TW201906875A

TW201906875A - Photosensitive resin composition, cured product, black matrix, and image display device

Info

Publication number: TW201906875A
Application number: TW107122656A
Authority: TW
Inventors: 植松卓也; 関口直人
Original assignee: 日商三菱化學股份有限公司
Priority date: 2017-06-29
Filing date: 2018-06-29
Publication date: 2019-02-16
Also published as: JPWO2019004365A1; WO2019004365A1; JP7120234B2

Abstract

Provided is a photosensitive resin composition having a superior substrate adhesion property and capable of suppressing and controlling line width change in high- temperature processing. The photosensitive resin composition of the present invention comprises (a) an alkali soluble resin, (b) a photopolymerizable monomer, (c) a photo-radical polymerization initiator, (d) an organosilicon compound, and (e) a coloring material, and characterized in that (a) the alkali soluble resin contains an epoxy(meta)acrylate resin having a carboxyl group, and the (d) the organosilicon compound contains an organosilicon vinyl polymer (d-1) having a repeating unit represented by the following general formula (1).

Description

感光性樹脂組合物、硬化物、黑色矩陣及圖像顯示裝置Photosensitive resin composition, cured product, black matrix and image display device

本發明係關於一種感光性樹脂組合物、硬化物、黑色矩陣及圖像顯示裝置。尤其是關於一種基板密接性優異，可實現高溫處理時之線寬變化之抑制及其控制之適於形成高精細圖案之感光性樹脂組合物、使該感光性樹脂組合物硬化而成之硬化物及黑色矩陣、具有該硬化物或該黑色矩陣之圖像顯示裝置。本發明之感光性樹脂組合物尤其是適於可形成高感度且高精細之細線之黑色矩陣(Black Matrix；以下有時簡稱為「BM」)形成用感光性樹脂組合物。將2017年6月29日於日本專利廳提出申請之日本專利特願2017-127704之說明書、申請專利範圍、圖式及發明摘要之全部內容、以及本說明書中所引用之文獻等所揭示之內容的一部分或全部引用至此處，並作為本說明書之揭示內容編入。The present invention relates to a photosensitive resin composition, a cured product, a black matrix, and an image display device. In particular, it relates to a photosensitive resin composition suitable for forming a high-definition pattern and capable of suppressing and controlling line width change during high-temperature processing and having excellent substrate adhesion, and a cured product obtained by curing the photosensitive resin composition And a black matrix, an image display device having the hardened object or the black matrix. The photosensitive resin composition of the present invention is particularly suitable for a photosensitive resin composition for forming a black matrix (Black Matrix; hereinafter sometimes simply referred to as "BM") which can form high-sensitivity and high-definition fine lines. The entire contents of the specification, patent application scope, drawings and abstract of the Japanese Patent Application 2017-127704 filed with the Japanese Patent Office on June 29, 2017, and the documents cited in this specification are disclosed Part or all of is cited here and incorporated as the disclosure of this specification.

彩色濾光片係通常於玻璃、塑膠等透明基板之表面形成黑色之黑色矩陣，繼而將紅、綠、藍等3種以上之不同顏色之像素依序以格子狀、條紋狀或鑲嵌狀等圖案形成所得者。圖案尺寸視彩色濾光片之用途以及各顏色而不同，但通常為5～700 μm左右。Color filters usually form a black matrix on the surface of glass, plastic and other transparent substrates, and then sequentially arrange pixels of three or more different colors such as red, green and blue in a lattice, stripe or mosaic pattern Form the income. The pattern size depends on the use of the color filter and each color, but it is usually about 5 to 700 μm.

作為彩色濾光片之代表性製造方法，目前已知有顏料分散法。於藉由顏料分散法製造彩色濾光片之情形時，首先將含有碳黑等黑色顏料之感光性樹脂組合物塗佈於透明基板上後使之乾燥，進而進行圖像曝光、顯影後，藉由200℃以上之高溫處理使之加熱硬化，藉此形成BM。於所形成之BM上，紅、綠、藍等每種顏色重複形成像素，從而形成具有BM及像素之彩色濾光片。As a representative manufacturing method of a color filter, a pigment dispersion method is currently known. In the case of manufacturing a color filter by the pigment dispersion method, first, a photosensitive resin composition containing black pigments such as carbon black is coated on a transparent substrate and then dried, and then the image is exposed and developed. BM is formed by heating and hardening by high-temperature treatment of 200°C or higher. On the formed BM, pixels of each color such as red, green, and blue are repeatedly formed to form a color filter having BM and pixels.

BM一般格子狀、條紋狀或鑲嵌狀地配置於紅、綠、藍等像素之間，有藉由各像素間之混色抑制來提高對比度或防止漏光之作用。因此，對於BM，要求較高之遮光性。又，形成BM後所形成之紅、綠、藍等像素之邊緣部由於一部分與該BM重疊，故而受到BM之膜厚之影響，於重疊部分形成階差。該重疊部分會損害像素之平坦性，導致產生液晶單元間隙之不均一化或液晶之配向混亂，而成顯示能力降低之原因。因此，近年來，尤其是要求使BM薄膜化，且為了即便於己薄膜化時亦顯現出充分之遮光性，有感光性樹脂組合物中之顏料含有比率變得更高之傾向。此種顏料增量會帶來可交聯之成分之減量，因此導致基板密接力降低。因此，要求有不會使基板密接力降低之對策。BM is generally arranged between red, green, and blue pixels in a lattice, stripe, or mosaic pattern, and has the effect of improving contrast or preventing light leakage by suppressing color mixture between the pixels. Therefore, for BM, higher light-shielding properties are required. In addition, the edge portions of the red, green, and blue pixels formed after forming the BM partially overlap the BM, and therefore are affected by the film thickness of the BM, so that a step is formed in the overlapping portion. The overlapping portion may impair the flatness of the pixel, resulting in non-uniformity in the gap of the liquid crystal cell or chaotic alignment of the liquid crystal, which causes a decrease in display capability. Therefore, in recent years, in particular, BM has been required to be thinned, and in order to exhibit sufficient light-shielding properties even when it has been thinned, the pigment content ratio in the photosensitive resin composition tends to be higher. This increase in pigment will bring about a reduction in cross-linkable components, thus resulting in reduced substrate adhesion. Therefore, countermeasures are not required to reduce the substrate adhesion.

於專利文獻1中記載有如下情況：藉由使用含有特定有機矽化合物之感光性樹脂組合物，而於高顏料濃度之情形、或高微細化之情形時，室溫下及高溫高濕下之基板密接性變得良好。又，於專利文獻2中記載有如下情況：藉由使用含有具有烷氧基矽烷基及酸基之特定化合物之著色硬化性組合物，而即便於顏料濃度較高之情形時，亦可形成保存穩定性、及硬化性優異，且與基板之密接性、及顯影性優異之著色膜。Patent Document 1 describes the case where, by using a photosensitive resin composition containing a specific organosilicon compound, in the case of high pigment concentration, or in the case of high fineness, at room temperature and under high temperature and high humidity The substrate adhesion becomes good. In addition, Patent Document 2 describes that by using a color-curing composition containing a specific compound having an alkoxysilane group and an acid group, even when the pigment concentration is high, it can be stored A coloring film excellent in stability and hardenability, and excellent in adhesion to the substrate and developability.

另一方面，為了省能源化或移動式電池之長壽命化，有背光裝置之輸出變低之傾向，為了即便於此種條件下亦可以高亮度進行圖像顯示，而進行作為遮光部之BM之細線化。又，近年來，於液晶顯示器之市場上，如平板等之小型化成為主流，且對於大型之電視，高解像度之要求變高。由於該等原因，對於BM之高精細化之期望變高，近年來，關於BM細線之線寬，要求已從先前之10 μm左右到目前之6 μm左右。 [先前技術文獻] [專利文獻]On the other hand, in order to save energy or extend the life of the mobile battery, the output of the backlight device tends to be low. In order to display images with high brightness even under such conditions, the BM is used as a light-shielding part Thinning. Moreover, in recent years, in the market of liquid crystal displays, miniaturization such as flat panels has become the mainstream, and the requirements for high resolution have become higher for large-scale TVs. For these reasons, the expectation of high-definition BM has become higher. In recent years, the line width of BM thin lines has been increased from the previous 10 μm to the current 6 μm. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利特開2016-24319號公報 [專利文獻2]日本專利特開2010-85723號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-24319 [Patent Document 2] Japanese Patent Laid-Open No. 2010-85723

[發明所欲解決之問題][Problems to be solved by the invention]

若為正錐之形狀，則於膜厚約1 μm時穩定地形成線寬6 μm之BM細線圖案存在極限，而要求更接近垂直之錐形角之細線圖案。進而，細線圖案係藉由高溫處理進行硬化所獲得，但樹脂成分於硬化反應之開始前會暫時軟化，進行流動(熔合)而引起線寬變粗之現象。因此，要求抑制高溫處理時之熔合，又，對該抑制之程度進行控制之手法。本發明者等人對專利文獻1及2所記載之感光性樹脂組合物進行研究，結果發現，雖對於基板之密接力大幅提昇，但由於高溫處理(加熱硬化)時之熔合而導致產生細線之線寬變粗，而變得難以形成細線圖案。因此，本發明之目的在於提供一種基板密接性優異，可實現高溫處理時之線寬變化之抑制及其控制之感光性樹脂組合物。 [解決問題之技術手段]If the shape is a positive cone, there is a limit to form a BM thin line pattern with a line width of 6 μm steadily when the film thickness is about 1 μm, and a thin line pattern closer to a vertical tapered angle is required. Furthermore, the thin line pattern is obtained by hardening by high-temperature treatment, but the resin component temporarily softens before the start of the curing reaction, and flows (fusions) to cause the line width to become thick. Therefore, it is required to suppress fusion during high-temperature treatment and to control the degree of suppression. The inventors of the present invention have studied the photosensitive resin compositions described in Patent Documents 1 and 2 and found that although the adhesion to the substrate is greatly improved, thin wires are produced due to fusion during high-temperature treatment (heat curing) The line width becomes thicker, and it becomes difficult to form a thin line pattern. Therefore, an object of the present invention is to provide a photosensitive resin composition that is excellent in substrate adhesion and can realize suppression and control of line width change during high-temperature processing. [Technical means to solve the problem]

本發明者等人為了解決上述課題而進行銳意研究，結果發現，藉由使感光性樹脂組合物含有特定之鹼可溶性樹脂及特定之有機矽化合物，可解決上述課題。即，本發明之主旨係存在於以下。The inventors of the present invention conducted intensive research in order to solve the above-mentioned problems, and found that the above-mentioned problems can be solved by including a specific alkali-soluble resin and a specific organosilicon compound in the photosensitive resin composition. That is, the gist of the present invention is as follows.

[1]一種感光性樹脂組合物，其特徵在於：其係含有(a)鹼可溶性樹脂、(b)光聚合性單體、(c)光自由基聚合起始劑、(d)有機矽化合物、及(e)色料者，且上述(a)鹼可溶性樹脂含有具有羧基之環氧(甲基)丙烯酸酯樹脂，上述(d)有機矽化合物含有具有下述通式(1)所表示之重複單元之有機矽乙烯系聚合物(d-1)。[1] A photosensitive resin composition, characterized in that it contains (a) alkali-soluble resin, (b) photopolymerizable monomer, (c) photoradical polymerization initiator, (d) organosilicon compound , And (e) colorants, and (a) the alkali-soluble resin contains an epoxy (meth)acrylate resin having a carboxyl group, and (d) the organosilicon compound contains the following general formula (1) Silicone polymer (d-1) of repeating unit.

[化1] [Chemical 1]

式(1)中，R¹ 表示氫原子或可具有取代基之烷基， R² ～R⁴ 分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、可具有取代基之芳基、或可具有取代基之芳氧基， L表示2價連結基， x表示0或1。In formula (1), R ¹ represents a hydrogen atom or an alkyl group which may have a substituent, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or An aryl group having a substituent, or an aryloxy group which may have a substituent, L represents a divalent linking group, and x represents 0 or 1.

[2]如[1]記載之感光性樹脂組合物，其中上述(e)色料含有碳黑。[2] The photosensitive resin composition according to [1], wherein the color material (e) contains carbon black.

[3]一種硬化物，其係使如[1]或[2]記載之感光性樹脂組合物硬化而成者。 [4]一種黑色矩陣，其包含如[3]記載之硬化物。 [5]一種圖像顯示裝置，其具有如[3]記載之硬化物或如[4]記載之黑色矩陣。 [發明之效果][3] A cured product obtained by curing the photosensitive resin composition as described in [1] or [2]. [4] A black matrix including the hardened product described in [3]. [5] An image display device having the cured product described in [3] or the black matrix described in [4]. [Effect of invention]

根據本發明，可提供一種基板密接性優異，可實現高溫處理時之線寬變化之抑制及其控制之感光性樹脂組合物。According to the present invention, it is possible to provide a photosensitive resin composition excellent in substrate adhesion and capable of suppressing and controlling line width variation during high-temperature processing.

以下，對本發明之實施形態具體地進行說明，但本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變更並實施。再者，於本發明中，所謂「(甲基)丙烯酸」意指「丙烯酸及/或甲基丙烯酸」，關於「(甲基)丙烯酸酯」、「(甲基)丙烯醯基」亦相同。Hereinafter, the embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and various modifications and implementations can be made within the scope of the gist thereof. In addition, in the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

本發明中，所謂「總固形物成分」意指感光性樹脂組合物中或下述之墨水中所含有之溶劑以外之全部成分。本發明中，所謂重量平均分子量係指利用GPC(凝膠滲透層析法)之聚苯乙烯換算之重量平均分子量(Mw)。又，本發明中，所謂「胺值」，只要無特別說明，則表示有效固形物成分換算之胺值，係以與分散劑之固形物成分每1 g之鹼量相當量之KOH的重量表示之值。再者，關於測定方法，於下文進行說明。又，於本發明中，所謂「酸值」，只要無特別說明，則為藉由JIS K 2501-2003所記載之方法所測得之值。In the present invention, the "total solid content component" means all components other than the solvent contained in the photosensitive resin composition or the ink described below. In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene converted by GPC (gel permeation chromatography). In addition, in the present invention, the "amine value", unless otherwise specified, indicates the amine value in terms of effective solid content conversion, and is expressed by the weight of KOH equivalent to the amount of alkali per 1 g of the solid content of the dispersant. Value. In addition, the measurement method will be described below. In addition, in the present invention, the "acid value" is a value measured by a method described in JIS K 2501-2003 unless otherwise specified.

[感光性樹脂組合物] 本發明之感光性樹脂組合物之特徵在於：其係含有(a)鹼可溶性樹脂、(b)光聚合性單體、(c)光自由基聚合起始劑、(d)有機矽化合物、及(e)色料者，且上述(a)鹼可溶性樹脂含有具有羧基之環氧(甲基)丙烯酸酯樹脂，上述(d)有機矽化合物含有具有下述通式(1)所表示之重複單元之有機矽乙烯系聚合物(d-1)。[Photosensitive resin composition] The photosensitive resin composition of the present invention is characterized by containing (a) alkali-soluble resin, (b) photopolymerizable monomer, (c) photoradical polymerization initiator, ( d) Organosilicon compound and (e) color material, and (a) the alkali-soluble resin contains an epoxy (meth)acrylate resin having a carboxyl group, and (d) the organosilicon compound contains the following general formula ( 1) The organosilicon polymer (d-1) of the repeating unit represented.

本發明之感光性樹脂組合物亦可進而含有分散劑、硫醇類，亦可視需要含有其他之密接提高劑、界面活性劑(塗佈性提高劑)、顏料衍生物、顯影改良劑、紫外線吸收劑、抗氧化劑等調配成分，通常將各調配成分於溶解或分散於有機溶劑中之狀態下使用。本發明之特徵之一在於如下方面：感光性樹脂組合物含有(d)有機矽化合物，尤其是上述(d)有機矽化合物含有具有下述通式(1)所表示之重複單元之有機矽乙烯系聚合物(d-1)。首先，對於(d)有機矽化合物進行說明。The photosensitive resin composition of the present invention may further contain a dispersant and a thiol, and may also contain other adhesion enhancers, surfactants (coatability improvers), pigment derivatives, development improvers, and ultraviolet absorbers as necessary. Agents, antioxidants and other formulated components are usually used in a state where each formulated component is dissolved or dispersed in an organic solvent. One of the characteristics of the present invention lies in the following aspects: the photosensitive resin composition contains (d) an organosilicon compound, especially the (d) organosilicon compound contains an organosilicon having a repeating unit represented by the following general formula (1) Series polymer (d-1). First, the (d) organosilicon compound will be described.

＜(d)有機矽化合物＞本發明之感光性樹脂組合物含有(d)有機矽化合物。藉由含有(d)有機矽化合物，可與成為支持體之玻璃等透明基板結合，而基板密接性變得良好。<(d) Organosilicon compound> The photosensitive resin composition of this invention contains (d) an organosilicon compound. By containing (d) an organosilicon compound, it can be combined with a transparent substrate such as glass that becomes a support, and the substrate adhesion becomes good.

＜有機矽乙烯系聚合物(d-1)＞尤其是於本發明之感光性樹脂組合物中，上述(d)有機矽化合物含有具有下述通式(1)所表示之重複單元之有機矽乙烯系聚合物(d-1)(以下，有時簡記為「有機矽乙烯系聚合物(d-1)」)。藉由如上述般含有有機矽乙烯系聚合物(d-1)，認為其含有有機矽原子之側鏈藉由縮合反應而形成大量交聯點，從而於塗膜內部形成立體網狀結構(團簇)。認為藉由使該立體網狀結構凝膠化而熔合得到抑制。又，認為由於為乙烯系聚合物，故而於感光性樹脂組合物之塗膜內融合擴散，而導致形成一樣之團簇。<Organic Silicone Polymer (d-1)> Especially in the photosensitive resin composition of the present invention, the (d) organosilicon compound contains an organosilicon having a repeating unit represented by the following general formula (1) Vinyl polymer (d-1) (hereinafter, sometimes simply referred to as "organosilicon vinyl polymer (d-1)"). By containing the organosilicon polymer (d-1) as described above, it is considered that the side chains containing organosilicon atoms form a large number of cross-linking points by condensation reaction, thereby forming a three-dimensional network structure (group in the coating film cluster). It is considered that fusion is suppressed by gelling the three-dimensional network structure. In addition, it is thought that because it is an ethylene-based polymer, it is fused and diffused in the coating film of the photosensitive resin composition, resulting in the formation of the same cluster.

[化2] [Chem 2]

(R¹ ) 上述式(1)中，R¹ 表示氫原子或可具有取代基之烷基。烷基可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，烷基之碳數並無特別限定，通常為1以上，又，較佳為5以下，更佳為3以下，進而較佳為2以下。藉由設為上述下限值以上，有溶劑溶解性提高之傾向，又，藉由設為上述上限值以下，有加熱硬化時之反應速度變快之傾向。(R ¹ ) In the above formula (1), R ¹ represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group may be linear, branched, cyclic, or any combination of these, and is preferably linear from the viewpoint of the reaction rate at the time of heat curing. The carbon number of the alkyl group is not particularly limited, but it is usually 1 or more, preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it to the above lower limit or more, the solubility of the solvent tends to increase, and by setting it to or less than the above upper limit, the reaction rate at the time of heat curing tends to increase.

作為烷基之具體例，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、戊基，就加熱硬化時之反應速度之觀點而言，較佳為甲基。Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and pentyl group. From the viewpoint of the reaction rate at the time of heat curing, methyl group is preferred .

作為烷基可具有之取代基，可列舉鹵素原子、烷氧基、芳基、羥基、硫醇基、烷硫基。就保存穩定性之觀點而言，較佳為未經取代。Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group, an aryl group, a hydroxyl group, a thiol group, and an alkylthio group. From the viewpoint of storage stability, it is preferably unsubstituted.

(R² ～R⁴ ) 上述式(1)中，R² ～R⁴ 分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、可具有取代基之芳基、或可具有取代基之芳氧基。(R ² to R ⁴ ) In the above formula (1), R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryl group which may have a substituent Or an aryloxy group which may have a substituent.

烷基可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，烷基之碳數並無特別限定，通常為1以上，又，較佳為5以下，更佳為3以下，進而較佳為2以下。藉由設為上述下限值以上，有溶劑溶解性提高之傾向，又，藉由設為上述上限值以下，有加熱硬化時之反應速度變快之傾向。The alkyl group may be linear, branched, cyclic, or any combination of these, and is preferably linear from the viewpoint of the reaction rate at the time of heat curing. The carbon number of the alkyl group is not particularly limited, but it is usually 1 or more, preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it to the above lower limit or more, the solubility of the solvent tends to increase, and by setting it to or less than the above upper limit, the reaction rate at the time of heat curing tends to increase.

作為烷基之具體例，可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、戊基，就加熱硬化時之反應速度之觀點而言，較佳為甲基。Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a pentyl group. From the viewpoint of the reaction rate at the time of heat curing, a methyl group is preferred.

烷氧基可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，烷基之碳數並無特別限定，通常為1以上，更佳為3以下，進而較佳為2以下。藉由設為上述上限值以下，有加熱硬化時之反應速度變快之傾向。The alkoxy group may be linear, branched, cyclic, or any combination thereof, and is preferably linear from the viewpoint of the reaction rate at the time of heat curing. In addition, the carbon number of the alkyl group is not particularly limited, but it is usually 1 or more, more preferably 3 or less, and still more preferably 2 or less. By setting it below the said upper limit, the reaction speed at the time of heat hardening tends to become faster.

作為烷氧基之具體例，可列舉甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、戊氧基，就加熱硬化時之反應速度之觀點而言，較佳為甲氧基。Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and pentoxy groups. From the viewpoint of the reaction rate at the time of heat curing In other words, methoxy is preferred.

作為烷氧基可具有之取代基，可列舉鹵素原子、烷氧基、芳基、羥基、硫醇基、烷硫基。就保存穩定性之觀點而言，較佳為未經取代。Examples of the substituent that the alkoxy group may have include a halogen atom, an alkoxy group, an aryl group, a hydroxyl group, a thiol group, and an alkylthio group. From the viewpoint of storage stability, it is preferably unsubstituted.

芳基所具有之環之數量並無特別限定，通常為1以上，較佳為4以下，更佳為3以下，進而較佳為2以下。藉由設為上述上限值以下，有加熱硬化時之反應速度變快之傾向。芳基之碳數並無特別限定，較佳為3以上，更佳為4以上，進而較佳為5以上，又，較佳為18以下，更佳為14以下，進而較佳為12以下。藉由設為上述下限值以上，有保存穩定性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The number of rings possessed by the aryl group is not particularly limited, but it is usually 1 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it below the said upper limit, the reaction speed at the time of heat hardening tends to become faster. The carbon number of the aryl group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more, and further preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. By setting it to the above lower limit or more, the storage stability tends to be improved, and by setting it to the upper limit or less, the developing solubility tends to be improved.

作為芳基，可列舉芳香族烴環基、芳香族雜環基。作為芳基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、䓛環、聯三伸苯環、苊環、螢蒽環、茀環等。該等之中，就加熱硬化時之反應速度之觀點而言，較佳為苯環。Examples of the aryl group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Specific examples of the aromatic ring in the aryl group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, beryllium ring, and biphenylene Ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. Among these, from the viewpoint of the reaction rate at the time of heat hardening, a benzene ring is preferred.

作為芳基可具有之取代基，可列舉烷基、烷氧基、羥基、硫醇基、烷硫基、鹵素原子。就保存穩定性之觀點而言，較佳為未經取代。Examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, a hydroxyl group, a thiol group, an alkylthio group, and a halogen atom. From the viewpoint of storage stability, it is preferably unsubstituted.

芳氧基所具有之環之數量並無特別限定，通常為1以上，較佳為4以下，更佳為3以下，進而較佳為2以下。藉由設為上述上限值以下，有加熱硬化時之反應速度變快之傾向。芳氧基之碳數並無特別限定，較佳為3以上，更佳為4以上，進而較佳為5以上，又，較佳為18以下，更佳為14以下，進而較佳為12以下。藉由設為上述下限值以上，有保存穩定性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The number of rings possessed by the aryloxy group is not particularly limited, but it is usually 1 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it below the said upper limit, the reaction speed at the time of heat hardening tends to become faster. The carbon number of the aryloxy group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more, and further preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less . By setting it to the above lower limit or more, the storage stability tends to be improved, and by setting it to the upper limit or less, the developing solubility tends to be improved.

作為芳氧基中之芳香族環，可列舉芳香族烴環、芳香族雜環。作為芳氧基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、䓛環、聯三伸苯環、苊環、螢蒽環、茀環等。作為芳氧基，可列舉苯氧基、1-萘氧基。該等之中，就加熱硬化時之反應速度之觀點而言，較佳為苯氧基。Examples of the aromatic ring in the aryloxy group include aromatic hydrocarbon rings and aromatic heterocycles. Specific examples of the aromatic ring in the aryloxy group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, beryllium ring, tandem ring Benzene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. Examples of the aryloxy group include phenoxy group and 1-naphthoxy group. Among these, from the viewpoint of the reaction rate at the time of heat hardening, phenoxy is preferred.

作為芳氧基可具有之取代基，可列舉烷基、烷氧基、羥基、硫醇基、烷硫基、鹵素原子。就保存穩定性之觀點而言，較佳為未經取代。Examples of the substituent that the aryloxy group may have include alkyl groups, alkoxy groups, hydroxyl groups, thiol groups, alkylthio groups, and halogen atoms. From the viewpoint of storage stability, it is preferably unsubstituted.

又，為了有效率地藉由縮合反應形成交聯點，較佳為R² ～R⁴ 中之至少任一個為可具有取代基之烷氧基、或可具有取代基之芳氧基，更佳為2個以上為可具有取代基之烷氧基、或可具有取代基之芳氧基，進而較佳為全部為可具有取代基之烷氧基、或可具有取代基之芳氧基。該等之中，就加熱硬化時之反應速度之觀點而言，R² ～R⁴ 較佳為分別獨立地為可具有取代基之烷氧基，更佳為甲氧基。Moreover, in order to efficiently form a crosslinking point by a condensation reaction, it is preferable that at least any one of R ² to R ⁴ is an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, more preferably Two or more alkoxy groups which may have a substituent or an aryloxy group which may have a substituent, and more preferably all of them are alkoxy groups which may have a substituent, or aryloxy groups which may have a substituent. Among these, from the viewpoint of the reaction rate at the time of heat hardening, R ² to R ⁴ are each preferably an alkoxy group which may have a substituent, more preferably a methoxy group.

(L) 上述式(1)中，L表示2價連結基。作為2價連結基，例如可列舉：伸烷基、伸芳基、-CONH-基、-CONH-R⁵ -基、-COO-基、-COO-R⁶ -基、組合有該等者。R⁵ 及R⁶ 分別獨立地表示伸烷基、-(CH₂ CH₂ O)_Z1 -基(Z1為1～100之整數)、或-(CH₂ CH₂ CH₂ O)_Z1 -基(Z1為1～100之整數)。(L) In the above formula (1), L represents a divalent linking group. Examples of the divalent linking group include alkylene groups, aryl groups, -CONH- groups, -CONH-R ⁵ -groups, -COO- groups, -COO-R ⁶ -groups, and combinations thereof. R ⁵ and R ⁶ independently represent an alkylene group, -(CH ₂ CH ₂ O) _Z1- group (Z1 is an integer from 1 to 100), or -(CH ₂ CH ₂ CH ₂ O) _Z1- group (Z1 Is an integer from 1 to 100).

作為2價連結基中之伸烷基，可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，伸烷基之碳數並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，較佳為16以下，更佳為10以下，進而較佳為8以下。藉由設為上述下限值以上，有溶劑溶解性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The alkylene group in the divalent linking group may be linear, branched, cyclic, or any combination of these. From the viewpoint of the reaction rate at the time of heat curing, it is preferably Straight chain. The carbon number of the alkylene group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 16 or less, more preferably 10 or less, and even more preferably 8 or less . By setting it to the above lower limit or more, the solubility of the solvent tends to increase, and by setting it to the upper limit or less, the solubility of the developing solution tends to increase.

作為伸烷基之具體例，可列舉亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,4-二基、己烷-1,6-二基、甲基亞甲基、1-甲基伸乙基，就溶劑溶解性與顯影溶解性之平衡性之觀點而言，較佳為丙烷-1,3-二基。Specific examples of the alkylene extension include methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, hexane-1,6-diyl, and methylidene The methyl group and 1-methylethylidene group are preferably propane-1,3-diyl from the viewpoint of the balance between the solubility of the solvent and the solubility of the development.

2價連結基中之伸芳基所具有之環之數量並無特別限定，通常為1以上，較佳為4以下，更佳為3以下，進而較佳為2以下。藉由設為上述上限值以下，有顯影溶解性提高之傾向。伸芳基之碳數並無特別限定，較佳為3以上，更佳為4以上，進而較佳為5以上，又，較佳為18以下，更佳為14以下，進而較佳為12以下。藉由設為上述下限值以上，有保存穩定性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The number of rings of the arylene group in the divalent linking group is not particularly limited, but it is usually 1 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it to the said upper limit or less, the development solubility tends to improve. The carbon number of the arylene group is not particularly limited, preferably 3 or more, more preferably 4 or more, further preferably 5 or more, and further preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less . By setting it to the above lower limit or more, the storage stability tends to be improved, and by setting it to the upper limit or less, the developing solubility tends to be improved.

作為伸芳基，可列舉2價芳香族烴環基、2價芳香族雜環基。作為伸芳基中之芳香族環之具體例，可列舉苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、䓛環、聯三伸苯環、苊環、螢蒽環、茀環等。該等之中，就加熱硬化時之反應速度之觀點而言，較佳為苯環。Examples of the arylene group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. Specific examples of the aromatic ring in the arylene group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzopyrene ring, a beryllium ring, and a biphenylene Ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. Among these, from the viewpoint of the reaction rate at the time of heat hardening, a benzene ring is preferred.

作為R⁵ 及R⁶ 中之伸烷基，可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，伸烷基之碳數並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，較佳為16以下，更佳為10以下，進而較佳為8以下。藉由設為上述下限值以上，有溶劑溶解性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The alkylene group in R ⁵ and R ⁶ may be linear, branched, cyclic, or any combination of these. From the viewpoint of the reaction rate at the time of heat curing, it is preferable Straight chain. The carbon number of the alkylene group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 16 or less, more preferably 10 or less, and even more preferably 8 or less . By setting it to the above lower limit or more, the solubility of the solvent tends to increase, and by setting it to the upper limit or less, the solubility of the developing solution tends to increase.

Z1表示1～100之整數。較佳為2以上，更佳為4以上，進而較佳為6以上，又，較佳為70以下，更佳為50以下，進而較佳為30以下，進而更佳為15以下，尤佳為10以下。藉由設為上述下限值以上，有顯影溶解性提高之傾向，又，藉由設為上述上限值以下，有抑制顯影殘渣之生成之傾向。作為上限與下限之組合，例如較佳為2～70，更佳為4～50，進而較佳為4～30，進而更佳為6～15，尤佳為6～10。Z1 represents an integer of 1-100. It is preferably 2 or more, more preferably 4 or more, and still more preferably 6 or more, and further preferably 70 or less, more preferably 50 or less, still more preferably 30 or less, still more preferably 15 or less, particularly preferably 10 or less. By setting it to the above lower limit value or more, there is a tendency for the solubility of the development to be improved, and by setting it to the above upper limit value or less, there is a tendency to suppress the generation of the development residue. The combination of the upper limit and the lower limit is, for example, preferably 2 to 70, more preferably 4 to 50, still more preferably 4 to 30, still more preferably 6 to 15, particularly preferably 6 to 10.

該等之中，就感光性樹脂組合物與其他素材之相溶性之觀點而言，較佳為L為-COO-R⁶ -基，更佳為-COO-R⁶ -基，且R⁶ 為伸烷基，進而較佳為-COO-C₃ H₆ -基。Among these, from the viewpoint of compatibility of the photosensitive resin composition with other materials, it is preferred that L is a -COO-R ⁶ -group, more preferably a -COO-R ⁶ -group, and R ⁶ is The alkylene group is more preferably a -COO-C ₃ H ₆ -group.

(x) 上述式(1)中，x表示0或1。該等之中，就加熱硬化時之反應速度之觀點而言，較佳為1。(x) In the above formula (1), x represents 0 or 1. Among these, from the viewpoint of the reaction rate at the time of heat hardening, 1 is preferable.

有機矽乙烯系聚合物(d-1)中所含有之上述通式(1)所表示之重複單元之含有比率並無特別限定，於全部重複單元中較佳為0.2莫耳%以上，更佳為1莫耳%以上，進而較佳為10莫耳%以上，進而更佳為20莫耳%以上，尤佳為30莫耳%以上，最佳為40莫耳%以上，又，較佳為100莫耳%以下，更佳為90莫耳%以下，進而較佳為80莫耳%以下。藉由設為上述下限值以上，有基板密接性或加熱硬化時之熔合抑制效果提高之傾向，又，藉由設為上述上限值以下，有保存穩定性提高之傾向。作為上限與下限之組合，例如較佳為0.2～100莫耳%，更佳為1～90莫耳%，進而較佳為10～90莫耳%，進而更佳為20～90莫耳%，尤佳為30～80莫耳%，最佳為40～80莫耳%。The content ratio of the repeating unit represented by the general formula (1) contained in the silicone-based polymer (d-1) is not particularly limited, and it is preferably 0.2 mol% or more in all the repeating units, more preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, particularly preferably 30 mol% or more, most preferably 40 mol% or more, and more preferably 100 mol% or less, more preferably 90 mol% or less, and further preferably 80 mol% or less. By setting it to the above-mentioned lower limit value or more, there exists a tendency for the substrate adhesion property or the fusion suppression effect at the time of heat hardening to improve, and by setting it to the above-mentioned upper limit value, it tends to improve storage stability. The combination of the upper limit and the lower limit is, for example, preferably 0.2 to 100 mol%, more preferably 1 to 90 mol%, still more preferably 10 to 90 mol%, still more preferably 20 to 90 mol%, It is particularly preferably 30 to 80 mol%, and most preferably 40 to 80 mol%.

又，有機矽乙烯系聚合物(d-1)就保存穩定性之觀點而言，較佳為含有下述通式(2)所表示之重複單元。In addition, the organosilicon polymer (d-1) preferably contains a repeating unit represented by the following general formula (2) from the viewpoint of storage stability.

[化3] [Chemical 3]

式(2)中，R¹¹ 表示氫原子或可具有取代基之烷基。 R¹² 表示氫原子、可具有取代基之烷基、或可具有取代基之芳基。 M表示2價連結基，y表示0或1。In formula (2), R ¹¹ represents a hydrogen atom or an alkyl group which may have a substituent. R ¹² represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. M represents a divalent linking group, and y represents 0 or 1.

(R¹¹ ) 上述式(2)中，R¹¹ 表示氫原子或可具有取代基之烷基。烷基可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，烷基之碳數並無特別限定，通常為1以上，又，較佳為5以下，更佳為3以下，進而較佳為2以下。藉由設為上述下限值以上，有溶劑溶解性提高之傾向，又，藉由設為上述上限值以下，有加熱硬化時之反應速度變快之傾向。(R ¹¹ ) In the above formula (2), R ¹¹ represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group may be linear, branched, cyclic, or any combination of these, and is preferably linear from the viewpoint of the reaction rate at the time of heat curing. The carbon number of the alkyl group is not particularly limited, but it is usually 1 or more, preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it to the above lower limit or more, the solubility of the solvent tends to increase, and by setting it to or less than the above upper limit, the reaction rate at the time of heat curing tends to increase.

(R¹² ) 上述式(2)中，R¹² 表示氫原子、可具有取代基之烷基、或可具有取代基之芳基。(R ¹² ) In the above formula (2), R ¹² represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

烷基可為直鏈狀、支鏈狀、環狀、及組合有該等者中之任一種，就加熱硬化時之反應速度之觀點而言，較佳為直鏈狀。又，烷基之碳數並無特別限定，通常為1以上，又，較佳為20以下，更佳為10以下，進而較佳為6以下。藉由設為上述下限值以上，有溶劑溶解性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The alkyl group may be linear, branched, cyclic, or any combination of these, and is preferably linear from the viewpoint of the reaction rate at the time of heat curing. The carbon number of the alkyl group is not particularly limited, but it is usually 1 or more, and preferably 20 or less, more preferably 10 or less, and still more preferably 6 or less. By setting it to the above lower limit or more, the solubility of the solvent tends to increase, and by setting it to the upper limit or less, the solubility of the developing solution tends to increase.

作為烷基之具體例，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基、第三戊基、2-乙基己基、癸基、十二烷基、十八烷基，就加熱硬化時之反應速度之觀點而言，較佳為甲基。Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl, neopentyl The third pentyl group, 2-ethylhexyl group, decyl group, dodecyl group, and octadecyl group are preferably methyl groups from the viewpoint of the reaction rate during heat curing.

芳基所具有之環之數量並無特別限定，通常為1以上，較佳為4以下，更佳為3以下，進而較佳為2以下。藉由設為上述上限值以下，有顯影溶解性提高之傾向。芳基之碳數並無特別限定，較佳為3以上，更佳為4以上，進而較佳為5以上，又，較佳為18以下，更佳為14以下，進而較佳為12以下。藉由設為上述下限值以上，有保存穩定性提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。The number of rings possessed by the aryl group is not particularly limited, but it is usually 1 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. By setting it to the said upper limit or less, the development solubility tends to improve. The carbon number of the aryl group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more, and further preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. By setting it to the above lower limit or more, the storage stability tends to be improved, and by setting it to the upper limit or less, the developing solubility tends to be improved.

