TW201905086A - Photosensitive resin composition, resin film, and electronic device - Google Patents
Photosensitive resin composition, resin film, and electronic deviceInfo
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- TW201905086A TW201905086A TW107121270A TW107121270A TW201905086A TW 201905086 A TW201905086 A TW 201905086A TW 107121270 A TW107121270 A TW 107121270A TW 107121270 A TW107121270 A TW 107121270A TW 201905086 A TW201905086 A TW 201905086A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Polyamides (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本發明係關於一種感光性樹脂組成物、樹脂膜及電子裝置。The present invention relates to a photosensitive resin composition, a resin film, and an electronic device.
迄今為止,在感光性樹脂組成物的領域中,以獲得即使在低溫下硬化時,亦能夠形成不脆弱且富有耐熱性之硬化膜之感光性樹脂組成物為目的,已開發出各種技術。作為該種技術,可列舉專利文獻1中記載之技術。 依專利文獻1,記載有對具有特定的結構之聚醯胺塗佈包含具有酚性羥基之化合物之樹脂組成物,於200℃以下進行硬化而成之膜顯示高斷裂伸長率。In the field of the photosensitive resin composition, various techniques have been developed so far for the purpose of obtaining a photosensitive resin composition capable of forming a non-fragile and heat-resistant cured film even when cured at a low temperature. Examples of such a technique include those described in Patent Document 1. According to Patent Document 1, it is described that a film obtained by applying a resin composition containing a compound having a phenolic hydroxyl group to a polyamide having a specific structure and curing at 200 ° C. or lower shows a high elongation at break.
專利文獻1:日本特開2007-213032號公報Patent Document 1: Japanese Patent Application Laid-Open No. 2007-213032
本發明人等對在使用專利文獻1中記載之感光性樹脂組成物作為電子裝置的永久膜時,設置成用於電子裝置的基板的輸入輸出之鋁(Al)墊及電路亦即銅(Cu)電路與永久膜之間的密接性進行研究。再者,所謂永久膜係藉由如下而獲得之硬化膜:對感光性樹脂組成物進行預烘、曝光及顯影,製作圖案化成所需形狀之樹脂膜,接著,藉由後烘使樹脂膜硬化。 上述研究之結果判斷出,使用專利文獻1中記載之感光性樹脂組成物而形成之硬化膜相對於Al墊、Cu電路,密接力不充分。 因此,本發明的課題為提高將感光性樹脂組成物進行後烘而獲得之硬化膜與Al、Cu等金屬之間的密接性。When using the photosensitive resin composition described in Patent Document 1 as a permanent film of an electronic device, the inventors of the present invention provided copper (Cu) as an aluminum (Al) pad and a circuit provided as input and output of a substrate of the electronic device. ) Study the tightness between the circuit and the permanent film. The so-called permanent film is a cured film obtained by pre-baking, exposing, and developing a photosensitive resin composition to produce a resin film patterned into a desired shape, and then curing the resin film by post-baking. . As a result of the above studies, it is determined that the cured film formed using the photosensitive resin composition described in Patent Document 1 has insufficient adhesion with respect to Al pads and Cu circuits. Therefore, an object of the present invention is to improve the adhesion between a cured film obtained by post-baking a photosensitive resin composition and metals such as Al and Cu.
本發明人等為提高後烘後的感光性樹脂組成物的硬化膜與Al、Cu等金屬之間的密接性而對感光性樹脂組成物的原料成分進行研究。其結果發現,藉由包含特定的溶劑作為原料成分,能夠提高後烘後的感光性樹脂組成物的硬化膜與Al、Cu等金屬之間的密接性,從而完成本發明。The present inventors studied the raw material components of the photosensitive resin composition in order to improve the adhesion between the cured film of the post-baking photosensitive resin composition and metals such as Al and Cu. As a result, it was found that by including a specific solvent as a raw material component, the adhesion between the cured film of the post-baking photosensitive resin composition and metals such as Al and Cu can be improved, and the present invention has been completed.
依本發明,提供一種感光性樹脂組成物,其包含: 鹼可溶性樹脂; 感光劑;及 溶劑, 前述溶劑包含尿素化合物或非環狀結構的醯胺化合物。According to the present invention, there is provided a photosensitive resin composition including: an alkali-soluble resin; a photosensitizer; and a solvent, wherein the solvent includes a urea compound or an amidine compound having a non-cyclic structure.
又,依本發明,可提供一種將上述感光性樹脂組成物硬化而成之樹脂膜。Also, according to the present invention, a resin film obtained by curing the photosensitive resin composition can be provided.
又,依本發明,可提供一種具備上述樹脂膜之電子裝置。Also, according to the present invention, an electronic device including the resin film can be provided.
本發明提供一種提高將感光性樹脂組成物進行後烘而獲得之硬化膜與Al、Cu等金屬之間的密接性之感光性樹脂組成物。The present invention provides a photosensitive resin composition that improves the adhesion between a cured film obtained by post-baking the photosensitive resin composition and metals such as Al and Cu.
上述目的及其他目的、特徵及優點藉由以下說明之較佳的實施形態及其附帶之以下圖式而變得更加明確。The above-mentioned objects and other objects, features, and advantages will be made clearer by the preferred embodiments described below and the accompanying drawings.
以下,適當利用圖式對本實施形態進行說明。另外,在所有圖式中,對相同的構成要件標註相同的符號,並省略其說明。Hereinafter, this embodiment will be described using drawings as appropriate. In all drawings, the same constituent elements are denoted by the same reference numerals, and descriptions thereof are omitted.
本實施形態之感光性樹脂組成物包含鹼可溶性樹脂、感光劑及溶劑,前述溶劑包含尿素化合物或非環狀結構的醯胺化合物。The photosensitive resin composition according to this embodiment includes an alkali-soluble resin, a sensitizer, and a solvent, and the solvent includes a urea compound or an amidine compound having a non-cyclic structure.
近年來,隨著電子裝置的微細化,存在電子裝置的Al墊、銅電路等金屬構件變小之趨勢。此處,在金屬構件變小之情況下,積層於該金屬構件而形成之感光性樹脂組成物的硬化膜與金屬構件的密接力低,並導致硬化膜剝離。在硬化膜剝離之情況下,從該剝離所產生之部位產生漏電流等,並存在電子裝置的電氣可靠性降低之不良情況。In recent years, with the miniaturization of electronic devices, there has been a tendency for metal members such as Al pads and copper circuits of electronic devices to become smaller. Here, when the metal member becomes smaller, the adhesion between the cured film of the photosensitive resin composition formed by laminating the metal member and the metal member is low, and the cured film is peeled. When the cured film is peeled off, a leakage current or the like is generated from a part where the peeling occurs, and there is a disadvantage that the electrical reliability of the electronic device is reduced.
本發明人等對能夠提高後烘後的感光性樹脂組成物的硬化膜與Al墊、銅電路等金屬之間的密接性之感光性樹脂組成物的原料成分進行研究。其結果發現,藉由包含尿素化合物或非環狀結構的醯胺化合物作為感光性樹脂組成物的溶劑,從而能夠提高密接性。 能夠提高密接性之詳細機制雖不明確,但可推測為如下。作為密接性得到提高之機制,首先,認為起因於尿素化合物及非環狀結構的醯胺化合物所具備之孤電子對與Al、Cu等金屬原子形成強力的配位鍵。藉此,認為乾燥前的感光性樹脂組成物的清漆的含有成分被溶劑所形成之配位鍵拉伸而與Al、Cu等金屬強力結合。其後,在對感光性樹脂組成物進行預烘、曝光及顯影,製作圖案化成所需形狀之樹脂膜,接著,將樹脂膜進行後烘而使其硬化,藉此製作硬化膜之情況下,推測為除了感光性樹脂組成物的溶劑以外的含有成分及金屬原子強力結合而成之配位的狀態下,能夠凍結除了感光性樹脂組成物的溶劑以外的含有成分的分子配位。因此,認為能夠提高後烘後的硬化膜與Al、Cu等金屬之間的密接性。 再者,推測為在尿素化合物與非環狀結構的醯胺化合物中,形成上述強力的配位鍵之機制不同。首先,作為前提,習知感光性樹脂組成物中,作為溶劑,使用N-甲基吡咯啶酮(NMP)等環狀結構的醯胺化合物等。尿素化合物由於脲鍵而在分子結構中具備2個以上具有孤電子對之氮原子。藉此,推測為配位鍵與孤電子對的數量成比例地變強。因此,認為當使用尿素化合物時,與習知感光性樹脂組成物的溶劑中所使用之化合物相比,能夠形成強力的配位鍵。又,推測非環狀結構的醯胺化合物與習知感光性樹脂組成物中所使用之環狀結構的醯胺化合物相比,容易形成配位鍵。認為這是因為,非環狀結構的醯胺化合物與環狀結構的醯胺化合物相比,分子運動的限制少,進而分子結構的變形的自由度大。因此認為,當使用非環狀結構的醯胺化合物時,與習知感光性樹脂組成物的溶劑中所使用之化合物相比,能夠形成強力的配位鍵。 由上述可推測為,本實施形態之感光性樹脂組成物含有特定的化合物作為溶劑,藉此能夠提高後烘後的硬化膜與Al、Cu等金屬之間的密接性。The present inventors have studied a raw material component of a photosensitive resin composition that can improve the adhesion between a cured film of a post-bake photosensitive resin composition and metals such as Al pads and copper circuits. As a result, it was found that adhesiveness can be improved by using a urea compound or a fluorene compound having a non-cyclic structure as a solvent for the photosensitive resin composition. Although the detailed mechanism that can improve the adhesion is not clear, it can be estimated as follows. As a mechanism for improving the adhesion, firstly, it is thought that the lone electron pair included in the urea compound and the amidine compound having a non-cyclic structure forms a strong coordination bond with a metal atom such as Al or Cu. From this, it is considered that the varnish-containing component of the photosensitive resin composition before drying is stretched by the coordination bond formed by the solvent and is strongly bonded to metals such as Al and Cu. Thereafter, when the photosensitive resin composition is pre-baked, exposed, and developed to produce a resin film patterned into a desired shape, and then the resin film is post-baked to harden, thereby producing a cured film, It is estimated that the molecular coordination of the contained components other than the solvent of the photosensitive resin composition can be frozen in a state where the contained components other than the solvent of the photosensitive resin composition and metal atoms are strongly bonded. Therefore, it is considered that the adhesion between the post-bake cured film and metals such as Al and Cu can be improved. In addition, it is presumed that the urea compound and the amidine compound having an acyclic structure have different mechanisms for forming the aforementioned strong coordination bond. First, as a premise, it is known that a photosensitive resin composition uses a cyclic amidine compound such as N-methylpyrrolidone (NMP) as a solvent. A urea compound has two or more nitrogen atoms having a lone electron pair in its molecular structure due to a urea bond. As a result, it is presumed that the coordination bond becomes stronger in proportion to the number of lone electron pairs. Therefore, when a urea compound is used, it is thought that a strong coordination bond can be formed compared with the compound used for the solvent of the conventional photosensitive resin composition. In addition, it is presumed that the amidine compound having a non-cyclic structure is easier to form a coordination bond than the amidine compound having a cyclic structure used in a conventional photosensitive resin composition. This is considered to be because the amidine compound having a non-cyclic structure has fewer restrictions on molecular motion than the amidine compound having a cyclic structure, and further has a large degree of freedom in deformation of the molecular structure. Therefore, when a fluorene compound having a non-cyclic structure is used, it is considered that a stronger coordination bond can be formed than a compound used in a solvent of a conventional photosensitive resin composition. From the above, it is presumed that the photosensitive resin composition of the present embodiment contains a specific compound as a solvent, whereby the adhesion between the post-bake cured film and metals such as Al and Cu can be improved.
再者,除了上述後烘後的硬化膜與Al、Cu等金屬之間的密接性的提高以外,從與習知感光性樹脂組成物中所使用之溶劑相比尿素化合物對人體的不良影響少的觀點考慮亦有利。一直以來所使用之N-甲基吡咯啶酮等環狀結構的醯胺化合物由於進入到人體中而存在生殖功能受損等各種不良影響,並且考慮到安全,需要對感光性樹脂組成物的生產步驟進行研究。然而,由於尿素化合物對人體的不良影響很小,因此在不需要生產步驟的研究等方面有利。 作為對人體的不良影響小的尿素化合物,例如可列舉四甲基脲等。Furthermore, in addition to the improvement in adhesion between the post-bake cured film and metals such as Al and Cu, urea compounds have less adverse effects on the human body than solvents used in conventional photosensitive resin compositions. The consideration of perspective is also beneficial. The cyclic amidine compounds, such as N-methylpyrrolidone, which have been used in the past, have various adverse effects such as impaired reproductive functions as they enter the human body. In consideration of safety, production of photosensitive resin compositions is required Steps to study. However, since the urea compound has a small adverse effect on the human body, it is advantageous in terms of studies that do not require production steps. Examples of the urea compound having less adverse effects on the human body include tetramethylurea.
首先,對本實施形態之感光性樹脂組成物的各原料成分進行說明。First, each raw material component of the photosensitive resin composition of this embodiment is demonstrated.
(鹼可溶性樹脂) 作為鹼可溶性樹脂並無限定,能夠依據樹脂膜所需之機械特性、光學特性等物性來選擇。作為鹼可溶性樹脂,具體而言可列舉聚醯胺樹脂、聚苯并㗁唑樹脂、酚樹脂、羥基苯乙烯樹脂等。作為鹼可溶性樹脂,在上述具體例中,例如使用聚醯胺樹脂或聚苯并㗁唑樹脂為較佳。藉此,認為能夠在聚醯胺樹脂的醯胺鍵與尿素化合物或非環狀結構的醯胺化合物之間形成氫鍵等強相互作用。因此,當將感光性樹脂組成物設為硬化膜時,可認為能夠藉由鹼可溶性樹脂和金屬分子更強力地鍵結而成之配位來凍結分子結構。再者,作為鹼可溶性樹脂,能夠包含上述具體例中的一種或兩種以上。(Alkali-soluble resin) The alkali-soluble resin is not limited, and can be selected according to physical properties such as mechanical properties and optical properties required for the resin film. Specific examples of the alkali-soluble resin include polyamine resin, polybenzoxazole resin, phenol resin, and hydroxystyrene resin. As the alkali-soluble resin, in the above-mentioned specific examples, for example, a polyfluorene resin or a polybenzoxazole resin is preferably used. From this, it is considered that strong interactions such as hydrogen bonding can be formed between the amidine bond of the polyamide resin and the urea compound or the amidine compound having a non-cyclic structure. Therefore, when the photosensitive resin composition is used as a cured film, it is considered that the molecular structure can be frozen by the coordination in which the alkali-soluble resin and metal molecules are more strongly bonded. The alkali-soluble resin may include one or two or more of the specific examples described above.
<聚醯胺樹脂、聚苯并㗁唑樹脂> 作為聚醯胺樹脂,例如使用在聚醯胺的結構單元中包含芳香族環之芳香族聚醯胺為較佳,包含下述式(PA1)所表示之結構單元者為更佳。藉此,聚醯胺樹脂的分子鏈彼此經由醯胺鍵而氫鍵結,進而芳香族環部分緊密地進行分子排列,藉此能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構。當溶劑包含四甲基脲作為尿素化合物時,該配位更適於提高密接性。因此,從密接性提高之觀點而言,包含聚醯胺樹脂作為鹼可溶性樹脂,且溶劑包含四甲基脲作為尿素化合物為較佳。 再者,在本實施形態中,所謂芳香族環,表示苯環;萘環、蒽環、芘環等縮合芳香環;吡啶環、吡咯環等雜芳香環等。從形成上述從緊密結構之觀點考慮,本實施形態的聚醯胺樹脂包含苯環作為芳香族環為較佳。<Polyamide resin, polybenzoxazole resin> As the polyamide resin, for example, an aromatic polyamine containing an aromatic ring in the structural unit of polyamine is preferably used, and contains the following formula (PA1) The structural unit shown is more preferred. Thereby, the molecular chains of the polyamide resin are hydrogen-bonded with each other via the amidine bond, and then the aromatic ring part is closely arranged in a molecular arrangement, whereby the alkali-soluble resin and the metal molecule can be more strongly bonded. Coordination to freeze molecular structure. When the solvent contains tetramethylurea as a urea compound, this coordination is more suitable for improving adhesion. Therefore, from the viewpoint of improving the adhesiveness, it is preferable to include a polyamine resin as the alkali-soluble resin and the solvent to include tetramethylurea as the urea compound. In the present embodiment, the term "aromatic ring" means a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, a fluorene ring; a heteroaromatic ring such as a pyridine ring or a pyrrole ring; From the viewpoint of forming the above-mentioned compact structure, it is preferable that the polyamidoamine resin of the present embodiment contains a benzene ring as an aromatic ring.
