TWI451194B - Radiosensitive resin composition, interlayer insulation film, microlens and methods for manufacturing them - Google Patents

Radiosensitive resin composition, interlayer insulation film, microlens and methods for manufacturing them Download PDF

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TWI451194B
TWI451194B TW098136281A TW98136281A TWI451194B TW I451194 B TWI451194 B TW I451194B TW 098136281 A TW098136281 A TW 098136281A TW 98136281 A TW98136281 A TW 98136281A TW I451194 B TWI451194 B TW I451194B
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compound
acrylate
radiation
resin composition
coating film
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TW201027252A (en
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Yoshinori Kinoshita
Masaaki Hanamura
Takashi Doi
Hideaki Takase
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Jsr Corp
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感放射線性樹脂組成物、層間絕緣膜與微透鏡及其製法Radiation-sensitive linear resin composition, interlayer insulating film and microlens and preparation method thereof

本發明係關於感放射線性樹脂組成物、層間絕緣膜和微透鏡以及它們的製造方法。The present invention relates to a radiation sensitive resin composition, an interlayer insulating film, and a microlens, and a method of manufacturing the same.

薄膜電晶體(以下稱為“TFT”)型液晶顯示元件及磁頭元件、積體電路元件、固體攝影元件等電子部件，通常在層狀佈置的配線之間設置絕緣用的層間絕緣膜。作為形成層間絕緣膜的材料由於獲得必要圖案形狀所需的步驟少，且具有足夠的平坦性的材料而為佳，所以感放射線性樹脂組成物被廣泛地使用(參照日本特開2001-354822號公報、日本特開2001-343743號公報)。In a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, an electronic component such as a magnetic head element, an integrated circuit element, or a solid-state imaging element, an interlayer insulating film for insulation is usually provided between the wirings arranged in layers. The material for forming the interlayer insulating film is preferably a material having a sufficient pattern and having a sufficient flatness, so that the radiation-sensitive resin composition is widely used (refer to Japanese Patent Laid-Open No. 2001-354822). Bulletin, Japanese Laid-Open Patent Publication No. 2001-343743.

上述電子部件中，例如TFT型液晶顯示元件，要經過在層間絕緣膜上形成透明電極膜，再在其上形成液晶取向膜的步驟而製造。因此，層間絕緣膜在透明電極膜形成步驟中要經受高溫條件，並且電極圖案形成時所使用之光阻被暴露於剝離液中，因此必須具有足夠的耐熱性和耐溶劑性。Among the above-mentioned electronic components, for example, a TFT-type liquid crystal display device is produced by a step of forming a transparent electrode film on an interlayer insulating film and forming a liquid crystal alignment film thereon. Therefore, the interlayer insulating film is subjected to high temperature conditions in the transparent electrode film forming step, and the photoresist used in the formation of the electrode pattern is exposed to the stripping liquid, and therefore it is necessary to have sufficient heat resistance and solvent resistance.

並且，近年來，TFT型液晶顯示元件正處於大螢幕化、高亮度化、高精細化、快速回應化、薄型化等的趨勢。因此，作為TFT型液晶顯示元件中所用的層間絕緣膜形成用組成物，要求具有高敏感度，並且，所形成的層間絕緣膜，要求具有比以往更優越的低介電常數、高透光率等的高性能。Further, in recent years, TFT liquid crystal display elements are in a trend of large screen, high brightness, high definition, fast response, and thinning. Therefore, a composition for forming an interlayer insulating film used in a TFT-type liquid crystal display device is required to have high sensitivity, and the interlayer insulating film to be formed is required to have a lower dielectric constant and a higher transmittance than those conventionally. High performance.

另外，作為傳真機、電子影印機、固體攝影元件等片裝彩色濾光片的成像光學系統或者光纖連接器的光學系統材料，使用具有3～100μm左右透鏡直徑的微透鏡，或者將這些微透鏡按規則排列而成的微透鏡陣列。Further, as an optical system material of an imaging optical system or an optical fiber connector of a chip-mounted color filter such as a facsimile machine, an electronic photocopier, or a solid-state imaging device, a microlens having a lens diameter of about 3 to 100 μm or a microlens is used. A microlens array arranged in a regular order.

微透鏡或者微透鏡陣列的形成，已知有：在形成相當於透鏡的透鏡圖案後，通過加熱處理使其進行熔融流動後直接作為透鏡使用的方法，或者將由熔融流動的透鏡圖案作為遮罩，通過乾式蝕刻向底層轉印透鏡形狀的方法等。在上述透鏡圖案的形成中，感放射線性樹脂組成物被廣泛使用(參照日本特開平6-18702號公報、日本特開平6-136239號公報)。In the formation of a microlens or a microlens array, a method of forming a lens pattern corresponding to a lens, forming a lens pattern by a heat treatment, and directly using it as a lens, or using a lens pattern of a molten flow as a mask, is known. A method of transferring a lens shape to a bottom layer by dry etching or the like. In the formation of the above-mentioned lens pattern, the radiation-sensitive resin composition is widely used (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

然而，如上所述的微透鏡或微透鏡陣列形成的元件，為了之後除去作為配線形成部分的焊接區上的各種絕緣膜，要塗布平坦化膜和蝕刻用光阻膜，再用所需遮罩進行曝光、顯影，以除去焊接區部分的蝕刻光阻膜，然後，通過蝕刻除去平坦化膜和各種絕緣膜，將焊接區部分供給曝光步驟。因此，微透鏡或者微透鏡陣列在平坦化膜和蝕刻光阻膜的塗布形成步驟以及蝕刻步驟中，必須具有耐溶劑性和耐熱性。However, in the element formed by the microlens or the microlens array as described above, in order to remove various insulating films on the land as the wiring forming portion, the planarizing film and the etching photoresist film are applied, and the desired mask is used. Exposure and development are performed to remove the etched photoresist film of the land portion, and then the planarization film and various insulating films are removed by etching, and the land portion is supplied to the exposure step. Therefore, the microlens or microlens array must have solvent resistance and heat resistance in the coating forming step and the etching step of the planarizing film and the etching photoresist film.

形成這種微透鏡所用的感放射線性樹脂組成物要求具有高敏感度。並且，由其形成的微透鏡要求具有所需的曲率半徑，並具有高耐熱性及高透光率等。The radiation sensitive resin composition used to form such a microlens is required to have high sensitivity. Further, the microlens formed therefrom is required to have a desired radius of curvature, and has high heat resistance, high light transmittance, and the like.

此外，如上所述而製得的層間絕緣膜和微透鏡，在其形成時的顯影步驟中，如果顯影時間哪怕是稍微超出最佳時間，則在圖案與基板之間很容易發生顯影液滲透而導致脫落。因此，必須嚴格控制顯影時間，並且製品的成品率方面很成問題。Further, in the development step at the time of formation of the interlayer insulating film and the microlens produced as described above, if the development time is slightly more than the optimum time, the developer penetration easily occurs between the pattern and the substrate. Causes falling off. Therefore, the development time must be strictly controlled, and the yield of the product is very problematic.

這樣，在由感放射線性樹脂組成物形成層間絕緣膜和微透鏡時，該組成物要求對放射線具有高敏感度。並且，要求能夠容易地形成顯示出即使在顯影步驟中顯影時間超出所定時間時也不會發生圖案的脫落的良好貼緊性的圖案狀薄膜。而且，由該組成物形成的層間絕緣膜要求具有高耐熱性、高耐溶劑性、低介電常數、高透光率等。另外，當形成微透鏡時，作為微透鏡要求具有良好的熔融形狀(是指具有所需曲率半徑的半凸透鏡形狀)。但是，滿足這種要求的感放射線性樹脂組成物還是未知的。近年來，在眾多所需的物性項目中，特別是為了使其能夠在短時間內形成更微小的圖案，高解析度、高敏感度的感放射線性樹脂組成物的開發已成為重要課題。Thus, when an interlayer insulating film and a microlens are formed from a radiation sensitive resin composition, the composition is required to have high sensitivity to radiation. Further, it is required to be able to easily form a pattern-like film which exhibits good adhesion without causing the pattern to fall off even when the development time exceeds the predetermined time in the development step. Further, the interlayer insulating film formed of the composition is required to have high heat resistance, high solvent resistance, low dielectric constant, high light transmittance, and the like. In addition, when a microlens is formed, it is required to have a good melt shape as a microlens (refer to a semi-convex lens shape having a desired radius of curvature). However, a radiation sensitive resin composition that satisfies such requirements is still unknown. In recent years, development of a high-resolution, high-sensitivity radiation-sensitive resin composition has become an important issue among many required physical property items, particularly in order to make it possible to form a finer pattern in a short time.

另外，在日本第3965868號專利中，公開了含有由具有至少一個乙烯性不飽和雙鍵的聚合性化合物形成的共聚物的感放射線性樹脂組成物。在該專利中，作為具有至少一個乙烯性不飽和雙鍵的聚合性化合物的例子，列舉了單官能(甲基)丙烯酸酯、二官能(甲基)丙烯酸酯、三官能以上的(甲基)丙烯酸酯，而對於其中通過具有特定結構的聚合性化合物能夠達到改善放射線敏感度的目的，沒有任何描述。另外，在韓國申請公開第2003-0010893號公報中，公開了含有具有二季戊四醇骨架的丙烯酸酯的感光性樹脂組成物。但是，在該公報中，涉及的是特定於具有二季戊四醇骨架的丙烯酸酯的技術，沒有涉及含有具有其以外的骨架的丙烯酸酯的組成物。Further, in Japanese Patent No. 3965868, a radiation-sensitive resin composition containing a copolymer formed of a polymerizable compound having at least one ethylenically unsaturated double bond is disclosed. In this patent, examples of the polymerizable compound having at least one ethylenically unsaturated double bond include a monofunctional (meth) acrylate, a difunctional (meth) acrylate, and a trifunctional or higher (meth) group. Acrylate, and there is no description for the purpose of improving radiation sensitivity by a polymerizable compound having a specific structure. In the Korean Patent Application Publication No. 2003-0010893, a photosensitive resin composition containing an acrylate having a dipentaerythritol skeleton is disclosed. However, this publication relates to a technique specific to an acrylate having a dipentaerythritol skeleton, and does not relate to a composition containing an acrylate having a skeleton other than the above.

先前技術文獻Prior technical literature

專利文獻1　日本特開2001-354822號公報Patent Document 1 Japanese Patent Laid-Open Publication No. 2001-354822

專利文獻2　日本特開2001-343743號公報Patent Document 2 Japanese Patent Laid-Open Publication No. 2001-343743

專利文獻3　日本特開平6-18702號公報Patent Document 3 Japanese Patent Laid-Open No. 6-187802

專利文獻4　日本特開平6-136239號公報Patent Document 4 Japanese Patent Laid-Open No. 6-136239

專利文獻5　日本第3965868號專利Patent Document 5 Japanese Patent No. 3965868

專利文獻6　韓國專利申請公開第2003-0010893號公報。Patent Document 6 Korean Patent Application Publication No. 2003-0010893.

本發明是基於現有技術中的這些問題而作出的，其第一目的是提供一種感放射線性樹脂組成物，其對放射線具有高敏感度，具有在顯影步驟中即使超出最佳顯影時間也能夠確保更好圖案形狀的貼緊性的顯影裕度(是指顯影時間的允許範圍)，能夠容易地形成貼緊性優良的圖案狀薄膜。The present invention has been made in view of these problems in the prior art, and a first object thereof is to provide a radiation sensitive resin composition which has high sensitivity to radiation and which can be ensured even if the optimum development time is exceeded in the developing step. The development margin of the adhesion of the pattern shape is better (refer to the allowable range of the development time), and the pattern-like film excellent in adhesion can be easily formed.

本發明的第二目的是提供一種感放射線性樹脂組成物，其在用於形成層間絕緣膜時，能夠形成具有高耐熱性、高耐溶劑性、高透光率、低介電常數的層間絕緣膜，並且在用於形成微透鏡時，能夠形成具有高透光率和良好的熔融形狀的微透鏡。A second object of the present invention is to provide a radiation sensitive resin composition capable of forming interlayer insulation having high heat resistance, high solvent resistance, high light transmittance, and low dielectric constant when used for forming an interlayer insulating film. The film, and when used to form a microlens, is capable of forming a microlens having high light transmittance and a good melt shape.

本發明的第三目的是提供一種用上述感放射線性樹脂組成物形成層間絕緣膜和微透鏡的方法，以及由該方法形成的層間絕緣膜和微透鏡。A third object of the present invention is to provide a method of forming an interlayer insulating film and a microlens using the above-described radiation-sensitive resin composition, and an interlayer insulating film and a microlens formed by the method.

本發明的第一目的由一種感放射線性樹脂組成物達成，其含有：The first object of the present invention is achieved by a radiation sensitive resin composition comprising:

[A]鹼可溶性樹脂；[A] an alkali soluble resin;

[B]1,2-醌二疊氮化合物；以及[B] 1,2-quinonediazide compound;

[C]分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的化合物。[C] A compound having at least one ethylenically unsaturated bond in the molecule and having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton.

該感放射線性樹脂組成物由於含有上述[A]、[B]和[C]的特定成分，因而具有高的放射線敏感度，在顯影步驟中對於圖案脫落具有顯影時間裕度，能夠容易地形成貼緊性優良的圖案狀薄膜。The radiation sensitive resin composition has high radiation sensitivity due to the specific components of the above [A], [B], and [C], and has a development time margin for pattern peeling in the development step, and can be easily formed. A pattern-like film with excellent adhesion.

上述[A]成分的鹼可溶性樹脂，為含有(a1)不飽和羧酸及/或不飽和羧酸酐與(a2)具有環氧基之不飽和化合物的不飽和化合物之共聚物即可。另外，上述[C]成分的化合物所具有的乙烯性不飽和鍵，典型地為丙烯酸酯或甲基丙烯酸酯的乙烯性不飽和鍵即可。藉由含有這種化合物的樹脂組成物，能夠發揮高放射線敏感度等良好的性能。The alkali-soluble resin of the above [A] component may be a copolymer containing an unsaturated compound of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and (a2) an unsaturated compound having an epoxy group. Further, the ethylenically unsaturated bond of the compound of the above [C] component may be an ethylenically unsaturated bond of an acrylate or a methacrylate. By the resin composition containing such a compound, it is possible to exhibit excellent performance such as high radiation sensitivity.

本發明的第二目的通過將上述感放射線性樹脂組成物用於形成層間絕緣膜或微透鏡而達成。另外，本發明的第三目的由包括以下步驟的層間絕緣膜或微透鏡的形成方法，以及由該方法形成的層間絕緣膜或微透鏡達成。A second object of the present invention is achieved by using the above-described radiation sensitive resin composition for forming an interlayer insulating film or a microlens. Further, the third object of the present invention is achieved by a method of forming an interlayer insulating film or a microlens comprising the following steps, and an interlayer insulating film or microlens formed by the method.

(1)在基板上形成該感放射線性樹脂組成物塗膜的步驟，(1) a step of forming a coating film of the radiation sensitive resin composition on a substrate,

(2)對步驟(1)中形成的塗膜的至少一部分照射放射線的步驟，(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(3)將步驟(2)中照射放射線後的塗膜進行顯影的步驟，和(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4)將步驟(3)中顯影後的塗膜進行加熱的步驟。(4) A step of heating the coating film developed in the step (3).

由上述方法形成的層間絕緣膜和微透鏡滿足所有所需的各種性能。也就是說，由本方法形成的層間絕緣膜具有高耐熱性、高耐溶劑性、高透光率、低介電常數，並且由本方法形成的微透鏡具有高透光率和良好的熔融形狀。The interlayer insulating film and the microlens formed by the above method satisfy all the various properties required. That is, the interlayer insulating film formed by the present method has high heat resistance, high solvent resistance, high light transmittance, low dielectric constant, and the microlens formed by the present method has high light transmittance and a good melt shape.

本發明的感放射線性樹脂組成物，具有高的放射線敏感度，具有在顯影步驟中即使超出最佳顯影時間也能夠確保更好圖案形狀的貼緊性的顯影裕度，能夠容易地形成貼緊性優良的圖案狀薄膜。並且，由該組成物形成的本發明層間絕緣膜，對基板的貼緊性良好，具有優良的耐溶劑性和耐熱性以及高透光率和低介電常數。因此，該層間絕緣膜可適用於電子產品。另外，由該組成物形成的本發明微透鏡，對基板的貼緊性良好，具有優良的耐溶劑性和耐熱性以及高透光率和良好的熔融形狀。因此，該微透鏡可適合作為固體攝影元件的微透鏡使用。The radiation sensitive resin composition of the present invention has high radiation sensitivity and has a development margin capable of ensuring a better pattern shape even if the optimum development time is exceeded in the development step, and can be easily formed in close contact with each other. Excellent pattern film. Further, the interlayer insulating film of the present invention formed of the composition has good adhesion to the substrate, and has excellent solvent resistance and heat resistance, high light transmittance, and low dielectric constant. Therefore, the interlayer insulating film can be applied to an electronic product. Further, the microlens of the present invention formed of the composition has good adhesion to the substrate, and has excellent solvent resistance and heat resistance, high light transmittance, and good melt shape. Therefore, the microlens can be suitably used as a microlens of a solid-state imaging element.