該等之中，就加熱硬化時之反應速度之觀點而言，較佳為可具有取代基之烷基，更佳為未經取代之烷基，進而較佳為甲基。Among these, from the viewpoint of the reaction rate at the time of heat hardening, an alkyl group which may have a substituent is preferred, an unsubstituted alkyl group is more preferred, and a methyl group is more preferred.

(M) 上述式(2)中，M表示2價連結基。作為2價連結基，例如可列舉：伸烷基、伸芳基、-CONH-基、-CONH-R⁵ -基、-COO-基、-COO-R⁶ -基、組合有該等者。R⁵ 及R⁶ 分別獨立地表示伸烷基、-(CH₂ CH₂ O)_Z1 -基(Z1為1～100之整數)、或-(CH₂ CH₂ CH₂ O)_Z1 -基(Z1為1～100之整數)。作為該等伸烷基、伸芳基、-CONH-R⁵ -基、-COO-R⁶ -基、R⁵ 、R⁶ 、Z1，可較佳地採用式(1)之L中所列舉者。該等之中，就與其他成分之相溶性之觀點而言，較佳為-COO-基、-COO-R⁶ -基。另一方面，就顯影溶解性、或由氧阻聚抑制帶來之感度提高之觀點而言，較佳為-COO-(CH₂ CH₂ O)_Z1 -基或-COO-(CH₂ CH₂ CH₂ O)_Z1 -基，更佳為-COO-(CH₂ CH₂ O)_Z1 -基。(M) In the above formula (2), M represents a divalent linking group. Examples of the divalent linking group include alkylene groups, aryl groups, -CONH- groups, -CONH-R ⁵ -groups, -COO- groups, -COO-R ⁶ -groups, and combinations thereof. R ⁵ and R ⁶ independently represent an alkylene group, -(CH ₂ CH ₂ O) _Z1- group (Z1 is an integer from 1 to 100), or -(CH ₂ CH ₂ CH ₂ O) _Z1- group (Z1 Is an integer from 1 to 100). As the alkylene group, aryl group, -CONH-R ⁵ -group, -COO-R ⁶ -group, R ⁵ , R ⁶ , and Z1, those listed in L of formula (1) can be preferably used . Among these, from the viewpoint of compatibility with other components, -COO- group and -COO-R ⁶ -group are preferred. On the other hand, from the viewpoint of developing solubility or improvement in sensitivity due to inhibition of oxygen inhibition, -COO-(CH ₂ CH ₂ O) _Z1 -group or -COO-(CH ₂ CH ₂ CH ₂ O) _Z1 -group, more preferably -COO-(CH ₂ CH ₂ O) _Z1 -group.

(y) 上述式(2)中，y表示0或1。該等之中，就溶劑溶解性之觀點而言，較佳為1。(y) In the above formula (2), y represents 0 or 1. Among these, from the viewpoint of solvent solubility, 1 is preferable.

有機矽乙烯系聚合物(d-1)中所含有之上述通式(2)所表示之重複單元之含有比率並無特別限定，於全部重複單元中較佳為1莫耳%以上，更佳為10莫耳%以上，進而較佳為20莫耳%以上，又，較佳為99.8莫耳%以下，更佳為99莫耳%以下，進而較佳為90莫耳%以下，進而更佳為80莫耳%以下，尤佳為70莫耳%以下，最佳為60莫耳%以下。藉由設為上述下限值以上，有保存穩定性提高之傾向，又，藉由設為上述上限值以下，有基板密接性或加熱硬化時之熔合抑制效果提高之傾向。作為上限與下限之組合，例如較佳為1～99.8莫耳%，更佳為1～99莫耳%，進而較佳為10～90莫耳%，進而更佳為10～80莫耳%，尤佳為20～70莫耳%，最佳為20～60莫耳%。The content ratio of the repeating unit represented by the general formula (2) contained in the silicone-based polymer (d-1) is not particularly limited, and it is preferably 1 mol% or more in all the repeating units, and more preferably 10 mol% or more, further preferably 20 mol% or more, and more preferably 99.8 mol% or less, more preferably 99 mol% or less, further preferably 90 mol% or less, still more preferably It is 80 mol% or less, particularly preferably 70 mol% or less, and most preferably 60 mol% or less. By setting it to the above lower limit or more, the storage stability tends to be improved, and by setting it to the above upper limit or less, the adhesion of the substrate or the fusion suppression effect at the time of heat curing tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 99.8 mol %, more preferably 1 to 99 mol %, still more preferably 10 to 90 mol %, and still more preferably 10 to 80 mol %, It is particularly preferably 20 to 70 mol%, and most preferably 20 to 60 mol%.

又，於有機矽乙烯系聚合物(d-1)含有上述通式(2)所表示其M為-COO-(CH₂ CH₂ O)_Z1 -基之重複單元之情形時，其含有比率並無特別限定，於全部重複單元中較佳為1莫耳%以上，更佳為10莫耳%以上，進而較佳為15莫耳%以上，尤佳為20莫耳%以上，又，較佳為50莫耳%以下，更佳為40莫耳%以下，進而較佳為35莫耳%以下，尤佳為30莫耳%以下。藉由設為上述下限值以上，有顯影溶解性變得良好，由於氧阻聚抑制而感度提高之傾向，又，藉由設為上述上限值以下，有基板密接性或加熱硬化時之熔合抑制效果提高之傾向。作為上限與下限之組合，例如較佳為1～50莫耳%，更佳為10～40莫耳%，進而較佳為15～35莫耳%，尤佳為20～30莫耳%。In addition, when the organosilicon polymer (d-1) contains a repeating unit represented by the general formula (2) whose M is -COO-(CH ₂ CH ₂ O) _Z1 -group, the content ratio is There is no particular limitation, and it is preferably 1 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more, and particularly preferably 20 mol% or more, and more preferably in all the repeating units. It is 50 mol% or less, more preferably 40 mol% or less, and further preferably 35 mol% or less, and particularly preferably 30 mol% or less. By setting it to the above lower limit or more, the developing solubility becomes good, and the sensitivity tends to increase due to the inhibition of oxygen inhibition, and by setting it to or less than the above upper limit, there is a case of substrate adhesion or heat curing The tendency of the fusion suppression effect to increase. The combination of the upper limit and the lower limit is, for example, preferably 1 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 35 mol%, and particularly preferably 20 to 30 mol%.

有機矽乙烯系聚合物(d-1)之重量平均分子量(Mw)並無特別限定，較佳為2000以上，更佳為5000以上，進而較佳為8000以上，又，較佳為100000以下，更佳為75000以下，進而較佳為40000以下，進而更佳為30000以下，尤佳為20000以下。藉由設為上述下限值以上，有熔合抑制效果提高之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高之傾向。作為上限與下限之組合，例如較佳為2000～100000，更佳為5000～75000，進而較佳為5000～40000，進而更佳為8000～30000，尤佳為8000～20000。The weight average molecular weight (Mw) of the organosilicon polymer (d-1) is not particularly limited, but it is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, and still more preferably 100,000 or less, It is more preferably 75,000 or less, further preferably 40,000 or less, still more preferably 30,000 or less, and particularly preferably 20,000 or less. By setting it to the above-mentioned lower limit value or more, there exists a tendency for the fusion suppression effect to improve, and by setting it to the said upper-limit value or less, there exists a tendency for development solubility to improve. The combination of the upper limit and the lower limit is, for example, preferably 2,000 to 100,000, more preferably 5,000 to 75,000, still more preferably 5,000 to 40,000, still more preferably 8,000 to 30,000, and particularly preferably 8,000 to 20,000.

有機矽乙烯系聚合物(d-1)之酸值並無特別限定，較佳為3 mgKOH/g以下，更佳為1 mgKOH/g以下，進而較佳為0.5 mgKOH/g以下，尤佳為0.3 mgKOH/g以下，最佳為0 mgKOH/g。藉由設為上述上限值以下，有有機矽乙烯系聚合物(d-1)之保存穩定性提高之傾向。The acid value of the organosilicon polymer (d-1) is not particularly limited, preferably 3 mgKOH/g or less, more preferably 1 mgKOH/g or less, and further preferably 0.5 mgKOH/g or less, particularly preferably Below 0.3 mgKOH/g, the best is 0 mgKOH/g. By setting it below the said upper limit, the storage stability of the organosilicon polymer (d-1) tends to improve.

有機矽乙烯系聚合物(d-1)之製造方法並無特別限定，例如可使含有矽原子之不飽和化合物與其他不飽和化合物進行共聚而獲得。The production method of the organosilicon polymer (d-1) is not particularly limited. For example, it can be obtained by copolymerizing unsaturated compounds containing silicon atoms with other unsaturated compounds.

作為含有矽原子之不飽和化合物，例如可列舉：如以下所例示之化合物。該等可單獨使用1種，亦可將2種以上以任意之組合與比率使用。再者，式中，C₂ H₄ 表示1,2-伸乙基，C₃ H₆ 表示正丙烷-1,3-二基，C₈ H₁₆ 表示正辛烷-1,8-二基。Examples of unsaturated compounds containing silicon atoms include the compounds exemplified below. One of these may be used alone, or two or more may be used in any combination and ratio. Furthermore, in the formula, C ₂ H ₄ represents 1,2-ethylidene, C ₃ H ₆ represents n-propane-1,3-diyl, and C ₈ H ₁₆ represents n-octane-1,8-diyl.

[化4] [Chemical 4]

作為其他不飽和化合物，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、2-乙基己基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸異酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸雙環戊酯。該等可單獨使用1種，亦可將2種以上以任意之組合與比率使用。又，就有機矽乙烯(d-1)之保存穩定性之觀點而言，作為不飽和化合物，較佳為使用不具有酸性基者並使之共聚。Examples of other unsaturated compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and third (meth)acrylic acid. Butyl ester, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, Butoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxydiethylene glycol ( Meth)acrylate, 2-ethylhexyl diethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxy (meth)acrylate Ethyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Propyl ester, phenoxy diethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, (methyl ) Cyclohexyl acrylate, tetrahydrofurfuryl (meth) acrylate, isopropyl (meth) acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, dicyclopentyl (meth)acrylate. One of these may be used alone, or two or more may be used in any combination and ratio. In addition, from the viewpoint of the storage stability of the organosilicon vinyl (d-1), as the unsaturated compound, it is preferable to use and copolymerize those that do not have an acidic group.

本發明之感光性樹脂組合物中之(d)有機矽化合物之含有比率並無特別限定，於感光性樹脂組合物之總固形物成分中較佳為0.1質量%以上，更佳為0.3質量%以上，進而較佳為1質量%以上，尤佳為2質量%以上，又，較佳為15質量%以下，更佳為10質量%以下，進而較佳為8質量%以下，尤佳為5質量%以下。藉由設為上述下限值以上，有基板密接性提高之傾向，又，藉由設為上述上限值以下，有抑制顯影殘渣之傾向。作為上限與下限之組合，例如較佳為0.1～15質量%，更佳為0.3～10質量%，進而較佳為1～8質量%，尤佳為2～5質量%。The content ratio of (d) organosilicon compound in the photosensitive resin composition of the present invention is not particularly limited, and it is preferably 0.1% by mass or more, and more preferably 0.3% by mass in the total solid content of the photosensitive resin composition The above is more preferably 1% by mass or more, particularly preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, particularly preferably 5 Mass% or less. By setting it to the above lower limit value or more, the substrate adhesion tends to be improved, and by setting it to the above upper limit value or less, the development residue tends to be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, still more preferably 1 to 8% by mass, and particularly preferably 2 to 5% by mass.

本發明之感光性樹脂組合物中之有機矽乙烯系聚合物(d-1)之含有比率並無特別限定，於感光性樹脂組合物之總固形物成分中較佳為0.1質量%以上，更佳為0.3質量%以上，進而較佳為1質量%以上，進而更佳為1.5質量%以上，尤佳為2質量%以上，又，較佳為10質量%以下，更佳為8質量%以下，進而較佳為5質量%以下。藉由設為上述下限值以上，有加熱硬化時之熔合抑制效果提高之傾向，又，藉由設為上述上限值以下，有抑制顯影殘渣之傾向。作為上限與下限之組合，例如較佳為0.1～10質量%，更佳為0.3～10質量%，進而較佳為1～8質量%，進而更佳為1.5～5質量%，尤佳為2～5質量%。又，有機矽乙烯系聚合物(d-1)亦可將2種以上以任意之組合及比率併用。The content ratio of the silicone polymer (d-1) in the photosensitive resin composition of the present invention is not particularly limited, and it is preferably 0.1% by mass or more in the total solid content of the photosensitive resin composition, and more It is preferably 0.3% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, particularly preferably 2% by mass or more, and further preferably 10% by mass or less, more preferably 8% by mass or less It is further preferably 5% by mass or less. By setting it to the above-mentioned lower limit value or more, there exists a tendency for the fusion suppression effect at the time of heat hardening to improve, and by setting it to or below the said upper limit value, there exists a tendency to suppress development residue. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, still more preferably 1 to 8% by mass, still more preferably 1.5 to 5% by mass, particularly preferably 2 ~ 5 mass%. In addition, the organosilicon polymer (d-1) may be used in combination of two or more in any combination and ratio.

＜其他有機矽化合物(d-2)＞又，作為(d)有機矽化合物，除有機矽乙烯系聚合物(d-1)以外，亦可含有其他有機矽化合物(d-2)。作為其他有機矽化合物，可列舉矽烷偶合劑，例如可列舉：具有如以下之乙烯基、環氧基、苯乙烯基、甲基丙烯醯基、丙烯醯基、一級～三級胺基、脲基、巰基、異氰酸基等者。再者，矽烷偶合劑可使用1種，亦可將2種以上以任意之組合及比率併用。再者，式中，C₂ H₄ 表示1,2-伸乙基，C₃ H₆ 表示正丙烷-1,3-二基。<Other organosilicon compound (d-2)> In addition, as the (d) organosilicon compound, in addition to the organosilicon vinyl polymer (d-1), other organosilicon compounds (d-2) may be contained. Examples of other organosilicon compounds include silane coupling agents. Examples include vinyl groups, epoxy groups, styryl groups, methacryl acetyl groups, propylene amide groups, primary to tertiary amine groups, and urea groups. , Mercapto, isocyanate, etc. In addition, one type of silane coupling agent may be used, or two or more types may be used in any combination and ratio. Furthermore, in the formula, C ₂ H ₄ represents 1,2-ethylidene and C ₃ H ₆ represents n-propane-1,3-diyl.

[化5] [Chem 5]

＜(a)鹼可溶性樹脂＞本發明之感光性樹脂組合物含有(a)鹼可溶性樹脂。(a)鹼可溶性樹脂只要為如對將感光性樹脂組合物塗佈、乾燥所獲得之硬化膜進行曝光後，曝光部與非曝光部之對於鹼顯影之溶解性產生變化者，則無特別限定，較佳為具有羧基之鹼可溶性樹脂。又，就光硬化性之觀點而言，較佳為具有乙烯性不飽和基者，就光硬化性與顯影溶解性之觀點而言，進而較佳為具有乙烯性不飽和基與羧基之鹼可溶性樹脂。具體而言，可列舉：具有羧基之環氧(甲基)丙烯酸酯樹脂或丙烯酸系共聚樹脂。<(a) Alkali soluble resin> The photosensitive resin composition of this invention contains (a) alkali soluble resin. (a) The alkali-soluble resin is not particularly limited as long as the cured film obtained by coating and drying the photosensitive resin composition changes the solubility of the exposed portion and the non-exposed portion with respect to alkali development. Is preferably an alkali-soluble resin having a carboxyl group. In addition, from the viewpoint of photocurability, those having an ethylenically unsaturated group are preferred, and from the viewpoint of photocurability and developing solubility, further preferably have alkali solubility of the ethylenically unsaturated group and the carboxyl group Resin. Specifically, an epoxy (meth)acrylate resin or an acrylic copolymer resin having a carboxyl group may be mentioned.

於製作彩色濾光片時，通常為了使非曝光部溶解於鹼顯影液中，而應用具有羥基、羧基、磷酸基、磺酸基等酸性官能基之高分子樹脂作為鹼可溶性樹脂。該等之中，就對於鹼顯影液之溶解性之觀點而言，較佳為具有羧基之高分子樹脂。又，磷酸基或磺酸基雖酸性度高於羧基，但有容易與感光性樹脂組合物中之具有鹼性基之起始劑、單體、分散劑、其他添加劑等進行反應，而保存穩定性變差之情形。When manufacturing a color filter, in order to dissolve the non-exposed portion in an alkaline developer, a polymer resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group is used as an alkali-soluble resin. Among these, from the viewpoint of the solubility of the alkali developer, a polymer resin having a carboxyl group is preferred. In addition, although the acidity of the phosphoric acid group or sulfonic acid group is higher than that of the carboxyl group, it is easy to react with the initiator, monomer, dispersant, other additives and the like having a basic group in the photosensitive resin composition, and the storage is stable Sexual deterioration.

本發明之感光性樹脂組合物中之(a)鹼可溶性樹脂含有具有羧基之環氧(甲基)丙烯酸酯樹脂。具有羧基之環氧(甲基)丙烯酸酯樹脂係具有乙烯性不飽和基者，認為藉此曝光時之交聯點增加，軟化起始溫度變高，而由樹脂流動引起之線寬變化得到抑制。又，具有羧基之環氧(甲基)丙烯酸酯樹脂除利用羧基或酯基之氫鍵結或偶極-偶極相互作用以外，亦發揮芳香族環彼此之π-π相互作用，而樹脂之主鏈間之自由體積變少而氧難以透過，因此認為聚合反應時之氧阻聚得到抑制，交聯進一步進行，而由樹脂流動引起之線寬變化得到抑制。(A) The alkali-soluble resin in the photosensitive resin composition of the present invention contains an epoxy (meth)acrylate resin having a carboxyl group. Epoxy (meth)acrylate resins with carboxyl groups have ethylenically unsaturated groups. It is believed that the cross-linking point during exposure increases, the softening initiation temperature becomes higher, and the change in line width caused by resin flow is suppressed . In addition, epoxy (meth)acrylate resins with carboxyl groups not only utilize hydrogen bonding of carboxyl groups or ester groups or dipole-dipole interactions, but also exert π-π interactions of aromatic rings with each other. Since the free volume between the main chains is reduced and oxygen is difficult to penetrate, it is considered that oxygen inhibition during polymerization is suppressed, crosslinking proceeds further, and line width changes caused by resin flow are suppressed.

具有羧基之環氧(甲基)丙烯酸酯樹脂係使環氧樹脂與α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之反應物之於反應中所生成之羥基進而與多元酸及/或其酐反應所獲得的樹脂。又，於使多元酸及/或其酐與羥基反應之前，使具有2個以上之可與該羥基反應之取代基之化合物反應後，使多元酸、及/或其酐反應所獲得的樹脂亦包含於環氧(甲基)丙烯酸酯樹脂中。進而，使上述反應中所獲得之樹脂之羧基進而與具有可反應之官能基之化合物進行反應所獲得之樹脂亦包含於環氧(甲基)丙烯酸酯樹脂中。如上所述，具有羧基之環氧(甲基)丙烯酸酯樹脂於化學結構上實質上不具有環氧基，且並不限定於「(甲基)丙烯酸酯」，但由於環氧樹脂為原料，且「(甲基)丙烯酸酯」為代表例，故而依據慣列如此命名。Epoxy (meth)acrylate resin with carboxyl group is used in the reaction of epoxy resin with α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester with carboxyl group The resulting hydroxyl group further reacts with the polyacid and/or its anhydride to obtain a resin. In addition, before reacting the polyacid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents that can react with the hydroxyl group, the resin obtained by reacting the polyacid and/or its anhydride is also reacted Included in epoxy (meth)acrylate resin. Furthermore, the resin obtained by reacting the carboxyl group of the resin obtained in the above reaction with a compound having a reactive functional group is also included in the epoxy (meth)acrylate resin. As mentioned above, the epoxy (meth)acrylate resin having a carboxyl group does not substantially have an epoxy group in the chemical structure, and is not limited to "(meth)acrylate", but since epoxy resin is the raw material, And "(meth)acrylate" is a representative example, so it is so named according to the convention.

作為具有羧基之環氧(甲基)丙烯酸酯樹脂，例如可列舉以下之環氧(甲基)丙烯酸酯樹脂(A1-1)及/或環氧(甲基)丙烯酸酯樹脂(A1-2)。Examples of the epoxy (meth)acrylate resin having a carboxyl group include the following epoxy (meth)acrylate resin (A1-1) and/or epoxy (meth)acrylate resin (A1-2) .

＜環氧(甲基)丙烯酸酯樹脂(A1-1)＞藉由使α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯加成於環氧樹脂，進而使多元酸及/或其酐反應所獲得之鹼可溶性樹脂。＜環氧(甲基)丙烯酸酯樹脂(A1-2)＞藉由使α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯加成於環氧樹脂，進而與多元醇、以及多元酸及/或其酐反應所獲得之鹼可溶性樹脂。<Epoxy (meth)acrylate resin (A1-1)> By adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having carboxyl group to epoxy resin In addition, the alkali-soluble resin obtained by reacting the polyacid and/or its anhydride. <Epoxy (meth)acrylate resin (A1-2)> By adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having carboxyl group to epoxy resin , Alkali-soluble resin obtained by reacting with polyol, polybasic acid and/or anhydride.

＜環氧(甲基)丙烯酸酯樹脂(A1-1)＞作為成為原料之環氧樹脂，可良好地使用雙酚A型環氧樹脂(例如，Mitsubishi Chemical公司製造之「jER(註冊商標；以下相同)828」、「jER1001」、「jER1002」、「jER1004」、日本化藥公司製造之「NER-1302」(環氧當量323，軟化點76℃)等)、雙酚F型樹脂(例如，Mitsubishi Chemical公司製造之「jER807」、「jER4004P」、「jER4005P」、「jER4007P」、日本化藥公司製造之「NER-7406」(環氧當量350，軟化點66℃)等)、雙酚S型環氧樹脂、聯苯縮水甘油醚(例如，Mitsubishi Chemical公司製造之「jERYX-4000」)、苯酚酚醛清漆型環氧樹脂(例如，日本化藥公司製造之「EPPN(註冊商標；以下相同)-201」、Mitsubishi Chemical公司製造之「jER-152」、「jER-154」、陶氏化學公司製造之「DEN-438」)、(鄰、間、對)甲酚酚醛清漆型環氧樹脂(例如，日本化藥公司製造之「EOCN(註冊商標；以下相同)-102S」、「EOCN-1020」、「EOCN-104S」)、異氰尿酸三縮水甘油酯(例如，日產化學公司製造之「TEPIC(註冊商標)」)、三苯酚甲烷型環氧樹脂(例如，日本化藥公司製造之「EPPN-501」、「EPPN-502」、「EPPN-503」)、脂環式環氧樹脂(Daicel公司製造之「Celloxide(註冊商標；以下相同)2021P」、「Celloxide EHPE」)、藉由二環戊二烯與苯酚之反應使苯酚樹脂縮水甘油基化所得之環氧樹脂(例如，DIC公司製造之「EXA-7200」、日本化藥公司製造之「NC-7300」)、下述通式(a1)～(a5)所表示之環氧樹脂等。具體而言，作為下述通式(a1)所表示之環氧樹脂，可列舉日本化藥公司製造之「XD-1000」，作為下述通式(a2)所表示之環氧樹脂，可列舉日本化藥公司製造之「NC-3000」，作為下述通式(a4)所表示之環氧樹脂，可列舉新日鐵住金化學公司製造之「ESF-300」等。<Epoxy (meth)acrylate resin (A1-1)> As the epoxy resin used as a raw material, bisphenol A type epoxy resin (for example, "jER (registered trademark; manufactured by Mitsubishi Chemical Corporation; the following Same) 828”, “jER1001”, “jER1002”, “jER1004”, “NER-1302” (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd., bisphenol F type resin (for example, "JER807", "jER4004P", "jER4005P", "jER4007P" manufactured by Mitsubishi Chemical, "NER-7406" (epoxy equivalent 350, softening point 66°C, etc.) manufactured by Nippon Kayaku, etc., bisphenol S type Epoxy resin, biphenyl glycidyl ether (for example, "jERYX-4000" manufactured by Mitsubishi Chemical), phenol novolac epoxy resin (for example, "EPPN (registered trademark; the same below) manufactured by Nippon Kayaku Co.- 201", "jER-152", "jER-154" manufactured by Mitsubishi Chemical Company, "DEN-438" manufactured by Dow Chemical Company), (o, m, p) cresol novolac epoxy resin (e.g. , "EOCN (registered trademark; the same below) -102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example, "TEPIC" manufactured by Nissan Chemical Co., Ltd. (Registered trademark)"), triphenol methane epoxy resin (for example, "EPPN-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resin (Daicel "Celloxide (registered trademark; the same below) 2021P", "Celloxide EHPE" manufactured by the company, epoxy resin obtained by glycidylation of phenol resin by the reaction of dicyclopentadiene and phenol (for example, manufactured by DIC Corporation) "EXA-7200", "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (a1) to (a5). Specifically, as the epoxy resin represented by the following general formula (a1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd. may be cited, and as the epoxy resin represented by the following general formula (a2), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (a4) includes "ESF-300" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. and the like.

[化6] [化6]

於上述通式(a1)中，b11為平均值，表示0～10之數，R¹¹ 表示氫原子、鹵素原子、碳數1～8之烷基、碳數3～10之環烷基、苯基、萘基、或聯苯基。再者，存在於1分子中之複數個R¹¹ 相互可相同亦可不同。In the above general formula (a1), b11 is an average value and represents a number of 0 to 10, R ¹¹ represents a hydrogen atom, a halogen atom, a C 1-8 alkyl group, a C 3-10 cycloalkyl group, and benzene Radical, naphthyl, or biphenyl. Furthermore, the plurality of R ¹¹ present in one molecule may be the same or different from each other.

[化7] [化7]

於上述通式(a2)中，b12為平均值，表示0～10之數，R²¹ 表示氫原子、鹵素原子、碳數1～8之烷基、碳數3～10之環烷基、苯基、萘基、或聯苯基。再者，存在於1分子中之複數個R²¹ 相互可相同亦可不同。In the above general formula (a2), b12 is an average value and represents a number from 0 to 10, R ²¹ represents a hydrogen atom, a halogen atom, a C 1-8 alkyl group, a C 3-10 cycloalkyl group, and benzene Radical, naphthyl, or biphenyl. Furthermore, the plurality of R ²¹ present in one molecule may be the same as or different from each other.

[化8] [Chem 8]

於上述通式(a3)中，X表示下述通式(a3-1)或(a3-2)所示之連結基，b13表示2或3之整數。其中，於分子結構中包含1個以上之金剛烷結構。In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2), and b13 represents an integer of 2 or 3. Among them, the molecular structure includes more than one adamantane structure.

[化9] [化9]

於上述通式(a3-1)及(a3-2)中，R³¹ ～R³⁴ 及R³⁵ ～R³⁷ 分別獨立地表示可具有取代基之金剛烷基、氫原子、可具有取代基之碳數1～12之烷基、或可具有取代基之苯基，式中之*表示上述通式(a3)中之鍵結部位。In the above general formulas (a3-1) and (a3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon which may have a substituent The alkyl group of 1-12, or the phenyl group which may have a substituent, * in a formula represents the bonding site in the said general formula (a3).

[化10] [化10]

於上述通式(a4)中，p及q分別獨立地表示0～4之整數，R⁴¹ 及R⁴² 分別獨立地表示烷基或鹵素原子，R⁴³ 及R⁴⁴ 分別獨立地表示伸烷基，x及y分別獨立地表示0以上之整數。In the above general formula (a4), p and q each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom, and R ⁴³ and R ⁴⁴ each independently represent an alkylene group, x and y each independently represent an integer of 0 or more.

[化11] [Chem 11]

於上述通式(a5)中，R⁵¹ ～R⁵⁴ 分別獨立地表示氫原子、碳數1～20之烷基、碳原子6～20之芳基、或碳原子7～20之芳烷基，R⁵⁵ 表示碳數1～20之烷基、碳數6～20之芳基、或碳數7～20之芳烷基，R⁵⁶ 表示碳數1～5之伸烷基，k表示1～5之整數，l表示0～13之整數，m表示0～5之整數。該等之中，較佳為使用通式(a1)～(a5)之任一者所表示之環氧樹脂。In the above general formula (a5), R ⁵¹ to R ⁵⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ⁵⁵ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ⁵⁶ represents an alkylene group having 1 to 5 carbon atoms, and k represents 1 to 5 Integer, l represents an integer from 0 to 13, m represents an integer from 0 to 5. Among these, it is preferable to use the epoxy resin represented by any one of the general formulas (a1) to (a5).

作為α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯，可列舉：(甲基)丙烯酸；丁烯酸；鄰乙烯基苯甲酸；間乙烯基苯甲酸；對乙烯基苯甲酸；(甲基)丙烯酸之α位鹵烷基、烷氧基、鹵素、硝基、氰基取代體等單羧酸；2-(甲基)丙烯醯氧基乙基琥珀酸；2-(甲基)丙烯醯氧基乙基己二酸；2-(甲基)丙烯醯氧基乙基鄰苯二甲酸；2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸；2-(甲基)丙烯醯氧基乙基順丁烯二酸；2-(甲基)丙烯醯氧基丙基琥珀酸；2-(甲基)丙烯醯氧基丙基己二酸；2-(甲基)丙烯醯氧基丙基四氫鄰苯二甲酸；2-(甲基)丙烯醯氧基丙基鄰苯二甲酸；2-(甲基)丙烯醯氧基丙基順丁烯二酸；2-(甲基)丙烯醯氧基丁基琥珀酸；2-(甲基)丙烯醯氧基丁基己二酸；2-(甲基)丙烯醯氧基丁基氫鄰苯二甲酸；2-(甲基)丙烯醯氧基丁基鄰苯二甲酸；2-(甲基)丙烯醯氧基丁基順丁烯二酸；使ε-己內酯、β-丙內酯、γ-丁內酯、δ-戊內酯等內酯類加成於(甲基)丙烯酸且於末端具有1個羥基之單體；或者使琥珀酸(酐)、鄰苯二甲酸(酐)、順丁烯二酸(酐)等酸(酐)加成於如(甲基)丙烯酸羥基烷基酯之於末端具有1個羥基之單體、或如季戊四醇三(甲基)丙烯酸酯之末端具有1個羥基之化合物，且具有1個以上之乙烯不飽和基及於末端具有1個羧基之(甲基)丙烯酸酯等。又，亦可列舉(甲基)丙烯酸二聚物等。該等之中，就感度之方面而言，尤佳者為(甲基)丙烯酸。Examples of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include: (meth)acrylic acid; crotonic acid; o-vinylbenzoic acid; m-vinylbenzoic acid; P-vinyl benzoic acid; α-haloalkyl, alkoxy, halogen, nitro, cyano and other monocarboxylic acids such as (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid ; 2-(meth)acryloyloxyethyladipic acid; 2-(meth)acryloyloxyethylphthalate; 2-(meth)acryloyloxyethylhexahydrophthalate Dicarboxylic acid; 2-(meth)acryloyloxyethyl maleic acid; 2-(meth)acryloyloxypropyl succinic acid; 2-(meth)acryloyloxypropyl adipate Acid; 2-(meth)acryloxypropyl tetrahydrophthalic acid; 2-(meth)acryloxypropyl phthalic acid; 2-(meth)acryloxypropyl propyl Maleic acid; 2-(meth)acryloyloxybutyl succinic acid; 2-(meth)acryloyloxybutyl adipic acid; 2-(meth)acryloyloxybutyl hydrogen Phthalic acid; 2-(meth)acryloyloxybutylphthalate; 2-(meth)acryloyloxybutylmaleic acid; ε-caprolactone, β-propiolactone , Γ-butyrolactone, δ-valerolactone and other lactones are added to (meth)acrylic acid and have a hydroxyl group at the end of the monomer; or succinic acid (anhydride), phthalic acid (anhydride) , Maleic acid (anhydride) and other acids (anhydrides) are added to monomers such as hydroxyalkyl (meth)acrylate with a hydroxyl group at the end, or to the end of pentaerythritol tri(meth)acrylate A compound having one hydroxyl group, and having more than one ethylenically unsaturated group, (meth)acrylate having one carboxyl group at the end, etc. Moreover, (meth)acrylic acid dimer etc. can also be mentioned. Among these, in terms of sensitivity, (meth)acrylic acid is particularly preferred.

作為使α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯加成於環氧樹脂之方法，可使用公知之手法。例如可於酯化觸媒之存在下且於50～150℃之溫度下，使α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯與環氧樹脂進行反應。作為此處所使用之酯化觸媒，可使用三乙胺、三甲胺、二甲苄胺、二乙苄胺等三級胺；四甲基氯化銨、四乙基氯化銨、十二烷基三甲基氯化銨等四級銨鹽等。As a method for adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester with carboxyl group and epoxy resin can be used in the presence of esterification catalyst and at a temperature of 50-150°C React. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and diethylbenzylamine can be used; tetramethylammonium chloride, tetraethylammonium chloride, dodecane Quaternary ammonium salts such as trimethylammonium chloride.

再者，環氧樹脂、α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯、及酯化觸媒均可單獨使用1種，亦可併用2種以上。關於α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之使用量，相對於環氧樹脂之環氧基1當量，較佳為0.5～1.2當量之範圍，進而較佳為0.7～1.1當量之範圍。於α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之使用量為上述下限值以上之情形時，有不飽和基之導入量變得充分，接下來與多元酸及/或其酐之反應亦變得充分之傾向。另一方面，於該使用量為上述上限值以下之情形時，有可抑制α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯作為未反應物殘留之傾向。Furthermore, the epoxy resin, α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst can be used alone or in combination. the above. The use amount of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of epoxy resin The range is more preferably 0.7 to 1.1 equivalents. In the case where the amount of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is above the above lower limit, the amount of the unsaturated group introduced becomes sufficient. The reaction with polyacids and/or anhydrides also tends to be sufficient. On the other hand, when the amount of use is less than the above upper limit, it may be possible to suppress the residue of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group as an unreacted substance tendency.

作為多元酸及/或其酐，可列舉：選自順丁烯二酸、琥珀酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、二苯甲酮四羧酸、甲基六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、氯菌酸、甲基四氫鄰苯二甲酸、聯苯四羧酸、及該等之酸酐等中之1種或2種以上。Examples of the polybasic acid and/or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic acid. , Trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, internal methylenetetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid One or more kinds of carboxylic acids, and anhydrides thereof.

較佳為順丁烯二酸、琥珀酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、聯苯四羧酸、或該等之酸酐。尤佳為四氫鄰苯二甲酸、聯苯四羧酸、四氫鄰苯二甲酸酐、或聯苯四羧酸二酐。Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid , Or such anhydrides. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

關於多元酸及/或其酐之加成反應，亦可使用公知之手法，可在與α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯對於環氧樹脂之加成反應同樣之條件下，繼續反應而獲得目標物。多元酸及/或其酐成分之加成量較佳為所生成之含有羧基之環氧(甲基)丙烯酸酯樹脂之酸值成為10～150 mgKOH/g之範圍的程度，進而較佳為所生成之含有羧基之環氧(甲基)丙烯酸酯樹脂之酸值成為20～140 mgKOH/g之範圍的程度。藉由設為上述下限值以上，有鹼顯影性變得良好之傾向，藉由設為上述上限值以下，有硬化性變得良好之傾向。Regarding the addition reaction of the polybasic acid and/or its anhydride, a well-known technique can also be used, and the α,β-unsaturated monocarboxylic acid ester with α,β-unsaturated monocarboxylic acid and/or a The addition reaction of the oxygen resin is continued under the same conditions to obtain the target. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the generated epoxy (meth)acrylate resin containing a carboxyl group is in the range of 10 to 150 mgKOH/g, and more preferably The acid value of the resulting epoxy (meth)acrylate resin containing carboxyl groups is in the range of 20 to 140 mgKOH/g. By setting it to the above lower limit or more, the alkali developability tends to be good, and by setting it to the above upper limit or less, the curability tends to be good.

＜環氧(甲基)丙烯酸酯樹脂(A1-2)＞於上述(A1-1)樹脂之多元酸及/或其酐之加成反應時，亦可添加三羥甲基丙烷、季戊四醇、二季戊四醇等多元醇而導入多分支結構，藉此獲得環氧(甲基)丙烯酸酯樹脂(A1-2)。環氧(甲基)丙烯酸酯樹脂(A1-1)及(A1-2)通常藉由於環氧樹脂與α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之反應物中混合多元酸及/或其酐後，或者於環氧樹脂與α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之反應物中混合多元酸及/或其酐以及多元醇後，進行加溫而獲得。於該情形時，多元酸及/或其酐與多元醇之混合順序並無特別限制。藉由加溫，多元酸及/或其酐對於存在於環氧樹脂與α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之反應物與多元醇之混合物中之任一羥基進行加成反應。<Epoxy (meth)acrylate resin (A1-2)> During the addition reaction of the polybasic acid and/or its anhydride of the above (A1-1) resin, trimethylolpropane, pentaerythritol and di Polyols such as pentaerythritol are introduced into a multi-branched structure to obtain epoxy (meth)acrylate resin (A1-2). Epoxy (meth)acrylate resins (A1-1) and (A1-2) are usually composed of epoxy resin and α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid with carboxyl group After mixing the polyacid and/or its anhydride in the reactant of the acid ester, or the reactant of the epoxy resin and α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester with carboxyl group After mixing the polybasic acid and/or its anhydride and the polyhydric alcohol, it is obtained by heating. In this case, the mixing order of the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. By heating, the polyacid and/or its anhydride reacts with the polyol and the polyhydric alcohol present in the epoxy resin and the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group Any hydroxyl group in the mixture undergoes addition reaction.