包含上述式(PA1)所表示之結構單元之聚醯胺樹脂係聚苯并㗁唑樹脂的前驅物。包含上述式(PA1)所表示之結構單元之聚醯胺樹脂例如能夠藉由在150℃以上且380℃以下的溫度以30分鐘以上且50小時以下的條件進行熱處理,藉此脫水閉環,形成聚苯并㗁唑樹脂。此處,上述式(PA1)的結構單元藉由脫水閉環而成為下述式(PBO1)所表示之結構單元。 在本實施形態之鹼可溶性樹脂係包含上述式(PA1)所表示之結構單元之聚醯胺樹脂之情況下,例如可藉由對感光性樹脂組成物進行上述熱處理,藉此脫水閉環,形成聚苯并㗁唑樹脂。亦即,進行上述熱處理之感光性樹脂組成物包含作為鹼可溶性樹脂之聚苯并㗁唑樹脂。 又,在鹼可溶性樹脂係包含上述式(PA1)所表示之結構單元之聚醯胺樹脂之情況下,可在製作後述之樹脂膜、電子裝置之後進行上述熱處理,藉此脫水閉環,形成聚苯并㗁唑樹脂。在藉由將聚醯胺樹脂進行脫水開環而形成聚苯并㗁唑樹脂之情況下,能夠增加拉伸斷裂伸長率、玻璃轉移溫度。藉此,就能夠提高樹脂膜、電子裝置的強度及耐熱性之觀點而言有利。A precursor of a polyfluorene resin-based polybenzoxazole resin containing a structural unit represented by the formula (PA1). The polyamide resin containing the structural unit represented by the above formula (PA1) can be subjected to heat treatment at a temperature of 150 ° C or higher and 380 ° C or lower for 30 minutes or longer and 50 hours or shorter, thereby dehydrating and closing the ring to form a polymer. Benzoxazole resin. Here, the structural unit of the above formula (PA1) becomes a structural unit represented by the following formula (PBO1) by dehydration closed loop. In the case where the alkali-soluble resin of this embodiment is a polyamide resin containing the structural unit represented by the formula (PA1), for example, the photosensitive resin composition may be subjected to the above-mentioned heat treatment to dehydrate and close the ring to form a polymer. Benzoxazole resin. That is, the photosensitive resin composition subjected to the heat treatment includes a polybenzoxazole resin as an alkali-soluble resin. In the case where the alkali-soluble resin is a polyamide resin containing a structural unit represented by the formula (PA1), the above-mentioned heat treatment may be performed after the resin film and electronic device described later are manufactured, thereby dehydrating and closing the ring to form polybenzene. And oxazole resin. When a polybenzoxazole resin is formed by dehydrating and ring-opening a polyfluorene resin, the tensile elongation at break and the glass transition temperature can be increased. Thereby, it is advantageous from a viewpoint that the strength and heat resistance of a resin film and an electronic device can be improved.
<聚醯胺樹脂的製造方法> 本實施形態之聚醯胺樹脂例如以如下聚合。 首先,藉由聚合步驟(S1)使二胺單體與二羧酸單體縮聚,從而使聚醯胺聚合。接著,藉由低分子量成分去除步驟(S2)去除低分子量成分,獲得以聚醯胺為主成分之聚醯胺樹脂。<The manufacturing method of a polyamide resin> The polyamide resin of this embodiment is polymerized as follows, for example. First, polyamine is polymerized by polymerizing a diamine monomer and a dicarboxylic acid monomer in a polymerization step (S1). Next, a low molecular weight component is removed in a low molecular weight component removal step (S2), and a polyamide resin containing polyamine as a main component is obtained.
(聚合步驟(S1)) 在聚合步驟(S1)中,使二胺單體與二羧酸單體縮聚。作為使聚醯胺聚合之縮聚的方法並無限定,具體而言可列舉熔融縮聚、醯氯法、直接縮聚等。 再者,代替二羧酸單體,亦可使用選自由四羧酸二酐、1,2,4-苯三甲酸酐、二氯化二羧酸或活性酯型二羧酸組成的群中之化合物。作為獲得活性酯型二羧酸之方法,具體而言能夠列舉使二羧酸與1-羥基-1,2,3-苯并三唑等反應之方法。(Polymerization Step (S1)) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing polyamine is not limited, and specific examples include melt polycondensation, chlorination, and direct polycondensation. Further, instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, dichlorinated dicarboxylic acid, or an active ester type dicarboxylic acid may be used. . Specific examples of a method for obtaining an active ester-type dicarboxylic acid include a method of reacting a dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole and the like.
以下對聚醯胺樹脂的聚合中所使用之二胺單體及二羧酸單體進行說明。再者,二胺單體及二羧酸單體可分別準備一種,亦可併用兩種以上而使用。The diamine monomer and the dicarboxylic acid monomer used in the polymerization of the polyamide resin are described below. In addition, one type of diamine monomer and one dicarboxylic acid monomer may be separately prepared, or two or more types may be used in combination.
<二胺單體> 作為用於聚合之二胺單體並無限定,例如使用結構中包含芳香族環之二胺單體為較佳,使用結構中包含酚性羥基之二胺單體為更佳。此處,作為結構中包含酚性羥基之二胺單體,例如係下述通式(DA1)所表示之者為較佳。藉由以該種二胺單體為原料來製造聚醯胺樹脂,控制聚醯胺樹脂的構形,聚醯胺樹脂的分子鏈彼此能夠形成更緊密結構。因此,能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構,並提高密接性。 再者,例如,在使用下述通式(DA1)所表示之二胺單體之情況下,聚醯胺樹脂包含下述通式(PA2)所表示之結構單元。亦即,本實施形態之聚醯胺樹脂例如包含下述通式(PA2)所表示之結構單元為較佳。<Diamine monomer> The diamine monomer used for polymerization is not limited. For example, a diamine monomer containing an aromatic ring in the structure is preferred, and a diamine monomer containing a phenolic hydroxyl group in the structure is more preferred. good. Here, as a diamine monomer containing a phenolic hydroxyl group in a structure, it is preferable that it is represented by the following general formula (DA1), for example. By using the diamine monomer as a raw material to manufacture a polyamide resin and controlling the configuration of the polyamide resin, the molecular chains of the polyamide resin can form a tighter structure with each other. Therefore, the molecular structure can be frozen and the adhesion can be improved by the coordination in which the alkali-soluble resin and the metal molecule are more strongly bonded. When a diamine monomer represented by the following general formula (DA1) is used, for example, the polyamide resin contains a structural unit represented by the following general formula (PA2). That is, it is preferable that the polyamide resin of this embodiment contains a structural unit represented by the following general formula (PA2), for example.
(在上述通式(DA1)中,R4 係藉由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成的群中之一種或兩種以上的原子所形成之基。R5 ~R10 分別獨立地表示、氫或碳數1以上且30以下的有機基。) (In the general formula (DA1), R 4 is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A group formed by one or two or more kinds of atoms. R 5 to R 10 each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.)
(在上述通式(PA2)中,R4 、R5 ~R10 係與上述通式(DA1)相同。) (In the general formula (PA2), R 4 and R 5 to R 10 are the same as the general formula (DA1).)
上述通式(DA1)及(PA2)中的R4 係藉由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成的群中之一種或兩種以上的原子所形成之基。 再者,R4 係2價的基。此處,所謂2價的基,表示原子價。亦即,表示R4 與其他原子鍵結之鍵結鍵係2個。R 4 in the general formulae (DA1) and (PA2) is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A radical formed by one or more atoms in a group. R 4 is a divalent radical. Here, the divalent radical means an atomic valence. In other words, there are two bond bonds showing that R 4 is bonded to other atoms.
在上述通式(DA1)及(PA2)中的R4 包含碳原子之情況下,R4 例如係碳數1以上且30以下的基,碳數1以上且10以下的基為較佳,碳數1以上5以下的基為更佳,碳數1以上且3以下的基為進一步較佳。When R 4 in the general formulae (DA1) and (PA2) contains a carbon atom, R 4 is, for example, a group having 1 to 30 carbon atoms, and a group having 1 to 10 carbon atoms is preferred. Carbon A group having a number of 1 to 5 is more preferred, and a group having a number of 1 to 3 is more preferred.
在上述通式(DA1)及(PA2)中的R4 包含碳原子之情況下,作為R4 ,具體而言可列舉伸烷基、伸芳基、經鹵素取代之伸烷基、經鹵素取代之伸芳基等。 作為伸烷基,例如可為直鏈狀的伸烷基,亦可為支鏈狀的伸烷基。作為直鏈狀的伸烷基,具體而言可列舉亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、三亞甲基、四亞甲基、五亞甲基、六亞甲基等。作為支鏈狀的伸烷基,具體而言可列舉-C(CH3 )2 -、-CH(CH3 )-、-CH(CH2 CH3 )-、-C(CH3 )(CH2 CH3 )-、-C(CH3 )(CH2 CH2 CH3 )-、-C(CH2 CH3 )2 -等烷基亞甲基;-CH(CH3 )CH2 -、-CH(CH3 )CH(CH3 )-、-C(CH3 )2 CH2 -、-CH(CH2 CH3 )CH2 -、-C(CH2 CH3 )2 -CH2 -等烷基伸乙基等。 作為伸芳基,具體而言可列舉伸苯基、伸聯苯基、伸萘基、伸蒽基及2個或2個以上的伸芳基彼此鍵結而成者等。 作為經鹵素取代之伸烷基、經鹵素取代之伸芳基,具體而言分別能夠使用將上述伸烷基、伸芳基中的氫原子經氟原子、氯原子、溴原子等鹵素原子取代而得者。該等中,使用藉由氟原子取代氫原子而得者為較佳。R in the general formula (DAl) and (PA2) contained in the case 4 carbon atoms, as R 4, specifically include alkylene, arylene, substituted alkylene group of halo, substituted by halogen Zhifang aryl and so on. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylidene, propylidene, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and xylenyl. Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Specific examples of the branched alkylene group include -C (CH 3 ) 2- , -CH (CH 3 )-, -CH (CH 2 CH 3 )-, and -C (CH 3 ) (CH 2 CH 3 )-, -C (CH 3 ) (CH 2 CH 2 CH 3 )-, -C (CH 2 CH 3 ) 2 -and other alkyl methylene groups; -CH (CH 3 ) CH 2- , -CH (CH 3 ) CH (CH 3 )-, -C (CH 3 ) 2 CH 2- , -CH (CH 2 CH 3 ) CH 2- , -C (CH 2 CH 3 ) 2 -CH 2- , etc. Ethyl etc. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthyl group, an anthracene group, and two or more arylenyl groups bonded to each other. As the halogen-substituted alkylene group and the halogen-substituted alkylene group, specifically, a hydrogen atom in the alkylene group and the alkylene group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. Winner. Among these, it is more preferable to use one obtained by replacing a hydrogen atom with a fluorine atom.
在上述通式(DA1)及(PA2)中的R4 不包含碳原子之情況下,作為R4 ,具體而言可列舉由氧原子或硫原子構成之基等。When R 4 in the general formulae (DA1) and (PA2) does not include a carbon atom, specific examples of R 4 include a group consisting of an oxygen atom or a sulfur atom.
上述通式(DA1)及(PA2)中的R5 ~R10 分別獨立地為氫或碳數1以上且30以下的有機基,例如係氫或碳數1以上且10以下的有機基為較佳,氫或碳數1以上且5以下的有機基為更佳,氫或碳數1以上且3以下的有機基為進一步較佳,氫或碳數1以上且2以下的有機基為更進一步較佳。藉此,聚醯胺樹脂的芳香族環彼此能夠緊密地排列。因此,能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構,並能夠提高密接性。R 5 to R 10 in the general formulae (DA1) and (PA2) are each independently hydrogen or an organic group having 1 to 30 carbon atoms. For example, hydrogen or an organic group having 1 to 10 carbon atoms is preferred. Preferably, hydrogen or an organic group having 1 or more and 5 or less carbon is more preferable, hydrogen or an organic group having 1 or more and 3 or less is more preferable, and hydrogen or an organic group having 1 or more and 2 or less is further Better. This allows the aromatic rings of the polyamide resin to be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved.
作為上述通式(DA1)及(PA2)中的R5 ~R10 的碳數1以上且30以下的有機基的具體例,可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基等烷基;烯丙基、戊烯基、乙烯基等烯基;乙炔基等炔基;次甲基、亞乙基等亞烷基;甲苯基、二甲苯基、苯基、萘基、蒽基等芳基;苄基、苯乙基等芳烷基;金剛烷基、環戊基、環己基、環辛基等環烷基;甲苯基、二甲苯基等烷芳基等。Specific examples of the organic group having 1 to 30 carbon atoms in R 5 to R 10 in the general formulae (DA1) and (PA2) include methyl, ethyl, n-propyl, isopropyl, and n- Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene Alkenyl groups such as ethynyl; alkynyl groups such as ethynyl; alkylene groups such as methine, ethylene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, and anthracenyl; aromatic groups such as benzyl, phenethyl Alkyl; cycloalkyl such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl; alkylaryl such as tolyl, xylyl, and the like.
作為上述通式(DA1)所表示之二胺單體,具體而言可列舉,2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、4,4’-亞甲基雙(2-胺基-3,6-二甲基酚)、4,4’-亞甲基雙(2-胺基酚)、1,1-雙(3-胺基-4-羥基苯基)乙烷、3,3’-二胺基-4,4’-二羥基二苯醚等。藉由使用該等二胺單體,聚醯胺樹脂的芳香族環彼此能夠緊密排列。因此,能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構,並能夠提高密接性。再者,作為二胺單體,能夠使用上述具體例中的一種或組合使用兩種以上。 以下示出該等二胺單體的結構式。Specific examples of the diamine monomer represented by the general formula (DA1) include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-methylene Bis (2-amino-3,6-dimethylphenol), 4,4'-methylenebis (2-aminophenol), 1,1-bis (3-amino-4-hydroxyphenyl) ) Ethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, etc. By using these diamine monomers, the aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved. Furthermore, as the diamine monomer, one of the above specific examples can be used or two or more of them can be used in combination. The structural formula of these diamine monomers is shown below.
<二羧酸單體> 作為用於聚合之二羧酸單體並無限定,例如使用結構中包含芳香族環之二羧酸單體為較佳。 作為包含芳香族環之二羧酸單體,例如使用下述通式(DC1)所表示者為較佳。 再者,例如,在使用下述通式(DC1)所表示之二羧酸單體之情況下,聚醯胺樹脂包含下述通式(PA3)所表示之結構單元。亦即,本實施形態之聚醯胺樹脂例如包含下述通式(DC1)所表示之結構單元為較佳。藉此,聚醯胺樹脂的芳香族環彼此能夠緊密地排列。因此,能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構,並能夠提高密接性。<Dicarboxylic acid monomer> There is no limitation as a dicarboxylic acid monomer used for polymerization, For example, it is preferable to use the dicarboxylic acid monomer which contains an aromatic ring in a structure. As the dicarboxylic acid monomer containing an aromatic ring, it is preferable to use, for example, one represented by the following general formula (DC1). When a dicarboxylic acid monomer represented by the following general formula (DC1) is used, for example, the polyamide resin includes a structural unit represented by the following general formula (PA3). That is, it is preferable that the polyamide resin of this embodiment contains a structural unit represented by the following general formula (DC1), for example. This allows the aromatic rings of the polyamide resin to be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved.
(上述通式(DC1)中,R11 係藉由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成的群中之一種或兩種以上的原子所形成之基。R12 ~R19 分別獨立地表示氫或碳數1以上且30以下的有機基。) (In the general formula (DC1), R 11 is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A group formed by one or two or more kinds of atoms. R 12 to R 19 each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.)
(在上述通式(PA3)中,R11 、R12 ~R19 係與上述通式(DC1)相同。) (In the general formula (PA3), R 11 and R 12 to R 19 are the same as the general formula (DC1).)
上述通式(DC1)及(PA3)中的R11 係藉由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成的群中之一種或兩種以上的原子所形成之基。 再者,R11 係2價的基。此處,所謂2價的基,表示原子價。亦即,表示R11 與其他原子鍵結之鍵結鍵係2個。R 11 in the general formulae (DC1) and (PA3) is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A radical formed by one or more atoms in a group. R 11 is a divalent radical. Here, the divalent radical means an atomic valence. In other words, there are two bond bonds showing that R 11 is bonded to other atoms.
在上述通式(DC1)及(PA3)中的R11 包含碳原子之情況下,R11 例如係碳數1以上且30以下的基,碳數1以上10且以下的基為較佳,碳數1以上5且以下的基為更佳,碳數1以上且3以下的基為進一步較佳。When R 11 in the general formulae (DC1) and (PA3) contains a carbon atom, R 11 is, for example, a group having 1 to 30 carbon atoms, and a group having 1 to 10 carbon atoms is preferred. Carbon Groups having a number of 1 to 5 are more preferred, and groups having a carbon number of 1 to 3 are more preferred.
在上述通式(DC1)及(PA3)中的R11 包含碳原子之情況下,作為R11 ,具體而言可列舉伸烷基、伸芳基、經鹵素取代之伸烷基、經鹵素取代之伸芳基等。 作為伸烷基,例如可為直鏈狀的伸烷基,亦可為支鏈狀的伸烷基。作為直鏈狀的伸烷基,具體而言可列舉亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、三亞甲基、四亞甲基、五亞甲基、六亞甲基等。作為支鏈狀的伸烷基,具體而言可列舉-C(CH3 )2 -、-CH(CH3 )-、-CH(CH2 CH3 )-、-C(CH3 )(CH2 CH3 )-、-C(CH3 )(CH2 CH2 CH3 )-、-C(CH2 CH3 )2 -等烷基亞甲基;-CH(CH3 )CH2 -、-CH(CH3 )CH(CH3 )-、-C(CH3 )2 CH2 -、-CH(CH2 CH3 )CH2 -、-C(CH2 CH3 )2 -CH2 -等烷基伸乙基等。 作為伸芳基,具體而言可列舉伸苯基、伸聯苯基、伸萘基、伸蒽基及2個或2個以上的伸芳基彼此鍵結而成者等。 作為經鹵素取代之伸烷基、經鹵素取代之伸芳基,具體而言能夠分別使用由氟原子、氯原子、溴原子等鹵素原子取代上述伸烷基、伸芳基中的氫原子而成者。該等中,使用由氟原子取代氫原子而成者為較佳。R in the general formula (DC1) and (PA3) contains 11 carbon atoms in the case, as R 11, specifically include alkylene, arylene, substituted alkylene group of halo, substituted by halogen Zhifang aryl and so on. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylidene, propylidene, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and xylenyl. Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Specific examples of branched alkylene include -C (CH 3 ) 2- , -CH (CH 3 )-, -CH (CH 2 CH 3 )-, and -C (CH 3 ) (CH 2 CH 3 )-, -C (CH 3 ) (CH 2 CH 2 CH 3 )-, -C (CH 2 CH 3 ) 2 -and other alkyl methylene groups; -CH (CH 3 ) CH 2- , -CH (CH 3 ) CH (CH 3 )-, -C (CH 3 ) 2 CH 2- , -CH (CH 2 CH 3 ) CH 2- , -C (CH 2 CH 3 ) 2 -CH 2- , etc. Ethyl etc. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthyl group, an anthracene group, and two or more arylenyl groups bonded to each other. As the halogen-substituted alkylene and halogen-substituted alkylene, specifically, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom can be used instead of a hydrogen atom in the alkylene group or the alkylene group. By. Among these, it is preferable to use a fluorine atom instead of a hydrogen atom.