實施發明之形態Form of implementing the invention

以下，對本發明的感放射線性樹脂組成物中所含的[A]～[C]成分以及其他任選成分進行詳細說明。Hereinafter, the [A] to [C] components and other optional components contained in the radiation sensitive resin composition of the present invention will be described in detail.

I．[A]成分I. [A] component

作為本發明中的[A]鹼可溶性樹脂，只要是在含該成分的感放射線性樹脂組成物的顯影處理步驟中對於所用的鹼顯影液具有可溶性，則對其沒有特別的限制。作為這種鹼可溶性樹脂，較佳為(a1)不飽和羧酸及/或不飽和羧酸酐及能夠與其共聚合的其他不飽和化合物之共聚物，更佳為含有(a1)不飽和羧酸及/或不飽和羧酸酐、及(a2)具有環氧基之不飽和化合物的不飽和化合物之共聚物(以下將含有化合物(a1)和化合物(a2)的不飽和化合物之共聚物稱為“共聚物[A]”)。共聚物[A]可通過在溶劑中，在聚合引發劑的存在下，將化合物(a1)和含有化合物(a2)的不飽和化合物進行自由基聚合而製備。另外，在共聚物[A]的製備中，還可以將化合物(a1)和化合物(a2)與作為化合物(a3)的上述(a1)和(a2)以外的不飽和化合物一起進行自由基聚合。共聚物[A]中，基於由化合物(a1)和(a2)(以及任意的化合物(a3))衍生的構成單元的合計量，較佳係含有5～40質量%由化合物(a1)衍生的構成單元，特佳係含有5～25質量%。通過使共聚物[A]中由化合物(a1)衍生的構成單元為5質量%以上，在顯影步驟中可以獲得對於鹼性水溶液的充分溶解性。另一方面，通過使共聚物[A]中該構成單元為40質量%以下，可以防止對於鹼性水溶液的溶解性過大。The [A] alkali-soluble resin in the present invention is not particularly limited as long as it is soluble in the alkali developer to be used in the development treatment step of the radiation-sensitive resin composition containing the component. The alkali-soluble resin is preferably a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and another unsaturated compound copolymerizable therewith, and more preferably contains (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, and (a2) a copolymer of an unsaturated compound having an epoxy group-containing unsaturated compound (hereinafter, a copolymer containing an unsaturated compound of the compound (a1) and the compound (a2) is referred to as "copolymerization". [A]"). The copolymer [A] can be produced by radically polymerizing the compound (a1) and the unsaturated compound containing the compound (a2) in the presence of a polymerization initiator in a solvent. Further, in the preparation of the copolymer [A], the compound (a1) and the compound (a2) may be subjected to radical polymerization together with the unsaturated compound other than the above (a1) and (a2) as the compound (a3). In the copolymer [A], the total amount of the constituent units derived from the compounds (a1) and (a2) (and any compound (a3)) is preferably 5 to 40% by mass derived from the compound (a1). The constituent unit is particularly preferably contained in an amount of 5 to 25% by mass. When the constituent unit derived from the compound (a1) in the copolymer [A] is 5% by mass or more, sufficient solubility for an alkaline aqueous solution can be obtained in the developing step. On the other hand, when the structural unit in the copolymer [A] is 40% by mass or less, the solubility in an alkaline aqueous solution can be prevented from being excessively large.

化合物(a1)是具有自由基聚合性的不飽和羧酸及/或不飽和羧酸酐。作為化合物(a1)的具體例子，可以列舉單羧酸、二羧酸、二羧酸酐、多元羧酸的單[(甲基)丙烯醯氧基烷基]酯、兩末端具有羧基和羥基的聚合物的單(甲基)丙烯酸酯、具有羧基的多環式化合物及其酸酐等。The compound (a1) is a radically polymerizable unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride. Specific examples of the compound (a1) include a monocarboxylic acid, a dicarboxylic acid, a dicarboxylic anhydride, a mono[(meth)acryloxyalkylalkyl]ester of a polyvalent carboxylic acid, and a polymerization of a carboxyl group and a hydroxyl group at both terminals. Mono (meth) acrylate, polycyclic compound having a carboxyl group, an acid anhydride thereof, and the like.

作為其具體例子，單羧酸可以列舉丙烯酸、甲基丙烯酸、巴豆酸等；二羧酸可以列舉馬來酸、富馬酸、檸康酸、中康酸、衣康酸等；二羧酸酐可以列舉作為上述二羧酸而例示的化合物的酸酐等；多元羧酸的單[(甲基)丙烯醯氧基烷基]酯可以列舉琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等；兩末端具有羧基和羥基的聚合物的單(甲基)丙烯酸酯可以列舉ω-羧基聚己內酯的單(甲基)丙烯酸酯等；具有羧基的多環式化合物及其酸酐可以列舉5-羧基二環[2.2.1]庚-2-烯、5,6-二羧基二環[2.2.1]庚-2-烯、5-羧基-5-甲基二環[2.2.1]庚-2-烯、5-羧基-5-乙基二環[2.2.1]庚-2-烯、5-羧基-6-甲基二環[2.2.1]庚-2-烯、5-羧基-6-乙基二環[2.2.1]庚-2-烯、5,6-二羧基二環[2.2.1]庚-2-烯酸酐等。Specific examples of the monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid; and the dicarboxylic acid may, for example, be maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, or the like; An acid anhydride or the like of the compound exemplified as the above dicarboxylic acid is exemplified; a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid may be exemplified by succinic acid mono [2-(methyl) propylene methoxyethyl group. An ester, a mono[2-(methyl)propenyloxyethyl] phthalate, or the like; a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, and an ω-carboxy polycap The ester mono-(meth) acrylate or the like; the polycyclic compound having a carboxyl group and an acid anhydride thereof may, for example, be 5-carboxybicyclo[2.2.1]hept-2-ene or 5,6-dicarboxybicyclo[2.2. 1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] Hept-2-ene anhydride and the like.

這些化合物(a1)中，較佳係使用單羧酸、二羧酸酐。從共聚合反應性、對於鹼性水溶液的溶解性和容易獲得性方面考慮，特佳係使用丙烯酸、甲基丙烯酸、馬來酸酐。這些化合物(a1)可以單獨或兩種以上組合使用。Among these compounds (a1), a monocarboxylic acid or a dicarboxylic anhydride is preferably used. From the viewpoints of copolymerization reactivity, solubility to an alkaline aqueous solution, and easy availability, it is particularly preferable to use acrylic acid, methacrylic acid, and maleic anhydride. These compounds (a1) may be used alone or in combination of two or more.

共聚物[A]中，基於由化合物(a1)和(a2)(以及任意的化合物(a3))衍生的構成單元的合計量，較佳係含有10～80質量%由化合物(a2)衍生的構成單元，特佳係含有30～80質量%。通過使共聚物[A]中由化合物(a2)衍生的構成單元為10質量%以上，可以抑制所得層間絕緣膜和微透鏡的耐熱性、表面硬度和耐剝離液性的下降。另一方面，通過使共聚物[A]中該構成單元為80質量%以下，可以使感放射線性樹脂組成物的保存穩定性保持在適當的範圍內。In the copolymer [A], the total amount of the constituent units derived from the compounds (a1) and (a2) (and any compound (a3)) is preferably 10 to 80% by mass derived from the compound (a2). The constituent unit is particularly preferably contained in an amount of 30 to 80% by mass. When the constituent unit derived from the compound (a2) in the copolymer [A] is 10% by mass or more, the heat resistance, surface hardness, and peeling resistance of the obtained interlayer insulating film and the microlens can be suppressed from decreasing. On the other hand, when the structural unit in the copolymer [A] is 80% by mass or less, the storage stability of the radiation-sensitive resin composition can be maintained within an appropriate range.

化合物(a2)是具有自由基聚合性的具有環氧基之不飽和化合物(包括具有氧雜環丁基的不飽和化合物)。作為具有環氧基之不飽和化合物的具體例子，可以列舉丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧基丁基酯、甲基丙烯酸-3,4-環氧基丁基酯、丙烯酸-6,7-環氧基庚基酯、甲基丙烯酸-6,7-環氧基庚基酯、α-乙基丙烯酸-6,7-環氧基庚基酯、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄基縮水甘油基醚、甲基丙烯酸-3,4-環氧基環己基酯等。The compound (a2) is an epoxy group-containing unsaturated compound having a radical polymerizable property (including an unsaturated compound having an oxetanyl group). Specific examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α-n-butyl Glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid -6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, pair Vinylbenzyl glycidyl ether, -3,4-epoxycyclohexyl methacrylate, and the like.

這些具有環氧基之不飽和化合物中，從提高共聚合反應性和所得層間絕緣膜或微透鏡的耐熱性和表面硬度的方面考慮，較佳係使用甲基丙烯酸縮水甘油酯、甲基丙烯酸-6,7-環氧基庚基酯、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄基縮水甘油基醚、甲基丙烯酸-3,4-環氧基環己基酯等。Among these epoxy group-containing unsaturated compounds, glycidyl methacrylate and methacrylic acid are preferably used from the viewpoint of improving copolymerization reactivity and heat resistance and surface hardness of the resulting interlayer insulating film or microlens. 6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid-3,4-ring Oxycyclohexyl ester and the like.

作為具有氧雜環丁基的不飽和化合物的具體例子，可以列舉3-(丙烯醯氧基甲基)氧雜環丁烷、3-(丙烯醯氧基甲基)-2-甲基氧雜環丁烷、3-(丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-苯基氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2-二氟氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(2-丙烯醯氧基乙基)氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-乙基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-3-乙基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-三氟甲基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-五氟乙基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-苯基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2,2-二氟氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的丙烯酸酯；3-(甲基丙烯醯氧基甲基)氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-苯基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2-二氟氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-乙基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-3-乙基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-三氟甲基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-五氟乙基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-苯基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2,2-二氟氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的甲基丙烯酸酯等。這些化合物(a2)可以單獨或兩種以上組合使用。Specific examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-2-methyloxalate. Cyclobutane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3- (propylene methoxymethyl)-2-pentafluoroethyl oxetane, 3-(acryloxymethyl)-2-phenyl oxetane, 3-(acrylomethoxy group -2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl) -2,2,4,4-tetrafluorooxetane, 3-(2-propenyloxyethyl)oxetane, 3-(2-propenyloxyethyl)-2- Ethyloxetane, 3-(2-propenyloxyethyl)-3-ethyloxetane, 3-(2-propenyloxyethyl)-2-trifluoromethyl Oxetane, 3-(2-propenyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-propenyloxyethyl)-2-phenyloxalate Cyclobutane, 3-(2-propenyloxyethyl)-2,2-difluorooxetane, 3-(2-propenyloxyethyl)-2,2,4-trifluoro Oxetane Acrylate of 3-(2-propenyloxyethyl)-2,2,4,4-tetrafluorooxetane; 3-(methacryloxymethyl)oxetane , 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-( Methyl propylene methoxymethyl)-2-trifluoromethyl oxetane, 3-(methacryloxymethyl)-2-pentafluoroethyl oxetane, 3-( Methyl propylene methoxymethyl)-2-phenyl oxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methyl Propylene methoxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane , 3-(2-methylpropenyloxyethyl)oxetane, 3-(2-methylpropenyloxyethyl)-2-ethyloxetane, 3-(2 -Methethyloxyethyl)-3-ethyloxetane, 3-(2-methylpropenyloxyethyl)-2-trifluoromethyloxetane, 3- (2-methacryloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methylpropenyloxyethyl)-2-phenyloxetane, 3-(2-methacryl oxime Oxyethyl)-2,2-difluorooxetane, 3-(2-methylpropenyloxyethyl)-2,2,4-trifluorooxetane, 3-( A methacrylate such as 2-methylpropenyloxyethyl)-2,2,4,4-tetrafluorooxetane or the like. These compounds (a2) may be used alone or in combination of two or more.

化合物(a3)只要是上述化合物(a1)和化合物(a2)以外的、具有自由基聚合性的不飽和化合物，則對其沒有特別的限制。作為化合物(a3)的例子，可以列舉甲基丙烯酸鏈狀烷基酯、甲基丙烯酸環狀烷基酯、具有羥基的甲基丙烯酸酯、丙烯酸環狀烷基酯、甲基丙烯酸芳基酯、丙烯酸芳基酯、不飽和二羧酸二酯、二環不飽和化合物、馬來醯亞胺化合物、不飽和芳香族化合物、共軛二烯、具有四氫呋喃骨架、呋喃骨架、四氫吡喃骨架、吡喃骨架、下述式(1)表示的骨架的不飽和化合物、具有下述式(2)表示的酚性羥基的不飽和化合物以及其他的不飽和化合物。The compound (a3) is not particularly limited as long as it is a radical polymerizable unsaturated compound other than the above compound (a1) and the compound (a2). Examples of the compound (a3) include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a methacrylate having a hydroxyl group, a cyclic alkyl acrylate, and an aryl methacrylate. Aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, An unsaturated compound having a pyran skeleton, a skeleton represented by the following formula (1), an unsaturated compound having a phenolic hydroxyl group represented by the following formula (2), and another unsaturated compound.

(式(1)中，R7 為氫原子或甲基，n為1以上的整數)。(In the formula (1), R 7 is a hydrogen atom or a methyl group, and n is an integer of 1 or more).

(式(2)中，R1 為氫原子或碳原子數為1～4的烷基，R2 ～R6 相同或不同，為氫原子、羥基或碳原子數為1～4的烷基，B為單鍵、-COO-、或-CONH-，m為0～3的整數，其中，R2 ～R6 中至少一者為羥基)。In the formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 2 to R 6 are the same or different and each is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. B is a single bond, -COO-, or -CONH-, and m is an integer of 0 to 3, and at least one of R 2 to R 6 is a hydroxyl group).