關於多元醇之使用量，相對於環氧樹脂與α,β-不飽和單羧酸及/或具有羧基之α,β-不飽和單羧酸酯之反應物，通常為0.01～0.5質量倍左右，較佳為0.02～0.2質量倍左右。藉由設為上述下限值以上，有容易獲得添加效果之傾向，又，藉由設為上述上限值以下，有可抑制增黏或凝膠化之傾向。The amount of polyol used is usually about 0.01 to 0.5 times the mass of the reactant of the epoxy resin with α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group , It is preferably about 0.02 to 0.2 mass times. By setting it to the above-mentioned lower limit value or more, there is a tendency that the addition effect is easily obtained, and by setting it to the above-mentioned upper limit value or less, there is a tendency that the thickening or gelation can be suppressed.

本發明之感光性樹脂組合物就表面硬化性之觀點而言，較佳為含有作為具有羧基之環氧(甲基)丙烯酸酯樹脂之環氧(甲基)丙烯酸酯樹脂(A1-1)及(A1-2)之至少任一種作為含有乙烯性不飽和基之鹼可溶性樹脂。From the viewpoint of surface curability, the photosensitive resin composition of the present invention preferably contains an epoxy (meth)acrylate resin (A1-1) as an epoxy (meth)acrylate resin having a carboxyl group and At least one of (A1-2) is an alkali-soluble resin containing an ethylenic unsaturated group.

具有羧基之環氧(甲基)丙烯酸酯樹脂可單獨使用1種，亦可將2種以上之樹脂混合使用。具有羧基之環氧(甲基)丙烯酸酯樹脂之酸值並無特別限定，通常為10 mgKOH/g以上，較佳為50 mgKOH/g以上，更佳為80 mgKOH/g以上，且較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，進而較佳為130 mgKOH/g以下。藉由設為上述下限值以上，有顯影性變得良好之傾向，藉由設為上述上限值以下，有可使鹼耐性變得良好之傾向。作為上限與下限之組合，例如較佳為10～200 mgKOH/g，更佳為50～150 mgKOH/g，進而較佳為80～130 mgKOH/g。The epoxy (meth)acrylate resin having a carboxyl group may be used alone, or two or more kinds of resins may be used in combination. The acid value of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and it is usually 10 mgKOH/g or more, preferably 50 mgKOH/g or more, more preferably 80 mgKOH/g or more, and preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and further preferably 130 mgKOH/g or less. By setting it to the above lower limit value or more, the developability tends to be good, and by setting it to the above upper limit value or less, the alkali resistance tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 10 to 200 mgKOH/g, more preferably 50 to 150 mgKOH/g, and still more preferably 80 to 130 mgKOH/g.

具有羧基之環氧(甲基)丙烯酸酯樹脂之利用凝膠滲透層析法(GPC)測定之聚苯乙烯換算之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為1500以上，進而較佳為2000以上。又，較佳為40000以下，更佳為20000以下，進而較佳為10000以下，進而更佳為8000以下，尤佳為6000以下。藉由設為上述下限值以上，有感度、塗膜強度、鹼耐性變得良好之傾向，藉由設為上述上限值以下，有可使顯影性或再溶解性變得良好之傾向。作為上限與下限之組合，例如較佳為1000～40000，更佳為1500～20000，進而較佳為1500～10000，進而更佳為2000～8000，尤佳為2000～6000。The weight-average molecular weight (Mw) of polystyrene-equivalent measured by gel permeation chromatography (GPC) of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but is preferably 1,000 or more, more preferably 1500 or more, and more preferably 2000 or more. Moreover, it is preferably 40,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less, still more preferably 8000 or less, and particularly preferably 6,000 or less. By setting it to the said lower limit value or more, sensitivity, coating film strength, and alkali resistance tend to become favorable, and by setting it to the said upper limit value or less, it will tend to make developability or resolubility favorable. The combination of the upper limit and the lower limit is, for example, preferably 1,000 to 40,000, more preferably 1,500 to 20,000, still more preferably 1,500 to 10,000, still more preferably 2,000 to 8,000, and particularly preferably 2,000 to 6,000.

具有羧基之環氧(甲基)丙烯酸酯樹脂之化學結構並無特別限定，就曝光感度之觀點而言，較佳為含有具有下述通式(a1-I)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(以下，有簡記為「(a1-I)環氧(甲基)丙烯酸酯樹脂」之情形)及/或具有下述通式(a1-II)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(以下，有簡記為「(a1-II)環氧(甲基)丙烯酸酯樹脂」之情形)。The chemical structure of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and from the viewpoint of exposure sensitivity, it is preferable to contain an epoxy having a partial structure represented by the following general formula (a1-I) (Meth)acrylate resin (hereinafter, abbreviated as "(a1-I) epoxy (meth)acrylate resin") and/or has a partial structure represented by the following general formula (a1-II) Epoxy (meth)acrylate resin (hereinafter, it may be abbreviated as "(a1-II) epoxy (meth)acrylate resin").

[化12] [化12]

式(a1-I)中，R¹¹ 表示氫原子或甲基，R¹² 表示可具有取代基之2價烴基，*表示鍵結鍵。式(a1-I)中之苯環可進而經任意之取代基取代。In formula (a1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, and * represents a bonding bond. The benzene ring in formula (a1-I) may be further substituted with any substituent.

[化13] [Chem 13]

式(a1-II)中，R¹³ 分別獨立地表示氫原子或甲基，R¹⁴ 表示具有環狀烴基作為側鏈之2價烴基，R¹⁵ 及R¹⁶ 分別獨立地表示可具有取代基之2價脂肪族基，m及n分別獨立地表示0～2之整數，*表示鍵結鍵。In formula (a1-II), R ¹³ independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R ¹⁵ and R ¹⁶ independently represent 2 which may have a substituent Valence aliphatic group, m and n each independently represent an integer of 0 to 2, and * represents a bonding bond.

＜(a1-I)環氧(甲基)丙烯酸酯樹脂＞首先，對具有上述通式(a1-I)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂詳細地進行說明。<(a1-I) Epoxy (meth)acrylate resin> First, an epoxy (meth)acrylate resin having a partial structure represented by the general formula (a1-I) will be described in detail.

[化14] [化14]

式(a1-I)中，R¹¹ 表示氫原子或甲基，R¹² 表示可具有取代基之2價烴基，*表示鍵結鍵。式(a1-I)中之苯環亦可進而經任意之取代基取代。In formula (a1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, and * represents a bonding bond. The benzene ring in formula (a1-I) may be further substituted with any substituent.

(R¹² ) 上述式(a1-I)中，R¹² 表示可具有取代基之2價烴基。作為2價烴基，可列舉：2價脂肪族基、2價芳香族環基、1個以上之2價脂肪族基與1個以上之2價芳香族環基連結而成之基。(R ¹² ) In the above formula (a1-I), R ¹² represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups.

2價脂肪族基可列舉：直鏈狀者、支鏈狀者、環狀者、組合有該等者。該等之中，就顯影溶解性之觀點而言，較佳為直鏈狀者。另一方面，就顯影液對於曝光部之滲透減少之觀點而言，較佳為環狀者。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～20、更佳為3～15、進而較佳為6～10。Examples of the divalent aliphatic group include linear ones, branched ones, cyclic ones, and combinations of these. Among these, from the viewpoint of developing solubility, a linear one is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a ring-shaped one is preferred. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. The combination of the upper limit and the lower limit includes, for example, preferably 1-20, more preferably 3-15, and even more preferably 6-10.

作為2價之直鏈狀之脂肪族基之具體例，可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基等。該等之中，就骨架之剛直性之觀點而言，較佳為亞甲基。作為2價之支鏈狀之脂肪族基，可列舉：於上述2價之直鏈狀之脂肪族基具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等作為側鏈之結構。 2價之環狀之脂肪族基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為12以下，較佳為10以下。藉由設為上述下限值以上，有成為牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為2價之環狀之脂肪族基之具體例，可列舉自環己烷環、環庚烷環、環癸烷環、環十二烷環、降烷環、異烷環、金剛烷環、二環戊二烯環等環去除2個氫原子而成之基。該等之中，就骨架之剛直性之觀點而言，較佳為自二環戊二烯環、金剛烷環去除2個氫原子而成之基。Specific examples of the divalent linear aliphatic group include methylene, ethylidene, n-propylene, n-butylene, n-pentylyl, n-hexyl, n-heptyl and the like. Among these, from the viewpoint of the rigidity of the skeleton, methylene is preferred. Examples of the divalent branched aliphatic group include the above-mentioned divalent linear aliphatic group having methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl group, the third butyl group, etc. serve as side chain structures. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. By setting it to the above lower limit value or more, there is a tendency to become a strong film, and by setting it to the above upper limit value or less, the resolution tends to be improved. Specific examples of the divalent cyclic aliphatic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoalkane ring, adamantane ring, The dicyclopentadiene ring and other rings are formed by removing 2 hydrogen atoms. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferred.

作為2價脂肪族基可具有之取代基，可列舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等之中，就合成容易性之觀點而言，較佳為未經取代。Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

又，作為2價之芳香族環基，可列舉2價之芳香族烴環基及2價之芳香族雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為4～20、更佳為5～15、進而較佳為6～10。In addition, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 4-20, more preferably 5-15, and still more preferably 6-10.

作為2價之芳香族烴環基中之芳香族烴環，可為單環亦可為縮合環。作為芳香族烴環基，例如可列舉：具有2個自由原子價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、䓛環、聯三伸苯環、苊環、螢蒽環、茀環等基。又，作為芳香族雜環基中之芳香族雜環，可為單環亦可為縮合環。作為2價之芳香族雜環基，例如可列舉：具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡環、嗒環、嘧啶環、三環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、啶環、喹唑啉環、喹唑啉酮環、薁環等基。該等之中，就解像性之觀點而言，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, beryllium ring, bivalent ring Triphenylene ring, acenaphthene ring, fluoranthene ring, stilbene ring and other groups. The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring having two free valences, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and a diazole Ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, ta ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline Ring, pyridine ring, Pyridinium ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among these, from the viewpoint of resolution, a benzene ring or a naphthalene ring having 2 free valences is preferred, and a benzene ring having 2 free valences is more preferred.

作為2價之芳香族環基可具有之取代基，可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。該等之中，就解像性之觀點而言，較佳為未經取代。Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of resolution, it is preferably unsubstituted.

又，作為將1個以上之2價脂肪族基與1個以上之2價芳香族環基連結而成之基，可列舉：將上述2價脂肪族基1個以上、與上述2價芳香族環基１個以上連結而成之基。 2價脂肪族基之數量並無特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有變得容易進行聚合之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為2～3。 2價芳香族環基之數量並無特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為2～3。In addition, examples of the group formed by connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include one or more of the above divalent aliphatic groups and the above divalent aromatic groups A ring base consisting of more than one link. The number of divalent aliphatic groups is not particularly limited, but it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. By setting it to the above-mentioned lower limit value or more, it tends to become easy to polymerize, and by setting it to the above-mentioned upper limit value, it tends to improve the resolution. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3. The number of divalent aromatic ring groups is not particularly limited, but it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

作為將1個以上之2價脂肪族基與1個以上之2價芳香族環基連結而成之基的具體例，可列舉：下述式(a1-I-A)～(a1-I-F)所表示之基等。該等之中，就解像性之觀點而言，較佳為下述式(a1-I-A)所表示之基。Specific examples of the group formed by connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include the following formulas (a1-IA) to (a1-IF) The basis and so on. Among these, from the viewpoint of resolution, the base represented by the following formula (a1-I-A) is preferable.

[化15] [化15]

如上所述，式(a1-I)中之苯環可進而經任意之取代基取代。作為該取代基，例如可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基之數量亦無特別限定，可為1個，亦可為2個以上。該等之中，就解像性之觀點而言，較佳為未經取代。As described above, the benzene ring in formula (a1-I) may be further substituted with any substituent. Examples of the substituent include hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of resolution, it is preferably unsubstituted.

又，關於上述式(a1-I)所表示之部分結構，就合成之容易性之觀點而言，較佳為下述式(a1-I-1)所表示之部分結構。In addition, the partial structure represented by the above formula (a1-I) is preferably a partial structure represented by the following formula (a1-I-1) from the viewpoint of ease of synthesis.

[化16] [Chem 16]

式(a1-I-1)中，R¹¹ 及R¹² 係與上述式(a1-I)者含義相同，R^X 表示氫原子或多元酸殘基，*表示鍵結鍵。式(a1-I-1)中之苯環可進而經任意之取代基取代。In the formula (a1-I-1), R ¹¹ and R ¹² have the same meaning as those of the above formula (a1-I), R ^X represents a hydrogen atom or a polyacid residue, and * represents a bonding bond. The benzene ring in formula (a1-I-1) may be further substituted with any substituent.

所謂多元酸殘基，意指自多元酸或其酸酐去除1個OH基而成之1價基。作為多元酸，可列舉：選自順丁烯二酸、琥珀酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、二苯甲酮四羧酸、甲基六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、氯菌酸、甲基四氫鄰苯二甲酸、聯苯四羧酸中之1種或2種以上。該等之中，就圖案化特性之觀點而言，較佳為順丁烯二酸、琥珀酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、聯苯四羧酸，更佳為四氫鄰苯二甲酸、均苯四甲酸、聯苯四羧酸。The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or its anhydride. Examples of the polybasic acid include: selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid , Benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, internal methylene tetrahydrophthalic acid, chloramphenic acid, methyl tetrahydrophthalic acid, biphenyltetracarboxylic acid 1 Species or more than two species. Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferably tetrahydrophthalic acid, pyromellitic acid, and biphenyltetracarboxylic acid.

(a1-I)環氧(甲基)丙烯酸酯樹脂1分子中所含有之上述式(a1-I-1)所表示之部分結構可為1種亦可為2種以上，例如亦可R^X 為氫原子者、與R^X 為多元酸殘基者混合存在。(a1-I) The partial structure represented by the above formula (a1-I-1) contained in 1 molecule of epoxy (meth)acrylate resin may be one kind or two or more kinds, for example, R ^X Those that are hydrogen atoms, and those where R ^X is a polybasic acid residue are mixed.

又，(a1-I)環氧(甲基)丙烯酸酯樹脂1分子中所含有之上述式(a1-I)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，進而較佳為15以下。藉由設為上述下限值以上，有顯影溶解性變高之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～20、更佳為3～15。In addition, the number of partial structures represented by the above formula (a1-I) contained in one molecule of (a1-I) epoxy (meth)acrylate resin is not particularly limited, but it is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, and more preferably 15 or less. By setting it to the above lower limit or more, the developing solubility tends to be higher, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1-20, more preferably 3-15.

(a1-I)環氧(甲基)丙烯酸酯樹脂之藉由凝膠滲透層析法(GPC)所測得之聚苯乙烯換算之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為1500以上，進而較佳為2000以上，進而更佳為2500以上，尤佳為3000以上，最佳為3500以上，又，較佳為30000以下，更佳為20000以下，進而較佳為10000以下，進而更佳為9000以下，尤佳為8000以下，最佳為7000以下。藉由設為上述下限值以上，有解像性變得良好之傾向，又，藉由設為上述上限值以下，有再溶解性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為1000～30000、更佳為1500～20000、進而較佳為2000～10000、進而更佳為2500～9000、尤佳為3000～8000、最佳為3500～7000。(a1-I) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of epoxy (meth)acrylate resin is not particularly limited, preferably 1000 Above, more preferably 1500 or more, further preferably 2000 or more, still more preferably 2500 or more, particularly preferably 3000 or more, and most preferably 3500 or more, and preferably, 30,000 or less, more preferably 20,000 or less, and more It is preferably 10,000 or less, further preferably 9000 or less, particularly preferably 8000 or less, and most preferably 7000 or less. By setting it to the above lower limit or more, the resolution tends to be good, and by setting it to the above upper limit or less, the resolubility tends to be good. The combination of the upper limit and the lower limit includes, for example, preferably 1,000 to 30,000, more preferably 1,500 to 20,000, still more preferably 2,000 to 10,000, still more preferably 2500 to 9000, and particularly preferably 3,000 to 8,000, most preferably It is 3500～7000.

(a1-I)環氧(甲基)丙烯酸酯樹脂之酸值並無特別限定，較佳為10 mgKOH/g以上，更佳為20 mgKOH/g以上，進而較佳為40 mgKOH/g以上，進而更佳為50 mgKOH/g以上，尤佳為80 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，進而更佳為130 mgKOH/g以下，尤佳為120 mgKOH/g以下。藉由設為上述下限值以上，有顯影溶解性提高，解像性變得良好之傾向，又，藉由設為上述上限值以下，有感光性樹脂組合物之殘膜率變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為10～200 mgKOH/g、更佳為20～150 mgKOH/g、進而較佳為40～150 mgKOH/g、進而更佳為50～130 mgKOH/g、尤佳為80～120 mgKOH/g。(a1-I) The acid value of the epoxy (meth)acrylate resin is not particularly limited, preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and still more preferably 40 mgKOH/g or more, Furthermore, it is more preferably 50 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, and more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and even more preferably 130 mgKOH/g or less, especially It is preferably below 120 mgKOH/g. By setting it to the above lower limit or more, the development solubility tends to be improved, and the resolvability tends to be good, and by setting it to the above upper limit or less, the residual film ratio of the photosensitive resin composition becomes good The tendency. Examples of the combination of the upper limit and the lower limit include: preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, still more preferably 40 to 150 mgKOH/g, and still more preferably 50 to 130 mgKOH /g, particularly preferably 80 to 120 mgKOH/g.

於以下列舉(a1-I)環氧(甲基)丙烯酸酯樹脂之具體例。再者，例中之*係表示鍵結鍵。Specific examples of (a1-I) epoxy (meth)acrylate resins are listed below. Furthermore, * in the example means a bond key.

[化17] [化17]

[化18] [Chemical 18]

[化19] [Chem 19]

[化20] [化20]

＜(a1-II)環氧(甲基)丙烯酸酯樹脂＞繼而，對具有上述通式(a1-II)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂詳細地進行說明。<(a1-II) Epoxy (meth)acrylate resin> Next, the epoxy (meth)acrylate resin having a partial structure represented by the general formula (a1-II) will be described in detail.

[化21] [化21]

(R¹⁴ ) 上述通式(a1-II)中，R¹⁴ 表示具有環狀烴基作為側鏈之2價烴基。作為環狀烴基，可列舉脂肪族環基或芳香族環基。(R ¹⁴ ) In the above general formula (a1-II), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為2～3。又，脂肪族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為4～40、更佳為6～30、進而較佳為8～20。作為脂肪族環基中之脂肪族環之具體例，可列舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降烷環、異烷環、金剛烷環等。該等之中，就感光性樹脂組合物之殘膜率與解像性之觀點而言，較佳為金剛烷環。The number of rings possessed by the aliphatic cyclic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3. The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less, particularly preferably 15 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 40, more preferably 6 to 30, and still more preferably 8 to 20. Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norkane ring, isoalkane ring, adamantane ring, etc. . Among these, from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition, an adamantane ring is preferred.

另一方面，芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，通常為10以下，較佳為5以下，更佳為4以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為3～4。作為芳香族環基，可列舉芳香族烴環基、芳香族雜環基。又，芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，進而更佳為10以上，尤佳為12以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有解像性變得良好之傾向，又，藉由設為上述上限值以下，有再溶解性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為4～40、更佳為6～30、進而較佳為8～20、尤佳為10～15。作為芳香族環基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、䓛環、聯三伸苯環、苊環、螢蒽環、茀環等。該等之中，就顯影溶解性之觀點而言，較佳為茀環。On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more It is preferably 4 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. The combination of the upper limit and the lower limit includes, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 4. Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and still more preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. By setting it to the above lower limit or more, the resolution tends to be good, and by setting it to the above upper limit or less, the resolubility tends to be good. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 10 to 15. Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, beryllium ring, triphenylene ring Benzene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. Among these, from the viewpoint of developing solubility, it is preferably a ring.

又，具有環狀烴基作為側鏈之2價烴基中之2價烴基並無特別限定，例如可列舉：2價脂肪族基、2價芳香族環基、將1個以上之2價脂肪族基與1個以上之2價芳香族環基連結而成之基。In addition, the divalent hydrocarbon group among the divalent hydrocarbon groups having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include divalent aliphatic groups, divalent aromatic ring groups, and one or more divalent aliphatic groups. A group formed by connecting one or more divalent aromatic ring groups.

2價脂肪族基可列舉：直鏈狀者、支鏈狀者、環狀者、該等之組合者。該等之中，就顯影溶解性之觀點而言，較佳為直鏈狀者，另一方面，就顯影液對於曝光部之滲透減少之觀點而言，較佳為環狀者。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為25以下，更佳為20以下，進而較佳為15以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～25、更佳為3～20、進而較佳為6～15。Examples of the divalent aliphatic group include linear ones, branched ones, cyclic ones, and combinations of these. Among these, from the viewpoint of development solubility, a linear one is preferable, and on the other hand, from the viewpoint of reduction in penetration of the developer into the exposed portion, a ring-shaped one is preferable. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. The combination of the upper limit and the lower limit includes, for example, preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15.

作為2價之直鏈狀之脂肪族基之具體例，可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基等。該等之中，就解像性之觀點而言，較佳為亞甲基。作為2價之支鏈狀之脂肪族基，可列舉：於上述2價之直鏈狀之脂肪族基具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等作為側鏈之結構。 2價之環狀之脂肪族基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下，進而較佳為3以下。藉由設為上述下限值以上，有成為牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為2～3。作為2價之環狀之脂肪族基之具體例，可列舉：自環己烷環、環庚烷環、環癸烷環、環十二烷環、降烷環、異烷環、金剛烷環等環去除2個氫原子而成之基。該等之中，就感光性樹脂組合物之殘膜率與解像性之觀點而言，較佳為自金剛烷環去除2個氫原子而成之基。Specific examples of the divalent linear aliphatic group include methylene, ethylidene, n-propylene, n-butylene, n-pentylyl, n-hexyl, n-heptyl and the like. Among these, from the viewpoint of resolution, methylene is preferable. Examples of the divalent branched aliphatic group include the above-mentioned divalent linear aliphatic group having methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl group, the third butyl group, etc. serve as side chain structures. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less . By setting it to the above lower limit value or more, there is a tendency to become a strong film, and by setting it to the above upper limit value or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3. Specific examples of divalent cyclic aliphatic groups include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoalkane ring, and adamantane ring. The base is formed by removing 2 hydrogen atoms from the isocycle. Among these, from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition, a group obtained by removing two hydrogen atoms from the adamantane ring is preferred.

又，作為2價芳香族環基，可列舉2價芳香族烴環基及2價芳香族雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，進而較佳為15以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為4～30、更佳為5～20、進而較佳為6～15。In addition, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15.

作為2價芳香族烴環基中之芳香族烴環，可為單環亦可為縮合環。作為芳香族烴環基，例如可列舉：具有2個自由原子價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、䓛環、聯三伸苯環、苊環、螢蒽環、茀環等基。又，作為芳香族雜環基中之芳香族雜環，可為單環亦可為縮合環。作為芳香族雜環基，例如可列舉：具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡環、嗒環、嘧啶環、三環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、啶環、喹唑啉環、喹唑啉酮環、薁環等基。該等之中，就解像性之觀點而言，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, beryllium ring, bivalent ring Triphenylene ring, acenaphthene ring, fluoranthene ring, stilbene ring and other groups. The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring having two free valences, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a diazole ring, and an indene Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzo Isoazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, thiamine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, brown Pyridine ring, Pyridinium ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among these, from the viewpoint of resolution, a benzene ring or a naphthalene ring having 2 free valences is preferred, and a benzene ring having 2 free valences is more preferred.

作為2價芳香族環基可具有之取代基，可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。該等之中，就解像性之觀點而言，較佳為未經取代。Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of resolution, it is preferably unsubstituted.

又，作為將1個以上之2價脂肪族基與1個以上之2價芳香族環基連結而成之基，可列舉：將上述2價脂肪族基1個以上、與上述2價芳香族環基1個以上連結而成之基。 2價脂肪族基之數量並無特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為2～3。 2價芳香族環基之數量並無特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為2～3。In addition, examples of the group formed by connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include one or more of the above divalent aliphatic groups and the above divalent aromatic groups A base formed by connecting more than one ring base. The number of divalent aliphatic groups is not particularly limited, but it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3. The number of divalent aromatic ring groups is not particularly limited, but it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

作為將1個以上之2價脂肪族基與1個以上之2價芳香族環基連結而成之基之具體例，可列舉：上述式(a1-I-A)～(a1-I-F)所表示之基等。該等之中，就解像性之觀點而言，較佳為上述式(a1-I-C)所表示之基。As a specific example of a group formed by connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the above formulas (a1-IA) to (a1-IF) Base etc. Among these, from the viewpoint of resolution, the base represented by the above formula (a1-I-C) is preferable.

作為側鏈之環狀烴基對於該等2價烴基之鍵結態樣並無特別限定，例如可列舉：脂肪族基或芳香族環基之1個氫原子經該側鏈取代之態樣；或包括脂肪族基之1個碳原子而構成作為側鏈之環狀烴基之態樣。As the cyclic hydrocarbon group of the side chain, there is no particular limitation on the bonding state of the divalent hydrocarbon groups. For example, a hydrogen atom of an aliphatic group or an aromatic ring group may be substituted by the side chain; or It includes one carbon atom of an aliphatic group to form a cyclic hydrocarbon group as a side chain.

(R¹⁵ 、R¹⁶ ) 上述通式(a1-II)中，R¹⁵ 及R¹⁶ 分別獨立地表示可具有取代基之2價脂肪族基。(R ¹⁵ , R ¹⁶ ) In the above general formula (a1-II), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

2價脂肪族基可列舉：直鏈狀者、支鏈狀者、環狀者、該等之組合者。該等之中，就顯影溶解性之觀點而言，較佳為直鏈狀者，另一方面，就感光性樹脂組合物之殘膜率與解像性之觀點而言，較佳為環狀者。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～20、更佳為3～15、進而較佳為6～10。Examples of the divalent aliphatic group include linear ones, branched ones, cyclic ones, and combinations of these. Among these, from the viewpoint of development solubility, it is preferably linear, and on the other hand, from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition, it is preferably cyclic By. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. The combination of the upper limit and the lower limit includes, for example, preferably 1-20, more preferably 3-15, and even more preferably 6-10.

作為2價之直鏈狀之脂肪族基之具體例，可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基等。該等之中，就解像性之觀點而言，較佳為亞甲基。作為2價之支鏈狀之脂肪族基，可列舉：於上述2價之直鏈狀之脂肪族基具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等作為側鏈之結構。 2價之環狀之脂肪族基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為12以下，較佳為10以下。藉由設為上述下限值以上，有成為牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～12、更佳為2～10。作為2價之環狀之脂肪族基之具體例，可列舉：自環己烷環、環庚烷環、環癸烷環、環十二烷環、降烷環、異烷環、金剛烷環、二環戊二烯等環去除2個氫原子而成之基。該等之中，就骨架之剛直性之觀點而言，較佳為自二環戊二烯環、金剛烷環去除2個氫原子而成之基。Specific examples of the divalent linear aliphatic group include methylene, ethylidene, n-propylene, n-butylene, n-pentylyl, n-hexyl, n-heptyl and the like. Among these, from the viewpoint of resolution, methylene is preferable. Examples of the divalent branched aliphatic group include the above-mentioned divalent linear aliphatic group having methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl group, the third butyl group, etc. serve as side chain structures. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. By setting it to the above lower limit value or more, there is a tendency to become a strong film, and by setting it to the above upper limit value or less, the resolution tends to be improved. Examples of the combination of the upper limit and the lower limit include: preferably 1 to 12, more preferably 2 to 10. Specific examples of divalent cyclic aliphatic groups include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoalkane ring, and adamantane ring. , Dicyclopentadiene and other rings by removing 2 hydrogen atoms. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferred.

(m、n) 上述通式(a1-II)中，m及n分別獨立地表示0～2之整數。藉由設為上述下限值以上，有表面硬化性變得良好之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。就顯影性之觀點而言，較佳為m及n為0。另一方面，就殘膜率之觀點而言，較佳為m及n為1以上。(m, n) In the above general formula (a1-II), m and n each independently represent an integer of 0 to 2. By setting it to the above lower limit value or more, the surface hardenability tends to be good, and by setting it to the above upper limit value or less, the resolution tends to be good. From the viewpoint of developability, m and n are preferably 0. On the other hand, from the viewpoint of the residual film ratio, m and n are preferably 1 or more.

又，關於上述通式(a1-II)所表示之部分結構，就與色料之親和性之觀點而言，較佳為下述通式(a1-II-1)所表示之部分結構。In addition, the partial structure represented by the general formula (a1-II) is preferably a partial structure represented by the following general formula (a1-II-1) from the viewpoint of affinity with the color material.

[化22] [化22]

式(a1-II-1)中，R¹³ 、R¹⁵ 、R¹⁶ 、m及n與上述式(a1-II)含義相同，R^α 表示可具有取代基之1價環狀烴基，p為1以上之整數，*表示鍵結鍵。式(a1-II-1)中之苯環可進而經任意之取代基取代。In the formula (a1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as the above formula (a1-II), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent, p is 1 The above integer, * indicates a bond key. The benzene ring in formula (a1-II-1) may be further substituted with any substituent.

(R^α ) 上述通式(a1-II-1)中，R^α 表示可具有取代基之1價環狀烴基。作為環狀烴基，可列舉脂肪族環基或芳香族環基。(R ^α ) In the above general formula (a1-II-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為6以下，較佳為4以下，更佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為1～6、更佳為2～4、進而較佳為2～3。又，脂肪族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為4～40、更佳為6～30、進而較佳為8～20、尤佳為8～15。作為脂肪族環基中之脂肪族環之具體例，可列舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降烷環、異烷環、金剛烷環等。該等之中，就牢固之膜特性之觀點而言，較佳為金剛烷環。The number of rings possessed by the aliphatic cyclic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be good. The combination of the upper limit and the lower limit includes, for example, preferably 1 to 6, more preferably 2 to 4, and even more preferably 2 to 3. The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less, particularly preferably 15 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be good. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 8 to 15. Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norkane ring, isoalkane ring, adamantane ring, etc. . Among these, from the viewpoint of firm film properties, an adamantane ring is preferred.

另一方面，芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為1～5、進而較佳為1～3。作為芳香族環基，可列舉：芳香族烴環基、芳香族雜環基。又，芳香族環基之碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，進而較佳為15以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為4～30、更佳為5～20、進而較佳為6～15。作為芳香族環基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、茀環等。該等之中，就顏料親和性之觀點而言，較佳為茀環。On the other hand, the number of rings included in the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be good. The combination of the upper limit and the lower limit includes, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be good. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and stilbene ring. Among these, from the viewpoint of the affinity of the pigment, it is preferably a ring.

作為環狀烴基可具有之取代基，可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等之中，就合成容易性之觀點而言，較佳為未經取代。Examples of the substituent that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, and isopentyl. 1 to 5 alkyl groups; methoxy, ethoxy and other alkoxy groups having 1 to 5 carbon atoms; hydroxyl; nitro; cyano; carboxyl and so on. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

p表示1以上之整數，較佳為2以上，又，較佳為3以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為1～3、更佳為2～3。p represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be good. Examples of the combination of the upper limit and the lower limit include: preferably 1 to 3, and more preferably 2 to 3.

該等之中，就解像性之觀點而言，R^α 較佳為1價之脂肪族環基，更佳為金剛烷基。Among these, from the viewpoint of resolution, R ^{α is} preferably a monovalent aliphatic cyclic group, more preferably adamantyl.

如上述般，式(a1-II-1)中之苯環可進而經任意之取代基取代。作為該取代基，例如可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基之數量亦無特別限定，可為1個，亦可為2個以上。該等之中，就圖案化特性之觀點而言，較佳為未經取代。As described above, the benzene ring in formula (a1-II-1) may be further substituted with any substituent. Examples of the substituent include hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of patterning characteristics, it is preferably unsubstituted.

於以下列舉上述式(a1-II-1)所表示之部分結構之具體例。Specific examples of partial structures represented by the above formula (a1-II-1) are listed below.

[化23] [化23]

[化24] [化24]

[化25] [化25]

[化26] [化26]

[化27] [化27]

又，關於上述通式(a1-II)所表示之部分結構，就與色料之親和性、顯影性之觀點而言，較佳為下述通式(a1-II-2)所表示之部分結構。In addition, regarding the partial structure represented by the general formula (a1-II), from the viewpoint of affinity with the colorant and developability, the part represented by the following general formula (a1-II-2) is preferred structure.

[化28] [Chem 28]

式(a1-II-2)中，R¹³ 、R¹⁵ 、R¹⁶ 、m及n與上述式(a1-II)含義相同，R^β 表示可具有取代基之2價環狀烴基，*表示鍵結鍵。式(a1-II-2)中之苯環可進而經任意之取代基取代。In the formula (a1-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as the above formula (a1-II), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond Knot. The benzene ring in formula (a1-II-2) may be further substituted with any substituent.

(R^β ) 上述式(a1-II-2)中，R^β 表示可具有取代基之2價環狀烴基。作為環狀烴基，可列舉脂肪族環基或芳香族環基。(R ^β ) In the above formula (a1-II-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為1～5。又，脂肪族環基之碳數通常為4以上，較佳為5以上，更佳為6以上，進而較佳為8以上，又，較佳為40以下，更佳為35以下，進而較佳為30以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為4～40、更佳為5～35、進而較佳為6～30。作為脂肪族環基中之脂肪族環之具體例，可列舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降烷環、異烷環、金剛烷環等。該等之中，就殘膜率、解像性之觀點而言，較佳為金剛烷環。The number of rings possessed by the aliphatic cyclic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. Examples of the combination of the upper limit and the lower limit include: preferably 1 to 10, and more preferably 1 to 5. In addition, the carbon number of the aliphatic cyclic group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and still more preferably 8 or more, and further preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 40, more preferably 5 to 35, and still more preferably 6 to 30. Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norkane ring, isoalkane ring, adamantane ring, etc. . Among these, the adamantane ring is preferred from the viewpoint of the residual film rate and resolution.

另一方面，芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，通常為10以下，較佳為5以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～10、更佳為2～5、進而較佳為3～5。作為芳香族環基，可列舉：芳香族烴環基、芳香族雜環基。又，芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，進而較佳為10以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為4～40、更佳為6～30、進而較佳為8～20、尤佳為8～15。作為芳香族環基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、茚滿環、茀環等。該等之中，就顯影性之觀點而言，較佳為茚滿環、或茀環，更佳為茀環。On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. The combination of the upper limit and the lower limit includes, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 5. Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and further preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, especially 15 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 8 to 15. Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indane ring, and stilbene ring. Among these, from the viewpoint of developability, an indane ring or a stilbene ring is preferred, and a stilbene ring is more preferred.

作為環狀烴基可具有之取代基，可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；苯基；羥基；硝基；氰基；羧基等。該等之中，就合成容易性之觀點而言，較佳為未經取代。Examples of the substituent that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, and isopentyl. 1 to 5 alkyl groups; methoxy, ethoxy and other alkoxy groups having 1 to 5 carbon atoms; phenyl; hydroxy; nitro; cyano; carboxyl, etc. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

該等之中，就殘膜率、解像性之觀點而言，R^β 較佳為2價脂肪族環基，更佳為2價金剛烷環基。另一方面，就顯影性之觀點而言，R^β 較佳為2價芳香族環基，更佳為2價茀環基、2價苯基茚滿環基。Among these, R ^{β is} preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group from the viewpoint of the residual film ratio and resolution. On the other hand, from the viewpoint of developability, R ^{β is} preferably a divalent aromatic ring group, more preferably a divalent stilbene ring group, and a divalent phenylindane ring group.

如上述般，式(a1-II-2)中之苯環可進而經任意之取代基取代。作為該取代基，例如可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基之數量亦無特別限定，可為1個，亦可為2個以上。又，亦可經由取代基而2個苯環連接。作為該情形時之取代基，可列舉：-O-、-S-、-NH-、-CH₂ -等2價基。該等之中，就解像性之觀點而言，較佳為未經取代。又，使膜減少等難以產生之觀點而言，較佳為經甲基取代。As described above, the benzene ring in formula (a1-II-2) may be further substituted with any substituent. Examples of the substituent include hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is also not particularly limited, and may be one or two or more. In addition, two benzene rings may be connected via a substituent. Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH ₂ -. Among these, from the viewpoint of resolution, it is preferably unsubstituted. In addition, from the viewpoint of making it difficult to reduce the film, it is preferably substituted with a methyl group.

於以下列舉上述式(a1-II-2)所表示之部分結構之具體例。再者，例中之*表示鍵結鍵。Specific examples of the partial structures represented by the above formula (a1-II-2) are listed below. In addition, * in the example represents a bond key.

[化29] [Chem 29]

[化30] [化30]

[化31] [化31]

[化32] [化32]

[化33] [化33]

另一方面，關於上述式(a1-II)所表示之部分結構，就殘膜率與解像性之觀點而言，較佳為下述式(a1-II-3)所表示之部分結構。On the other hand, the partial structure represented by the above formula (a1-II) is preferably a partial structure represented by the following formula (a1-II-3) from the viewpoints of residual film ratio and resolution.

[化34] [化34]

式(a1-II-3)中，R¹³ 、R¹⁴ 、R¹⁵ 、R¹⁶ 、m及n與上述式(a1-II)含義相同，R^Z 表示氫原子或多元酸殘基。In formula (a1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m, and n have the same meanings as in the above formula (a1-II), and R ^Z represents a hydrogen atom or a polybasic acid residue.

