TWI806161B - Manufacturing method of polyimide hardened film - Google Patents
Manufacturing method of polyimide hardened film Download PDFInfo
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- TWI806161B TWI806161B TW110134872A TW110134872A TWI806161B TW I806161 B TWI806161 B TW I806161B TW 110134872 A TW110134872 A TW 110134872A TW 110134872 A TW110134872 A TW 110134872A TW I806161 B TWI806161 B TW I806161B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/5329—Insulating materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
本發明之課題在於提供一種表現出低介電損耗正切、介電損耗正切之頻率依存性較少且熱重量減少溫度較高之聚醯亞胺硬化膜之製造方法。 本發明之聚醯亞胺硬化膜之製造方法包括：(1)將包含聚醯亞胺前驅物之感光性樹脂組合物塗佈於基板上，於該基板上形成感光性樹脂層之步驟；(2)對所獲得之感光性樹脂層進行乾燥、加熱之步驟；(3)對所獲得之感光性樹脂層進行曝光之步驟；(4)對所獲得之感光性樹脂層進行顯影之步驟；及(5)對殘留於該基板上之感光性樹脂層以150℃～250℃進行加熱處理而形成硬化膜之步驟；步驟(2)及/或(5)係於50 torr以上且580 torr以下之壓力下實施，於所獲得之聚醯亞胺硬化膜之聚醯亞胺中，相對於包含源自四羧酸與二胺之結構之重複單元之分子量，醯亞胺基所占之比率即醯亞胺基濃度為12 wt%～30 wt%。 The object of the present invention is to provide a method for producing a polyimide cured film exhibiting low dielectric loss tangent, less frequency dependence of dielectric loss tangent and high thermogravimetric reduction temperature. The manufacturing method of the polyimide cured film of the present invention comprises: (1) the photosensitive resin composition that will comprise polyimide precursor is coated on the substrate, the step of forming photosensitive resin layer on this substrate; 2) a step of drying and heating the obtained photosensitive resin layer; (3) a step of exposing the obtained photosensitive resin layer; (4) a step of developing the obtained photosensitive resin layer; and (5) A step of heat-treating the photosensitive resin layer remaining on the substrate at 150°C to 250°C to form a cured film; steps (2) and/or (5) are performed at temperatures above 50 torr and below 580 torr Implemented under pressure, in the polyimide of the obtained polyimide cured film, relative to the molecular weight of the repeating unit including the structure derived from tetracarboxylic acid and diamine, the ratio of the imide group is the acyl group. The imine group concentration is 12 wt% to 30 wt%.
Description
本發明係關於一種聚醯亞胺硬化膜之製造方法。The invention relates to a manufacturing method of a polyimide cured film.
先前，電子零件之絕緣材料及半導體裝置之鈍化膜、表面保護膜、層間絕緣膜等使用兼具優異之耐熱性、電特性及機械特性之聚醯亞胺樹脂。該聚醯亞胺樹脂之中，以感光性聚醯亞胺前驅物組合物之形態提供者可藉由該組合物之塗佈、曝光、顯影、及基於固化之熱醯亞胺化處理而容易地形成耐熱性凹凸圖案皮膜。此種感光性聚醯亞胺前驅物組合物具有與先前之非感光型聚醯亞胺材料相比能夠大幅縮減步驟之特徵。Previously, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials of electronic parts and passivation films, surface protection films, and interlayer insulating films of semiconductor devices. Among the polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can be easily processed by coating, exposing, developing, and curing-based thermal imidization of the composition. Form a heat-resistant concave-convex pattern film. Compared with the previous non-photosensitive polyimide materials, the photosensitive polyimide precursor composition can greatly reduce the steps.
且說，半導體裝置(以下，亦稱為「元件」)對應於目的以各種方法安裝於印刷基板。先前之元件通常係藉由自元件之外部端子(焊墊)至引線框架以較細之金屬線連接之打線接合法而製作，但最近，就高速傳輸化及封裝高度之薄型化等觀點而言，提出有被稱為扇出型晶圓級封裝(FOWLP)之半導體晶片安裝技術。所謂FOWLP，係對已完成前步驟之晶圓進行切割而製造單片晶片，於支持體上對單片晶片進行重組後利用塑模樹脂進行密封，並將支持體剝離後形成再配線層之安裝技術。In addition, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to purposes. The previous components were usually manufactured by wire bonding method connecting the external terminal (pad) of the component to the lead frame with a thinner metal wire, but recently, from the viewpoint of high-speed transmission and thinning of package height, etc. , a semiconductor chip mounting technique called fan-out wafer-level packaging (FOWLP) has been proposed. The so-called FOWLP is to cut the wafer that has completed the previous steps to manufacture a single chip. After reorganizing the single chip on the support, it is sealed with molding resin, and the support is peeled off to form the installation of the rewiring layer. technology.
近年來，當務之急係開發面向作為新通信標準之第5代移動通信系統(5G)之封裝。5G與先前技術之4G不同，藉由使用毫米波(10 Gz～80 GHz)之頻帶，能夠實現先前之通信所不存在之高速大容量化/信號之低延遲/多終端之同時連接。毫米頻帶於印刷配線板之信號配線中傳輸損耗之影響較大，存在發熱或傳輸延遲之顧慮。因此，為了降低傳輸損耗，將進行電波收發之前端模組(FEM)與天線一體化而開發出天線封裝(AiP)(例如，參照以下專利文獻1)。AiP由於配線長度較短，故而能夠抑制與配線長度成比例增大之傳輸損耗。 [先前技術文獻] [專利文獻] In recent years, it is imperative to develop packages for the fifth generation mobile communication system (5G), which is a new communication standard. 5G is different from the 4G of the previous technology. By using the frequency band of millimeter waves (10 Gz ~ 80 GHz), 5G can achieve high-speed and large-capacity/low-delay of signals/simultaneous connection of multiple terminals that did not exist in previous communications. The millimeter frequency band has a greater impact on the transmission loss in the signal wiring of the printed wiring board, and there are concerns about heat generation or transmission delay. Therefore, in order to reduce transmission loss, an antenna in package (AiP) has been developed by integrating a front-end module (FEM) and an antenna for transmitting and receiving radio waves (see, for example, Patent Document 1 below). AiP can suppress the transmission loss which increases in proportion to the wiring length due to the short wiring length. [Prior Art Literature] [Patent Document]
[專利文獻1]美國專利申請公開第2016/0104940號說明書[Patent Document 1] Specification of U.S. Patent Application Publication No. 2016/0104940
[發明所欲解決之問題][Problem to be solved by the invention]
另一方面，封裝設計上之傳輸損耗之抑制亦存在極限，亦期待材料方面之改善。於用於形成配線之絕緣材料之介電常數或介電損耗正切(tanδ)較高之情形時，介電損耗增大，傳輸損耗增加。尤其是聚醯亞胺雖然絕緣性能或膜物性優異，但由於醯亞胺基本身為極性官能基，故而介電常數或介電損耗正切之值較高，需要降低介電特性。On the other hand, there is a limit to the suppression of transmission loss in packaging design, and improvement in materials is expected. In the case where the dielectric constant or dielectric loss tangent (tan δ) of the insulating material used to form the wiring is high, the dielectric loss increases and the transmission loss increases. In particular, although polyimide has excellent insulation performance or film physical properties, since the imide group itself is a polar functional group, the value of dielectric constant or dielectric loss tangent is relatively high, and the dielectric properties need to be reduced.
鑒於以上技術水準，本發明所欲解決之課題在於提供一種表現出低介電損耗正切、介電損耗正切之頻率依存性較少且熱重量減少溫度較高之聚醯亞胺硬化膜之製造方法、硬化凹凸圖案之製造方法、及藉由該方法所獲得之聚醯亞胺硬化膜。In view of the above technical level, the problem to be solved by the present invention is to provide a method for producing a cured polyimide film exhibiting low dielectric loss tangent, less frequency dependence of dielectric loss tangent and higher thermal weight loss temperature , A method for producing a cured concave-convex pattern, and a polyimide cured film obtained by the method.
本發明者意外發現：於將包含聚醯亞胺前驅物之感光性樹脂組合物用作原料之聚醯亞胺硬化膜之製造方法中，藉由將加熱時之壓力控制在特定範圍，能夠解決上述課題，從而完成了本發明。The inventors of the present invention unexpectedly found that in the method of producing a polyimide cured film using a photosensitive resin composition containing a polyimide precursor as a raw material, by controlling the pressure during heating within a specific range, the problem can be solved. The above problems have been solved, and the present invention has been accomplished.
即，本發明如下所述。
[1]一種聚醯亞胺硬化膜之製造方法，其特徵在於包括以下步驟：
(1)將包含聚醯亞胺前驅物之感光性樹脂組合物塗佈於基板上，於該基板上形成感光性樹脂層之步驟；
(2)對所獲得之感光性樹脂層進行乾燥、加熱之步驟；
(3)對所獲得之感光性樹脂層進行曝光之步驟；
(4)對所獲得之感光性樹脂層進行顯影之步驟；及
(5)對殘留於該基板上之感光性樹脂層以150℃～250℃進行加熱處理而形成硬化膜之步驟；
上述步驟(2)及/或(5)係於50 torr以上且580 torr以下之壓力下實施，且於所獲得之聚醯亞胺硬化膜之聚醯亞胺中，相對於包含源自四羧酸與二胺之結構之重複單元之分子量，醯亞胺基所占之比率即醯亞胺基濃度為12 wt%～30 wt%。
[2]如上述[1]之聚醯亞胺硬化膜之製造方法，其中藉由步驟(5)所獲得之硬化膜藉由擾動方式分體圓柱共振器法所得之頻率10 GHz下之介電損耗正切為0.001～0.007。
[3]如上述[1]或[2]之聚醯亞胺硬化膜之製造方法，其中上述步驟(5)係於50 torr以上且580 torr以下之壓力下實施。
[4]如上述[3]之聚醯亞胺硬化膜之製造方法，其中於上述步驟(5)中，達到設定之加熱硬化溫度時之自設定溫度之溫度變化為30.0℃以下。
[5]如上述[3]至[4]中任一項之聚醯亞胺硬化膜之製造方法，其中於上述步驟(5)中之溫度變化為9.5℃/分鐘以下之區域中，壓力之變化為150 torr以內。
[6]如上述[1]至[5]中任一項之聚醯亞胺硬化膜之製造方法，其中將獲得之聚醯亞胺硬化膜加熱至320℃時之重量減少率為0.01%～0.5%。
[7]如上述[1]至[6]中任一項之聚醯亞胺硬化膜之製造方法，其中將獲得之聚醯亞胺硬化膜加熱至350℃時之重量減少率為0.1%～1.5%。
[8]如上述[1]至[7]中任一項之聚醯亞胺硬化膜之製造方法，其中獲得之聚醯亞胺硬化膜滿足下述數式(i)：
0.001＜(tanδ40－tanδ10)/tanδ10＜0.2 (i)
{式中，tanδ40係藉由擾動方式分體圓柱共振器法所得之頻率40 GHz下之介電損耗正切，並且tanδ10係藉由擾動方式分體圓柱共振器法所得之頻率10 GHz下之介電損耗正切}。
[9]一種再配線用層間絕緣膜形成用聚醯亞胺硬化膜，其藉由擾動方式分體圓柱共振器法以頻率10 GHz進行測定時之介電損耗正切為0.001～0.009，且該聚醯亞胺具有下述通式(10)所表示之結構：
[化1]
本發明之聚醯亞胺硬化膜之製造方法於減壓下進行加熱，藉此能夠提供一種介電損耗正切之頻率依存性較低、加熱硬化溫度以上之溫度下之熱重量減少得到抑制之聚醯亞胺硬化膜。The method for producing a polyimide cured film of the present invention heats under reduced pressure, whereby a polyimide having low frequency dependence of dielectric loss tangent and suppressed thermogravimetric decrease at a temperature above the heating hardening temperature can be provided. Imide hardened film.
以下，對用以實施本發明之方式(以下，簡記為「實施方式」)詳細地進行說明。再者，本發明並不限定於以下實施方式，可於其主旨之範圍內進行各種變化後實施。通過本說明書，通式中由相同符號表示之結構於在分子中存在複數個之情形時，只要未另行規定，則分別獨立地選擇，可相互相同，亦可不同。又，在不同通式中由共用之符號表示之結構亦只要未另行規定，則分別獨立地選擇，可相互相同，亦可不同。Hereinafter, modes for implementing the present invention (hereinafter, simply referred to as "embodiments") will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement after making various changes within the range of the summary. Throughout the present specification, when there are plural structures in the molecule, the structures represented by the same symbols in the general formula are independently selected, and may be the same or different from each other unless otherwise specified. Furthermore, structures represented by common symbols in different general formulas are also independently selected unless otherwise specified, and may be the same as or different from each other.