作為化合物(a3)的具體例子，甲基丙烯酸鏈狀烷基酯可以列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁基酯、甲基丙烯酸第二丁基酯、甲基丙烯酸第三丁基酯、甲基丙烯酸2-乙基己基酯、甲基丙烯酸異癸基酯、甲基丙烯酸正十二烷基酯、甲基丙烯酸十三烷基酯、甲基丙烯酸正十八烷基酯等；甲基丙烯酸環狀烷基酯可以列舉甲基丙烯酸環己基酯、甲基丙烯酸2-甲基環己基酯、甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯、甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基氧基乙基酯、甲基丙烯酸異冰片基酯等；具有羥基的甲基丙烯酸酯可以列舉甲基丙烯酸羥基甲酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸3-羥基丙酯、甲基丙烯酸4-羥基丁酯、二甘醇單甲基丙烯酸酯、甲基丙烯酸2,3-二羥基丙酯、2-甲基丙烯醯氧基乙基糖苷、甲基丙烯酸4-羥基苯基酯等；丙烯酸環狀烷基酯可以列舉丙烯酸環己基酯、丙烯酸2-甲基環己基酯、丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯、丙烯酸三環[5.2.1.02,6 ]癸烷-8-基氧基乙基酯、丙烯酸異冰片基酯等；甲基丙烯酸芳基酯可以列舉甲基丙烯酸苯基酯、甲基丙烯酸苄基酯等；丙烯酸芳基酯可以列舉丙烯酸苯基酯、丙烯酸苄基酯等；不飽和二羧酸二酯可以列舉馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等；二環不飽和化合物可以列舉二環[2.2.1]庚-2-烯、5-甲基二環[2.2.1]庚-2-烯、5-乙基二環[2.2.1]庚-2-烯、5-甲氧基二環[2.2.1]庚-2-烯、5-乙氧基二環[2.2.1]庚-2-烯、5,6-二甲氧基二環[2.2.1]庚-2-烯、5,6-二乙氧基二環[2.2.1]庚-2-烯、5-第三丁氧羰基二環[2.2.1]庚-2-烯、5-環己基氧基羰基二環[2.2.1]庚-2-烯、5-苯氧基羰基二環[2.2.1]庚-2-烯、5,6-二(第三丁氧羰基)二環[2.2.1]庚-2-烯、5,6-二(環己基氧基羰基)二環[2.2.1]庚-2-烯、5-(2’-羥基乙基)二環[2.2.1]庚-2-烯、5,6-二羥基二環[2.2.1]庚-2-烯、5,6-二(羥基甲基)二環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)二環[2.2.1]庚-2-烯、5-羥基-5-甲基二環[2.2.1]庚-2-烯、5-羥基-5-乙基二環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基二環[2.2.1]庚-2-烯等；馬來醯亞胺化合物可以列舉N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-(4-羥基苯基)馬來醯亞胺、N-(4-羥基苄基)馬來醯亞胺、N-琥珀醯亞胺基-3-馬來醯亞胺基苯甲酸酯、N-琥珀醯亞胺基-4-馬來醯亞胺基丁酸酯、N-琥珀醯亞胺基-6-馬來醯亞胺基己酸酯、N-琥珀醯亞胺基-3-馬來醯亞胺基丙酸酯、N-(9-吖啶基)馬來醯亞胺等；不飽和芳香族化合物可以列舉苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯等；共軛二烯可以列舉1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等；具有四氫呋喃骨架的不飽和化合物可以列舉(甲基)丙烯酸四氫糠基酯、2-甲基丙烯醯氧基-丙酸四氫糠基酯、3-(甲基)丙烯醯氧基四氫呋喃-2-酮等；具有呋喃骨架的不飽和化合物可以列舉2-甲基-5-(3-呋喃基)-1-戊烯-3-酮、(甲基)丙烯酸糠基酯、1-呋喃-2-丁基-3-烯-2-酮、1-呋喃-2-丁基-3-甲氧基-3-烯-2-酮、6-(2-呋喃基)-2-甲基-1-己烯-3-酮、6-呋喃-2-基-己-1-烯-3-酮、丙烯酸2-呋喃-2-基-1-甲基-乙基酯、6-(2-呋喃基)-6-甲基-1-庚烯-5-酮等；具有四氫吡喃骨架的不飽和化合物可以列舉甲基丙烯酸(四氫吡喃-2-基)甲基酯、2,6-二甲基-8-(四氫吡喃-2-基氧基)-辛-1-烯-3-酮、2-甲基丙烯酸四氫吡喃-2-基酯、1-(四氫吡喃-2-氧基)-丁基-3-烯-2-酮等；具有吡喃骨架的不飽和化合物可以列舉4-(1,4-二氧雜-5-氧代-6-庚烯基)-6-甲基-2-吡喃、4-(1,5-二氧雜-6-氧代-7-辛烯基)-6-甲基-2-吡喃等；具有上述式(1)表示的骨架的不飽和化合物可以列舉聚乙二醇(n=2~10)單(甲基)丙烯酸酯、聚丙二醇(n=2~10)單(甲基)丙烯酸酯等；另外，作為具有酚骨架的不飽和化合物，由上述式(2)表示的化合物，根據B與m的定義，可以列舉下述式(3)～(7)表示的化合物等。Specific examples of the compound (a3) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, and methyl group. Tert-butyl acrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, tridecyl methacrylate, methacrylic acid Alkyl esters and the like; methacrylic acid cyclic alkyl esters may, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, trimethyl methacrylate [5.2.1.0 2,6 ]decane-8 - a base ester, a tricyclo[cyclopropyl] methacrylate [5.2.1.0 2,6 ]decane-8-yloxyethyl ester, an isobornyl methacrylate, etc.; a methacrylate having a hydroxyl group may be methacrylic acid Hydroxymethyl ester, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate Ester, 2-methacryloxyethyl glucoside, 4-hydroxyphenyl methacrylate, etc.; Include acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6] decan-8-yl acrylate, tricyclo [5.2.1.0 2,6] decane -8 - ethoxyethyl ester, isobornyl acrylate or the like; aryl methacrylate may, for example, be phenyl methacrylate or benzyl methacrylate; and aryl acrylate may, for example, be phenyl acrylate or acrylic acid. The benzyl ester or the like; the unsaturated dicarboxylic acid diester may, for example, be diethyl maleate, diethyl fumarate or diethyl itaconate; and the bicyclic unsaturated compound may be bicyclo[2.2.1] Hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2. 1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6 -Diethoxybicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2. 1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2- Alkene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5- (2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl) Bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[ 2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]heptane- 2-ene and the like; the maleimide compound may, for example, be N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-(4-hydroxybenzene Methyl quinone imine, N-(4-hydroxybenzyl) maleimide, N-amber succinimide-3-maleimido benzoate, N-succinimide Base-4-maleimido butyrate, N-succinimide-6-maleimidohexanoate, N-succinimide-3-maleimido Propionate, N-(9-acridinyl)maleimide, etc.; unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and ethylene. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth)acrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, and 3-(meth)acryloxytetrahydrofuran-2. a ketone or the like; an unsaturated compound having a furan skeleton; 2-methyl-5-(3-furyl)-1-penten-3-one, decyl (meth)acrylate, 1-furan-2 -butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1 -hexen-3-one, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furan (6)-methyl-1-hepten-5-one or the like; an unsaturated compound having a tetrahydropyran skeleton, which may be exemplified by (tetrahydropyran-2-yl)methyl methacrylate, 2,6 -Dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, 2-tetrahydropyran-2-yl methacrylate, 1-(tetrahydrogen) Pyran-2-oxy)-butyl-3-en-2-one and the like; an unsaturated compound having a pyran skeleton can be exemplified by 4-(1,4-dioxa-5-oxo-6-heptane Alkenyl)-6-methyl-2-pyran, 4-(1,5-dioxa-6-oxo-7-octenyl)-6-methyl-2-pyran, etc.; Formula (1) Examples of the unsaturated compound of the skeleton include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, and the like; The unsaturated compound of the skeleton, the compound represented by the above formula (2), and the compounds represented by the following formulas (3) to (7), and the like, may be exemplified by the definitions of B and m.

(式(3)中，p為1～3的整數，R1 、R2 、R3 、R4 、R5 和R6 的定義與上述式(2)中的定義相同)。(In the formula (3), p is an integer of 1 to 3, and the definitions of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as defined in the above formula (2)).

(式(4)中，R1 、R2 、R3 、R4 、R5 和R6 的定義與上述式(2)中的定義相同)。(In the formula (4), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as defined in the above formula (2)).

(式(5)中，q為1～3的整數，R1 、R2 、R3 、R4 、R5 和R6 的定義與上述式(2)中的定義相同)。(In the formula (5), q is an integer of 1 to 3, and the definitions of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as defined in the above formula (2)).

(式(6)中，R1 、R2 、R3 、R4 、R5 和R6 的定義與上述式(2)中的定義相同)。(In the formula (6), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as defined in the above formula (2)).

(式(7)中，R1 、R2 、R3 、R4 、R5 和R6 的定義與上述式(2)中的定義相同)。(In the formula (7), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as defined in the above formula (2)).

作為其他不飽和化合物的例子，可以列舉丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯。Examples of the other unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

這些化合物(a3)的例子中，較佳係使用甲基丙烯酸鏈狀烷基酯、甲基丙烯酸環狀烷基酯、馬來醯亞胺化合物、具有四氫呋喃骨架、呋喃骨架、四氫吡喃骨架、吡喃骨架、上述式(1)表示的骨架的不飽和化合物、具有上述式(2)表示的酚性羥基的不飽和化合物、不飽和芳香族化合物、丙烯酸環狀烷基酯。其中，從共聚合反應性和對於鹼性水溶液的溶解性方面考慮，特佳係苯乙烯、甲基丙烯酸第三丁基酯、甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯、對甲氧基苯乙烯、丙烯酸2-甲基環己基酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、(甲基)丙烯酸四氫糠基酯、聚乙二醇(n=2~10)單(甲基)丙烯酸酯、3-(甲基)丙烯醯氧基四氫呋喃-2-酮、(甲基)丙烯酸4-羥基苄基酯、(甲基)丙烯酸4-羥基苯基酯、鄰羥基苯乙烯、對羥基苯乙烯、α-甲基-對羥基苯乙烯。這些化合物(a3)可以單獨或2種以上組合使用。In the examples of the compound (a3), a chain alkyl ester of methacrylic acid, a cyclic alkyl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton is preferably used. And a pyran skeleton, an unsaturated compound of a skeleton represented by the above formula (1), an unsaturated compound having a phenolic hydroxyl group represented by the above formula (2), an unsaturated aromatic compound, or a cyclic alkyl acrylate. Wherein, for the solubility of the aqueous alkali solution from the viewpoint of the copolymerization reaction and, particularly preferred styrene-based, methacrylate, tert-butyl methacrylate, tricyclo [5.2.1.0 2,6] decane -8 -yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth)acrylate , polyethylene glycol (n=2~10) mono(meth)acrylate, 3-(meth)acryloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth)acrylate, (a) Base) 4-hydroxyphenyl acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene. These compounds (a3) may be used alone or in combination of two or more.

本發明中使用的共聚物[A]，基於由化合物(a1)和(a2)(以及任意的化合物(a3))衍生的構成單元的合計量，較佳係含有0～60質量%由化合物(a3)衍生的構成單元，特佳係含有5～50質量%。通過使該構成單元的量為60質量%以下，可以使感放射線性樹脂組成物獲得高顯影性。The copolymer [A] used in the present invention is preferably contained in an amount of from 0 to 60% by mass based on the total amount of the constituent units derived from the compounds (a1) and (a2) (and any compound (a3)). A3) The constituent unit derived is particularly preferably 5 to 50% by mass. By setting the amount of the constituent unit to 60% by mass or less, high sensitivity can be obtained for the radiation sensitive resin composition.

作為共聚物[A]的各構成成分的較佳具體例子，可以列舉甲基丙烯酸/甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯/丙烯酸2-甲基環己基酯/甲基丙烯酸縮水甘油酯/N-(3,5-二甲基-4-羥基苄基)甲基丙烯醯胺、甲基丙烯酸/甲基丙烯酸四氫糠基酯/甲基丙烯酸縮水甘油酯/N-環己基馬來醯亞胺/甲基丙烯酸十二烷基酯/α-甲基-對羥基苯乙烯、苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油酯/甲基丙烯酸(3-乙基氧雜環丁烷-3-基酯)/甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯、甲基丙烯酸/甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯/丙烯酸2-甲基環己基酯/甲基丙烯酸縮水甘油酯/苯乙烯。Preferable specific examples of the respective constituent components of the copolymer [A] include methacrylic acid/trimethyl methacrylate [5.2.1.0 2,6 ]decane-8-yl ester/2-methylcyclohexyl acrylate. Ester/glycidyl methacrylate/N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide, methacrylic acid/tetrahydrofurfuryl methacrylate/glycidyl methacrylate Ester/N-cyclohexylmaleimide/dodecyl methacrylate/α-methyl-p-hydroxystyrene, styrene/methacrylic acid/glycidyl methacrylate/methacrylic acid (3 -ethyloxetan-3-yl ester)/tricyclomethacrylate [5.2.1.0 2,6 ]decane-8-yl ester, methacrylic acid/methacrylic acid tricyclic [5.2.1.0 2 , 6 ]decane-8-yl ester / 2-methylcyclohexyl acrylate / glycidyl methacrylate / styrene.

共聚物[A]的GPC(凝膠滲透色譜)測定的聚苯乙烯換算的重量平均分子量(以下稱為“Mw”)較佳為2×103 ～1×105 ，更佳為5×103 ～5×104 。通過使共聚物[A]的Mw為2×103 以上，可以確保足夠好的顯影裕度，結果可以抑制所得塗膜的殘膜率(是指圖案狀薄膜適當殘留的比率)下降以及所得層間絕緣膜或微透鏡的圖案形狀、耐熱性的劣化。另一方面，通過使共聚物[A]的Mw為1×105 以下，可以保持對放射線的高敏感度，結果可以獲得良好的圖案形狀。另外，共聚物[A]的分子量分佈(以下稱為“Mw/Mn”)較佳為5.0以下，更佳為3.0以下。通過使共聚物[A]的Mw/Mn為5.0以下，可以獲得良好圖案形狀的層間絕緣膜或微透鏡。含有共聚物[A]的感放射線性樹脂組成物，在顯影時不會產生顯影殘留，能夠容易地形成預定的圖案形狀。The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by GPC (gel permeation chromatography) of the copolymer [A] is preferably 2 × 10 3 to 1 × 10 5 , more preferably 5 × 10 3 to 5 × 10 4 . When the Mw of the copolymer [A] is 2 × 10 3 or more, a sufficiently good development margin can be ensured, and as a result, the residual film ratio of the obtained coating film (refer to the ratio of the pattern film remaining properly) can be suppressed from decreasing and the resulting interlayer The pattern shape and heat resistance of the insulating film or the microlens are deteriorated. On the other hand, when the Mw of the copolymer [A] is 1 × 10 5 or less, high sensitivity to radiation can be maintained, and as a result, a good pattern shape can be obtained. Further, the molecular weight distribution of the copolymer [A] (hereinafter referred to as "Mw/Mn") is preferably 5.0 or less, more preferably 3.0 or less. When the Mw/Mn of the copolymer [A] is 5.0 or less, an interlayer insulating film or a microlens having a good pattern shape can be obtained. The radiation sensitive resin composition containing the copolymer [A] does not cause development residue during development, and can easily form a predetermined pattern shape.

在共聚物[A]的製備中所用的溶劑中，較佳為乙二醇烷基醚乙酸酯、二甘醇二烷基醚、丙二醇單烷基醚、丙二醇烷基醚乙酸酯、3-甲氧基丙酸甲酯。這些溶劑中，特佳係二甘醇二甲基醚、二甘醇乙基甲基醚、丙二醇甲基醚、丙二醇乙基醚、丙二醇甲基醚乙酸酯、3-甲氧基丙酸甲酯。Among the solvents used in the preparation of the copolymer [A], preferred are ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and 3 Methyl methoxypropionate. Among these solvents, particularly preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, and 3-methoxypropionic acid. ester.

作為共聚物[A]的製備中所用的聚合引發劑，可以使用通常已知作為自由基聚合引發劑的聚合引發劑。作為聚合引發劑的具體例子，可以列舉2,2’-偶氮雙異丁腈、2,2’-偶氮雙-(2,4-二甲基戊腈)2,2’-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物；過氧化苯甲醯、過氧化月桂醯、第三丁基過氧化特戊酸酯、1,1’-二(第三丁基過氧化)環己烷等有機過氧化物；以及過氧化氫。當使用過氧化物作為自由基聚合引發劑時，還可以與還原劑一起作為氧化還原型引發劑使用。As the polymerization initiator used in the preparation of the copolymer [A], a polymerization initiator generally known as a radical polymerization initiator can be used. Specific examples of the polymerization initiator include 2,2'-azobisisobutyronitrile and 2,2'-azobis-(2,4-dimethylvaleronitrile) 2,2'-azobis. An azo compound such as -(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, t-butyl peroxypivalate, 1,1'- An organic peroxide such as di(t-butylperoxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it can also be used as a redox type initiator together with a reducing agent.

在共聚物[A]的製備中，還可以使用調節分子量用的分子量調節劑。作為分子量調節劑的具體例子，可以列舉氯仿、四溴化碳等鹵代烴；正己硫醇、正辛硫醇、正十二烷硫醇、第三-十二烷硫醇、巰基乙酸等硫醇；硫化二甲基黃原酸、二硫化二異丙基黃原酸等黃原酸；萜品油烯、α-甲基苯乙烯二聚物等。In the preparation of the copolymer [A], a molecular weight modifier for adjusting the molecular weight can also be used. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; sulfur such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tri-dodecanethiol, and mercaptoacetic acid; Alcohol; xanthogen such as dimethyl xanthate sulfide, diisopropyl xanthogen disulfide; terpinolene, α-methylstyrene dimer, and the like.

II．[B]成分II. [B] ingredient

本發明中所用的[B]成分是通過照射放射線能夠產生羧酸的1,2-醌二疊氮化合物。作為1,2-醌二疊氮化合物，可以使用酚性化合物或醇性化合物(以下稱為“母核”)與1,2-萘醌二疊氮磺醯鹵的縮合物。The component [B] used in the present invention is a 1,2-quinonediazide compound capable of generating a carboxylic acid by irradiation with radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used.

作為[B]成分的母核的例子，可以列舉三羥基二苯基酮、四羥基二苯基酮、五羥基二苯基酮、六羥基二苯基酮、(多羥基苯基)烷烴和其他的母核。Examples of the core of the component [B] include trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, pentahydroxydiphenyl ketone, hexahydroxydiphenyl ketone, (polyhydroxyphenyl) alkane, and others. Mother core.

