TW201520695A - Photo-sensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device and organic EL display device - Google Patents
Photo-sensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device and organic EL display device Download PDFInfo
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Abstract
Description
本發明是有關於一種感光性樹脂組成物(以下有時簡稱為「本發明的組成物」)。另外,本發明是有關於一種使用所述感光性樹脂組成物的硬化膜的製造方法、使感光性組成物硬化而成的硬化膜、使用所述硬化膜的各種圖像顯示裝置。 The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as "the composition of the present invention"). Further, the present invention relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing a photosensitive composition, and various image display devices using the cured film.
更詳細而言,本發明是有關於一種適於形成液晶顯示裝置、有機電致發光(有機EL(Electroluminescence))顯示裝置、積體電路元件、固體攝像元件等電子零件的平坦化膜、保護膜或層間絕緣膜的感光性樹脂組成物及使用其的硬化膜的製造方法。 More specifically, the present invention relates to a planarizing film and a protective film suitable for forming electronic components such as a liquid crystal display device, an organic electroluminescence (organic luminescence) display device, an integrated circuit device, and a solid-state imaging device. Or a photosensitive resin composition of an interlayer insulating film, and a method of producing a cured film using the same.
於有機EL顯示裝置或液晶顯示裝置等中設置有經圖案形成的層間絕緣膜。於所述層間絕緣膜的形成中,因用以獲得必要圖案形狀的步驟數少且可獲得充分的平坦性,故廣泛使用感光性樹脂組成物。 A patterned interlayer insulating film is provided in an organic EL display device, a liquid crystal display device, or the like. In the formation of the interlayer insulating film, since the number of steps for obtaining a necessary pattern shape is small and sufficient flatness can be obtained, a photosensitive resin composition is widely used.
針對所述顯示裝置中的層間絕緣膜,除絕緣性、耐溶劑 性、耐熱性、硬度以及氧化銦錫(Indium tin oxide,ITO)濺鍍適應性優異等硬化膜的物性以外,亦期望高透明性。因此,嘗試將透明性優異的丙烯酸系樹脂用作膜形成成分。例如,已知有專利文獻1~專利文獻3所記載者。 Insulation and solvent resistance for the interlayer insulating film in the display device High transparency is also desired in addition to the physical properties of the cured film such as heat resistance, heat resistance, hardness, and excellent indium tin oxide (ITO) sputtering compatibility. Therefore, an acrylic resin excellent in transparency has been tried as a film forming component. For example, those described in Patent Document 1 to Patent Document 3 are known.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2011-209681號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-209681
[專利文獻2]日本專利特開2011-221471號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-221471
[專利文獻3]日本專利特開2012-150494號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-150494
然而,專利文獻1及專利文獻2所記載的感光性樹脂組成物存在如下問題:於形成層間絕緣膜的微影(lithography)步驟中,當對感光性樹脂組成物層進行曝光繼而進行顯影時,感光性樹脂組成物層在暴露於顯影液中時自基板側剝落而使液晶顯示裝置製作的良率降低。 However, the photosensitive resin composition described in Patent Document 1 and Patent Document 2 has a problem in that, in the lithography step of forming the interlayer insulating film, when the photosensitive resin composition layer is exposed and then developed, When the photosensitive resin composition layer is peeled off from the substrate side when exposed to the developer, the yield of the liquid crystal display device is lowered.
另一方面,於專利文獻3中,藉由對感光性樹脂組成物添加矽烷偶合劑而改善基板與感光性樹脂組成物層的密著性。然而,於專利文獻3所記載的矽烷偶合劑中的烷氧基矽烷基中,藉由烷氧化物基水解而Si-OH與基板界面的OH基形成氫鍵,且其後於烘烤時進行脫水縮合反應而達成表面修飾。然而,於專利文獻3中存在如下問題:因與基板界面進行的氫鍵結不充分,故矽 烷偶合劑無法存在於界面附近,基板與膜未遍及整個面而均勻密著,於經表面修飾的面與未經表面修飾的面之間產生不均。而且,引用文獻3所記載的矽烷偶合劑為低分子成分,因此亦存在感光性樹脂組成物的膜軟質化且因過熱而錐角減少、孔徑擴大,結果有損高解析性的問題。 On the other hand, in Patent Document 3, the adhesion of the substrate to the photosensitive resin composition layer is improved by adding a decane coupling agent to the photosensitive resin composition. However, in the alkoxyalkylene group in the decane coupling agent described in Patent Document 3, the OH group at the interface between the Si-OH and the substrate is hydrogen-bonded by hydrolysis of the alkoxide group, and then it is carried out at the time of baking. Dehydration condensation reaction to achieve surface modification. However, in Patent Document 3, there is a problem in that hydrogen bonding due to the interface with the substrate is insufficient, so that The alkane coupling agent cannot exist in the vicinity of the interface, and the substrate and the film are not uniformly spread over the entire surface, and unevenness occurs between the surface-modified surface and the surface which is not surface-modified. In addition, since the decane coupling agent described in the literature 3 is a low molecular component, the film of the photosensitive resin composition is softened, and the taper angle is reduced by the overheating, and the pore diameter is enlarged, resulting in a problem of high resolution.
本申請案發明解決所述課題,且目的在於提供一種於顯影步驟時感光性樹脂組成物層與基底基板的密著性優異、且於烘烤步驟時感光性樹脂組成物不會熱熔融而錐角高的感光性樹脂組成物、以及使用所述感光性樹脂組成物的硬化膜的製造方法、硬化膜、液晶顯示裝置及有機EL顯示裝置。 The present invention has been made in view of the above problems, and an object of the invention is to provide an adhesive which is excellent in adhesion between a photosensitive resin composition layer and a base substrate in a developing step, and which is not thermally melted in a baking step. A photosensitive resin composition having a high angle, a method for producing a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, and an organic EL display device.