[硬化膜及之製造方法] 本發明之一實施方式係一種聚醯亞胺硬化膜之製造方法，其特徵在於包括以下步驟： (1)將包含聚醯亞胺前驅物之感光性樹脂組合物塗佈於基板上，於該基板上形成感光性樹脂層之步驟； (2)對所獲得之感光性樹脂層進行乾燥、加熱之步驟； (3)對所獲得之感光性樹脂層進行曝光之步驟； (4)對所獲得之感光性樹脂層進行顯影之步驟；及 (5)對殘留於該基板上之感光性樹脂層以150℃～250℃進行加熱處理而形成硬化膜之步驟； 上述步驟(2)及/或(5)係於50 torr以上且580 torr以下之壓力下實施，且於所獲得之聚醯亞胺硬化膜之聚醯亞胺中，相對於包含源自四羧酸與二胺之結構之重複單元之分子量，醯亞胺基所占之比率即醯亞胺基濃度為12 wt%～30 wt%。 就介電損耗正切之觀點而言，較佳為上述步驟(5)於50 torr以上且580 torr以下之壓力下實施。 該壓力較佳為80 torr～580 torr，較佳為100 torr～500 torr，更佳為120 torr～450 torr，進而較佳為160 torr～420 torr。雖不受特定理論約束，但以580 torr以下之壓力加熱時，膜中所存在之低分子化合物之沸點降低，因此容易氣化而自膜中去除，藉此獲得高頻區域中之介電損耗降低之硬化膜。同時，由於對硬化膜進行加熱時會揮發之成分較少，故而加熱時之重量減少率降低。又，同樣雖不受理論約束，但藉由以50 torr以上加熱，減壓後溶劑分子不會立刻氣化，從而不會阻礙藉由加熱硬化而進行之醯亞胺化。 [Cured film and its manufacturing method] One embodiment of the present invention is a method for manufacturing a polyimide cured film, which is characterized in that it includes the following steps: (1) coating a photosensitive resin composition comprising a polyimide precursor on a substrate, and forming a photosensitive resin layer on the substrate; (2) Steps of drying and heating the obtained photosensitive resin layer; (3) a step of exposing the obtained photosensitive resin layer; (4) a step of developing the obtained photosensitive resin layer; and (5) heat-treating the photosensitive resin layer remaining on the substrate at 150°C to 250°C to form a cured film; The above-mentioned steps (2) and/or (5) are implemented under a pressure of more than 50 torr and less than 580 torr, and in the polyimide of the obtained polyimide hardened film, relative to the polyimide derived from tetracarboxylic The molecular weight of the repeating unit of the structure of the acid and the diamine, the ratio of the imide group, that is, the concentration of the imide group is 12 wt% to 30 wt%. From the viewpoint of dielectric loss tangent, it is preferable to carry out the above-mentioned step (5) under a pressure of not less than 50 torr and not more than 580 torr. The pressure is preferably from 80 torr to 580 torr, preferably from 100 torr to 500 torr, more preferably from 120 torr to 450 torr, and still more preferably from 160 torr to 420 torr. Although not bound by a specific theory, when heated at a pressure below 580 torr, the boiling point of the low-molecular compound present in the film decreases, so it is easily vaporized and removed from the film, thereby obtaining dielectric loss in the high-frequency region Reduced hardened film. At the same time, since there are fewer components that will volatilize when the cured film is heated, the weight loss rate during heating is reduced. Also, although not bound by theory, by heating above 50 torr, the solvent molecules will not be vaporized immediately after decompression, so that the imidization by heat hardening will not be hindered.
以下，對各步驟進行說明。 [(1)將包含聚醯亞胺前驅物之感光性樹脂組合物塗佈於基板上，於該基板上形成感光性樹脂層之步驟] 於步驟(1)中，將包含聚醯亞胺前驅物之感光性樹脂組合物塗佈於基材上，視需要其後使之乾燥，形成感光性樹脂層。作為塗佈方法，可使用先前以來用於塗佈感光性樹脂組合物之方法，例如利用旋轉塗佈機、棒式塗佈機、刮刀塗佈機、簾幕式塗佈機、網版印刷機等塗佈之方法、利用噴霧塗佈機進行噴霧塗佈之方法等。 Each step will be described below. [(1) A step of coating a photosensitive resin composition comprising a polyimide precursor on a substrate, and forming a photosensitive resin layer on the substrate] In step (1), the photosensitive resin composition containing the polyimide precursor is coated on the substrate, and then dried if necessary to form a photosensitive resin layer. As the coating method, methods conventionally used for coating photosensitive resin compositions can be used, for example, using a spin coater, bar coater, blade coater, curtain coater, screen printing machine The method of coating etc., the method of spray coating using a spray coater, etc.
[(2)對所獲得之感光性樹脂層進行乾燥、加熱之步驟] 於步驟(2)中，可視需要使包含感光性樹脂組合物之塗膜乾燥。作為乾燥方法，例如使用風乾、藉由烘箱或加熱板進行之加熱乾燥、真空乾燥等方法。具體而言，於進行風乾或加熱乾燥之情形時，可於溫度20℃～140℃內進行，更佳為80℃～140℃，更佳為80℃～120℃。可於乾燥時間1分鐘～1小時內進行，更佳為2分鐘～30分鐘，更佳為2分鐘～10分鐘。於上述條件下進行乾燥，藉此能夠於基板上形成感光性樹脂層。 於以真空乾燥進行(2)乾燥、加熱步驟之情形時，熱源較佳為自加熱板或紅外線燈中選擇。進而，就減壓下之加熱效率之觀點而言，較佳為將形成有塗膜之晶圓放置於熱源進行加熱。(2)乾燥、加熱步驟可於50 torr以上且580 torr以下之壓力下實施。自設定值之壓力之變化較佳為150 torr以內，更佳為100 torr以內，進而較佳為80 torr以內，進而更佳為60 torr以內。 [(2) Step of drying and heating the obtained photosensitive resin layer] In step (2), the coating film containing the photosensitive resin composition may be dried as needed. As a drying method, methods, such as air drying, heat drying with an oven or a hot plate, and vacuum drying, are used, for example. Specifically, when air-drying or heat-drying is performed, it can be carried out at a temperature of 20°C to 140°C, more preferably 80°C to 140°C, more preferably 80°C to 120°C. The drying time can be carried out within 1 minute to 1 hour, more preferably 2 minutes to 30 minutes, more preferably 2 minutes to 10 minutes. Drying is performed on the above conditions, whereby a photosensitive resin layer can be formed on the substrate. When performing (2) drying and heating steps by vacuum drying, the heat source is preferably selected from a heating plate or an infrared lamp. Furthermore, from the viewpoint of heating efficiency under reduced pressure, it is preferable to place the wafer on which the coating film is formed on a heat source and heat it. (2) The drying and heating steps can be carried out under a pressure of not less than 50 torr and not more than 580 torr. The change in pressure from the set point is preferably within 150 torr, more preferably within 100 torr, further preferably within 80 torr, still more preferably within 60 torr.
[(3)對所獲得之感光性樹脂層進行曝光之步驟] 於步驟(3)中，使用接觸式對準機、鏡面投影曝光機、步進機等曝光裝置，並藉由紫外線光源等經由具有圖案之光罩或主光罩或直接對上述步驟(1)中所形成之感光性樹脂層進行曝光。 此後，為了提高感光度等，亦可視需要實施基於任意溫度及時間之組合之曝光後烘烤(PEB)及/或顯影前烘烤。關於烘烤條件之範圍，溫度較佳為40℃～120℃，時間較佳為10秒～240秒，但並不限定於該範圍，只要無損負型感光性樹脂組合物之各特性即可。 [(3) Step of exposing the obtained photosensitive resin layer] In step (3), exposure devices such as contact aligners, mirror projection exposure machines, and steppers are used, and ultraviolet light sources are used to pass through patterned masks or master masks or directly to the above step (1). The photosensitive resin layer formed in is exposed. Thereafter, post-exposure baking (PEB) and/or pre-development baking may be performed as necessary in any combination of temperature and time in order to increase the sensitivity and the like. Regarding the range of baking conditions, the temperature is preferably 40° C. to 120° C., and the time is preferably 10 seconds to 240 seconds, but it is not limited to this range, as long as the properties of the negative photosensitive resin composition are not damaged.
[(4)對所獲得之感光性樹脂層進行顯影之步驟] 於步驟(4)中，於感光性樹脂組合物為負型之情形時，將曝光後之感光性樹脂層中之未曝光部顯影去除。作為對曝光(照射)後之感光性樹脂層進行顯影之顯影方法，可自先前已知之光阻之顯影方法、例如旋轉噴霧法、覆液法、伴有超音波處理之浸漬法等中選擇任意方法來使用。又，顯影後，為了調整凹凸圖案之形狀等，亦可視需要以任意溫度及時間之組合實施顯影後烘烤。作為用於顯影之顯影液，例如較佳為針對負型感光性樹脂組合物之良溶劑或該良溶劑與不良溶劑之組合。作為良溶劑，例如較佳為N-甲基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N,N-二甲基乙醯胺、環戊酮、環己酮、γ-丁內酯、α-乙醯基-γ-丁內酯等。作為不良溶劑，例如較佳為甲苯、二甲苯、甲醇、乙醇、異丙醇、乳酸乙酯、丙二醇甲醚乙酸酯及水等。於將良溶劑與不良溶劑混合使用之情形時，較佳為藉由負型感光性樹脂組合物中之聚合物之溶解性調整不良溶劑相對於良溶劑之比率。又，亦可將2種以上、例如數種各溶劑組合使用。 [(4) Step of developing the obtained photosensitive resin layer] In step (4), when the photosensitive resin composition is a negative type, the unexposed portion in the exposed photosensitive resin layer is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of the previously known photoresist developing methods, such as the rotary spray method, the flooding method, the dipping method with ultrasonic treatment, etc., can be selected. method to use. Moreover, after image development, in order to adjust the shape of an uneven|corrugated pattern, etc., you may perform post-development baking at any combination of temperature and time as needed. As a developing solution used for image development, for example, a good solvent for a negative photosensitive resin composition, or the combination of this good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ -butyrolactone, α-acetyl-γ-butyrolactone and the like. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, and the like are preferable. When using a good solvent and a poor solvent in mixture, it is preferable to adjust the ratio of a poor solvent to a good solvent by the solubility of the polymer in a negative photosensitive resin composition. In addition, two or more kinds of solvents, for example, several kinds of solvents may be used in combination.
[(5)對殘留於該基板上之感光性樹脂層以150℃～250℃進行加熱處理而形成硬化膜之步驟] 於步驟(5)(加熱硬化步驟)中，對藉由上述顯影而獲得之殘留於板上之感光性樹脂層(凹凸圖案)進行加熱而使感光成分分散，並且使(A)聚醯亞胺前驅物醯亞胺化，藉此轉化成包含聚醯亞胺之硬化膜。作為加熱硬化之方法，例如可選擇藉由加熱板之方法、使用烘箱之方法、使用可設定溫度程式之升溫式烘箱之方法等各種方法，較佳為升溫式烘箱。可於升溫式烘箱中之加熱壓力為常壓下(760 torr)、減壓下、加壓下進行，較佳為減壓下(760 torr以下)。 [(5) Step of forming a cured film by heating the photosensitive resin layer remaining on the substrate at 150°C to 250°C] In step (5) (heat curing step), the photosensitive resin layer (concave-convex pattern) remaining on the plate obtained by the above-mentioned development is heated to disperse the photosensitive component, and (A) polyimide The precursor is imidized, thereby converting into a hardened film comprising polyimide. As the method of heating and hardening, various methods such as a method using a heating plate, a method using an oven, and a method using a temperature-intensive oven with a temperature program that can be set can be selected, and a temperature-intensive oven is preferred. The heating pressure in the temperature-raising oven can be carried out under normal pressure (760 torr), under reduced pressure, or under increased pressure, preferably under reduced pressure (below 760 torr).
加熱硬化步驟較佳為包括升溫步驟、恆溫步驟、降溫步驟，恆溫步驟可以1種溫度進行，亦可以2種以上之溫度進行。升溫步驟較佳為於1分鐘內變化10～30℃。可於恆溫步驟之加熱溫度為150℃～250℃內進行，較佳為於170～250℃內進行，就加熱前後之殘膜率之觀點而言，更佳為於170～230℃內進行。恆溫步驟中之爐內之溫度自設定值之變化較佳為30.0℃以下，更佳為20.0℃以下，就加熱效率之觀點而言，較佳為15.0℃以下。 於恆溫步驟中，將壓力保持固定時壓力自設定值之變化較佳為150 torr以內，更佳為100 torr以內，進而較佳為80 torr以內，進而更佳為60 torr以內。藉由將壓力保持固定，恆溫步驟中之爐內溫度穩定。壓力之調整步驟可於任一步驟中進行，但就溫度之均勻化之觀點而言，較佳為於升溫步驟之前進行。壓力調整時，可將腔室內部進行氮氣置換，較佳為將減壓與氮氣置換重複進行2次以上。腔室內部之氧濃度較佳為10 ppm以下。降溫步驟較佳為於1分鐘內變化10～50℃。加熱硬化步驟之加熱可於30分鐘～5小時之條件下進行，更佳為1小時～3小時，更佳為90分鐘～3小時。作為加熱硬化時之氛圍氣體，可使用空氣，亦可使用氮氣、氬氣等惰性氣體。 The heat hardening step preferably includes a temperature raising step, a temperature constant step, and a temperature drop step, and the constant temperature step may be performed at one temperature, or may be performed at two or more temperatures. The heating step is preferably to change the temperature by 10-30° C. within 1 minute. It can be carried out at a heating temperature of 150°C to 250°C in the constant temperature step, preferably at 170°C to 250°C, and more preferably at 170°C to 230°C from the viewpoint of the residual film rate before and after heating. The change in the temperature in the furnace in the constant temperature step from the set value is preferably 30.0°C or less, more preferably 20.0°C or less, and more preferably 15.0°C or less from the viewpoint of heating efficiency. In the constant temperature step, the change in pressure from the set value while keeping the pressure constant is preferably within 150 torr, more preferably within 100 torr, further preferably within 80 torr, and even more preferably within 60 torr. By keeping the pressure constant, the temperature inside the furnace in the constant temperature step is stabilized. The pressure adjustment step may be performed in any step, but it is preferably performed before the temperature raising step from the viewpoint of temperature uniformity. When adjusting the pressure, the inside of the chamber may be replaced with nitrogen, and it is preferable to repeat decompression and nitrogen replacement two or more times. The oxygen concentration inside the chamber is preferably below 10 ppm. The cooling step is preferably to change the temperature by 10-50° C. within 1 minute. The heating in the heating hardening step can be carried out under the condition of 30 minutes to 5 hours, more preferably 1 hour to 3 hours, more preferably 90 minutes to 3 hours. As the atmosphere gas at the time of heating and hardening, air may be used, and inert gases such as nitrogen gas and argon gas may also be used.