作為這些母核的具體例子，三羥基二苯基酮可以列舉2,3,4-三羥基二苯基酮、2,4,6-三羥基二苯基酮等；四羥基二苯基酮可以列舉2,2’,4,4’-四羥基二苯基酮、2,3,4,3’-四羥基二苯基酮、2,3,4,4’-四羥基二苯基酮、2,3,4,2’-四羥基-4’-甲基二苯基酮、2,3,4,4’-四羥基-3’-甲氧基二苯基酮等；五羥基二苯基酮可以列舉2,3,4,2’,6’-五羥基二苯基酮等；六羥基二苯基酮可以列舉2,4,6,3’,4’,5’-六羥基二苯基酮、3,4,5,3’,4’,5’-六羥基二苯基酮等；(多羥基苯基)烷烴可以列舉二(2,4-二羥基苯基)甲烷、二(對羥基苯基)甲烷、三(對羥基苯基)甲烷、1,1,1-三(對羥基苯基)乙烷、二(2,3,4-三羥基苯基)甲烷、2,2-二(2,3,4-三羥基苯基)丙烷、1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷、4,4’-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚、二(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷、3,3,3’,3’-四甲基-1,1’-螺雙茚-5,6,7,5’,6’,7’-六醇、2,2,4-三甲基-7,2’,4’-三羥基黃烷等；其他母核可以列舉2-甲基-2-(2,4-二羥基苯基)-4-(4-羥基苯基)-7-羥基唍、2-[雙{(5-異丙基-4-羥基-2-甲基)苯基}甲基]、1-[1-(3-{1-(4-羥基苯基)-1-甲基乙基}-4,6,-二羥基苯基)-1-甲基乙基]-3-(1-(3-{1-(4-羥基苯基)-1-甲基乙基}-4,6-二羥基苯基)-1-甲基乙基)苯、4,6-雙{1-(4-羥基苯基)-1-甲基乙基}-1,3-二羥基苯。Specific examples of these cores include trishydroxydiphenyl ketone, 2,3,4-trihydroxydiphenyl ketone, 2,4,6-trihydroxydiphenyl ketone, and the like; tetrahydroxydiphenyl ketone can be used. Listed 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3,4,3'-tetrahydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2,3,4,2'-tetrahydroxy-4'-methyldiphenyl ketone, 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl ketone, etc.; pentahydroxydiphenyl The ketone may, for example, be 2,3,4,2',6'-pentahydroxydiphenyl ketone or the like; and the hexahydroxydiphenyl ketone may be exemplified by 2,4,6,3',4',5'-hexahydroxydi Phenyl ketone, 3,4,5,3',4',5'-hexahydroxydiphenyl ketone, etc.; (polyhydroxyphenyl)alkane can be exemplified by bis(2,4-dihydroxyphenyl)methane, two (p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2, 2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4' -[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl) )-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiguan-5 , 6,7,5',6'-hexaol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.; other parent cores can be exemplified by 2-methyl -2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxyl 唍, 2-[bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl], 1-[1-(3-{1-(4-hydroxyphenyl)-1 -methylethyl}-4,6,-dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methyl-ethyl) }}-4,6-dihydroxyphenyl)-1-methylethyl)benzene, 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3- Dihydroxybenzene.

另外，還可以適當使用將以上例示的母核的酯鍵改為醯胺鍵後的1,2-萘醌二疊氮磺醯胺，例如2,3,4-三羥基二苯基酮-1,2-萘醌二疊氮-4-磺醯胺等。Further, 1,2-naphthoquinonediazidesulfonamide, such as 2,3,4-trihydroxydiphenylketone-1, which is obtained by changing the ester bond of the parent core exemplified above to a guanamine bond can also be suitably used. , 2-naphthoquinonediazide-4-sulfonamide, and the like.

這些母核當中，特佳係2,3,4,4’-四羥基二苯基酮、4,4’-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚。Among these mother cores, the best is 2,3,4,4'-tetrahydroxydiphenyl ketone, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl Ethyl]phenyl]ethylidene]bisphenol.

另外，作為1,2-萘醌二疊氮磺醯鹵，較佳為1,2-萘醌二疊氮磺醯氯。作為1,2-萘醌二疊氮磺醯氯的具體例子，可以列舉1,2-萘醌二疊氮-4-磺醯氯和1,2-萘醌二疊氮-5-磺醯氯。其中，較佳係使用1,2-萘醌二疊氮-5-磺醯氯。Further, as the 1,2-naphthoquinonediazidesulfonium halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Specific examples of the 1,2-naphthoquinonediazidesulfonium chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. . Among them, 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferably used.

在母核與1,2-萘醌二疊氮磺醯鹵的縮合反應中，相對於酚性化合物或醇性化合物中的OH基數，可使用較佳係相當於30～85莫耳%、更佳係相當於50～70莫耳%的1,2-萘醌二疊氮磺醯鹵。縮合反應可以採用已知的方法進行。In the condensation reaction of the mother nucleus with the 1,2-naphthoquinonediazide sulfonium halide, the number of OH groups in the phenolic compound or the alcoholic compound can be preferably used in an amount of 30 to 85 mol%, more preferably The best is equivalent to 50 to 70 mol% of 1,2-naphthoquinonediazide sulfonium halide. The condensation reaction can be carried out by a known method.

[B]成分1,2-醌二疊氮化合物可以單獨或者2種以上組合使用。[B]成分的使用比率，相對於100質量份[A]成分鹼可溶性樹脂，較佳為5～100質量份，更佳為10～50質量份。通過使[B]成分的使用比率相對於100質量份[A]成分鹼可溶性樹脂為5質量份以上，照射放射線的部分與未照射部分對於作為顯影液的鹼性水溶液的溶解度之差保持在適當的範圍，容易形成圖案，由此可以確保所得層間絕緣膜或微透鏡具有足夠的耐熱性和耐溶劑性。另一方面，通過使該比率為100質量份以下，可以使照射放射線的部分獲得足夠大的向鹼性水溶液的溶解度，從而防止顯影難以進行。The [1] component 1,2-quinonediazide compound may be used singly or in combination of two or more kinds. The use ratio of the component [B] is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the alkali-soluble resin of the component [A]. When the use ratio of the component [B] is 5 parts by mass or more based on 100 parts by mass of the [A] component alkali-soluble resin, the difference between the solubility of the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution as the developer is maintained at an appropriate level. The range is easy to form a pattern, whereby it is ensured that the obtained interlayer insulating film or microlens has sufficient heat resistance and solvent resistance. On the other hand, by setting the ratio to 100 parts by mass or less, it is possible to obtain a sufficiently large solubility to the alkaline aqueous solution in the portion irradiated with the radiation, thereby preventing development from being difficult.

III．[C]成分III. [C] component

本發明中使用的[C]成分，是分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的化合物。通過採用具有這種骨架的含乙烯性不飽和鍵的化合物，與使用不具有這種骨架的含乙烯性不飽和鍵的化合物時相比，能夠顯著地提高感放射線性樹脂組成物的感光性能。The component [C] used in the present invention is a compound having at least one ethylenically unsaturated bond in the molecule and having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton. By using a compound having an ethylenically unsaturated bond having such a skeleton, the photosensitivity of the radiation-sensitive resin composition can be remarkably improved as compared with the case of using a compound containing an ethylenically unsaturated bond having no such skeleton.

對於[C]化合物中的乙烯性不飽和鍵的數量，沒有特別的限制，例如可以是分子中為1～4個。[C]化合物的分子量較佳為1000以下。另外，[C]化合物的具有乙烯性不飽和鍵的部分，為由具有乙烯性不飽和鍵的羧酸形成的酯基即可，較佳為由(甲基)丙烯酸形成的酯基較好。另外，[C]化合物還可以具有羧基。並且，作為[C]化合物，還可以將具有羧基的化合物與沒有羧基的化合物倂用。The number of ethylenically unsaturated bonds in the [C] compound is not particularly limited, and may be, for example, 1 to 4 in the molecule. The molecular weight of the [C] compound is preferably 1,000 or less. Further, the moiety having an ethylenically unsaturated bond of the [C] compound may be an ester group formed of a carboxylic acid having an ethylenically unsaturated bond, and an ester group formed of (meth)acrylic acid is preferred. Further, the [C] compound may further have a carboxyl group. Further, as the compound [C], a compound having a carboxyl group and a compound having no carboxyl group may be used in combination.

作為[C]成分使用的具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的單官能(甲基)丙烯酸酯的具體例子，可以列舉三羥甲基丙烷單(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、單(2-丙烯醯氧基乙基)二乙基異三聚氰酸酯等。另外，作為[C]成分使用的具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的二官能(甲基)丙烯酸酯的具體例子，可以列舉三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、二(2-丙烯醯氧基乙基)羥基乙基異三聚氰酸酯等。Specific examples of the monofunctional (meth) acrylate having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton used as the component [C] include trimethylolpropane mono( Methyl) acrylate, pentaerythritol mono (meth) acrylate, mono(2-propenyl methoxyethyl) diethyl isomeric cyanate, and the like. Further, specific examples of the difunctional (meth) acrylate having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton used as the component [C] include trimethylolpropane. Di(meth)acrylate, pentaerythritol di(meth)acrylate, bis(2-propenyloxyethyl)hydroxyethyl isocyanurate, and the like.

作為[C]成分使用的具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的三官能以上的(甲基)丙烯酸酯的具體例子，可以列舉三羥甲基丙烷三(甲基)丙烯酸酯、琥珀酸改性的季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、參(2-丙烯醯氧基乙基)異三聚氰酸酯等。Specific examples of the trifunctional or higher (meth) acrylate having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton used as the component [C] include trimethylolpropane. Tris(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ginseng (2-propenyloxyethyl) ) isomeric cyanurate or the like.

作為[C]成分的分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的化合物，可以單獨或者組合使用。[C]成分的使用比率，相對於100質量份[A]成分鹼可溶性樹脂，較佳為20質量份以下，更佳為1～10質量份。通過使其以這種比率含有[C]成分，可以有效地提高感放射線性樹脂組成物的感光性能。通過使該比率為20質量份以下，可以使後烘焙後所形成的圖案的形狀變化保持得較小，同時，可以抑制殘膜率的下降。The compound having at least one ethylenically unsaturated bond in the molecule of the [C] component and having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton may be used singly or in combination. The use ratio of the component [C] is preferably 20 parts by mass or less, more preferably 1 to 10 parts by mass, per 100 parts by mass of the alkali-soluble resin of the component [A]. By containing the [C] component in such a ratio, the photosensitivity of the radiation sensitive resin composition can be effectively improved. By setting the ratio to 20 parts by mass or less, the shape change of the pattern formed after post-baking can be kept small, and at the same time, the decrease in the residual film ratio can be suppressed.

IV．其他成分IV. Other ingredients

本發明的感放射線性樹脂組成物，含有上述[A]、[B]和[C]成分，而根據需要，還可以含有[D]分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇以外的化合物並且為異三聚氰酸酯骨架以外的骨架(即具有作為[C]成分所規定的骨架以外的骨架)的化合物；[E]熱敏性產酸化合物；[F]上述[A]成分以外的環氧樹脂；[G]界面活性劑；或者[H]黏合助劑。The radiation sensitive resin composition of the present invention contains the above [A], [B] and [C] components, and may further contain at least one ethylenically unsaturated bond in the [D] molecule, if necessary, and has a compound other than trimethylolpropane or pentaerythritol and a skeleton other than the isocyanurate skeleton (that is, a skeleton having a skeleton other than the skeleton specified by the [C] component); [E] heat-sensitive acid generating compound; F] an epoxy resin other than the above [A] component; [G] a surfactant; or [H] an adhesion aid.

作為[D]成分的分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇以外的化合物並且為異三聚氰酸酯骨架以外的骨架的化合物，可以在不損害具有特定骨架的上述[C]化合物所發揮的效果的情況下，提高含有這些成分的感放射線性樹脂組成物的感光性能。a compound having at least one ethylenically unsaturated bond in the molecule of the [D] component and having a compound other than trimethylolpropane or pentaerythritol and which is a skeleton other than the isocyanurate skeleton, can be harmless In the case of the effect exerted by the above-mentioned [C] compound having a specific skeleton, the photosensitivity of the radiation sensitive resin composition containing these components is improved.

作為[D]成分使用的單官能(甲基)丙烯酸酯的具體例子，可以列舉ω-羧基-聚己內酯單(甲基)丙烯酸酯、琥珀醯乙基單(甲基)丙烯酸酯、苯氧基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸4-羥基丁基酯、(甲基)丙烯酸異丁基酯、(甲基)丙烯酸第三丁基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸卡必醇酯、(甲基)丙烯酸2-對枯基苯氧基乙基酯、(甲基)丙烯酸壬基苯氧基乙基酯、丙烯酸2-乙基己基卡必醇酯、N-丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、(甲基)丙烯酸異冰片基酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸乙基卡必醇酯、(甲基)丙烯酸苯氧基乙基酯、(甲基)丙烯酸3-甲氧基丁基酯、(甲基)丙烯酸甲氧基三丙二醇酯、(甲基)丙烯酸2-羥基-3-苯氧基丙基酯、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸氫酯、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸氫酯、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸氫酯、2-(甲基)丙烯醯氧基丙基四氫鄰苯二甲酸氫酯、2-(甲基)丙烯醯氧基乙基-2-羥基丙基鄰苯二甲酸酯、聚乙二醇單(甲基)丙烯酸酯等。作為它們的市售品，可以列舉例如ARONIX M-101、ARONIX M-102、ARONIX M-110、ARONIX M-111、ARONIX M-114、ARONIX M-113、ARONIX M-117、ARONIX M-120、ARONIX M-140、ARONIX M-5300、ARONIX M-5400、ARONIX M-5600、ARONIX M-5710(以上由東亞合成(股)生產)；KAYARAD TC-110S、KAYARAD TC-120S(以上由日本化藥(股)生產)；HEA、HPA、4-HBA、AIB、TBA、IOAA、LA、STA、IBXA、2-MTA、V-MTG、2-ETAVISCOAT 158、VISCOAT 155、VISCOAT 150、VISCOAT 160、VISCOAT 190、VISCOAT 192、VISCOAT 320、VISCOAT 220、VISCOAT 2000、VISCOAT 2100、VISCOAT 2150、VISCOAT 2180、VISCOAT 2311(以上由大阪有機化學工業(股)生產);BLEMMER PE-90、BLEMMER PE-200、BLEMMER PE-350(以上由日本油脂工業(股)生產)等。Specific examples of the monofunctional (meth) acrylate used as the component [D] include ω-carboxy-polycaprolactone mono(meth)acrylate, amber oxime ethyl mono(meth)acrylate, and benzene. Oxycarbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (A) Isobutyl acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, cyclohexyl (meth)acrylate, dodecyl (meth)acrylate, ( Octadecylmethyl methacrylate, carbitol (meth) acrylate, 2-p-cumylphenoxyethyl (meth) acrylate, decyl phenoxyethyl (meth) acrylate , 2-ethylhexyl carbitol acrylate, N-propylene methoxyethyl hexahydrophthalimide, isobornyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl ester, methoxyethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, ( Methyl acrylate ethyl carbitol, (methyl Phenyloxyethyl acrylate, 3-methoxybutyl (meth)acrylate, methoxytripropylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Base ester, 2-(methyl) propylene oxiranyl ethyl phthalate, 2-(methyl) propylene methoxy propyl phthalate, 2-(methyl) propylene oxime Hydroxypropyl hexahydrophthalate, 2-(methyl)propenyloxypropyltetrahydrophthalate, 2-(methyl)propenyloxyethyl-2-hydroxypropane Phthalates, polyethylene glycol mono(meth)acrylates, and the like. As their commercial products, for example, ARONIX M-101, ARONIX M-102, ARONIX M-110, ARONIX M-111, ARONIX M-114, ARONIX M-113, ARONIX M-117, ARONIX M-120, ARONIX M-140, ARONIX M-5300, ARONIX M-5400, ARONIX M-5600, ARONIX M-5710 (above produced by East Asia Synthetic Co., Ltd.); KAYARAD TC-110S, KAYARAD TC-120S (above by Japanese Chemicals) (share) production); HEA, HPA, 4-HBA, AIB, TBA, IOAA, LA, STA, IBSA, 2-MTA, V-MTG, 2-ETAVISCOAT 158, VISCOAT 155, VISCOAT 150, VISCOAT 160, VISCOAT 190 , VISCOAT 192, VISCOAT 320, VISCOAT 220, VISCOAT 2000, VISCOAT 2100, VISCOAT 2150, VISCOAT 2180, VISCOAT 2311 (above produced by Osaka Organic Chemical Industry Co., Ltd.); BLEMMER PE-90, BLEMMER PE-200, BLEMMER PE- 350 (above produced by Japan Oil Industry Co., Ltd.) and so on.