本申請案發明者根據所述狀況進行研究,結果發現:藉由在感光性樹脂組成物中調配具有烷氧基矽烷基及既定的氫鍵結性基的化合物((S)成分)可解決所述課題。 The inventors of the present invention conducted research based on the above-mentioned conditions, and found that the compound ((S) component) having an alkoxyalkyl group and a predetermined hydrogen bonding group can be prepared by disposing a photosensitive resin composition. The subject.
具體而言,藉由以下的解決手段<1>、較佳為解決手段<2>~解決手段<17>解決了所述課題。 Specifically, the above problem is solved by the following solution <1>, preferably by means <2> to resolution <17>.
<1>一種感光性樹脂組成物,含有:(A-1)包含滿足下述(1)及(2)的至少一個的聚合物的聚合物成分,(1)含有(a1-1)具有酸基經酸分解性基保護的基團的結構單元、及(a1-2)具有交聯性基的結構單元的聚合物,(2)含有(a1-1)具有酸基經酸分解性基保護的基團的結構
單元的聚合物、及含有(a1-2)具有交聯性基的結構單元的聚合物;(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物;(B-1)光酸產生劑;以及(C-1)溶劑;通式(1)
通式(1)中,R1及R2分別獨立地表示碳數1~4的烷基,n表示0~2的整數;L1表示單鍵或2價的連結基;X1表示-S-或-NH-,R3表示1價的有機基;通式(2)
通式(2)中,R5及R6分別獨立地表示碳數1~4的烷基,n表示0~2的整數;L2表示單鍵或2價的連結基;X2表示-S-或-NH-,A表示包含碳原子及氮原子的雜環。 In the formula (2), R 5 and R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L 2 represents a single bond or a divalent linking group; and X 2 represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom.
<2>一種感光性樹脂組成物,含有:(A-2)包含滿足下述(1)及(2)的至少一個的聚合物的聚合物成分,(1)含有(a2-1)具有酸基的結構單元、及(a2-2)具有交聯性基的結構單元的聚合物,(2)含有(a2-1)具有酸基的結構單元的聚合物、及含有(a2-2)具有交聯性基的結構單元的聚合物;(B-2)醌二疊氮化合物;以及(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物;(C-2)溶劑;通式(1)
通式(1)中,R1及R2分別獨立地表示碳數1~4的烷基,n
表示0~2的整數;L1表示單鍵或2價的連結基;X1表示-S-或-NH-,R3表示1價的有機基;通式(2)
通式(2)中,R5及R6分別獨立地表示碳數1~4的烷基,n表示0~2的整數;L2表示單鍵或2價的連結基;X2表示-S-或-NH-,A表示包含碳原子及氮原子的雜環。 In the formula (2), R 5 and R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L 2 represents a single bond or a divalent linking group; and X 2 represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom.
<3>一種感光性樹脂組成物,含有:(A-3)聚合性單體;(B-3)光聚合起始劑;(A-4)包含滿足下述(1)及(2)的至少一個的聚合物的聚合物成分,(1)含有(a4-1)具有酸基的結構單元、及(a4-2)具有交聯性基的結構單元的聚合物,(2)含有(a4-1)具有酸基的結構單元的聚合物、及含有(a4-2)具有交聯性基的結構單元的聚合物;(S)通式(1)所表示的化合物及/或通式(2)所表示的化
合物;以及(C-3)溶劑;通式(1)
通式(1)中,R1及R2分別獨立地表示碳數1~4的烷基,n表示0~2的整數;L1表示單鍵或2價的連結基;X1表示-S-或-NH-,R3表示1價的有機基;通式(2)
通式(2)中,R5及R6分別獨立地表示碳數1~4的烷基,n表示0~2的整數;L2表示單鍵或2價的連結基;X2表示-S-或-NH-,A表示包含碳原子及氮原子的雜環。 In the formula (2), R 5 and R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L 2 represents a single bond or a divalent linking group; and X 2 represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom.
<4>如<1>至<3>中任一項所記載的感光性樹脂組成物,其中相對於感光性樹脂組成物的固體成分,(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物的調配量為0.1質量%~20質量%。 The photosensitive resin composition of any one of the above-mentioned <1>, and the compound of the formula (1) and / / (S) with respect to the solid component of the photosensitive resin composition. The compounding amount of the compound represented by the formula (2) is from 0.1% by mass to 20% by mass.
<5>如<1>至<4>中任一項所記載的感光性樹脂組成物,其中通式(1)中的R3表示碳數1~10的烷基或碳數6~20的芳基。 <5><1> to <4> described in any one of photosensitive resin composition, wherein the general formula R (1) 3 represents alkyl having 1 to 10 carbon atoms or 6 to 20 Aryl.
<6>如<1>至<5>中任一項所記載的感光性樹脂組成物,其中通式(2)中的R4表示吡啶基或噻唑基。 <6> The <1> to <5> described in any one of photosensitive resin composition, wherein the general formula R (2) represents a 4-pyridyl or thiazolyl.
<7>如<1>至<6>中任一項所記載的感光性樹脂組成物,其中通式(1)中的L1或通式(2)中的L2分別為碳數2~8的伸烷基。 <7> The <1> to <6> The photosensitive resin composition according to any one of claims, wherein the carbon number of L 2 respectively Formula 1 or Formula L (2) (1) 2 to 8 alkylene.
<8>如<1>至<7>中任一項所記載的感光性樹脂組成物,其中(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物的分子量分別為1000以下。 The photosensitive resin composition of any one of the above-mentioned (1), and (S) the compound represented by General formula (1) and / or the compound represented by General formula (2). The molecular weights are each 1000 or less.