[硬化膜] 所獲得之聚醯亞胺硬化膜較佳為滿足特定之介電損耗正切，IR(infrared radiation，紅外線輻射)光譜中之1380 cm -1附近與1500 cm -1附近之波峰之比滿足特定值。 本實施方式之聚醯亞胺硬化膜之製造方法用作原料之感光性樹脂組合物就滿足以下要說明之數式(i)及/或(ii)之觀點而言，較佳為包含聚醯亞胺前驅物：100質量份、感光劑：0.1～10質量份、及溶劑：50～300質量份，更佳為包含光自由基聚合起始劑作為感光劑，進而較佳為感光性樹脂組合物為負型。 [Curated film] The obtained polyimide cured film is preferably one that satisfies a specific dielectric loss tangent, the ratio of peaks around 1380 cm -1 to 1500 cm -1 in the IR (infrared radiation) spectrum satisfy a specific value. The method for producing a polyimide cured film according to this embodiment preferably contains polyimide from the viewpoint of satisfying formula (i) and/or (ii) as a raw material for the photosensitive resin composition to be used as a raw material. Imine precursor: 100 parts by mass, photosensitizer: 0.1-10 parts by mass, and solvent: 50-300 parts by mass, more preferably including a photoradical polymerization initiator as a photosensitizer, and more preferably a photosensitive resin combination The object is negative.
＜介電損耗正切＞ 所獲得之聚醯亞胺硬化膜較佳為利用擾動方式分體圓柱共振器法以10 GHz進行測定之情形時之介電損耗正切為0.001～0.009，較佳為0.001～0.007，進而較佳為0.003～0.0065。 以28 GHz進行測定之情形時之介電損耗正切較佳為0.0021～0.008，更佳為0.0030～0.0075，更佳為0.0035～0.0075。 以40 GHz進行測定之情形時之介電損耗正切較佳為0.0021～0.0085，更佳為0.0030～0.0075，更佳為0.0035～0.0075。 以60 GHz進行測定之情形時之介電損耗正切較佳為0.0021～0.009，更佳為0.0030～0.0085，更佳為0.0035～0.0082。藉由設為該範圍，於製成AiP等封裝時，有信號延遲等減少之傾向。 ＜Dielectric loss tangent＞ The obtained polyimide cured film preferably has a dielectric loss tangent of 0.001 to 0.009, preferably 0.001 to 0.007, and more preferably 0.003～0.0065. The dielectric loss tangent when measured at 28 GHz is preferably from 0.0021 to 0.008, more preferably from 0.0030 to 0.0075, still more preferably from 0.0035 to 0.0075. The dielectric loss tangent when measured at 40 GHz is preferably from 0.0021 to 0.0085, more preferably from 0.0030 to 0.0075, still more preferably from 0.0035 to 0.0075. The dielectric loss tangent when measured at 60 GHz is preferably from 0.0021 to 0.009, more preferably from 0.0030 to 0.0085, still more preferably from 0.0035 to 0.0082. By setting it as this range, there exists a tendency for signal delay etc. to be reduced when it manufactures a package, such as AiP.
所獲得之聚醯亞胺硬化膜較佳為滿足下述數式(i)： 0.001＜(tanδ 40－tanδ 10)/tanδ 10＜0.2 (i) {式中，tanδ 40係藉由擾動方式分體圓柱共振器法所得之頻率40 GHz下之介電損耗正切，並且tanδ 10係藉由擾動方式分體圓柱共振器法所得之頻率10 GHz下之介電損耗正切}、及/或 下述數式(ii)： 0.001＜(tanδ 60－tanδ 10)/tanδ 10＜0.29 (ii) {式中，tanδ 60係藉由擾動方式分體圓柱共振器法所得之頻率60 GHz下之介電損耗正切，並且tanδ 10係藉由擾動方式分體圓柱共振器法所得之頻率10 GHz下之介電損耗正切}所表示之關係。 當滿足上述數式(i)及/或(ii)時，會使硬化膜之極性降低，藉此可降低介電損耗正切，又，由於樹脂彼此之相溶性較佳，故而有可不使硬化前之樹脂組合物相分離而進行保存、可維持凹凸圖案形成時之解像度之傾向。 The obtained polyimide cured film preferably satisfies the following formula (i): 0.001<(tanδ 40 -tanδ 10 )/tanδ 10 <0.2 (i) {wherein, tanδ 40 is divided by disturbance The dielectric loss tangent at the frequency of 40 GHz obtained by the bulk cylindrical resonator method, and tanδ 10 is the dielectric loss tangent at the frequency of 10 GHz obtained by the perturbation split cylindrical resonator method}, and/or the following numbers Formula (ii): 0.001<(tanδ 60 -tanδ 10 )/tanδ 10 <0.29 (ii) {In the formula, tanδ 60 is the dielectric loss tangent at a frequency of 60 GHz obtained by the method of split cylindrical resonator in the perturbation mode , and tanδ 10 is the relationship expressed by the dielectric loss tangent at a frequency of 10 GHz obtained by the perturbation method of split cylindrical resonators}. When the above formulas (i) and/or (ii) are satisfied, the polarity of the cured film will be reduced, thereby reducing the dielectric loss tangent, and because the resins have better compatibility with each other, it is possible not to make the The resin composition is stored in phase separation to maintain the tendency of the resolution when the concave-convex pattern is formed.
＜IR光譜＞ 所獲得之聚醯亞胺硬化膜較佳為於IR光譜中，1380 cm -1附近之波峰與1500 cm -1附近之波峰之比滿足0.30～0.54，更佳為0.35～0.54，進而較佳為0.40～0.54，進而更佳為0.45～0.54。 藉由將IR光譜中之1380 cm -1與1500 cm -1之波峰比設為0.54以下，可使膜整體之極性降低，抑制介電損耗正切之上升。另一方面，將該波峰比設為0.30以上對於維持樹脂之韌性、與金屬之密接性及熱物性有效。 再者，IR光譜可藉由下述實施例所示之ATR-FTIR測定裝置進行測定。 <IR Spectrum> The obtained polyimide cured film is preferably such that in the IR spectrum, the ratio of the peak near 1380 cm -1 to the peak near 1500 cm -1 satisfies 0.30-0.54, more preferably 0.35-0.54, More preferably, it is 0.40 to 0.54, and still more preferably, it is 0.45 to 0.54. By setting the peak ratio of 1380 cm -1 to 1500 cm -1 in the IR spectrum to be 0.54 or less, the polarity of the entire film can be reduced, and the increase in dielectric loss tangent can be suppressed. On the other hand, setting the peak ratio to 0.30 or more is effective for maintaining the toughness of the resin, the adhesiveness with metal, and the thermophysical properties. In addition, IR spectrum can be measured with the ATR-FTIR measurement apparatus shown in the following Example.
＜重量減少率＞ 就介電損耗正切之頻率依存性之觀點而言，所獲得之聚醯亞胺硬化膜加熱至320℃時之重量減少率較佳為0.01%～0.5%，更佳為0.05%～0.4%，又，加熱至350℃時之重量減少率較佳為0.1%～1.5%，更佳為0.2%～1.2%。 ＜Weight loss rate＞ From the viewpoint of the frequency dependence of the dielectric loss tangent, the weight loss rate of the obtained polyimide cured film when heated to 320°C is preferably 0.01% to 0.5%, more preferably 0.05% to 0.4%, Also, the weight loss rate when heated to 350°C is preferably from 0.1% to 1.5%, more preferably from 0.2% to 1.2%.
[感光性樹脂組合物] 包含聚醯亞胺前驅物之感光性樹脂組合物包含(A)聚醯亞胺前驅物、(B)感光劑、及(D)溶劑，感光性樹脂組合物視需要包含其他成分。以下依序對各成分進行說明。[Photosensitive resin composition] The photosensitive resin composition comprising polyimide precursor includes (A) polyimide precursor, (B) sensitizer, and (D) solvent, and the photosensitive resin composition is optional Contains other ingredients. Each component will be described in order below.
感光性樹脂組合物可對應於所需用途為負型或正型之任一者，就下述(A)聚醯亞胺前驅物之物性之觀點而言，較佳為負型
(A)聚醯亞胺前驅物
聚醯亞胺前驅物係包含於感光性樹脂組合物中之樹脂成分，較佳為具有下述通式(1)所表示之結構單元之聚醯胺：
[化8]
就高解像度之觀點而言，聚醯亞胺前驅物中所包含之上述通式(2)所表示之一價有機基相對於上述通式(1)所表示之前驅物之全部R 1及R 2之比率較佳為50莫耳%～100莫耳%，進而就高耐化學品性與感度之觀點而言，更佳為75莫耳%～100莫耳%。 From the point of view of high resolution, the valent organic group represented by the above-mentioned general formula (2) contained in the polyimide precursor is relative to all R 1 and R of the precursor represented by the above-mentioned general formula (1). The ratio of 2 is preferably from 50 mol % to 100 mol %, and more preferably from 75 mol % to 100 mol % from the viewpoint of high chemical resistance and sensitivity.
就感光性樹脂組合物之感光特性及機械特性之觀點而言，上述通式(1)中之n1較佳為3～100之整數，更佳為5～70之整數。In terms of the photosensitive properties and mechanical properties of the photosensitive resin composition, n1 in the general formula (1) is preferably an integer of 3-100, more preferably an integer of 5-70.
上述通式(1)中，就兼顧耐熱性與感光特性之方面而言，X
1所表示之四價有機基較佳為碳數6～40之有機基，更佳為-COOR
1基及-COOR
2基與-CONH-基相互位於鄰位之芳香族基或脂環式脂肪族基。作為X
1所表示之四價有機基，具體而言，可例舉含有芳香族環之碳原子數6～40之有機基，例如具有下述通式(20)所表示之結構之基：
[化10]
作為X
1所表示之結構，就低介電損耗正切之觀點而言，上述式(20)所表示之結構之中，尤佳為下述式(X1)所表示之結構：
[化12]
作為X
1所表示之結構，就熱重量減少率之觀點而言，較佳為下述式所表示之結構：
[化16]
上述通式(1)中，就兼顧耐熱性與感光特性之方面而言，Y
1所表示之二價有機基較佳為碳數6～40之芳香族基，例如可例舉下述式(21)所表示之結構：
[化17]
作為Y
1基，就低介電損耗正切化之觀點而言，上述式(21)所表示之結構中，尤佳為下述式(Y1)所表示之結構：
[化19]
上述通式(2)中之R 3較佳為氫原子或甲基，就感光特性之觀點而言，R 4及R 5較佳為氫原子。又，就感光特性之觀點而言，m 1為2以上且10以下之整數，較佳為2以上且4以下之整數。 R 3 in the above general formula (2) is preferably a hydrogen atom or a methyl group, and R 4 and R 5 are preferably hydrogen atoms from the viewpoint of photosensitive properties. Moreover, m 1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitivity.