作為[D]成分使用的二官能(甲基)丙烯酸酯的具體例子，可以列舉三環癸烷二羥甲基二(甲基)丙烯酸酯、雙酚F二卡必醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、四甘醇二(甲基)丙烯酸酯等。作為它們的市售品，可以列舉例如ARONIX M-203、ARONIX M-208、ARONIX M-215、ARONIX M-220、ARONIX M-240、ARONIX M-243(以上由東亞合成(股)生產)；KAYARAD HDDA、KAYARAD HX-220、KAYARAD R-604(以上由日本化藥(股)生產)；VISCOAT 260、VISCOAT 312、VISCOAT 335HP(以上由大阪有機化學工業(股)生產)等。Specific examples of the difunctional (meth) acrylate used as the component [D] include tricyclodecane dimethylol di(meth) acrylate and bisphenol F dia carbitol di(meth) acrylate. Ester, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethyl b Diol (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and the like. Examples of the commercially available products thereof include ARONIX M-203, ARONIX M-208, ARONIX M-215, ARONIX M-220, ARONIX M-240, and ARONIX M-243 (above produced by East Asia Synthetic Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (produced by Nippon Kayaku Co., Ltd.); VISCOAT 260, VISCOAT 312, VISCOAT 335HP (above produced by Osaka Organic Chemical Industry Co., Ltd.).

作為[D]成分使用的三官能以上的(甲基)丙烯酸酯的具體例子，可以列舉三((甲基)丙烯醯氧基乙基)磷酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇二五丙烯酸酯、二季戊四醇二六丙烯酸酯等。此外，還可以列舉使具有直鏈烷基和脂環式結構，且具有2個以上異氰酸酯基的化合物與分子內具有1個以上羥基，且具有3個、4個或5個丙烯醯氧基及/或甲基丙烯醯氧基的化合物反應所得的多官能尿烷丙烯酸酯類化合物等。作為它們的市售品，可以列舉例如ARONIX M-315、ARONIX M-408(以上由東亞合成(股)生產)，作為含多官能尿烷丙烯酸酯類化合物的市售品，可以列舉New-Frontier R-1150(第一工業製藥(股)生產)KAYARAD DPHA-40H(由日本化藥(股)生產)等。Specific examples of the trifunctional or higher (meth) acrylate used as the component [D] include tris((meth)acryloxyethyl)phosphate and ditrimethylolpropane tetra(methyl). Acrylate, dipentaerythritol dipentaacrylate, dipentaerythritol dihexaacrylate, and the like. Further, a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanate groups may have one or more hydroxyl groups in the molecule, and have three, four or five acryloxy groups and And a polyfunctional urethane acrylate compound obtained by reacting a compound of a methacryloxy group. As a commercially available product, for example, ARONIX M-315, ARONIX M-408 (produced by East Asia Synthetic Co., Ltd.), and a commercially available product containing a polyfunctional urethane acrylate compound can be cited, and New-Frontier can be cited. R-1150 (produced by First Industrial Pharmaceutical Co., Ltd.) KAYARAD DPHA-40H (produced by Nippon Kayaku Co., Ltd.) and the like.

作為[D]成分的分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇以外的化合物並且為異三聚氰酸酯骨架以外的骨架的化合物，可以單獨或組合使用。a compound having at least one ethylenically unsaturated bond in the molecule of the [D] component and having a compound other than trimethylolpropane or pentaerythritol and which is a skeleton other than the isocyanurate skeleton, either alone or in combination use.

[D]成分的使用比率，相對於[C]的使用量為60質量%以下。通過使[D]成分的使用比率相對於[C]的使用量為60質量%以下，可以使層間絕緣膜或微透鏡的顯影裕度保持良好。The use ratio of the component [D] is 60% by mass or less based on the amount of use of [C]. When the use ratio of the component [D] is 60% by mass or less based on the use amount of [C], the development margin of the interlayer insulating film or the microlens can be kept good.

[E]成分熱敏性產酸化合物可以為了提高耐熱性和硬度而使用。作為該化合物的例子，可以列舉鋶鹽、苯並噻唑鎓鹽、銨鹽、鏻鹽等已知的鎓鹽。作為這種鋶鹽的具體例子，可以列舉烷基鋶鹽、苄基鋶鹽、二苄基鋶鹽、取代的苄基鋶鹽等。The heat-sensitive acid generating compound of the [E] component can be used for the purpose of improving heat resistance and hardness. Examples of the compound include known onium salts such as an onium salt, a benzothiazolium salt, an ammonium salt, and a phosphonium salt. Specific examples of such a phosphonium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and the like.

作為這些熱敏性產酸化合物的具體例子，烷基鋶鹽可以列舉4-乙醯苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶六氟砷酸鹽、二甲基-4-(苄氧羰氧基)苯基鋶六氟銻酸鹽、二甲基-4-(苯甲醯氧基)苯基鋶六氟銻酸鹽、二甲基-4-(苯甲醯氧基)苯基鋶六氟砷酸鹽、二甲基-3-氯-4-乙醯氧基苯基鋶六氟銻酸鹽等；苄基鋶鹽可以列舉苄基-4-羥基苯基甲基鋶六氟銻酸鹽、苄基-4-羥基苯基甲基鋶六氟磷酸鹽、4-乙醯氧基苯基苄基甲基鋶六氟銻酸鹽、苄基-4-甲氧苯基甲基鋶六氟銻酸鹽、苄基-2-甲基-4-羥基苯基甲基鋶六氟銻酸鹽、苄基-3-氯-4-羥基苯基甲基鋶六氟砷酸鹽、4-甲氧基苄基-4-羥基苯基甲基鋶六氟磷酸鹽等；二苄基鋶鹽可以列舉二苄基-4-羥基苯基鋶六氟銻酸鹽、二苄基-4-羥基苯基鋶六氟磷酸鹽、4-乙醯氧基苯基二苄基鋶六氟銻酸鹽、二苄基-4-甲氧基苯基鋶六氟銻酸鹽、二苄基-3-氯-4-羥基苯基鋶六氟砷酸鹽、二苄基-3-甲基-4-羥基-5-第三丁基苯基鋶六氟銻酸鹽、苄基-4-甲氧基苄基-4-羥基苯基鋶六氟磷酸鹽等；取代的苄基鋶鹽可以列舉對氯苄基-4-羥基苯基甲基鋶六氟銻酸鹽、對硝基苄基-4-羥基苯基甲基鋶六氟銻酸鹽、對氯苄基-4-羥基苯基甲基鋶六氟磷酸鹽、對硝基苄基-3-甲基-4-羥基苯基甲基鋶六氟銻酸鹽、3,5-二氯苄基-4-羥基苯基甲基鋶六氟銻酸鹽、鄰氯苄基-3-氯-4-羥基苯基甲基鋶六氟銻酸鹽等。Specific examples of the heat-sensitive acid-producing compound include 4-ethyl phenyl phenyl hexafluoroantimonate and 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate. Dimethyl-4-(benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4- (benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate, etc.; benzylsulfonium salt can be benzyl-4 -Hydroxyphenylmethylhydrazine hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 4-ethoxycarbonylphenylbenzylmethylphosphonium hexafluoroantimonate, benzyl 4-methoxyphenylmethylhydrazine hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenyl Methyl hydrazine hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, etc.; dibenzyl sulfonium salt can be exemplified by dibenzyl-4-hydroxyphenyl fluorene hexafluorophosphate Citrate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-acetoxyphenyl dibenzyl hexafluoroantimonate, dibenzyl-4-methoxyphenyl fluorene Fluoroquinone Acid salt, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylphosphonium hexafluoroantimonate , benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, etc.; substituted benzyl sulfonium salt may be p-chlorobenzyl-4-hydroxyphenylmethyl hexafluoroantimonate , p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p-nitrobenzyl-3-methyl- 4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxybenzene Methyl hydrazine hexafluoroantimonate or the like.

作為苯並噻唑鎓鹽的具體例子，可以列舉3-苄基苯並噻唑鎓六氟銻酸鹽、3-苄基苯並噻唑鎓六氟磷酸鹽、3-苄基苯並噻唑鎓四氟硼酸鹽、3-(對甲氧基苄基)苯並噻唑鎓六氟銻酸鹽、3-苄基-2-甲硫基苯並噻唑鎓六氟銻酸鹽、3-苄基-5-氯苯並噻唑鎓六氟銻酸鹽等。Specific examples of the benzothiazolium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, and 3-benzylbenzothiazolium tetrafluoroborate. Salt, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chloro Benzothiazolium hexafluoroantimonate.

這些熱敏性產酸化合物中，較佳係使用鋶鹽和苯並噻唑鎓鹽。特佳係使用4-乙醯氧基苯基二甲基鋶六氟砷酸鹽、苄基-4-羥基苯基甲基鋶六氟銻酸鹽、4-乙醯氧基苯基苄基甲基鋶六氟銻酸鹽、二苄基-4-羥基苯基鋶六氟銻酸鹽、4-乙醯氧基苯基苄基鋶六氟銻酸鹽、3-苄基苯並噻唑鎓六氟銻酸鹽。作為它們的市售品，可以列舉Sun-Aid SI-L85、Sun-Aid SI-L110、Sun-Aid SI-L145、Sun-Aid SI-L150、Sun-Aid SI-L160(三新化學工業(股)生產)等。Among these heat-sensitive acid generating compounds, an onium salt and a benzothiazole salt are preferably used. Tetraethyloxy phenyl dimethyl hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 4-ethyl methoxy phenyl benzyl group Hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, 4-acetoxyphenylbenzylphosphonium hexafluoroantimonate, 3-benzylbenzothiazolyl Fluoride. As their commercial products, Sun-Aid SI-L85, Sun-Aid SI-L110, Sun-Aid SI-L145, Sun-Aid SI-L150, Sun-Aid SI-L160 (Sanxin Chemical Industry Co., Ltd.) ) production) and so on.

[E]成分的使用比率，相對於100質量份[A]成分鹼可溶性樹脂，較佳為20質量份以下，更佳為5質量份以下。通過使[E]成分的使用比率為20質量份以下，可以避免塗膜形成步驟中析出析出物而給塗膜的形成帶來障礙的情況。The use ratio of the component [E] is preferably 20 parts by mass or less, and more preferably 5 parts by mass or less based on 100 parts by mass of the [A] component alkali-soluble resin. When the use ratio of the component [E] is 20 parts by mass or less, it is possible to avoid the occurrence of a problem in the formation of the coating film by depositing precipitates in the coating film forming step.

作為[F]成分的[A]成分以外的環氧樹脂，只要對與[A]成分鹼可溶性樹脂的相容性沒有影響，則沒有限制。作為[F]成分的例子，較佳的可以列舉雙酚A型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、環狀脂肪族環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油基胺型環氧樹脂、雜環式環氧樹脂、與甲基丙烯酸縮水甘油酯(共)聚合的樹脂等。其中，特佳係雙酚A型環氧樹脂、甲酚酚醛型環氧樹脂、縮水甘油酯型環氧樹脂等。The epoxy resin other than the component [A] as the component [F] is not limited as long as it does not affect the compatibility with the alkali-soluble resin of the component [A]. Preferred examples of the component [F] include bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin, and glycidyl ester epoxy resin. Resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, resin (co)polymerized with glycidyl methacrylate, and the like. Among them, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin, and the like are particularly preferable.

[F]成分的使用比率，相對於100質量份[A]成分鹼可溶性樹脂，較佳為30質量份以下。通過使其以這種比率含有[F]成分，可以進一步提高由感放射線性樹脂組成物製得的層間絕緣膜或微透鏡的耐熱性和表面硬度等性能。通過使[F]成分的使用比率為30質量份以下，可以在基板上形成感放射線性樹脂組成物塗膜時，使塗膜獲得非常好的膜厚均一性。另外，[A]成分的鹼可溶性樹脂根據情況也可以稱為“環氧樹脂”，但是[A]成分在具有鹼可溶性方面與[F]成分不同。[F]成分為鹼不溶性的。The use ratio of the component [F] is preferably 30 parts by mass or less based on 100 parts by mass of the alkali-soluble resin of the component [A]. By including the [F] component in such a ratio, the properties such as heat resistance and surface hardness of the interlayer insulating film or the microlens obtained from the radiation sensitive resin composition can be further improved. When the use ratio of the component [F] is 30 parts by mass or less, it is possible to obtain a film thickness uniformity of the coating film when the radiation-sensitive resin composition coating film is formed on the substrate. Further, the alkali-soluble resin of the component [A] may be referred to as "epoxy resin" depending on the case, but the component [A] is different from the component [F] in terms of alkali solubility. The [F] component is alkali-insoluble.

通過使用[G]成分的界面活性劑，可以進一步提高感放射線性樹脂組成物的塗布性能。作為這裏可以使用的[G]成分，可以適當地使用氟類界面活性劑、聚矽氧烷類界面活性劑和非離子類界面活性劑。By using the surfactant of the [G] component, the coating property of the radiation sensitive resin composition can be further improved. As the component [G] which can be used herein, a fluorine-based surfactant, a polyoxyalkylene surfactant, and a nonionic surfactant can be suitably used.

作為氟類界面活性劑的具體例子，可以列舉1,1,2,2-四氟辛基(1,1,2,2-四氟丙基)醚、1,1,2,2-四氟辛基己基醚、八乙二醇二(1,1,2,2-四氟丁基)醚、六乙二醇(1,1,2,2,3,3-六氟戊基)醚、八丙二醇二(1,1,2,2-四氟丁基)醚、六丙二醇二(1,1,2,2,3,3-六氟戊基)醚、全氟十二烷基磺酸鈉、1,1,2,2,8,8,9,9,10,10-十氟十二烷、1,1,2,2,3,3-六氟癸烷等，除此之外，還可以列舉氟代烷基苯磺酸鈉類；氟代烷基氧乙烯醚類；碘化氟代烷基銨類；氟代烷基聚氧乙烯醚類；全氟烷基聚氧乙醇類；全氟代烷基烷氧化物類；氟類烷基酯等。作為它們的市售品，可以列舉BM-1000、BM-1100(以上，由BM Chemie公司生產)Megaface F142D、Megaface F172、Megaface F173、Megaface F183、Megaface F178、Megaface F191、Megaface F471(以上，由大日本油墨化學工業(股)生產)Fluorad FC-170C、FC-171、FC-430、FC-431(以上由住友3M(股)生產)Surflon S-112、、Surflon S-113、Surflon S-131、Surflon S-141、Surflon S-145、Surflon S-382、Surflon SC-101、Surflon SC-102、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-106(由旭硝子(股)生產)FTOP EF 301、FTOP EF 303、FTOP EF 352(新秋田化成(股)生產)等。Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluoro. Octyl hexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, Octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, perfluorododecyl sulfonic acid Sodium, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Further, sodium fluoroalkylbenzenesulfonate; fluoroalkyl oxyethylene ether; fluoroalkylammonium iodide; fluoroalkyl polyoxyethylene ether; perfluoroalkyl polyoxyethylene ; perfluoroalkyl alkoxides; fluorine alkyl esters. As such commercial products, BM-1000, BM-1100 (above, produced by BM Chemie) Megaface F142D, Megaface F172, Megaface F173, Megaface F183, Megaface F178, Megaface F191, Megaface F471 (above, Japan ink chemical industry (stock) production) Fluorad FC-170C, FC-171, FC-430, FC-431 (above produced by Sumitomo 3M (share)) Surflon S-112, Surflon S-113, Surflon S-131 , Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (by Asahi Glass) ) Production) FTOP EF 301, FTOP EF 303, FTOP EF 352 (new Akita Chemicals Co., Ltd.).

作為聚矽氧烷類界面活性劑的具體例子，可以列舉以DC3PA、DC7PA、FS-1265、SF-8428、SH11PA、SH21PA、SH28PA、SH29PA、SH30PA、SH-190、SH-193、SZ-6032(以上，由東麗DOW CORNING SILICONE(股)生產)TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452(以上由GE東芝SILICONE(股)生產)等商品名銷售的聚矽氧烷類界面活性劑。Specific examples of the polyoxyalkylene type surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032 ( The above are produced by Toray DOW CORNING SILICONE Co., Ltd.) TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (the above are produced by GE Toshiba SILICONE Co., Ltd.) A polyoxyalkylene surfactant sold.

作為非離子類界面活性劑，可以使用例如聚氧乙烯十二烷基醚、聚氧乙烯十八烷基醚、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；(甲基)丙烯酸類共聚物等。作為非離子類界面活性劑的代表性市售品，可以列舉POLYFLOW No. 57、95(共榮社化學(股)生產)。這些界面活性劑可以單獨或者2種以上組合使用。As the nonionic surfactant, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like; polyoxyethylene octylbenzene can be used. Polyoxyethylene aryl ethers such as alkyl ethers and polyoxyethylene nonylphenyl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (methyl) Acrylic copolymer and the like. Typical commercial products of the nonionic surfactants include POLYFLOW No. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more.