<9>如<1>至<8>中任一項所記載的感光性樹脂組成物,其中交聯性基為選自環氧基、氧雜環丁基及-NH-CH2-O-R(R為氫原子或碳數1~20的烷基)所表示的基團中的至少一種。 The photosensitive resin composition as described in any one of <1> to <8>, wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR ( R is at least one of a group represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
<10>如<1>、<4>~<9>中任一項所記載的感光性樹脂組成物,其中酸分解性基為具有以縮醛的形式受到保護的結構的基團。 The photosensitive resin composition as described in any one of <1>, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.
<11>如<1>~<10>中任一項所記載的感光性樹脂組成
物,其中(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物為下述(S-1)~(S-2)、(S-9)及(S-14)~(S-16)所表示的化合物的任一者;式中,Me表示甲基,Et表示乙基;
<12>一種硬化膜的製造方法,包括:(1)將如<1>至<11>中任一項所記載的感光性樹脂組成物塗佈於基板上的步驟;(2)自所塗佈的感光性樹脂組成物中去除溶劑的步驟;(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟;(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟;以及 (5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 <12> A method for producing a cured film, comprising: (1) a step of applying the photosensitive resin composition according to any one of <1> to <11> to a substrate; a step of removing a solvent in the photosensitive resin composition of the cloth; (3) a step of exposing the photosensitive resin composition from which the solvent is removed by using actinic rays; (4) a composition of the exposed photosensitive resin using an aqueous developing solution a step of developing the object; (5) A post-baking step of thermally curing the developed photosensitive resin composition.
<13>如<12>所記載的硬化膜的製造方法,其中於顯影步驟後、後烘烤步驟前,包括(6)對經顯影的感光性樹脂組成物進行整面曝光的步驟。 <13> The method for producing a cured film according to <12>, which comprises, after the developing step and before the post-baking step, a step of (6) performing a full-surface exposure of the developed photosensitive resin composition.
<14>如<12>或<13>所記載的硬化膜的製造方法,其包括:對具有利用後烘烤步驟進行熱硬化而得的硬化膜的基板進行乾式蝕刻的步驟。 <14> The method for producing a cured film according to <13>, which comprises the step of dry etching a substrate having a cured film obtained by thermal curing using a post-baking step.
<15>一種硬化膜,其是使如<1>至<11>中任一項所記載的感光性樹脂組成物硬化而成,或藉由如<12>至<14>中任一項所記載的硬化膜的製造方法而形成。 <15> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <11>, or by any one of <12> to <14> It is formed by the manufacturing method of the hardened film described.
<16>如<15>所記載的硬化膜,其為層間絕緣膜。 <16> The cured film according to <15>, which is an interlayer insulating film.
<17>一種有機EL顯示裝置或液晶顯示裝置,具有如<15>或<16>所記載的硬化膜。 <17> An organic EL display device or a liquid crystal display device comprising the cured film according to <15> or <16>.
根據本發明,可提供一種於顯影步驟時感光性樹脂組成物層與基底基板的密著性優異、且於烘烤步驟時感光性樹脂組成物層不會熱熔融而錐角高的感光性樹脂組成物、硬化膜的製造方法、硬化膜、液晶顯示裝置及有機EL顯示裝置。 According to the present invention, it is possible to provide a photosensitive resin which is excellent in adhesion between the photosensitive resin composition layer and the base substrate in the developing step, and which does not thermally melt the photosensitive resin composition layer in the baking step and has a high taper angle. A composition, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device.
1‧‧‧TFT(薄膜電晶體) 1‧‧‧TFT (thin film transistor)
2‧‧‧配線 2‧‧‧Wiring
3‧‧‧絕緣膜 3‧‧‧Insulation film
4‧‧‧平坦化膜 4‧‧‧Flat film
5‧‧‧第一電極 5‧‧‧First electrode
6‧‧‧玻璃基板 6‧‧‧ glass substrate
7‧‧‧接觸孔 7‧‧‧Contact hole
8‧‧‧絕緣膜 8‧‧‧Insulation film
10‧‧‧液晶顯示裝置 10‧‧‧Liquid crystal display device
12‧‧‧背光單元 12‧‧‧Backlight unit
14、15‧‧‧玻璃基板 14, 15‧‧‧ glass substrate
16‧‧‧TFT 16‧‧‧TFT
17‧‧‧硬化膜 17‧‧‧ hardened film
18‧‧‧接觸孔 18‧‧‧Contact hole
19‧‧‧ITO透明電極 19‧‧‧ITO transparent electrode
20‧‧‧液晶 20‧‧‧LCD
22‧‧‧彩色濾光片 22‧‧‧Color filters
100‧‧‧基板 100‧‧‧Substrate
圖1表示液晶顯示裝置的一例的構成概念圖。其表示液晶顯示裝置中的主動式矩陣基板的示意性剖面圖,具有作為層間 絕緣膜的硬化膜17。 FIG. 1 is a conceptual diagram showing an example of a liquid crystal display device. It shows a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device, having interlayer A cured film 17 of an insulating film.
圖2表示有機EL顯示裝置的一例的構成概念圖。其表示底部發光(bottom emission)型的有機EL顯示裝置中的基板的示意性剖面圖,具有平坦化膜4。 FIG. 2 is a conceptual diagram showing an example of an organic EL display device. It shows a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarizing film 4.
圖3為表示本發明的推測機制的一例的概略圖。 Fig. 3 is a schematic view showing an example of a speculative mechanism of the present invention.
圖4為表示本發明的推測機制的另一例的概略圖。 Fig. 4 is a schematic view showing another example of the estimation mechanism of the present invention.
以下,對本發明的內容加以詳細說明。以下記載的構成要件的說明有時是根據本發明的具代表性的實施態樣來進行,但本發明不限定於此種實施態樣。另外,本申請案說明書中,「~」是以包括其前後所記載的數值作為下限值及上限值的含意而使用。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be carried out in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.