在上述通式(DC1)及(PA3)中的R11 不包含碳原子之情況下,作為R11 ,具體而言可列舉由氧原子或硫原子構成之基等。When R 11 in the general formulae (DC1) and (PA3) does not include a carbon atom, examples of R 11 include a group consisting of an oxygen atom or a sulfur atom.
上述通式(DC1)及(PA3)中的R12 ~R19 分別獨立地為氫或碳數1以上且30以下的有機基,例如係氫或碳數1以上且10以下的有機基為較佳,氫或碳數1以上且5以下的有機基為更佳,氫或碳數1以上且3以下的有機基為進一步較佳,氫為更進一步較佳。R 12 to R 19 in the general formulae (DC1) and (PA3) are each independently hydrogen or an organic group having 1 to 30 carbon atoms. For example, hydrogen or an organic group having 1 to 10 carbon atoms is preferred. Preferably, hydrogen or an organic group having 1 or more and 5 or less carbon is more preferred, hydrogen or an organic group having 1 or more and 3 or less carbon is further preferred, and hydrogen is still more preferred.
作為上述通式(DC1)及(PA3)中的R12 ~R19 的碳數1以上且30以下的有機基的具體例,可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基等烷基;烯丙基、戊烯基、乙烯基等烯基;乙炔基等炔基;次甲基、亞乙基等亞烷基;甲苯基、二甲苯基、苯基、萘基、蒽基等芳基;苄基、苯乙基等芳烷基;金剛烷基、環戊基、環己基、環辛基等環烷基;甲苯基、二甲苯基等烷芳基等。Specific examples of the organic group having 1 to 30 carbon atoms in R 12 to R 19 in the general formulae (DC1) and (PA3) include methyl, ethyl, n-propyl, isopropyl, and n-propyl. Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene Alkenyl groups such as ethynyl; alkynyl groups such as ethynyl; alkylene groups such as methine, ethylene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, and anthracenyl; aromatic groups such as benzyl, phenethyl Alkyl; cycloalkyl such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl; alkylaryl such as tolyl, xylyl, and the like.
作為二羧酸單體,具體而言能夠使用二苯醚-4,4’-二羧酸、間苯二甲酸、對苯二甲酸、4,4’-聯苯二羧酸等。作為二羧酸單體,使用上述具體例中的二苯醚-4,4’-二羧酸或間苯二甲酸為較佳,使用二苯醚-4,4’-二羧酸為更佳。聚醯胺樹脂的芳香族環彼此能夠緊密地排列。因此,能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構,並能夠提高密接性。As the dicarboxylic acid monomer, specifically, diphenyl ether-4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, and the like can be used. As the dicarboxylic acid monomer, diphenyl ether-4,4'-dicarboxylic acid or isophthalic acid in the above specific examples is preferred, and diphenyl ether-4,4'-dicarboxylic acid is more preferred. . The aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved.
再者,與聚合步驟(S1)同時或在聚合步驟(S1)之後修飾存在於聚醯胺樹脂的末端之胺基為較佳。修飾例如能夠藉由使特定的酸酐或特定的單羧酸與二胺單體或聚醯胺樹脂反應而進行。因此,本實施形態之聚醯胺樹脂係末端的胺基經特定的酸酐或特定的單羧酸修飾而成為較佳。再者,上述特定的酸酐、上述特定的單羧酸係具有選自由烯基、炔基及羥基組成的群中之一種以上的官能基者。又,作為上述特定的酸酐、特定的單羧酸,例如係包含氮原子者為較佳。藉此,能夠提高後烘後的感光性樹脂組成物與Al、Cu等金屬之間的密接性。 作為上述特定的酸酐,具體而言可列舉順丁烯二酸酐、檸康酸酐、2,3-二甲基順丁烯二酸酐、4-環己烯-1,2-二羧酸酐、外-3,6-環氧-1,2,3,6-四氫鄰苯二甲酸酐、5-降莰烯-2,3-二羧酸酐、甲基-5-降莰烯-2,3-二羧酸酐、伊康酸酐、氯橋酸酐、4-乙炔基鄰苯二甲酸酐、4-苯基乙炔基鄰苯二甲酸酐、4-羥基鄰苯二甲酸酐等。作為特定的酸酐,能夠使用上述具體例中的一種或組合使用兩種以上。 再者,在藉由環形狀的特定的酸酐修飾存在於聚醯胺樹脂的末端之胺基之情況下,環形狀的特定的酸酐進行開環。此處,可在修飾聚醯胺樹脂之後,使來自於環形狀的特定的酸酐之結構單元進行閉環,藉此形成醯亞胺環。作為進行閉環之方法,例如可列舉熱處理等。 又,作為上述特定的單羧酸,具體而言可列舉5-降莰烯-2-羧酸、4-羥基苯甲酸、3-羥基苯甲酸等。作為上述特定的單羧酸,能夠使用上述具體例中的一種或組合使用兩種以上。Furthermore, it is preferable to modify the amine group existing at the terminal of the polyamide resin at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, it is preferred that the amine group at the polyamine resin-based terminal of this embodiment is modified with a specific acid anhydride or a specific monocarboxylic acid. The specific acid anhydride and the specific monocarboxylic acid have one or more functional groups selected from the group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. The specific acid anhydride and the specific monocarboxylic acid are preferably those containing a nitrogen atom, for example. This can improve the adhesion between the post-baking photosensitive resin composition and metals such as Al and Cu. Specific examples of the specific acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethyl maleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, and exo- 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic anhydride, itaconic anhydride, chlorobridged anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, etc. As the specific acid anhydride, one of the above specific examples can be used or two or more of them can be used in combination. When the amine group present at the terminal of the polyamide resin is modified with a specific acid anhydride having a ring shape, the specific acid anhydride having a ring shape undergoes ring opening. Here, after modifying the polyamidamine resin, the structural unit derived from a specific acid anhydride derived from a ring may be closed to form a fluoreneimine ring. Examples of the method for performing the closed loop include heat treatment and the like. Moreover, as said specific monocarboxylic acid, 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, etc. are mentioned specifically ,. As the specific monocarboxylic acid, one of the specific examples described above can be used or two or more of them can be used in combination.
又,亦可在與聚合步驟(S1)同時或在聚合步驟(S1)之後修飾存在於聚醯胺樹脂的末端之羧基。修飾例如能夠藉由使特定的含氮原子之雜芳香族化合物與二羧酸單體或聚醯胺樹脂反應而進行。因此,本實施形態之聚醯胺樹脂係較佳由末端的羧基經特定的含氮原子之雜芳香族化合物修飾而成。再者,上述特定的含氮原子之雜芳香族化合物係具有選自由1-(5-1H-三唑基)甲基胺基、3-(1H-吡唑基)胺基、4-(1H-吡唑基)胺基、5-(1H-吡唑基)胺基、1-(3-1H-吡唑基)甲基胺基、1-(4-1H-吡唑基)甲基胺基、1-(5-1H-吡唑基)甲基胺基、(1H-四唑-5-基)胺基、1-(1H-四唑-5-基)甲基-胺基及3-(1H-四唑-5-基)苯-胺基組成的群中之一種以上的官能基者。藉此,能夠增加感光性樹脂組成物中的孤電子對的數量。因此,能夠提高預烘後、後烘後的感光性樹脂組成物與Al等金屬之間的密接性。 作為上述特定的含氮原子之雜芳香族化合物,具體而言可列舉5-胺基四唑等。The carboxyl group existing at the terminal of the polyamide resin may be modified at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or a polyamide resin. Therefore, the polyamide resin of the present embodiment is preferably formed by modifying a terminal carboxyl group with a specific nitrogen atom-containing heteroaromatic compound. The specific nitrogen atom-containing heteroaromatic compound is selected from the group consisting of 1- (5-1H-triazolyl) methylamino, 3- (1H-pyrazolyl) amino, and 4- (1H -Pyrazolyl) amino, 5- (1H-pyrazolyl) amino, 1- (3-1H-pyrazolyl) methylamino, 1- (4-1H-pyrazolyl) methylamine Base, 1- (5-1H-pyrazolyl) methylamino, (1H-tetrazol-5-yl) amino, 1- (1H-tetrazol-5-yl) methyl-amino, and 3 -(1H-tetrazol-5-yl) benzene-amine group having one or more functional groups. This makes it possible to increase the number of lone electron pairs in the photosensitive resin composition. Therefore, it is possible to improve the adhesion between the photosensitive resin composition after prebaking and after baking, and a metal such as Al. Examples of the specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole and the like.
(低分子量成分去除步驟(S2)) 繼上述聚合步驟(S1)之後,進行低分子量成分去除步驟(S2),並去除低分子量成分,獲得以聚醯胺樹脂為主成分之聚醯胺樹脂。 藉由過濾等將含有低分子量成分與聚醯胺樹脂的混合物之有機層進行濃縮之後,使其再次溶解於水/異丙醇等有機溶劑中。藉此,過濾沉澱物,能夠獲得低分子量成分被去除之聚醯胺樹脂。(Low-molecular-weight component removal step (S2)) Following the above-mentioned polymerization step (S1), a low-molecular-weight component removal step (S2) is performed, and low-molecular-weight components are removed to obtain a polyamide resin containing a polyamide resin as a main component. The organic layer containing the mixture of the low molecular weight component and the polyamide resin is concentrated by filtration or the like, and then dissolved in an organic solvent such as water / isopropanol again. Thereby, a precipitate can be filtered, and the polyamine resin from which a low molecular weight component was removed can be obtained.
作為聚醯胺樹脂,例如係將上述通式(DA1)所表示之二胺單體及上述通式(DC1)所表示之二羧酸單體進行縮合而得者為較佳。亦即,作為聚醯胺樹脂,具備上述通式(PA2)及(PA3)的結構單元者為較佳,交替具備上述通式(PA2)及(PA3)的結構單元者為更佳。As the polyamide resin, for example, one obtained by condensing a diamine monomer represented by the general formula (DA1) and a dicarboxylic acid monomer represented by the general formula (DC1) is preferable. That is, as the polyamide resin, it is preferable to include the structural units of the general formulae (PA2) and (PA3), and it is more preferable to provide the structural units of the general formulae (PA2) and (PA3) alternately.
<酚樹脂> 作為酚樹脂,具體而言可列舉苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆樹脂、苯酚-聯苯酚醛清漆樹脂等酚醛清漆型酚樹脂;酚醛清漆型酚樹脂、可溶酚醛樹脂型酚樹脂、甲酚酚醛樹脂型酚樹脂等酚化合物與醛化合物的反應物;苯酚芳烷基樹脂等酚化合物與二甲醇化合物的反應物等。再者,作為酚樹脂,能夠包含上述具體例中的一種或兩種以上。<Phenol resin> Specific examples of the phenol resin include phenol novolac resin, cresol novolac resin, bisphenol novolac resin, phenol-biphenol novolac resin, and other novolac phenol resins; novolac phenol resins, Reactants of phenol compounds such as soluble phenol resin type phenol resin and cresol novolac resin type with aldehyde compound; reactants of phenol compound such as phenol aralkyl resin and dimethanol compound, etc. The phenol resin may include one, two or more of the specific examples described above.
上述作為用於酚化合物與醛化合物的反應物或酚化合物與二甲醇化合物的反應物之酚化合物並無限定。 作為該種酚化合物,具體而言可列舉苯酚、鄰甲酚、間甲酚、對甲酚等甲酚類;2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚等二甲酚類;鄰乙基酚、間乙基酚、對乙基酚等乙基酚類;異丙基酚、丁基酚、對三級丁基酚等烷基酚類;間苯二酚、兒茶酚、對苯二酚、五倍子酚、間苯三酚等多元酚類;4,4’-聯苯酚等聯苯系酚類。作為酚化合物,能夠使用上述具體例中的一種或兩種以上。The phenol compound used as a reactant of a phenol compound and an aldehyde compound or a reactant of a phenol compound and a dimethanol compound is not limited. Specific examples of such phenol compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, and 2,5-diphenol Xylenols such as cresol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol Class; alkylphenols such as isopropylphenol, butylphenol, p-tertiary butylphenol; polyphenols such as resorcinol, catechol, hydroquinone, gallophenol, resorcinol; 4 , 4'-biphenol and other biphenyl phenols. As the phenol compound, one or two or more of the above specific examples can be used.
上述作為用於酚化合物與醛化合物的反應物之醛化合物只要係具有醛基之化合物則並無限定。 作為該種醛化合物,具體而言可列舉甲醛、聚甲醛、乙醛、苯甲醛、柳醛等。作為醛化合物,能夠使用上述具體例中的一種或兩種以上。The aldehyde compound described above as a reactant for a phenol compound and an aldehyde compound is not limited as long as it is a compound having an aldehyde group. Specific examples of such an aldehyde compound include formaldehyde, polyformaldehyde, acetaldehyde, benzaldehyde, and salaldehyde. As the aldehyde compound, one, two or more of the above specific examples can be used.
上述作為用於酚化合物與二甲醇化合物的反應物之二甲醇化合物並無限定。 作為該種二甲醇化合物,具體而言可列舉1,4-苯二甲醇、1,3-苯二甲醇、4,4’-聯苯二甲醇、3,4’-聯苯二甲醇、3,3’-聯苯二甲醇、2,6-萘二甲醇、2,6-雙(羥甲基)-對甲酚等二甲醇化合物;1,4-雙(甲氧基甲基)苯、1,3-雙(甲氧基甲基)苯、4,4’-雙(甲氧基甲基)聯苯、3,4’-雙(甲氧基甲基)聯苯、3,3’-雙(甲氧基甲基)聯苯、2,6-萘二羧酸甲酯等雙(烷氧基甲基)化合物、或1,4-雙(氯甲基)苯、1,3-雙(氯甲基)苯、1,4-雙(溴甲基)苯、1,3-雙(溴甲基)苯、4,4’-雙(氯甲基)聯苯、3,4’-雙(氯甲基)聯苯、3,3’-雙(氯甲基)聯苯、4,4’-雙(溴甲基)聯苯、3,4’-雙(溴甲基)聯苯或3,3’-雙(溴甲基)聯苯等雙(鹵代烷基)化合物、4,4’-雙(甲氧基甲基)聯苯、4,4’-雙(甲氧基甲基)聯苯等聯苯芳烷基化合物等。作為二甲醇化合物,能夠使用上述具體例中的一種或兩種以上。The above-mentioned dimethanol compound as a reactant for a phenol compound and a dimethanol compound is not limited. Specific examples of such dimethanol compounds include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3, 3'-biphenyldimethanol, 2,6-naphthalenedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, and other dimethanol compounds; 1,4-bis (methoxymethyl) benzene, 1 , 3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'- Bis (methoxymethyl) biphenyl, bis (alkoxymethyl) compounds such as methyl 2,6-naphthalene dicarboxylate, or 1,4-bis (chloromethyl) benzene, 1,3-bis (Chloromethyl) benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 3,4'- Bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl Or bis (haloalkyl) compounds such as 3,3'-bis (bromomethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (methoxymethyl) ) Biphenyl aralkyl compounds such as biphenyl. As the dimethanol compound, one or two or more of the above specific examples can be used.
<羥基苯乙烯樹脂> 作為羥基苯乙烯樹脂並無限定,具體而言能夠使用將選自由羥基苯乙烯、羥基苯乙烯衍生物、苯乙烯及苯乙烯衍生物組成的群中之一種或兩種以上聚合或共聚而成之聚合反應物或共聚反應物。 再者,作為羥基苯乙烯衍生物、苯乙烯衍生物,具體而言可列舉由一價的有機基取代羥基苯乙烯、苯乙烯的芳香族環所具備之氫原子而成者。作為取代氫原子之一價的有機基,例如可列舉甲基、乙基、正丙基等烷基;烯丙基、乙烯基等烯基;乙炔基等炔基;次甲基、亞乙基等亞烷基;環丙基等環烷基;環氧基、氧環丁烷(oxetanyl)基等雜環基等。<Hydroxystyrene resin> The hydroxystyrene resin is not limited. Specifically, one or two or more selected from the group consisting of hydroxystyrene, a hydroxystyrene derivative, styrene, and a styrene derivative can be used. Polymerization or copolymerization reactants formed by polymerization or copolymerization. Moreover, as a hydroxystyrene derivative and a styrene derivative, the thing which substituted the hydrogen atom which the aromatic ring of hydroxystyrene and styrene has with the monovalent organic group specifically is mentioned. Examples of the monovalent organic group substituted for a hydrogen atom include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine and ethylene And other alkylene groups; cycloalkyl groups such as cyclopropyl groups; heterocyclic groups such as epoxy groups and oxetanyl groups.