[G]成分界面活性劑可以單獨或者2種以上組合使用。這些界面活性劑，相對於100質量份[A]成分鹼可溶性樹脂，較佳係使用5質量份以下，更佳係使用2質量份以下。通過使[G]成分界面活性劑的用量為5質量份以下，可以在基板上形成塗膜時，防止塗膜發生膜龜裂。The [G] component surfactants may be used singly or in combination of two or more kinds. The amount of the surfactant is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the [A] component alkali-soluble resin. When the amount of the [G] component surfactant is 5 parts by mass or less, it is possible to prevent film cracking of the coating film when a coating film is formed on the substrate.

通過使用[H]成分黏合助劑，可以提高感放射線性樹脂組成物與基板的黏合性。作為這種黏合助劑，較佳係使用官能性矽烷偶合劑，作為官能性矽烷偶合劑的例子，可以列舉具有羧酸基、甲基丙烯醯基、異氰酸酯基、環氧基等反應性取代基的矽烷偶合劑。作為官能性矽烷偶合劑的具體例子，可以列舉三甲氧基矽烷基安息香酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸酯丙基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等。By using the [H] component adhesion aid, the adhesion of the radiation sensitive resin composition to the substrate can be improved. As such a binder, a functional decane coupling agent is preferably used. Examples of the functional decane coupling agent include reactive substituents such as a carboxylic acid group, a methacryl fluorenyl group, an isocyanate group, and an epoxy group. Decane coupling agent. Specific examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethoxy decane. Γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyltrimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

[H]成分黏合助劑可以單獨或者2種以上組合使用。這些黏合助劑，相對於100質量份[A]成分鹼可溶性樹脂，較佳為以20質量份以下，更佳為10質量份以下的量進行使用。通過使黏合助劑的量為20質量份以下，可以在顯影步驟中抑制顯影殘留的發生。The [H] component binder may be used singly or in combination of two or more. These binder additives are preferably used in an amount of 20 parts by mass or less, more preferably 10 parts by mass or less based on 100 parts by mass of the alkali-soluble resin of the component [A]. By setting the amount of the adhesion aid to 20 parts by mass or less, the occurrence of development residue can be suppressed in the development step.

V．感放射線性樹脂組成物V. Radiation-sensitive resin composition

本發明的感放射線性樹脂組成物可以通過將上述[A]、[B]和[C]成分與作為根據需要任選成分的[D]～[H]成分均勻地混合而調製。感放射線性樹脂組成物較佳為溶於適當的溶劑中以溶液狀態使用。作為感放射線性樹脂組成物的調製中所用的溶劑，使用能夠均勻地溶解[A]、[B]、[C]成分以及作為任選成分的[D]～[H]成分，且不與各成分反應的溶劑。作為這種溶劑，可以列舉與以上作為可以用於製備[A]成分鹼可溶性樹脂的溶劑示例而列舉的同樣的溶劑。The radiation sensitive resin composition of the present invention can be prepared by uniformly mixing the above [A], [B] and [C] components with the [D] to [H] components as optional components as necessary. The radiation sensitive resin composition is preferably dissolved in a suitable solvent to be used in a solution state. As a solvent used for preparation of the radiation sensitive resin composition, [D] to [H] components capable of uniformly dissolving [A], [B], and [C] components and optional components are used, and The solvent for the component reaction. As such a solvent, the same solvent as exemplified above as a solvent which can be used for the preparation of the alkali-soluble resin of the component [A] can be mentioned.

作為這種溶劑，從各成分的溶解性、與各成分的反應性、形成塗膜的容易性等角度出發，較佳係使用醇、乙二醇醚、乙二醇烷基醚乙酸酯、酯和二甘醇。其中，可特佳係使用苄醇、2-苯基乙醇、3-苯基-1-丙醇、乙二醇單丁基醚乙酸酯、二甘醇單乙基醚乙酸酯、二甘醇二***、二甘醇乙基甲基醚、二甘醇二甲醚、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯。As such a solvent, alcohol, glycol ether, ethylene glycol alkyl ether acetate, and the like are preferably used from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like. Ester and diethylene glycol. Among them, Benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and digan are used. Alcohol diethyl ether, diethylene glycol ethyl methyl ether, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxy propionate .

為了提高膜厚的面內均一性，還可以與這些溶劑一起倂用高沸點溶劑。作為可以倂用的高沸點溶劑的具體例子，可以列舉N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞碸、苄基乙基醚、二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙二酯、碳酸丙二酯、苯基溶纖劑乙酸酯等。其中，較佳為N-甲基吡咯烷酮、γ-丁內酯、N,N-二甲基乙醯胺。In order to increase the in-plane uniformity of the film thickness, it is also possible to use a high boiling point solvent together with these solvents. Specific examples of the high-boiling solvent which can be used include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, and N. , N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol , 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate Ester and the like. Among them, preferred are N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide.

當將一般的溶劑與高沸點溶劑倂用作為感放射線性樹脂組成物的溶劑時，高沸點溶劑的用量，相對於溶劑總量，可較佳為50質量%以下，更佳為40質量%以下，進一步較佳為30質量%以下。通過使高沸點溶劑的用量處於這種範圍，可以保持適當的感放射線性樹脂組成物的敏感度、塗膜厚度均一性和殘膜率。When a general solvent and a high-boiling solvent are used as a solvent for the radiation-sensitive resin composition, the amount of the high-boiling solvent is preferably 50% by mass or less, and more preferably 40% by mass or less based on the total amount of the solvent. Further, it is more preferably 30% by mass or less. By setting the amount of the high boiling point solvent in this range, the sensitivity, film thickness uniformity, and residual film ratio of the appropriate radiation sensitive resin composition can be maintained.

當將感放射線性樹脂組成物調製成溶液狀態時，溶劑以外的成分(即上述[A]、[B]、[C]成分以及作為任選成分的[D]～[H]成分的合計量)在溶液中所占的比率，可以根據使用目的和所需膜厚度值等任意地設定。這種溶劑以外的成分的比率，較佳為5～50質量%，更佳為10～40質量%，進一步較佳為15～35質量%。如此調製的組成物溶液還可以用孔徑為0.2μm左右的微孔濾器等過濾後再供給使用。When the radiation sensitive resin composition is prepared into a solution state, the components other than the solvent (that is, the components [A], [B], and [C] described above and the components [D] to [H] as optional components are combined. The ratio in the solution can be arbitrarily set depending on the purpose of use, the desired film thickness value, and the like. The ratio of the components other than the solvent is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, even more preferably from 15 to 35% by mass. The composition solution thus prepared can also be filtered by a micropore filter having a pore diameter of about 0.2 μm or the like and then supplied.

VI．層間絕緣膜、微透鏡的形成VI. Formation of interlayer insulating film and microlens

接下來，對用本發明感放射線性樹脂組成物形成層間絕緣膜、微透鏡的方法進行說明。本發明的層間絕緣膜或微透鏡的形成方法按照下述順序包括以下步驟。Next, a method of forming an interlayer insulating film and a microlens using the radiation sensitive resin composition of the present invention will be described. The method of forming the interlayer insulating film or the microlens of the present invention includes the following steps in the following order.

(1)在基板上形成本發明感放射線性樹脂組成物塗膜的步驟，(1) a step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate,

(2)對步驟(1)中形成的塗膜的至少一部分照射放射線的步驟，(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(3)將步驟(2)中照射放射線後的塗膜進行顯影的步驟，和(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4)將步驟(3)中顯影後的塗膜進行加熱的步驟。(4) A step of heating the coating film developed in the step (3).

(1)在基板上形成本發明感放射線性樹脂組成物塗膜的步驟(1) Step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate

在本步驟中，將由本發明感放射線性樹脂組成物製成的溶液塗布於基板表面上，較佳為通過進行預烘焙除去溶劑，形成感放射線性樹脂組成物的塗膜。作為可以使用的基板的種類，可以列舉例如玻璃基板、矽片以及在它們表面上形成各種金屬的基板。In this step, a solution prepared from the radiation sensitive resin composition of the present invention is applied onto the surface of the substrate, and it is preferred to remove the solvent by prebaking to form a coating film of the radiation sensitive resin composition. Examples of the type of the substrate that can be used include a glass substrate, a tantalum sheet, and a substrate on which various metals are formed on the surface.

作為組成物溶液的塗布方法，對其沒有特別的限制，可以採用例如噴塗法、輥塗法、旋轉塗布法(旋塗法)縫模塗布法、棒塗法、噴墨法等適當的方法。特佳係旋塗法、縫模塗布法。作為預烘焙的合適條件，根據各成分的種類、使用比率等而不同。例如，可以在60～110℃下進行30秒鐘～15分鐘左右的預烘焙。預烘焙後的塗膜的厚度，例如，在形成層間絕緣膜的情況下，較佳為約3～6μm，在形成微透鏡的情況下，較佳為約0.5～3μm。The coating method of the composition solution is not particularly limited, and an appropriate method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method, a bar coating method, or an inkjet method can be employed. Very good spin coating method, slit die coating method. Suitable conditions for prebaking differ depending on the type of each component, the ratio of use, and the like. For example, prebaking can be carried out at 60 to 110 ° C for about 30 seconds to 15 minutes. The thickness of the coating film after the prebaking is, for example, preferably about 3 to 6 μm in the case of forming the interlayer insulating film, and preferably about 0.5 to 3 μm in the case of forming the microlens.

(2)對步驟(1)的塗膜的至少一部分照射放射線的步驟在本步驟中，通過具有規定圖案的遮罩，對步驟(1)中形成的塗膜照射放射線。作為此時所用的放射線的例子，可以列舉紫外線、遠紫外線、X放射線、帶電粒子束等。作為紫外線的例子，可以列舉g線(波長436nm)i線(波長365nm)等。作為遠紫外線的例子，可以列舉KrF准分子雷射等。作為X放射線的例子，可以列舉同步加速放射線等。作為帶電粒子束的例子，可以列舉電子束等。這些放射線中，較佳為紫外線，特佳係含g線及/或i線的放射線。曝光量，在形成層間絕緣膜的情況下，較佳為50～1500J/m2 ，在形成微透鏡的情況下，較佳為50～2000J/m2 。(2) Step of Irradiating at least Part of the Coating Film of the Step (1) In this step, the coating film formed in the step (1) is irradiated with radiation by a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. Examples of the ultraviolet rays include a g-line (wavelength 436 nm) i-line (wavelength 365 nm). Examples of the far ultraviolet rays include KrF excimer lasers and the like. Examples of the X-ray radiation include synchronous acceleration radiation and the like. Examples of the charged particle beam include an electron beam and the like. Among these radiations, ultraviolet rays are preferred, and radiation containing g-line and/or i-line is particularly preferred. Exposure amount, in the case of forming the interlayer insulating film, is preferably 50 ~ 1500J / m 2, in the case where the microlenses are formed, is preferably 50 ~ 2000J / m 2.

(3)將步驟(2)中照射放射線後的塗膜進行顯影的步驟(3) a step of developing the coating film after irradiating the radiation in the step (2)

在本步驟中，通過用顯影液對步驟(2)中照射放射線後的塗膜進行顯影處理來除去照射放射線的部分而形成圖案。作為顯影處理中使用的顯影液的例子，可以使用氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二乙氨基乙醇、二正丙胺、三乙胺、甲基二乙基胺、二甲基乙醇胺、三乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、吡咯、呱啶、1,8-二氮雜二環[5.4.0]-7-十一碳烯、1,5-二氮雜二環[4.3.0]-5-壬烯等鹼(鹼性化合物)的水溶液。此外，還可以將在這種鹼性水溶液中添加適量的甲醇、乙醇等水溶性有機溶劑或界面活性劑的水溶液，或者溶解本發明組成物的各種有機溶劑作為顯影液使用。另外，作為顯影方法，可以適當地實施例如盛液法(液盛法)浸漬法、震盪浸漬法、沖洗法等方法。顯影時間，根據所用組成物的組成而不同，可以為例如30～120秒。In this step, a portion where the radiation is irradiated is removed by developing the coating film irradiated with the radiation in the step (2) with a developing solution to form a pattern. As an example of the developer used in the development treatment, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, or the like can be used. Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, acridine, 1,8-diaza An aqueous solution of a base (basic compound) such as a ring [5.4.0]-7-undecene or 1,5-diazabicyclo[4.3.0]-5-nonene. Further, an appropriate amount of an aqueous solution of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or various organic solvents in which the composition of the present invention is dissolved may be added to the alkaline aqueous solution as a developing solution. Further, as the developing method, for example, a method such as a liquid-filling method, a shaking method, a washing method, or the like can be suitably employed. The development time varies depending on the composition of the composition to be used, and may be, for example, 30 to 120 seconds.

(4)將步驟(3)中顯影後的塗膜進行加熱的步驟(4) a step of heating the developed coating film in the step (3)

在本步驟中，將步驟(3)中顯影後的塗膜進行加熱使其乾燥。即，在(3)的顯影步驟後，對形成圖案的薄膜較佳為進行流水清洗等沖洗處理，並且，較佳為通過採用高壓汞燈等進行全面照射放射線(後曝光步驟)，將該薄膜中殘留的1,2-醌二疊氮化合物進行分解處理。然後，通過將該薄膜用加熱板、烘箱等加熱裝置進行加熱處理(後烘焙處理)，對該薄膜進行固化處理。上述後曝光步驟中的曝光量，較佳為2000～5000J/m2 左右。另外，該固化處理中的加熱溫度為例如120～250℃。加熱時間根據加熱機器的種類而不同，例如，當在加熱板上進行加熱處理時，可以為5～30分鐘，當在烘箱中進行加熱處理時，可以為30～90分鐘。此時，還可以採用進行2次以上加熱步驟的分步烘焙法等。In this step, the developed film in the step (3) is heated and dried. That is, after the development step of (3), it is preferable to perform the rinsing treatment such as running water cleaning on the film forming the pattern, and it is preferable to perform the total irradiation of the radiation by a high pressure mercury lamp or the like (post exposure step), and the film is preferably used. The residual 1,2-quinonediazide compound is subjected to decomposition treatment. Then, the film is subjected to a heat treatment (post-baking treatment) by a heating means such as a hot plate or an oven, and the film is subjected to a curing treatment. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J/m 2 . Further, the heating temperature in the curing treatment is, for example, 120 to 250 °C. The heating time varies depending on the type of the heating machine. For example, when heat treatment is performed on the hot plate, it may be 5 to 30 minutes, and when heat treatment is performed in an oven, it may be 30 to 90 minutes. In this case, a stepwise baking method or the like which performs a heating step twice or more may be employed.

如上形成的層間絕緣膜，對基板的黏合性良好，耐溶劑性和耐熱性優良，並具有高透光率和低介電常數。因此，該層間絕緣膜可適用於電子產品。另外，如上形成的微透鏡，對基板的貼緊性良好，耐溶劑性和耐熱性優良，並且具有高透光率和良好的熔融形狀。因此，該微透鏡可適合作為固體攝影元件的微透鏡使用。另外，本發明微透鏡的形狀，如圖1(a)所示，為半凸透鏡形狀。The interlayer insulating film formed as described above has good adhesion to a substrate, is excellent in solvent resistance and heat resistance, and has high light transmittance and low dielectric constant. Therefore, the interlayer insulating film can be applied to an electronic product. Further, the microlens formed as described above has good adhesion to the substrate, is excellent in solvent resistance and heat resistance, and has high light transmittance and a good melt shape. Therefore, the microlens can be suitably used as a microlens of a solid-state imaging element. Further, the shape of the microlens of the present invention is a semiconvex lens shape as shown in Fig. 1(a).

[實施例][Examples]

以下通過例示合成例和實施例對本發明進行更具體的說明，但是本發明並不局限於這些合成例和實施例。The present invention will be more specifically described below by way of the exemplified synthetic examples and examples, but the present invention is not limited to these synthetic examples and examples.