本說明書中，用語「醯亞胺基濃度」係指於對本實施方式之感光性樹脂組合物進行加熱、硬化而獲得之聚醯亞胺硬化膜之聚醯亞胺中，相對於包含源自四羧酸與二胺之結構之重複單元之分子量，醯亞胺基所占之質量之比率。 於本實施方式中，所獲得之聚醯亞胺硬化膜之醯亞胺基濃度為12 wt%～30 wt%，較佳為12 wt%～24 wt%。若醯亞胺基濃度為12 wt%以上，則有塑模樹脂與硬化凹凸圖案之密接性良好之傾向。醯亞胺基濃度較佳為12.5 wt%以上，更佳為13.5 wt%以上。另一方面，藉由使醯亞胺基濃度為30 wt%以下，有所獲得之聚醯亞胺硬化膜之介電損耗正切良好之傾向。醯亞胺基濃度較佳為24.0 wt%以下，更佳為23.0 wt%以下，進而較佳為21.0 wt%以下。 In this specification, the term "imide group concentration" refers to the polyimide content of the polyimide cured film obtained by heating and curing the photosensitive resin composition of this embodiment relative to the The molecular weight of the repeating unit of the structure of carboxylic acid and diamine, and the mass ratio of imide groups. In this embodiment, the obtained polyimide cured film has an imide group concentration of 12 wt% to 30 wt%, preferably 12 wt% to 24 wt%. When the imide group concentration is 12% by weight or more, the adhesion between the molding resin and the cured uneven pattern tends to be good. The imide group concentration is preferably at least 12.5 wt%, more preferably at least 13.5 wt%. On the other hand, by making the imide group concentration 30 wt% or less, the dielectric loss tangent of the polyimide cured film obtained tends to be favorable. The imide group concentration is preferably not more than 24.0 wt%, more preferably not more than 23.0 wt%, and still more preferably not more than 21.0 wt%.
聚醯亞胺之各重複單元中之醯亞胺基濃度係使用聚醯亞胺前驅物之製備時所使用之四羧酸與二胺之分子量，並由下述式(I)所表示： 70.02×2/[Mw(A)＋Mw(B)]×100 (I) {式(I)中，Mw(A)表示四羧酸之分子量，並且Mw(B)表示二胺之分子量}。再者，於使用2種以上之四羧酸及/或二胺類之情形時，例如於使用2種四羧酸及/或二胺類進行製備時，係由下述式(II)所表示： 70.02×2/[Mw(A1)×a 1＋Mw(A2)×a 2＋Mw(B1)×b 1＋Mw(B2)×b 2]×100 (II) {式(II)中，Mw(A1)表示第一四羧酸之分子量，Mw(A2)表示第二四羧酸之分子量，a 1表示第一四羧酸之含量，a 2表示第二四羧酸之含量，Mw(B1)表示第一二胺之分子量，Mw(B2)表示第二二胺之分子量，b 1表示第一二胺之含量，並且b 2表示第二二胺之含量；其中，a 1、a 2、b 1、b 2分別滿足a 1＋a 2＝1、b 1＋b 2＝1}。 於使用3種以上之四羧酸及/或二胺類之情形時，以相同方式求出。於將四羧酸二酐用作原料之情形時，換算成四羧酸後進行計算。 The concentration of imide groups in each repeating unit of polyimide refers to the molecular weight of tetracarboxylic acid and diamine used in the preparation of polyimide precursor, and is represented by the following formula (I): 70.02 ×2/[Mw(A)+Mw(B)]×100 (I) {In formula (I), Mw(A) represents the molecular weight of tetracarboxylic acid, and Mw(B) represents the molecular weight of diamine}. Furthermore, when two or more tetracarboxylic acids and/or diamines are used, for example, when two kinds of tetracarboxylic acids and/or diamines are used for preparation, it is represented by the following formula (II): : 70.02×2/[Mw(A1)×a 1 ＋Mw(A2)×a 2 ＋Mw(B1)×b 1 ＋Mw(B2)×b 2 ]×100 (II) {In formula (II), Mw(A1 ) represents the molecular weight of the first tetracarboxylic acid, Mw (A2) represents the molecular weight of the second tetracarboxylic acid, a 1 represents the content of the first tetracarboxylic acid, a 2 represents the content of the second tetracarboxylic acid, Mw (B1) represents The molecular weight of the first diamine, Mw(B2) represents the molecular weight of the second diamine, b 1 represents the content of the first diamine, and b 2 represents the content of the second diamine; wherein, a 1 , a 2 , b 1 , b 2 respectively satisfy a 1 +a 2 =1, b 1 +b 2 =1}. When using three or more tetracarboxylic acids and/or diamines, it obtains in the same manner. When using tetracarboxylic dianhydride as a raw material, it calculates after converting into tetracarboxylic acid.
(A)聚醯亞胺前驅物之製備方法 包含上述通式(1)所表示之結構之聚醯亞胺前驅物例如係藉由包含如下之方法而獲得：使上述包含碳數6～40之四價有機基X 1之四羧酸二酐與(a)具有上述通式(2)所表示之一價有機基與羥基鍵結之結構之醇類、及視需要之(b)具有上述通式(2)所表示之基以外之結構之醇類反應，製備局部經酯化之四羧酸(以下，亦稱為酸/酯體)；繼而，使所獲得之酸/酯體與上述包含碳數6～40之二價有機基Y 1之二胺類縮聚。 (A) Preparation method of polyimide precursor The polyimide precursor comprising the structure represented by the above-mentioned general formula (1) is obtained, for example, by the following method: making the above-mentioned polyimide containing 6 to 40 carbon Tetracarboxylic dianhydride of tetravalent organic group X1 and (a) alcohols having a structure in which a valent organic group represented by the above-mentioned general formula (2) is bonded to a hydroxyl group, and optionally (b) having the above-mentioned general formula Alcohols of structures other than the group represented by formula (2) are reacted to prepare partially esterified tetracarboxylic acid (hereinafter, also referred to as acid/ester body); then, the obtained acid/ester body is combined with the above-mentioned Diamine polycondensation of divalent organic group Y1 with carbon number 6-40.
(酸/酯體之製備) 作為包含碳數6～40之四價有機基X 1之四羧酸二酐，例如可例舉：均苯四甲酸二酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、聯苯-3,3',4,4'-四羧酸二酐、二苯基碸-3,3',4,4'-四羧酸二酐、二苯甲烷-3,3',4,4'-四羧酸二酐、2,2-雙(3,4-鄰苯二甲酸酐)丙烷、2,2-雙(3,4-鄰苯二甲酸酐)-1,1,1,3,3,3-六氟丙烷、4,4'-(4,4'-亞異丙基二苯氧基)酸二酐等。又，該等可單獨使用1種，或將2種以上混合後使用。 (Preparation of acid/ester body) As the tetracarboxylic dianhydride containing a tetravalent organic group X1 having 6 to 40 carbon atoms, for example, pyromellitic dianhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride , Diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-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, 4,4'-(4 , 4'-isopropylidene diphenoxy) acid dianhydride, etc. Moreover, these can be used individually by 1 type or in mixture of 2 or more types.
作為(b)具有上述通式(2)所表示之基以外之結構之醇類，例如可例舉碳數5～30之脂肪族或碳數6～30之芳香族醇類，例如1-戊醇、2-戊醇、3-戊醇、新戊醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、3-辛醇、1-壬醇、三乙二醇單甲醚、三乙二醇單***、四乙二醇單甲醚、四乙二醇單***、苄醇等。As (b) alcohols having a structure other than the group represented by the above-mentioned general formula (2), for example, aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, such as 1-pentane Alcohol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc.
使上述四羧酸二酐與上述(a)之醇類於吡啶等鹼性觸媒之存在下於反應溶劑中溶解及混合，藉此進行酸二酐之半酯化反應，可獲得所需酸/酯體。反應條件較佳為於反應溫度20～50℃下攪拌4～10小時。Dissolve and mix the above-mentioned tetracarboxylic dianhydride and the above-mentioned (a) alcohol in the presence of a basic catalyst such as pyridine in a reaction solvent, thereby performing a half-esterification reaction of the acid dianhydride to obtain the desired acid / ester body. The reaction conditions are preferably stirring at a reaction temperature of 20-50° C. for 4-10 hours.
作為上述反應溶劑，較佳為使該酸/酯體、及作為該酸/酯體與二胺類之縮聚產物之聚醯亞胺前驅物溶解者。反應溶劑例如可例舉：N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、四甲基脲、γ-丁內酯、酮類、酯類、內酯類、醚類、鹵化烴類、烴類、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、草酸二乙酯、乙二醇二甲醚、二乙二醇二甲醚、四氫呋喃、二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、氯苯、鄰二氯苯、己烷、庚烷、苯、甲苯、二甲苯等。該等可視需要單獨使用，亦可將2種以上混合使用。As the above-mentioned reaction solvent, it is preferable to dissolve the polyimide precursor which is the polycondensation product of the acid/ester body and the acid/ester body and diamines. The reaction solvent can be exemplified, for example: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea , γ-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, Ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane Alkanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These may be used individually or in mixture of 2 or more types as needed.
(聚醯亞胺前驅物之製備) 於上述酸/酯體(典型而言為上述反應溶劑中之溶液)中，於冰冷下混合已知之脫水縮合劑而將酸/酯體製成多酸酐後，向其中滴加投入使包含碳數6～40之二價有機基Y 1之二胺類另外溶解或分散於溶劑中而成者並進行縮聚，藉此可獲得聚醯亞胺前驅物。作為脫水縮合劑，例如可例舉：二環己基碳二醯亞胺、1-乙氧基羰基-2-乙氧基-1,2-二氫喹啉、1,1-羰基二氧基-二-1,2,3-苯并***、N,N'-二丁二醯亞胺碳酸酯等。 (Preparation of polyimide precursor) In the above-mentioned acid/ester body (typically, a solution in the above-mentioned reaction solvent), a known dehydration condensation agent is mixed under ice-cooling to make the acid/ester body into a polyacid anhydride A polyimide precursor can be obtained by adding dropwise thereto diamines containing a divalent organic group Y1 having 6 to 40 carbon atoms which are separately dissolved or dispersed in a solvent and performing polycondensation. As the dehydration condensation agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy- Bis-1,2,3-benzotriazole, N,N'-dibutanediimide carbonate, etc.
作為包含碳數6～40之二價有機基Y 1之二胺類，例如亦可例舉：對苯二胺、間苯二胺、4,4-二胺基二苯醚、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚、4,4'-二胺基二苯硫醚、3,4'-二胺基二苯硫醚、3,3'-二胺基二苯硫醚、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、4,4'-二胺基聯苯、3,4'-二胺基聯苯、3,3'-二胺基聯苯、4,4'-二胺基二苯甲酮、3,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、3,3'-二胺基二苯甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、4,4-雙(4-胺基苯氧基)聯苯、4,4-雙(3-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、9,10-雙(4-胺基苯基)蒽、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、1,4-雙(3-胺基丙基二甲基矽烷基)苯、鄰-聯甲苯胺碸、9,9-雙(4-胺基苯基)茀、2,2-雙{3-甲基-4-(4-胺基苯氧基)苯基}丙烷、雙{4-(4-胺基苯氧基)苯基}酮、及該等之苯環上之氫原子之一部分被取代為甲基、乙基、羥甲基、羥乙基、鹵素等者、例如3,3'-二甲基-4,4'-二胺基聯苯、2,2'-二甲基-4,4'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基二苯甲烷、2,2'-二甲基-4,4'-二胺基二苯甲烷、3,3'-二甲氧基-4,4'-二胺基聯苯、3,3'-二氯-4,4'-二胺基聯苯、該等之混合物等。然而，二胺類並不限定於該等。 Examples of diamines containing a divalent organic group Y having 6 to 40 carbon atoms include: p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4' -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3' -Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4, 4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-bis Aminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane Aminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) Base) benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 4,4-bis(4-amino Phenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-amine phenyloxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl) Phenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl ) benzene, o-toluidine, 9,9-bis(4-aminophenyl) terrene, 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl} Propane, bis{4-(4-aminophenoxy)phenyl} ketone, and some of the hydrogen atoms on the benzene ring of these are substituted by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Methyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4' - Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, a mixture thereof, and the like. However, diamines are not limited to these.
為了提高藉由將感光性樹脂組合物塗佈於基板上而形成於基板上之感光性樹脂層與各種基板之間之密接性，於(A)聚醯亞胺前驅物之製備時，亦可使1,3-雙(3-胺基丙基)四甲基二矽氧烷、1,3-雙(3-胺基丙基)四苯基二矽氧烷等二胺基矽氧烷類共聚。In order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by coating the photosensitive resin composition on the substrate, during the preparation of the (A) polyimide precursor, it is also possible to Diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane copolymerization.
上述縮聚反應結束後，亦可視需要對該反應液中所共存之脫水縮合劑之吸水副產物進行過濾分離，然後將水、脂肪族低級醇或其混合液等不良溶劑投入反應液中而使聚合物成分析出。進而，亦可藉由反覆進行上述再溶解及再沈澱析出操作等而對聚合物進行精製。接下來，可對聚合物進行真空乾燥而將聚醯亞胺前驅物單離。為了提高精製度，亦可使該聚合物之溶液通過利用適當之有機溶劑使陰離子及/或陽離子交換樹脂膨潤後填充之管柱而將離子性雜質去除。After the above polycondensation reaction is completed, the water-absorbing by-products of the dehydration condensing agent coexisting in the reaction liquid can also be filtered and separated if necessary, and then poor solvents such as water, aliphatic lower alcohols or their mixtures are put into the reaction liquid to polymerize The composition was analyzed. Furthermore, the polymer can also be purified by repeating the above-mentioned redissolution and reprecipitation operations, and the like. Next, the polymer may be vacuum-dried to isolate the polyimide precursor. In order to increase the degree of purification, the polymer solution can also be passed through a column filled with an anion and/or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.