所謂多元酸殘基，意指自多元酸或其酸酐去除1個OH基而成之1價基。再者，亦可進而去除另一個OH基，與式(a1-II-3)所表示之其他分子中之R^Z 共用，即，亦可經由R^Z 而複數個式(a1-II-3)連結。作為多元酸，可列舉：選自順丁烯二酸、琥珀酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、二苯甲酮四羧酸、甲基六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、氯菌酸、甲基四氫鄰苯二甲酸、聯苯四羧酸中之1種或2種以上。該等之中，就解像性之觀點而言，作為多元酸，較佳為順丁烯二酸、琥珀酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、聯苯四羧酸，更佳為四氫鄰苯二甲酸、聯苯四羧酸、聯苯四羧酸。The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or its anhydride. Furthermore, another OH group can be further removed and shared with R ^{Z in} other molecules represented by the formula (a1-II-3), that is, a plurality of formulas (a1-II-3) can also be formed through R ^Z link. Examples of the polybasic acid include: selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid , Benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, internal methylene tetrahydrophthalic acid, chloramphenic acid, methyl tetrahydrophthalic acid, biphenyltetracarboxylic acid 1 Species or more than two species. Among these, from the viewpoint of resolution, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid Dicarboxylic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, biphenyltetracarboxylic acid.

(a1-II)環氧(甲基)丙烯酸酯樹脂1分子中所含有之上述式(a1-II-3)所表示之部分結構可為1種，亦可為2種以上，例如亦可R^Z 為氫原子者、與R^Z 為多元酸殘基者混合存在。(a1-II) The partial structure represented by the above formula (a1-II-3) contained in 1 molecule of epoxy (meth)acrylate resin may be one kind, or two or more kinds, for example, R ^Z is a hydrogen atom, and R ^Z is a mixture of polybasic acid residues.

又，(a1-II)環氧(甲基)丙烯酸酯樹脂1分子中所含有之上述式(a1-II)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。藉由設為上述下限值以上，有變得容易獲得牢固之膜之傾向，又，藉由設為上述上限值以下，有解像性提高之傾向。作為上限與下限之組合，例如可列舉：較佳為1～20、更佳為3～15、進而較佳為3～10。In addition, the number of partial structures represented by the above formula (a1-II) contained in one molecule of (a1-II) epoxy (meth)acrylate resin is not particularly limited, preferably 1 or more, and more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it to the above lower limit or more, it is easy to obtain a strong film, and by setting it to the upper limit or less, the resolution tends to be improved. As a combination of the upper limit and the lower limit, for example, it is preferably 1-20, more preferably 3-15, and still more preferably 3-10.

(a1-II)環氧(甲基)丙烯酸酯樹脂之藉由凝膠滲透層析法(GPC)所測得之聚苯乙烯換算之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為2000以上，又，較佳為30000以下，更佳為20000以下，進而較佳為10000以下，進而更佳為7000以下，尤佳為6000以下。藉由設為上述下限值以上，有顯影性變得良好之傾向，又，藉由設為上述上限值以下，有再溶解性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為1000～30000、更佳為1000～20000、進而較佳為2000～10000、進而更佳為2000～7000、尤佳為2000～6000。(a1-II) The weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth)acrylate resin is not particularly limited, preferably 1000 The above, more preferably 2,000 or more, and more preferably 30,000 or less, more preferably 20,000 or less, further preferably 10,000 or less, still more preferably 7,000 or less, particularly preferably 6,000 or less. By setting it to the above lower limit value or more, the developability tends to be good, and by setting it to the above upper limit value or less, the resolubility tends to be good. The combination of the upper limit and the lower limit includes, for example, preferably 1,000 to 30,000, more preferably 1,000 to 20,000, still more preferably 2,000 to 10,000, still more preferably 2,000 to 7,000, and particularly preferably 2,000 to 6,000.

(a1-II)環氧(甲基)丙烯酸酯樹脂之酸值並無特別限定，較佳為10 mgKOH/g以上，更佳為20 mgKOH/g以上，進而較佳為40 mgKOH/g以上，進而更佳為60 mgKOH/g以上，尤佳為80 mgKOH/g以上，最佳為90 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，進而較佳為120 mgKOH/g以下。藉由設為上述下限值以上，有未硬化部之顯影溶解性變高之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如可列舉：較佳為10～200 mgKOH/g、更佳為20～150 mgKOH/g、進而較佳為40～150 mgKOH/g、進而更佳為60～120 mgKOH/g、尤佳為80～120 mgKOH/g。(a1-II) The acid value of the epoxy (meth)acrylate resin is not particularly limited, preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and further preferably 40 mgKOH/g or more, Furthermore, it is more preferably 60 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, most preferably 90 mgKOH/g or more, and more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and more It is preferably below 120 mgKOH/g. By setting it to the said lower limit or more, the developing solubility of an unhardened part tends to become high, and by setting it to the said upper limit or less, the resolution will tend to become favorable. The combination of the upper limit and the lower limit includes, for example, preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, still more preferably 40 to 150 mgKOH/g, and still more preferably 60 to 120 mgKOH. /g, particularly preferably 80 to 120 mgKOH/g.

本發明之感光性樹脂組合物中之(a)鹼可溶性樹脂係含有具有羧基之環氧(甲基)丙烯酸酯樹脂者，亦可進而含有其他鹼可溶性樹脂。作為其他鹼可溶性樹脂，例如可列舉丙烯酸系共聚樹脂。(A) The alkali-soluble resin in the photosensitive resin composition of this invention contains epoxy (meth)acrylate resin which has a carboxyl group, and may further contain other alkali-soluble resin. Examples of other alkali-soluble resins include acrylic copolymer resins.

作為丙烯酸系共聚樹脂，例如可使用日本專利特開平7-207211號、日本專利特開平8-259876號、日本專利特開平10-300922號、日本專利特開平11-140144號、日本專利特開平11-174224號、日本專利特開2000-56118號、日本專利特開2003-233179號、日本專利特開2007-270147號等各公報等所記載之各種高分子化合物，較佳為可列舉以下之(A2-1)～(A2-4)之樹脂等，其中，尤佳為(A2-1)之樹脂。As the acrylic copolymer resin, for example, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-open No. 11-140144, Japanese Patent Laid-open No. 11 -174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2003-233179, Japanese Patent Laid-Open No. 2007-270147, etc. Various polymer compounds described in various publications, etc., preferably include the following ( A2-1) to (A2-4) resins, etc. Among them, (A2-1) is particularly preferred.

(A2-1)：對於含有環氧基之(甲基)丙烯酸酯、與其他自由基聚合性單體之共聚物，使不飽和一元酸加成於該共聚物所具有之環氧基之至少一部分而成之樹脂、或者使多元酸酐加成於藉由該加成反應所產生之羥基之至少一部分所獲得之樹脂 (A2-2)：主鏈含有羧基之直鏈狀鹼可溶性樹脂 (A2-3)：使含有環氧基之不飽和化合物加成於上述(A2-2)之樹脂之羧基部分而成之樹脂 (A2-4)：(甲基)丙烯酸系樹脂(A2-1): For copolymers of (meth)acrylates containing epoxy groups and other radically polymerizable monomers, an unsaturated monobasic acid is added to at least the epoxy groups of the copolymer A part of the resin, or a resin obtained by adding polybasic acid anhydride to at least a part of the hydroxyl group produced by the addition reaction (A2-2): a linear alkali-soluble resin containing a carboxyl group in the main chain (A2- 3): A resin obtained by adding an unsaturated compound containing an epoxy group to the carboxyl part of the resin (A2-2) (A2-4): (meth)acrylic resin

本發明之感光性樹脂組合物就感度及熔合抑制之觀點而言，較佳為含有包含乙烯性不飽和基之鹼可溶性樹脂。作為含有乙烯性不飽和基之鹼可溶性樹脂，較佳為除上述具有羧基之環氧(甲基)丙烯酸酯樹脂以外，亦含有(A2-1)之樹脂及(A2-3)之樹脂之至少任一種。The photosensitive resin composition of the present invention preferably contains an alkali-soluble resin containing an ethylenically unsaturated group from the viewpoint of sensitivity and fusion inhibition. As the alkali-soluble resin containing an ethylenically unsaturated group, it is preferable that, in addition to the above-mentioned epoxy (meth)acrylate resin having a carboxyl group, at least a resin containing (A2-1) and a resin (A2-3) Any kind.

本發明之感光性樹脂組合物亦可併用上述丙烯酸系共聚樹脂以外之鹼可溶性樹脂作為其他鹼可溶性樹脂。於併用作為其他鹼可溶性樹脂之上述丙烯酸系共聚樹脂以外之鹼可溶性樹脂之情形時，只要自彩色濾光片用感光性樹脂組合物所通常使用之樹脂中進行選擇即可。例如可列舉：日本專利特開2007-271727號公報、日本專利特開2007-316620號公報、日本專利特開2007-334290號公報等所記載之鹼可溶性樹脂等。The photosensitive resin composition of the present invention may use an alkali-soluble resin other than the acrylic copolymer resin as another alkali-soluble resin. In the case of using alkali-soluble resins other than the above-mentioned acrylic copolymer resin as other alkali-soluble resins, it is sufficient to select from the resins generally used for photosensitive resin compositions for color filters. For example, alkali-soluble resins described in Japanese Patent Laid-Open No. 2007-271727, Japanese Patent Laid-Open No. 2007-316620, Japanese Patent Laid-Open No. 2007-334290, etc. can be cited.

關於(a)鹼可溶性樹脂之含有比率，於感光性樹脂組合物之總固形物成分中，通常為5質量%以上，較佳為10質量%以上，更佳為15質量%以上，進而較佳為20質量%以上，且通常為90質量%以下，較佳為70質量%以下，更佳為50質量%以下，進而較佳為30質量%以下。藉由設為上述下限值以上，有未曝光部分對於顯影液之溶解性變得良好之傾向，又，藉由設為上述上限值以下，有可抑制顯影液向曝光部過度滲透，圖像之鮮明製或密接性變得良好之傾向。作為上限與下限之組合，例如較佳為5～90質量%、更佳為10～70質量%、進而較佳為15～50質量%、尤佳為20～30質量%。Regarding the content ratio of (a) alkali-soluble resin, the total solid content of the photosensitive resin composition is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably It is 20% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less. By setting it to the above lower limit value, the solubility of the unexposed portion in the developing solution tends to be good, and by setting it to the above upper limit value, it is possible to suppress excessive penetration of the developing solution into the exposed portion. Like the sharpness of the system or the tendency of good adhesion. The combination of the upper limit and the lower limit is, for example, preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 50% by mass, and particularly preferably 20 to 30% by mass.

又，具有羧基之環氧(甲基)丙烯酸酯樹脂之含有比率並無特別限定，於感光性樹脂組合物之總固形物成分中，通常為5質量%以上，較佳為10質量%以上，更佳為15質量%以上，進而較佳為20質量%以上，且通常為90質量%以下，較佳為70質量%以下，更佳為50質量%以下，進而較佳為30質量%以下。藉由設為上述下限值以上，有抑制顯影殘渣之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。作為上限與下限之組合，例如較佳為5～90質量%、更佳為10～70質量%、進而較佳為15～50質量%、尤佳為20～30質量%。In addition, the content ratio of the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited. The total solid content of the photosensitive resin composition is usually 5% by mass or more, preferably 10% by mass or more. It is more preferably 15% by mass or more, and further preferably 20% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less. By setting it to the above lower limit value or more, there is a tendency to suppress the development residue, and by setting it to the above upper limit value or less, the resolution tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 50% by mass, and particularly preferably 20 to 30% by mass.

又，(a)鹼可溶性樹脂中之具有羧基之環氧(甲基)丙烯酸酯樹脂之含有比率亦無特別限定，於(a)鹼可溶性樹脂中，較佳為20質量%以上，更佳為40質量%以上，進而較佳為60質量%以上，進而更佳為80質量%以上，尤佳為90質量%以上，最佳為95質量%以上，又，通常為100質量%以下。藉由設為上述下限值以上，有解像性變得良好之傾向。作為上限與下限之組合，例如較佳為20～100質量%、更佳為40～100質量%、進而較佳為60～100質量%、進而更佳為80～100質量%、尤佳為90～100質量%、最佳為95～100質量%。In addition, the content ratio of the epoxy (meth)acrylate resin having a carboxyl group in (a) alkali-soluble resin is also not particularly limited, and in (a) alkali-soluble resin, it is preferably 20% by mass or more, more preferably 40% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, most preferably 95% by mass or more, and usually, 100% by mass or less. By setting it to the above lower limit or more, the resolution tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 20 to 100% by mass, more preferably 40 to 100% by mass, still more preferably 60 to 100% by mass, still more preferably 80 to 100% by mass, particularly preferably 90 ~100% by mass, preferably 95~100% by mass.

再者，於如上述般本發明之感光性樹脂組合物在(a)鹼可溶性樹脂中含有其他鹼可溶性樹脂之情形時，其含有比率並無特別限定，相對於(a)鹼可溶性樹脂，通常為20質量%以下，較佳為10質量%以下，尤佳為0質量%。In addition, in the case where the photosensitive resin composition of the present invention contains other alkali-soluble resin in (a) alkali-soluble resin as described above, the content ratio is not particularly limited. Compared with (a) alkali-soluble resin, it is usually It is 20% by mass or less, preferably 10% by mass or less, and particularly preferably 0% by mass.

又，相對於(b)光聚合性單體100質量份之(a)鹼可溶性樹脂之含有比率亦無特別限定，較佳為100質量份以上，更佳為130質量份以上，進而較佳為160質量份以上，尤佳為200質量份以上，又，較佳為2000質量份以下，更佳為1500質量份以下，進而較佳為1000質量份以下，尤佳為500質量份以下。藉由設為上述下限值以上，有抑制顯影殘渣之傾向，又，藉由設為上述上限值以下，有曝光感度變高之傾向。作為上限與下限之組合，例如較佳為100～2000質量份、更佳為130～1500質量份、進而較佳為160～1000質量份、尤佳為200～500質量份。Moreover, the content ratio of (a) alkali-soluble resin with respect to 100 parts by mass of (b) photopolymerizable monomer is not particularly limited, preferably 100 parts by mass or more, more preferably 130 parts by mass or more, and still more preferably 160 parts by mass or more, particularly preferably 200 parts by mass or more, and more preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, further preferably 1000 parts by mass or less, particularly preferably 500 parts by mass or less. Setting it to the above lower limit value tends to suppress development residues, and setting it to the above upper limit value tends to increase the exposure sensitivity. The combination of the upper limit and the lower limit is, for example, preferably 100 to 2000 parts by mass, more preferably 130 to 1500 parts by mass, still more preferably 160 to 1000 parts by mass, and particularly preferably 200 to 500 parts by mass.

＜(b)光聚合性單體＞本發明之感光性樹脂組合物就感度等方面而言，含有(b)光聚合性單體。作為本發明所使用之(b)光聚合性單體，可列舉於分子內具有至少1個乙烯性不飽和基之化合物(以下，有時稱為「乙烯性單體」)。具體而言，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸烷基酯、丙烯腈、苯乙烯、及具有1個乙烯性不飽和鍵之羧酸、與多元醇或一元之單酯等。<(b) Photopolymerizable monomer> The photosensitive resin composition of the present invention contains (b) photopolymerizable monomer in terms of sensitivity and the like. Examples of the (b) photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, sometimes referred to as "ethylene monomer"). Specifically, for example, (meth)acrylic acid, alkyl (meth)acrylate, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a polyhydric alcohol or a monovalent monoester Wait.

本發明中，尤其理想為使用於1分子中具有2個以上之乙烯性不飽和基之多官能乙烯性單體。多官能乙烯性單體中之乙烯性不飽和基之數量通常為2個以上，較佳為3個以上，更佳為4個以上，進而較佳為5個以上，尤佳為6個以上，又，通常為10個以下，較佳為8個以下。藉由設為上述下限值以上，而有成為高感度之傾向，又，藉由設為上述上限值以下，而有聚合時之硬化收縮變小之傾向。作為上限與下限之組合，例如較佳為2～10，更佳為3～10，進而較佳為4～8，進而更佳為5～8，尤佳為6～8。作為多官能乙烯性單體之例，例如可列舉：脂肪族多羥基化合物與不飽和羧酸之酯；芳香族多羥基化合物與不飽和羧酸之酯；藉由脂肪族多羥基化合物、芳香族多羥基化合物等多價羥基化合物、與不飽和羧酸及多鹼性羧酸之酯化反應所獲得之酯等。In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the multifunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, further preferably 5 or more, particularly preferably 6 or more, In addition, it is usually 10 or less, preferably 8 or less. By setting it above the said lower limit, it tends to become high sensitivity, and by setting it below the said upper limit, the hardening shrinkage at the time of polymerization tends to become small. The combination of the upper limit and the lower limit is, for example, preferably 2 to 10, more preferably 3 to 10, still more preferably 4 to 8, still more preferably 5 to 8, and particularly preferably 6 to 8. Examples of polyfunctional ethylenic monomers include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; by aliphatic polyhydroxy compounds, aromatic Polyvalent hydroxyl compounds such as polyhydroxy compounds, esters obtained by esterification reaction with unsaturated carboxylic acids and polybasic carboxylic acids, etc.

作為上述脂肪族多羥基化合物與不飽和羧酸之酯，可列舉：乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基乙烷三丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、丙烯酸甘油酯等脂肪族多羥基化合物之丙烯酸酯、將該等例示化合物之丙烯酸酯換為甲基丙烯酸酯而成之甲基丙烯酸酯、同樣地將該等例示化合物之丙烯酸酯換為伊康酸酯而成之伊康酸酯、將該等例示化合物之丙烯酸酯換為丁烯酸酯而成之丁烯酸酯或者將該等例示化合物之丙烯酸酯換為順丁烯二酸酯而成之順丁烯二酸酯等。Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Esters, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, acrylate of aliphatic polyhydroxy compounds such as glyceryl acrylate, etc. Methacrylates obtained by changing acrylates of exemplified compounds to methacrylates, and itaconic acid esters obtained by replacing acrylates of these exemplified compounds with itaconic acid esters, An acrylic acid ester is replaced by a crotonate ester or a crotonate ester ester of the exemplified compound is replaced by a maleate ester.

作為芳香族多羥基化合物與不飽和羧酸之酯，可列舉：對苯二酚二丙烯酸酯、對苯二酚二甲基丙烯酸酯、間苯二酚二丙烯酸酯、間苯二酚二甲基丙烯酸酯、鄰苯三酚三丙烯酸酯等芳香族多羥基化合物之丙烯酸酯及甲基丙烯酸酯等。作為藉由多鹼性羧酸及不飽和羧酸、與多價羥基化合物之酯化反應所獲得之酯，未必為單一物，若列舉具代表性之具體例，則可列舉：丙烯酸、鄰苯二甲酸、及乙二醇之縮合物；丙烯酸、順丁烯二酸、及二乙二醇之縮合物；甲基丙烯酸、對苯二甲酸及季戊四醇之縮合物；丙烯酸、己二酸、丁二醇及甘油之縮合物等。Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethyl Acrylate, methacrylate, etc. of aromatic polyhydroxy compounds such as acrylate, pyrogallol triacrylate, etc. The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance. If a representative specific example is given, acrylic acid, o-benzene Condensates of dicarboxylic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; acrylic acid, adipic acid and succinic acid Condensate of alcohol and glycerin, etc.

除此以外，作為本發明所使用之多官能乙烯性單體之例，有用的是如使多異氰酸酯化合物與含羥基之(甲基)丙烯酸酯或多異氰酸酯化合物與多元醇及含羥基之(甲基)丙烯酸酯進行反應所獲得之(甲基)丙烯酸胺基甲酸酯類；如多元環氧化合物與(甲基)丙烯酸羥酯或(甲基)丙烯酸之加成反應物之環氧丙烯酸酯類；伸乙基雙丙烯醯胺等丙烯醯胺類；鄰苯二甲酸二烯丙酯等烯丙酯類；鄰苯二甲酸二乙烯酯等含乙烯基之化合物等。該等可單獨使用1種，亦可將2種以上併用。In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, it is useful to use a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate or polyisocyanate compound and a polyol and a hydroxyl group-containing (method (Meth)acrylic acid urethanes obtained by the reaction of acrylates; such as epoxy acrylates of addition reaction of polyepoxy compounds with hydroxy (meth)acrylates or (meth)acrylic acid ; Acrylamides such as ethylidene diacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate. These can be used alone or in combination of two or more.

(b)光聚合性單體之含有比率於感光性樹脂組合物之總固形物成分中，通常為1質量%以上，較佳為5質量%以上，又，通常為90質量%以下，較佳為70質量%以下，更佳為50質量%以下，進而較佳為30質量%以下，進而更佳為20質量%以下，尤佳為10質量%以下。藉由將光聚合性單體之含有比率設為上述下限值以上，有使利用紫外線照射之光硬化提高並且鹼顯影性亦變得良好之傾向，又，藉由設為上述上限值以下，有顯影液對於曝光部之滲透性變得適度而可獲得良好之圖像之傾向。作為上限與下限之組合，較佳為1～90質量%，更佳為1～70質量%，進而較佳為1～50質量%，進而更佳為1～30質量%，尤佳為5～20質量%，最佳為5～10質量%。(b) The content ratio of the photopolymerizable monomer to the total solid content of the photosensitive resin composition is usually 1% by mass or more, preferably 5% by mass or more, and usually, 90% by mass or less, preferably It is 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less. By setting the content ratio of the photopolymerizable monomer to the above lower limit or more, there is a tendency to improve the light curing by ultraviolet irradiation and the alkali developability is also good, and by setting to the upper limit or less There is a tendency that the developer's permeability to the exposed part becomes moderate and a good image can be obtained. The combination of the upper limit and the lower limit is preferably 1 to 90% by mass, more preferably 1 to 70% by mass, still more preferably 1 to 50% by mass, still more preferably 1 to 30% by mass, particularly preferably 5 to 20% by mass, preferably 5-10% by mass.

＜(c)光自由基聚合起始劑＞本發明之感光性樹脂組合物含有(c)光自由基聚合起始劑。光自由基聚合起始劑係具有直接吸收光，引起分解反應或奪氫反應，而產生聚合活性自由基之功能之成分。亦可視需要添加增感色素等加成劑而使用。<(c) Photo radical polymerization initiator> The photosensitive resin composition of this invention contains (c) photo radical polymerization initiator. The photo-radical polymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and generates a polymerization active radical. Additives such as sensitizing pigments can also be used as needed.

作為光自由基聚合起始劑，例如可列舉：日本專利特開昭59-152396號公報、日本專利特開昭61-151197號各公報所記載之包含二茂鈦化合物之茂金屬化合物；日本專利特開2000-56118號公報所記載之六芳基聯咪唑衍生物類；日本專利特開平10-39503號公報記載之鹵甲基化㗁二唑衍生物類、鹵甲基-s-三衍生物類、N-苯基甘胺酸等N-芳基-α-胺基酸類、N-芳基-α-胺基酸鹽類、N-芳基-α-胺基酸酯類等自由基活性劑、α-胺烷基苯酮衍生物類；日本專利特開2000-80068號公報、日本專利特開2006-36750號公報等所記載之肟酯衍生物類等。Examples of the photo-radical polymerization initiator include: metallocene compounds containing a titanocene compound described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Japanese Patent Hexaarylbiimidazole derivatives described in Japanese Patent Laid-Open No. 2000-56118; halomethylated oxadiazole derivatives and halogenated methyl-s-tri derivatives described in Japanese Patent Laid-Open No. 10-39503 Free radical activity such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters Agents, α-aminoalkyl benzophenone derivatives; oxime ester derivatives described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, etc.

具體而言，例如作為茂金屬化合物，可列舉：二氯化二環戊二烯基鈦、二環戊二烯基鈦聯苯、雙(2,3,4,5,6-五氟苯基)二環戊二烯基鈦、雙(2,3,5,6-四氟苯基)二環戊二烯基鈦、雙(2,4,6-三氟苯基)二環戊二烯基鈦、雙(2,6-二氟苯基)二環戊二烯基鈦、雙(2,4-二氟苯基)二環戊二烯基鈦、雙(2,3,4,5,6-五氟苯基)二(甲基環戊二烯基)鈦、雙(2,6-二氟苯基)二(甲基環戊二烯基)鈦、雙[2,6-二氟-3-(1-吡咯基)苯基]二環戊二烯基鈦等。Specifically, examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium biphenyl, and bis(2,3,4,5,6-pentafluorophenyl ) Dicyclopentadienyl titanium, bis (2,3,5,6-tetrafluorophenyl) dicyclopentadienyl titanium, bis (2,4,6-trifluorophenyl) dicyclopentadiene Titanium, bis(2,6-difluorophenyl) dicyclopentadienyl titanium, bis(2,4-difluorophenyl) dicyclopentadienyl titanium, bis(2,3,4,5 ,6-pentafluorophenyl)bis(methylcyclopentadienyl) titanium, bis(2,6-difluorophenyl)di(methylcyclopentadienyl) titanium, bis(2,6-di Fluoro-3-(1-pyrrolyl)phenyl]dicyclopentadienyl titanium and the like.

又，作為聯咪唑衍生物類，可列舉：2-(2'-氯苯基)-4,5-二苯基咪唑二聚物、2-(2'-氯苯基)-4,5-雙(3'-甲氧基苯基)咪唑二聚物、2-(2'-氟苯基)-4,5-二苯基咪唑二聚物、2-(2'-甲氧基苯基)-4,5-二苯基咪唑二聚物、(4'-甲氧基苯基)-4,5-二苯基咪唑二聚物等。In addition, examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5- Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl) )-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.

又，作為鹵甲基化㗁二唑衍生物類，可列舉：2-三氯甲基-5-(2'-苯并呋喃基)-1,3,4-㗁二唑、2-三氯甲基-5-[β-(2'-苯并呋喃基)乙烯基]-1,3,4-㗁二唑、2-三氯甲基-5-[β-(2'-(6''-苯并呋喃基)乙烯基)]-1,3,4-㗁二唑、2-三氯甲基-5-呋喃基-1,3,4-㗁二唑等。In addition, examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole and 2-trichloro Methyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6' '-Benzofuranyl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furan-1,3,4-oxadiazole, etc.

又，作為鹵甲基-s-三衍生物類，可列舉：2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-s-三、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)-s-三、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)-s-三等。In addition, examples of the halomethyl-s-tri derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri and 2-(4- Methoxynaphthyl)-4,6-bis(trichloromethyl)-s-tris, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-tris , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-three.

又，作為α-胺烷基苯酮衍生物類，可列舉：2-甲基-1[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)丁烷-1-酮、4-二甲胺基乙基苯甲酸酯、4-二甲胺基異戊基苯甲酸酯、4-二乙胺基苯乙酮、4-二甲胺基苯丙酮、2-乙基己基-1,4-二甲胺基苯甲酸酯、2,5-雙(4-二乙胺基亞苄基)環己酮、7-二乙胺基-3-(4-二乙胺基苯甲醯基)香豆素、4-(二乙胺基)查耳酮等。In addition, examples of the α-aminoalkyl benzophenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinylpropane-1-one and 2-benzyl -2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane -1-one, 4-dimethylaminoethyl benzoate, 4-dimethylamino isoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminoacetophenone , 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-( 4-diethylaminobenzyl) coumarin, 4-(diethylamino) chalcone, etc.

作為光自由基聚合起始劑，尤其是於感度之方面上，有效的是肟衍生物類(肟酯系化合物及酮肟酯系化合物)。肟衍生物類中，尤其是就與基板之密接性之觀點而言，較佳為肟酯系化合物。肟酯系化合物由於在其結構中一併具有吸收紫外線之結構、傳遞光能之機構、及產生自由基之結構，故而少量時感度較高，且對於熱反應穩定，而能夠以少量實現高感度之感光性樹脂組合物之設計。尤其是就對於曝光光源之i線(365 nm)之光吸收性之觀點而言，於含有可經取代之咔唑基(具有可經取代之咔唑環之基)之肟酯系化合物之情形時，上述結構特性良好地顯現出，故而更佳。目前，在市場上，要求遮光度較高且薄膜之BM，且色料之含有比率亦日益變高。於此種狀況下，肟酯系化合物尤其有效。As photoradical polymerization initiators, especially in terms of sensitivity, oxime derivatives (oxime ester-based compounds and ketoxime ester-based compounds) are effective. Among the oxime derivatives, the oxime ester-based compound is preferred from the viewpoint of adhesion to the substrate. The oxime ester-based compound has a structure that absorbs ultraviolet rays, a mechanism for transmitting light energy, and a structure that generates free radicals in its structure, so it has high sensitivity in a small amount and is stable to thermal reactions, and can achieve high sensitivity in a small amount. The design of the photosensitive resin composition. Especially in the case of the light absorption of the i-line (365 nm) of the exposure light source, in the case of oxime ester compounds containing a substituted carbazolyl group (a group having a substituted carbazole ring) At this time, the above-mentioned structural characteristics are exhibited well, so it is better. At present, in the market, high opacity and thin film BM are required, and the content ratio of colorants is becoming higher and higher. Under such circumstances, oxime ester compounds are particularly effective.

作為肟酯系化合物，可列舉包含下述通式(22)所示之部分結構之化合物，較佳為可列舉下述通式(23)所示之肟酯系化合物。Examples of the oxime ester-based compound include compounds having a partial structure represented by the following general formula (22), and preferred examples include oxime ester-based compounds represented by the following general formula (23).

[化35] [化35]

上述式(22)中，R²² 表示分別可經取代之碳數2～12之烷醯基、碳數1～20之雜芳基烷醯基、碳數3～25之烯醯基、碳數3～8之環烷醯基、碳數3～20之烷氧基羰基烷醯基、碳數8～20之苯氧基羰基烷醯基、碳數3～20之雜芳氧基羰基烷醯基、碳數2～10之胺基烷基羰基、碳數7～20之芳醯基、碳數1～20之雜芳醯基、碳數2～10之烷氧基羰基、或碳數7～20之芳氧基羰基。In the above formula (22), R ²² represents a C2-C12 alkynyl group, a C1-C20 heteroaryl alkynyl group, a C3-C25 alkenyl group, a carbon number 3 to 8 cycloalkanoyl groups, C 3-20 alkoxycarbonyl alkanoyl groups, C 8-20 phenoxycarbonyl alkanoyl groups, C 3 to 20 heteroaryloxycarbonyl alkanoyl groups Group, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aryl group having 7 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or 7 carbon atoms ~20 aryloxycarbonyl.

[化36] [化36]

式(23)中，R^21a 表示氫原子、或分別可經取代之碳數1～20之烷基、碳數2～25之烯基、碳數1～20之雜芳基烷基、碳數3～20之烷氧基羰基烷基、碳數8～20之苯氧基羰基烷基、碳數1～20之雜芳氧基羰基烷基或雜芳硫基烷基、碳數1～20之胺基烷基、碳數2～12之烷醯基、碳數3～25之烯醯基、碳數3～8之環烷醯基、碳數7～20之芳醯基、碳數1～20之雜芳醯基、碳數2～10之烷氧基羰基、碳數7～20之芳氧基羰基、或碳數1～10之環烷基烷基，R^21b 表示含有芳香族環之任意取代基，R^22a 表示與上述式(22)中之R²² 相同之基。In formula (23), R ^21a represents a hydrogen atom, or a C 1-20 alkyl group, a C 2-25 alkenyl group, a C 1-20 heteroaryl alkyl group, a carbon number 3-20 alkoxycarbonylalkyl group, phenoxycarbonylalkyl group having 8-20 carbon atoms, heteroaryloxycarbonylalkyl group having 1-20 carbon atoms or heteroarylthioalkyl group, 1-20 carbon atoms Aminoalkyl group, C2-C12 alkynyl group, C3-C25 alkenyl group, C3-C8 cycloalkyl group, C7-C20 arylamide group, C-number 1 ～20 heteroaromatic aryl group, C 2-10 alkoxycarbonyl group, C 7-20 aryloxycarbonyl group, or C 1-10 cycloalkylalkyl group, R ^21b means containing aromatic ring R ^22a represents the same group as R ²² in the above formula (22).

再者，R^21a 亦可與R^21b 一併形成環，作為其連結基，可列舉：分別可具有取代基之碳數1～10之伸烷基、聚伸乙基(-(CH=CH)_r -)、聚伸乙炔基(-(C≡C)_r -)或組合該等而成之基(再者，r為0～3之整數)。作為上述通式(22)中之R²² 及上述通式(23)中之R^22a ，較佳為可列舉：碳數2～12之烷醯基、碳數1～20之雜芳基烷醯基、碳數3～8之環烷醯基。In addition, R ^21a may also form a ring together with R ^21b . Examples of the linking group include: alkylene groups having 1 to 10 carbon atoms and polyethylidene groups (-(CH=CH) which may have substituents, respectively) _r -), polyethynyl (-(C≡C) _r -) or a combination of these (also, r is an integer from 0 to 3). As R ^{22 in} the general formula (22) and R ^22a in the general formula (23), preferably, an alkyl group having 2 to 12 carbon atoms and a heteroaryl alkyl group having 1 to 20 carbon atoms are exemplified. Group, a cycloalkanoyl group having 3 to 8 carbon atoms.

作為上述通式(23)中之R^21a ，較佳為可列舉：未經取代之甲基、乙基、丙基等直鏈烷基；環烷基烷基；經N-乙醯基-N-乙醯氧基胺基取代之丙基。又，作為上述通式(23)中之R^21b ，較佳為可列舉：可經取代之咔唑基、可經取代之9-氧硫基、可經取代之苯硫醚基。As R ^21a in the general formula (23), preferably, straight chain alkyl groups such as unsubstituted methyl, ethyl, and propyl groups; cycloalkylalkyl groups; and N-acetyl-N -Propyl substituted with acetoxyamine. In addition, as R ^21b in the general formula (23), preferably, a carbazolyl group which may be substituted, or 9-oxosulfur which may be substituted may be mentioned. Group, phenyl sulfide group which may be substituted.

作為肟酯系化合物，就上述理由而言，更佳為含有可經取代之咔唑基作為R^21b 者。進而較佳為具有選自由可經取代之碳數6～25之芳基、可經取代之碳數7～25之芳基羰基、可經取代之碳數5～25之雜芳基、可經取代之碳數6～25之雜芳基羰基、及硝基所組成之群中之至少1種基之咔唑基。尤佳為具有選自由苯甲醯基、甲苯醯基、萘甲醯基、噻吩基羰基、及硝基所組成之群中之至少1種基之咔唑基。又，該等基較理想為鍵結於咔唑基之3位。As the oxime ester-based compound, for the above reasons, it is more preferable to contain a substituted carbazolyl group as R ^21b . Furthermore, it is preferable to have a aryl group selected from the group consisting of 6 to 25 carbon atoms that can be substituted, an arylcarbonyl group that can be substituted from 7 to 25 carbon atoms, and a heteroaryl group which can be substituted from 5 to 25 carbon atoms. A carbazolyl group of at least one group in the group consisting of a substituted heteroarylcarbonyl group having 6 to 25 carbon atoms and a nitro group. Particularly preferred is a carbazolyl group having at least one group selected from the group consisting of benzyl group, tolyl group, naphthyl group, thienylcarbonyl group, and nitro group. Moreover, these groups are preferably bonded to the 3-position of the carbazolyl group.

作為此種肟酯系化合物之市售品，有BASF公司製造之OXE-02、常州強力電子新材料公司製造之TR-PBG-304或TR-PBG-314等。As a commercially available product of such an oxime ester-based compound, there are OXE-02 manufactured by BASF Corporation, TR-PBG-304 or TR-PBG-314 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd. and the like.

作為適於本發明之肟酯系化合物，具體而言，可列舉如以下所例示之化合物，但不受該等化合物任何限定。Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but these compounds are not limited at all.

[化37] [化37]

[化38] [化38]

[化39] [化39]

作為酮肟酯系化合物，可列舉含有下述通式(24)所示之部分結構之化合物，較佳為可列舉下述通式(25)所示之肟酯系化合物。Examples of the ketoxime ester-based compound include compounds having a partial structure represented by the following general formula (24), and preferred examples include the oxime ester-based compound represented by the following general formula (25).

[化40] [化40]

上述通式(24)中，R²⁴ 係與上述通式(22)中之R²² 含義相同。In the above general formula (24), R ²⁴ has the same meaning as R ²² in the above general formula (22).

[化41] [化41]

上述通式(25)中，R^23a 表示分別可經取代之苯基、碳數1～20之烷基、碳數2～25之烯基、碳數1～20之雜芳基烷基、碳數3～20之烷氧基羰基烷基、碳數8～20之苯氧基羰基烷基、碳數2～20之烷硫基烷基、碳數1～20之雜芳氧基羰基烷基或雜芳硫基烷基、碳數1～20之胺基烷基、碳數2～12之烷醯基、碳數3～25之烯醯基、碳數3～8之環烷醯基、碳數7～20之芳醯基、碳數1～20之雜芳醯基、碳數2～10之烷氧基羰基、碳數7～20之芳氧基羰基、或碳數1～10之環烷基烷基。In the above general formula (25), R ^23a represents a phenyl group which may be substituted, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and carbon C3-20 alkoxycarbonylalkyl, C8-20 phenoxycarbonylalkyl, C2-20 alkylthioalkyl, C1-20 heteroaryloxycarbonylalkyl Or heteroarylthioalkyl, amine alkyl having 1 to 20 carbons, alkynyl having 2 to 12 carbons, alkenyl having 3 to 25 carbons, cycloalkane having 3 to 8 carbons, C7-20 aromatic aryl group, C1-20 heteroaromatic aryl group, C2-10 alkoxycarbonyl group, C7-20 aryloxycarbonyl group, or C1-10 Cycloalkylalkyl.