合成例1　共聚物[A-1]的合成Synthesis Example 1 Synthesis of Copolymer [A-1]

向裝有冷卻管和攪拌器的燒瓶中，加入7質量份2,2’-偶氮雙(2,4-二甲基戊腈)和200質量份二甘醇乙基甲基醚。繼續加入16質量份甲基丙烯酸、16質量份甲基丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯、20質量份丙烯酸2-甲基環己基酯、40質量份甲基丙烯酸縮水甘油酯、10質量份苯乙烯和3質量份α-甲基苯乙烯二聚物，用氮氣置換後，開始緩慢攪拌。使溶液的溫度升至70℃，保持該溫度4小時，得到含共聚物[A-1]的聚合物溶液。共聚物[A-1]的聚苯乙烯換算的重量平均分子量(Mw)為8000，分子量分佈(Mw/Mn)為2.3。另外，在此製得的聚合物溶液的固體含量濃度為34.4質量%。To the flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Further, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 2,6 ]decane-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, and 40 parts by mass of methyl group were added. Glycidyl acrylate, 10 parts by mass of styrene, and 3 parts by mass of α-methylstyrene dimer, after replacement with nitrogen, started to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The copolymer [A-1] had a polystyrene-equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw/Mn) of 2.3. Further, the polymer solution prepared herein had a solid content concentration of 34.4% by mass.

合成例2　共聚物[A-2]的合成Synthesis Example 2 Synthesis of Copolymer [A-2]

向裝有冷卻管和攪拌器的燒瓶中，加入8質量份2,2’-偶氮雙(2,4-二甲基戊腈)和220質量份二甘醇乙基甲基醚。繼續加入11質量份甲基丙烯酸、12質量份甲基丙烯酸四氫糠基酯、40質量份甲基丙烯酸縮水甘油酯、15質量份N-環己基馬來醯亞胺、10質量份甲基丙烯酸十二烷基酯、10質量份α-甲基-對羥基苯乙烯和3質量份α-甲基苯乙烯二聚物，用氮氣置換後，開始緩慢攪拌。使溶液的溫度升至70℃，保持該溫度5小時，得到含共聚物[A-2]的聚合物溶液。共聚物[A-2]的聚苯乙烯換算的重量平均分子量(Mw)為8000，分子量分佈(Mw/Mn)為2.3。另外，在此製得的聚合物溶液的固體含量濃度為31.9質量%。Into a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were added. Continue to add 11 parts by mass of methacrylic acid, 12 parts by mass of tetrahydrofurfuryl methacrylate, 40 parts by mass of glycidyl methacrylate, 15 parts by mass of N-cyclohexylmaleimide, 10 parts by mass of methacrylic acid The dodecyl ester, 10 parts by mass of α-methyl-p-hydroxystyrene, and 3 parts by mass of the α-methylstyrene dimer were slowly stirred after being replaced with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The copolymer [A-2] had a polystyrene-equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw/Mn) of 2.3. Further, the polymer solution prepared herein had a solid content concentration of 31.9% by mass.

實施例1Example 1

[感放射線性樹脂組成物的調製][Modulation of Radiation-Linear Resin Composition]

將相當於100質量份共聚物[A-1](固體成分)的量的作為[A]成分的上述合成例1中合成的含共聚物[A-1]的溶液、30質量份作為[B]成分的4,4’-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚(1.0莫耳)與1,2-萘醌二疊氮-5-磺醯氯(2.0莫耳)的縮合物[B-1]、以及5質量份作為[C]成分的[C-1](固體成分)進行混合，將其溶於二甘醇乙基甲基醚，使其固體含量濃度為30質量%，然後用孔徑為0.2μm的濾膜過濾，調製出感放射線性樹脂組成物的溶液(S-1)。A solution containing the copolymer [A-1] synthesized in the above Synthesis Example 1 as the component [A] in an amount corresponding to 100 parts by mass of the copolymer [A-1] (solid content), and 30 parts by mass of [B] a component of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) with 1,2 a condensate [B-1] of naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) and 5 parts by mass of [C-1] (solid component) as a component [C], and mixing The solution was dissolved in diethylene glycol ethyl methyl ether to have a solid content concentration of 30% by mass, and then filtered through a filter having a pore size of 0.2 μm to prepare a solution (S-1) of the radiation sensitive resin composition.

實施例2～4、6～21、比較例1～8Examples 2 to 4, 6 to 21, and Comparative Examples 1 to 8

[感放射線性樹脂組成物的調製][Modulation of Radiation-Linear Resin Composition]

除了[A]～[C]成分以及作為任選成分的[D]、[H]成分使用如表1中所述的種類、用量以外，與實施例1同樣地操作，調製出感放射線性樹脂組成物的溶液(S-2)～(S-4)(S-6)～(S-21)以及(s-1)～(s-8)。另外，在實施例2、13中，將具有羧基的[C]化合物與沒有羧基的[C]化合物進行倂用。此外，在實施例3、4、14、15中，除[C]化合物外，還使用了[D]化合物。The radiation sensitive resin was prepared in the same manner as in Example 1 except that the [A] to [C] components and the [D] and [H] components as the optional components were used in the same manner as in Example 1. Solutions (S-2) to (S-4) (S-6) to (S-21) and (s-1) to (s-8) of the composition. Further, in Examples 2 and 13, a [C] compound having a carboxyl group and a [C] compound having no carboxyl group were used. Further, in Examples 3, 4, 14, and 15, a compound [D] was used in addition to the [C] compound.

實施例5Example 5

[感放射線性樹脂組成物的調製][Modulation of Radiation-Linear Resin Composition]

在實施例1中，溶於二甘醇乙基甲基醚/丙二醇單甲醚乙酸酯=6/4中，使其固體含量濃度為20質量%，並添加了作為[G]成分的聚矽氧烷類界面活性劑，除此以外，與實施例1同樣地操作，調製出感放射線性樹脂組成物的溶液(S-5)。實施例1～21和比較例1～8中配入的各成分及其比率列於表1。In Example 1, it was dissolved in diethylene glycol ethyl methyl ether/propylene glycol monomethyl ether acetate = 6/4 to have a solid content concentration of 20% by mass, and a polycondensation as a [G] component was added. A solution (S-5) of the radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the siloxane-based surfactant was used. The components and their ratios in Examples 1 to 21 and Comparative Examples 1 to 8 are shown in Table 1.

表1中的成分的簡稱表示以下化合物。The abbreviations of the components in Table 1 represent the following compounds.

[C-1]：琥珀酸改性的季戊四醇三丙烯酸酯[C-1]: succinic acid-modified pentaerythritol triacrylate

[C-2]：三羥甲基丙烷三丙烯酸酯[C-2]: Trimethylolpropane triacrylate

[C-3]：季戊四醇三丙烯酸酯[C-3]: pentaerythritol triacrylate

[C-4]：季戊四醇二丙烯酸酯[C-4]: pentaerythritol diacrylate

[C-5]：參(2-丙烯醯氧基乙基)異三聚氰酸酯[C-5]: ginseng (2-propenyloxyethyl) isocyanate

[D-1]：二季戊四醇五丙烯酸酯[D-1]: dipentaerythritol pentaacrylate

[D-2]：二季戊四醇六丙烯酸酯[D-2]: dipentaerythritol hexaacrylate

[D-3]：ω-羧基-聚己內酯單丙烯酸酯[D-3]: ω-carboxy-polycaprolactone monoacrylate

[G]：聚矽氧烷類界面活性劑(東麗DOW CORNING SILICONE(股)生產的“SH-28PA”)[G]: Polyoxane type surfactant ("SH-28PA" produced by Toray DOW CORNING SILICONE)

[H]：γ-環氧丙氧基丙基三甲氧基矽烷(CHISSO(股)生產的“S-510”)[H]: γ-glycidoxypropyltrimethoxydecane ("S-510" produced by CHISSO)

實施例22～42、比較例9～16Examples 22 to 42 and Comparative Examples 9 to 16

<層間絕緣膜的物性評價><Evaluation of physical properties of interlayer insulating film>

使用如上調製的感放射線性樹脂組成物，對其作為層間絕緣膜的各種物性如下進行評價。Using the radiation sensitive resin composition prepared as above, various physical properties as an interlayer insulating film were evaluated as follows.

[敏感度的評價][Evaluation of sensitivity]

對於實施例22～25、27～42和比較例9～16，採用旋塗機將表2中所列的各組成物溶液塗布於矽基板上後，在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。對於實施例26，採用縫模塗布器進行矽基板上組成物溶液(S-5)的塗布，在0.5Torr下進行真空乾燥後，再在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。採用Canon(股)製造的PLA-501F曝光機(超高壓汞燈)，使曝光時間進行變化，通過具有預定圖案的圖案遮罩對塗膜進行曝光。然後，採用表2中所示濃度的氫氧化四甲基銨水溶液(顯影液)，採用盛液法在25℃下進行顯影處理。顯影處理的時間，當採用0.4質量%濃度的顯影液時，為80秒，當採用2.38質量%濃度的顯影液時，為50秒，當採用0.28質量%濃度的顯影液時，為50秒。顯影處理後，用超純水對塗膜進行1分鐘流水沖洗，並使其乾燥，在矽片上形成圖案。在這種曝光和顯影處理中，測定使3.0μm線條和間隙(10對1)的間隙‧圖案完全溶解所需的曝光量。以各組成物的該值作為敏感度[J/m2 ]列於表2。當該值為620J/m2 以下時，敏感度判定為良好。For Examples 22 to 25, 27 to 42, and Comparative Examples 9 to 16, the respective composition solutions listed in Table 2 were applied onto a ruthenium substrate by a spin coater, and then prebaked at 90 ° C on a hot plate. In minutes, a coating film having a film thickness of 3.0 μm was formed. In Example 26, the composition of the composition solution (S-5) on the crucible substrate was applied by a slit die coater, vacuum-dried at 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 3.0 μm. The exposure time was changed by using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon, and the coating film was exposed by a pattern mask having a predetermined pattern. Then, development treatment was carried out at 25 ° C by a liquid-filling method using an aqueous solution of tetramethylammonium hydroxide (developing solution) at a concentration shown in Table 2. The development treatment time was 80 seconds when a developer having a concentration of 0.4% by mass was used, 50 seconds when a developer having a concentration of 2.38 mass% was used, and 50 seconds when a developer having a concentration of 0.28 mass% was used. After the development treatment, the coating film was rinsed with ultrapure water for 1 minute, and dried to form a pattern on the enamel sheet. In this exposure and development treatment, the amount of exposure required to completely dissolve the gap ‧ pattern of the line of 3.0 μm and the gap (10 to 1) was measured. This value of each composition was used as the sensitivity [J/m 2 ] and is shown in Table 2. When the value is 620 J/m 2 or less, the sensitivity is judged to be good.

[顯影裕度的評價][Evaluation of development margin]

對於實施例22～25、27～42和比較例9～16，採用旋塗機將表2中所示的各組成物溶液塗布於矽基板上後，在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。對於實施例26，採用縫模塗布器進行矽基板上組成物溶液(S-5)的塗布，在0.5Torr下進行真空乾燥後，再在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。採用Canon(股)製造的PLA-501F曝光機(超高壓汞燈)，通過具有3.0μm線條和間隙(10對1)圖案的遮罩，以相當於上述[敏感度評價]中測定的敏感度值的曝光量對塗膜進行曝光。然後，採用表2中所示濃度的氫氧化四甲基銨水溶液(顯影液)，採用盛液法在25℃下進行塗膜的顯影處理。顯影處理後，用超純水對塗膜進行1分鐘流水沖洗，並使其乾燥，在矽片上形成圖案。這裏，以使線條的線寬為3.0μm所需的顯影時間為最佳顯影時間(秒)列於表2。並且，在自最佳顯影時間起進一步繼續顯影時，測定直到3.0μm線條圖案脫落時的時間，作為顯影裕度(秒)列於表2。當該值為35秒以上時，顯影裕度判定為良好。For Examples 22 to 25, 27 to 42, and Comparative Examples 9 to 16, the respective composition solutions shown in Table 2 were applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C. In minutes, a coating film having a film thickness of 3.0 μm was formed. In Example 26, the composition of the composition solution (S-5) on the crucible substrate was applied by a slit die coater, vacuum-dried at 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 3.0 μm. The PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon was passed through a mask having a pattern of 3.0 μm lines and gaps (10 to 1) to correspond to the sensitivity measured in the above [sensitivity evaluation]. The exposure amount of the value is exposed to the coating film. Then, using a tetramethylammonium hydroxide aqueous solution (developing solution) having the concentration shown in Table 2, development treatment of the coating film was carried out at 25 ° C by a liquid-filling method. After the development treatment, the coating film was rinsed with ultrapure water for 1 minute, and dried to form a pattern on the enamel sheet. Here, the development time required for the line width of the line to be 3.0 μm as the optimum development time (second) is shown in Table 2. Further, when the development was further continued from the optimum development time, the time until the line pattern of 3.0 μm was dropped was measured, and the development margin (second) is shown in Table 2. When the value is 35 seconds or more, the development margin is judged to be good.

[耐溶劑性的評價][Evaluation of solvent resistance]

對於實施例22～25、27～42和比較例9～16，採用旋塗機將表2中所示的各組成物溶液塗布於矽基板上後，在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。對於實施例26，採用縫模塗布器進行矽基板上組成物溶液(S-5)的塗布，在0.5Torr下進行真空乾燥後，再在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。採用Canon(股)製造的PLA-501F曝光機(超高壓汞燈)以累積照射量為3000J/m2 對塗膜進行曝光，將該矽基板在潔淨烘箱中於220℃下加熱1小時，得到固化膜。這裏，測定所得固化膜的膜厚(T1)。然後，將形成了該固化膜的矽基板在溫度控制在70℃的二甲亞碸中浸漬20分鐘後，測定固化膜的膜厚(t1)，算出由浸漬導致的膜厚變化率{|t1-T1|/T1}×100[%]。膜厚變化率的計算結果列於表2。當該值為5%以下時，耐溶劑性判定為良好。另外，在耐溶劑性評價中形成的膜由於不需要形成圖案，故省略了顯影步驟，僅供對放射線照射步驟、塗膜形成步驟和加熱步驟進行評價。For Examples 22 to 25, 27 to 42, and Comparative Examples 9 to 16, the respective composition solutions shown in Table 2 were applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C. In minutes, a coating film having a film thickness of 3.0 μm was formed. In Example 26, the composition of the composition solution (S-5) on the crucible substrate was applied by a slit die coater, vacuum-dried at 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 3.0 μm. The coating film was exposed by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon, and the substrate was exposed to a cumulative irradiation amount of 3000 J/m 2 , and the substrate was heated in a clean oven at 220 ° C for 1 hour. Cured film. Here, the film thickness (T1) of the obtained cured film was measured. Then, the tantalum substrate on which the cured film was formed was immersed in dimethyl hydrazine having a temperature controlled at 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the film thickness change rate by the immersion was calculated as {|t1 -T1|/T1}×100[%]. The calculation results of the film thickness change rate are shown in Table 2. When the value is 5% or less, the solvent resistance is judged to be good. Further, since the film formed in the evaluation of the solvent resistance does not need to be patterned, the development step is omitted, and only the radiation irradiation step, the coating film forming step, and the heating step are evaluated.

[耐熱性的評價][Evaluation of heat resistance]

與上述耐溶劑性的評價時同樣地形成固化膜，測定所得固化膜的膜厚(T2)。然後，將該矽基板置於潔淨烘箱中在240℃下追加烘焙1小時後，測定該固化膜的厚度(t2)，計算由追加烘焙導致的膜厚變化率{|t2-T2|/T2}×100[%]。膜厚變化率的計算結果列於表2。當該值為5%以下時，耐熱性可認定為良好。A cured film was formed in the same manner as in the evaluation of the solvent resistance described above, and the film thickness (T2) of the obtained cured film was measured. Then, the ruthenium substrate was placed in a clean oven and additionally baked at 240 ° C for 1 hour, and then the thickness (t2) of the cured film was measured, and the film thickness change rate by the additional baking was calculated {|t2-T2|/T2} ×100[%]. The calculation results of the film thickness change rate are shown in Table 2. When the value is 5% or less, the heat resistance can be considered to be good.

[透明性的評價][Evaluation of transparency]

在上述耐溶劑性評價中，除了採用玻璃基板“CORNING 7059(由CORNING公司製造)”代替矽基板以外，同樣地進行操作，在玻璃基板上形成固化膜。採用分光光度計“150-20型雙光束(日立(股)製作所製造)”，在400～800nm波長範圍內測定具有該固化膜的玻璃基板的透光率(%)。此時的最低透光率值列於表2。當該最低透光率值為95%以上時，透明性判定為良好。In the evaluation of the solvent resistance, a glass substrate "CORNING 7059 (manufactured by CORNING)" was used instead of the ruthenium substrate, and a cured film was formed on the glass substrate in the same manner. The light transmittance (%) of the glass substrate having the cured film was measured in a wavelength range of 400 to 800 nm using a spectrophotometer "150-20 type double beam (manufactured by Hitachi Co., Ltd.)". The lowest transmittance values at this time are listed in Table 2. When the minimum light transmittance value is 95% or more, the transparency is judged to be good.