於本說明書中的基團(原子團)的表述中,未記載經取代及未經取代的表述包含不具有取代基的基團(原子團),並且亦包含具有取代基的基團(原子團)。例如所謂「烷基」,不僅包含不具有取代基的烷基(未經取代的烷基),而且亦包含具有取代基的烷基(經取代的烷基)。 In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
再者,本說明書中,「(甲基)丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯,「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸,「(甲基)丙烯醯基」表示丙烯醯基及甲基丙烯醯基。 In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene oxime. And methacryl oxime.
本發明的感光性樹脂組成物含有聚合物成分、後述的(S)成分及溶劑,例如可藉由將感光性樹脂組成物塗佈於基板 上,將溶劑去除,利用光化射線進行曝光,利用水性顯影液(較佳為鹼顯影液)進行顯影並進行熱硬化,而製成硬化膜。 The photosensitive resin composition of the present invention contains a polymer component, a component (S) to be described later, and a solvent, and for example, a photosensitive resin composition can be applied to a substrate. The solvent is removed, exposed to actinic rays, developed with an aqueous developing solution (preferably an alkali developing solution), and thermally cured to form a cured film.
根據本發明,可提供一種於顯影時感光性樹脂組成物層與基板的密著性良好、且烘烤後的錐形形狀優異的感光性樹脂組成物。 According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in adhesion between a photosensitive resin composition layer and a substrate during development and which has a tapered shape after baking.
所述機制雖為推測,但考慮為如下所述。 Although the mechanism is speculative, it is considered as follows.
於本發明中,當(S)成分為通式(1)所表示的化合物時,如圖3中示出的一例所示,硫脲部位因鹼性度高,故容易與基板100的OH基形成氫鍵。即,硫脲部位的硫原子與基板的OH基的氫原子進行氫鍵結,且-NH-R3部位與基板的OH基的氧原子形成氫鍵,結果,(S)成分可緻密地存在於界面上。 In the present invention, when the component (S) is a compound represented by the formula (1), as shown in the example shown in FIG. 3, since the thiourea portion has a high basicity, it is easy to form an OH group with the substrate 100. Hydrogen bonds are formed. That is, the sulfur atom at the thiourea site is hydrogen-bonded to the hydrogen atom of the OH group of the substrate, and the -NH-R 3 moiety forms a hydrogen bond with the oxygen atom of the OH group of the substrate, and as a result, the (S) component can be densely present. On the interface.
另一方面,當(S)成分為通式(2)所表示的化合物時,如圖4中示出的一例所示,-C(=O)-基的氧原子與基板的OH基形成氫鍵,且R4所表示的雜環的雜原子(圖4中為氮原子)與基板100的OH基的氫原子形成氫鍵,結果,(S)成分可緻密地存在於界面上。 On the other hand, when the (S) component is a compound represented by the formula (2), as shown in the example shown in FIG. 4, the oxygen atom of the -C(=O)- group forms hydrogen with the OH group of the substrate. The bond, and the hetero atom of the hetero ring represented by R 4 (a nitrogen atom in FIG. 4) forms a hydrogen bond with the hydrogen atom of the OH group of the substrate 100, and as a result, the (S) component can be densely present at the interface.
進而認為,藉由通式(1)及通式(2)中的烷氧基矽烷基的烷氧化物水解而Si-OH與基板界面的OH基形成氫鍵後,於烘烤時進行脫水縮合反應而於表面固定化,從而密著性提高。藉此,Si-OH與基板界面的OH基的氫鍵結充分,故認為可無不均而均勻地進行表面修飾。 Further, it is considered that the hydrocarbyl group of the alkoxyalkylalkyl group in the general formula (1) and the general formula (2) is hydrolyzed to form a hydrogen bond between the Si-OH and the OH group at the interface of the substrate, and then dehydrated and condensed at the time of baking. The reaction is fixed on the surface, so that the adhesion is improved. Thereby, since the hydrogen bonding of the OH group at the interface of Si-OH and the substrate is sufficient, it is considered that the surface modification can be performed uniformly without unevenness.
而且認為,藉由通式(1)中的硫脲部位及通式(2)中的脲部位為鹼性而對交聯基起到硬化觸媒性的作用,因此,可促進硬 化速度,並可防止過熱所致的錐角的降低。本發明者進行研究的結果得知,於所述鹼性度高的化合物存在下,(A-1)中的交聯性基與羧酸容易反應,從而交聯密度提高。 Further, it is considered that the thiourea moiety in the general formula (1) and the urea moiety in the general formula (2) are alkaline and act to harden the cross-linking group, thereby promoting hardening. Speed and prevent the reduction of the taper angle caused by overheating. As a result of investigation, the inventors have found that the crosslinkable group in (A-1) reacts easily with the carboxylic acid in the presence of the compound having a high basicity, and the crosslinking density is improved.
以下,以第1態樣~第3態樣的順序對本發明的組成物加以說明。本發明的組成物的第1態樣及第2態樣可較佳地用作正型的感光性樹脂組成物。本發明的組成物的第3態樣可較佳地用作負型的感光性樹脂組成物。 Hereinafter, the composition of the present invention will be described in the order of the first aspect to the third aspect. The first aspect and the second aspect of the composition of the present invention can be preferably used as a positive photosensitive resin composition. The third aspect of the composition of the present invention can be preferably used as a negative photosensitive resin composition.