R^23b 表示含有芳香環之任意取代基。再者，R^23a 亦可與R^23b 一併形成環，其連結基可列舉：分別可具有取代基之碳數1～10之伸烷基、聚伸乙基(-(CH=CH)_r -)、聚伸乙炔基(-(C≡C)_r -)或組合該等而成之基(再者，r為0～3之整數)。R ^23b represents any substituent containing an aromatic ring. In addition, R ^23a may form a ring together with R ^23b , and the linking group may include a C 1-10 alkylene group and a polyethylene group (-(CH=CH) _r- ), polyethynyl (-(C≡C) _r -) or a combination of these (also, r is an integer from 0 to 3).

R^24a 表示分別可經取代之碳數2～12之烷醯基、碳數3～25之烯醯基、碳數4～8之環烷醯基、碳數7～20之苯甲醯基、碳數3～20之雜芳醯基、碳數2～10之烷氧基羰基、碳數7～20之芳氧基羰基、碳數2～20之雜芳基、或碳數2～20之烷基胺基羰基。作為上述通式(24)中之R²⁴ 及上述通式(25)中之R^24a ，較佳為可列舉：碳數2～12之烷醯基、碳數1～20之雜芳基烷醯基、碳數3～8之環烷醯基、碳數7～20之芳醯基。R ^24a represents a C2-C12 alkanoyl group, a C3-C25 alkenyl group, a C4-C8 cycloalkanoyl group, a C4-C20 benzyl group, Heteroaromatic aryl groups with 3 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 20 carbon atoms, heteroaryl groups with 2 to 20 carbon atoms, or those with 2 to 20 carbon atoms Alkylaminocarbonyl. Examples of R ²⁴ in the above general formula (24) and R ^24a in the above general formula (25) include preferably alkyl alkoxy groups having 2 to 12 carbon atoms and heteroarylalkyl alkoxy groups having 1 to 20 carbon atoms. Group, naphthenoyl group having 3 to 8 carbon atoms, and arylamide group having 7 to 20 carbon atoms.

作為上述通式(25)中之R^23a ，較佳為可列舉：未經取代之乙基、丙基、丁基；經甲氧基羰基取代之乙基或丙基。又，作為上述通式(25)中之R^23b ，較佳為可列舉：可經取代之咔唑基、可經取代之苯硫醚基。作為適於本發明之酮肟酯系化合物，具體而言，可列舉如以下所例示之化合物，但不受該等化合物任何限定。R ^23a in the general formula (25) preferably includes unsubstituted ethyl, propyl, and butyl; ethyl or propyl substituted with methoxycarbonyl. In addition, as R ^23b in the general formula (25), preferably, a carbazolyl group which may be substituted, or a phenylsulfide group which may be substituted may be mentioned. Specific examples of the ketoxime ester-based compound suitable for the present invention include the compounds exemplified below, but these compounds are not limited at all.

[化42] [化42]

[化43] [化43]

[化44] [化44]

作為此種酮肟酯系化合物之市售品，有BASF公司製造之OXE-01、常州強力電子新材料公司製造之TR-PBG-305等。As a commercially available product of such a ketoxime ester-based compound, there are OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Qiangli Electronic New Materials Corporation.

該等肟酯系化合物及酮肟酯系化合物係其本身公知之化合物，例如為日本專利特開2000-80068號公報、或日本專利特開2006-36750號公報所記載之一系列化合物之一種。上述肟衍生物類可單獨使用1種，亦可將2種以上併用。These oxime ester-based compounds and ketoxime ester-based compounds are compounds known per se, for example, one of a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 or Japanese Patent Laid-Open No. 2006-36750. The above oxime derivatives may be used alone or in combination of two or more.

作為光自由基聚合起始劑，除此以外，亦可列舉：安息香甲醚、安息香苯醚、安息香異丁醚、安息香異丙醚等安息香烷基醚類；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等蒽醌衍生物類；二苯甲酮、米其勒酮、2-甲基二苯甲酮、3-甲基二苯甲酮、4-甲基二苯甲酮、2-氯二苯甲酮、4-溴二苯甲酮、2-羧基二苯甲酮等二苯甲酮衍生物類；2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、1-羥基環己基苯基酮、α-羥基-2-甲基苯基丙酮、1-羥基-1-甲基乙基-(對異丙基苯基)酮、1-羥基-1-(對十二烷基苯基)酮、2-甲基-(4'-甲硫基苯基)-2-嗎啉基-1-丙酮、1,1,1-三氯甲基-(對丁基苯基)酮等苯乙酮衍生物類；9-氧硫、2-乙基9-氧硫、2-異丙基9-氧硫、2-氯9-氧硫、2,4-二甲基9-氧硫、2,4-二乙基9-氧硫、2,4-二異丙基9-氧硫等9-氧硫衍生物類；對二甲胺基苯甲酸乙酯、對二乙胺基苯甲酸乙酯等苯甲酸酯衍生物類；9-苯基吖啶、9-(對甲氧基苯基)吖啶等吖啶衍生物類；9,10-二甲基苯并啡等啡衍生物類；苯并蒽酮等蒽酮衍生物類等。該等光自由基聚合起始劑之中，就上述之理由而言，尤佳為肟衍生物類。As the photo radical polymerization initiator, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, etc.; 2-methylanthraquinone, 2- Anthraquinone derivatives such as ethyl anthraquinone, 2-third butyl anthraquinone, 1-chloroanthraquinone; benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methyldibenzophenone Benzophenone derivatives such as benzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc.; 2,2-bis Methoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1 -Methylethyl-(p-isopropylphenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-(4'-methylthiophenyl)-2 -Acetophenone derivatives such as morpholinyl-1-acetone, 1,1,1-trichloromethyl-(p-butylphenyl) ketone; 9-oxysulfide , 2-ethyl 9-oxysulfur , 2-isopropyl 9-oxysulfur , 2-chloro9-oxysulfur , 2,4-Dimethyl 9-oxysulfur , 2,4-Diethyl 9-oxysulfur , 2,4-Diisopropyl 9-oxysulfur 9-oxygen sulfur Derivatives; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenyl acridine, 9-(p-methoxyphenyl) acridine Acridine derivatives such as pyridine; morphine derivatives such as 9,10-dimethylbenzophine; anthrone derivatives such as benzanthrone. Among these photo-radical polymerization initiators, oxime derivatives are particularly preferred for the reasons mentioned above.

＜增感色素＞於光自由基聚合起始劑中，可視需要，以提高感應感度為目的而併用與圖像曝光光源之波長對應之增感色素。作為該等增感色素，可列舉：日本專利特開平4-221958號公報、日本專利特開平4-219756號公報所記載之色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報所記載之具有雜環之香豆素色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報所記載之3-酮香豆素化合物；日本專利特開平6-19240號公報所記載之吡咯亞甲基色素；此外，日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本國特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報所記載之具有二烷基胺基苯骨架之色素等。<Sensitizing dye> In the photo-radical polymerization initiator, if necessary, for the purpose of improving sensitivity, a sensitizing dye corresponding to the wavelength of the image exposure light source is used in combination. Examples of such sensitizing dyes include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756 Pigment; coumarin pigment with heterocycle described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335; Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335 3-ketocoumarin compound described in Japanese Patent Publication; pyrrole methylene pigment described in Japanese Patent Laid-Open No. 6-19240; In addition, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54 -155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761 , Japanese Patent Laid-Open No. 5-210240, Japanese Patent Laid-Open No. 4-288818 described in the pigment having a dialkylaminobenzene skeleton and the like.

該等增感色素中，較佳者為含有胺基之增感色素，進而較佳者為於分子內具有胺基及苯基之化合物。尤佳者例如為4,4'-二甲胺基二苯甲酮、4,4'-二乙胺基二苯甲酮、2-胺基二苯甲酮、4-胺基二苯甲酮、4,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、3,4-二胺基二苯甲酮等二苯甲酮系化合物；2-(對二甲胺基苯基)苯并㗁唑、2-(對二乙胺基苯基)苯并㗁唑、2-(對二甲胺基苯基)苯并[4,5]苯并㗁唑、2-(對二甲胺基苯基)苯并[6,7]苯并㗁唑、2,5-雙(對二乙胺基苯基)-1,3,4-㗁唑、2-(對二甲胺基苯基)苯并噻唑、2-(對二乙胺基苯基)苯并噻唑、2-(對二甲胺基苯基)苯并咪唑、2-(對二乙胺基苯基)苯并咪唑、2,5-雙(對二乙胺基苯基)-1,3,4-噻二唑、(對二甲胺基苯基)吡啶、(對二乙胺基苯基)吡啶、(對二甲胺基苯基)喹啉、(對二乙胺基苯基)喹啉、(對二甲胺基苯基)嘧啶、(對二乙胺基苯基)嘧啶等含有對二烷基胺基苯基之化合物等。其中，最佳者為4,4'-二烷基胺基二苯甲酮。增感色素可單獨使用1種，亦可併用2種以上。Among these sensitizing dyes, the sensitizing dye containing an amine group is preferable, and the compound having an amine group and a phenyl group in the molecule is more preferable. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone , 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone compounds; 2-(pair Dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole , 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2- (P-dimethylaminophenyl) benzothiazole, 2-(p-diethylaminophenyl) benzothiazole, 2-(p-dimethylaminophenyl) benzimidazole, 2-(p-diethylamine Phenyl) benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylamino Phenyl)pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine Compounds containing p-dialkylaminophenyl, etc. Among them, the best one is 4,4'-dialkylaminobenzophenone. One type of sensitizing pigment may be used alone, or two or more types may be used in combination.

(c)光自由基聚合起始劑之含有比率並無特別限定，於本發明之感光性樹脂組合物之總固形物成分中，通常為1質量%以上，較佳為2質量%以上，更佳為3質量以上，進而較佳為4質量%以上，且通常為30質量%以下，較佳為20質量%以下，更佳為15質量%以下，進而較佳為10質量%以下，尤佳為8質量%以下。藉由設為上述下限值以上，有可抑制感度降低之傾向，又，藉由設為上述上限值以下，有可使未曝光部分對於顯影液之溶解性變得良好之傾向。作為上限與下限之組合，較佳為1～30質量%、更佳為2～20質量%、進而較佳為3～15質量%、進而更佳為4～10質量%、尤佳為4～8質量%。(c) The content ratio of the photo-radical polymerization initiator is not particularly limited. The total solid content of the photosensitive resin composition of the present invention is usually 1% by mass or more, preferably 2% by mass or more, and more Preferably it is 3 mass% or more, further preferably 4 mass% or more, and usually 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, further preferably 10 mass% or less, particularly preferably 8% by mass or less. By setting it to the above lower limit value, it is possible to suppress the decrease in sensitivity, and by setting it to the above upper limit value, there is a tendency to improve the solubility of the unexposed portion in the developer. As a combination of the upper limit and the lower limit, it is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, still more preferably 3 to 15% by mass, still more preferably 4 to 10% by mass, and particularly preferably 4 to 8% by mass.

又，於使用增感色素之情形時，增感色素之含有比率並無特別限定，於感光性樹脂組合物之總固形物成分中，通常為0～20質量%，較佳為0～15質量%，進而較佳為0～10質量%。In addition, when the sensitizing dye is used, the content ratio of the sensitizing dye is not particularly limited, and it is usually 0 to 20% by mass, preferably 0 to 15% by mass in the total solid content of the photosensitive resin composition %, more preferably 0 to 10% by mass.

＜(e)色料＞本發明之感光性樹脂組合物含有(e)色料。色料係對本發明之感光性樹脂組合物進行著色者。作為(e)色料，可使用顏料或染料，就耐熱性、耐光性等方面而言，較佳為顏料。<(e) Color material> The photosensitive resin composition of this invention contains (e) a color material. The color material is the one that colors the photosensitive resin composition of the present invention. As the (e) color material, a pigment or a dye can be used, and in terms of heat resistance, light resistance, etc., a pigment is preferred.

作為顏料，可使用藍色顏料、綠色顏料、紅色顏料、黃色顏料、紫色顏料、橙色顏料、棕色顏料、黑色顏料等各種顏色之顏料。又，作為其結構，除偶氮系、酞菁系、喹吖啶酮系、苯并咪唑酮系、異吲哚啉酮系、二㗁系、陰丹士林系、苝系等有機顏料以外，亦可應用各種無機顏料等。As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. In addition, as its structure, other than organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxin-based, indanthrene-based, and perylene-based , Various inorganic pigments can also be applied.

於以下以顏料編號表示可用於本發明之顏料之具體例。再者，以下所列舉之「C.I.顏料紅2」等用語意指色指數(C.I.)。作為紅色顏料，可列舉：C.I.顏料紅1、2、3、4、5、6、7、8、9、12、14、15、16、17、21、22、23、31、32、37、38、41、47、48、48：1、48：2、48：3、48：4、49、49：1、49：2、50：1、52：1、52：2、53、53：1、53：2、53：3、57、57：1、57：2、58：4、60、63、63：1、63：2、64、64：1、68、69、81、81：1、81：2、81：3、81：4、83、88、90：1、101、101：1、104、108、108：1、109、112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、258、259、260、262、263、264、265、266、267、268、269、270、271、272、273、274、275、276。其中，較佳為可列舉C.I.顏料紅48：1、122、168、177、202、206、207、209、224、242、254，進而較佳為可列舉C.I.顏料紅177、209、224、254。In the following, specific examples of pigments that can be used in the present invention are indicated by pigment numbers. In addition, the terms "C.I. Pigment Red 2" and the like listed below mean the color index (C.I.). Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, preferably CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and more preferably CI Pigment Red 177, 209, 224, 254 .

作為藍色顏料，可列舉：C.I.顏料藍1、1：2、9、14、15、15：1、15：2、15：3、15：4、15：6、16、17、19、25、27、28、29、33、35、36、56、56：1、60、61、61：1、62、63、66、67、68、71、72、73、74、75、76、78、79。其中，較佳為可列舉C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6，進而較佳為可列舉C.I.顏料藍15：6。作為綠色顏料，可列舉：C.I.顏料綠1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55、58、59。其中，較佳為可列舉：C.I.顏料綠7、36、58、59。Examples of blue pigments include: CI Pigment Blue 1, 1: 2, 9, 14, 15, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 , 79. Among them, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 is preferred, and C.I. Pigment Blue 15:6 is preferred. Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. Among them, preferably, C.I. Pigment Green 7, 36, 58, 59 are cited.

作為黃色顏料，可列舉：C.I.顏料黃1、1：1、2、3、4、5、6、9、10、12、13、14、16、17、24、31、32、34、35、35：1、36、36：1、37、37：1、40、41、42、43、48、53、55、61、62、62：1、63、65、73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、126、127、127：1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191：1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208。其中，較佳為可列舉C.I.顏料黃83、117、129、138、139、150、154、155、180、185，進而較佳為可列舉C.I.顏料黃83、138、139、150、180。Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferably, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferred, and C.I. Pigment Yellow 83, 138, 139, 150, 180 is further preferred.

作為橙色顏料，可列舉：C.I.顏料橙1、2、5、13、16、17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79。其中，較佳為可列舉C.I.顏料橙38、71。Examples of orange pigments include: CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, C.I. Pigment Orange 38 and 71 are preferably mentioned.

作為紫色顏料，可列舉：C.I.顏料紫1、1：1、2、2：2、3、3：1、3：3、5、5：1、14、15、16、19、23、25、27、29、31、32、37、39、42、44、47、49、50。其中，較佳為可列舉C.I.顏料紫19、23，進而較佳為可列舉C.I.顏料紫23。Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is more preferred.

又，除該等顏料以外，亦可使用染料。作為染料，可列舉：偶氮系染料、蒽醌系染料、酞菁系染料、醌亞胺系染料、喹啉系染料、硝基系染料、羰基系染料、次甲基系染料等。In addition to these pigments, dyes can also be used. Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

作為偶氮系染料，例如可列舉：C.I.酸性黃11、C.I.酸性橙7、C.I.酸性紅37、C.I.酸性紅180、C.I.酸性藍29、C.I.直接紅28、C.I.直接紅83、C.I.直接黃12、C.I.直接橙26、C.I.直接綠28、C.I.直接綠59、C.I.活性黃2、C.I.活性紅17、C.I.活性紅120、C.I.活性黑5、C.I.分散橙5、C.I.分散紅58、C.I.分散藍165、C.I.鹼性藍41、C.I.鹼性紅18、C.I.媒介紅7、C.I.媒介黃5、C.I.媒介黑7等。Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Active Yellow 2, CI Active Red 17, CI Active Red 120, CI Active Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Medium Red 7, CI Medium Yellow 5, CI Medium Black 7, etc.

作為蒽醌系染料，例如可列舉：C.I.還原藍4、C.I.酸性藍40、C.I.酸性綠25、C.I.活性藍19、C.I.活性藍49、C.I.分散紅60、C.I.分散藍56、C.I.分散藍60等。此外，作為酞菁系染料，例如可列舉C.I.還原藍5等，作為醌亞胺系染料，例如可列舉C.I.鹼性藍3、C.I.鹼性藍9等，作為喹啉系染料，例如可列舉C.I.溶劑黃33、C.I.酸性黃3、C.I.分散黃64等，作為硝基系染料，例如可列舉C.I.酸性黃1、C.I.酸性橙3、C.I.分散黃42等。Examples of anthraquinone-based dyes include CI reduced blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI dispersion red 60, CI dispersion blue 56, CI dispersion blue 60, etc. . In addition, examples of the phthalocyanine-based dye include CI reduction blue 5 and the like, examples of the quinoneimine-based dye include CI basic blue 3 and CI basic blue 9 and the like, and examples of the quinoline-based dye include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, etc. As the nitro-based dye, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42 and the like can be mentioned.

又，於將本發明之感光性樹脂組合物用於彩色濾光片之樹脂黑色矩陣等遮光用途之情形時，作為(e)色料，可使用黑色之色料。黑色色料可為單獨之黑色色料，亦可與紅色、綠色、藍色等混合。又，該等色料可自無機或有機之顏料、染料之中適當選擇。作為用以製備黑色色料之可混合使用之色料，可列舉：維多利亞純藍(42595)、金胺O(41000)、凱絲倫亮黃(Cathilon brilliant flavin)(鹼性13)、玫瑰紅6GCP(45160)、玫瑰紅B(45170)、番紅OK70：100(50240)、罌紅X(42080)、No.120/雷奧諾爾黃(21090)、雷奧諾爾黃GRO(21090)、斯姆勒耐曬黃8GF(21105)、聯苯胺黃4T-564D(21095)、斯姆勒耐曬紅4015(12355)、雷奧諾爾紅7B4401(15850)、Fastogen blue TGR-L(74160)、雷奧諾爾藍SM(26150)、雷奧諾爾藍ES(顏料藍15：6)、Lionogen red GD(顏料紅168)、雷奧諾爾綠2YS(顏料綠36)等(再者，上述( )內之數字意指色指數(C.I.))。In addition, when the photosensitive resin composition of the present invention is used for light-shielding applications such as a resin black matrix of a color filter, as the (e) color material, a black color material can be used. The black color material can be a separate black color material, or it can be mixed with red, green, blue, etc. Moreover, these colorants can be appropriately selected from inorganic or organic pigments and dyes. Examples of the color materials that can be mixed for preparing black color materials include Victoria pure blue (42595), auramine O (41000), Cathilon brilliant flavin (alkaline 13), and rose red 6GCP (45160), Rose Red B (45170), Saffron OK70: 100 (50240), Poppy X (42080), No. 120/Reynold Yellow (21090), Reynold Yellow GRO (21090), Sri Lanka Müller Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Müller Fast Red 4015 (12355), Rayonol Red 7B4401 (15850), Fastogen blue TGR-L (74160), Lei Onor Blue SM (26150), Leonor Blue ES (Pigment Blue 15:6), Lionogen red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36), etc. (Furthermore, within the above () The number means color index (CI).

又，若進而以C.I.編號表示其他可混合使用之顏料，則例如可列舉：C.I.顏料黃20、24、86、93、109、110、117、125、137、138、147、148、153、154、166、C.I.顏料橙36、43、51、55、59、61、C.I.顏料紅9、97、122、123、149、168、177、180、192、215、216、217、220、223、224、226、227、228、240、C.I.顏料紫19、23、29、30、37、40、50、C.I.顏料藍15、15：1、15：4、22、60、64、C.I.顏料綠7、C.I.顏料棕23、25、26等。Furthermore, if CI numbers are used to indicate other pigments that can be mixed, examples include CI Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, and 154 , 166, CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224 , 226, 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 22, 60, 64, CI Pigment Green 7, CI Pigment Brown 23, 25, 26, etc.

又，作為可單獨使用之黑色色料，可列舉：碳黑、乙炔黑、燈黑、骨黑、石墨、鐵黑、苯胺黑、花青黑、鈦黑、苝黑、內醯胺黑等。於使用該等(e)色料中之黑色之色料之情形時，就遮光率、圖像特性之觀點而言，較佳為碳黑。In addition, examples of the black color that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and amide black. In the case of using a black color material among the (e) color materials, carbon black is preferred from the viewpoint of light shielding rate and image characteristics.

又，於含有碳黑之情形時，有塗膜之疏水性變高，基板密接力變差之傾向，又，由於充分吸收紫外光～可見光範圍之光，故而有即便於曝光後，塗膜內部之光硬化亦變得不充分，而於加熱硬化步驟中容易產生由熔合引起之線寬變化之傾向。因此，藉由使用有機矽乙烯系聚合物(d-1)，於加熱開始時於基板界面及塗膜內部進行交聯反應，該等問題得到解決，而有容易兼顧基板密接性之提高與加熱硬化時之線寬變化之抑制之傾向。In addition, when carbon black is contained, the hydrophobicity of the coating film tends to be high, and the substrate adhesion tends to be poor. In addition, since the light in the ultraviolet to visible range is sufficiently absorbed, there is a possibility that the interior of the coating film even after exposure The photo-curing also becomes insufficient, and in the heat-hardening step, there is a tendency to change the line width caused by fusion. Therefore, by using the organosilicon polymer (d-1), the cross-linking reaction is carried out at the substrate interface and inside the coating film at the beginning of heating, these problems are solved, and it is easy to balance the improvement of substrate adhesion and heating The tendency to suppress line width changes during hardening.

作為碳黑之例，可列舉如以下者。 Mitsubishi Chemical公司製造：MA7、MA77、MA8、MA11、MA100、MA100R、MA220、MA230、MA600、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、#750、#850、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、#3050、#3150、#3250、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31B 德固賽公司製造：Printex(註冊商標；以下相同)3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、Printex G、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170 Cabot公司製造：Monarch(註冊商標；以下相同)120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL(註冊商標；以下相同)99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN(註冊商標)XC72R、ELFTEX(註冊商標)-8Examples of carbon black include the following. Made by Mitsubishi Chemical: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350 , #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Made by Degussa: Printex (registered trademark) ; The same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550 , SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Manufactured by Cabot: Monarch( Registered trademarks; the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark; the same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEA RLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8

Birla公司製造：RAVEN11、RAVEN14、RAVEN15、RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000Made by Birla: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1170, RAVEN1 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

碳黑亦可使用經樹脂被覆者。若使用經樹脂被覆之碳黑，則有提高對於玻璃基板之密接性或體積電阻值之效果。作為經樹脂被覆之碳黑，例如可較佳地使用日本專利特開平09-71733號公報所記載之碳黑等。作為供進行被覆處理之碳黑，較佳為Na與Ca之合計含量為100 ppm以下。碳黑係將通常製造時之原料油或燃燒油(或者瓦斯)、反應終止水或造粒水、進而自反應爐之爐材等混入之Na、或以Ca、K、Mg、Al、Fe等作為組成之灰分以百分比之等級含有。其中，關於Na或Ca，一般分別含有數百ppm以上，其原因在於：若該等大量存在，則有滲透至透明電極(ITO)或其他電極，而成為電氣短路之原因之情形。Carbon black can also be used with resin coating. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate or the volume resistance value. As the resin-coated carbon black, for example, the carbon black described in Japanese Patent Laid-Open No. 09-71733 can be preferably used. As the carbon black for coating treatment, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is Na mixed with raw material oil or combustion oil (or gas), reaction termination water or granulation water, and further from furnace materials of the reaction furnace, or Ca, K, Mg, Al, Fe, etc. The ash content as a component is contained in a percentage grade. Among them, Na or Ca generally contain hundreds of ppm or more, respectively. The reason for this is that if such a large amount exists, it may penetrate into the transparent electrode (ITO) or other electrodes and cause electrical short circuits.

作為減少該等含有Na或Ca之灰分之含量之方法，可藉由如下方式實現：嚴格選擇製造碳黑時之原料油或燃料油(或瓦斯)以及反應終止水之含量極少者；及極力減少調整結構之鹼性物質之添加量。作為其他方法，可列舉：利用水或鹽酸等清洗自爐製造出來之碳黑而將Na或Ca溶解去除之方法。As a method of reducing the content of ash containing Na or Ca, it can be achieved by: strictly selecting the raw material oil or fuel oil (or gas) and the content of the reaction termination water when carbon black is manufactured; and reducing it as much as possible Adjust the amount of alkaline substances added to the structure. As another method, there is a method of dissolving and removing Na or Ca by washing carbon black produced in the furnace with water, hydrochloric acid, or the like.

(e)色料之含有比率並無特別限定，於感光性樹脂組合物之總固形物成分中較佳為1質量%以上，更佳為20質量%以上，進而較佳為40質量%以上，進而更佳為45質量%以上，尤佳為50質量%以上，又，較佳為70質量%以下，更佳為60質量%以下，進而較佳為55質量%以下。藉由設為上述下限值以上，有著色性變得良好之傾向，又，藉由設為上述上限值以下，有圖案形成性或基板密接性提高之傾向。作為上限與下限之組合，例如較佳為1～70質量%、更佳為20～60質量%、進而較佳為45～60質量%、尤佳為50～55質量%。(e) The content ratio of the color material is not particularly limited, and it is preferably 1% by mass or more, more preferably 20% by mass or more, and still more preferably 40% by mass or more in the total solid content of the photosensitive resin composition, Furthermore, it is more preferably 45% by mass or more, particularly preferably 50% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less. By setting it to the above lower limit value or more, the coloring property tends to be good, and by setting it to the above upper limit value or less, the pattern formability or substrate adhesion tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 45 to 60% by mass, and particularly preferably 50 to 55% by mass.

又，於(e)色料含有碳黑之情形時，碳黑之含有比率亦無特別限定，於感光性樹脂組合物中之總固形物成分中較佳為35質量%以上，更佳為45質量%以上，進而較佳為50質量%以上，又，較佳為70質量%以下，更佳為60質量%以下，進而較佳為55質量%以下。藉由設為上述下限值以上，有遮光性變高之傾向，又，藉由設為上述上限值以下，有圖案形成性或基板密接性提高之傾向。作為上限與下限之組，例如較佳為35～70質量%、更佳為40～60質量%、進而較佳為50～55質量%。In addition, in the case where (e) the color material contains carbon black, the content ratio of carbon black is also not particularly limited, and the total solid content in the photosensitive resin composition is preferably 35% by mass or more, and more preferably 45 The mass% or more, more preferably 50 mass% or more, and further preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 55 mass% or less. By setting it to the above lower limit value or more, the light-shielding property tends to become higher, and by setting it to the above upper limit value or less, the pattern formability or substrate adhesion tends to be improved. The group of the upper limit and the lower limit is, for example, preferably 35 to 70% by mass, more preferably 40 to 60% by mass, and still more preferably 50 to 55% by mass.

再者，於感光性樹脂組合物中，(e)色料之含有比率係(a)鹼可溶性樹脂每100質量份，通常為20～500質量份，較佳為30～300質量份，更佳為40～280質量份之範圍。藉由設為上述下限值以上，有容易抑制未曝光部分對於顯影液之溶解性降低之傾向，又，藉由設為上述上限值以下，有容易獲得所需之圖像膜厚之傾向。Furthermore, in the photosensitive resin composition, the content ratio of (e) colorant is (a) alkali soluble resin per 100 parts by mass, usually 20 to 500 parts by mass, preferably 30 to 300 parts by mass, more preferably It is in the range of 40 to 280 parts by mass. By setting it to the above lower limit value, it is easy to suppress the decrease in the solubility of the unexposed portion to the developer, and by setting it to the above upper limit value, there is a tendency to easily obtain the desired image film thickness .

＜(f)分散劑＞於本發明中，為了確保品質之穩定性，重要的是使(e)色料微細地分散，且使其分散狀態穩定，因此較佳為含有(f)分散劑。作為分散劑，較佳為具有官能基之高分子分散劑，進而就分散穩定性之方面而言，較佳為具有羧基；磷酸基；磺酸基；或該等之鹽基；一級、二級或三級胺基；四級銨鹽基；源自吡啶、嘧啶、吡等含氮雜環之基等官能基之高分子分散劑。其中，尤佳為具有一級、二級或三級胺基；四級銨鹽基；源自吡啶、嘧啶、吡等含氮雜環之基等鹼性官能基之高分子分散劑。藉由使用該等具有鹼性官能基之高分子分散劑，有可使分散性變得良好，可達成較高之遮光性之傾向。<(f) Dispersant> In the present invention, in order to ensure the stability of quality, it is important to finely disperse the (e) colorant and stabilize its dispersion state, so it is preferable to contain (f) a dispersant. As the dispersant, a polymer dispersant having a functional group is preferred, and in terms of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a salt group thereof; primary and secondary Or tertiary amine groups; quaternary ammonium salt groups; polymer dispersants derived from functional groups such as pyridine, pyrimidine, pyridine and other nitrogen-containing heterocyclic groups. Among them, particularly preferred are high-molecular dispersants with primary, secondary or tertiary amine groups; quaternary ammonium salt groups; basic functional groups such as pyridine, pyrimidine, pyridine and other nitrogen-containing heterocyclic groups. By using these polymer dispersants with basic functional groups, there is a tendency that the dispersibility becomes good and a higher light-shielding property can be achieved.

又，作為高分子分散劑，例如可列舉：胺基甲酸酯系分散劑、丙烯酸系分散劑、聚伸乙基亞胺系分散劑、聚烯丙胺系分散劑、包含具有胺基之單體與巨單體之分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙烯二酯系分散劑、聚醚磷酸系分散劑、聚酯磷酸系分散劑、山梨醇酐脂肪族酯系分散劑、脂肪族改性聚酯系分散劑等。Examples of the polymer dispersant include urethane-based dispersants, acrylic dispersants, polyethylenimine-based dispersants, polyallylamine-based dispersants, and monomers containing amine groups. Dispersant with macromonomer, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan aliphatic ester dispersant , Aliphatic modified polyester dispersant, etc.

作為此種分散劑之具體例，可列舉：商品名為EFKA(註冊商標；EFKA公司製造)、DISPERBYK(註冊商標；BYK-Chemie公司製造)、Disparlon(註冊商標；楠本化成公司製造)、SOLSPERSE(註冊商標；Lubrizol公司製造)、KP(信越化學工業公司製造)、Polyflow或Flowlen(註冊商標；共榮社化學公司製造)、Ajisper(註冊商標；Ajinomoto Fine-Techno公司製造)等。該等高分子分散劑可單獨使用1種，或亦可將2種以上併用。Specific examples of such a dispersant include: EFKA (registered trademark; manufactured by EFKA), DISPERBYK (registered trademark; manufactured by BYK-Chemie), Disparlon (registered trademark; manufactured by Nanben Chemical), SOLSPERSE ( Registered trademark; manufactured by Lubrizol, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Flowlen (registered trademark; manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark; manufactured by Ajinomoto Fine-Techno), etc. One type of these polymer dispersants may be used alone, or two or more types may be used in combination.

該等之中，就密接性及直線性之方面而言，尤佳為(f)分散劑含有具有鹼性官能基之胺基甲酸酯系高分子分散劑及/或丙烯酸系高分子分散劑。胺基甲酸酯系高分子分散劑尤其是於密接性之方面上較佳。又，就分散性、保存性之方面而言，較佳為具有鹼性官能基，且具有聚酯鍵及/或聚醚鍵之高分子分散劑。Among these, in terms of adhesion and linearity, it is particularly preferable that (f) the dispersant contains an amino acid-based polymer dispersant having a basic functional group and/or an acrylic polymer dispersant . The urethane-based polymer dispersant is particularly preferable in terms of adhesion. Further, in terms of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferred.

高分子分散劑之重量平均分子量(Mw)通常為700以上，較佳為1000以上，又，通常為100000以下，較佳為50000以下，更佳為30000以下。藉由設為上述上限值以下，有即便於色料之含有比率較高時鹼顯影性亦變得良好之傾向。作為胺基甲酸酯系及丙烯酸系高分子分散劑，例如可列舉：DISPERBYK160～167、182系列(均為胺基甲酸酯系)、DISPERBYK2000、2001等(均為丙烯酸系)(以上全部BYK-Chemie公司製造)。作為上述具有鹼性官能基，具有聚酯鍵及/或聚醚鍵之胺基甲酸酯系高分子分散劑且重量平均分子量30000以下之尤佳者，可列舉DISPERBYK167、182等。The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. By setting it to the above upper limit or less, the alkali developability tends to be good even when the content ratio of the color material is high. Examples of the urethane-based and acrylic polymer dispersants include: DISPERBYK 160-167, 182 series (all urethane-based), DISPERBYK 2000, 2001, etc. (all acrylic) (all of the above BYK -Manufactured by Chemie). As the above-mentioned basic functional group, a urethane-based polymer dispersant having a polyester bond and/or a polyether bond, and particularly preferably having a weight average molecular weight of 30,000 or less, DISPERBYK167, 182, etc. may be mentioned.

＜胺基甲酸酯系高分子分散劑＞若具體地例示作為胺基甲酸酯系高分子分散劑較佳之化學結構，則例如可列舉：藉由使多異氰酸酯化合物、於分子內具有1個或2個羥基之數量平均分子量300～10000之化合物、及於分子內具有活性氫及三級胺基之化合物進行反應所獲得之重量平均分子量1000～200000之分散樹脂等。<Carbamate-based polymer dispersant> Specific examples of the preferred chemical structure as a carbamate-based polymer dispersant include, for example, a polyisocyanate compound having one in the molecule. Or a compound having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having two hydroxyl groups with an average molecular weight of 300 to 10,000 and a compound having active hydrogen and tertiary amine groups in the molecule.

作為上述多異氰酸酯化合物之例，可列舉：對苯二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、萘-1,5-二異氰酸酯、聯甲苯胺二異氰酸酯等芳香族二異氰酸酯；六亞甲基二異氰酸酯、離胺酸甲酯二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、二聚物酸二異氰酸酯等脂肪族二異氰酸酯；異佛爾酮二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、ω,ω'-二異氰酸基二甲基環己烷等脂環族二異氰酸酯；苯二甲基二異氰酸酯、α,α,α',α'-四甲基苯二甲基二異氰酸酯等具有芳香族環之脂肪族二異氰酸酯；離胺酸酯三異氰酸酯、1,6,11-十一烷三異氰酸酯、1,8-二異氰酸基-4-異氰酸基甲基辛烷、1,3,6-六亞甲基三異氰酸酯、二環庚烷三異氰酸酯、三(異氰酸基苯基甲烷)、三(異氰酸基苯基)硫代磷酸酯等三異氰酸酯；及該等之三聚物、水加成物、及該等之多元醇加成物等。作為多異氰酸酯，較佳為有機二異氰酸酯之三聚物，最佳為甲苯二異氰酸酯之三聚物及異佛爾酮二異氰酸酯之三聚物。該等可單獨使用1種，亦可將2種以上併用。Examples of the polyisocyanate compound include terephthalic diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and naphthalene-1,5- Aromatic diisocyanates such as diisocyanate and tolidine diisocyanate; hexamethylene diisocyanate, methyl imidate diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Aliphatic diisocyanates such as isocyanate; isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), ω,ω'-diisocyanato dimethylcyclohexane and other alicyclic diisocyanates Isocyanates; xylene dimethyl diisocyanate, α,α,α',α'-tetramethyl xylylene diisocyanate and other aliphatic diisocyanates with aromatic rings; amine triisocyanate, 1,6, 11-undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tri (Isocyanatophenylmethane), tri(isocyanatophenyl) phosphorothioate, and other triisocyanates; and their terpolymers, water adducts, and polyol adducts, etc. . The polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably is a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate. These can be used alone or in combination of two or more.

作為異氰酸酯之三聚物之製造方法，可列舉如下方法：使用適當之三聚作用觸媒、例如三級胺類、膦類、烷氧化物類、金屬氧化物、羧酸鹽類等，對上述多異氰酸酯類進行異氰酸基之局部三聚作用，藉由添加觸媒毒而使三聚作用終止後，藉由溶劑萃取、薄膜蒸餾去除未反應之多異氰酸酯，而獲得目標之含有異氰尿酸酯基之多異氰酸酯。As a method for producing the isocyanate trimer, the following method may be mentioned: using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. Polyisocyanates are used for local trimerization of isocyanate groups. After the trimerization is terminated by adding catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the target isocyanurate Polyisocyanate ester group.

作為於分子內具有1個或2個羥基之數量平均分子量300～10000之化合物，可列舉：聚醚二醇、聚酯二醇、聚碳酸酯二醇、聚烯烴二醇等、及該等化合物之單末端羥基經碳數1～25之烷基烷氧基化而成者及該等2種以上之混合物。Examples of compounds having a number average molecular weight of 300 to 10,000 in a molecule of one or two hydroxyl groups include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, etc., and these compounds The single-terminal hydroxyl group is alkoxylated by an alkyl group having 1 to 25 carbon atoms and a mixture of two or more of these.

作為聚醚二醇，可列舉：聚醚二醇、聚醚酯二醇、及該等2種以上之混合物。作為聚醚二醇，可列舉：使環氧烷單獨或共聚所得者、例如聚乙二醇、聚丙二醇、聚乙烯-丙二醇、聚氧四亞甲基二醇、聚氧六亞甲基二醇、聚氧八亞甲基二醇及該等2種以上之混合物。Examples of polyether diols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether glycols include those obtained by singly or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, and polyoxyhexamethylene glycol. , Polyoxy octamethylene glycol and mixtures of two or more of these.