於(A)聚醯亞胺前驅物之分子量係以藉由凝膠滲透層析法所得之聚苯乙烯換算重量平均分子量測得之情形時，較佳為8,000～150,000，更佳為9,000～50,000，尤佳為18,000～40,000。若重量平均分子量為8,000以上，則機械物性良好，故而較佳，另一方面，若為150,000以下，則對顯影液之分散性及凹凸圖案之解像性能良好，故而較佳。作為凝膠滲透層析法之展開溶劑，推薦四氫呋喃、及N-甲基-2-吡咯啶酮。又，分子量係根據使用標準單分散聚苯乙烯而製作之校準曲線求出。作為標準單分散聚苯乙烯，推薦選自昭和電工公司製造之有機溶劑系標準試樣STANDARD SM-105。(A) When the molecular weight of the polyimide precursor is measured by polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography, it is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, preferably 18,000-40,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, so it is preferable. On the other hand, if it is 150,000 or less, the dispersibility to the developing solution and the resolution performance of the concave-convex pattern are good, so it is preferable. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, molecular weight was calculated|required from the calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, an organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko is recommended.
(B)感光劑 感光性樹脂組合物含有感光劑。於一實施方式中，感光劑亦可為光聚合起始劑。光聚合起始劑促進基於光照射之凹凸圖案之硬化，故而較佳。作為光聚合起始劑，較佳為光自由基聚合起始劑，可較佳地例舉：二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基酮、二苄基酮、茀酮等二苯甲酮衍生物；2,2'-二乙氧基苯乙酮、2-羥基-2-甲基苯丙酮、1-羥基環己基苯基酮等苯乙酮衍生物；9-氧硫
相對於(A)聚醯亞胺前驅物100質量份，光聚合起始劑之調配量較佳為0.1質量份以上且10質量份以下，更佳為1質量份以上且8質量份以下。就感光度或圖案化性之觀點而言，上述調配量為0.1質量份以上，就感光性樹脂組合物之硬化後之感光性樹脂層之物性之觀點而言，較佳為10質量份以下。The compounding quantity of a photoinitiator is preferably 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of (A) polyimide precursors, More preferably, it is 1 mass part or more and 8 mass parts or less. The said compounding quantity is 0.1 mass part or more from a viewpoint of sensitivity or patternability, Preferably it is 10 mass parts or less from a viewpoint of the physical property of the photosensitive resin layer after hardening of the photosensitive resin composition.
(C)溶劑(溶劑) 本實施方式之感光性樹脂組合物含有溶劑。作為溶劑，就對(A)聚醯亞胺前驅物之溶解性之方面而言，較佳為使用極性有機溶劑。作為溶劑，具體而言，可例舉：N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N,N-二甲基乙醯胺、二甲基亞碸、二乙二醇二甲醚、環戊酮、γ-丁內酯、α-乙醯基-γ-丁內酯、四甲基脲、1,3-二甲基-2-咪唑啉酮、N-環己基-2-吡咯啶酮、2-辛酮等；該等可單獨或以2種以上之組合使用。(C) Solvent (solvent) The photosensitive resin composition of this embodiment contains a solvent. As a solvent, it is preferable to use a polar organic solvent from the point of solubility to (A) polyimide precursor. As the solvent, specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide Acetamide, dimethyl sulfide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3- Dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, 2-octanone, etc.; these can be used alone or in combination of two or more.
上述溶劑對應於感光性樹脂組合物之所需塗佈膜厚及黏度，相對於(A)聚醯亞胺前驅物100質量份，例如可於50質量份～300質量份、較佳為100質量份～300質量份之範圍內使用。The above-mentioned solvent corresponds to the required coating film thickness and viscosity of the photosensitive resin composition, relative to (A) 100 parts by mass of the polyimide precursor, for example, it can be used at 50 parts by mass to 300 parts by mass, preferably 100 parts by mass Parts to 300 parts by mass are used.
就提高感光性樹脂組合物之保存穩定性之觀點而言，較佳為包含醇類之溶劑。可較佳地使用之醇類典型而言為分子內具有醇性羥基且不具有烯烴系雙鍵之醇，作為具體例，可例舉：甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇等烷醇類；乳酸乙酯等乳酸酯類；丙二醇-1-甲醚、丙二醇-2-甲醚、丙二醇-1-***、丙二醇-2-***、丙二醇-1-(正丙基)醚、丙二醇-2-(正丙基)醚等丙二醇單烷基醚類；乙二醇甲醚、乙二醇***、乙二醇-正丙醚等單醇類；2-羥基異丁酸酯類；乙二醇、及丙二醇等二醇類。該等之中，較佳為乳酸酯類、丙二醇單烷基醚類、2-羥基異丁酸酯類、及乙醇，尤其更佳為乳酸乙酯、丙二醇-1-甲醚、丙二醇-1-***、及丙二醇-1-(正丙基)醚。From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferable. Alcohols that can be preferably used are typically those that have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond. As specific examples, methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, etc. Alcohols such as alcohol, isobutanol and tertiary butanol; lactate esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol -1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether and other propylene glycol monoalkyl ethers; ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether and other monoalcohols ; 2-hydroxyisobutyrates; glycols such as ethylene glycol and propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrates, and ethanol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1- Diethyl ether, and propylene glycol-1-(n-propyl) ether.
於溶劑含有不具有烯烴系雙鍵之醇之情形時，將總溶劑之質量作為基準，總溶劑中之不具有烯烴系雙鍵之醇之含量較佳為5質量%～50質量%，更佳為10質量%～30質量%。於不具有烯烴系雙鍵之醇之上述含量為5質量%以上之情形時，感光性樹脂組合物之保存穩定性變得良好，另一方面，於50質量%以下之情形時，(A)聚醯亞胺前驅物之溶解性變得良好。When the solvent contains alcohols without olefinic double bonds, based on the mass of the total solvent, the content of alcohols without olefinic double bonds in the total solvent is preferably 5% by mass to 50% by mass, more preferably It is 10 mass % - 30 mass %. When the said content of the alcohol which does not have an olefinic double bond is 5 mass % or more, the storage stability of a photosensitive resin composition becomes favorable, on the other hand, when it is 50 mass % or less, (A) The solubility of the polyimide precursor becomes good.
[其他成分] 感光性樹脂組合物亦可進而含有上述(A)、(B)、(C)成分以外之成分。作為其他成分，例如可例舉：(A)聚醯亞胺前驅物以外之樹脂成分；增感劑；具有光聚合性不飽和鍵之單體；接著助劑；熱聚合抑制劑；唑化合物；及受阻酚化合物等。[Other Components] The photosensitive resin composition may further contain components other than the above-mentioned (A), (B), and (C) components. Examples of other components include: (A) resin components other than polyimide precursors; sensitizers; monomers having photopolymerizable unsaturated bonds; adhesive additives; thermal polymerization inhibitors; azole compounds; and hindered phenolic compounds.
感光性樹脂組合物亦可進而含有(A)聚醯亞胺前驅物以外之樹脂成分。作為可含於感光性樹脂組合物中之樹脂成分，例如可例舉：聚醯亞胺、聚㗁唑、聚㗁唑前驅物、酚系樹脂、聚醯胺、環氧樹脂、矽氧烷樹脂、丙烯酸系樹脂等。相對於(A)聚醯亞胺前驅物100質量份，該等樹脂成分之調配量較佳為0.01質量份～20質量份之範圍。The photosensitive resin composition may further contain resin components other than (A) polyimide precursor. As the resin component that can be contained in the photosensitive resin composition, for example, polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, silicone resin , Acrylic resin, etc. It is preferable that the compounding quantity of these resin components is the range of 0.01 mass part - 20 mass parts with respect to 100 mass parts of (A) polyimide precursors.
於一併使用(A)聚醯亞胺前驅物以及聚㗁唑前驅物來製備正型感光性樹脂組合物之情形時，作為正型感光材，可將具有醌二疊氮基之化合物、例如具有1,2-苯醌二疊氮結構或1,2-萘醌二疊氮結構之化合物等併用。When (A) polyimide precursor and polyoxazole precursor are used together to prepare a positive photosensitive resin composition, as a positive photosensitive material, a compound having a quinone diazide group, such as Compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure are used in combination.
為了提高感光度，感光性樹脂組合物可任意包含增感劑。作為該增感劑，例如可例舉：米其勒酮、4,4'-雙(二乙基胺基)二苯甲酮、2,5-雙(4'-二乙胺基苯亞甲基)環戊烷、2,6-雙(4'-二乙基胺基苯亞甲基)環己酮、2,6-雙(4'-二乙基胺基苯亞甲基)-4-甲基環己酮、4,4'-雙(二甲基胺基)查耳酮、4,4'-雙(二乙基胺基)查耳酮、對二甲基胺基亞桂皮基、對二甲基胺基亞苄基茚酮、2-(對二甲基胺基苯基伸聯苯基)-苯并噻唑、2-(對二甲基胺基苯基伸乙烯基)苯并噻唑、2-(對二甲基胺基苯基伸乙烯基) 異萘并噻唑、1,3-雙(4'-二甲基胺基苯亞甲基)丙酮、1,3-雙(4'-二乙基胺基苯亞甲基)丙酮、3,3'-羰基-雙(7-二乙基胺基香豆素)、3-乙醯基-7-二甲基胺基香豆素、3-乙氧基羰基-7-二甲基胺基香豆素、3-苄氧基羰基-7-二甲基胺基香豆素、3-甲氧基羰基-7-二乙基胺基香豆素、3-乙氧基羰基-7-二乙基胺基香豆素、N-苯基-N'-乙基乙醇胺、N-苯基二乙醇胺、N-對甲苯基二乙醇胺、N-苯基乙醇胺、4-嗎啉基二苯甲酮、二甲基胺基苯甲酸異戊酯、二乙基胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-(對二甲基胺基苯乙烯基)苯并㗁唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯等。該等可單獨或以複數種(例如2～5種)之組合使用。 相對於(A)聚醯亞胺前驅物100質量份，增感劑之調配量較佳為0.1質量份～25質量份。 The photosensitive resin composition may optionally contain a sensitizer in order to increase the sensitivity. As the sensitizer, for example, Michelerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene base) cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4 -Methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamiclidene , p-Dimethylaminobenzylidene indanone, 2-(p-Dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-Dimethylaminophenylvinylidene)benzothiazole , 2-(p-Dimethylaminophenylvinylidene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'- Diethylaminobenzylidene) acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin Coumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N -Phenylethanolamine, 4-Morpholinylbenzophenone, Isoamyl Dimethylaminobenzoate, Isoamyl Diethylaminobenzoate, 2-Mercaptobenzimidazole, 1-Phenyl-5 -Mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl) benzothiazole, 2-(p-dimethylaminostyryl) benzothiazole, 2-( p-Dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like. These can be used individually or in combination of plural types (for example, 2-5 types). The compounding quantity of a sensitizer is preferably 0.1-25 mass parts with respect to 100 mass parts of (A) polyimide precursors.
相對於(A)聚醯亞胺前驅物100質量份，增感劑之調配量較佳為0.1質量份～25質量份。The compounding quantity of a sensitizer is preferably 0.1-25 mass parts with respect to 100 mass parts of (A) polyimide precursors.
為了提高凹凸圖案之解像度，感光性樹脂組合物可任意包含具有光聚合性不飽和鍵之單體。作為此種單體，較佳為藉由光聚合起始劑進行自由基聚合反應之(甲基)丙烯酸化合物，並非特別限定於以下，可例舉以二乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯為代表之乙二醇或聚乙二醇之單或二丙烯酸酯或甲基丙烯酸酯、丙二醇或聚丙二醇之單或二丙烯酸酯或甲基丙烯酸酯、甘油之單、二或三丙烯酸酯或甲基丙烯酸酯、環己烷二丙烯酸酯或二甲基丙烯酸酯、1,4-丁二醇之二丙烯酸酯或二甲基丙烯酸酯、1,6-己二醇之二丙烯酸酯或二甲基丙烯酸酯、新戊二醇之二丙烯酸酯或二甲基丙烯酸酯、雙酚A之單或二丙烯酸酯或甲基丙烯酸酯、苯三甲基丙烯酸酯、丙烯酸異𦯉酯或甲基丙烯酸酯、丙烯醯胺、其衍生物、甲基丙烯醯胺、其衍生物、三羥甲基丙烷三丙烯酸酯或甲基丙烯酸酯、甘油之二或三丙烯酸酯或甲基丙烯酸酯、季戊四醇之二、三或四丙烯酸酯或甲基丙烯酸酯、該等化合物之環氧乙烷或環氧丙烷加成物等化合物。又，該等單體可使用1種，亦可以2種以上之混合物使用。In order to improve the resolution of the concave-convex pattern, the photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, but is not particularly limited to the following, and diethylene glycol dimethacrylate, tetra Ethylene glycol dimethacrylate is represented by ethylene glycol or polyethylene glycol mono- or diacrylate or methacrylate, propylene glycol or polypropylene glycol mono- or diacrylate or methacrylate, glycerin mono , di- or triacrylate or methacrylate, cyclohexane diacrylate or dimethacrylate, 1,4-butanediol diacrylate or dimethacrylate, 1,6-hexanediol Diacrylate or dimethacrylate, diacrylate or dimethacrylate of neopentyl glycol, mono- or diacrylate or methacrylate of bisphenol A, benzenetrimethacrylate, isoacrylate Methacrylate or methacrylate, acrylamide, its derivatives, methacrylamide, its derivatives, trimethylolpropane triacrylate or methacrylate, glycerol di- or triacrylate or methyl Compounds such as acrylates, pentaerythritol di-, tri- or tetraacrylates or methacrylates, ethylene oxide or propylene oxide adducts of these compounds. In addition, these monomers may be used alone or as a mixture of two or more.