[本發明的第1態樣] [First aspect of the invention]
本發明的第1態樣的感光性組成物的特徵在於含有:(A-1)包含滿足下述(1)及(2)的至少一個的聚合物的聚合物成分,(1)含有(a1)具有酸基經酸分解性基保護的基團的結構單元、及(a2)具有交聯性基的結構單元的聚合物,(2)含有(a1)具有酸基經酸分解性基保護的基團的結構單元的聚合物、及含有(a2)具有交聯性基的結構單元的聚合物;(S)通式(1)及/或通式(2)所表示的化合物;(B-1)光酸產生劑;以及(C-1)溶劑。 The photosensitive composition of the first aspect of the present invention is characterized in that (A-1) contains a polymer component which satisfies at least one of the following (1) and (2), and (1) contains (a1) a structural unit having a group protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) containing (a1) having an acid group protected by an acid-decomposable group a polymer of a structural unit of a group, and a polymer containing (a2) a structural unit having a crosslinkable group; (S) a compound represented by the formula (1) and/or the formula (2); (B- 1) a photoacid generator; and (C-1) a solvent.
通式(1)[化8]
通式(2)
(通式(1)中,R1及R2分別獨立地表示碳數1~4的烷基,n表示0~2的整數。L1表示單鍵或2價的連結基。X1表示-S-或-NH-,R3表示1價的有機基。 (In the formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L 1 represents a single bond or a divalent linking group. X 1 represents - S- or -NH-, R 3 represents a monovalent organic group.
通式(2)中,R5及R6分別獨立地表示碳數1~4的烷基,n表示0~2的整數。L2表示單鍵或2價的連結基。X2表示-S-或-NH-,A表示包含碳原子及氮原子的雜環。) In the formula (2), R 5 and R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L 2 represents a single bond or a divalent linking group. X 2 represents -S- or -NH-, and A represents a hetero ring containing a carbon atom and a nitrogen atom. )
以下,對本發明的組成物的第1態樣加以詳細說明。 Hereinafter, the first aspect of the composition of the present invention will be described in detail.
<(A-1)聚合物成分> <(A-1) polymer component>
本發明的組成物含有以下聚合物的至少一種作為聚合物成分:含有(a1-1)具有酸基經酸分解性基保護的基團的結構單元及(a1-2)具有交聯性基的結構單元的聚合物(1)、以及含有(a1-1) 具有酸基經酸分解性基保護的基團的結構單元的聚合物及含有(a1-2)具有交聯性基的結構單元的聚合物(2)。進而,亦可含有該等以外的聚合物。本發明的(A-1)聚合物成分只要無特別說明,則是指除了所述聚合物(1)及/或所述聚合物(2)以外,含有視需要而添加的其他聚合物。 The composition of the present invention contains at least one of the following polymers as a polymer component: a structural unit containing (a1-1) a group having an acid group which is protected by an acid-decomposable group and (a1-2) having a crosslinkable group Polymer (1) of structural unit, and contains (a1-1) A polymer having a structural unit of a group having an acid group protected by an acid-decomposable group and a polymer (2) containing (a1-2) a structural unit having a crosslinkable group. Further, a polymer other than these may be contained. The polymer component (A-1) of the present invention means that other polymer added as needed, in addition to the polymer (1) and/or the polymer (2), unless otherwise specified.
於包含(2)含有(a1-1)具有酸基經酸分解性基保護的基團的結構單元的聚合物及含有(a1-2)具有交聯性基的結構單元的聚合物的情形時,含有(a1-1)具有酸基經酸分解性基保護的基團的結構單元的聚合物與含有(a1-2)具有交聯性基的結構單元的聚合物之比例較佳為95:5~5:95,更佳為80:20~20:80,進而佳為70:30~30:70。 In the case of a polymer comprising (2) a structural unit containing (a1-1) a structural group having an acid group-protected group, and a polymer containing (a1-2) a structural unit having a crosslinkable group The ratio of the polymer containing (a1-1) a structural unit having a group having an acid group which is protected by an acid-decomposable group to the polymer containing (a1-2) a structural unit having a crosslinkable group is preferably 95: 5~5:95, better 80:20~20:80, and then 70:30~30:70.
(A-1)聚合物成分較佳為加成聚合型的樹脂,更佳為含有來源於(甲基)丙烯酸及/或其酯的結構單元的聚合物。再者,亦可含有來源於(甲基)丙烯酸及/或其酯的結構單元以外的結構單元、例如來源於苯乙烯的結構單元或來源於乙烯系化合物的結構單元等。再者,將「來源於(甲基)丙烯酸及/或其酯的結構單元」亦稱為「丙烯酸系結構單元」。 The polymer component (A-1) is preferably an addition polymerization type resin, more preferably a polymer containing a structural unit derived from (meth)acrylic acid and/or an ester thereof. Further, a structural unit other than the structural unit derived from (meth)acrylic acid and/or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound may be contained. Further, the "structural unit derived from (meth)acrylic acid and/or its ester" is also referred to as "acrylic structural unit".
<<(a1-1)具有酸基經酸分解性基保護的基團的結構單元>> <<(a1-1) Structural unit of a group having an acid group protected by an acid-decomposable group>>
(A-1)聚合物成分至少含有具有酸基經酸分解性基保護的基團的結構單元(a1-1)。藉由(A-1)聚合物成分含有結構單元(a1-1),可製成感度極高的感光性樹脂組成物。 (A-1) The polymer component contains at least a structural unit (a1-1) having a group in which an acid group is protected by an acid-decomposable group. By containing the structural unit (a1-1) in the polymer component (A-1), a photosensitive resin composition having an extremely high sensitivity can be obtained.
本發明中的「酸基經酸分解性基保護的基團」可使用作為酸基及酸分解性基而公知的基團,並無特別限定。 In the present invention, the "acid group-protected group which is protected by an acid-decomposable group" is not particularly limited as long as it is a group known as an acid group and an acid-decomposable group.
具體的酸基可較佳地列舉羧基及酚性羥基。 Specific acid groups are preferably exemplified by a carboxyl group and a phenolic hydroxyl group.