作為聚醚酯二醇，可列舉：藉由使含有醚基之二醇或與其他二醇之混合物與二羧酸或該等之酸酐進行反應，或者使聚酯二醇與環氧烷進行反應所獲得者、例如聚(聚氧四亞甲基)己二酸酯等。作為聚醚二醇，最佳為聚乙二醇、聚丙二醇、聚氧四亞甲基二醇或該等化合物之單末端羥基經碳數1～25之烷基烷氧基化而成之化合物。Examples of polyetherester diols include the reaction of a glycol containing an ether group or a mixture with other diols with a dicarboxylic acid or such anhydride, or a reaction between a polyester diol and an alkylene oxide The obtained person is, for example, poly(polyoxytetramethylene) adipate. As the polyether glycol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound having a single terminal hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms is preferred .

作為聚酯二醇，可列舉：使二羧酸(琥珀酸、戊二酸、己二酸、癸二酸、反丁烯二酸、順丁烯二酸、鄰苯二甲酸等)或該等之酸酐與二醇(乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、3-甲基-1,5-戊二醇、新戊二醇、2-甲基-1,3-丙二醇、2-甲基-2-丙基 -1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、1,5-戊二醇、1,6-己二醇、2-甲基-2,4-戊二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,8-八亞甲基二醇、2-甲基-1,8-八亞甲基二醇、1,9-壬二醇等脂肪族二醇、雙羥基甲基環己烷等脂環族二醇、苯二甲醇、雙羥基乙氧基苯等芳香族二醇、N-甲基二乙醇胺等N-烷基二烷醇胺等)進行縮聚所獲得者、例如聚己二酸乙二酯、聚己二酸丁二酯、聚己二酸六亞甲酯、聚己二酸丁二酯/聚己二酸丙二酯等、或者使用上述二醇類或碳數1～25之一元醇作為起始劑所獲得之聚內酯二醇或聚內酯單醇、例如聚己內酯二醇、聚甲基戊內酯及該等2種以上之混合物。作為聚酯二醇，最佳為聚己內酯二醇或以碳數1～25之醇為起始劑所得之聚己內酯。Examples of polyester diols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or these Anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol Alcohol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8 -Aliphatic diols such as octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, and alicyclic diols such as dihydroxymethylcyclohexane , Aromatic diols such as benzenedimethanol and bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.) are obtained by polycondensation, such as polyethylene adipate, poly Butylene adipate, polyhexamethylene adipate, polybutylene adipate/polypropylene adipate, etc., or using the above-mentioned diols or monohydric alcohols having 1 to 25 carbon atoms Polylactone diol or polylactone monool obtained from the starting agent, for example, polycaprolactone diol, polymethylvalerolactone, and a mixture of two or more of these. The polyester diol is preferably a polycaprolactone diol or a polycaprolactone obtained by using an alcohol having 1 to 25 carbon atoms as an initiator.

作為聚碳酸酯二醇，可列舉聚碳酸(1,6-伸己基)酯、聚碳酸(3-甲基-1,5-伸戊基)酯等，作為聚烯烴二醇，可列舉聚丁二烯二醇、氫化型聚丁二烯二醇、氫化型聚異戊二烯二醇等。該等可單獨使用1種，亦可將2種以上併用。Examples of the polycarbonate diol include poly(1,6-hexanyl) carbonate and poly(3-methyl-1,5-pentyl) carbonate. Examples of the polyolefin diol include polybutylene Dienediol, hydrogenated polybutadienediol, hydrogenated polyisoprenediol, etc. These can be used alone or in combination of two or more.

於分子內具有1個或2個羥基之化合物之數量平均分子量通常為300～10,000，較佳為500～6,000，進而較佳為1,000～4,000。對本發明所使用之於分子內具有活性氫及三級胺基之化合物進行說明。作為活性氫、即直接鍵結於氧原子、氮原子或硫原子之氫原子，可列舉羥基、胺基、硫醇基等官能基中之氫原子，其中，較佳為胺基之氫原子，尤佳為一級胺基之氫原子。The number average molecular weight of the compound having one or two hydroxyl groups in the molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000. The compound used in the present invention having active hydrogen and tertiary amine groups in the molecule will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amine group, and a thiol group. Among them, a hydrogen atom of an amine group is preferred. Particularly preferred is a hydrogen atom of a primary amine group.

三級胺基並無特別限定，例如可列舉：具有碳數1～4之烷基之胺基、或雜環結構，更具體而言，可列舉咪唑環或***環等。若例示此種於分子內具有活性氫及三級胺基之化合物，則可列舉：N,N-二甲基-1,3-丙二胺、N,N-二乙基-1,3-丙二胺、N,N-二丙基-1,3-丙二胺、N,N-二丁基-1,3-丙二胺、N,N-二甲基乙二胺、N,N-二乙基乙二胺、N,N-二丙基乙二胺、N,N-二丁基乙二胺、N,N-二甲基-1,4-丁二胺、N,N-二乙基-1,4-丁二胺、N,N-二丙基-1,4-丁二胺、N,N-二丁基-1,4-丁二胺等。The tertiary amine group is not particularly limited, and examples thereof include an amine group having a C 1-4 alkyl group or a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring. Examples of such compounds having active hydrogen and tertiary amine groups in the molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3- Propylenediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N -Diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N- Diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

又，作為三級胺基為含氮雜環結構之情形時之該含氮雜環，可列舉：吡唑環、咪唑環、***環、四唑環、吲哚環、咔唑環、吲唑環、苯并咪唑環、苯并***環、苯并㗁唑環、苯并噻唑環、苯并噻二唑環等含N雜5員環；吡啶環、嗒環、嘧啶環、三環、喹啉環、吖啶環、異喹啉環等含氮雜6員環。該等含氮雜環中，較佳者為咪唑環或***環。The nitrogen-containing heterocyclic ring in the case where the tertiary amine group has a nitrogen-containing heterocyclic structure includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, and an indole N-containing 5-membered ring such as azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring; pyridine ring, thiamine ring, pyrimidine ring, tricyclic ring , Quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing 6-membered rings. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferred.

若具體地例示該等具有咪唑環及胺基之化合物，則可列舉：1-(3-胺基丙基)咪唑、組胺酸、2-胺基咪唑、1-(2-胺基乙基)咪唑等。又，若具體地例示具有***環及胺基之化合物，則可列舉：3-胺基-1,2,4-***、5-(2-胺基-5-氯苯基)-3-苯基-1H-1,2,4-***、4-胺基-4H-1,2,4-***-3,5-二醇、3-胺基-5-苯基-1H-1,3,4-***、5-胺基-1,4-二苯基-1,2,3-***、3-胺基-1-苄基-1H-2,4-***等。其中，較佳為N,N-二甲基-1,3-丙二胺、N,N-二乙基-1,3-丙二胺、1-(3-胺基丙基)咪唑、3-胺基-1,2,4-***。Specific examples of such compounds having an imidazole ring and an amine group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl) ) Imidazole and so on. In addition, if a compound having a triazole ring and an amine group is specifically exemplified, examples include 3-amino-1,2,4-triazole and 5-(2-amino-5-chlorophenyl)-3 -Phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H- 1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. . Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3 -Amino-1,2,4-triazole.

該等可單獨使用1種，亦可將2種以上併用。關於製造胺基甲酸酯系高分子分散劑時之原料之較佳調配比率，相對於多異氰酸酯化合物100質量份，於分子內具有1個或2個羥基之數量平均分子量300～10000之化合物為10～200質量份，較佳為20～190質量份，進而較佳為30～180質量份，於分子內具有活性氫及三級胺基之化合物為0.2～25質量份，較佳為0.3～24質量份。These can be used alone or in combination of two or more. The preferred compounding ratio of raw materials when manufacturing a urethane-based polymer dispersant is a compound having a number average molecular weight of 300 to 10,000 with one or two hydroxyl groups in the molecule relative to 100 parts by mass of the polyisocyanate compound. 10 to 200 parts by mass, preferably 20 to 190 parts by mass, further preferably 30 to 180 parts by mass, and a compound having an active hydrogen and a tertiary amine group in the molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

胺基甲酸酯系高分子分散劑之製造係依據聚胺基甲酸酯樹脂製造之公知方法進行。作為製造時之溶劑，通常使用丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、異佛爾酮等酮類；乙酸乙酯、乙酸丁酯、乙酸溶纖劑等酯類；苯、甲苯、二甲苯、己烷等烴類；二丙酮醇、異丙醇、第二丁醇、第三丁醇等一部分醇類；二氯甲烷、氯仿等氯化物；四氫呋喃、二乙基醚等醚類；二甲基甲醯胺、N-甲基吡咯啶酮、二甲基亞碸等非質子性極性溶劑等。該等可單獨使用1種，亦可將2種以上併用。The production of the urethane-based polymer dispersant is performed according to a known method for the production of polyurethane resin. As a solvent during production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone are generally used; ethyl acetate, butyl acetate, and cellosolve acetate Ester and other esters; benzene, toluene, xylene, hexane and other hydrocarbons; diacetone alcohol, isopropanol, second butanol, third butanol and other alcohols; methylene chloride, chloroform and other chlorides; tetrahydrofuran , Ethers such as diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. These can be used alone or in combination of two or more.

上述製造時，通常使用胺基甲酸酯化反應觸媒。作為該觸媒，例如可列舉：二月桂酸二丁基錫、二月桂酸二辛基錫、二辛酸二丁基錫、辛酸亞錫等錫系；乙醯丙酮酸鐵、氯化鐵等鐵系；三乙胺、三乙二胺等三級胺系等之1種或2種以上。In the above production, a urethane reaction catalyst is usually used. Examples of the catalyst include tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron systems such as ferric acetylacetonate and ferric chloride; and triethyl One or more types of tertiary amines such as amine and triethylenediamine.

＜胺值之測定方法＞分散劑之胺值係以與分散劑試樣中之除溶劑外之固形物成分每1 g之鹼量相當量之KOH的質量表示，可藉由如下方法進行測定。將分散劑試樣之0.5～1.5 g精確稱量至100 mL之燒杯中，於50 mL之乙酸中進行溶解。使用具備pH電極之自動滴定裝置，利用0.1 mol/L之HClO₄ (過氯酸)乙酸溶液對該溶液進行中和滴定。將滴定pH曲線之反曲點設為滴定終點，藉由下式求出胺值。<Measurement method of amine value> The amine value of the dispersant is expressed by the mass of KOH equivalent to 1 g of alkali content of the solid content of the dispersant sample except for the solvent, and can be measured by the following method. Weigh 0.5 to 1.5 g of the dispersant sample accurately into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titration device equipped with a pH electrode, the solution was neutralized and titrated with a 0.1 mol/L HClO ₄ (perchloric acid) acetic acid solution. The inverse curve point of the titration pH curve was set as the end point of the titration, and the amine value was obtained by the following formula.

胺值[mgKOH/g]＝(561×V)/(W×S) [其中，W：分散劑試樣稱取量[g]、V：於滴定終點之滴定量[mL]、S：分散劑試樣之固形物成分濃度[質量%]] 於分子內具有活性氫及三級胺基之化合物之導入量較佳為將反應後之胺值控制在1～100 mgKOH/g之範圍內。更佳為5～95 mgKOH/g之範圍。胺值係藉由酸對鹼性胺基進行中和滴定，以與酸值相對應之KOH之mg數表示之值。藉由設為上述下限值以上，有分散性變得良好之傾向，又，藉由設為上述上限值以下，有顯影性變得良好之傾向。Amine value [mgKOH/g]=(561×V)/(W×S) [W, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Dispersion The solid content concentration [mass %] of the agent sample is preferably introduced in a compound having an active hydrogen and a tertiary amine group in the molecule to control the amine value after the reaction within a range of 1 to 100 mgKOH/g. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing the basic amine group by acid. By setting it to the above lower limit value or more, the dispersibility tends to be good, and by setting it to the above upper limit value or less, the developability tends to be good.

再者，於在以上之反應中在高分子分散劑中殘留異氰酸基之情形時，若進而利用醇或胺基化合物破壞異氰酸基，則生成物之經時穩定性變高，故而較佳。胺基甲酸酯系高分子分散劑之重量平均分子量(Mw)為通常1000～200000、較佳為2000～100000、更佳為3000～50000之範圍。尤佳為30000以下。藉由設為上述下限值以上，有分散性及分散穩定性變得良好之傾向，又，藉由設為上述上限值以下，有溶解性變得良好之傾向。若分子量為30000以下，則有即便於尤其是色料之含有比率較高之情形時，鹼顯影性亦變得良好之傾向。作為此種尤佳之市售之胺基甲酸酯分散劑之例，可列舉DISPERBYK167、182(BYK-Chemie公司)等。Furthermore, in the case where the isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further destroyed by an alcohol or an amine compound, the temporal stability of the product becomes high, so Better. The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. Especially preferred is below 30,000. By setting it to the above lower limit value or more, the dispersibility and dispersion stability tend to be good, and by setting it to the above upper limit value or less, the solubility tends to be good. If the molecular weight is 30,000 or less, the alkali developability tends to be good even when the content ratio of the coloring material is particularly high. Examples of such particularly preferred commercially available urethane dispersants include DISPERBYK167 and 182 (BYK-Chemie).

於本發明之感光性樹脂組合物含有(f)分散劑之情形時，關於(f)分散劑之含有比率，於感光性樹脂組合物之總固形物成分中，通常為1質量%以上，較佳為3質量%以上，更佳為5質量%以上，進而較佳為7質量%以上，又，通常為50質量%以下，較佳為30質量%以下，更佳為20質量%以下，進而較佳為15質量%以下，尤佳為10質量%以下。藉由設為上述下限值以上，有容易確保充分之分散性之傾向，又，藉由設為上述上限值以下，有不會減少其他成分之比率，容易使色濃度、感度、成膜性等變得充分之傾向。作為上限與下限之組合，例如較佳為1～50質量%、更佳為3～30質量%、進而較佳為5～20質量%、進而更佳為7～15質量%、尤佳為7～10質量%。In the case where the photosensitive resin composition of the present invention contains (f) a dispersant, the content ratio of (f) dispersant is usually 1% by mass or more in the total solid content of the photosensitive resin composition, compared with It is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less, and further It is preferably 15% by mass or less, and particularly preferably 10% by mass or less. By setting it to the above lower limit value, it is easy to ensure sufficient dispersibility, and by setting it to the above upper limit value, it is easy to make the color density, sensitivity, and film formation without reducing the ratio of other components The tendency for sex to become full. The combination of the upper limit and the lower limit is, for example, preferably 1 to 50% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 20% by mass, still more preferably 7 to 15% by mass, and particularly preferably 7 ~10% by mass.

又，於本發明之感光性樹脂組合物含有(f)分散劑之情形時，關於(f)分散劑之含有比率，相對於(e)色料100質量份，通常為5質量份以上，較佳為10質量份以上，且通常為200質量份以下，較佳為80質量份以下，更佳為50質量份以下，進而較佳為30質量份以下。藉由設為上述下限值以上，有容易確保充分之分散性之傾向，又，藉由設為上述上限值以下，有不會減少其他成分之比率，容易使色濃度、感度、成膜性等變得充分之傾向。作為上限與下限之組合，例如較佳為5～200質量份、更佳為5～80質量份、進而較佳為10～50質量份、尤佳為10～30質量份。In addition, when the photosensitive resin composition of the present invention contains (f) a dispersing agent, the content ratio of (f) the dispersing agent is usually 5 parts by mass or more with respect to 100 parts by mass of the colorant, which is It is preferably 10 parts by mass or more, and usually 200 parts by mass or less, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less. By setting it to the above lower limit value, it is easy to ensure sufficient dispersibility, and by setting it to the above upper limit value, it is easy to make the color density, sensitivity, and film formation without reducing the ratio of other components The tendency for sex to become full. The combination of the upper limit and the lower limit is, for example, preferably 5 to 200 parts by mass, more preferably 5 to 80 parts by mass, still more preferably 10 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass.

＜硫醇類＞本發明之感光性樹脂組合物為了高感度化、對於基板之密接性之提高，較佳為含有硫醇類。作為硫醇類之種類，可列舉：己二硫醇、癸二硫醇、1,4-二甲基巰基苯、丁二醇雙硫代丙酸酯、丁二醇雙硫代乙醇酸酯、乙二醇雙硫代乙醇酸酯、三羥甲基丙烷三硫代乙醇酸酯、丁二醇雙硫代丙酸酯、三羥甲基丙烷三硫代丙酸酯、三羥甲基丙烷三硫代乙醇酸酯、季戊四醇四硫代丙酸酯、季戊四醇四硫代乙醇酸酯、三羥基乙基三硫代丙酸酯、乙二醇雙(3-巰基丁酸酯)、丙二醇雙(3-巰基丁酸酯)(縮寫為PGMB)、丁二醇雙(3-巰基丁酸酯)、1,4-雙(3-巰基丁醯氧基)丁烷(商品名：Karenz MT BD1、昭和電工公司製造)、丁二醇三羥甲基丙烷三(3-巰基丁酸酯)、季戊四醇四(3-巰基丁酸酯)(商品名：Karenz MT PE1，昭和電工公司製造)、季戊四醇三(3-巰基丁酸酯)、乙二醇雙(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、三羥甲基丙烷三(3-巰基異丁酸酯)、三羥甲基丙烷三(3-巰基丁酸酯)(縮寫為TPMB)、三羥甲基丙烷三(2-巰基異丁酸酯)(縮寫為TPMIB)、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮(商品名：Karenz MT NR1，昭和電工公司製造)等，該等各種者可單獨使用1種，或者將2種以上混合使用。較佳為上述，且較佳為PGMB、TPMB、TPMIB、Karenz MT BD1、Karenz MT PE1、Karenz MT NR1等多官能硫醇，其中，進而較佳為Karenz MT BD1、Karenz MT PE1、Karenz MT NR1，尤佳為Karenz MT PE1。<Mercaptans> The photosensitive resin composition of the present invention preferably contains mercaptans in order to increase the sensitivity and improve the adhesion to the substrate. Examples of the types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, Ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane triacetate Thioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3 -Mercaptobutyrate) (abbreviated as PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane (trade name: Karenz MT BD1, Showa Electrician), butanediol trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko), pentaerythritol tri( 3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tri(3-mercaptoisobutyrate) ), trimethylolpropane tris(3-mercaptobutyrate) (abbreviated as TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (abbreviated as TPMIB), 1,3,5-tris (3-mercaptobutoxyethyl)-1,3,5-tri-2,4,6 (1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko), etc. You can use one kind alone or a mixture of two or more kinds. It is preferably the above, and preferably PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 and other multifunctional thiols, among which, further preferably Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, You Jia is Karenz MT PE1.

於使用硫醇化合物之情形時，關於硫醇化合物之含有比率，於本發明之感光性樹脂組合物之總固形物成分中，通常為0.1質量%以上，較佳為0.3質量%以上，進而較佳為0.5質量以上，且通常為10質量%以下，較佳為5質量%以下。藉由設為上述下限值以上，有可抑制感度降低之傾向，藉由設為上述上限值以下，有容易使保存穩定性變得良好之傾向。In the case of using a thiol compound, the content ratio of the thiol compound in the total solid content of the photosensitive resin composition of the present invention is usually 0.1% by mass or more, preferably 0.3% by mass or more, and further It is preferably 0.5 mass% or more, and usually 10 mass% or less, preferably 5 mass% or less. By setting it to the above-mentioned lower limit value or more, there is a tendency that the decrease in sensitivity can be suppressed, and by setting it to the above-mentioned upper limit value, there is a tendency that the storage stability tends to be good.

＜溶劑＞本發明之感光性樹脂組合物通常以於有機溶劑中溶解或分散有(a)鹼可溶性樹脂、(b)光聚合性單體、(c)光自由基聚合起始劑、(d)有機矽化合物、(e)色料及視需要使用之各種成分之狀態使用。作為有機溶劑，較佳為選擇沸點(於壓力1013.25[hPa]條件下；以下，關於沸點，全部相同)為100～300℃之範圍者。更佳為具有120～280℃之沸點之溶劑。作為此種有機溶劑，例如可列舉如下者。<Solvent> The photosensitive resin composition of the present invention is usually dissolved or dispersed in an organic solvent (a) alkali-soluble resin, (b) photopolymerizable monomer, (c) photoradical polymerization initiator, (d )Organic silicon compounds, (e) colorants and various components used as needed. As the organic solvent, it is preferable to select a boiling point (under a pressure of 1013.25 [hPa]; below, all boiling points are the same) within a range of 100 to 300°C. More preferably, it has a boiling point of 120 to 280°C. Examples of such organic solvents include the following.

如乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單正丁基醚、丙二醇第三丁基醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丁基醚、甲氧基甲基戊醇、二丙二醇單***、二丙二醇單甲醚、3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、三乙二醇單甲醚、三乙二醇單***、三丙二醇甲醚之二醇單烷基醚類；Such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol third butyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy Glycol monoalkyl ethers of butanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

如乙二醇二甲基醚、乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、二丙二醇二甲基醚之二醇二烷基醚類；如乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單正丁基醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、乙酸甲氧基丁酯、乙酸3-甲氧基丁酯、乙酸甲氧基戊酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單正丁基醚乙酸酯、二丙二醇單甲醚乙酸酯、三乙二醇單甲醚乙酸酯、三乙二醇單***乙酸酯、乙酸3-甲基-3-甲氧基丁酯之二醇烷基醚乙酸酯類；Such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Glycol dialkyl ethers of base ethers, dipropylene glycol dimethyl ether; such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxyacetate Amyl amyl ester, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Glycol alkyl ether acetates of alcohol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

乙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己醇二乙酸酯等二醇二乙酸酯類；環己醇乙酸酯等乙酸烷基酯類；如戊基醚、二乙基醚、二丙基醚、二異丙基醚、二丁基醚、二戊基醚、乙基異丁基醚、二己基醚之醚類；如丙酮、甲基乙基酮、甲基戊基酮、甲基異丙基酮、甲基異戊基酮、二異丙基酮、二異丁基酮、甲基異丁基酮、環己酮、乙基戊基酮、甲基丁基酮、甲基己基酮、甲基壬基酮、甲氧基甲基戊酮之酮類；如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丁二醇、二乙二醇、二丙二醇、三乙二醇、甲氧基甲基戊醇、甘油、苄醇之一元或多元醇類；如正戊烷、正辛烷、二異丁烯、正己烷、己烯、異戊二烯、雙戊烯、十二烷之脂肪族烴類；如環己烷、甲基環己烷、甲基環己烯、聯環己烷之脂環式烴類；Ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate and other glycol diacetates; Cyclohexanol acetate and other alkyl acetates ; Such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether; such as acetone, methyl ether Ethyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl Amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentyl ketone; such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylenedioxide Monohydric or polyhydric alcohols of alcohol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; such as n-pentane, n-octane, di Aliphatic hydrocarbons of isobutene, n-hexane, hexene, isoprene, dipentene, dodecane; such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexane Hydrocarbons

如苯、甲苯、二甲苯、異丙苯之芳香族烴類；如甲酸戊酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、乙酸戊酯、異丁酸甲酯、乙二醇乙酸酯、丙酸乙酯、丙酸丙酯、丁酸丁酯、丁酸異丁酯、異丁酸甲酯、辛酸乙酯、硬脂酸丁酯、苯甲酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、γ-丁內酯之鏈狀或環狀酯類；如3-甲氧基丙酸、3-乙氧基丙酸之烷氧基羧酸類；Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene dichloride Alcohol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, 3-ethyl Methyl oxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Chain or cyclic esters of butyl oxypropionate and γ-butyrolactone; such as alkoxycarboxylic acids of 3-methoxypropionic acid and 3-ethoxypropionic acid;

如氯丁烷、氯戊烷之鹵化烴類；如甲氧基甲基戊酮之醚酮類；如乙腈、苯甲腈之腈類等：作為符合上述之市售溶劑，可列舉：礦油精、BARSOL#2、Apco#18溶劑、Apco稀釋劑、Socal溶劑No.1及No.2、Solvesso#150、Shell TS28 溶劑、卡必醇、乙基卡必醇、丁基卡必醇、甲基溶纖劑(「溶纖劑」為註冊商標；以下相同)、乙基溶纖劑、乙基溶纖劑乙酸酯、甲基溶纖劑乙酸酯、二乙二醇二甲醚(均為商品名)等。Halogenated hydrocarbons such as chlorobutane, chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile, benzonitrile, etc.: As commercially available solvents that meet the above, may include: mineral oil Fine, BARSOL#2, Apco#18 solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso#150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl alcohol Base cellosolve ("cellosolve" is a registered trademark; the same below), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether ( All are trade names) etc.

該等有機溶劑可單獨使用，亦可將2種以上併用。於利用光微影法形成彩色濾光片之像素或黑色矩陣之情形時，作為有機溶劑，較佳為選擇沸點為100～250℃之範圍者。更佳為具有120～230℃之沸點者。上述有機溶劑中，就塗佈性、表面張力等之平衡性良好，組合物中之構成成分之溶解度相對較高之方面而言，較佳為二醇烷基醚乙酸酯類。These organic solvents may be used alone or in combination of two or more. In the case of forming a pixel or a black matrix of a color filter by photolithography, as the organic solvent, it is preferable to select a boiling point in the range of 100 to 250°C. More preferably, it has a boiling point of 120 to 230°C. Among the above-mentioned organic solvents, in terms of good balance between coating properties, surface tension, and the like, and relatively high solubility of constituent components in the composition, glycol alkyl ether acetates are preferred.

又，二醇烷基醚乙酸酯類可單獨地使用，亦可併用其他有機溶劑。作為可併用之其他有機溶劑，尤佳為二醇單烷基醚類。其中，尤其是就組合物中之構成成分之溶解性而言，較佳為丙二醇單甲醚。再者，二醇單烷基醚類有極性較高，若添加量過多，則顏料容易凝集，之後所獲得之感光性樹脂組合物之黏度上升等保存穩定性降低之傾向，因此溶劑中之二醇單烷基醚類之比率較佳為5質量%～30質量%，更佳為5質量%～20質量%。In addition, glycol alkyl ether acetates can be used alone or in combination with other organic solvents. As other organic solvents that can be used in combination, glycol monoalkyl ethers are particularly preferred. Among them, propylene glycol monomethyl ether is particularly preferred in terms of the solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers have a high polarity, and if the added amount is too large, the pigment tends to agglomerate, and the viscosity of the photosensitive resin composition obtained afterwards tends to decrease such as the increase in viscosity and other storage stability, so the second of the solvents The ratio of alcohol monoalkyl ethers is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

又，亦較佳為併用具有200℃以上之沸點之有機溶劑(以下有稱為「高沸點溶劑」之情形)。藉由併用此種高沸點溶劑，而感光性樹脂組合物變得難以乾燥，但有防止組合物中之顏料之均一分散狀態因急遽乾燥而被破壞之效果。即，例如有防止於狹縫噴嘴前端由色料等之析出、固化引起之異物缺陷產生的效果。就此種效果較高之方面而言，上述各種溶劑之中，尤佳為二丙二醇甲醚乙酸酯、二乙二醇單正丁基醚乙酸酯、及二乙二醇單***乙酸酯、1,4-丁二醇二乙酸酯、1,3-丁二醇二乙酸酯、三乙酸酯、1,6-己二醇二乙酸酯。Furthermore, it is also preferable to use an organic solvent having a boiling point of 200° C. or higher (hereinafter referred to as “high boiling point solvent”). By using such a high boiling point solvent together, the photosensitive resin composition becomes difficult to dry, but it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the generation of foreign matter defects caused by the precipitation and solidification of the color material at the tip of the slit nozzle. In terms of such high effects, among the above-mentioned various solvents, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. , 1,4-butanediol diacetate, 1,3-butanediol diacetate, triacetate, 1,6-hexanediol diacetate.

於併用高沸點溶劑之情形時，有機溶劑中之高沸點溶劑之含有比率較佳為0質量%～50質量%，更佳為0.5質量%～40質量%，尤佳為1質量%～30質量%。藉由將高沸點溶劑之含有比率設為上述下限值以上，例如有可抑制於狹縫噴嘴前端色料等析出、固化而引起異物缺陷之傾向，又，藉由設為上述上限值以下，有可抑制組合物之乾燥速度變得過慢，容易避免彩色濾光片製造步驟中之減壓乾燥製程之節拍(tact)不良、或預烘烤之氣孔痕跡等問題之傾向。In the case of using a high boiling point solvent together, the content ratio of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass %. By setting the content ratio of the high-boiling-point solvent to the above lower limit value, for example, it is possible to suppress the precipitation and solidification of the color material at the tip of the slit nozzle and the tendency to cause foreign matter defects, and by setting it to the above upper limit value , It is possible to suppress the drying speed of the composition from becoming too slow, and it is easy to avoid problems such as poor tact in the vacuum drying process in the color filter manufacturing process, or stomatal marks of pre-baking.

於本發明之感光性樹脂組合物中，有機溶劑之含有比率並無特別限定，就塗佈容易性或黏度穩定性之觀點而言，以感光性樹脂組合物中之總固形物成分量成為較佳為5質量%以上、更佳為8質量%以上、進而較佳為10質量%以上，又，較佳為40質量%以下、更佳為30質量%以下、進而較佳為25質量%以下、尤佳為20質量%以下之方式進行調液。作為上限與下限之組合，例如較佳為5～40質量%、更佳為8～30質量%、進而較佳為10～25質量%、尤佳為10～20質量%。In the photosensitive resin composition of the present invention, the content ratio of the organic solvent is not particularly limited. From the viewpoint of ease of coating or viscosity stability, the total solid content of the photosensitive resin composition becomes It is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more, and further preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less , Youjia adjusts the liquid by 20% by mass or less. The combination of the upper limit and the lower limit is, for example, preferably 5 to 40% by mass, more preferably 8 to 30% by mass, still more preferably 10 to 25% by mass, and particularly preferably 10 to 20% by mass.

＜感光性樹脂組合物之其他調配成分＞於本發明之感光性樹脂組合物中，除上述成分以外，亦可適當調配密接提高劑、界面活性劑(塗佈性提高劑)、顏料衍生物、進而顯影改良劑、紫外線吸收劑、抗氧化劑等。<Other formulation components of photosensitive resin composition> In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, an adhesion enhancer, a surfactant (coatability improver), a pigment derivative, Furthermore, development improvers, ultraviolet absorbers, antioxidants, etc.

＜密接提高劑＞為了改善與基板之密接性，亦可含有(d)有機矽化合物以外之密接提高劑，例如可列舉：磷酸系密接提高劑、其他密接提高劑等。<Adhesion Improver> In order to improve the adhesion to the substrate, an adhesion enhancer other than the (d) organosilicon compound may be contained. For example, a phosphoric acid-based adhesion improver and other adhesion improvers may be mentioned.

作為磷酸系密接提高劑，較佳為含有(甲基)丙烯醯氧基之磷酸酯類，其中，較佳為下述通式(g1)、(g2)、(g3)所表示者。As the phosphoric acid-based adhesion-improving agent, (meth)acryloyloxy-containing phosphates are preferred, and among them, those represented by the following general formulas (g1), (g2), and (g3) are preferred.

[化45] [化45]

於上述通式(g1)、(g2)、(g3)中，R⁵¹ 表示氫原子或甲基，l及l'為1～10之整數，m為1、2或3。作為其他密接提高劑，可列舉：TEGO^* Add Bond LTH(Evonik公司製造)等。該等含磷酸基之化合物或其他密接劑可單獨使用1種，亦可將2種以上組合使用。In the above general formulas (g1), (g2), (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l'are integers from 1 to 10, and m is 1, 2, or 3. Examples of other adhesion improving agents include TEGO ^* Add Bond LTH (manufactured by Evonik). These phosphate group-containing compounds or other adhesives may be used alone or in combination of two or more.

＜界面活性劑＞於本發明之感光性樹脂組合物中，為了提高塗佈性，亦可含有界面活性劑。作為界面活性劑，例如可使用陰離子系、陽離子系、非離子系及兩性界面活性劑等各種者。其中，就對於各種特性造成不良影響之可能性較低之方面而言，較佳為使用非離子系界面活性劑，其中，氟系或矽系之界面活性劑於塗佈性之方面上有效。<Surfactant> The photosensitive resin composition of the present invention may contain a surfactant in order to improve coatability. As the surfactant, for example, various kinds such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, it is preferable to use nonionic surfactants in terms of low possibility of adversely affecting various characteristics, and among them, fluorine-based or silicon-based surfactants are effective in coating properties.

作為此種界面活性劑，例如可列舉：TSF4460(邁圖高新材料公司製造)、DFX-18(NEOS公司製造)、BYK-300、BYK-325、BYK-330(BYK-Chemie公司製造)、KP340(Shin-Etsu Silicones公司製造)、F-470、F-475、F-478、F-554、F-559(DIC公司製造)、SH7PA(東麗道康寧公司製造)、DS-401(Daikin公司製造)、L-77(Nippon Unicar公司製造)及FC4430(3M Japan公司製造)等。再者，界面活性劑可使用1種，亦可將2種以上以任意之組合及比率併用。於本發明之感光性樹脂組合物含有界面活性劑之情形時，其含有比率並無特別限定，於感光性樹脂組合物之總固形物成分中，較佳為0.01質量%以上，更佳為0.05質量%以上，又，較佳為1.0質量%以下，更佳為0.7質量%以下，進而較佳為0.5質量%以下，尤佳為0.3質量%以下。藉由設為上述下限值以上，有塗佈均一性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度降低之傾向。作為上限與下限之組合，例如較佳為0.01～1.0質量%、更佳為0.01～0.7質量%、進而較佳為0.05～0.5質量%、尤佳為0.05～0.3質量%。Examples of such surfactants include TSF4460 (manufactured by Meitu High-Tech Materials Co., Ltd.), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), and KP340. (Made by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, F-559 (made by DIC), SH7PA (made by Toray Dow Corning), DS-401 (made by Daikin) ), L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M Japan), etc. Furthermore, one type of surfactant may be used, or two or more types may be used in combination in any combination and ratio. When the photosensitive resin composition of the present invention contains a surfactant, the content ratio is not particularly limited, and the total solid content of the photosensitive resin composition is preferably 0.01% by mass or more, and more preferably 0.05 The mass% or more is preferably 1.0 mass% or less, more preferably 0.7 mass% or less, and further preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less. By setting it to the above lower limit or more, the coating uniformity tends to be good, and by setting it to the above upper limit or less, it is easy to suppress the decrease in sensitivity. The combination of the upper limit and the lower limit is, for example, preferably 0.01 to 1.0% by mass, more preferably 0.01 to 0.7% by mass, still more preferably 0.05 to 0.5% by mass, and particularly preferably 0.05 to 0.3% by mass.

＜顏料衍生物＞於本發明之感光性樹脂組合物中，為了提高分散性、保存性，亦可含有顏料衍生物。作為顏料衍生物，可列舉：偶氮系、酞菁系、喹吖啶酮系、苯并咪唑酮系、喹酞酮系、異吲哚啉酮系、二㗁系、蒽醌系、陰丹士林系、苝系、芘系、吡咯并吡咯二酮系、二㗁系等衍生物，其中，較佳為酞菁系、喹酞酮系。<Pigment derivative> The photosensitive resin composition of the present invention may contain a pigment derivative in order to improve dispersibility and storage stability. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxin-based, anthraquinone-based, and indanthrene Derivatives such as Shihlin-based, Perylene-based, Pyrene-based, pyrrolopyrrole-dione-based, and dioxin-based derivatives, among which phthalocyanine-based and quinophthalone-based, are preferred.

作為顏料衍生物之取代基，可列舉：磺酸基、磺醯胺基及其四級鹽、鄰苯二甲醯亞胺甲基、二烷基胺基烷基、羥基、羧基、醯胺基等直接或經由烷基、芳基、雜環基等鍵結於顏料骨架上而成者，較佳為磺酸基。又，該等取代基亦可於一個顏料骨架上進行複數取代。作為顏料衍生物之具體例，可列舉：酞菁之磺酸衍生物、喹酞酮之磺酸衍生物、蒽醌之磺酸衍生物、喹吖啶酮之磺酸衍生物、吡咯并吡咯二酮之磺酸衍生物、二㗁之磺酸衍生物等。該等可單獨使用1種，亦可將2種以上併用。Examples of the substituent of the pigment derivative include sulfonic acid group, sulfonylamido group and its quaternary salt, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group It is preferably a sulfonic acid group if it is directly or via an alkyl group, an aryl group, a heterocyclic group or the like bonded to the pigment skeleton. In addition, these substituents can also be substituted in plural on one pigment skeleton. Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and pyrrolopyrrole. Sulfonic acid derivatives of ketones, disulfonic acid derivatives of dioxins, etc. These can be used alone or in combination of two or more.

顏料衍生物較佳為與分散劑一併使用。於本發明之感光性樹脂組合物含有顏料衍生物之情形時，其含有比率並無特別限定，於本發明之感光性樹脂組合物之總固形物成分中，通常為0.1質量%以上，較佳為0.5質量%以上，且通常為10質量%以下，較佳為5質量%以下。作為上限與下限之組合，例如，較佳為0.1～10質量%，更佳為0.5～5質量%。The pigment derivative is preferably used together with the dispersant. When the photosensitive resin composition of the present invention contains a pigment derivative, the content ratio is not particularly limited, but the total solid content of the photosensitive resin composition of the present invention is usually 0.1% by mass or more, preferably It is 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

＜感光性樹脂組合物之物性＞本發明之感光性樹脂組合物可較佳地用於黑色矩陣形成用，就此種觀點而言，較佳為呈黑色。又，其硬化膜之膜厚每1 μm之光學濃度(OD)較佳為1.0以上，更佳為2.0以上，進而較佳為3.0以上，尤佳為4.0以上，最佳為4.5以上，且通常為6.0以下。藉由設為上述下限值以上，有可確保充分之遮光性之傾向。<Physical Properties of Photosensitive Resin Composition> The photosensitive resin composition of the present invention can be preferably used for forming a black matrix. From such a viewpoint, it is preferably black. Furthermore, the optical density (OD) per 1 μm of the thickness of the cured film is preferably 1.0 or more, more preferably 2.0 or more, and further preferably 3.0 or more, particularly preferably 4.0 or more, and most preferably 4.5 or more, and usually Below 6.0. By setting it to the above lower limit or more, there is a tendency to ensure sufficient light-shielding property.