相對於(A)聚醯亞胺前驅物100質量份，具有光聚合性不飽和鍵之單體之調配量較佳為1質量份～50質量份。It is preferable that the compounding quantity of the monomer which has a photopolymerizable unsaturated bond is 1 mass part - 50 mass parts with respect to 100 mass parts of (A) polyimide precursors.
為了提高使用感光性樹脂組合物而形成之膜與基材之接著性，感光性樹脂組合物可任意包含接著助劑。作為接著助劑，例如可例舉：γ-胺基丙基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基二甲氧基甲基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、二甲氧基甲基-3-哌啶基丙基矽烷、二乙氧基-3-縮水甘油氧基丙基甲基矽烷、N-(3-二乙氧基甲基矽烷基丙基)丁二醯亞胺、N-[3-(三乙氧基矽烷基)丙基]鄰苯二甲醯胺酸、二苯甲酮-3,3'-雙(N-[3-三乙氧基矽烷基]丙基醯胺)-4,4'-二羧酸、苯-1,4-雙(N-[3-三乙氧基矽烷基]丙基醯胺)-2,5-二羧酸、3-(三乙氧基矽烷基)丙基丁二酸酐、N-苯基胺基丙基三甲氧基矽烷等矽烷偶合劑、及三(乙基乙醯乙酸)鋁、三(乙醯丙酮酸)鋁等鋁系接著助劑等。又，該等接著助劑可使用1種，亦可以2種以上之混合物使用。In order to improve the adhesion between the film formed by using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain an adhesive auxiliary agent. Examples of adhesive additives include: γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-shrink Glyceryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryl Oxypropyltrimethoxysilane, Dimethoxymethyl-3-piperidylpropylsilane, Diethoxy-3-glycidyloxypropylmethylsilane, N-(3-diethoxy methylsilylpropyl) succinimide, N-[3-(triethoxysilyl)propyl]phthalimide, benzophenone-3,3'-bis( N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide Amine)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane and other silane coupling agents, and tris(ethyl ethyl Aluminum-based adhesive additives such as aluminum acetylacetate and aluminum tris(acetylpyruvate). Moreover, these adhesive auxiliary agents may be used 1 type, and may use it as a mixture of 2 or more types.
該等接著助劑之中，就接著力之方面而言，更佳為使用矽烷偶合劑。相對於(A)聚醯亞胺前驅物100質量份，接著助劑之調配量較佳為0.5質量份～25質量份之範圍。Among these adhesive aids, it is more preferable to use a silane coupling agent in terms of adhesive force. With respect to 100 parts by mass of the (A) polyimide precursor, the blending amount of the bonding agent is preferably in the range of 0.5 parts by mass to 25 parts by mass.
為了提高尤其是以包含溶劑之溶液之狀態保存時之感光性樹脂組合物之黏度及感光度之穩定性，感光性樹脂組合物可任意包含熱聚合抑制劑。作為熱聚合抑制劑，例如使用：對苯二酚、N-亞硝基二苯基胺、對第三丁基鄰苯二酚、啡噻𠯤、N-苯基萘基胺、乙二胺四乙酸、1,2-環己烷二胺四乙酸、二醇醚二胺四乙酸、2,6-二-第三丁基-對甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺丙基胺基)苯酚、N-亞硝基-N-苯基羥基胺銨鹽、N-亞硝基-N(1-萘基)羥基胺銨鹽等。又，該等熱聚合抑制劑可使用1種，亦可以2種以上之混合物使用。In order to improve the stability of the viscosity and sensitivity of the photosensitive resin composition especially when it preserve|saves in the state of the solution containing a solvent, a thermal polymerization inhibitor may be contained in a photosensitive resin composition arbitrarily. As thermal polymerization inhibitors, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenanthylamine, N-phenylnaphthylamine, ethylenediaminetetra Acetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso Base-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. Moreover, these thermal polymerization inhibitors may be used 1 type, and may use it as a mixture of 2 or more types.
作為熱聚合抑制劑之調配量，相對於(A)聚醯亞胺前驅物100質量份，較佳為0.005質量份～12質量份之範圍。As a compounding quantity of a thermal polymerization inhibitor, it is preferable that it is the range of 0.005-12 mass parts with respect to 100 mass parts of (A) polyimide precursors.
例如，於使用包含銅或銅合金之基板之情形時，為了抑制基板變色，感光性樹脂組合物可任意包含唑化合物。作為唑化合物，例如可例舉：1H-***、5-甲基-1H-***、5-乙基-1H-***、4,5-二甲基-1H-***、5-苯基-1H-***、4-第三丁基-5-苯基-1H-***、5-羥基苯基-1H-***、苯基***、對乙氧基苯基***、5-苯基-1-(2-二甲基胺基乙基)***、5-苄基-1H-***、羥基苯基***、1,5-二甲基***、4,5-二乙基-1H-***、1H-苯并***、2-(5-甲基-2-羥基苯基)苯并***、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-苯并***、2-(3,5-二-第三丁基-2-羥基苯基)苯并***、2-(3-第三丁基-5-甲基-2-羥基苯基)-苯并***、2-(3,5-二-第三戊基-2-羥基苯基)苯并***、2-(2'-羥基-5'-第三辛基苯基)苯并***、羥基苯基苯并***、甲苯基***、5-甲基-1H-苯并***、4-甲基-1H-苯并***、4-羧基-1H-苯并***、5-羧基-1H-苯并***、1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑、1-甲基-1H-四唑等。尤佳為例舉甲苯基***、5-甲基-1H-苯并***、4-甲基-1H-苯并***。又，該等唑化合物可使用1種，亦可以2種以上之混合物使用。For example, when using the board|substrate containing copper or copper alloy, in order to suppress discoloration of a board|substrate, the photosensitive resin composition may contain an azole compound arbitrarily. Examples of the azole compound include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-benzene Base-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5 -Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5- Diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl Base-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'- Hydroxy-5'-tertoctylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzene Triazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole , 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred examples include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used alone or in mixture of two or more.
相對於(A)聚醯亞胺前驅物100質量份，唑化合物之調配量較佳為0.1質量份～20質量份，就感光度特性之觀點而言，更佳為0.5質量份～5質量份。若唑化合物相對於(A)聚醯亞胺前驅物100質量份之調配量為0.1質量份以上，則於銅或銅合金之上形成感光性樹脂組合物時，銅或銅合金表面之變色得到抑制，另一方面，若為20質量份以下，則感光度優異，故而較佳。The blending amount of the azole compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A), more preferably 0.5 to 5 parts by mass from the viewpoint of sensitivity characteristics . If the blending amount of the azole compound relative to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition is formed on copper or copper alloy, the discoloration of the surface of copper or copper alloy will be reduced. On the other hand, since the sensitivity is excellent when it is 20 parts by mass or less, it is preferable.
為了抑制銅之變色，感光性樹脂組合物可包含受阻酚化合物。作為受阻酚化合物，例如可例舉：2,6-二-第三丁基-4-甲基苯酚、2,5-二-第三丁基-對苯二酚、3-(3,5-二-第三丁基-4-羥基苯基)丙酸十八烷基酯、3-(3,5-二-第三丁基-4-羥基苯基)丙酸異辛酯、4,4'-亞甲基雙(2,6-二-第三丁基苯酚)、4,4'-硫代-雙(3-甲基-6-第三丁基苯酚)、4,4'-亞丁基-雙(3-甲基-6-第三丁基苯酚)、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,2-硫代-二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、N,N'-六亞甲基雙(3,5-二-第三丁基-4-羥基-苯丙醯胺)、2,2'-亞甲基-雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基-雙(4-乙基-6-第三丁基苯酚)、季戊四醇基-四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、三-(3,5-二-第三丁基-4-羥基苄基)-異三聚氰酸酯、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯、1,3,5-三(3-羥基-2,6-二甲基-4-異丙基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第二丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-(1-乙基丙基)-3-羥基-2,6-二甲基苄基]-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-三乙基甲基-3-羥基-2,6-二甲基苄基]-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(3-羥基-2,6-二甲基-4-苯基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5,6-三甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2,6-二甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2-甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2,5-二甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5,6-二乙基-3-羥基-2-甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2-甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5-二甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2-甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮等；但並不限定於此。該等之中，尤佳為1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮。In order to suppress discoloration of copper, the photosensitive resin composition may contain a hindered phenol compound. As hindered phenol compounds, for example, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-(3,5- Di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, 4,4 '-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene Base-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] , 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy- phenylacrylamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-th tributylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri-(3,5-di-tert-butyl- 4-Hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene , 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris-2,4,6-(1H,3H, 5H)-Triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trione-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-second-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trisyl -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl ]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2, 6-Dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6 -Dimethyl-4-phenylbenzyl)-1,3,5-tri-(4-)-trione, 1,3,5-tri(4- Tributyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H, 3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(3)-2 ,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-5,6-diethyl- 3-Hydroxy-2-methylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-third Butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H )-triketone, etc.; but not limited thereto. Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 ,6-(1H,3H,5H)-trione.
相對於(A)聚醯亞胺前驅物100質量份，受阻酚化合物之調配量較佳為0.1質量份～20質量份，就感光度特性之觀點而言，更佳為0.5質量份～10質量份。若受阻酚化合物相對於(A)聚醯亞胺前驅物100質量份之調配量為0.1質量份以上，則於例如於銅或銅合金之上形成有感光性樹脂組合物之情形時，銅或銅合金之變色、腐蝕得以防止，另一方面，若為20質量份以下，則感光度優異，故而較佳。The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A), more preferably 0.5 to 10 parts by mass from the viewpoint of sensitivity characteristics share. If the blending amount of the hindered phenol compound relative to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition is formed on copper or copper alloy, for example, copper or Discoloration and corrosion of the copper alloy are prevented, and on the other hand, since the sensitivity is excellent when it is 20 parts by mass or less, it is preferable.
亦可使感光性樹脂組合物中含有包含選自鈦或鋯之金屬元素之有機化合物。上述有機化合物較佳為於一分子中包含選自鈦或鋯之1種金屬元素。作為有機基，較佳為包括烴基、包含雜原子之烴基。藉由含有上述有機化合物，感光性樹脂組合物之醯亞胺化率上升，硬化膜之介電損耗正切降低。An organic compound containing a metal element selected from titanium or zirconium may also be contained in the photosensitive resin composition. The aforementioned organic compound preferably contains one metal element selected from titanium and zirconium in one molecule. As the organic group, a hydrocarbon group including a hydrocarbon group and a hydrocarbon group including a heteroatom are preferable. By containing the above-mentioned organic compound, the imidization ratio of the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases.
作為可使用之有機鈦或鋯化合物，例如可例舉有機化學物質經由共價鍵或離子鍵而鍵結於鈦或鋯原子者。As the organotitanium or zirconium compound that can be used, for example, one in which an organic chemical substance is bonded to a titanium or zirconium atom via a covalent bond or an ionic bond.
將有機鈦或鋯化合物之具體例示於以下I)～VII)： 作為I)螯合物化合物，就感光性樹脂組合物之保存穩定性及獲得良好之圖案之方面而言，更佳為具有2個以上之烷氧基之化合物。作為螯合物化合物，具體例可例舉：雙(三乙醇胺)二異丙醇鈦、雙(2,4-戊二酸)二正丁醇鈦、雙(2,4-戊二酸)二異丙醇鈦、雙(四甲基庚二酸)二異丙醇鈦、二異丙醇鈦雙(乙醯乙酸乙酯)、該等化合物之鈦原子被取代為鋯原子之化合物；但並不限定於該等。 Specific examples of organotitanium or zirconium compounds are shown in the following I) to VII): As I) a chelate compound, the compound which has 2 or more alkoxy groups is more preferable from the viewpoint of the storage stability of a photosensitive resin composition, and a favorable pattern acquisition. Specific examples of the chelate compound include: titanium bis(triethanolamine) diisopropoxide, titanium bis(2,4-glutarate) di-n-butoxide, bis(2,4-glutarate) di-n-butoxide, Titanium isopropoxide, titanium bis(tetramethylpimelate) diisopropoxide, titanium diisopropoxide bis(ethyl acetate), compounds in which titanium atoms are replaced by zirconium atoms; but not Not limited to these.