<環狀烯烴系樹脂> 作為上述環狀烯烴系樹脂並無限定,具體而言能夠使用將選自由降莰烯及降莰烯衍生物組成的群中之一種或兩種以上聚合或共聚而成之聚合反應物或共聚反應物。 再者,作為降莰烯衍生物,具體而言可列舉由一價的有機基取代與降莰烯骨架鍵結之氫原子而成者。作為取代氫原子之一價的有機基,例如可列舉甲基、乙基、正丙基等烷基;烯丙基、乙烯基等烯基;乙炔基等炔基;次甲基、亞乙基等亞烷基;環丙基等環烷基;環氧基、氧環丁烷基等雜環基等。<Cyclic olefin-based resin> The cyclic olefin-based resin is not limited. Specifically, one or two or more selected from the group consisting of norbornene and norbornene derivatives can be polymerized or copolymerized. Polymerization or copolymerization reactants. Further, as the norbornene derivative, specifically, a hydrogen atom bonded to a norbornene skeleton by a monovalent organic group may be mentioned. Examples of the monovalent organic group substituted for a hydrogen atom include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine and ethylene And other alkylene groups; cycloalkyl groups such as cyclopropyl groups; heterocyclic groups such as epoxy groups and oxocyclobutane groups.
例如將感光性樹脂組成物的總固體成分設為100質量份時,感光性樹脂組成物中的鹼可溶性樹脂的含量的下限值係30質量份以上為較佳,40質量份以上為更佳,50質量份以上為進一步較佳,60質量份以上為更進一步較佳,70質量份以上為尤佳。藉此,感光性樹脂組成物中的鹼可溶性樹脂能夠與溶劑中的尿素化合物或非環狀結構的醯胺化合物適當地相互作用。因此,能夠藉由鹼可溶性樹脂與金屬分子更強力地鍵結而成之配位來凍結分子結構,並能夠提高密接性。 又,例如,將感光性樹脂組成物的總固體成分設為100質量份時,感光性樹脂組成物中的鹼可溶性樹脂的含量的上限值係95質量份以下為較佳,90質量份以下為更佳,85質量份以下為進一步較佳。 再者,在本實施形態中,所謂感光性樹脂組成物的總固體成分,表示除了溶劑以外的感光性樹脂組成物的含有成分的總計。For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the lower limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more. 50 mass parts or more is further preferred, 60 mass parts or more is further preferred, and 70 mass parts or more is particularly preferred. This allows the alkali-soluble resin in the photosensitive resin composition to appropriately interact with the urea compound or the amidine compound having a non-cyclic structure in the solvent. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved. For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the upper limit value of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 95 parts by mass or less, and 90 parts by mass or less. More preferably, 85 parts by mass or less is more preferable. In addition, in this embodiment, the total solid content of the photosensitive resin composition means the total of the content of the photosensitive resin composition other than the solvent.
(感光劑) 作為感光劑,能夠使用藉由吸收光能而產生酸之光酸產生劑。 作為光酸產生劑,具體而言可列舉重氮醌(diazoquinone)化合物;二芳基錪鹽;2-硝基苄基酯化合物;N-亞胺基磺酸鹽化合物;醯亞胺磺酸鹽化合物;2,6-雙(三氯甲基)-1,3,5-三口井化合物;二氫吡啶化合物等。該等中,使用感光性重氮醌化合物為較佳。藉此,能夠提高感光性樹脂組成物的靈敏度。因此,能夠提高圖案的精度,並能夠改善外觀。再者,作為光酸產生劑,能夠包含上述具體例中的一種或兩種以上。 又,在感光性樹脂組成物係正型之情況下,作為感光劑,除了上述具體例之外,還可併用三芳基鋶鹽;鋶-硼酸鹽等鎓鹽等。藉此,能夠進一步提高感光性樹脂組成物的靈敏度。 以下示出能夠作為感光劑較佳地使用之重氮醌化合物的具體例。(Photosensitizer) As the photosensitizer, a photoacid generator that generates an acid by absorbing light energy can be used. Specific examples of the photoacid generator include a diazoquinone compound; a diarylsulfonium salt; a 2-nitrobenzyl ester compound; an N-iminosulfonate compound; and a pyrimidate sulfonate Compounds; 2,6-bis (trichloromethyl) -1,3,5-three well compounds; dihydropyridine compounds, etc. Among these, it is preferable to use a photosensitive diazoquinone compound. This can improve the sensitivity of the photosensitive resin composition. Therefore, the accuracy of the pattern can be improved, and the appearance can be improved. The photoacid generator can include one or two or more of the specific examples described above. When the photosensitive resin composition is of the positive type, in addition to the specific examples described above, as the photosensitizer, a triarylsulfonium salt, an onium salt such as fluorene-borate, or the like may be used in combination. This can further improve the sensitivity of the photosensitive resin composition. Specific examples of the diazoquinone compound that can be preferably used as a photosensitizer are shown below.
(n係1以上且5以下之整數。) (N is an integer from 1 to 5.)
在以上各重氮醌化合物中,Q係下式(a)、下式(b)及下式(c)中所表示之結構或氫原子。其中,各重氮醌化合物的Q中的至少一個係由下式(a)、下式(b)及下式(c)所表示之結構。 作為重氮醌化合物的Q,包含下式(a)或下式(b)為較佳。藉此,能夠提高感光性樹脂組成物的透明性。因此,能夠改善感光性樹脂組成物的外觀。In each of the above diazoquinone compounds, Q is a structure or a hydrogen atom represented by the following formula (a), (b), and (c). Among them, at least one of Q of each diazoquinone compound has a structure represented by the following formula (a), (b), and (c). The Q of the diazoquinone compound preferably contains the following formula (a) or (b). This can improve the transparency of the photosensitive resin composition. Therefore, the appearance of the photosensitive resin composition can be improved.
將鹼可溶性樹脂設為100質量份時,感光性樹脂組成物中的感光劑的含量的下限值例如係1質量份以上為較佳,3質量份以上為更佳,5質量份以上為進一步較佳。藉此,感光性樹脂組成物能夠發揮適當的靈敏度。 又,將鹼可溶性樹脂設為100質量份時,感光性樹脂組成物中的感光劑的含量的上限值例如係30質量份以下為較佳,20質量份以下為更佳。藉此,感光性樹脂組成物適當地硬化,能夠在預烘後及後烘後對Al、Cu等金屬顯現密接性。When the alkali-soluble resin is 100 parts by mass, the lower limit value of the content of the photosensitizer in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass or more. Better. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity. When the alkali-soluble resin is 100 parts by mass, the upper limit of the content of the photosensitizer in the photosensitive resin composition is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. Thereby, the photosensitive resin composition is appropriately hardened, and adhesion to metals such as Al and Cu can be exhibited after pre-baking and after-baking.
(溶劑) 本實施形態之感光性樹脂組成物包含尿素化合物或非環狀結構的醯胺化合物作為溶劑。作為溶劑,例如包含尿素化合物為較佳。藉此,能夠進一步提高感光性樹脂組成物的硬化物與Al、Cu等金屬之間的密接性。 再者,本說明書中,所謂尿素化合物,表示具備尿素鍵,亦即脲鍵之化合物。又,所謂醯胺化合物,表示具備醯胺鍵之化合物、亦即醯胺。再者,所謂醯胺,具體而言可列舉1級醯胺、2級醯胺、3級醯胺。 又,在本實施形態中,所謂非環狀結構,係指化合物的結構中不具備碳環、無機環、雜環等環狀結構。作為不具備環狀結構之化合物的結構,例如可列舉直鏈狀結構、支鏈狀結構等。(Solvent) The photosensitive resin composition of this embodiment contains a urea compound or an amidine compound having a non-cyclic structure as a solvent. As the solvent, for example, a urea compound is preferably contained. Thereby, the adhesiveness between the hardened | cured material of a photosensitive resin composition and metals, such as Al and Cu, can be improved further. In addition, in this specification, a urea compound means the compound which has a urea bond, ie, a urea bond. The amidine compound refers to a compound having an amidine bond, that is, amidine. Furthermore, the amidines specifically include first-grade amidines, second-grade amidines, and third-grade amidines. In the present embodiment, the acyclic structure refers to a compound that does not include a cyclic structure such as a carbocyclic ring, an inorganic ring, or a heterocyclic ring. Examples of the structure of a compound having no cyclic structure include a linear structure and a branched structure.
作為尿素化合物、非環狀結構的醯胺化合物,分子結構中的氮原子的數量多者為較佳。具體而言,分子結構中的氮原子的數量係2個以上為較佳。藉此,能夠增加孤電子對的數量。因此,能夠提高與Al、Cu等金屬之間的密接性。As the urea compound and the amidine compound having a non-cyclic structure, it is preferable that the number of nitrogen atoms in the molecular structure is large. Specifically, the number of nitrogen atoms in the molecular structure is preferably two or more. Thereby, the number of lone electron pairs can be increased. Therefore, it is possible to improve the adhesion with metals such as Al and Cu.
作為尿素化合物的結構,具體而言可列舉環狀結構、非環狀結構等。作為尿素化合物的結構,上述具體例中係非環狀結構為較佳。藉此,能夠提高感光性樹脂組成物的硬化物與Al、Cu等金屬之間的密接性。該原因推測為如下。推測為非環狀結構的尿素化合物與環狀結構的尿素化合物相比,容易形成配位鍵。認為這是因為,非環狀結構的尿素化合物與環狀結構的尿素化合物相比,分子運動的限制少,進而分子結構的變形的自由度大。因此,當使用非環狀結構的尿素化合物時,能夠形成強力的配位鍵,並能夠提高密接性。Specific examples of the structure of the urea compound include a cyclic structure and an acyclic structure. The structure of the urea compound is preferably a non-cyclic structure in the above specific examples. Thereby, the adhesiveness between the hardened | cured material of a photosensitive resin composition and metals, such as Al and Cu, can be improved. The reason is presumed as follows. It is estimated that a urea compound having an acyclic structure is more likely to form a coordination bond than a urea compound having a cyclic structure. This is considered to be because the urea compound having a non-cyclic structure has fewer restrictions on molecular motion than the urea compound having a cyclic structure, and further has a large degree of freedom in deforming the molecular structure. Therefore, when a urea compound having a non-cyclic structure is used, a strong coordination bond can be formed, and adhesion can be improved.
作為尿素化合物,具體而言可列舉四甲基脲(TMU)、1,3-二甲基-2-咪唑啶酮、N,N-二甲基乙醯胺、四丁基脲、N,N’-二甲基丙烯脲、1,3-二甲氧基-1,3-二甲基脲、N,N’-二異丙基-O-甲基異脲、O,N,N’-三異丙基異脲、O-三級丁基-N,N’-二異丙基異脲、O-乙基-N,N’-二異丙基異脲、O-苄基-N,N’-二異丙基異脲等。作為尿素化合物,能夠使用上述具體例中的一種或組合使用兩種以上。作為尿素化合物,上述具體例中,例如使用選自由四甲基脲(TMU)、四丁基脲、1,3-二甲氧基-1,3-二甲基脲、N,N’-二異丙基-O-甲基異脲、O,N,N’-三異丙基異脲、O-三級丁基-N,N’-二異丙基異脲、O-乙基-N,N’-二異丙基異脲及O-苄基-N,N’-二異丙基異脲組成的群中之一種或兩種以上為較佳,使用四甲基脲(TMU)為更佳。藉此,能夠形成強力的配位鍵,並能夠提高密接性。Specific examples of the urea compound include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, tetrabutylurea, N, N '-Dimethacryl urea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N, N'- Triisopropylisourea, O-tertiary butyl-N, N'-diisopropylisourea, O-ethyl-N, N'-diisopropylisourea, O-benzyl-N, N'-diisopropylisourea and the like. As the urea compound, one of the above specific examples may be used or two or more of them may be used in combination. As the urea compound, for example, a compound selected from tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-di Isopropyl-O-methylisourea, O, N, N'-triisopropylisourea, O-tertiary butyl-N, N'-diisopropylisourea, O-ethyl-N One or two or more of the group consisting of, N'-diisopropylisourea and O-benzyl-N, N'-diisopropylisourea are preferred. The use of tetramethylurea (TMU) is Better. Thereby, a strong coordination bond can be formed, and adhesiveness can be improved.
作為非環狀結構的醯胺化合物,具體而言可列舉3-甲氧基-N、N-二甲基丙醯胺、N,N-二甲基甲醯胺、N,N-二甲基丙醯胺、N,N-二乙基乙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N,N-二丁基甲醯胺等。Specific examples of the amidine compound having a non-cyclic structure include 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, and N, N-dimethyl Propamide, N, N-diethylacetamide, 3-butoxy-N, N-dimethylpropanamide, N, N-dibutylformamide, and the like.
本實施形態之感光性樹脂組成物除了尿素化合物、非環狀結構的醯胺化合物以外,亦可包含不具備氮原子之溶劑作為溶劑。 作為不具備氮原子之溶劑,具體而言可列舉醚系溶劑、乙酸酯系溶劑、醇系溶劑、酮系溶劑、內酯系溶劑、碳酸酯系溶劑、碸系溶劑、酯系溶劑、芳香族烴系溶劑等。作為不具備氮原子之溶劑,能夠使用上述具體例中的一種或組合使用兩種以上。 作為上述醚系溶劑,具體而言可列舉丙二醇單甲醚(PGME)、丙二醇單乙醚、乙二醇單乙醚、二乙二醇二甲醚、二乙二醇單乙醚、二乙二醇、乙二醇二乙醚、二乙二醇二乙醚、二乙二醇二丁醚、二丙二醇單甲醚、1,3-丁二醇-3-單甲醚等。 作為上述乙酸酯系溶劑,具體而言可列舉丙二醇單甲醚乙酸酯(PGMEA)、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲基-1,3-丁二醇乙酸酯等。 作為上述醇系溶劑,具體而言可列舉四氫糠醇、苯甲醇、2-乙基己醇、丁二醇、異丙醇等。 作為上述酮系溶劑,具體而言可列舉環戊酮、環己酮、二丙酮醇、2-庚酮等。 作為上述內酯系溶劑,具體而言可列舉γ-丁內酯(GBL)、γ-戊內酯等。 作為上述碳酸酯系溶劑,具體而言可列舉碳酸伸乙酯、碳酸丙烯酯等。 作為上述碸系溶劑,具體而言可列舉二甲基亞碸(DMSO)、環丁碸等。 作為上述酯系溶劑,具體而言可列舉丙酮酸甲酯、丙酮酸乙酯、甲基-3-甲氧基丙酸酯等。 作為上述芳香族烴系溶劑,具體而言可列舉對稱三甲苯、甲苯、二甲苯等。The photosensitive resin composition according to this embodiment may contain, as a solvent, a solvent having no nitrogen atom in addition to a urea compound and a fluorene compound having a non-cyclic structure. Specific examples of the solvent having no nitrogen atom include ether-based solvents, acetate-based solvents, alcohol-based solvents, ketone-based solvents, lactone-based solvents, carbonate-based solvents, fluorene-based solvents, ester-based solvents, and aromatic solvents. Group hydrocarbon solvents and the like. As the solvent having no nitrogen atom, one of the above specific examples can be used or two or more of them can be used in combination. Specific examples of the ether-based solvent include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, and ethylene glycol. Diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butanediol-3-monomethyl ether, and the like. Specific examples of the acetate-based solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, and the like. . Specific examples of the alcohol-based solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropanol. Specific examples of the ketone-based solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone. Specific examples of the lactone-based solvent include γ-butyrolactone (GBL) and γ-valerolactone. Specific examples of the carbonate-based solvent include ethyl carbonate and propylene carbonate. Specific examples of the fluorene-based solvent include dimethyl fluorene (DMSO), cyclobutane, and the like. Specific examples of the ester-based solvent include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate. Specific examples of the aromatic hydrocarbon-based solvent include symmetric xylene, toluene, and xylene.
將溶劑設為100質量份時,作為溶劑中的尿素化合物及非環狀結構的醯胺化合物的含量的下限值,例如係10質量份以上為較佳,20質量份以上為更佳,30質量份以上為進一步較佳,50質量份以上為更進一步較佳,70質量份以上為尤佳。藉此,能夠進一步提高感光性樹脂組成物的硬化物與Al、Cu等金屬之間的密接性。 又,將溶劑設為100質量份時,作為溶劑中的尿素化合物及非環狀結構的醯胺化合物的含量的下限值,例如能夠設為100質量份以下。溶劑中,從密接性提高的觀點考慮,尿素化合物及非環狀結構的醯胺化合物的含量多為較佳。When the solvent is 100 parts by mass, the lower limit of the content of the urea compound and the acyclic amine compound in the solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30. It is more preferable that it is more than mass part, it is more preferable that it is 50 mass part or more, and it is more preferable that it is 70 mass part or more. Thereby, the adhesiveness between the hardened | cured material of a photosensitive resin composition and metals, such as Al and Cu, can be improved further. When the solvent is 100 parts by mass, the lower limit of the content of the urea compound and the acyclic amine compound in the solvent can be, for example, 100 parts by mass or less. In the solvent, from the viewpoint of improving the adhesion, the content of the urea compound and the amidine compound having a non-cyclic structure is more preferable.
本實施形態之感光性樹脂組成物可進一步添加密接助劑、矽烷偶合劑、熱交聯劑、界面活性劑、抗氧化劑、溶解促進劑、填料、敏化劑等添加劑。 以下對代表性添加成分進行詳細說明。The photosensitive resin composition of this embodiment may further be added with additives such as adhesion aids, silane coupling agents, thermal crosslinking agents, surfactants, antioxidants, dissolution accelerators, fillers, and sensitizers. Hereinafter, representative additive components will be described in detail.