＜感光性樹脂組合物之製造方法＞本發明之感光性樹脂組合物係依據常規方法而製造。通常，(e)色料較佳為預先使用塗料調節器、砂磨機、球磨機、輥磨機、石磨機、噴射磨機、均質器等進行分散處理。由於藉由分散處理而將(e)色料微粒子化，故而感光性樹脂組合物之塗佈特性提高。又，於使用黑色色料作為(e)色料之情形時，有助於提高遮光能力。<Manufacturing method of photosensitive resin composition> The photosensitive resin composition of this invention is manufactured according to a conventional method. Generally, (e) the coloring material is preferably dispersed in advance using a paint conditioner, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, or the like. Since (e) the colorant particles are made fine by dispersion treatment, the coating characteristics of the photosensitive resin composition improve. In addition, when a black color material is used as the (e) color material, it contributes to improving the light-shielding ability.

分散處理較佳為於通常併用有(e)色料、有機溶劑、及視需要之(f)分散劑、(a)鹼可溶性樹脂之一部分或全部之系統內進行(以下，有時將供於分散處理之混合物、及藉由該處理所獲得之組合物稱為「墨水」或「顏料分散液」)。尤其是若使用高分子分散劑作為分散劑，則所獲得之墨水及感光性樹脂組合物之經時增黏得到抑制(分散穩定性優異)，故而較佳。再者，於對含有調配於感光性樹脂組合物之全部成分之液體進行分散處理之情形時，由於分散處理時所產生之發熱，故而有高反應性之成分改性之可能性。因此，較佳為於含有高分子分散劑之系統內進行分散處理。The dispersion treatment is preferably carried out in a system in which (e) colorant, organic solvent, and (f) dispersant, (a) part or all of the alkali-soluble resin are used in combination (hereinafter, sometimes it will be The dispersion-processed mixture and the composition obtained by the process are called "ink" or "pigment dispersion"). In particular, when a polymer dispersant is used as a dispersant, the obtained ink and photosensitive resin composition are preferably prevented from thickening with time (excellent dispersion stability). Furthermore, when the liquid containing all the components formulated in the photosensitive resin composition is subjected to dispersion treatment, there is a possibility of modification of highly reactive components due to heat generated during the dispersion treatment. Therefore, it is preferable to perform dispersion treatment in a system containing a polymer dispersant.

於利用砂磨機使(e)色料分散之情形時，可較佳地使用0.1～8 mm左右直徑之玻璃珠或氧化鋯珠。關於分散處理條件，溫度通常為0℃至100℃、較佳為室溫至80℃之範圍。關於分散時間，視液體之組成及分散處理裝置之尺寸等而精確時間不同，故而適當進行調節。以感光性樹脂組合物之20度鏡面光澤度(JIS Z8741)成為100～200之範圍之方式控制墨水之光澤為分散之標準。於感光性樹脂組合物之光澤度較低之情形時，有大多情況下分散處理不充分而粗糙顏料(色料)粒子殘留，而顯影性、密接性、解像性等變得不充分之可能性。又，若進行分散處理至光澤值超過上述範圍，則顏料粉碎而產生大量超微粒子，因此反而有損害分散穩定性之傾向。In the case of dispersing the (e) color material with a sand mill, glass beads or zirconia beads with a diameter of about 0.1 to 8 mm can be preferably used. Regarding the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, preferably room temperature to 80°C. Regarding the dispersion time, the precise time differs depending on the composition of the liquid and the size of the dispersion processing device, so it is appropriately adjusted. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 100 to 200. In the case where the glossiness of the photosensitive resin composition is low, in many cases, the dispersion treatment is insufficient and the rough pigment (colorant) particles remain, but the developability, adhesion, resolution, etc. may become insufficient. Sex. In addition, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is pulverized and a large amount of ultrafine particles are generated, so there is a tendency to impair the dispersion stability.

繼而，將藉由上述分散處理所獲得之墨水、與感光性樹脂組合物中所含有之上述其他成分進行混合，而製成均一之溶液。於感光性樹脂組合物之製造步驟中，大多情況下微細之污物會混入至液體中，因此所獲得之感光性樹脂組合物較理想為藉由過濾器等進行過濾處理。Then, the ink obtained by the above-mentioned dispersion treatment and the above-mentioned other components contained in the photosensitive resin composition are mixed to prepare a uniform solution. In the manufacturing process of the photosensitive resin composition, fine dirt is often mixed into the liquid in many cases, so the obtained photosensitive resin composition is preferably filtered by a filter or the like.

[硬化物] 本發明之硬化物係藉由使本發明之感光性樹脂組合物硬化而獲得。使感光性樹脂組合物硬化而成之硬化物可較佳地用作像素、黑色矩陣、著色間隔件等構成彩色濾光片之構件。[Cured product] The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. The cured product obtained by curing the photosensitive resin composition can be preferably used as a member constituting a color filter such as a pixel, a black matrix, a colored spacer, or the like.

[黑色矩陣] 針對包含本發明之硬化物之本發明之黑色矩陣，依據其製造方法進行說明。[Black Matrix] The black matrix of the present invention including the hardened product of the present invention will be described based on its manufacturing method.

(1)支持體作為用以形成黑色矩陣之支持體，只要有適度之強度，則其材質並無特別限定。主要使用透明基板，作為材質，例如可列舉：聚對苯二甲酸乙二酯等聚酯系樹脂、聚丙烯、聚乙烯等聚烯烴系樹脂、聚碳酸酯、聚甲基丙烯酸甲酯、聚碸等熱塑性樹脂製片材、環氧樹脂、不飽和聚酯樹脂、聚(甲基)丙烯酸系樹脂等熱硬化性樹脂片材、或各種玻璃等。其中，就耐熱性之觀點而言，較佳為玻璃、耐熱性樹脂。又，亦有於基板之表面成膜有ITO、IZO等透明電極之情形。於透明基板以外，亦可形成於TFT陣列上。(1) Support As the support used to form the black matrix, the material is not particularly limited as long as it has moderate strength. A transparent substrate is mainly used, and as a material, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polystyrene Thermoplastic resin sheets such as thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, poly(meth)acrylic resins, various glass, etc. Among them, from the viewpoint of heat resistance, glass and heat-resistant resin are preferred. In addition, transparent electrodes such as ITO and IZO may be formed on the surface of the substrate. Besides the transparent substrate, it can also be formed on the TFT array.

對於支持體，為了改良接著性等表面物性，亦可視需要進行電暈放電處理、臭氧處理、大氣壓電漿處理、矽烷偶合劑、或胺基甲酸酯系樹脂等各種樹脂之薄膜形成處理等。透明基板之厚度係視為通常0.05～10 mm、較佳為0.1～7 mm之範圍。又，於進行各種樹脂之薄膜形成處理之情形時，其膜厚係通常0.01～10 μm、較佳為0.05～5 μm之範圍。For the support, in order to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, or urethane-based resin film formation treatment of various resins, etc. may be performed as necessary. The thickness of the transparent substrate is considered to be generally in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. In addition, in the case of performing thin film forming treatment of various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2)黑色矩陣於藉由上述本發明之感光性樹脂組合物形成本發明之黑色矩陣時，於透明基板上塗佈本發明之感光性樹脂組合物並乾燥後，於該試樣之上設置光罩，經由該光罩進行圖像曝光、顯影，且視需要進行熱硬化或光硬化，藉此形成黑色矩陣。(2) Black matrix When the black matrix of the present invention is formed from the photosensitive resin composition of the present invention described above, the photosensitive resin composition of the present invention is coated on a transparent substrate and dried, and then placed on the sample A photomask is used to expose and develop an image through the photomask, and if necessary, thermally or photoharden to form a black matrix.

(3)黑色矩陣之形成 (3-1)感光性樹脂組合物之塗佈黑色矩陣用之感光性樹脂組合物向透明基板上之塗佈可藉由旋轉塗佈法、線棒塗佈法、流塗法、模嘴塗佈法、輥塗法、或噴塗法等進行。其中，根據模嘴塗佈法，而大幅削減塗佈液使用量，且完全沒有藉由旋轉塗佈法時所附著之霧等影響，而抑制異物產生等，就綜合性之觀點而言較佳。(3) Formation of black matrix (3-1) Coating of photosensitive resin composition The coating of the photosensitive resin composition for black matrix onto a transparent substrate can be performed by spin coating method, wire bar coating method, The flow coating method, die coating method, roll coating method, or spray coating method is used. Among them, according to the die nozzle coating method, the amount of coating liquid used is greatly reduced, and there is no influence of mist or the like attached by the spin coating method at all, and the generation of foreign materials is suppressed, etc., which is preferable from a comprehensive viewpoint .

若塗膜之厚度過厚，則有時圖案顯影變得困難，並且於液晶單元化步驟中之間隙調整變得困難，若過薄，則有時難以提高顏料濃度而無法實現所需之顏色顯現。關於塗膜之厚度，以乾燥後之膜厚計，通常較佳為設為0.2～10 μm之範圍，更佳為0.5～6 μm之範圍、進而較佳為0.5～4 μm之範圍。If the thickness of the coating film is too thick, pattern development may become difficult, and the gap adjustment in the liquid crystal cell formation step may become difficult. If it is too thin, it may be difficult to increase the pigment concentration and the desired color development may not be achieved. . Regarding the thickness of the coating film, based on the thickness of the film after drying, it is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 0.5 to 4 μm.

(3-2)塗膜之乾燥於基板塗佈感光性樹脂組合物後之塗膜之乾燥較佳為利用使用加熱板、IR烘箱、或對流烘箱之乾燥法。乾燥之條件可視上述溶劑成分之種類、所使用之乾燥機之性能等而適當選擇。乾燥時間係視溶劑成分之種類、所使用之乾燥機之性能等，於通常40～200℃之溫度下於15秒～5分鐘之範圍內選擇，較佳為於50～130℃之溫度下於30秒～3分鐘之範圍內選擇。(3-2) Drying of coating film The drying of the coating film after applying the photosensitive resin composition to the substrate is preferably a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected according to the types of the above-mentioned solvent components and the performance of the dryer used. The drying time depends on the type of solvent component, the performance of the dryer used, etc., and is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200°C, preferably at a temperature of 50 to 130°C Select from 30 seconds to 3 minutes.

乾燥溫度越高，塗膜對於透明基板之接著性越提高，若乾燥溫度過高，則有鹼可溶性樹脂分解，誘發熱聚合而產生顯影不良之情形。再者，該塗膜之乾燥步驟亦可為不提高溫度，於減壓腔室內進行乾燥之減壓乾燥法。The higher the drying temperature, the higher the adhesion of the coating film to the transparent substrate. If the drying temperature is too high, the alkali-soluble resin may decompose and thermal polymerization may be induced to cause poor development. Furthermore, the drying step of the coating film may be a reduced-pressure drying method in which the temperature is not increased and drying is performed in the reduced-pressure chamber.

(3-3)曝光圖像曝光係於感光性樹脂組合物之塗膜上重疊負之遮罩圖案，經由該遮罩圖案照射紫外光範圍至可見光範圍之波長之光而進行。此時，亦可視需要，為了防止由氧導致之光聚合性層之感度降低，而於光聚合性之塗膜上形成聚乙烯醇層等隔氧層後進行曝光。上述圖像曝光所使用之光源並無特別限定。作為光源，例如可列舉：氙氣燈、鹵素燈、鎢絲燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、中壓水銀燈、低壓水銀燈、碳弧等燈光源等。於照射特定波長之光而使用之情形時，亦可利用光學濾光片。(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition, and irradiating light with a wavelength in the ultraviolet range to the visible range through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer caused by oxygen from decreasing, an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film and then exposed. The light source used for the above image exposure is not particularly limited. Examples of the light source include xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arc lamps. When irradiated with light of a specific wavelength and used, an optical filter can also be used.

(3-4)顯影本發明之黑色矩陣可以下述方式製作，即藉由上述光源對由感光性樹脂組合物形成之塗膜進行圖像曝光後，藉由使用有機溶劑、或包含界面活性劑與鹼性化合物之水溶液之顯影於基板上形成圖像而製作。於該水溶液中，可進而含有有機溶劑、緩衝劑、錯合劑、染料或顏料。(3-4) The development of the black matrix of the present invention can be made in such a manner that after the image exposure of the coating film formed of the photosensitive resin composition by the above light source, by using an organic solvent or containing a surfactant It is produced by developing an aqueous solution with an alkaline compound to form an image on a substrate. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

作為鹼性化合物，可列舉：氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、磷酸鈉、磷酸鉀、磷酸氫鈉、磷酸氫鉀、磷酸二氫鈉、磷酸二氫鉀、氫氧化銨等無機鹼性化合物；或者單、二或三乙醇胺、單、二或三甲胺、單、二或三乙胺、單或二異丙基胺、正丁基胺、單、二或三異丙醇胺、伸乙基亞胺、伸乙基二亞胺、四甲基氫氧化銨(TMAH)、膽鹼等有機鹼性化合物。該等鹼性化合物亦可為2種以上之混合物。Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds; or mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or tri- Ethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethylidene imide, ethylidene diimide, tetramethylammonium hydroxide (TMAH), bile Organic alkaline compounds such as alkali. These basic compounds may also be a mixture of two or more.

作為界面活性劑，例如可列舉：聚氧乙烯烷基醚類、聚氧乙烯烷基芳基醚類、聚氧乙烯烷基酯類、山梨醇酐烷基酯類、單甘油酯烷基酯類等非離子系界面活性劑；烷基苯磺酸鹽類、烷基萘磺酸鹽類、烷基硫酸鹽類、烷基磺酸鹽類、磺基琥珀酸酯鹽類等陰離子性界面活性劑；烷基甜菜鹼類、胺基酸類等兩性界面活性劑。Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. And other nonionic surfactants; anionic surfactants such as alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates, etc. ; Amphoteric surfactants such as alkyl betaines and amino acids.

作為有機溶劑，例如可列舉：異丙醇、苄醇、乙基溶纖劑、丁基溶纖劑、苯基溶纖劑、丙二醇、二丙酮醇等。有機溶劑可單獨使用，又，亦可與水溶液併用。顯影處理之條件並無特別限制，通常顯影溫度為10～50℃之範圍，其中，為15～45℃、尤佳為20～40℃，且顯影方法可藉由浸漬顯影法、噴霧顯影法、刷顯影法、超音波顯影法等任一種方法。Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent can be used alone or in combination with an aqueous solution. The conditions of the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50°C, of which, 15 to 45°C, particularly preferably 20 to 40°C, and the development method can be by dipping development method, spray development method, Either brush development method, ultrasonic development method, etc.

(3-5)熱硬化處理對於顯影後之基板，實施熱硬化處理或光硬化處理、較佳為熱硬化處理。關於此時之熱硬化處理條件，溫度係於100～280℃之範圍、較佳為150～250℃之範圍內進行選擇，時間係於5～60分鐘之範圍內選擇。以上述方式形成之黑色矩陣之高度通常為0.5～5 μm，較佳為0.7～4 μm，更佳為0.8～2 μm。進而，厚度每1 μm之光學濃度(OD)為3.0以上，較佳為3.5以上，更佳為3.8以上，尤佳為4.0以上。(3-5) Thermal curing treatment The substrate after development is subjected to thermal curing treatment or light curing treatment, preferably thermal curing treatment. Regarding the thermal curing treatment conditions at this time, the temperature is selected within the range of 100 to 280°C, preferably 150 to 250°C, and the time is selected within the range of 5 to 60 minutes. The height of the black matrix formed in the above manner is usually 0.5 to 5 μm, preferably 0.7 to 4 μm, and more preferably 0.8 to 2 μm. Furthermore, the optical density (OD) per 1 μm thickness is 3.0 or more, preferably 3.5 or more, more preferably 3.8 or more, and particularly preferably 4.0 or more.

[其他彩色濾光片圖像之形成] 於設置有黑色矩陣之透明基板上，以與上述(3-1)～(3-5)相同之製程塗佈含有紅色、綠色、藍色中之一種顏色之色料之感光性樹脂組合物，乾燥後，於塗膜之上重疊光罩，經由該光罩進行圖像曝光、顯影，且視需要進行熱硬化或光硬化，藉此形成像素圖像，而製作著色層。紅色、綠色、藍色之三種顏色之感光性樹脂組合物分別進行該操作，藉此可形成彩色濾光片圖像。該等之順序並不限定於上述。[Formation of other color filter images] On a transparent substrate provided with a black matrix, apply one of red, green, and blue in the same process as the above (3-1) to (3-5) The photosensitive resin composition of the color material, after drying, overlays a photomask on the coating film, exposes and develops the image through the photomask, and if necessary, thermally or photocures to form a pixel image , And make a colored layer. The photosensitive resin composition of three colors of red, green, and blue performs this operation separately, whereby a color filter image can be formed. The order of these is not limited to the above.

彩色濾光片係直接於圖像上形成ITO等透明電極，而作為彩色顯示器、液晶顯示裝置等之零件之一部分使用，但為了提高表面平滑性或耐久性，亦可視需要於圖像上設置聚醯胺、聚醯亞胺等面塗層。又，於一部分平面配向型驅動方式(IPS模式)等用途中，亦有時不形成透明電極。The color filter forms transparent electrodes such as ITO directly on the image, and is used as part of components such as color displays and liquid crystal display devices. However, in order to improve the smoothness or durability of the surface, it is also possible to provide a polymer on the image. Topcoats such as amide and polyimide. Moreover, in some applications such as the planar alignment driving method (IPS mode), transparent electrodes may not be formed.

[著色間隔件] 本發明之感光性樹脂組合物除黑色矩陣以外，亦可用作著色間隔件用之感光性樹脂組合物。於將間隔件用於TFT型LCD之情形時，有時由於入射至TFT之光而作為開關元件之TFT產生誤動作，著色間隔件係用以防止上述情況產生，例如於日本專利特開平8-234212號公報中記載將間隔件設為遮光性。著色間隔件除使用著色間隔件用之遮罩以外，可利用與上述黑色矩陣相同之方法形成。[Colored Spacer] In addition to the black matrix, the photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers. When the spacer is used in a TFT LCD, the TFT as a switching element may malfunction due to light incident on the TFT. The colored spacer is used to prevent the above situation, for example, in Japanese Patent Laid-Open No. 8-234212 The publication discloses that the spacer is light-shielding. The colored spacer can be formed by the same method as the black matrix described above, except that the mask for the colored spacer is used.

[圖像顯示裝置] 本發明之圖像顯示裝置係具有本發明之硬化物者，例如可列舉具有本發明之黑色矩陣者。作為圖像顯示裝置，只要為顯示圖像或影像之裝置，則不受特別限定，可列舉下述之液晶顯示裝置或有機EL顯示器等。[Image Display Device] The image display device of the present invention is one having the hardened product of the present invention, and for example, one having the black matrix of the present invention can be cited. The image display device is not particularly limited as long as it is an image or video display device, and examples thereof include the following liquid crystal display devices and organic EL displays.

[液晶顯示裝置] 本發明之液晶顯示裝置係具有上述本發明之黑色矩陣者，彩色像素或黑色矩陣之形成順序或形成位置等不受特別制限。[Liquid Crystal Display Device] The liquid crystal display device of the present invention includes the black matrix of the present invention described above, and the formation order or formation position of the color pixels or the black matrix is not particularly limited.

液晶顯示裝置係通常於彩色濾光片上形成配向膜，於該配向膜上散佈間隔件後，與對向基板貼合而形成液晶單元，將液晶注入至所形成之液晶單元中，與對向電極接線而完成。作為配向膜，較佳為聚醯亞胺等樹脂膜。為了形成配向膜，通常採用凹版印刷法及/或軟版印刷法，配向膜之厚度係視為數10 nm。藉由熱燒成而進行配向膜之硬化處理後，藉由紫外線之照射或利用磨擦布之處理而進行表面處理，加工成可調整液晶之斜率之表面狀態。The liquid crystal display device is usually formed with an alignment film on the color filter. After the spacer is spread on the alignment film, it is bonded to the counter substrate to form a liquid crystal cell, and the liquid crystal is injected into the formed liquid crystal cell. The electrode wiring is completed. As the alignment film, a resin film such as polyimide is preferable. In order to form an alignment film, a gravure printing method and/or a flexographic printing method are generally used, and the thickness of the alignment film is regarded as several 10 nm. After curing the alignment film by thermal firing, the surface treatment is performed by ultraviolet irradiation or rubbing cloth treatment, and the surface state can be adjusted to adjust the slope of the liquid crystal.

作為間隔件，使用對應於與對向基板之間隙(clearance)之尺寸者，通常2～8 μm者較佳。亦可於彩色濾光片基板上藉由光微影法形成透明樹脂膜之感光性間隔件(PS)，用其替代間隔件進行利用。作為對向基板，通常使用陣列基板，尤其是TFT(薄膜電晶體)基板較佳。As the spacer, a size corresponding to the clearance with the counter substrate is used, and usually 2 to 8 μm is preferable. A photosensitive spacer (PS) of a transparent resin film can also be formed on the color filter substrate by photolithography, and it can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and particularly a TFT (thin film transistor) substrate is preferable.

與對向基板之貼合間隙係視液晶顯示裝置之用途而不同，通常於2～8 μm之範圍內選擇。與對向基板貼合後，液晶注入口以外之部分係藉由環氧樹脂等密封材進行密封。密封材係藉由UV照射及/或加熱而硬化，從而將液晶單元周邊密封。周邊已被密封之液晶單元係切割成面板單位後，於真空腔室內進行減壓，將上述液晶注入口浸漬至液晶中後，藉由使腔室內洩漏而將液晶注入至液晶單元內。液晶單元內之減壓度通常為1×10^-2 ～1×10^-7 Pa，較佳為1×10^-3 ～1×10^-6 Pa。又，較佳為於減壓時對液晶單元進行加溫，加溫溫度通常為30～100℃，更佳為50～90℃。減壓時之加溫保持係通常設為10～60分鐘之範圍，於其後浸漬於液晶中。注入有液晶之液晶單元係藉由使UV硬化樹脂硬化來密封液晶注入口而完成液晶顯示裝置(面板)。The bonding gap with the counter substrate is different depending on the application of the liquid crystal display device, and is usually selected in the range of 2 to 8 μm. After bonding with the counter substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is hardened by UV irradiation and/or heating, thereby sealing the periphery of the liquid crystal cell. After the liquid crystal cell whose periphery is sealed is cut into panel units, the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of decompression in the liquid crystal cell is usually 1×10 ^-2 to 1×10 ^-7 Pa, preferably 1×10 ^-3 to 1×10 ^-6 Pa. In addition, it is preferable to heat the liquid crystal cell under reduced pressure, and the heating temperature is usually 30 to 100°C, more preferably 50 to 90°C. The heating and holding system under reduced pressure is usually set in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is a liquid crystal display device (panel) by curing the UV curing resin to seal the liquid crystal injection port.

液晶之種類並無特別限制，可為芳香族系、脂肪族系、多環狀化合物等先前以來已知之液晶，亦可為溶致型液晶、熱致型液晶等之任一種。關於熱致型液晶，已知向列型液晶、層列型液晶及膽固醇狀液晶等，可為該等中之任一種。The type of liquid crystal is not particularly limited, and may be a liquid crystal known in the past, such as an aromatic system, an aliphatic system, or a polycyclic compound, or may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. Regarding the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, etc. are known, and any of them may be used.

[有機EL顯示器] 本發明之有機EL顯示器係使用本發明之彩色濾光片所製作者。[Organic EL Display] The organic EL display of the present invention is produced using the color filter of the present invention.

於使用本發明之彩色濾光片而製作有機EL顯示器之情形時，例如如圖1所示，首先製作於透明支持基板10上形成由感光性樹脂組合物所形成之圖案(即，像素20、及設置於鄰接之像素20間之樹脂黑色矩陣(未圖示))而成之彩色濾光片，於該彩色濾光片上經由有機保護層30及無機氧化膜40而積層有機發光體500，藉此可製作有機EL元件100。再者，於像素20及樹脂黑色矩陣中，至少一個係使用本發明之感光性樹脂組合物所製作者。作為有機發光體500之積層方法，可列舉：於彩色濾光片上表面依序形成透明陽極50、電洞注入層51、電洞傳輸層52、發光層53、電子注入層54、及陰極55之方法，或者將形成於另一基板上之有機發光體500貼合於無機氧化膜40上之方法等。可使用以上述方式製作之有機EL元件100，例如藉由「有機EL顯示器」(歐姆社，2004年8月20日發行，時任靜士、安達千波矢、村田英幸著)所記載之方法等而製作有機EL顯示器。In the case of manufacturing an organic EL display using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern formed by a photosensitive resin composition is formed on a transparent support substrate 10 (ie, pixels 20, And a color filter formed of a resin black matrix (not shown) provided between adjacent pixels 20, and an organic light-emitting body 500 is laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40, Thereby, the organic EL element 100 can be produced. Furthermore, at least one of the pixel 20 and the resin black matrix is produced using the photosensitive resin composition of the present invention. As a method for stacking the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are formed on the upper surface of the color filter in order A method, or a method of bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40. The organic EL device 100 manufactured in the above manner can be used, for example, by the method described in the "organic EL display" (Omsha Corporation, issued on August 20, 2004, when Shizuzu Shizu, Anda Chiba, Hideki Murata) Production of organic EL displays.

再者，本發明之彩色濾光片可應用於被動驅動方式之有機EL顯示器，亦可應用於主動驅動方式之有機EL顯示器。 [實施例]Furthermore, the color filter of the present invention can be applied to an organic EL display of a passive driving method, and can also be applied to an organic EL display of an active driving method. [Example]

繼而，列舉實施例及比較例而對本發明更具體地進行說明，但本發明只要不超越其主旨，則並不限定於以下之實施例。Next, the present invention will be described more specifically by citing examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

＜碳黑墨水之製備＞以下述之組成及方法調合顏料、分散劑、分散助劑、溶劑而製備碳黑墨水。具體而言，首先將顏料、分散劑、分散助劑之固形物成分與溶劑以成為以下之質量比之方式進行調合。・顏料：RAVEN1060U(R1060)(Birla公司製造之碳黑)；100.0質量份・分散劑：DISPERBYK-167(BYK-Chemie公司製造之鹼性胺基甲酸酯系分散劑)；14.0質量份(固形物成分換算) ・分散助劑(顏料衍生物)：Solsperse12000(Lubrizol公司製造，具有酸性基之酞菁系顏料衍生物)；2.0質量份・溶劑：丙二醇單甲醚乙酸酯(PGMEA)；215.5質量份<Preparation of carbon black ink> A carbon black ink is prepared by mixing pigments, dispersants, dispersing aids, and solvents with the following composition and method. Specifically, first, the solid content of the pigment, dispersant, and dispersion aid and the solvent are blended so that the mass ratio becomes as follows.・Pigment: RAVEN1060U (R1060) (carbon black manufactured by Birla); 100.0 parts by mass ・Dispersant: DISPERBYK-167 (alkaline carbamate-based dispersant manufactured by BYK-Chemie); 14.0 parts by mass (solid Material composition conversion) ・Dispersion aid (pigment derivative): Solsperse12000 (made by Lubrizol company, phthalocyanine pigment derivative with acid group); 2.0 parts by mass ・Solvent: propylene glycol monomethyl ether acetate (PGMEA); 215.5 Quality

將該等充分地進行攪拌、混合而獲得分散液。繼而，對於該分散液，藉由塗料振盪機於25～45℃之範圍內進行6小時分散處理。作為珠粒，使用直徑0.5 mm之氧化鋯珠，且以相對於分散液60質量份，珠粒為180質量份之比率進行添加。分散處理結束後，藉由過濾器將珠粒與分散液分離，而製備總固形物成分之含有比率為35質量%之碳黑墨水。These are sufficiently stirred and mixed to obtain a dispersion liquid. Then, the dispersion liquid was subjected to dispersion treatment in a range of 25 to 45°C for 6 hours by a paint shaker. As the beads, zirconia beads with a diameter of 0.5 mm were used, and the beads were added at a ratio of 180 parts by mass with respect to 60 parts by mass of the dispersion liquid. After the dispersion process was completed, the beads were separated from the dispersion liquid by a filter, and a carbon black ink with a total solid content content ratio of 35% by mass was prepared.

＜鹼可溶性樹脂(1)＞以下述之程序合成鹼可溶性樹脂(1)。<Alkali-soluble resin (1)> The alkali-soluble resin (1) was synthesized in the following procedure.

[化46] [化46]

將上述化學結構之環氧化合物(環氧當量264)50 g、丙烯酸13.65 g、乙酸3-甲氧基丁酯60.5 g、三苯基膦0.936 g、及對甲氧基苯酚0.032 g加入至安裝有溫度計、攪拌機、冷凝管之燒瓶中，一面進行攪拌一面於90℃下進行反應直至酸值成為5 mgKOH/g以下。反應需要12小時，獲得環氧丙烯酸酯溶液。將上述環氧丙烯酸酯溶液25質量份及三羥甲基丙烷(TMP)0.76質量份、聯苯四羧酸二酐(BPDA)3.3質量份、四氫鄰苯二甲酸酐(THPA)3.5質量份加入至安裝有溫度計、攪拌機、冷凝管之燒瓶中，一面進行攪拌一面緩慢地升溫至105℃而進行反應。於樹脂溶液變得透明時，利用乙酸3-甲氧基丁酯(MBA)進行稀釋，以固形物成分成為50質量%之方式進行製備，獲得酸值115 mgKOH/g且藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)2600之鹼可溶性樹脂(1)。Add 50 g of epoxy compound (epoxy equivalent 264) of the above chemical structure, 13.65 g of acrylic acid, 60.5 g of 3-methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol to the installation In a flask equipped with a thermometer, stirrer, and condenser, the reaction was carried out at 90°C while stirring until the acid value became 5 mgKOH/g or less. The reaction requires 12 hours to obtain an epoxy acrylate solution. 25 parts by mass of the above epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) It was added to a flask equipped with a thermometer, a stirrer, and a condenser, and while stirring, the temperature was slowly raised to 105°C to carry out a reaction. When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate (MBA) and prepared in such a way that the solid content became 50% by mass. The acid value was 115 mgKOH/g and was measured by GPC Alkali-soluble resin (1) having a weight average molecular weight (Mw) of 2,600 in terms of polystyrene.

＜鹼可溶性樹脂(2)＞以下述之程序合成鹼可溶性樹脂(2)。<Alkali-soluble resin (2)> The alkali-soluble resin (2) was synthesized in the following procedure.

[化47] [化47]

將上述化學結構之環氧化合物(環氧當量240)7.3 g、丙烯酸2.2 g、丙二醇單甲醚乙酸酯6.4 g、四乙基氯化銨0.18 g、及對甲氧基苯酚0.007 g加入至安裝有溫度計、攪拌機、冷凝管之燒瓶中，一面進行攪拌一面於100℃下進行反應直至酸值成為5 mgKOH/g以下。反應需要9小時，獲得環氧丙烯酸酯溶液。將所獲得之環氧丙烯酸酯溶液16質量份、三羥甲基丙烷(TMP)0.4質量份、聯苯四羧酸二酐(BPDA)3.5質量份、四氫鄰苯二甲酸酐(THPA)0.06質量份、及丙二醇單甲醚乙酸酯(PGMEA)14質量份加入至安裝有溫度計、攪拌機、冷凝管之燒瓶中，一面進行攪拌一面緩慢地升溫至105℃而進行反應，獲得固形物成分40質量%、酸值100 mgKOH/g、藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)10400之鹼可溶性樹脂(2)。Add 7.3 g of epoxy compound (epoxy equivalent 240) of the above chemical structure, 2.2 g of acrylic acid, 6.4 g of propylene glycol monomethyl ether acetate, 0.18 g of tetraethylammonium chloride, and 0.007 g of p-methoxyphenol to In a flask equipped with a thermometer, stirrer, and condenser, the reaction was carried out at 100°C while stirring until the acid value became 5 mgKOH/g or less. The reaction required 9 hours to obtain an epoxy acrylate solution. 16 parts by mass of the obtained epoxy acrylate solution, 0.4 parts by mass of trimethylolpropane (TMP), 3.5 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 0.06 of tetrahydrophthalic anhydride (THPA) 14 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was added to a flask equipped with a thermometer, a stirrer, and a condenser, and the reaction was slowly heated to 105°C while stirring to obtain a solid content 40 Alkali-soluble resin (2) with a mass %, an acid value of 100 mgKOH/g, and a polystyrene-equivalent weight average molecular weight (Mw) of 10400 measured by GPC.

＜鹼可溶性樹脂(3)＞以下述之程序合成鹼可溶性樹脂(3)。將丙二醇單甲醚乙酸酯114.0 g加入至500 mL之四口燒瓶中，一面通入氮氣一面升溫至85℃。向其中歷時4小時滴加使甲基丙烯酸苄酯96.8 g(0.55 mol)、甲基丙烯酸33.3 g(0.45 mol)、2,2'-偶氮雙(異丁腈)4.93 g(0.03 mol)溶解於丙二醇單甲醚乙酸酯96.45 g中所得者。滴加後於將反應液保持在85℃之狀態下進而攪拌2小時，其後終止通入氮氣，升溫至100℃，攪拌1小時來進行反應，獲得固形物成分39質量%、酸值180 mgKOH/g、藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)15000之鹼可溶性樹脂(3)。<Alkali-soluble resin (3)> The alkali-soluble resin (3) was synthesized in the following procedure. 114.0 g of propylene glycol monomethyl ether acetate was added to a 500 mL four-necked flask, and the temperature was raised to 85°C while introducing nitrogen gas. To this was added dropwise over 4 hours to dissolve 96.8 g (0.55 mol) of benzyl methacrylate, 33.3 g (0.45 mol) of methacrylic acid, and 4.93 g (0.03 mol) of 2,2'-azobis(isobutyronitrile) It is obtained from 96.45 g of propylene glycol monomethyl ether acetate. After dropping, the reaction solution was kept at 85°C and stirred for 2 hours. After that, the nitrogen flow was terminated, the temperature was raised to 100°C, and the reaction was stirred for 1 hour. The solid content was 39% by mass and the acid value was 180 mgKOH. /g, alkali soluble resin (3) having a weight average molecular weight (Mw) of 15,000 in terms of polystyrene measured by GPC.

＜鹼可溶性樹脂(4)＞以下述之程序合成鹼可溶性樹脂(4)。<Alkali-soluble resin (4)> The alkali-soluble resin (4) was synthesized in the following procedure.

[化48] [Chemical 48]

將上述化學結構之環氧化合物(NC-3000-H，日本化藥公司製造)400質量份、丙烯酸100質量份、對甲氧基苯酚0.3質量份、三苯基膦5質量份、丙二醇單甲醚乙酸酯264質量份添加至反應容器中，於95℃下進行攪拌直至酸值成為3 mgKOH/g以下。直至達到目標酸值2.2 mgKOH/g需要9小時。繼而，添加四氫鄰苯二甲酸酐190質量份，於95℃下反應4小時，獲得酸值98 mgKOH/g、藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)4500之鹼可溶性樹脂(4)。400 parts by mass of epoxy compound (NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.) of the above chemical structure, 100 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and propylene glycol monomethyl 264 parts by mass of ether acetate was added to the reaction vessel, and the mixture was stirred at 95°C until the acid value became 3 mgKOH/g or less. It takes 9 hours to reach the target acid value of 2.2 mgKOH/g. Then, 190 parts by mass of tetrahydrophthalic anhydride was added and reacted at 95°C for 4 hours to obtain an acid value of 98 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 4500 measured by GPC. Alkali soluble resin (4).

＜鹼可溶性樹脂(5)＞以下述之程序合成鹼可溶性樹脂(5)。<Alkali-soluble resin (5)> The alkali-soluble resin (5) was synthesized in the following procedure.

[化49] [Chem 49]

將上述化學結構之環氧化合物(雙酚茀型環氧樹脂，環氧當量235)235 g、三苯基膦3.73 g、2,6-二-第三丁基-4-甲基苯酚100 mg及丙烯酸72.0 g添加至500 ml四口燒瓶中，一面將含有氧5%之氮氣吹入至其中一面以90～100℃進行加熱後，加熱至120℃而使之完全溶解。測定酸值，繼續加熱攪拌直至未達1.0 mgKOH/g。直至酸值達到目標需要12小時。然後，冷卻至室溫，獲得無色透明且固體狀之雙酚茀型環氧丙烯酸酯。繼而，於以上述方式獲得之上述雙酚茀型環氧丙烯酸酯307.0 g中添加丙二醇單甲醚乙酸酯600 g，使之溶解後，混合二苯甲酮四羧酸二酐80.5 g，緩慢地升溫，以110～115℃進行反應。其後，混合1,2,3,6-四氫鄰苯二甲酸酐38.0 g，於90℃下進行反應，獲得固形物成分41.5質量%、酸值100 mgKOH/g、藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)5000之鹼可溶性樹脂(5)。The above chemical structure of the epoxy compound (bisphenol stilbene epoxy resin, epoxy equivalent 235) 235 g, triphenylphosphine 3.73 g, 2,6-di-tert-butyl-4-methylphenol 100 mg 72.0 g of acrylic acid was added to a 500 ml four-necked flask. While nitrogen gas containing 5% of oxygen was blown into it, it was heated at 90-100°C and heated to 120°C to completely dissolve it. Determine the acid value, continue heating and stirring until it does not reach 1.0 mgKOH/g. It takes 12 hours until the acid value reaches the target. Then, it was cooled to room temperature to obtain a colorless transparent solid bisphenol fusiform epoxy acrylate. Then, after adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the above-mentioned bisphenol fusiform epoxy acrylate obtained in the above manner and dissolving it, mix 80.5 g of benzophenone tetracarboxylic dianhydride and slowly The temperature was raised and the reaction was carried out at 110 to 115°C. Thereafter, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. to obtain a solid content of 41.5 mass %, an acid value of 100 mgKOH/g, as measured by GPC Alkali-soluble resin (5) with a weight average molecular weight (Mw) of 5000 in terms of polystyrene.