另外,具體的酸分解性基可使用:藉由酸而相對較容易分解的基團(例如後述的酯結構、四氫吡喃酯基或四氫呋喃酯基等縮醛系官能基)、或藉由酸而相對較難分解的基團(例如第三丁酯基等三級烷基、碳酸第三丁酯基等碳酸三級烷基酯基)。 Further, as the specific acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group described later), or A group which is relatively difficult to decompose by acid (for example, a tertiary alkyl group such as a tert-butyl group such as a tert-butyl group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
結構單元(a1-1)較佳為具有經酸分解性基保護的保護羧基的結構單元、或具有經酸分解性基保護的保護酚性羥基的結構單元。 The structural unit (a1-1) is preferably a structural unit having a carboxyl group protected by an acid-decomposable group or a structural unit having a phenolic hydroxyl group protected by an acid-decomposable group.
以下,依序對具有經酸分解性基保護的保護羧基的結構單元(a1-1-1)、及具有經酸分解性基保護的保護酚性羥基的結構單元(a1-1-2)分別加以說明。 Hereinafter, the structural unit (a1-1-1) having a protective carboxyl group protected by an acid-decomposable group and the structural unit (a1-1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group are respectively sequentially Explain.
<<<(a1-1-1)具有經酸分解性基保護的保護羧基的結構單元>>> <<<(a1-1-1) Structural unit having a protected carboxyl group protected by an acid-decomposable group>>>
結構單元(a1-1-1)為具有藉由以下將詳細說明的酸分解性基將具有羧基的結構單元的羧基保護而成的保護羧基的結構單元。 The structural unit (a1-1-1) is a structural unit having a protective carboxyl group which is obtained by protecting a carboxyl group of a structural unit having a carboxyl group by an acid-decomposable group described below in detail.
具有可用於所述結構單元(a1-1-1)的所述羧基的結構單元並無特別限制,可使用公知的結構單元。例如可列舉:來源於不飽和單羧酸、不飽和二羧酸、不飽和三羧酸等分子中具有至少1個羧基的不飽和羧酸等的結構單元(a1-1-1-1)。 The structural unit having the carboxyl group usable in the structural unit (a1-1-1) is not particularly limited, and a known structural unit can be used. For example, a structural unit (a1-1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid may be mentioned.
以下,對被用作所述具有羧基的結構單元的結構單元 (a1-1-1-1)加以說明。 Hereinafter, a structural unit used as the structural unit having a carboxyl group is used. (a1-1-1-1) is explained.
<<<<(a1-1-1-1)來源於分子中具有至少1個羧基的不飽和羧酸等的結構單元>>>> <<<<(a1-1-1-1) is derived from a structural unit of an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>>
本發明中所用的不飽和羧酸可使用以下所列舉般的不飽和羧酸。 As the unsaturated carboxylic acid used in the present invention, an unsaturated carboxylic acid as exemplified below can be used.
即,不飽和單羧酸例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸、α-氯丙烯酸、肉桂酸、2-(甲基)丙烯醯氧基乙基-琥珀酸、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-鄰苯二甲酸等。 That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloxyethyl-succinic acid, and 2-(methyl group). Propylene methoxyethyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl-phthalic acid, and the like.
另外,不飽和二羧酸例如可列舉:馬來酸、富馬酸、衣康酸、檸康酸、中康酸等。 Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
另外,用於獲得具有羧基的結構單元的不飽和多元羧酸亦可為其酸酐。具體可列舉:馬來酸酐、衣康酸酐、檸康酸酐等。另外,不飽和多元羧酸亦可為多元羧酸的單(2-甲基丙烯醯氧基烷基)酯,例如可列舉:琥珀酸單(2-丙烯醯氧基乙基)酯、琥珀酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯等。進而,不飽和多元羧酸亦可為其兩末端二羧基聚合物的單(甲基)丙烯酸酯,例如可列舉:ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。另外,不飽和羧酸亦可使用:丙烯酸-2-羧基乙酯、甲基丙烯酸-2-羧基乙酯、馬來酸單烷基酯、富馬酸單烷基酯、4-羧基苯乙烯等。 Further, the unsaturated polycarboxylic acid used to obtain a structural unit having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and succinic acid. Mono(2-methylpropenyloxyethyl)ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Wait. Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4-carboxystyrene, etc. may be used. .
其中,就顯影性的觀點而言,為了形成所述結構單元(a1-1-1-1),較佳為使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基-琥珀酸、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-鄰苯二甲酸或不飽和多元羧酸的酸酐等,更佳為使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸。 Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1-1), acrylic acid, methacrylic acid, 2-(meth)acryloyloxyethyl-amber is preferably used. More preferably, acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl-phthalic acid or an anhydride of an unsaturated polycarboxylic acid, etc. To use acrylic acid, methacrylic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid.
結構單元(a1-1-1-1)可由單獨一種所構成,亦可由兩種以上構成。 The structural unit (a1-1-1-1) may be composed of a single type or two or more types.
<<<<可用於結構單元(a1-1-1)的酸分解性基>>>> <<<< Acid decomposable group available for structural unit (a1-1-1)>>>>
可用於結構單元(a1-1-1)的所述酸分解性基可使用上文所述的酸分解性基。 The acid-decomposable group which can be used for the structural unit (a1-1-1) can use the acid-decomposable group described above.