(密接助劑) 本實施形態之感光性樹脂組成物可進而含有密接助劑。作為密接助劑,具體而言能夠使用三唑化合物、胺基矽烷或醯亞胺化合物。藉此,能夠進一步增加來自於氮原子之孤電子對的數量。因此,能夠使除了感光性樹脂組成物的溶劑以外的含有物相對於金屬原子配位,並能夠進一步提高密接性。作為密接助劑,可使用三唑化合物、胺基矽烷或醯亞胺化合物中的任一種,亦可併用三唑化合物、胺基矽烷、醯亞胺化合物中的兩種以上。(Adhesion Aid) The photosensitive resin composition of this embodiment may further include an adhesion aid. As the adhesion adjuvant, specifically, a triazole compound, an aminosilane, or a sulfonimine compound can be used. Thereby, the number of lone electron pairs derived from a nitrogen atom can be further increased. Therefore, the content other than the solvent of the photosensitive resin composition can be coordinated with the metal atom, and adhesion can be further improved. As the adhesion adjuvant, any one of a triazole compound, an aminosilane, or a sulfonimine compound may be used, or two or more of a triazole compound, an aminosilane, and a sulfonimine compound may be used in combination.
作為三唑化合物,具體而言可列舉4-胺基-1,2,4-三唑、4H-1,2,4-三唑-3-胺、4-胺基-3,5-二-2-吡啶基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、4-甲基-4H-1,2,4-三唑-3-胺、3,4-二胺基-4H-1,2,4-三唑、3,5-二胺基-4H-1,2,4-三唑、1,2,4-三唑-3,4,5-三胺、3-吡啶基-4H-1,2,4-三唑、4H-1,2,4-三唑-3-羰醯胺、3,5-二胺基-4-甲基-1,2,4-三唑、3-吡啶基-4-甲基-1,2,4-三唑、4-甲基-1,2,4-三唑-3-甲醯胺等1,2,4-三唑。作為三唑化合物,能夠使用上述具體例中的一種或組合使用兩種以上。Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, and 4-amino-3,5-di- 2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4- Triazole-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2,4 -Triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carboxamide, 3,5- Diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, 4-methyl-1,2,4-triazole 1,2,4-triazole such as 3-formamidine. As the triazole compound, one of the above specific examples can be used or two or more can be used in combination.
作為胺基矽烷,具體而言可列舉環己烯-1,2-二羧酸酐及3-胺基丙基三乙氧基矽烷的縮合物、3,3’,4,4’-二苯基酮四羧酸二酐及3-胺基丙基三乙氧基矽烷的縮合物、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、N,N’-雙[3-(三甲氧基甲矽基)丙基]乙二胺、N,N’-雙(3-三乙氧基甲矽基丙基)乙二胺、N,N’-雙[3-(甲基二甲氧基甲矽基)丙基]乙二胺、N,N’-雙[3-(甲基二乙氧基甲矽基)丙基]乙二胺、N,N’-雙[3-(二甲基甲氧基甲矽基)丙基]乙二胺、N-[3-(甲基二甲氧基甲矽基)丙基]-N’-[3-(三甲氧基甲矽基)丙基]乙二胺、N,N’-雙[3-(三甲氧基甲矽基)丙基]二胺基丙烷、N,N’-雙[3-(三甲氧基甲矽基)丙基]二胺基己烷、N,N’-雙[3-(三甲氧基甲矽基)丙基]二乙烯三胺等。作為胺基矽烷,能夠使用上述具體例中的一種或組合使用兩種以上。Specific examples of the aminosilane include a condensate of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, and 3,3 ', 4,4'-diphenyl. Ketotetracarboxylic dianhydride and 3-aminopropyltriethoxysilane condensate, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Silyl, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-amino Propyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis (3-triethoxysilylpropyl) Ethylenediamine, N, N'-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (methyldiethoxysilyl) ) Propyl] ethylenediamine, N, N'-bis [3- (dimethylmethoxysilyl) propyl] ethylenediamine, N- [3- (methyldimethoxysilyl) ) Propyl] -N '-[3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (trimethyl Oxysilyl) propyl] diaminopropane, N, N'-bis [3- (trimethoxysilyl) propyl] diaminohexane, N, N'-bis [3- ( Trimethoxysilyl) propyl] diethylenetriamine and the like. As the aminosilane, one of the above specific examples can be used or two or more of them can be used in combination.
作為醯亞胺化合物,具體而言可列舉以下例示之化合物。該等能夠使用一種或組合使用兩種以上。Specific examples of the fluorene imine compound include the compounds exemplified below. These can be used singly or in combination of two or more.
感光性樹脂組成物中的密接助劑的含量的下限值例如相對於鹼可溶性樹脂100質量份,係0.1質量份以上為較佳,1.0質量份以上為更佳,2.0質量份以上為進一步較佳,3.0質量份以上為更進一步較佳。藉此,可充分提高密接力。 又,感光性樹脂組成物中的密接助劑的含量的上限值例如相對於鹼可溶性樹脂100質量份,例如係10質量份以下為較佳,7質量份以下為更佳,5質量份以下為進一步較佳。藉此,密接助劑適當地分散於感光性樹脂組成物中,能夠提高密接力。The lower limit value of the content of the adhesion promoter in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more relative to 100 parts by mass of the alkali-soluble resin, more preferably 1.0 parts by mass or more, and 2.0 parts by mass or more. Preferably, 3.0 parts by mass or more is further preferred. Thereby, the close contact force can be fully improved. The upper limit of the content of the adhesion assistant in the photosensitive resin composition is, for example, 100 parts by mass of the alkali-soluble resin. Is even better. Accordingly, the adhesion assistant is appropriately dispersed in the photosensitive resin composition, and the adhesion can be improved.
(矽烷偶合劑) 本實施形態之感光性樹脂組成物可進而含有矽烷偶合劑。作為矽烷偶合劑,可列舉除了作為密接助劑例示之胺基矽烷以外者。 作為與上述矽烷化合物不同之結構的矽烷偶合劑,具體而言可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等乙烯基矽烷;2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷等環氧矽烷;對苯乙烯基三甲氧基矽烷等苯乙烯基矽烷;3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等甲基丙烯酸矽烷;3-丙烯醯氧基丙基三甲氧基矽烷等丙烯酸矽烷;三聚異氰酸酯矽烷;烷基矽烷;3-脲基丙基三烷氧基矽烷等脲基矽烷;3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等巰基矽烷;3-異氰酸酯丙基三乙氧基矽烷等異氰酸酯矽烷;鈦系化合物;鋁螯合物類;鋁/鋯系化合物等。作為矽烷偶合劑,能夠摻合上述具體例中的一種或兩種以上。(Silane coupling agent) The photosensitive resin composition of this embodiment may further contain a silane coupling agent. Examples of the silane coupling agent include those other than the amine silanes exemplified as the adhesion assistant. Specific examples of the silane coupling agent having a structure different from that of the above-mentioned silane compound include vinylsilane such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Siloxane such as oxysilane, 3-glycidoxypropyltriethoxysilane; Styrylsilane such as p-styryltrimethoxysilane; 3-Methacryloxypropylmethyldi Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethyl Silanes such as methacrylic acid; acrylic silanes such as 3-propenyloxypropyltrimethoxysilane; triisocyanate silane; alkylsilanes; urea-based silane such as 3-ureidopropyltrialkoxysilane; Mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; 3-isocyanatepropyltriethoxysilane Silane isocyanate; titanium compound; aluminum chelate; aluminum / zirconium compounds. As the silane coupling agent, one or two or more of the specific examples described above can be blended.
(熱交聯劑) 本實施形態之感光性樹脂組成物可包含能夠藉由熱而與鹼可溶性樹脂反應之熱交聯劑。藉此,關於將感光性樹脂組成物進行後烘之後的硬化物,能夠提高拉伸斷裂伸長率之機械特性。又,從能夠提高由感光性樹脂組成物所形成之樹脂膜的靈敏度之觀點考慮亦有利。 作為熱交聯劑,具體而言可列舉1,2-苯二甲醇、1,3-苯二甲醇、1,4-苯二甲醇(對二甲苯乙二醇)、1,3,5-苯三甲醇、4,4-聯苯二甲醇、2,6-吡啶二甲醇、2,6-雙(羥甲基)-對甲酚、4,4’-亞甲基雙(2,6-二烷氧基甲基苯酚)等具有羥甲基之化合物;五羥基聯苯(phloroglucide)等酚類;1,4-雙(甲氧基甲基)苯、1,3-雙(甲氧基甲基)苯、4,4’-雙(甲氧基甲基)聯苯、3,4’-雙(甲氧基甲基)聯苯、3,3’-雙(甲氧基甲基)聯苯、2,6-萘二羧酸甲酯、4,4’-亞甲基雙(2,6-二甲氧基甲基苯酚)等具有烷氧基甲基之化合物;以六羥甲基三聚氰胺、六丁醇三聚氰胺等為代表之羥甲基三聚氰胺化合物;六甲氧基三聚氰胺等烷氧基三聚氰胺化合物;四甲氧基甲基乙炔脲等烷氧基甲基乙炔脲化合物;羥甲基苯并胍胺化合物、二羥甲基乙烯脲等羥甲基脲化合物;二氰基苯胺、二氰基苯酚、氰基苯磺酸等氰基化合物;1,4-伸苯基二異氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二異氰酸酯等異氰酸酯化合物;乙二醇二環氧丙基醚、雙酚A二環氧丙基醚、異三聚氰酸三環氧丙酯、雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘系環氧樹脂、聯苯型環氧樹脂、苯酚酚醛清漆樹脂型環氧樹脂等含環氧基之化合物;N,N’-1,3-伸苯基二順丁烯二醯亞胺、N,N’-亞甲基二順丁烯二醯亞胺等順丁烯二醯亞胺化合物等。作為熱交聯劑,能夠使用上述具體例中的一種或組合使用兩種以上。(Thermal Crosslinking Agent) The photosensitive resin composition of this embodiment may include a thermal crosslinking agent capable of reacting with an alkali-soluble resin by heat. Thereby, the hardened | cured material after post-baking the photosensitive resin composition can improve the mechanical characteristic of tensile elongation at break. It is also advantageous from the viewpoint of improving the sensitivity of a resin film formed from a photosensitive resin composition. Specific examples of the thermal crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (p-xylylene glycol), and 1,3,5-benzene Trimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dimethyl Alkoxymethylphenol) and other compounds with methylol groups; phenols such as pentahydroxybiphenyl (phloroglucide); 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) Group) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl Compounds with alkoxymethyl groups such as benzene, methyl 2,6-naphthalenedicarboxylate, 4,4'-methylenebis (2,6-dimethoxymethylphenol); hexamethylol Methylol melamine compounds such as melamine and hexabutanol melamine; alkoxymelamine compounds such as hexamethoxymelamine; alkoxymethyl acetylene urea compounds such as tetramethoxymethyl acetylene urea; hydroxymethyl benzo Hydroxymethyl urea compounds such as guanamine compounds, dimethylol vinyl urea; dicyanoanilines, dicyanobenzenes And cyano compounds such as cyanobenzenesulfonic acid; 1,4-phenylene diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and other isocyanate compounds; ethylene glycol bicyclic Oxypropyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl Epoxy-containing compounds such as epoxy resins, phenol novolac resin epoxy resins; N, N'-1,3-phenylene dicis-butene difluorene imine, N, N'-methylene A maleimide compound such as a maleimide diimide and the like. As the thermal crosslinking agent, one of the above-mentioned specific examples can be used or two or more kinds can be used in combination.
相對於鹼可溶性樹脂100質量份,感光性樹脂組成物中的熱交聯劑的含量的上限值例如係20質量份以下為較佳,15質量份以下為更佳,12質量份以下為進一步較佳,10質量份以下為更進一步較佳。藉此,即使在熱交聯劑具備酚性羥基等溶劑化之官能基之情況下,亦能夠抑制後烘後的耐化學品性降低。 又,相對於鹼可溶性樹脂100質量份,感光性樹脂組成物中的熱交聯劑的含量的下限值例如係0.1質量份以上為較佳,1質量份以上為更佳,3質量份以上為進一步較佳,5質量份以上為更進一步較佳,8質量份以上為尤佳。The upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 12 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. Preferably, 10 parts by mass or less is more preferable. Accordingly, even when the thermal cross-linking agent includes a solvated functional group such as a phenolic hydroxyl group, it is possible to suppress a decrease in chemical resistance after the post-baking. The lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. To be more preferable, 5 parts by mass or more is further preferable, and 8 parts by mass or more is particularly preferable.
(界面活性劑) 本實施形態之感光性樹脂組成物可進而包含界面活性劑。 作為界面活性劑並無限定,具體而言可列舉聚氧乙烯十二烷基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類;聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等聚氧乙烯芳基醚類;聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等聚氧乙烯二烷基酯類等非離子系界面活性劑;以EFTOP EF301、EFTOP EF303、EFTOP EF352(Shin-Akita Chemical 公司製造)、MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F177、MEGAFACE F444、MEGAFACE F470、MEGAFACE F471、MEGAFACE F475、MEGAFACE F482、MEGAFACE F477(DIC公司製造)、FLUORAD FC-430、FLUORAD FC-431、NOVEC FC4430、NOVEC FC4432(3M Japan公司製造)、SURFLON S-381、SURFLON S-382、SURFLON S-383、SURFLON S-393、SURFLON SC-101、SURFLON SC-102、SURFLON SC-103、SURFLON SC-104、SURFLON SC-105、SURFLON SC-106、(AGC SEIMI CHEMICAL公司製造)等名稱市售之氟系界面活性劑;有機矽氧烷共聚物KP341(Shin-Etsu Chemical公司製造);(甲基)丙烯酸系共聚物Polyflow No.57、95(KYOEISHA CHEMICAL公司製造)等。(Surfactant) The photosensitive resin composition of this embodiment may further contain a surfactant. The surfactant is not limited, and specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl Polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; non-ionic systems such as polyoxyethylene dilaurate and polyoxyethylene distearate surfactant; to EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured Shin-Akita Chemical company), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC), FLUORAD FC-430, FLUORAD FC-431, NOVEC FC4430, NOVEC FC4432 (manufactured by 3M Japan), SURFLON S-381, SURFLON S-382, SURFLON S-383, SURFLON S-393, SURFLON Commercially available fluorine-based surfactants such as SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106, (manufactured by AGC SEIMI CHEMICAL); organic silicon oxygen KP341 Shin-Etsu Chemical Co., Ltd.); (meth) acrylic copolymer Polyflow No.57,95 (KYOEISHA CHEMICAL Co., Ltd.).
該等中,使用具有全氟烷基之氟系界面活性劑為較佳。作為具有全氟烷基之氟系界面活性劑,使用上述具體例中的選自MEGAFACE F171、MEGAFACE F173、MEGAFACE F444、MEGAFACE F470、MEGAFACE F471、MEGAFACE F475、MEGAFACE F482、MEGAFACE F477(DIC公司製造)、SURFLON S-381、SURFLON S-383、SURFLON S-393(AGC SEIMI CHEMICAL公司製造)、NOVEC FC4430及NOVEC FC4432(3M Japan公司製造)之一種或兩種以上為較佳。Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. As the fluorine-based surfactant having a perfluoroalkyl group, the above-mentioned specific examples are selected from the group consisting of MEGAFACE F171, MEGAFACE F173, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC Corporation), One or two or more of SURFLON S-381, SURFLON S-383, SURFLON S-393 (manufactured by AGC SEIMI CHEMICAL), NOVEC FC4430, and NOVEC FC4432 (manufactured by 3M Japan) are preferred.
又,作為界面活性劑,以能夠較佳地使用聚矽氧系界面活性劑(例如聚醚改質二甲基矽氧烷等)。作為聚矽氧系界面活性劑,具體而言能夠列舉Dow Corning Toray 公司的SH系列、SD系列及ST系列、BYK Japan公司的BYK系列、Shin-Etsu Chemical股份有限公司的KP系列、NOF股份有限公司的DISFOAM(註冊商標)系列、Toshiba Silicones股份有限公司的TSF系列等。In addition, as the surfactant, a polysiloxane-based surfactant (for example, polyether modified dimethylsiloxane) can be preferably used. Specific examples of the polysiloxane surfactant include SH series, SD series and ST series of Dow Corning Toray, BYK series of BYK Japan, KP series of Shin-Etsu Chemical Co., Ltd., and NOF Co., Ltd. DISFOAM (registered trademark) series, Toshiba Silicones Co., Ltd. TSF series and so on.
相對於感光性樹脂組成物整體(包含溶劑),感光性樹脂組成物中的界面活性劑的含量的上限值係1質量%(10000ppm)以下為較佳,0.5質量%(5000ppm)以下為更佳,0.1質量%(1000ppm)以下為進一步較佳。 又,感光性樹脂組成物中的界面活性劑的含量的下限值並無特別限制,但從充分獲得基於界面活性劑之效果之觀點考慮,例如相對於感光性樹脂組成物整體(包含溶劑),係0.001質量%(10ppm)以上。 藉由適當地調整界面活性劑的量,能夠維持其他性能,並提高塗佈性或塗膜的均勻性等。The upper limit of the content of the surfactant in the photosensitive resin composition is preferably 1% by mass (10000ppm) or less, and more preferably 0.5% by mass (5000ppm) with respect to the entire photosensitive resin composition (including the solvent). It is more preferable that it is 0.1 mass% (1000 ppm) or less. The lower limit value of the content of the surfactant in the photosensitive resin composition is not particularly limited, but from the viewpoint of sufficiently obtaining the effect based on the surfactant, for example, with respect to the entire photosensitive resin composition (including the solvent) , Above 0.001% by mass (10ppm). By appropriately adjusting the amount of the surfactant, it is possible to maintain other properties and improve coating properties, uniformity of the coating film, and the like.