＜光聚合性單體(1)、(2)＞準備以下之光聚合性單體。光聚合性單體(1)：KAYARAD DPCA20(日本化藥公司製造)<Photopolymerizable monomers (1), (2)> The following photopolymerizable monomers were prepared. Photopolymerizable monomer (1): KAYARAD DPCA20 (manufactured by Nippon Kayaku)

[化50] [化50]

光聚合性單體(2)：Light acrylate PE4A(季戊四醇四丙烯酸酯)(共榮社化學公司製造)Photopolymerizable monomer (2): Light acrylate PE4A (pentaerythritol tetraacrylate) (made by Kyoeisha Chemical Company)

[化51] [化51]

＜光自由基聚合起始劑(1)＞準備以下之光自由基聚合起始劑(1)。光自由基聚合起始劑(1)：TR-PBG-314(常州強力電子新材料公司製造)<Photo radical polymerization initiator (1)> The following photo radical polymerization initiator (1) was prepared. Photo-radical polymerization initiator (1): TR-PBG-314 (manufactured by Changzhou Qiangli Electronic New Material Company)

[化52] [化52]

＜有機矽乙烯系聚合物(1)～(4)＞作為有機矽乙烯系聚合物(d-1)，以下述程序準備有機矽乙烯系聚合物(1)～(4)。<Silicone-based polymer (1) to (4)> As the silicone-based polymer (d-1), the silicone-based polymer (1) to (4) was prepared according to the following procedure.

有機矽乙烯系聚合物(1)：稱取作為溶劑之丙二醇單甲醚乙酸酯(PGMEA)200 g至具備攪拌裝置、滴液漏斗、冷凝器、溫度計、氣體導入管之燒瓶中，一面進行氮氣置換一面進行攪拌，升溫至120℃。繼而，於包含KBM-503(信越化學工業公司製造，下述式(d1)之化合物；再者，式中，C₃ H₆ 表示正丙烷-1,3-二基)111.6 g與甲基丙烯酸甲酯(MMA，下述式(d2)之化合物)45.0 g(混合莫耳比率為KBM-503：MMA＝50：50)之聚合性單體混合物中添加熱自由基聚合起始劑第三丁基過氧化氫(日本油脂公司製造之PERBUTYL O)7.0 g並進行混合。將該混合物自滴液漏斗歷時2小時滴加至上述燒瓶中，進而於120℃下攪拌2小時後恢復至室溫，獲得具有下述式(d3)所表示之重複單元之共聚物(m：n＝50：50)之溶液。所獲得之共聚物溶液之固形物成分濃度為45質量%。又，共聚物之藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)為12000。Silicone-based polymer (1): Weigh 200 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and proceed on one side The nitrogen was replaced while stirring, and the temperature was raised to 120°C. Then, it contains 111.6 g of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., the following formula (d1); in the formula, C ₃ H ₆ represents n-propane-1,3-diyl) and methacrylic acid A third radical of thermal radical polymerization initiator was added to the polymerizable monomer mixture of methyl ester (MMA, compound of the following formula (d2)) 45.0 g (mixed molar ratio KBM-503: MMA=50:50) Hydrogen peroxide (PERBUTYL O manufactured by Nippon Oil & Fats Corporation) 7.0 g was mixed. This mixture was added dropwise from the dropping funnel to the flask over 2 hours, and after stirring at 120°C for 2 hours, it was returned to room temperature to obtain a copolymer (m: having a repeating unit represented by the following formula (d3): n=50:50) solution. The solid content concentration of the obtained copolymer solution was 45% by mass. In addition, the weight average molecular weight (Mw) of the copolymer in terms of polystyrene measured by GPC was 12,000.

[化53] [化53]

[化54] [化54]

[化55] [化55]

有機矽乙烯系聚合物(2)：於上述有機矽乙烯系聚合物(1)之合成中，將KBM-503變更為89.6 g且將MMA變更為67.0 g(混合莫耳比率為KBM-503：MMA＝35：65)並投入，除此以外，以相同之程序獲得具有上述式(d3)所表示之重複單元之共聚物(m：n＝35：65)之溶液。所獲得之共聚物溶液之固形物成分濃度為45質量%。又，共聚物之藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)為12000。Silicone-based polymer (2): In the synthesis of the above-mentioned silicone-based polymer (1), KBM-503 was changed to 89.6 g and MMA was changed to 67.0 g (mixed molar ratio KBM-503: MMA=35:65) and input, except that, a solution of a copolymer (m:n=35:65) having a repeating unit represented by the above formula (d3) is obtained in the same procedure. The solid content concentration of the obtained copolymer solution was 45% by mass. In addition, the weight average molecular weight (Mw) of the copolymer in terms of polystyrene measured by GPC was 12,000.

有機矽乙烯系聚合物(3)：於上述有機矽乙烯系聚合物(1)之合成中，將KBM-503變更為133.5 g且將MMA變更為23.1 g(混合莫耳比率為KBM-503：MMA＝70：30)並投入，除此以外，以相同之程序獲得具有上述式(d3)所表示之重複單元之共聚物(m：n＝70：30)之溶液。所獲得之共聚物溶液之固形物成分濃度為45質量%。又，共聚物之藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)為12000。Silicone-based polymer (3): In the synthesis of the above-mentioned silicone-based polymer (1), KBM-503 was changed to 133.5 g and MMA was changed to 23.1 g (mixed molar ratio KBM-503: MMA=70:30) and input, except that the solution of the copolymer (m:n=70:30) having the repeating unit represented by the above formula (d3) is obtained in the same procedure. The solid content concentration of the obtained copolymer solution was 45% by mass. In addition, the weight average molecular weight (Mw) of the copolymer in terms of polystyrene measured by GPC was 12,000.

有機矽乙烯系聚合物(4)：於上述有機矽乙烯系聚合物(1)之合成中，將KBM-503變更為78.3 g，將MMA變更為15.8 g，將Lightester 130MA(共榮社化學公司製造，下述式(d4)之化合物)變更為62.5 g(混合莫耳比率為KBM-503：MMA：Lightester 130MA＝50：25：25)並投入，除此以外，以相同之程序獲得具有下述式(d5)所表示之重複單元之共聚物(p：q：r＝50：25：25)之溶液。所獲得之共聚物溶液之固形物成分濃度為45質量%。又，共聚物之藉由GPC所測得之聚苯乙烯換算之重量平均分子量(Mw)為12000。Silicone-based polymer (4): In the synthesis of the above-mentioned silicone-based polymer (1), KBM-503 was changed to 78.3 g, MMA was changed to 15.8 g, and Lightester 130MA (Kyoeisha Chemical Company) Manufactured, the compound of the following formula (d4)) was changed to 62.5 g (mixed molar ratio KBM-503: MMA: Lightester 130MA=50: 25: 25) and put in, except that the same procedure was used to obtain the following A solution of a copolymer of repeating units (p:q:r=50:25:25) represented by the formula (d5). The solid content concentration of the obtained copolymer solution was 45% by mass. In addition, the weight average molecular weight (Mw) of the copolymer in terms of polystyrene measured by GPC was 12,000.

[化56] [化56]

[化57] [化57]

＜其他有機矽化合物＞準備以下之有機矽化合物。有機矽化合物(1)：具有以下之化學結構之化合物(再者，式中，C₂ H₄ 表示1,2-伸乙基，C₃ H₆ 表示正丙烷-1,3-二基)<Other organosilicon compounds> Prepare the following organosilicon compounds. Organosilicon compound (1): a compound having the following chemical structure (in addition, in the formula, C ₂ H ₄ represents 1,2-ethylidene and C ₃ H ₆ represents n-propane-1,3-diyl)

[化58] [化58]

有機矽化合物(2)：Z-6040(東麗道康寧公司製造)(再者，式中，C₃ H₆ 表示正丙烷-1,3-二基)Organosilicon compound (2): Z-6040 (manufactured by Toray Dow Corning Corporation) (Furthermore, in the formula, C ₃ H ₆ represents n-propane-1,3-diyl)

[化59] [化59]

＜界面活性劑＞作為界面活性劑，準備以下之界面活性劑(1)。界面活性劑(1)：MEGAFAC F-554(DIC公司製造，氟系界面活性劑)<Surfactant> As a surfactant, the following surfactant (1) was prepared. Surfactant (1): MEGAFAC F-554 (DIC Corporation, fluorine-based surfactant)

＜實施例1＞ (黑色抗蝕劑1之調合) 使用上述＜碳黑墨水之製備＞中所製備之碳黑墨水，以成為表1所記載之比率之方式添加各成分，藉由攪拌器進行攪拌，藉此使之溶解或分散，而製備黑色抗蝕劑1。黑色抗蝕劑1中之總固形物成分之含有比率為15質量%。<Example 1> (Blending of Black Resist 1) Using the carbon black ink prepared in the above <Preparation of Carbon Black Ink>, each component was added at a ratio described in Table 1, and was performed by a stirrer Stir to dissolve or disperse, thereby preparing black resist 1. The content ratio of the total solid content in the black resist 1 is 15% by mass.

[表1] [Table 1]

再者，表1中之縮寫之含義係如下所示。 PGMEA：丙二醇單甲醚乙酸酯 MBA：乙酸3-甲氧基丁酯 EDGAC：二乙二醇單***乙酸酯In addition, the meaning of the abbreviations in Table 1 is as follows. PGMEA: propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate EDGAC: diethylene glycol monoethyl ether acetate

＜實施例2＞ (黑色抗蝕劑2之調合) 於實施例1中，將有機矽乙烯系聚合物(1)變更為有機矽乙烯系聚合物(2)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑2。<Example 2> (Blending of black resist 2) In Example 1, the organosilicon polymer (1) was changed to the organosilicon polymer (2). Black resist 1 of 1 is prepared in the same manner as black resist 2.

＜實施例3＞ (黑色抗蝕劑3之調合) 於實施例1中，將有機矽乙烯系聚合物(1)變更為有機矽乙烯系聚合物(3)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑3。<Example 3> (blending of black resist 3) In Example 1, the organosilicon vinyl polymer (1) was changed to the organosilicon vinyl polymer (3). Black resist 1 of 1 is prepared in the same manner as black resist 3.

＜實施例4＞ (黑色抗蝕劑4之調合) 於實施例1中，以有機矽乙烯系聚合物(1)之量於總固形物成分中成為0.75質量%之方式減量，且以鹼可溶性樹脂(1)之量於總固形物成分中成為18.15質量%之方式增量，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑4。<Example 4> (blending of black resist 4) In Example 1, the amount of the organosilicon polymer (1) was reduced to 0.75 mass% of the total solid content, and it was alkali soluble A black resist 4 was prepared in the same manner as the black resist 1 of Example 1 except that the amount of the resin (1) was increased to 18.15 mass% in the total solid content.

＜實施例5＞ (黑色抗蝕劑5之調合) 於實施例1中，以有機矽乙烯系聚合物(1)之量於總固形物成分中成為3.00質量%之方式增量，且以鹼可溶性樹脂(1)之量於總固形物成分中成為15.90質量%之方式減量，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑5。<Example 5> (blending of black resist 5) In Example 1, the amount of the organosilicon polymer (1) was increased so that it became 3.00% by mass in the total solid content, and the alkali The amount of the soluble resin (1) was reduced so that the total solid content became 15.90% by mass, except that the black resist 5 was prepared in the same manner as the black resist 1 of Example 1.

＜實施例6＞ (黑色抗蝕劑6之調合) 於實施例1中，將有機矽乙烯系聚合物(1)變更為有機矽乙烯系聚合物(4)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑6。<Example 6> (blending of black resist 6) In Example 1, the organosilicon vinyl polymer (1) was changed to the organosilicon vinyl polymer (4). The black resist 1 of 1 was prepared in the same manner as the black resist 6.

＜實施例7＞ (黑色抗蝕劑7之調合) 於實施例1中，將鹼可溶性樹脂(1)及鹼可溶性樹脂(2)之總量(固形物成分量)變更為鹼可溶性樹脂(4)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑7。<Example 7> (blending of black resist 7) In Example 1, the total amount (solid content) of the alkali-soluble resin (1) and the alkali-soluble resin (2) was changed to the alkali-soluble resin (4 ), except that the black resist 7 is prepared in the same manner as the black resist 1 of Example 1.

＜實施例8＞ (黑色抗蝕劑8之調合) 於實施例1中，將鹼可溶性樹脂(1)及鹼可溶性樹脂(2)之總量(固形物成分量)變更為鹼可溶性樹脂(5)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑8。<Example 8> (blending of black resist 8) In Example 1, the total amount (solid content amount) of alkali-soluble resin (1) and alkali-soluble resin (2) was changed to alkali-soluble resin (5 ), except that the black resist 8 was prepared in the same manner as the black resist 1 of Example 1.

＜比較例1＞ (黑色抗蝕劑9之調合) 於實施例1中，不添加有機矽乙烯系聚合物(1)(於有機矽乙烯系聚合物(1)所占之1.5質量%量中添加PGMEA)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑9。<Comparative Example 1> (blending of black resist 9) In Example 1, the silicone polymer (1) was not added (in the amount of 1.5% by mass of the silicone polymer (1) PGMEA was added, except that the black resist 9 was prepared in the same manner as the black resist 1 of Example 1.

＜比較例2＞ (黑色抗蝕劑10之調合) 於實施例1中，將有機矽乙烯系聚合物(1)變更為有機矽化合物(1)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑10。<Comparative Example 2> (blending of black resist 10) In Example 1, the organosilicon polymer (1) was changed to an organosilicon compound (1), and the black color of Example 1 was used Black resist 10 is prepared in the same manner as resist 1.

＜比較例3＞ (黑色抗蝕劑11之調合) 於實施例1中，將有機矽乙烯系聚合物(1)變更為有機矽化合物(2)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑11。<Comparative Example 3> (blending of black resist 11) In Example 1, the organosilicon polymer (1) was changed to the organosilicon compound (2), and the black color of Example 1 was used Black resist 11 is prepared in the same manner as resist 1.

＜比較例4＞ (黑色抗蝕劑12之調合) 於實施例1中，將鹼可溶性樹脂(1)及鹼可溶性樹脂(2)之總量(固形物成分量)變更為鹼可溶性樹脂(3)，除此以外，以與實施例1之黑色抗蝕劑1相同之方式製備黑色抗蝕劑12。<Comparative Example 4> (blending of black resist 12) In Example 1, the total amount (solid content amount) of alkali-soluble resin (1) and alkali-soluble resin (2) was changed to alkali-soluble resin (3 ), except that the black resist 12 was prepared in the same manner as the black resist 1 of Example 1.

(抗蝕劑之評價) (1)黑色抗蝕劑硬化膜之製作利用旋轉塗佈機將所製備之黑色抗蝕劑1～12塗佈於玻璃基板上，進行減壓乾燥後，利用加熱板以100℃乾燥120秒鐘。再者，以塗佈膜厚分別成為約1.2 μm之方式調整塗佈條件。繼而，對於所獲得之乾燥塗佈膜，使用曝光機(ORC製作所公司製造之EXF-2829-F-00)，並藉由高壓水銀燈(ORC製作所製造之ADH-3000M-F-N，無光學濾光片)，無曝光遮罩而以40 mJ/cm² 進行全面曝光。其後，使用利用超純水調整至0.04質量%之KOH水溶液作為鹼顯影液，於室溫(23℃)下以溶解時間之1.8倍之時間進行噴霧顯影(噴霧壓力：0.1 MPa)，進而利用超純水進行噴霧洗淨(噴霧壓力：0.1 MPa)，而獲得黑色抗蝕劑膜。其後，於230℃之烘箱中進行30分鐘加熱硬化，而製作附帶膜厚1.0 μm之黑色抗蝕劑硬化膜之基板。再者，所謂溶解時間，係於顯影處理時未曝光部之感光層溶解而開始可見基板整體之時間，各黑色抗蝕劑之溶解時間為38～67秒之間。再者，黑色抗蝕劑硬化膜之膜厚係利用切割器切削膜之一部分而設置階差部後，利用階差測定裝置Alpha-Step-500(KLA-Tencor公司製造)所測得。再者，膜厚可藉由改變旋轉塗佈機之轉數而進行調整。(Evaluation of resist) (1) Preparation of black resist cured film The prepared black resists 1 to 12 were coated on a glass substrate with a spin coater, dried under reduced pressure, and then heated on a hot plate Dry at 100°C for 120 seconds. In addition, the coating conditions were adjusted so that the coating film thickness became approximately 1.2 μm. Then, for the obtained dry coating film, an exposure machine (EXF-2829-F-00 manufactured by ORC Manufacturing Co., Ltd.) was used, and a high-pressure mercury lamp (ADH-3000M-FN manufactured by ORC Manufacturing, no optical filter) ), full exposure at 40 mJ/cm ² without exposure mask. Thereafter, a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water was used as an alkaline developer, and spray development (spray pressure: 0.1 MPa) was carried out at room temperature (23° C.) for 1.8 times the dissolution time, and then used The ultrapure water was spray-washed (spray pressure: 0.1 MPa) to obtain a black resist film. Thereafter, the substrate was heated and cured in an oven at 230° C. for 30 minutes to produce a black resist cured film with a film thickness of 1.0 μm. In addition, the dissolution time is the time when the photosensitive layer of the unexposed portion dissolves during the development process and the entire substrate is visible, and the dissolution time of each black resist is between 38 and 67 seconds. In addition, the thickness of the black resist cured film was measured by cutting a part of the film with a cutter to provide a stepped portion, and then measured with a step difference measuring device Alpha-Step-500 (manufactured by KLA-Tencor). Furthermore, the film thickness can be adjusted by changing the rotation speed of the spin coater.

(2)基板密接性之評價針對上述(1)中所製作之附帶各黑色抗蝕劑硬化膜之基板，於恢復至室溫後切出2.5 cm見方之測定用基板，利用熱硬化型密封劑Stractbond XN-21-S(三井化學公司製造)接合鋁製柱螺栓銷(P/N：901106U，直徑2.7 mm，Quad Group公司製造)，而製作測定用樣品。針對所製作之樣品，使用薄膜密接強度測定機Romulus(Quad Group公司製造)，以2.0 kg/s之速度進行拉伸試驗，根據黑色抗蝕劑硬化膜與玻璃基板斷裂時之斷裂強度及接著面積，藉由以下之式求出基板密接應力。基板密接應力(kg/cm² )＝斷裂強度(kg)/接著面積(cm² )(2) Evaluation of substrate adhesion For the substrate with each black resist cured film prepared in (1) above, a 2.5 cm square measurement substrate was cut out after returning to room temperature, and a thermosetting sealant was used. Stractbond XN-21-S (manufactured by Mitsui Chemicals Co., Ltd.) joined aluminum stud bolts (P/N: 901106U, diameter 2.7 mm, manufactured by Quad Group) to prepare samples for measurement. For the produced samples, a tensile test at a speed of 2.0 kg/s was performed using a film adhesion strength measuring machine Romulus (manufactured by Quad Group), based on the breaking strength and bonding area when the black resist cured film and the glass substrate were broken Calculate the substrate adhesion stress by the following formula. Substrate adhesion stress (kg/cm ² ) = breaking strength (kg)/adhesion area (cm ² )

此處，將基板密接強度(%)作為以比較例1中之基板密接應力(kg/cm² )之值為100%時之相對值(%)求出。將其結果及評價結果示於表2。評價基準係如下所示。Here, the substrate adhesion strength (%) was obtained as the relative value (%) when the value of the substrate adhesion stress (kg/cm ² ) in Comparative Example 1 was 100%. The results and evaluation results are shown in Table 2. The evaluation criteria are as follows.

(基板密接性之評價判定基準) ・A：基板密接強度為150%以上。・B：基板密接強度為120%以上且未達150%。・C：基板密接強度為110%以上且未達120%。・D：基板密接強度未達110%。(Evaluation criteria for substrate adhesion) • A: The substrate adhesion strength is 150% or more.・B: The substrate adhesion strength is 120% or more and less than 150%.・C: The substrate adhesion strength is 110% or more and less than 120%.・D: The substrate adhesion strength has not reached 110%.

(3)黑色矩陣(BM)硬化膜之製作針對以與上述(1)相同之程序獲得之乾燥塗佈膜，使用曝光機(ORC製作所公司製造之EXF-2829-F-00)，藉由高壓水銀燈(ORC製作所製造之ADH-3000M-F-N，無光學濾光片)，以40 mJ/cm² 經由具有圖案寬度8 μm之直線狀開口部之曝光遮罩進行圖案曝光(近接間隙180 μm)。其後，使用利用超純水調整至0.04質量%之KOH水溶液作為鹼顯影液，於室溫(23℃)下進行溶解時間之1.8倍時間之噴霧顯影(噴霧壓力：0.1 MPa)，進而利用超純水進行噴霧洗淨(噴霧壓力：0.1 MPa)而獲得BM膜。其後，於230℃之烘箱中進行30分鐘加熱硬化，而製作膜厚1.0 μm之BM硬化膜。(3) Production of black matrix (BM) cured film For the dry coating film obtained by the same procedure as in (1) above, an exposure machine (EXF-2829-F-00 manufactured by ORC Manufacturing Co., Ltd.) was used by high pressure The mercury lamp (ADH-3000M-FN manufactured by ORC, no optical filter) was subjected to pattern exposure (proximity gap 180 μm) through an exposure mask having a linear opening with a pattern width of 8 μm at 40 mJ/cm ² . Thereafter, a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water was used as an alkali developer, and spray development (spray pressure: 0.1 MPa) at a time 1.8 times longer than the dissolution time at room temperature (23°C) was performed. Pure water was spray-washed (spray pressure: 0.1 MPa) to obtain a BM film. Thereafter, heat curing was performed in an oven at 230° C. for 30 minutes to produce a BM cured film with a film thickness of 1.0 μm.

(4)BM線路線寬變化量之評價利用光學顯微鏡對上述BM膜及上述BM硬化膜之BM線路圖案之線寬進行測定，測定加熱硬化前後之線寬變化量。將其結果示於表2。(4) Evaluation of BM circuit line width change amount The line width of the BM line pattern of the BM film and the BM cured film was measured using an optical microscope, and the line width change amount before and after heat curing was measured. The results are shown in Table 2.

(5)BM線路線寬之評價對實施例6之BM膜測定線寬，結果較比較例1之BM膜增加了0.5 μm線寬。(5) Evaluation of the line width of the BM line The line width of the BM film of Example 6 was measured. As a result, the line width of the BM film of Comparative Example 1 was increased by 0.5 μm.

[表2] [Table 2]

如表2所示，本發明之感光性樹脂組合物(實施例1～8)含有有機矽乙烯系聚合物(d-1)，藉此加熱硬化後之基板密接性提高。進而，可實現使加熱硬化前後之線寬變化量縮小之控制，尤其是確認到藉由增加上述有機矽乙烯系聚合物(d-1)之添加量而線寬變化量減少。As shown in Table 2, the photosensitive resin composition of the present invention (Examples 1 to 8) contains an organosilicon polymer (d-1), whereby the substrate adhesion after heat curing is improved. Furthermore, it is possible to control the amount of change in line width before and after heat hardening, and it is confirmed that the amount of change in line width is reduced by increasing the addition amount of the above-mentioned organosilicon polymer (d-1).

相對於此，於比較例1中，由於完全不含有(d)有機矽化合物，故而基板密接性較低。又，可知於比較例2、3中，由於含有作為矽烷偶合劑之有機矽化合物(1)、(2)，故而基板密接性係A～B判定，與比較例1相比，基板密接性能得到提高。另一方面，關於BM線路線寬變化量，可知為與比較例1相同程度之大小，沒有特別之附加效果。On the other hand, in Comparative Example 1, since the (d) organosilicon compound is not contained at all, the substrate adhesion is low. In addition, it can be seen that in Comparative Examples 2 and 3, since the organosilicon compounds (1) and (2) as a silane coupling agent are contained, the substrate adhesion is judged by A to B, and the substrate adhesion performance is obtained as compared with Comparative Example 1. improve. On the other hand, the amount of change in the line width of the BM line is known to be about the same size as Comparative Example 1, and there is no particular additional effect.

另一方面，於比較例4中，藉由含有有機矽乙烯系聚合物(d-1)而基板密接性成為A判定，但由於不含有作為(a)鹼可溶性樹脂之具有羧基之環氧(甲基)丙烯酸酯樹脂，故而判明BM線路線寬變化量較大，利用有機矽乙烯系聚合物(d-1)之線寬變化抑制效果較小。On the other hand, in Comparative Example 4, the adhesiveness of the substrate was judged as A by containing the silicone polymer (d-1), but since it did not contain (a) an epoxy resin having a carboxyl group as an alkali-soluble resin ( Methacrylate resin, it is found that the BM line has a large line width change, and the effect of suppressing the line width change using the organosilicon polymer (d-1) is small.

相對於此，於實施例1～8中，發現藉由添加有機矽乙烯系聚合物(d-1)而基板密接性成為A判定，基板密接性能提高。進而，藉由除有機矽乙烯系聚合物(d-1)以外，亦含有作為(a)鹼可溶性樹脂之具有羧基之環氧(甲基)丙烯酸酯樹脂，而即便對於BM線路線寬，亦發現抑制加熱硬化時之線寬變化之效果。尤其是根據實施例1、4及5之結果之比較可知，可藉由有機矽乙烯系聚合物(d-1)之添加量來調整線寬變化量，亦可設為線寬基本上不會因增量而變化之程度。On the other hand, in Examples 1 to 8, it was found that the addition of the organosilicon polymer (d-1) resulted in the substrate adhesion being determined as A, and the substrate adhesion performance was improved. Furthermore, in addition to the silicone-based polymer (d-1), it also contains an epoxy (meth)acrylate resin having a carboxyl group as the (a) alkali-soluble resin, even for the BM line width, The effect of suppressing the change in line width during heat hardening was found. In particular, according to the comparison of the results of Examples 1, 4 and 5, it can be seen that the amount of change in line width can be adjusted by the amount of addition of the organosilicon polymer (d-1), and it can also be set that the line width does not substantially The degree of change due to increments.

根據以上之結果可知，藉由於含有具有羧基之環氧(甲基)丙烯酸酯樹脂之感光性樹脂組合物中添加有機矽乙烯系聚合物(d-1)，可實現基板密接性之提高，並且可調整為縮小加熱硬化時之線寬變化量之方向。伴隨著液晶面板之多樣化，BM裾部形狀之要求亦多樣化，亦可藉由熔合控制而調整BM裾部之弧度情況或錐形角度等。From the above results, it can be seen that by adding an organosilicon polymer (d-1) to the photosensitive resin composition containing an epoxy (meth)acrylate resin having a carboxyl group, the adhesion of the substrate can be improved, and It can be adjusted to reduce the direction of the line width change during heating and hardening. With the diversification of the liquid crystal panel, the requirements for the shape of the BM cover are also diversified, and the curvature or tapered angle of the BM cover can also be adjusted by fusion control.

本發明中之有機矽乙烯系聚合物(d-1)之作用係認為如下。首先，於不含有(d)有機矽化合物之情形時，基板密接力係基於分子間相互作用者，不可謂充分。又，認為於加熱硬化步驟中，於在升溫中超過樹脂成分之軟化溫度之階段發生樹脂流動，而導致較大之線寬變化。尤其是於含有碳黑之情形時，有塗膜之疏水性變高，基板密接力變差之傾向，又，由於充分吸收紫外光範圍～可見光範圍之光，故而曝光後塗膜內部之光硬化亦變得不充分，因此於加熱硬化步驟容易引起線寬變化。The role of the organosilicon polymer (d-1) in the present invention is considered as follows. First of all, when (d) organic silicon compound is not contained, the substrate adhesion is based on intermolecular interaction, which is not sufficient. In addition, it is considered that in the heat-hardening step, resin flow occurs at a stage where the softening temperature of the resin component is exceeded during the temperature increase, resulting in a large line width change. Especially in the case of containing carbon black, the hydrophobicity of the coating film tends to increase, and the substrate adhesion tends to be poor. In addition, since the light in the ultraviolet range to the visible range is fully absorbed, the light inside the coating film is hardened after exposure It also becomes inadequate, so the heat-hardening step is likely to cause line width changes.

相對於此，於含有(d)有機矽化合物之情形時，由於具有烷氧基矽烷基等含有矽原子之官能基，故而可與玻璃等無機材料基板之表面形成化學鍵。又，藉由該官能基與BM膜中之有機素材鍵結或相互作用，而於有機素材與無機材料基板之間搭橋，從而有助於提高基板密接力。在此方面上，與實施例1～8、比較例2～4共通。On the other hand, in the case of containing (d) an organosilicon compound, since it has a functional group containing a silicon atom such as an alkoxysilane group, it can form a chemical bond with the surface of an inorganic material substrate such as glass. In addition, by bonding or interacting with the organic material in the BM film, the functional group bridges between the organic material and the inorganic material substrate, thereby helping to improve the substrate adhesion. In this respect, it is common to Examples 1 to 8 and Comparative Examples 2 to 4.

(d)有機矽化合物之中，有機矽乙烯系聚合物(d-1)由於該聚合物於分子內具有複數個烷氧基矽烷基等含有矽原子之側鏈，故而可實現與無機材料基板之多點鍵結，而有助於提高基板密接性。進而，認為未與基板多點鍵結而殘留之含有矽原子之側鏈彼此於加熱硬化之升溫中產生自縮合反應而使交聯進行，從而相互鍵結而於膜內形成巨大之立體網狀結構(團簇)。認為藉由該立體網狀結構凝膠化而由熔合引起之線寬變化得到抑制。又，認為藉由為乙烯系聚合物，可於感光性樹脂組合物之塗膜內融合擴散，從而同樣地於塗膜內形成立體網狀結構，而有效地顯現出線寬變化之抑制。進而，認為藉由改變有機矽乙烯系聚合物(d-1)之添加量，亦可調整所形成之團簇之尺寸，而變得可實現線寬變化量之控制。尤其是認為藉由使用具有乙烯性不飽和基者作為(a)鹼可溶性樹脂，而曝光時之交聯點增加，軟化起始溫度變高。具有乙烯性不飽和基之樹脂中，藉由含有具有羧基之環氧(甲基)丙烯酸酯樹脂，除利用酯基之氫鍵結或偶極-偶極相互作用、芳香族環彼此之π-π相互作用以外，利用羧基之氫鍵結亦發揮作用，而樹脂之主鏈間之自由體積變少，而氧難以透過，因此認為聚合反應時之氧阻聚得到抑制，交聯進一步進行而由熔合引起之線寬變化變小。(d) Among the organosilicon compounds, the organosilicon polymer (d-1) has a side chain containing silicon atoms such as a plurality of alkoxysilyl groups in the molecule, so it can be realized with an inorganic material substrate. The multi-point bonding helps to improve the adhesion of the substrate. Furthermore, it is considered that the side chains containing silicon atoms remaining without multi-point bonding with the substrate generate self-condensation reaction during the temperature rise of heat hardening to cause crosslinking to proceed, thereby bonding each other to form a huge three-dimensional network in the film Structure (clusters). It is considered that the change in line width caused by fusion is suppressed by the gelation of the three-dimensional network structure. In addition, it is believed that by being an ethylene-based polymer, it can be fused and diffused in the coating film of the photosensitive resin composition, thereby similarly forming a three-dimensional network structure in the coating film, and effectively showing the suppression of line width variation. Furthermore, it is considered that by changing the amount of the silicone polymer (d-1) added, the size of the formed clusters can also be adjusted, thereby making it possible to control the amount of change in line width. In particular, it is considered that by using an ethylenically unsaturated group as the (a) alkali-soluble resin, the crosslinking point at the time of exposure increases, and the softening starting temperature becomes higher. Among resins having an ethylenic unsaturated group, by containing an epoxy (meth)acrylate resin having a carboxyl group, in addition to hydrogen bonding or dipole-dipole interaction using ester groups, π- between aromatic rings In addition to the π interaction, the hydrogen bonding by the carboxyl group also plays a role, and the free volume between the main chain of the resin becomes less, and oxygen is difficult to penetrate, so it is considered that the oxygen inhibition during polymerization is suppressed, and the crosslinking proceeds further. The line width change caused by fusion becomes smaller.

另一方面，於如比較例1～3般為並非聚合物之有機矽化合物即有機矽化合物(1)、(2)之情形時，原本之分子尺寸較小。因此，認為即便於加熱硬化之升溫中，產生與有機矽乙烯系聚合物(d-1)之情形相同次數之交聯反應，亦不至於形成團簇，結果軟化熔融開始，對於線寬變化量之影響變得微小。On the other hand, in the case of organosilicon compounds (1) and (2) that are organosilicon compounds that are not polymers as in Comparative Examples 1 to 3, the original molecular size is small. Therefore, it is considered that even if the crosslinking reaction occurs in the same number of times as in the case of the organosilicon vinyl polymer (d-1) during heating and heating, clusters are not formed, and as a result, softening and melting start, and the amount of change in line width The effect becomes small.

另一方面，認為即便為如比較例4般含有有機矽乙烯系聚合物(d-1)者，於不含有具有羧基之環氧(甲基)丙烯酸酯樹脂作為鹼可溶性樹脂之情形時，曝光時之交聯點亦變少，而於較基於含有矽原子之側鏈彼此之交聯反應起始之溫度低的溫度下熔合進行，而線寬變化量變大。On the other hand, it is considered that even if it contains an organosilicon polymer (d-1) as in Comparative Example 4, when it does not contain an epoxy (meth)acrylate resin having a carboxyl group as an alkali-soluble resin, it is exposed The number of cross-linking points at the time also becomes less, and fusion proceeds at a temperature lower than the temperature at which cross-linking reactions based on the side chains containing silicon atoms start, and the amount of line width change becomes larger.

如上所述，藉由使用本發明之感光性樹脂組合物，基板密接性提高，可控制加熱硬化時之線寬變化，而可形成高精細圖案。As described above, by using the photosensitive resin composition of the present invention, the adhesion of the substrate is improved, the change in line width during heat curing can be controlled, and a high-definition pattern can be formed.

10‧‧‧透明支持基板10‧‧‧Transparent support substrate

20‧‧‧像素20‧‧‧ pixels

30‧‧‧有機保護層30‧‧‧ organic protective layer

40‧‧‧無機氧化膜40‧‧‧Inorganic oxide film

50‧‧‧透明陽極50‧‧‧Transparent anode

51‧‧‧電洞注入層51‧‧‧Electron injection layer

52‧‧‧電洞傳輸層52‧‧‧Electric transmission layer

53‧‧‧發光層53‧‧‧luminous layer

54‧‧‧電子注入層54‧‧‧Electron injection layer

55‧‧‧陰極55‧‧‧Cathode

100‧‧‧有機EL元件100‧‧‧ organic EL element

500‧‧‧有機發光體500‧‧‧ organic luminous body

圖1係表示具備本發明之彩色濾光片之有機電致發光(有機EL)元件之一例的剖面概略圖。FIG. 1 is a schematic cross-sectional view showing an example of an organic electroluminescence (organic EL) device provided with a color filter of the present invention.

Claims

一種感光性樹脂組合物，其特徵在於：其係含有(a)鹼可溶性樹脂、(b)光聚合性單體、(c)光自由基聚合起始劑、(d)有機矽化合物、及(e)色料者，上述(a)鹼可溶性樹脂含有具有羧基之環氧(甲基)丙烯酸酯樹脂，且上述(d)有機矽化合物含有具有下述通式(1)所表示之重複單元之有機矽乙烯系聚合物(d-1)； [化1](式(1)中，R¹ 表示氫原子或可具有取代基之烷基，R² ～R⁴ 分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、可具有取代基之芳基、或可具有取代基之芳氧基，L表示2價連結基，x表示0或1)。A photosensitive resin composition, characterized in that it contains (a) alkali-soluble resin, (b) photopolymerizable monomer, (c) photoradical polymerization initiator, (d) organosilicon compound, and ( e) For colorants, the (a) alkali-soluble resin contains an epoxy (meth)acrylate resin having a carboxyl group, and the (d) organosilicon compound contains a repeating unit represented by the following general formula (1) Silicone polymer (d-1); [Chemical 1] (In formula (1), R ¹ represents a hydrogen atom or an alkyl group which may have a substituent, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, An aryl group which may have a substituent, or an aryloxy group which may have a substituent, L represents a divalent linking group, and x represents 0 or 1).

如請求項1之感光性樹脂組合物，其中上述(e)色料含有碳黑。The photosensitive resin composition according to claim 1, wherein the above-mentioned (e) color material contains carbon black.

一種硬化物，其係使如請求項1或2之感光性樹脂組合物硬化而成者。A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

一種黑色矩陣，其包含如請求項3之硬化物。A black matrix containing the hardened product as in claim 3.

一種圖像顯示裝置，其具有如請求項3之硬化物或如請求項4之黑色矩陣。An image display device having a hardened product as in claim 3 or a black matrix as in claim 4.