該些酸分解性基中,較佳為具有以縮醛的形式保護酸分解性基的結構的基團。例如,就感光性樹脂組成物的基本物性、特別是感度或圖案形狀、接觸孔的形成性、感光性樹脂組成物的保存穩定性的觀點而言,較佳為以縮醛的形式保護羧基的保護羧基。進而,就感度的觀點而言,更佳為以通式(a1-10)所表示的縮醛的形式保護羧基的保護羧基。再者,於為以下述通式(a1-10)所表示的縮醛的形式保護羧基的保護羧基的情形時,保護羧基總體成為-(C=O)-O-CR101R102(OR103)的結構。 Among these acid-decomposable groups, a group having a structure for protecting an acid-decomposable group in the form of an acetal is preferred. For example, from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity or pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition, it is preferred to protect the carboxyl group in the form of an acetal. Protect the carboxyl group. Further, from the viewpoint of sensitivity, it is more preferred to protect the carboxyl group from protecting the carboxyl group in the form of an acetal represented by the formula (a1-10). Further, in the case where the protective carboxyl group of the carboxyl group is protected in the form of an acetal represented by the following general formula (a1-10), the protective carboxyl group as a whole becomes -(C=O)-O-CR 101 R 102 (OR 103 )Structure.
通式(a1-10)[化10]
(式(a1-10)中,R101及R102分別獨立地表示氫原子或烷基,其中,將R101與R102均為氫原子的情形除外。R103表示烷基。R101或R102與R103亦可連結而形成環狀醚) (In the formula (a1-10), R 101 and R 102 each independently represent a hydrogen atom or an alkyl group, wherein R 101 and R 102 are each a hydrogen atom. R 103 represents an alkyl group. R 101 or R 102 and R 103 may also be linked to form a cyclic ether)
所述通式(a1-10)中,R101~R103分別獨立地表示氫原子或烷基,所述烷基可為直鏈狀、分支鏈狀、環狀的任一種。此處,R101及R102兩者表示氫原子的情況不存在,R101及R102的至少一個表示烷基。 In the above formula (a1-10), R 101 to R 103 each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, the case where both R 101 and R 102 represent a hydrogen atom is absent, and at least one of R 101 and R 102 represents an alkyl group.
所述直鏈狀或分支鏈狀的烷基較佳為碳數1~12,更佳為碳數1~6,進而佳為碳數1~4。具體可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、新戊基、正己基、2,3-二甲基-2-丁基(thexyl)、正庚基、正辛基、2-乙基己基、正壬基、正癸基等。 The linear or branched alkyl group is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and more preferably a carbon number of 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2,3 - dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.
所述通式(a1-10)中,R101~R103分別獨立地表示氫原子或烷基。所述烷基可為直鏈狀、分支鏈狀、環狀的任一種。此處,R101及R102兩者表示氫原子的情況不存在,R101及R102的至少一個表示烷基。 In the above formula (a1-10), R 101 to R 103 each independently represent a hydrogen atom or an alkyl group. The alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, the case where both R 101 and R 102 represent a hydrogen atom is absent, and at least one of R 101 and R 102 represents an alkyl group.
所述直鏈狀或分支鏈狀的烷基較佳為碳數1~12,更佳為碳數 1~6,進而佳為碳數1~4。具體可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、新戊基、正己基、2,3-二甲基-2-丁基(thexyl)、正庚基、正辛基、2-乙基己基、正壬基、正癸基等。 The linear or branched alkyl group preferably has a carbon number of 1 to 12, more preferably a carbon number. 1~6, and then the carbon number is 1~4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2,3 - dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.
所述環狀烷基較佳為碳數3~12,更佳為碳數4~8,進而佳為碳數4~6。所述環狀烷基例如可列舉:環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異冰片基等。 The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and further preferably has a carbon number of 4 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, and the like.
所述烷基亦可具有取代基,取代基可例示鹵素原子、芳基、烷氧基。於具有鹵素原子作為取代基的情形時,R101、R102、R103成為鹵代烷基,於具有芳基作為取代基的情形時,R101、R102、R103成為芳烷基。 The alkyl group may have a substituent, and the substituent may, for example, be a halogen atom, an aryl group or an alkoxy group. When a halogen atom is used as a substituent, R 101 , R 102 and R 103 are a halogenated alkyl group, and when an aryl group is used as a substituent, R 101 , R 102 and R 103 are aralkyl groups.
所述鹵素原子可例示:氟原子、氯原子、溴原子、碘原子,該等中,較佳為氟原子或氯原子。 The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these, a fluorine atom or a chlorine atom is preferred.
另外,所述芳基較佳為碳數6~20的芳基,更佳為碳數6~12,具體可例示苯基、α-甲基苯基、萘基等,經芳基取代的烷基總體、即芳烷基可例示:苄基、α-甲基苄基、苯乙基、萘基甲基等。 Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a carbon number of 6 to 12, and specifically, an aryl group-substituted alkane such as a phenyl group, an α-methylphenyl group or a naphthyl group. The base group, that is, the aralkyl group can be exemplified by a benzyl group, an α-methylbenzyl group, a phenethyl group, a naphthylmethyl group or the like.
所述烷氧基較佳為碳數1~6的烷氧基,更佳為碳數1~4,進而佳為甲氧基或乙氧基。 The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
另外,於所述烷基為環烷基的情形時,所述環烷基亦可具有碳數1~10的直鏈狀或分支鏈狀的烷基作為取代基,於烷基為直鏈狀或分支鏈狀的烷基的情形時,亦可具有碳數3~12的環烷基 作為取代基。 Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be linear. Or a branched alkyl group, or a cycloalkyl group having 3 to 12 carbon atoms As a substituent.
該些取代基亦可經所述取代基進一步取代。 These substituents may also be further substituted via the substituents.
所述通式(a1-10)中,於R101、R102及R103表示芳基的情形時,所述芳基較佳為碳數6~12,更佳為碳數6~10。所述芳基亦可具有取代基,所述取代基可較佳地例示碳數1~6的烷基。芳基例如可例示:苯基、甲苯基、二甲苯基、枯烯基、1-萘基等。 In the above formula (a1-10), when R 101 , R 102 and R 103 represent an aryl group, the aryl group is preferably a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and the substituent may preferably be an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like.