[耐熱透明性的評價][Evaluation of heat-resistant transparency]

與上述透明性評價同樣地在玻璃基板上形成固化膜，與上述耐熱性評價同樣地在潔淨烘箱中於240℃下進行1小時追加烘焙。然後，在與透明性評價時相同的條件下評價該基板的透光率。並且，按照下式求出透明性的變化率。結果列於表2。當該變化率為5%以下時，耐熱透明性可認定為良好。In the same manner as the above-described transparency evaluation, a cured film was formed on a glass substrate, and in the same manner as the heat resistance evaluation described above, additional baking was performed at 240 ° C for 1 hour in a clean oven. Then, the light transmittance of the substrate was evaluated under the same conditions as in the evaluation of the transparency. Further, the rate of change in transparency was obtained by the following formula. The results are shown in Table 2. When the rate of change is 5% or less, heat-resistant transparency can be considered to be good.

透明性變化率(%)=(透明性評價時的透光率-上述追加烘焙後的透光率)/透明性評價時的透光率×100Transparency change rate (%) = (light transmittance at the time of transparency evaluation - light transmittance after the above additional baking) / transmittance at the time of transparency evaluation × 100

[相對介電常數的評價][Evaluation of relative dielectric constant]

對於實施例22～25、27～42和比較例9～16，採用旋塗機將表2中所示的各組成物溶液塗布於研磨後的SUS 304制基板上後，在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。對於實施例26，採用縫模塗布器進行矽基板上組成物溶液(S-5)的塗布，在0.5Torr下進行真空乾燥後，再在加熱板上於90℃下預烘焙2分鐘，形成膜厚為3.0μm的塗膜。採用Canon(股)製造的PLA-501F曝光機(超高壓汞燈)，以累積照射量為3000J/m2 對塗膜進行曝光，將該矽基板在潔淨烘箱中於220℃下加熱1小時，得到膜厚為3.0μm的固化膜。採用蒸鍍法對該固化膜製作Pt/Pd電極圖案，製作出相對介電常數測定用的樣品。對該基板，採用橫河.Hewlett-Packard(股)製造的HP16451B電極和HP4284A精密LCR儀，通過CV法以10kHz的頻率測定該基板的相對介電常數。相對介電常數測定結果列於表2。當該值為3.9以下時，低介電常數性判定為良好。另外，在相對介電常數評價中形成的膜由於不需要形成圖案，故省略了顯影步驟，僅供對放射線照射步驟、塗膜形成步驟和加熱步驟進行評價。In each of Examples 22 to 25, 27 to 42, and Comparative Examples 9 to 16, the respective composition solutions shown in Table 2 were applied onto the polished SUS 304 substrate by a spin coater, and then dried on a hot plate. The film was prebaked at ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. In Example 26, the composition of the composition solution (S-5) on the crucible substrate was applied by a slit die coater, vacuum-dried at 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 3.0 μm. The coating film was exposed to a cumulative irradiation amount of 3000 J/m 2 using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon, and the crucible substrate was heated in a clean oven at 220 ° C for 1 hour. A cured film having a film thickness of 3.0 μm was obtained. A Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for measuring the relative dielectric constant. For the substrate, the HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd. and the HP4284A precision LCR meter were used, and the relative dielectric constant of the substrate was measured by a CV method at a frequency of 10 kHz. The results of the relative dielectric constant measurement are shown in Table 2. When the value is 3.9 or less, the low dielectric constant is judged to be good. Further, since the film formed in the evaluation of the relative dielectric constant does not need to be patterned, the development step is omitted, and only the radiation irradiation step, the coating film forming step, and the heating step are evaluated.

實施例43～62、比較例17～24Examples 43 to 62 and Comparative Examples 17 to 24

<微透鏡的物性評價><Physical property evaluation of microlenses>

使用如上調製的感放射線性樹脂組成物，對其作為微透鏡的各種物性如下進行評價。另外，這些實施例和比較例的耐溶劑性、耐熱性和透明性的評價，與採用相應的感放射線性樹脂組成物的上述層間絕緣膜的物性評價中的結果相同。Using the radiation sensitive resin composition prepared as above, various physical properties as microlenses were evaluated as follows. In addition, the evaluation of the solvent resistance, heat resistance, and transparency of these Examples and Comparative Examples was the same as the evaluation of the physical properties of the above-mentioned interlayer insulating film using the corresponding radiation sensitive resin composition.

[敏感度的評價][Evaluation of sensitivity]

對於實施例43～62和比較例17～24，採用旋塗機將表3中所示的各組成物溶液塗布於矽基板上後，在加熱板上於90℃下預烘焙2分鐘，形成膜厚為2.0μm的塗膜。採用Nikon(股)製造的NSR1755i7A縮小投影曝光機(NA=0.50，λ=365nm)，使曝光時間進行變化，通過具有規定圖案的圖案遮罩對塗膜進行曝光。然後，採用表3中所示濃度的氫氧化四甲基銨水溶液(顯影液)，採用盛液法在25℃下進行1分鐘顯影處理。顯影處理後，將塗膜用水沖洗，並使其乾燥，在矽片上形成圖案。在這種曝光和顯影處理中，測定使0.8μm線條和間隙圖案(1對1)的間隙線寬為0.8μm所需的曝光時間。以各組成物的該值作為敏感度(J/m2 )列於表3。當該值為1200J/m2 以下時，敏感度判定為良好。For Examples 43 to 62 and Comparative Examples 17 to 24, each of the composition solutions shown in Table 3 was applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 2.0 μm. The NSR1755i7A reduced projection projection machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Co., Ltd. was used to change the exposure time, and the coating film was exposed by a pattern mask having a predetermined pattern. Then, using a tetramethylammonium hydroxide aqueous solution (developing solution) at a concentration shown in Table 3, development treatment was carried out at 25 ° C for 1 minute by a liquid-filling method. After the development treatment, the coating film was rinsed with water and dried to form a pattern on the crepe sheet. In this exposure and development treatment, the exposure time required to make the gap line width of the 0.8 μm line and the gap pattern (1 to 1) 0.8 μm was measured. This value of each composition was listed as the sensitivity (J/m 2 ) in Table 3. When the value is 1200 J/m 2 or less, the sensitivity is judged to be good.

[顯影裕度的評價][Evaluation of development margin]

對於實施例43～62和比較例17～24，採用旋塗機將表3中所示的各組成物溶液塗布於矽基板上後，在加熱板上於90℃下預烘焙2分鐘，形成膜厚為2.0μm的塗膜。採用Nikon(股)製造的NSR1755i7A縮小投影曝光機(NA=0.50，λ=365nm)，通過具有規定圖案的圖案遮罩，以相當於上述[敏感度評價]中測定的敏感度值的曝光量對塗膜進行曝光。然後，採用表3中所示濃度的氫氧化四甲基銨水溶液(顯影液)，採用盛液法在25℃下進行1分鐘塗膜顯影處理。顯影處理後，將塗膜用水沖洗，並使其乾燥，在矽片上形成圖案。這裏，以使0.8μm線條和間隙圖案(1對1)的間隙線寬為0.8μm所需的顯影時間作為最佳顯影時間列於表3。並且，在自最佳顯影時間起進一步繼續顯影時，測定直到0.8μm的圖案脫落時的時間(秒)，作為顯影裕度列於表3。當該值為30秒以上時，顯影裕度判定為良好。For Examples 43 to 62 and Comparative Examples 17 to 24, each of the composition solutions shown in Table 3 was applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 2.0 μm. The NSR1755i7A reduction projection exposure machine (NA=0.50, λ=365 nm) manufactured by Nikon Co., Ltd. was masked by a pattern having a predetermined pattern, and the exposure amount corresponding to the sensitivity value measured in the above [sensitivity evaluation] was used. The film is exposed. Then, using a tetramethylammonium hydroxide aqueous solution (developing solution) having the concentration shown in Table 3, a coating film development treatment was carried out at 25 ° C for 1 minute by a liquid-filling method. After the development treatment, the coating film was rinsed with water and dried to form a pattern on the crepe sheet. Here, the development time required to make the gap line width of the 0.8 μm line and the gap pattern (1 to 1) 0.8 μm as the optimum development time is shown in Table 3. Further, when the development was further continued from the optimum development time, the time (seconds) until the pattern of 0.8 μm was dropped was measured, and the development margin is shown in Table 3. When the value is 30 seconds or longer, the development margin is judged to be good.

[微透鏡的形成][Formation of microlenses]

對於實施例43～62和比較例17～24，採用旋塗機將表3中所示的各組成物溶液塗布於矽基板上後，在加熱板上於90℃下預焙燒2分鐘，形成膜厚為2.0μm的塗膜。採用Nikon(股)製造的NSR1755i7A縮小投影曝光機(NA=0.50，λ=365nm)，通過具有4.0μm點‧2.0μm間隙圖案的圖案遮罩，以相當於上述[敏感度評價]中測定的敏感度值的曝光量，對塗膜進行曝光。然後，採用表3中所示濃度的氫氧化四甲基銨水溶液(顯影液)，採用盛液法於25℃下進行1分鐘塗膜顯影處理。顯影處理後，將塗膜用水沖洗，並使其乾燥，在矽片上形成圖案。然後，採用Canon(股)製造的PLA-501F曝光機(超高壓汞燈)，以累積照射量為3000J/m2 對塗膜進行曝光。然後，採用加熱板，在160℃下加熱塗膜10分鐘後，進一步在230℃下加熱10分鐘，使其熔融流動出圖案，形成微透鏡。所形成的微透鏡的底部(與基板接合的面)的尺寸(直徑)和剖面形狀列於表3。剖面形狀，如圖1所示，當為半凸透鏡形狀時記作(a)，當為近似梯形狀時記作(b)。當微透鏡底部的尺寸超過4.0μm且不足4.6μm時，該底部尺寸判定為良好。若微透鏡底部的尺寸為5.0μm以上，則其處於與相鄰透鏡相互接觸的狀態，是不佳的。此外，剖面形狀，當其為如(a)所示的半凸透鏡形狀時判定為良好，而為如(b)所示的近似梯形時判定為不合格。For each of Examples 43 to 62 and Comparative Examples 17 to 24, each of the composition solutions shown in Table 3 was applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film. A coating film having a thickness of 2.0 μm. The NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Co., Ltd. was masked by a pattern having a gap pattern of 4.0 μm dots and ‧ 2.0 μm to correspond to the sensitivity measured in the above [sensitivity evaluation] The exposure amount of the degree is used to expose the coating film. Then, using a tetramethylammonium hydroxide aqueous solution (developing solution) having a concentration shown in Table 3, a coating film development treatment was carried out at 25 ° C for 1 minute by a liquid-filling method. After the development treatment, the coating film was rinsed with water and dried to form a pattern on the crepe sheet. Then, the coating film was exposed to a cumulative irradiation amount of 3000 J/m 2 using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon. Then, the coating film was heated at 160 ° C for 10 minutes using a hot plate, and further heated at 230 ° C for 10 minutes to melt and flow out a pattern to form a microlens. The dimensions (diameter) and cross-sectional shape of the bottom of the formed microlens (the surface joined to the substrate) are shown in Table 3. The cross-sectional shape, as shown in Fig. 1, is referred to as (a) when it is a semi-convex lens shape, and is referred to as (b) when it is an approximate trapezoidal shape. When the size of the bottom of the microlens exceeds 4.0 μm and is less than 4.6 μm, the bottom size is judged to be good. If the size of the bottom of the microlens is 5.0 μm or more, it is in a state of being in contact with an adjacent lens, which is not preferable. Further, the cross-sectional shape was judged to be good when it was in the shape of a semiconvex lens as shown in (a), and was judged to be unacceptable when it was approximately trapezoidal as shown in (b).

由表2和表3所示的結果可知，若採用含有分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的化合物的本發明感放射線性樹脂組成物，可以獲得具有良好的放射線敏感度、顯影裕度、耐溶劑性、耐熱性、透明性和低介電常數，特別是放射線敏感度格外優異的層間絕緣膜。並且可知，若採用該組成物，除了其優異的物性以外，還能夠形成具有良好的熔融形狀的微透鏡。From the results shown in Tables 2 and 3, it is understood that a compound containing a skeleton having at least one ethylenically unsaturated bond in the molecule and having a skeleton derived from trimethylolpropane or pentaerythritol or an isocyanurate skeleton is used. The radiation sensitive linear resin composition of the present invention can obtain an interlayer insulating film which is excellent in radiation sensitivity, development margin, solvent resistance, heat resistance, transparency, and low dielectric constant, and particularly excellent in radiation sensitivity. Further, it has been found that the composition can form a microlens having a good melt shape in addition to excellent physical properties.

第1圖(a)、(b)為微透鏡剖面形狀的示意圖。Fig. 1 (a) and (b) are schematic views showing the cross-sectional shape of the microlens.

Claims (8)

一種感放射線性樹脂組成物，其含有：[A]鹼可溶性樹脂；[B]1,2-醌二疊氮化合物；以及[C]分子中具有至少一個乙烯性不飽和鍵，且具有來自於三羥甲基丙烷或季戊四醇的骨架、或者異三聚氰酸酯骨架的化合物：[A]成分的鹼可溶性樹脂為含有(a1)不飽和羧酸及/或不飽和羧酸酐，以及(a2)具有環氧基之不飽和化合物的不飽和化合物之共聚物，且(a2)具有環氧基之不飽和化合物為甲基丙烯酸縮水甘油酯、甲基丙烯酸-6,7-環氧基庚基酯、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄基縮水甘油基醚或甲基丙烯酸3,4-環氧基環己基酯。 A radiation sensitive resin composition comprising: [A] an alkali-soluble resin; [B] 1,2-quinonediazide compound; and [C] having at least one ethylenically unsaturated bond in the molecule, and having a skeleton of trimethylolpropane or pentaerythritol or a compound of an isocyanurate skeleton: the alkali-soluble resin of the component [A] contains (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) a copolymer of an unsaturated compound having an epoxy group-containing unsaturated compound, and (a2) an epoxy group-containing unsaturated compound is glycidyl methacrylate or methacrylic acid-6,7-epoxyheptyl ester , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether or 3,4-epoxycyclohexyl methacrylate. 如申請專利範圍第1項之感放射線性樹脂組成物，其中[C]成分的化合物所具有的乙烯性不飽和鍵為丙烯酸酯或甲基丙烯酸酯的乙烯性不飽和鍵。 The radiation sensitive linear resin composition according to claim 1, wherein the ethylenically unsaturated bond of the compound of the [C] component is an ethylenically unsaturated bond of an acrylate or a methacrylate. 如申請專利範圍第1或2項之感放射線性樹脂組成物，其係用於形成層間絕緣膜。 A radiation sensitive resin composition as claimed in claim 1 or 2, which is used for forming an interlayer insulating film. 如申請專利範圍第1或2項之感放射線性樹脂組成物，其係用於形成微透鏡。 A radiation sensitive resin composition as claimed in claim 1 or 2, which is used to form a microlens. 一種形成層間絕緣膜之方法，其包括：(1)在基板上形成如申請專利範圍第3項之感放射線性樹 脂組成物的塗膜的步驟，(2)對步驟(1)中形成的塗膜的至少一部分照射放射線的步驟，(3)將步驟(2)中照射放射線後的塗膜進行顯影的步驟，及(4)將步驟(3)中顯影後的塗膜進行加熱的步驟。 A method of forming an interlayer insulating film, comprising: (1) forming a radiation-sensitive linear tree as in claim 3 of the patent application scope on a substrate a step of coating a film of the fat composition, (2) a step of irradiating at least a part of the coating film formed in the step (1), and (3) a step of developing the coating film irradiated with the radiation in the step (2), And (4) a step of heating the coating film developed in the step (3). 一種層間絕緣膜，其係藉由如申請專利範圍第5項之方法而形成。 An interlayer insulating film formed by the method of claim 5 of the patent application. 一種形成微透鏡之方法，其包括：(1)在基板上形成如申請專利範圍第4項之感放射線性樹脂組成物的塗膜的步驟，(2)對步驟(1)中形成的塗膜的至少一部分照射放射線的步驟，(3)將步驟(2)中照射放射線後的塗膜進行顯影的步驟，及(4)將步驟(3)中顯影後的塗膜進行加熱的步驟。 A method of forming a microlens, comprising: (1) a step of forming a coating film of a radiation sensitive resin composition as in claim 4 of the patent application, and (2) a coating film formed in the step (1) At least a part of the step of irradiating the radiation, (3) the step of developing the coating film irradiated with the radiation in the step (2), and (4) the step of heating the coating film developed in the step (3). 一種微透鏡，其係藉由如申請專利範圍第7項之方法而形成。 A microlens formed by the method of claim 7 of the patent application.
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