(抗氧化劑) 本實施形態之感光性樹脂組成物可進而包含抗氧化劑。作為抗氧化劑,能夠使用選自酚系抗氧化劑、磷系抗氧化劑及硫醚系抗氧化劑中之一種以上。抗氧化劑能夠抑制由感光性樹脂組成物所形成之樹脂膜的氧化。 作為酚系抗氧化劑,可列舉新戊四醇-四〔3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯〕、3,9-雙{2-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基〕-1,1-二甲基乙基}2,4,8,10-四氧雜螺〔5,5〕十一烷、十八烷基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯、1,6-己二醇-雙〔3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯〕、1,3,5-三甲基-2,4,6-三(3,5-二-三級丁基-4-羥基苄基)苯、2,6-二-三級丁基-4-甲基酚、2,6-二-三級丁基-4-乙基酚、2,6-二苯基-4-十八烷氧基酚、硬脂基(3,5-二-三級丁基-4-羥基苯基)丙酸酯、二硬脂基(3,5-二-三級丁基-4-羥基苄基)膦酸酯、硫二乙二醇雙〔(3,5-二-三級丁基-4-羥基苯基)丙酸酯〕、4,4’-硫代雙(6-三級丁基-間甲酚)、2-辛硫基-4,6-二(3,5-二-三級丁基-4-羥基苯氧基)-對稱三口井、2,2’-亞甲基雙(4-甲基-6-三級丁基-6-丁基酚)、2,-2’-亞甲基雙(4-乙基-6-三級丁基酚)、雙〔3,3-雙(4-羥基-3-三級丁基苯基)丁酸〕乙二醇酯、4,4’-亞丁基雙(6-三級丁基-間甲酚)、2,2’-亞乙基雙(4,6-二-三級丁基酚)、2,2’-亞乙基雙(4-二級丁基-6-三級丁基酚)、1,1,3-三(2-甲基-4-羥基-5-三級丁基苯基)丁烷、雙〔2-三級丁基-4-甲基-6-(2-羥基-3-三級丁基-5-甲基苄基)苯基〕對苯二甲酸酯、1,3,5-三(2,6-二甲基-3-羥基-4-三級丁基苄基)三聚異氰酸酯、1,3,5-三(3,5-二-三級丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-三〔(3,5-二-三級丁基-4-羥基苯基)丙醯氧基乙基〕三聚異氰酸酯、四〔亞甲基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯〕甲烷、2-三級丁基-4-甲基-6-(2-丙烯醯氧基-3-三級丁基-5-甲基苄基)酚、3,9-雙(1,1-二甲基-2-羥乙基)-2,4,8,10-四氧雜螺[5,5]十一烷-雙〔β-(3-三級丁基-4-羥基-5-甲基苯基)丙酸酯〕、三乙二醇雙〔β-(3-三級丁基-4-羥基-5-甲基苯基)丙酸酯〕、1,1’-雙(4-羥基苯基)環己烷、2,2’-亞甲基雙(4-甲基-6-三級丁基酚)、2,2’-亞甲基雙(4-乙基-6-三級丁基酚)、2,2’-亞甲基雙(6-(1-甲基環己基)-4-甲基酚)、4,4’-亞丁基雙(3-甲基-6-三級丁基酚)、3,9-雙(2-(3-三級丁基-4-羥基-5-甲基苯基丙醯氧基)1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、4,4’-硫代雙(3-甲基-6-三級丁基酚)、4,4’-雙(3,5-二-三級丁基-4-羥基苄基)硫化物、4,4’-硫代雙(6-三級丁基-2-甲基酚)、2,5-二-三級丁基氫醌、2,5-二-三級戊基氫醌、2-三級丁基-6-(3-三級丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2,4-二甲基-6-(1-甲基環己基)、苯乙烯化苯酚、2,4-雙((辛硫基)甲基)-5-甲基酚等。 作為磷系抗氧化劑,可列舉雙(2,6-二-三級丁基-4-甲基苯基)新戊四醇二亞磷酸酯、三(2,4-二-三級丁基苯基亞磷酸酯)、四(2,4-二-三級丁基-5-甲基苯基)-4,4’-伸聯苯基二亞磷酸酯、3,5-二-三級丁基-4-羥基苄基磷酸酯-二乙基酯、雙-(2,6-二異丙苯基苯基)新戊四醇二亞磷酸酯、2,2-亞甲基雙(4,6-二-三級丁基苯基)辛基磷酸酯、三(混合單及二-壬基苯基亞磷酸酯)、雙(2,4-二-三級丁基苯基)新戊四醇二亞磷酸酯、雙(2,6-二-三級丁基-4-甲氧基羰基乙基-苯基)新戊四醇二亞磷酸酯、雙(2,6-二-三級丁基-4-十八烷氧基羰基乙基苯基)新戊四醇二亞磷酸酯等。 作為硫醚系抗氧化劑,可列舉3,3’-硫代二丙酸二月桂酯、雙(2-甲基-4-(3-正十二烷基)硫代丙醯氧基)-5-三級丁基苯基)硫化物、3,3’-硫代二丙酸酯、新戊四醇-四(3-月桂基)硫代丙酸酯等。(Antioxidant) The photosensitive resin composition of this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be used. The antioxidant can suppress the oxidation of the resin film formed of the photosensitive resin composition. Examples of the phenolic antioxidant include neopentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3 -(3-tertiarybutyl-4-hydroxy-5-methylphenyl) propanyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5 , 5] undecane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, 2,6-di-tertiary-butyl-4-methylphenol, 2,6-di-tertiary-butyl-4-ethylphenol, 2,6-diphenyl- 4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl- 4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6 -Tertiary butyl-m-cresol), 2-octylthio-4,6-bis (3,5-di-tertiary butyl-4-hydroxyphenoxy)-symmetrical three wells, 2,2 ' -Methylenebis (4-methyl-6-tertiarybutyl-6-butylphenol), 2, -2'-methylenebis (4- -6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] ethylene glycol ester, 4,4'-butylene bis (6 -Tertiary butyl-m-cresol), 2,2'-ethylenebis (4,6-di-tertiary butylphenol), 2,2'-ethylenebis (4-second butyl) -6-tertiary-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tertiary-butylphenyl) butane, bis [2-tertiary-butyl-4- Methyl-6- (2-hydroxy-3-tertiarybutyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl- 3-hydroxy-4-tertiary-butylbenzyl) trimeric isocyanate, 1,3,5-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) -2,4,6-tris Methylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] trimeric isocyanate, tetrakis [methylene-3- ( 3,5-di-tertiary butyl-4-hydroxyphenyl) propionate] methane, 2-tertiary butyl-4-methyl-6- (2-propenyloxy-3-tertiary butyl 5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] deca Monoalkane-bis [β- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-sub Methylbis (4-methyl-6-tertiary-butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiary-butylphenol), 2,2'-methylene Bis (6- (1-methylcyclohexyl) -4-methylphenol), 4,4'-butylene bis (3-methyl-6-tertiary butylphenol), 3,9-bis (2 -(3-tertiarybutyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5, 5) Undecane, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-bis (3,5-di-tert-butyl-4-hydroxy Benzyl) sulfide, 4,4'-thiobis (6-tertiarybutyl-2-methylphenol), 2,5-di-tertiary butylhydroquinone, 2,5-di-tertiary Amylhydroquinone, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-dimethyl -6- (1-methylcyclohexyl), styrenated phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like. Examples of the phosphorus-based antioxidant include bis (2,6-di-tert-butyl-4-methylphenyl) neopentaerythritol diphosphite and tris (2,4-di-tert-butylbenzene). Diphosphite), tetra (2,4-di-tertiarybutyl-5-methylphenyl) -4,4'-biphenylphenyl phosphite, 3,5-di-tertiary butyl 4-hydroxybenzyl phosphate-diethyl ester, bis- (2,6-dicumylphenyl) neopentaerythritol diphosphite, 2,2-methylenebis (4, 6-di-tertiary butylphenyl) octyl phosphate, tri (mixed mono and di-nonylphenyl phosphite), bis (2,4-di-tertiary butylphenyl) neopentyl Alcohol diphosphite, bis (2,6-di-tertiary butyl-4-methoxycarbonylethyl-phenyl) neopentyl tetraol diphosphite, bis (2,6-di-tertiary Butyl-4-octadecyloxycarbonylethylphenyl) neopentaerythritol diphosphite and the like. Examples of the thioether-based antioxidant include 3,3'-thiodipropionate dilauryl and bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5 -Tertiary butylphenyl) sulfide, 3,3'-thiodipropionate, neopentaerythritol-tetrakis (3-lauryl) thiopropionate, and the like.
(填料) 本實施形態之感光性樹脂組成物可進而包含填料。作為填料,能夠依據由感光性樹脂組成物製成之樹脂膜所需之機械特性、熱特性來選擇適當的填充材料。 作為填料,具體而言可列舉無機填料或有機填料等。 作為上述無機填料,具體而言可列舉熔融破碎二氧化矽、熔融球狀二氧化矽、結晶性二氧化矽、二次凝集二氧化矽、微粉二氧化矽等二氧化矽;氧化鋁、氮化矽、氮化鋁、氮化硼、氧化鈦、碳化矽、氫氧化鋁、氫氧化鎂、鈦白等金屬化合物;滑石;黏土;雲母;玻璃纖維等。作為無機填料,能夠使用上述具體例中的一種或組合使用兩種以上。 作為上述有機填料,具體而言可列舉有機聚矽氧粉末、聚乙烯粉末等。作為有機填料,能夠使用上述具體例中的一種或組合使用兩種以上。(Filler) The photosensitive resin composition of this embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to the mechanical characteristics and thermal characteristics required for a resin film made of a photosensitive resin composition. Specific examples of the filler include inorganic fillers and organic fillers. Specific examples of the inorganic filler include silicon dioxide such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica; alumina, nitride Silicon, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium white and other metal compounds; talc; clay; mica; glass fiber, etc. As the inorganic filler, one of the above specific examples can be used or two or more of them can be used in combination. Specific examples of the organic filler include organic polysiloxane powder and polyethylene powder. As the organic filler, one of the above specific examples can be used or two or more of them can be used in combination.
(感光性樹脂組成物的製備) 製備本實施形態中的感光性樹脂組成物之方法並無限定,依據感光性樹脂組成物中所含之成分,能夠使用公知的方法。 例如,能夠藉由將上述各成分與溶劑混合並使其溶解而製備。藉此,能夠獲得作為清漆之感光性樹脂組成物。(Preparation of photosensitive resin composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition. For example, it can prepare by mixing each said component with a solvent, and making it melt | dissolve. Thereby, a photosensitive resin composition as a varnish can be obtained.
(感光性樹脂組成物) 本實施形態之感光性樹脂組成物可藉由如下來使用:將該感光性樹脂組成物的清漆塗佈於具備Al、Cu等金屬之面,接著,藉由進行預烘使其乾燥而形成樹脂膜,接著,藉由進行曝光及顯影而將樹脂膜圖案化成所期望的形狀,接著,藉由將樹脂膜進行後烘使其硬化而形成硬化膜。 再者,當製作上述永久膜時,作為預烘的條件,例如能夠設為溫度90℃以上且130℃以下且30秒鐘以上且1小時以下的熱處理。又,作為後烘的條件,例如能夠設為溫度150℃以上且350℃以下且30分鐘以上且10小時以下的熱處理。(Photosensitive resin composition) The photosensitive resin composition of this embodiment can be used by applying the varnish of the photosensitive resin composition to a surface provided with a metal such as Al, Cu, and the like, and then performing The resin film is dried to form a resin film, and then the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by post-baking to form a cured film. When the permanent film is produced, the pre-baking condition can be, for example, a heat treatment at a temperature of 90 ° C. or higher and 130 ° C. or lower and 30 seconds or longer and 1 hour or shorter. The post-baking condition can be, for example, a heat treatment at a temperature of 150 ° C. or higher and 350 ° C. or lower and 30 minutes or longer and 10 hours or shorter.
能夠依據所期望的樹脂膜的厚度適當地設定本實施形態之感光性樹脂組成物的黏度。感光性樹脂組成物的黏度的調整能夠藉由添加溶劑來進行。再者,進行調整時,需要將溶劑中的尿素化合物及非環狀結構的醯胺化合物的含量維持恆定。 本實施形態之感光性樹脂組成物的黏度的上限值例如可為2000mPa・s以下,亦可為1800mPa・s以下,亦可為1500mPa・s以下。又,依據所期望的樹脂膜的厚度,本實施形態之感光性樹脂組成物的黏度的下限值例如可為10mPa・s以上,亦可為50mPa・s以上。 再者,在本實施形態中,感光性樹脂組成物的黏度例如能夠藉由E型黏度計在溫度25℃開始旋轉300秒後進行測量。The viscosity of the photosensitive resin composition of this embodiment can be appropriately set according to the thickness of a desired resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. In addition, when adjusting, it is necessary to keep the content of the urea compound and the acyclic amine compound in the solvent constant. The upper limit of the viscosity of the photosensitive resin composition of this embodiment may be, for example, 2000 mPa ・ s or less, 1800 mPa ・ s or less, or 1500 mPa ・ s or less. In addition, depending on the thickness of the desired resin film, the lower limit value of the viscosity of the photosensitive resin composition of this embodiment may be, for example, 10 mPa ・ s or more, and may be 50 mPa ・ s or more. In addition, in this embodiment, the viscosity of the photosensitive resin composition can be measured, for example, by using an E-type viscometer at a temperature of 25 ° C. for 300 seconds after the rotation is started.
本實施形態之感光性樹脂組成物藉由E型黏度計,以在旋轉頻率100rpm、溫度25℃旋轉300秒鐘之後測量之黏度成為50mPa・s之方式進行黏度調整,在溫度25℃滴加2mL到銅箔之10秒後的接觸角的上限值例如係71°以下為較佳,69°以下為更佳,65°以下為進一步較佳,62°以下為更進一步較佳,57°以下為尤佳。藉由接觸角係上述數值範圍以下,感光性樹脂組成物的清漆與Cu等金屬之間的親和性提高,感光性樹脂組成物能夠滲入到Cu等金屬表面所產生之微細的間隙。藉此,將感光性樹脂組成物作為硬化膜時,能夠在該硬化膜及Cu等金屬之間顯現出定錨效果,並能夠提高密接力。 又,藉由E型黏度計,以在旋轉頻率100rpm、溫度25℃旋轉300秒鐘之後測量之黏度成為50mPa・s之方式進行黏度調整,在溫度25℃滴加2mL到銅箔之10秒後的接觸角的下限值例如可以設為40°以上,亦可以設為45°以上。The viscosity of the photosensitive resin composition of this embodiment is adjusted by a E-type viscometer so that the measured viscosity becomes 50 mPa ・ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL is added dropwise at a temperature of 25 ° C The upper limit value of the contact angle after 10 seconds from the copper foil is preferably 71 ° or less, more preferably 69 ° or less, more preferably 65 ° or less, even more preferably 62 ° or less, and 57 ° or less. Especially good. When the contact angle is below the above numerical range, the affinity between the varnish of the photosensitive resin composition and metals such as Cu is improved, and the photosensitive resin composition can penetrate into the fine gaps generated by the surface of the metal such as Cu. Accordingly, when the photosensitive resin composition is used as a cured film, an anchoring effect can be exhibited between the cured film and a metal such as Cu, and adhesion can be improved. In addition, with an E-type viscometer, the viscosity was adjusted so that the measured viscosity became 50 mPa ・ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL was added dropwise to a copper foil at a temperature of 25 ° C for 10 seconds. The lower limit value of the contact angle may be, for example, 40 ° or more, or 45 ° or more.
本實施形態之感光性樹脂組成物藉由E型黏度計,以在旋轉頻率100rpm、溫度25℃旋轉300秒鐘之後測量之黏度成為50mPa・s之方式進行黏度調整,在溫度25℃滴加2mL到鋁箔之10秒後的接觸角的上限值例如係14°以下為較佳,13°以下為更佳,12°以下為進一步較佳,11°以下為更進一步為較佳。藉由接觸角係上述數值範圍以下,感光性樹脂組成物的清漆與Al等金屬之間的親和性提高,感光性樹脂組成物能夠滲入到Al等金屬表面所產生之微細的間隙。藉此,將感光性樹脂組成物作為硬化膜時,能夠在該硬化膜及Al等金屬之間顯現出定錨效果,並能夠提高密接力。 又,藉由E型黏度計,以在旋轉頻率100rpm、溫度25℃旋轉300秒鐘之後測量之黏度成為50mPa・s之方式進行黏度調整,在溫度25℃滴加2mL到鋁箔之10秒後的接觸角的下限值例如可以設為1°以上,亦可以設為5°以上。The viscosity of the photosensitive resin composition of this embodiment is adjusted by a E-type viscometer so that the measured viscosity becomes 50 mPa ・ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL is added dropwise at a temperature of 25 ° C The upper limit value of the contact angle after 10 seconds from the aluminum foil is, for example, preferably 14 ° or less, more preferably 13 ° or less, even more preferably 12 ° or less, and even more preferably 11 ° or less. When the contact angle is below the above-mentioned numerical range, the affinity between the varnish of the photosensitive resin composition and metal such as Al is improved, and the photosensitive resin composition can penetrate into the fine gaps generated by the surface of metal such as Al. Accordingly, when the photosensitive resin composition is used as a cured film, an anchor effect can be exhibited between the cured film and a metal such as Al, and adhesion can be improved. In addition, with an E-type viscometer, the viscosity was adjusted such that the measured viscosity became 50 mPa ・ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL was added dropwise to the aluminum foil at 25 ° C for 10 seconds. The lower limit value of the contact angle may be, for example, 1 ° or more, or 5 ° or more.