作為II)四烷氧基化合物，例如可例舉：四正丁醇鈦、四乙醇鈦、四(2-乙基己醇)鈦、四異丁醇鈦、四異丙醇鈦、四甲醇鈦、四甲氧基丙醇鈦、四甲基苯酚鈦、四正壬醇鈦、四正丙醇鈦、四硬脂醇鈦、四[雙{2,2-(烯丙氧基甲基)丁醇}]鈦、該等化合物之鈦原子被取代為鋯原子之化合物；但並不限定於該等。As II) tetraalkoxy compounds, for example, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetrakis(2-ethylhexyloxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra-n-nonanolate, titanium tetra-n-propoxide, titanium tetrastearate, tetrakis[bis{2,2-(allyloxymethyl)butyl Alcohol}] titanium, a compound in which the titanium atom of these compounds is replaced by a zirconium atom; but it is not limited to these.
作為III)二茂鈦或二茂鋯化合物，例如可例舉：五甲基環戊二烯基三甲醇鈦、雙(η 5-2,4-環戊二烯-1-基)雙(2,6-二氟苯基)鈦、雙(η 5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦、該等化合物之鈦原子被取代為鋯原子之化合物；但並不限定於該等。 As III) titanocene or zirconocene compounds, for example, there may be mentioned: pentamethylcyclopentadienyl titanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl) bis(2 ,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl ) Titanium, compounds in which the titanium atoms of these compounds are replaced by zirconium atoms; but not limited to these.
作為IV)單烷氧基化合物，例如可例舉：三(二辛基磺酸)異丙醇鈦、三(十二烷基苯磺酸)異丙醇鈦、該等化合物之鈦原子被取代為鋯原子之化合物；但並不限定於該等。As IV) a monoalkoxy compound, for example, titanium tris(dioctylsulfonate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, the titanium atoms of these compounds are substituted Compounds of zirconium atoms; but not limited to these.
作為V)氧鈦或氧鋯化合物，例如可例舉：雙(戊二酸)氧鈦、雙(四甲基庚二酸)氧鈦、酞菁氧鈦、該等化合物之鈦原子被取代為鋯原子之化合物；但並不限定於該等。As V) titanyl or zirconyl compounds, for example, titanyl bis(glutarate), titanyl bis(tetramethylpimelate), titanyl phthalocyanine, the titanium atoms of these compounds are substituted by Compounds of zirconium atoms; but not limited to these.
作為VI)四乙醯丙酮酸鈦或四乙醯丙酮酸鋯化合物，例如可例舉：四乙醯丙酮酸鈦、該等化合物之鈦原子被取代為鋯原子之化合物；但並不限定於該等。As VI) titanium tetraacetylpyruvate or zirconium tetraacetylpyruvate compound, for example, can exemplify: titanium tetraacetylpyruvate, the compound that the titanium atom of these compounds is replaced by zirconium atom; But not limited to this wait.
作為VII)鈦酸酯偶合劑，例如可例舉三(十二烷基苯磺醯基)鈦酸異丙酯等，但並不限定於該等。VII) The titanate coupling agent may, for example, be isopropyl tris(dodecylbenzenesulfonyl) titanate or the like, but is not limited thereto.
上述I)～VII)之中，就實現更良好之介電損耗正切之觀點而言，有機鈦化合物較佳為選自由上述I)鈦螯合物化合物、II)四烷氧基鈦化合物、及III)二茂鈦化合物所組成之群中之至少1種化合物。尤佳為鈦二異丙醇雙(乙醯乙酸乙酯)、四正丁醇鈦、及雙(η 5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦。 Among the above-mentioned I) to VII), from the viewpoint of realizing a better dielectric loss tangent, the organic titanium compound is preferably selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) At least one compound of the group consisting of titanocene compounds. Particularly preferred are titanium diisopropanol bis(ethyl acetate), titanium tetra-n-butoxide, and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro -3-(1H-pyrrol-1-yl)phenyl)titanium.
相對於(A)樹脂100質量份，調配有機鈦或鋯化合物之情形時之調配量較佳為0.05質量份～10質量份，更佳為0.1質量份～2質量份。若該調配量為0.05質量份以上，則表現出良好之感光性樹脂組合物之醯亞胺化率、及硬化膜之介電損耗正切，另一方面，若為10質量份以下，則感光性樹脂組合物之保存穩定性優異，故而較佳。When compounding an organic titanium or zirconium compound with respect to 100 mass parts of (A) resins, the compounding quantity becomes like this. Preferably it is 0.05 mass part - 10 mass parts, More preferably, it is 0.1 mass part - 2 mass parts. If the blending amount is 0.05 parts by mass or more, the imidization rate of the photosensitive resin composition and the dielectric loss tangent of the cured film are good, while if it is 10 parts by mass or less, the photosensitive Since the storage stability of a resin composition is excellent, it is preferable.
[聚醯亞胺] 由上述聚醯亞胺前驅物組合物形成之包含於硬化凹凸圖案(聚醯亞胺硬化膜)中之聚醯亞胺之結構較佳為由下述通式(11)所表示：
[化24]
本發明之另一實施方式係再配線用層間絕緣膜形成用聚醯亞胺硬化膜本身，其加熱至320℃時之重量減少率為0.01%～0.5%，加熱至350℃時之重量減少率為0.1%～1.5%，且藉由擾動方式分體圓柱共振器法以頻率40 GHz進行測定時之介電損耗正切為0.0021～0.0085。Another embodiment of the present invention is the polyimide cured film itself for forming an interlayer insulating film for rewiring. The weight loss rate when heated to 320°C is 0.01% to 0.5%, and the weight loss rate when heated to 350°C It is 0.1% to 1.5%, and the dielectric loss tangent is 0.0021 to 0.0085 when it is measured at a frequency of 40 GHz by the split cylindrical resonator method of the disturbance method.
[半導體裝置] 本發明之又一實施方式亦為半導體裝置，其係具有藉由上述硬化凹凸圖案之製造方法而獲得之硬化凹凸圖案之半導體裝置，即具有作為半導體元件之基材、及藉由上述硬化凹凸圖案製造方法形成於該基材上之聚醯亞胺之硬化凹凸圖案的半導體裝置。又，本發明之聚醯亞胺硬化膜之製造方法亦可應用於將半導體元件用作基材且包含上述硬化凹凸圖案之製造方法作為步驟之一部分的半導體裝置之製造方法。本實施方式之半導體裝置可藉由如下方式製造：形成利用上述硬化凹凸圖案製造方法而形成之硬化凹凸圖案作為表面保護膜、層間絕緣膜、再配線用絕緣膜、覆晶裝置用保護膜、具有凸塊結構之半導體裝置之保護膜等，並與公知之半導體裝置之製造方法進行組合。[Semiconductor device] Still another embodiment of the present invention is also a semiconductor device having a hardened concave-convex pattern obtained by the above-mentioned method of manufacturing a hardened concave-convex pattern, that is, having a substrate as a semiconductor element, and by The method for manufacturing the hardened concave-convex pattern is a semiconductor device with a hardened concave-convex pattern of polyimide formed on the base material. In addition, the method for producing a polyimide cured film of the present invention can also be applied to a method for producing a semiconductor device that uses a semiconductor element as a base material and includes the above-mentioned method for producing a cured uneven pattern as a part of the steps. The semiconductor device of this embodiment mode can be manufactured by forming the hardened unevenness pattern formed by the above-mentioned hardened unevenness pattern manufacturing method as a surface protection film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip-chip devices, having Protective films of semiconductor devices with bump structures, etc., combined with known manufacturing methods of semiconductor devices.
[顯示體裝置] 本發明之又一實施方式亦為一種顯示體裝置，其具備顯示體元件及設置於該顯示體元件之上部之硬化膜，且該硬化膜為上述硬化凹凸圖案。此處，該硬化凹凸圖案可與該顯示體元件直接相接地積層，亦可隔著其他層積層。例如，作為該硬化膜，可例舉：TFT(Thin Film Transistor，薄膜電晶體)液晶顯示元件及彩色濾光片元件之表面保護膜、絕緣膜、平坦化膜、MVA(Multi-Domain Vertical Alignment，多域垂直配向)型液晶顯示裝置用之突起、有機EL(Electroluminescence，電致發光)元件陰極用之間隔壁。[Display device] Still another embodiment of the present invention is also a display device including a display element and a cured film provided on the upper part of the display element, and the cured film is the above-mentioned cured concave-convex pattern. Here, the hardened concave-convex pattern may be directly laminated with the display element, or may be interposed by other laminated layers. For example, as the cured film, there may be mentioned: TFT (Thin Film Transistor, Thin Film Transistor) liquid crystal display element and color filter element surface protection film, insulating film, planarizing film, MVA (Multi-Domain Vertical Alignment, Multi-domain vertical alignment) protrusions for liquid crystal display devices, partition walls for cathodes of organic EL (Electroluminescence, electroluminescence) elements.
本發明之聚醯亞胺硬化膜之製造方法除可應用於如上述之半導體裝置以外，亦可應用於多層電路之層間絕緣、可撓性覆銅板之硬塗層、阻焊劑膜、液晶配向膜等用途。 [實施例] The manufacturing method of the polyimide cured film of the present invention can be applied not only to the above-mentioned semiconductor devices, but also to interlayer insulation of multilayer circuits, hard coating of flexible copper clad laminates, solder resist films, and liquid crystal alignment films. and other purposes. [Example]
以下，藉由實施例對本發明具體地進行說明，但本發明並不限定於實施例。於實施例、比較例、製造例中，使用以下測定及評價方法對各種物性等進行測定、評價。Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to an Example. In Examples, Comparative Examples, and Production Examples, various physical properties and the like were measured and evaluated using the following measurement and evaluation methods.
[測定及評價方法] (1)重量平均分子量 利用凝膠滲透層析法(標準聚苯乙烯換算)測定各樹脂之重量平均分子量(Mw)。用於測定之管柱為昭和電工(股)製造之商標名「Shodex 805M/806M串聯」，標準單分散聚苯乙烯選擇昭和電工(股)製造之商標名「Shodex STANDARD SM-105」，展開溶劑為N-甲基-2-吡咯啶酮，檢測器使用昭和電工(股)製造之商標名「Shodex RI-930」。[Measurement and evaluation method] (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is the trade name "Shodex 805M/806M series" manufactured by Showa Denko Co., Ltd., the standard monodisperse polystyrene is selected from the trade name "Shodex STANDARD SM-105" manufactured by Showa Denko Co., Ltd., and the developing solvent It was N-methyl-2-pyrrolidone, and the detector used was the trade name "Shodex RI-930" manufactured by Showa Denko Co., Ltd.
(2)介電常數(Dk)、介電損耗正切(Df)之測定 使用濺鍍裝置(型號L-440S-FHL，CANON ANELVA公司製造)於6英吋矽晶圓(Fujimi電子工業股份有限公司製造，厚度625±25 μm)上濺鍍厚100 nm之鋁(Al)，準備濺鍍Al晶圓基板。 使用旋轉塗佈裝置(型號D-spin60A，SOKUDO公司製造)將負型感光性樹脂組合物旋轉塗佈於上述濺鍍Al晶圓基板，於110℃下加熱乾燥3分鐘，製作旋轉塗佈膜。其後，使用對準機(PLA-501F，Canon公司製造)以曝光量600 mJ/cm 2之ghi射線進行整面曝光，使用真空氣體置換烘箱(450PB8-2P-CP、YES公司製造)於氮氣氛圍下於特定溫度下實施2小時加熱硬化處理，製作硬化膜。硬化膜之膜厚係使用階差儀(P-15、KLA-Tenchore公司製造)進行測定。使用晶圓切割機(DISCO製造，型號名DAD-2H/6T)將該硬化膜切成長80 mm、寬60 mm或長40 mm、寬30 mm，浸漬於10%鹽酸水溶液中並自矽晶圓上剝離，製成膜樣品。 (2) The measurement of dielectric constant (Dk) and dielectric loss tangent (Df) uses a sputtering device (model L-440S-FHL, manufactured by CANON ANELVA) on a 6-inch silicon wafer (Fujimi Electronics Industry Co., Ltd. Manufacturing, sputtering aluminum (Al) with a thickness of 100 nm on a thickness of 625±25 μm, and preparing a sputtered Al wafer substrate. The negative photosensitive resin composition was spin-coated on the sputtered Al wafer substrate using a spin coater (model D-spin60A, manufactured by SOKUDO Corporation), and heated and dried at 110° C. for 3 minutes to prepare a spin-coated film. Thereafter, an aligner (PLA-501F, manufactured by Canon Corporation) was used to expose the entire surface with ghi rays at an exposure dose of 600 mJ/cm 2 , and a vacuum gas replacement oven (450PB8-2P-CP, manufactured by YES Corporation) was used to expose the surface under nitrogen gas. Under the atmosphere, a heat curing treatment is performed at a specific temperature for 2 hours to produce a cured film. The film thickness of the cured film was measured using a step meter (P-15, manufactured by KLA-Tenchore). Using a wafer dicing machine (manufactured by DISCO, model name DAD-2H/6T), the cured film is cut into 80 mm in length and 60 mm in width or 40 mm in length and 30 mm in width, dipped in 10% hydrochloric acid aqueous solution and cut from the silicon wafer Peel off to make a film sample.
