旋轉,進行了乾燥。 藉由以上的步驟,能夠在樹脂膜開出10μmΦ的通孔。亦即,確認到藉由使用光罩之曝光,能夠形成「圖案」。 The photosensitive resin composition using the above-mentioned polyimide/polyimide resin was applied on an 8-inch silicon wafer using a spin coater so that the film thickness after drying was 5 μm. Then, it dried at 100 degreeC for 3 minutes with a hotplate, and obtained the photosensitive resin film. Using an i-ray stepper (NSR-4425i, manufactured by Nikon Corporation), while changing the exposure amount, a mask (test pattern No. 1: a residual pattern and a punching pattern with a width of 0.5 to 50 μm are drawn) made by TOPPAN INC. The photosensitive resin film was irradiated with i-rays. Then, using cyclopentanone as a developer, development was performed for 30 seconds, and it was rotated at 2500 revolutions for 10 seconds, and dried. Through the above steps, a through hole of 10 μmΦ can be opened in the resin film. That is, it was confirmed that a "pattern" can be formed by exposure using a mask.
本申請主張以於2020年7月16日申請之日本申請特願2020-121920號及於2021年7月8日申請之日本申請特願2021-113582號為基礎之優先權,並將其揭示的所有內容援用於此。This application claims priority based on Japanese Application No. 2020-121920 filed on Jul. 16, 2020 and Japanese Application No. 2021-113582 filed on Jul. 8, 2021, and discloses the same All content referenced here.
1:基板
3:感光性樹脂膜
3A:樹脂膜
5:開口
10:段差
11:Cu再配線
20:光罩
1: Substrate
3:
[圖1]係用於說明電子裝置之製造方法之圖。[FIG. 1] It is a figure for demonstrating the manufacturing method of an electronic device.
1:基板 1: Substrate
3:感光性樹脂膜 3: Photosensitive resin film
3A:樹脂膜 3A: Resin film
5:開口 5: Opening
10:段差 10: Stage difference
11:Cu再配線 11: Cu rewiring
20:光罩 20: Photomask
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JP2020121920 | 2020-07-16 | ||
JP2021113582A JP2022019609A (en) | 2020-07-16 | 2021-07-08 | Photosensitive resin composition, method for manufacturing electronic device, electronic device and method for producing photosensitive resin composition |
JPJP2021-113582 | 2021-07-08 |
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