對測量上述接觸角時的黏度調整進行補充說明。 針對基於上述E型黏度計之測量方法中的黏度大於50mPa・s之感光性樹脂組成物,使用與該感光性樹脂組成物所包含之溶劑相同的溶劑,將黏度調整為50mPa・s而測量接觸角。再者,當該感光性樹脂組成物包含混合溶劑時,藉由其混合溶劑來調整黏度。 又,針對基於上述測量方法之黏度小於50mPa・s之感光性樹脂組成物,能夠以如下方式求出相當於黏度50mPa・s之接觸角。 例如,假設存在基於上述測量方法之黏度為40mPa・s之感光性樹脂組成物。使用與該感光性樹脂組成物所包含之溶劑相同的溶劑進一步稀釋該感光性樹脂組成物,製作黏度為30、20、10mPa・s等的感光性樹脂組成物。並且,標繪該等黏度10~40mPa・s的感光性樹脂組成物的黏度與接觸角之間的關係,藉由最小二乘法畫出直線,外插相當於黏度50mPa・s之接觸角而求出。再者,標繪以最低2點,較佳為以3點或4點進行。 順帶一提,作為本發明人等的發現,在50mPa・s以下的低黏度區域中,例如30mPa・s和50mPa・s,接觸角幾乎沒有差異。Supplementary explanation will be given for viscosity adjustment when measuring the above-mentioned contact angle. For the photosensitive resin composition having a viscosity of more than 50 mPa ・ s in the above-mentioned measuring method based on the E-type viscometer, the same solvent as the solvent contained in the photosensitive resin composition was used to adjust the viscosity to 50 mPa ・ s to measure the contact angle. When the photosensitive resin composition contains a mixed solvent, the viscosity is adjusted by the mixed solvent. In addition, for a photosensitive resin composition having a viscosity of less than 50 mPa ・ s based on the above-mentioned measurement method, a contact angle corresponding to a viscosity of 50 mPa ・ s can be obtained as follows. For example, it is assumed that there is a photosensitive resin composition having a viscosity of 40 mPa 基于 s based on the above-mentioned measurement method. The photosensitive resin composition is further diluted with the same solvent as the solvent contained in the photosensitive resin composition to prepare a photosensitive resin composition having a viscosity of 30, 20, 10 mPa ・ s, or the like. In addition, the relationship between the viscosity of the photosensitive resin composition with a viscosity of 10 to 40 mPa ・ s and the contact angle is plotted, and a straight line is drawn by the least square method, and the contact angle equivalent to the viscosity of 50 mPa ・ s is calculated. Out. Furthermore, the plotting is performed at the lowest 2 points, preferably at 3 or 4 points. Incidentally, as the findings of the present inventors, there is almost no difference in contact angle in a low viscosity region below 50 mPa50s, for example, 30 mPa ・ s and 50 mPa ・ s.
本發明人針對感光性樹脂組成物的清漆,對將相對於銅箔、鋁箔之接觸角設為上述數值範圍內之方法進行研究之結果發現,適當地控制溶劑中所含之尿素化合物、非環狀結構的醯胺化合物的結構以及溶劑中的尿素化合物及非環狀結構的醯胺化合物的含量係重要。 作為溶劑中所含之尿素化合物、非環狀結構的醯胺化合物的結構,共振結構更多者為較佳。具體而言,在尿素化合物的脲鍵或非環狀結構的醯胺化合物的醯胺鍵中,由氮原子的孤電子對和酮部位C=O形成之共振結構的數量多者為較佳。作為尿素化合物、非環狀結構的醯胺化合物的共振結構的數量,例如係2個以上為較佳,3個以上為更佳。藉此,尿素化合物、非環狀結構的醯胺化合物的電子雲擴散,電子狀態得到穩定。因此,認為尿素化合物、非環狀結構的醯胺化合物的表面自由能降低,能夠提高對Cu之潤濕性。作為共振結構的數量列舉一例。例如,四甲基脲(TMU)等尿素化合物的共振結構的數量係3個。 又,針對溶劑中的尿素化合物及非環狀結構的醯胺化合物的含量,亦取決於上述結構,例如將溶劑設為100質量份時,設為30質量份以上為較佳,50質量份以上為更佳,70質量份以上為進一步較佳,100質量份為更進一步較佳。藉此,能夠使溶劑中的電子狀態穩定,並能夠將接觸角設為上述數值範圍內。The inventors have studied the method of setting the contact angle with copper foil and aluminum foil to the above-mentioned numerical range with respect to the varnish of the photosensitive resin composition, and found that the urea compound and the acyclic compound contained in the solvent are appropriately controlled. The structure of the amidine compound having a crystalline structure, and the content of the urea compound and the acyclic amidine compound in the solvent are important. As the structure of the urea compound and the amidine compound having a non-cyclic structure contained in the solvent, more resonance structures are preferred. Specifically, the urea bond of the urea compound or the amidine bond of the amidine compound having a non-cyclic structure is preferably one having a large number of resonance structures formed by a lone electron pair of a nitrogen atom and a ketone site C = 0. The number of resonance structures of the urea compound and the amidine compound having a non-cyclic structure is, for example, preferably two or more, and more preferably three or more. Thereby, the electron cloud of the urea compound and the amidine compound having a non-cyclic structure is diffused, and the electronic state is stabilized. Therefore, it is considered that the surface free energy of the urea compound and the amidine compound having an acyclic structure is reduced, and the wettability to Cu can be improved. An example is given as the number of resonance structures. For example, the number of resonance structures of urea compounds such as tetramethylurea (TMU) is three. The content of the urea compound and the acyclic amine compound in the solvent also depends on the structure. For example, when the solvent is 100 parts by mass, it is preferably 30 parts by mass or more, and 50 parts by mass or more. More preferably, 70 parts by mass or more is further preferred, and 100 parts by mass is further preferred. Thereby, the state of the electrons in the solvent can be stabilized, and the contact angle can be set within the above-mentioned numerical range.
(用途) 本實施形態的感光性樹脂組成物用於形成永久膜、阻劑等電子裝置用的樹脂膜。該等中,從以良好的平衡顯現預烘後的感光性樹脂組成物和Al墊的密接性提高及顯影時的感光性樹脂組成物的殘渣的產生的抑制之觀點、提高後烘後的感光性樹脂組成物的硬化膜與金屬之間的密接性之觀點以及提高後烘後的感光性樹脂組成物的耐化學性之觀點考慮,用於使用永久膜之用途中為較佳。 再者,在本實施形態中,樹脂膜係指感光性樹脂組成物的乾燥膜或硬化膜。亦即,本實施形態之樹脂膜係指將感光性樹脂組成物進行乾燥或硬化而成者。(Application) The photosensitive resin composition of this embodiment is used to form a resin film for electronic devices such as a permanent film and a resist. Among these, from the viewpoints of improving the adhesion between the photosensitive resin composition after pre-baking and the Al pad and suppressing the generation of residues of the photosensitive resin composition during development in a good balance, the sensitivity after post-baking is improved. From the viewpoint of the adhesion between the cured film of the flexible resin composition and the metal, and from the viewpoint of improving the chemical resistance of the photosensitive resin composition after post-baking, it is preferably used for applications using a permanent film. In addition, in this embodiment, a resin film means the dry film or hardened film of a photosensitive resin composition. That is, the resin film of this embodiment refers to a product obtained by drying or curing the photosensitive resin composition.
上述永久膜由樹脂膜構成,該樹脂膜藉由以下方法而獲得:對感光性樹脂組成物進行預烘、曝光及顯影並圖案化為所需形狀之後進行後烘而使其硬化。永久膜能夠用於電子裝置的保護膜、層間膜、壩材等。The permanent film is made of a resin film obtained by pre-baking, exposing and developing a photosensitive resin composition, patterning it into a desired shape, and then post-baking to harden it. The permanent film can be used for protective films, interlayer films, dam materials, and the like of electronic devices.
上述阻劑例如由樹脂膜構成,該樹脂膜藉由如下方法而獲得:藉由旋塗、輥塗、流塗、浸塗、噴塗、刮塗等方法將感光性樹脂組成物塗佈於用阻劑遮蓋之對象上,從感光性樹脂組成物中去除溶劑。The above-mentioned resist is made of, for example, a resin film obtained by applying a photosensitive resin composition to the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating. The solvent is removed from the photosensitive resin composition on the object covered by the agent.
在圖1中示出本實施形態之電子裝置的一例。 本實施形態之電子裝置100能夠設為具備上述樹脂膜之電子裝置。具體而言,能夠將電子裝置100中的由鈍化膜32、絕緣層42及絕緣層44組成的群中之一個以上設為樹脂膜。此處,樹脂膜係上述永久膜為較佳。An example of the electronic device of this embodiment is shown in FIG. The electronic device 100 according to this embodiment can be an electronic device including the resin film. Specifically, one or more of the group consisting of the passivation film 32, the insulating layer 42 and the insulating layer 44 in the electronic device 100 can be a resin film. Here, the resin film is preferably the permanent film.
電子裝置100例如為半導體晶片。在此情況下,例如將電子裝置100經由凸點52搭載於配線基板上,藉此獲得半導體封裝體。電子裝置100具備:半導體基板,其設置有電晶體等半導體元件;及多層配線層(未圖示),其設置於半導體基板上。在多層配線層中之最上層設置有層間絕緣膜30及設置於層間絕緣膜30上之最上層配線34。最上層配線34例如由鋁Al構成。又,在層間絕緣膜30上及最上層配線34上設置有鈍化膜32。在鈍化膜32之一部分設置有露出最上層配線34之開口。The electronic device 100 is, for example, a semiconductor wafer. In this case, for example, the electronic device 100 is mounted on a wiring substrate via the bumps 52 to obtain a semiconductor package. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided on the uppermost layer of the multilayer wiring layers. The uppermost layer wiring 34 is made of, for example, aluminum Al. A passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening for exposing the uppermost layer wiring 34 is provided in a part of the passivation film 32.
在鈍化膜32上設置有再配線層40。再配線層40具有:絕緣層42,其設置於鈍化膜32上;再配線46,其設置於絕緣層42上;及絕緣層44,其設置於絕緣層42上及再配線46上。在絕緣層42上形成有與最上層配線34連接之開口。再配線46形成於絕緣層42上及設置於絕緣層42之開口內,與最上層配線34連接。在絕緣層44上設置有與再配線46連接之開口。A redistribution layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. An opening is formed in the insulating layer 42 to be connected to the uppermost wiring 34. The rewiring 46 is formed on the insulating layer 42 and provided in the opening of the insulating layer 42, and is connected to the uppermost wiring 34. An opening connected to the redistribution wiring 46 is provided in the insulating layer 44.
在設置於絕緣層44之開口內,例如經由UBM(Under Bump Metallurgy)層50而形成凸點52。電子裝置100例如經由凸點52與配線基板等連接。In the opening provided in the insulating layer 44, for example, a bump 52 is formed through an UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via a bump 52, for example.
再者,本發明不限定於前述實施形態,在能夠實現本發明的目的之範圍內的變形、改良等係包含於本發明者。 〔實施例〕In addition, the present invention is not limited to the aforementioned embodiments, and modifications, improvements, and the like within a range where the object of the present invention can be achieved are included by the inventor. [Example]
以下,利用實施例對本發明進行詳細說明,但本發明不受該等實施例所記載之任何限定。Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited in any way by the examples.
首先,對實施例及比較例中所使用之原料進行詳細說明。First, the raw materials used in Examples and Comparative Examples will be described in detail.
<鹼可溶性樹脂> 首先,對各實施例及各比較例中所使用之鹼可溶性樹脂進行詳細說明。<Alkali-soluble resin> First, the alkali-soluble resin used in each Example and each comparative example is demonstrated in detail.
(鹼可溶性樹脂1) 藉由以下步驟合成作為聚醯胺樹脂之鹼可溶性樹脂1。 在具備溫度計、攪拌機、原料投入口及乾燥氮氣導入管之四口玻璃製的可分離式燒瓶內放入使下述式(DC2)所表示之二苯醚-4,4’-二羧酸206.58g(0.800mol)與1-羥基-1,2,3-苯并三唑・一水合物216.19g(1.600mol)進行反應而獲得之二羧酸衍生物的混合物170.20g(0.346mol)、5-胺基四唑4.01g(0.047mol)、下述式(DA2)所表示之4,4’-亞甲基雙(2-胺基酚)45.22g(0.196mol)及下述式(DA3)所表示之4,4’-亞甲基雙(2-胺基-3,6-二甲基酚)56.24g(0.196mol)。其後,在上述可分離式燒瓶內加入578.3g的N-甲基-2-吡咯啶酮,使各原料成分溶解。接著,使用油浴在90℃使之反應5小時。接著,在上述可分離式燒瓶內加入24.34g(0.141mol)的4-乙炔基鄰苯二甲酸酐和121.7g的N-甲基-2-吡咯啶酮,在90℃攪拌2小時並同時使其反應之後,冷卻至23℃後結束反應。 將過濾可分離式燒瓶內之反應混合物而獲得之過濾液投入至水/異丙醇=7/4(容積比)的溶液中。其後,濾取沉澱物,用水充分清洗之後,在真空下進行乾燥,藉此獲得鹼可溶性樹脂1。所獲得之鹼可溶性樹脂1的重量平均分子量Mw為18081。(Alkali-soluble resin 1) The alkali-soluble resin 1 as a polyamide resin was synthesized by the following steps. In a four-necked glass separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, diphenyl ether-4,4'-dicarboxylic acid 206.58 represented by the following formula (DC2) was placed. 170.20 g (0.346 mol) of dicarboxylic acid derivative mixture obtained by reacting g (0.800 mol) with 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole hydrazone monohydrate, 5 -4.01 g (0.047 mol) of aminotetrazole, 45.22 g (0.196 mol) of 4,4'-methylenebis (2-aminophenol) represented by the following formula (DA2) and the following formula (DA3) The indicated 4,4'-methylenebis (2-amino-3,6-dimethylphenol) is 56.24 g (0.196 mol). Thereafter, 578.3 g of N-methyl-2-pyrrolidone was placed in the separable flask to dissolve each raw material component. Then, it was made to react at 90 degreeC for 5 hours using the oil bath. Next, in the separable flask, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added, and stirred at 90 ° C for 2 hours while simultaneously After the reaction, the reaction was terminated after cooling to 23 ° C. The filtrate obtained by filtering the reaction mixture in the separable flask was put into a solution of water / isopropanol = 7/4 (volume ratio). Thereafter, the precipitate was collected by filtration, sufficiently washed with water, and then dried under vacuum, thereby obtaining an alkali-soluble resin 1. The weight-average molecular weight Mw of the obtained alkali-soluble resin 1 was 18,081.
<感光劑> 接著,對各實施例及比較例中所使用之感光劑進行詳細說明。<Photosensitizer> Next, the photosensitizer used in each Example and a comparative example is demonstrated in detail.
(感光劑1) 藉由以下步驟合成作為重氮醌化合物之感光劑1。 在具備溫度計、攪拌機、原料投入口、乾燥氮氣導入管之四口可分離式燒瓶中放入下述式(P-1)所表示之苯酚11.04g(0.026mol)、1,2-萘醌-2-二疊氮-5-磺醯氯18.81g(0.070mol)、丙酮170g,並進行攪拌,使該等溶解。 接著,以反應溶液的溫度不會成為35℃以上之方式藉由水浴而冷卻燒瓶,並同時緩慢滴加三乙胺7.78g(0.077mol)與丙酮5.5g的混合溶液。在此狀態下在室溫反應3小時之後,添加乙酸1.05g(0.017mol),進而反應30分鐘。接著,過濾反應混合物之後,將濾液投入至水/乙酸(990mL/10mL)的混合溶液中。接著,濾集沉澱物並利用水充分清洗之後,在真空下進行乾燥。藉此,獲得下述式(Q-1)的結構所表示之感光劑1。(Photosensitizer 1) Photosensitizer 1 as a diazoquinone compound was synthesized by the following steps. In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, 11.04 g (0.026 mol) of phenol represented by the following formula (P-1) and 1,2-naphthoquinone- 18.81 g (0.070 mol) of 2-diazide-5-sulfosulfonyl chloride and 170 g of acetone were stirred to dissolve these. Next, while cooling the flask by a water bath so that the temperature of the reaction solution does not become 35 ° C or higher, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise at the same time. After reacting at room temperature for 3 hours in this state, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further performed for 30 minutes. Next, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). Next, the precipitate was collected by filtration and sufficiently washed with water, and then dried under vacuum. Thereby, the photosensitive agent 1 represented by the structure of following formula (Q-1) was obtained.
<溶劑> 作為溶劑,使用以下的溶劑1~3。 ・溶劑1:作為直鏈狀的尿素化合物之四甲基脲(TMU) ・溶劑2:γ-丁內酯(GBL) ・溶劑3:作為環狀形狀的醯胺化合物之N-甲基吡咯啶酮(NMP)<Solvent> As the solvent, the following solvents 1 to 3 were used. ・ Solvent 1: Tetramethylurea (TMU) as a linear urea compound ・ Solvent 2: Gamma-butyrolactone (GBL) ・ Solvent 3: N-methylpyrrolidine as a cyclic amidine compound Ketone (NMP)
<密接助劑> 作為密接助劑,使用以下密接助劑1~3。 ・密接助劑1:作為下述式(S1)所表示之胺基矽烷之N,N’-雙[3-(三甲氧基甲矽基)丙基]乙烷-1,2-二胺(Shin-Etsu Chemical公司製造之X-12-5263HP) ・密接助劑2:藉由以下說明之方法來合成且作為下述式(S2)所表示之胺基矽烷之羧酸酐及3-胺基丙基三乙氧基矽烷的縮合物<Adhesion aid> As the adhesion aid, the following adhesion aids 1 to 3 were used. Adhesion Adhesion Aid: N, N'-bis [3- (trimethoxysilyl) propyl] ethane-1,2-diamine (aminosilane) represented by the following formula (S1): X-12-5263HP manufactured by Shin-Etsu Chemical Co., Ltd.) Adhesion Adhesion Aid 2: Synthesized by the method described below and used as the carboxylic anhydride and 3-aminopropyl amine silane represented by the following formula (S2) Triethoxysilane
以下,對作為羧酸酐及3-胺基丙基三乙氧基矽烷的縮合物之密接助劑2的合成方法進行詳細說明。 在具備攪拌機及冷卻管之適當尺寸之反應容器中,使環己烯-1,2-二羧酸酐(45.6g,300mmol)溶解於N-甲基-2-吡咯啶酮(970g)中,並在恆溫槽中調整為30℃。接著,在滴液漏斗中裝入3-胺基丙基三乙氧基矽烷(62g,280mmol),經60分鐘滴加到溶解液中。滴加結束後,在30℃、18小時的條件下進行攪拌,獲得下述式(S2)所表示之密接助劑2。Hereinafter, the synthesis method of the adhesion promoter 2 which is a condensation product of a carboxylic acid anhydride and 3-aminopropyltriethoxysilane is demonstrated in detail. In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, cyclohexene-1,2-dicarboxylic anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g), and Adjust to 30 ° C in a thermostatic bath. Next, a dropping funnel was charged with 3-aminopropyltriethoxysilane (62 g, 280 mmol), and the solution was added dropwise over 60 minutes. After completion of the dropwise addition, stirring was performed under the conditions of 30 ° C. and 18 hours to obtain the adhesion promoter 2 represented by the following formula (S2).