針對膜樣品，利用共振微擾法算出10、28、40、60 GHz下之比介電常數、介電損耗正切。測定方法之詳細內容如下所述。 (測定方法) 擾動方式分體圓柱共振器法 (裝置構成) 網路分析儀：PNA Network analyzer E5224B (Agilent technologies公司製造) 分體圓柱共振器：CR-710(關東電子應用開發公司製造，測定頻率：約10 GHz)、CR-728(關東電子應用開發公司製造，測定頻率：約28 GHz)、CR-740(關東電子應用開發公司製造，測定頻率：約40 GHz)、CR-760(關東電子應用開發公司製造，測定頻率：約60 GHz) For film samples, the specific permittivity and dielectric loss tangent at 10, 28, 40, and 60 GHz were calculated by using the resonance perturbation method. The details of the measurement method are as follows. (test methods) Perturbation Mode Split Cylindrical Resonator Method (device configuration) Network analyzer: PNA Network analyzer E5224B (manufactured by Agilent Technologies) Split cylindrical resonator: CR-710 (manufactured by Kanto Denshi Applied Development Co., Ltd., measurement frequency: about 10 GHz), CR-728 (manufactured by Kanto Denshi Applied Development Co., Ltd., measurable frequency: about 28 GHz), CR-740 (manufactured by Kanto Denshi Applied Development Co., Ltd. Manufactured by Application Development Co., Ltd., measurement frequency: about 40 GHz), CR-760 (manufactured by Kanto Denshi Application Development Co., Ltd., measurement frequency: about 60 GHz)
(3)重量減少率測定 將感光性樹脂組合物以硬化後之膜厚成為約10 μm之方式旋轉塗佈於6英吋矽晶圓上，利用加熱板於110℃下進行180秒預烘烤後，使用真空氣體置換烘箱(450PB8-2P-CP、YES公司製造)於氮氣氛圍下並於230℃下進行2小時加熱，獲得硬化聚醯亞胺塗膜。膜厚係利用膜厚測定裝置、Lambda ACE(大日本網屏公司製造)所測定。削取所獲得之聚醯亞胺塗膜，使用熱重量測定裝置(島津公司製造，TGA-50)自室溫以10℃/min升溫時，將達到230℃時之膜之重量設為W 230，將達到320℃時之膜之重量設為W 320，將達到350℃時之膜之重量設為W 350，分別算出下述式： 320℃重量減少率(%)＝(W 230－W 320)/W 230350℃重量減少率(%)＝(W 230－W 350)/W 230 (3) Measurement of Weight Loss Rate Spin-coat the photosensitive resin composition on a 6-inch silicon wafer so that the cured film thickness becomes about 10 μm, and pre-bake it at 110°C for 180 seconds on a hot plate Thereafter, heating was performed at 230° C. for 2 hours in a nitrogen atmosphere using a vacuum gas displacement oven (450PB8-2P-CP, manufactured by YES Corporation), to obtain a cured polyimide coating film. The film thickness was measured with a film thickness measuring device, Lambda ACE (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating film was scraped off, and when the temperature was raised from room temperature at 10° C./min using a thermogravimetric measuring device (manufactured by Shimadzu Corporation, TGA-50), the weight of the film at 230° C. was set as W 230 , Set the weight of the film at 320°C as W 320 , and set the weight of the film at 350°C as W 350 , respectively calculate the following formula: 320°C weight loss rate (%)=(W 230 -W 320 ) /W 230 350℃ weight reduction rate (%)＝(W 230 －W 350 )/W 230
[(A)聚醯亞胺前驅物之製造] ＜製造例1＞((A)聚醯亞胺前驅物(聚合物A-1)之合成) 將4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g放入2升容量之可分離式燒瓶中，添加甲基丙烯酸2-羥基乙酯(HEMA)134.0 g及γ-丁內酯400 ml，一面於室溫下進行攪拌，一面添加吡啶79.1 g，獲得反應混合物。基於反應之發熱結束後，放冷至室溫為止，進而靜置16小時。 [(A) Manufacture of polyimide precursor] <Production Example 1> (Synthesis of (A) Polyimide Precursor (Polymer A-1)) Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a 2-liter separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butylene 400 ml of ester was stirred at room temperature, and 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generated by the reaction ended, it was allowed to cool down to room temperature, and then left still for 16 hours.
繼而，於冰冷下，一面進行攪拌，一面將二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 ml中而成之溶液歷時40分鐘添加至反應混合物中，繼而一面進行攪拌，一面歷時60分鐘添加將2,2-雙{4-(4-胺基苯氧基)苯基}丙烷(BAPP)175.9 g懸浮於γ-丁內酯350 ml中而成之懸浮液。進而於室溫下攪拌2小時後，添加乙醇30 ml並攪拌1小時，然後添加γ-丁內酯400 ml。藉由過濾將反應混合物中所產生之沈澱物去除，獲得反應液。Then, while stirring under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes, and then While stirring, add a suspension obtained by suspending 175.9 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (BAPP) in 350 ml of γ-butyrolactone over 60 minutes . Furthermore, after stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
將所獲得之反應液添加至3升之乙醇中，生成包含粗聚合物之沈澱物。對所生成之粗聚合物進行濾取，將其溶解於四氫呋喃1.5升中，獲得粗聚合物溶液。使用陰離子交換樹脂(Organo股份有限公司製造之「Amberlyst TM15」)對所獲得之粗聚合物溶液進行精製，獲得聚合物溶液。將所獲得之聚合物溶液滴加至28升之水中而使聚合物沈澱，濾取所獲得之沈澱物後進行真空乾燥，藉此獲得粉末狀聚合物A-1。 測定該聚合物A-1之重量平均分子量(Mw)，結果為22,000。由聚合物A-1獲得之聚醯亞胺硬化膜之各重複單元之醯亞胺基濃度為19.4 wt%。 The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was collected by filtration, and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst ™ 15" manufactured by Organo Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum-dried to obtain powdery polymer A-1. When the weight average molecular weight (Mw) of this polymer A-1 was measured, it was 22,000. The concentration of imide groups in each repeating unit of the polyimide cured film obtained from polymer A-1 was 19.4 wt%.
＜製造例2＞((A)聚醯亞胺前驅物(聚合物A-2)之合成) 於上述製造例1中，使用4,4'-氧二苯胺(ODA)93.0 g代替BAPP175.9 g，除此以外，以與製造例1所記載之方法相同之方式進行反應，藉此獲得聚合物A-2。 測定該聚合物A-2之重量平均分子量(Mw)，結果為22,000。由聚合物A-2獲得之聚醯亞胺硬化膜之各重複單元之醯亞胺基濃度為27.4 wt%。 <Manufacturing example 2> ((A) Synthesis of polyimide precursor (polymer A-2)) In the above Production Example 1, except that 93.0 g of 4,4'-oxydiphenylamine (ODA) was used instead of 175.9 g of BAPP, the reaction was carried out in the same manner as described in Production Example 1 to obtain polymerization Object A-2. When the weight average molecular weight (Mw) of this polymer A-2 was measured, it was 22,000. The concentration of imide groups in each repeating unit of the polyimide cured film obtained from polymer A-2 was 27.4 wt%.
＜製造例3＞((A)聚醯亞胺前驅物(聚合物A-3)之合成) 於上述製造例1中，使用4,4'-(4,4'-亞異丙基二苯氧基)酸二酐(BPADA)260.2 g代替ODPA155.1 g，使用2,2'-二甲基聯苯基-4,4'-二胺(m-TB)92.88 g代替BAPP175.9 g，除此以外，以與製造例1所記載之方法相同之方式進行反應，藉此獲得聚合物A-3。 測定該聚合物A-3之重量平均分子量(Mw)，結果為23,000。由聚合物A-3獲得之聚醯亞胺硬化膜之各重複單元之醯亞胺基濃度為19.1 wt%。 <Production Example 3> (Synthesis of (A) Polyimide Precursor (Polymer A-3)) In Production Example 1 above, 260.2 g of 4,4'-(4,4'-isopropylidene diphenoxy) dianhydride (BPADA) was used instead of 155.1 g of ODPA, and 2,2'-dimethyl Except that 92.88 g of phenylbiphenyl-4,4'-diamine (m-TB) was substituted for 175.9 g of BAPP, the reaction was carried out in the same manner as described in Production Example 1 to obtain Polymer A -3. When the weight average molecular weight (Mw) of this polymer A-3 was measured, it was 23,000. The concentration of imide groups in each repeating unit of the polyimide cured film obtained from polymer A-3 was 19.1 wt%.
＜製造例4＞((A)聚醯亞胺前驅物(聚合物A-4)之合成) 於上述製造例1中，使用均苯四甲酸酐109.1 g代替ODPA155.1 g，使用ODA93.0 g代替BAPP175.9 g，除此以外，以與製造例1所記載之方法相同之方式進行反應，藉此獲得聚合物A-4。 測定該聚合物A-4之重量平均分子量(Mw)，結果為20,000。由聚合物A-4獲得之聚醯亞胺硬化膜之各重複單元之醯亞胺基濃度為33.5 wt%。 <Production Example 4> (Synthesis of (A) Polyimide Precursor (Polymer A-4)) In the above-mentioned production example 1, 109.1 g of pyromellitic anhydride was used instead of 155.1 g of ODPA, and 93.0 g of ODA was used instead of 175.9 g of BAPP, and the reaction was carried out in the same manner as described in production example 1. , whereby polymer A-4 was obtained. When the weight average molecular weight (Mw) of this polymer A-4 was measured, it was 20,000. The concentration of imide groups in each repeating unit of the polyimide cured film obtained from polymer A-4 was 33.5 wt%.
[感光性樹脂組合物之製造] 實施例使用下述化合物。 光聚合起始劑B-1：TR-PBG-3057(常州強力電子公司製造) 溶劑D-1：γ-丁內酯(GBL) [Manufacture of Photosensitive Resin Composition] Examples The following compounds were used. Photopolymerization initiator B-1: TR-PBG-3057 (manufactured by Changzhou Qiangli Electronics Co., Ltd.) Solvent D-1: γ-butyrolactone (GBL)
＜實施例1＞ 使用聚醯亞胺前驅物A-1並利用以下方法製備負型感光性樹脂組合物。溶解於作為(A)聚醯亞胺前驅物之A-1：100 g、作為(B)光聚合起始劑之B-1：5 g、作為(D)D-1：100 g中。進而添加少量GBL，藉此將所獲得之溶液之黏度調整為約40泊，製成負型感光性樹脂組合物。將該組合物依據上述方法製作硬化膜並進行評價。再者，加熱硬化步驟(步驟(5))係以壓力380 torr於230℃下進行2小時。將結果示於以下表1中。<Example 1> Using the polyimide precursor A-1, a negative photosensitive resin composition was prepared by the following method. It was dissolved in A-1: 100 g as (A) polyimide precursor, B-1: 5 g as (B) photopolymerization initiator, and (D) D-1: 100 g. Furthermore, a small amount of GBL was added to adjust the viscosity of the obtained solution to about 40 poises to prepare a negative photosensitive resin composition. A cured film was prepared and evaluated from this composition according to the method described above. Furthermore, the heat hardening step (step (5)) was carried out at 230° C. for 2 hours at a pressure of 380 torr. The results are shown in Table 1 below.
＜實施例1～7、比較例1～4＞ 以如以下表1所示之調配比製備，並使用如表1所示之加熱硬化步驟之溫度與壓力進行與實施例1相同之評價。 <Examples 1-7, Comparative Examples 1-4> It was prepared at the compounding ratio shown in Table 1 below, and the same evaluation as in Example 1 was carried out using the temperature and pressure of the heat hardening step shown in Table 1.
＜實施例8、9＞ 以如以下表1所示之調配比製備，並使用如表1所示之壓力進行與實施例1相同之評價。再者，加熱硬化步驟係於150℃進行1小時，其後升溫並於230℃下進行1小時。<Examples 8 and 9> Prepared with the mixing ratio shown in Table 1 below, and used the pressure shown in Table 1 to perform the same evaluation as Example 1. Furthermore, the heat hardening step was carried out at 150° C. for 1 hour, and then the temperature was raised and carried out at 230° C. for 1 hour.
[表1]
根據表1得知，實施例之硬化膜可獲得介電損耗正切之頻率依存性較低之硬化膜。又，相對於比較例而言，將硬化膜加熱至320℃、350℃時之重量減少率降低。 [產業上之可利用性] According to Table 1, it can be seen that the cured film of the embodiment can obtain a cured film with a lower frequency dependence of the dielectric loss tangent. Moreover, the weight loss rate at the time of heating a cured film to 320 degreeC and 350 degreeC fell compared with a comparative example. [Industrial availability]
根據本發明之聚醯亞胺硬化膜之製造方法，能夠提供一種介電損耗正切之頻率依存性較低、加熱硬化溫度以上之溫度下之熱重量減少得到抑制之硬化膜。因此，本發明之聚醯亞胺硬化膜之製造方法例如能夠於半導體裝置、多層配線基板等領域中較佳地利用。According to the method for producing a polyimide cured film of the present invention, it is possible to provide a cured film in which the frequency dependence of the dielectric loss tangent is low and the thermogravimetric decrease at a temperature higher than the heat curing temperature is suppressed. Therefore, the manufacturing method of the polyimide cured film of this invention can be utilized preferably in fields, such as a semiconductor device and a multilayer wiring board, for example.
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