<熱交聯劑> 作為熱交聯劑,使用以下熱交聯劑1。 ・熱交聯劑1:對二甲苯乙二醇(IHARANIKKEI CHEMICAL INDUSTRY公司製造之PXG)<Thermal Crosslinking Agent> As the thermal crosslinking agent, the following thermal crosslinking agent 1 was used. ・ Heat crosslinker 1: P-xylene glycol (PXG manufactured by IHARANIKKEI CHEMICAL INDUSTRY)
<界面活性劑> 作為界面活性劑,使用以下界面活性劑1。 ・界面活性劑1:氟系界面活性劑(3M Japan公司製造之FC4430)<Surfactant> As the surfactant, the following surfactant 1 was used. ・ Surfactant 1: Fluorine surfactant (FC4430 manufactured by 3M Japan)
(各實施例、各比較例的感光性樹脂組成物的製備) 以如下方式製備實施例1~3、比較例1的感光性樹脂組成物。 首先,準備上述各原料成分。接著,針對使用兩種以上的溶劑者,依據下述表1所示之摻合比例混合溶劑,製作混合溶劑。接著將除溶劑以外的各原料添加到溶劑或混合溶劑中並進行攪拌,接著,利用孔徑0.2μm的PTFE製膜濾器進行過濾,藉此獲得各實施例、各比較例的感光性樹脂組成物的清漆。 再者,下述表1所示之各原料的摻合比例以質量份記載。(Preparation of photosensitive resin composition of each Example and each comparative example) The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared as follows. First, each of the above raw material components is prepared. Next, for those who use two or more solvents, the solvents are mixed according to the blending ratio shown in Table 1 below to prepare a mixed solvent. Next, each raw material other than the solvent was added to a solvent or a mixed solvent and stirred, and then filtered through a PTFE membrane filter having a pore size of 0.2 μm to obtain the photosensitive resin composition of each example and each comparative example. Varnish. The blending ratio of each raw material shown in Table 1 below is described in parts by mass.
對實施例1~3、比較例1的感光性樹脂組成物進行以下評價。The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were evaluated as follows.
(黏度) 關於實施例1~3、比較例1的感光性樹脂組成物的清漆,藉由E型黏度計(Toki Sangyo公司製造之TVE-22H)以旋轉頻率100rpm、溫度25℃旋轉300秒鐘之後測量黏度。將評價結果示於下述表1中。此處,黏度的單位係mPa・s。(Viscosity) The varnishes of the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were rotated at a rotation frequency of 100 rpm and a temperature of 25 ° C. for 300 seconds using an E-type viscometer (TVE-22H manufactured by Toki Sangyo). The viscosity was then measured. The evaluation results are shown in Table 1 below. Here, the unit of viscosity is mPa ・ s.
(接觸角) 使用實施例1~3、比較例1的感光性樹脂組成物的清漆,以如下方式對清漆的接觸角進行評價。 首先,作為基材準備平滑的銅箔。接著,利用液滴法對在溫度25℃將感光性樹脂組成物的清漆2mL滴落到基材上之後10秒後的接觸角進行評價。再者,使用接觸角計(Kyowa Interface Science公司製造之DROPMASTER-501)來進行測量。 又,亦對代替上述平滑的銅箔使用平滑的鋁箔作為基材者進行評價。 將各評價結果示於下述表1中。此處,接觸角的單位為°。此處,在下述表1中,「-」之記載表示未進行評價。 再者,藉由E型黏度計以旋轉頻率100rpm、溫度25℃旋轉300秒鐘之後進行測量時,實施例1~3、比較例1的各感光性樹脂組成物的清漆的黏度為50mPa・s。(Contact Angle) Using the varnish of the photosensitive resin composition of Examples 1 to 3 and Comparative Example 1, the contact angle of the varnish was evaluated as follows. First, a smooth copper foil is prepared as a base material. Next, the contact angle after 10 seconds after 2 mL of the varnish of the photosensitive resin composition was dripped on a base material at the temperature of 25 degreeC by the droplet method was evaluated. The measurement was performed using a contact angle meter (DROPMASTER-501 manufactured by Kyowa Interface Science). In addition, those who used a smooth aluminum foil as a substrate instead of the smooth copper foil were also evaluated. The evaluation results are shown in Table 1 below. Here, the unit of the contact angle is °. Here, in Table 1 below, the description of 「-」 indicates that the evaluation was not performed. In addition, when measured by an E-type viscometer at a rotation frequency of 100 rpm and a temperature of 25 ° C. for 300 seconds, the viscosity of the varnish of each photosensitive resin composition of Examples 1 to 3 and Comparative Example 1 was 50 mPams. .
(密接性) 使用實施例1~3、比較例1的感光性樹脂組成物,以如下方式對後烘後的感光性樹脂組成物和鋁(Al)的密接性進行評價。 首先,作為基材準備矽晶圓。接著,將鈦(Ti)以成為厚度0.05μm(500Å)之方式塗佈於基材之後,將Al以成為厚度0.3μm(3000Å)之方式濺射到Ti上,接著,使用旋轉塗佈機將感光性樹脂組成物的清漆塗佈於Al上。接著,使用加熱板,在溫度120℃預烘4分鐘之後,進一步使用烘箱在氮氣氛圍下以溫度220℃後烘1小時,獲得厚度7μm的硬化膜。此處,硬化膜與Al密接。亦即,獲得基材、Ti、Al、硬化膜依次積層而成之積層結構。使用該積層結構,並依據JIS D 0202評價密接性。具體而言,從積層結構中之硬化膜所存在之面,對硬化膜及Al以形成100個1mm見方的正方形之方式進行劃痕並進行單片化。接著,使玻璃紙(cellophane)膠帶附著於硬化膜上。附著1分鐘後,將玻璃紙膠帶從硬化膜剝離。剝離後,在100個正方形中,計算硬化膜與Al未剝離而殘留之正方形的個數及剝離後之正方形的個數,並將此作為PCT程序為0h之評價結果。所謂PCT程序0h,表示並未進行加速試驗。將評價結果示於下述表1中。在表1中示出剝離後之正方形的數量。 又,在上述中,使玻璃紙膠帶附著於硬化膜之後,以溫度125℃、濕度100%、氣壓2.3atm放置特定時間之後,將玻璃紙膠帶從硬化膜剝離。剝離後,在100個正方形中,計算硬化膜與Al未剝離而殘留之正方形的個數及剝離後之正方形的個數。將此作為PCT程序為特定時間之評價結果。作為PCT程序的時間,分別對48h、100h、150h、200h、300h進行評價。將評價結果示於下述表1中。表1中示出經剝離後之正方形的數量。 進一步對後烘後的感光性樹脂組成物及銅(Cu)的密接性進行評價。具體而言,代替將Al以成為厚度0.05μm(500Å)之方式濺射到Ti上,將銅(Cu)以成為厚度0.5μm(300Å)之方式進行濺射,除此以外,以與評價相同的方法對上述感光性樹脂組成物及鋁(Al)的密接性進行評價。將評價結果示於下述表1中。 另外,密接性的評價結果均為值小,亦即表示剝離後之正方形的數量越少,硬化膜與Al、Cu的密接性越高。 又,PCT程序係意圖加速試驗者,且用於評價後烘後的感光性樹脂組成物與Al、Cu的長期密接性而進行。(Adhesiveness) Using the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1, the adhesion between the post-baking photosensitive resin composition and aluminum (Al) was evaluated as follows. First, a silicon wafer is prepared as a base material. Next, titanium (Ti) was coated on the substrate so as to have a thickness of 0.05 μm (500 Å), and then Al was sputtered onto Ti so as to have a thickness of 0.3 μm (3000 Å). Next, a spin coater was used to apply The varnish of the photosensitive resin composition is applied on Al. Next, using a hot plate, pre-baking at a temperature of 120 ° C. for 4 minutes, and then using an oven under a nitrogen atmosphere at a temperature of 220 ° C. for 1 hour to obtain a cured film having a thickness of 7 μm. Here, the cured film is in close contact with Al. That is, a laminated structure in which a base material, Ti, Al, and a cured film are sequentially laminated is obtained. Using this laminated structure, the adhesion was evaluated in accordance with JIS D 0202. Specifically, the hardened film and Al were scratched from the surface where the hardened film in the laminated structure existed so as to form 100 squares of 1 mm square and singulated. Next, a cellophane tape was attached to the cured film. After 1 minute of adhesion, the cellophane tape was peeled from the cured film. After peeling, among the 100 squares, the number of squares remaining after the cured film and Al were not peeled and the number of squares after peeling were calculated, and this was used as the evaluation result of the PCT program at 0h. The so-called PCT program 0h means that no accelerated test has been performed. The evaluation results are shown in Table 1 below. Table 1 shows the number of squares after peeling. In the above, after the cellophane tape is adhered to the cured film, the cellophane tape is peeled from the cured film after being left at a temperature of 125 ° C., a humidity of 100%, and an air pressure of 2.3 atm for a specific time. After peeling, among the 100 squares, the number of squares remaining after the cured film and Al were not peeled and the number of squares after peeling were counted. Take this as the result of the PCT procedure evaluation at a specific time. As the time of the PCT procedure, 48h, 100h, 150h, 200h, and 300h were evaluated. The evaluation results are shown in Table 1 below. Table 1 shows the number of squares after peeling. The adhesiveness of the post-baking photosensitive resin composition and copper (Cu) was further evaluated. Specifically, instead of sputtering Al to a thickness of 0.05 μm (500 Å) on Ti, and sputtering copper (Cu) to a thickness of 0.5 μm (300 Å), the same procedure was used except for the sputtering. The method evaluated the adhesion of the photosensitive resin composition and aluminum (Al). The evaluation results are shown in Table 1 below. In addition, the evaluation results of the adhesion are all small, that is, the smaller the number of squares after peeling, the higher the adhesion between the cured film and Al and Cu. The PCT program is intended to accelerate the tester and is used to evaluate the long-term adhesion between the photosensitive resin composition after post-baking and Al and Cu.
[表1]
如上述表1所示,確認到各實施例的感光性樹脂組成物與比較例1的感光性樹脂組成物相比,對Cu、Al等金屬之接觸角小且親和性良好。又,確認到對各實施例的感光性樹脂組成物進行後烘而獲得之硬化膜與對各比較例的感光性樹脂組成物進行後烘而獲得之硬化膜相比,對Cu、Al等金屬之密接性得到提高。As shown in Table 1 above, it was confirmed that the photosensitive resin composition of each Example has a smaller contact angle with metals such as Cu and Al than the photosensitive resin composition of Comparative Example 1 and good affinity. In addition, it was confirmed that the cured film obtained by post-baking the photosensitive resin composition of each example is more resistant to metals such as Cu and Al than the cured film obtained by post-baking the photosensitive resin composition of each comparative example. The tightness is improved.
又,確認到除了上述實施例1~3以外,針對溶劑的摻合量少的感光性樹脂組成物亦能夠適當地進行塗佈,與實施例1~3同樣地,密接性得到提高,因此製備實施例4~7的感光性樹脂組成物。實施例4~7的感光性樹脂組成物的製備方法與上述實施例1~3相同。將實施例4~7的摻合比例示於下述表2中。 再者,下述表2所示之各原料的摻合比例以質量份記載。 針對所製備之實施例4~7的感光性樹脂組成物,藉由與上述實施例1~3相同的方法進行黏度、密接性的評價。此處,能夠與實施例1~3同樣地毫無問題地進行塗佈。將評價結果示於下述表2中。In addition, it was confirmed that, in addition to the above Examples 1 to 3, a photosensitive resin composition having a small blending amount of the solvent can be appropriately applied. As in Examples 1 to 3, the adhesiveness is improved, and therefore the preparation is performed. The photosensitive resin composition of Examples 4-7. The preparation method of the photosensitive resin composition of Examples 4-7 is the same as that of the said Examples 1-3. The blending ratios of Examples 4 to 7 are shown in Table 2 below. In addition, the blending ratio of each raw material shown in the following Table 2 is described in mass parts. With respect to the prepared photosensitive resin compositions of Examples 4 to 7, the same methods as those of Examples 1 to 3 were used to evaluate the viscosity and adhesion. Here, coating can be performed without any problems in the same manner as in Examples 1 to 3. The evaluation results are shown in Table 2 below.
[表2]
如上所述,確認到實施例4~7的感光性樹脂組成物與實施例1~3的感光性樹脂組成物相比,係溶劑的摻合量少者,但能夠毫無問題地進行塗佈,與實施例1~3的感光性樹脂組成物同樣地顯現出對後烘後之Cu、Al等金屬之密接性。As described above, it was confirmed that the photosensitive resin composition of Examples 4 to 7 has a smaller blending amount of the solvent than the photosensitive resin composition of Examples 1 to 3, but can be applied without any problems. In the same manner as the photosensitive resin composition of Examples 1 to 3, it exhibited adhesion to metals such as Cu and Al after post-baking.
進一步進行以下實施例8~13及比較例2的評價。實施例8~13係包含非環狀結構的醯胺化合物作為溶劑者。 首先,準備表3所示之各原料成分。接著,針對使用兩種以上的溶劑者,依據下述表3所示之摻合比例混合溶劑,並製作混合溶劑。 接著,將除溶劑以外的各原料添加到溶劑或混合溶劑中並進行攪拌,其後,藉由孔徑0.2μm的PTFE製膜濾器進行過濾,藉此獲得感光性樹脂組成物的清漆。 再者,表3的各原料的摻合比例係質量份。The evaluations of Examples 8 to 13 and Comparative Example 2 below were further performed. Examples 8 to 13 are those containing an amidamine compound having a non-cyclic structure as a solvent. First, each raw material component shown in Table 3 was prepared. Next, for those who use two or more solvents, the solvents are mixed according to the blending ratios shown in Table 3 below, and mixed solvents are prepared. Next, each raw material other than the solvent was added to a solvent or a mixed solvent and stirred, and then filtered through a PTFE membrane filter having a pore size of 0.2 μm to obtain a varnish of a photosensitive resin composition. In addition, the blending ratio of each raw material in Table 3 is a mass part.
在表3所示之各原料成分中,溶劑4係以下者。關於其他原料成分,係與表1或表2中所記載者相同。 ・溶劑4:作為非環狀結構的醯胺化合物之3-甲氧基-N,N-二甲基丙醯胺Among the raw material components shown in Table 3, the solvent 4 is the following. The other raw material components are the same as those described in Table 1 or Table 2. ・ Solvent 4: 3-methoxy-N, N-dimethylpropanamide as a fluorene compound having a non-cyclic structure
針對表3的感光性樹脂組成物,利用與實施例1~3相同的方法進行黏度、密接性的評價。此處,能夠與實施例1~3同樣地毫無問題地進行塗佈。 又,針對實施例11~13,利用與實施例1~3相同的方法測量接觸角。 將評價結果示於表3中。About the photosensitive resin composition of Table 3, the viscosity and adhesiveness were evaluated by the same method as Examples 1-3. Here, coating can be performed without any problems in the same manner as in Examples 1 to 3. In addition, for Examples 11 to 13, the contact angle was measured by the same method as in Examples 1 to 3. The evaluation results are shown in Table 3.
[表3]
如表3所示,即使在作為溶劑使用非環狀結構的醯胺化合物之情況下,對後烘後的Cu、Al等金屬之密接性顯著良好。As shown in Table 3, even when the amidine compound having a non-cyclic structure is used as a solvent, the adhesion to metals such as Cu and Al after post-baking is remarkably good.
本申請案主張基於2017年6月30日提出申請之日本申請專利特願2017-129670號之優先權,並將其揭示之全部內容併入本文中。This application claims the priority based on Japanese Patent Application No. 2017-129670 filed on June 30, 2017, and incorporates the entire disclosure thereof into this document.
30‧‧‧層間絕緣膜30‧‧‧ interlayer insulation film
32‧‧‧鈍化膜32‧‧‧ passivation film
34‧‧‧最上層配線34‧‧‧ Top-level wiring
40‧‧‧再配線層40‧‧‧ redistribution layer
42‧‧‧絕緣層42‧‧‧ Insulation
44‧‧‧絕緣層44‧‧‧ Insulation
46‧‧‧再配線46‧‧‧Re-wiring
50‧‧‧UBM層50‧‧‧UBM floor
52‧‧‧凸點52‧‧‧ bump
100‧‧‧電子裝置100‧‧‧ electronic device
圖1係表示本實施形態之電子裝置的一例之剖面圖。FIG. 1 is a cross-sectional view showing an example of an electronic device according to this embodiment.
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JPH11352676A (en) * | 1998-04-08 | 1999-12-24 | Toray Ind Inc | Positive radiosensitive resist composition and production of resist pattern using the same |
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