另外,R101、R102及R103可相互鍵結並與該等所鍵結的碳原子一起形成環。R101與R102、R101與R103或R102與R103鍵結的情形的環結構例如可列舉:環丁基、環戊基、環己基、環庚基、四氫呋喃基、金剛烷基及四氫吡喃基等。 Further, R 101 , R 102 and R 103 may be bonded to each other and form a ring together with the carbon atoms bonded thereto. R 101 and R 102, R 102 of the case 103, or R 103 and R 101 bonded ring structures such as R include: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl and Tetrahydropyranyl and the like.
再者,所述通式(a1-10)中,較佳為R101及R102的任一個為氫原子或甲基。 Further, in the above formula (a1-10), it is preferred that any of R 101 and R 102 is a hydrogen atom or a methyl group.
用於形成含有所述通式(a1-10)所表示的保護羧基的結構單元的自由基聚合性單體可使用市售品,亦可使用藉由公知的方法而合成者。例如可利用日本專利特開2011-221494號公報的段落編號0037~段落編號0040中記載的合成方法等來合成,將其內容併入至本申請案說明書中。 A commercially available product may be used as the radical polymerizable monomer for forming a structural unit containing the protective carboxyl group represented by the above formula (a1-10), or may be synthesized by a known method. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494, and the content thereof is incorporated into the specification of the present application.
所述結構單元(a1-1-1)的第一較佳態樣為下述通式(A2')所表示的結構單元。 The first preferred aspect of the structural unit (a1-1-1) is a structural unit represented by the following general formula (A2').
[化11]
(式(A2')中,R1及R2分別表示氫原子、烷基或芳基,至少R1及R2的任一個表示烷基或芳基,R3表示烷基或芳基,R1或R2與R3亦可連結而形成環狀醚,R4表示氫原子或甲基,X表示單鍵或伸芳基) (In the formula (A2'), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may also be bonded to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group)
於R1及R2為烷基的情形時,較佳為碳數為1~10的烷基。於R1及R2為芳基的情形時,較佳為苯基。R1及R2分別較佳為氫原子或碳數1~4的烷基。 When R 1 and R 2 are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In the case where R 1 and R 2 are an aryl group, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R3表示烷基或芳基,較佳為碳數1~10的烷基,更佳為1~6的烷基。 R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X表示單鍵或伸芳基,較佳為單鍵。 X represents a single bond or an extended aryl group, preferably a single bond.
所述結構單元(a1-1-1)的第二較佳態樣為下述通式(1-12)所表示的結構單元。 The second preferred aspect of the structural unit (a1-1-1) is a structural unit represented by the following general formula (1-12).
通式(1-12)[化12]
(式(1-12)中,R121表示氫原子或碳數1~4的烷基,L1表示羰基或伸苯基,R122~R128分別獨立地表示氫原子或碳數1~4的烷基) (In the formula (1-12), R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenyl group, and R 122 to R 128 each independently represent a hydrogen atom or a carbon number of 1 to 4; Alkyl)
R121較佳為氫原子或甲基。 R 121 is preferably a hydrogen atom or a methyl group.
L1較佳為羰基。 L 1 is preferably a carbonyl group.
R122~R128較佳為氫原子。 R 122 to R 128 are preferably a hydrogen atom.
所述結構單元(a1-1-1)的較佳具體例可例示下述結構單元。再者,下述結構單元中,R表示氫原子或甲基。 A preferred specific example of the structural unit (a1-1-1) can exemplify the following structural unit. Further, in the following structural unit, R represents a hydrogen atom or a methyl group.
<<<(a1-1-2)具有經酸分解性基保護的保護酚性羥基的結構單元>>> <<<(a1-1-2) Structural unit having a phenolic hydroxyl group protected by an acid-decomposable group>>>
結構單元(a1-1-2)為具有藉由以下將詳細說明的酸分解性基將具有酚性羥基的結構單元保護而成的保護酚性羥基的結構單元(a1-1-2-1)。 The structural unit (a1-1-2) is a structural unit (a1-1-2-1) having a phenolic hydroxyl group protected by a structural unit having a phenolic hydroxyl group by an acid-decomposable group described in detail below. .
<<<<(a1-1-2-1)具有酚性羥基的結構單元>>>> <<<<(a1-1-2-1) Structural unit with phenolic hydroxyl group>>>>
所述具有酚性羥基的結構單元可列舉羥基苯乙烯系結構單元或酚醛清漆系樹脂中的結構單元,該等中,就感度的觀點而言,較佳為來源於羥基苯乙烯或α-甲基羥基苯乙烯的結構單元。另外,就感度的觀點而言,具有酚性羥基的結構單元亦較佳為下述通式(a1-20)所表示的結構單元。 The structural unit having a phenolic hydroxyl group may be a structural unit in a hydroxystyrene structural unit or a novolak-based resin, and among these, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene or α-A. A structural unit of a hydroxystyrene. Further, from the viewpoint of sensitivity, the structural unit having a phenolic hydroxyl group is also preferably a structural unit represented by the following formula (a1-20).
通式(a1-20)
(通式(a1-20)中,R220表示氫原子或甲基,R221表示單鍵或二價連結基,R222表示鹵素原子或者碳數1~5的直鏈或分支鏈狀的烷基,a表示1~5的整數,b表示0~4的整數,a+b為5以下。再者,於存在2個以上的R222的情形時,該些R222可互不相 同亦可相同) (In the formula (a1-20), R 220 represents a hydrogen atom or a methyl group, R 221 represents a single bond or a divalent linking group, and R 222 represents a halogen atom or a linear or branched alkane having 1 to 5 carbon atoms. Base, a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a+b is 5 or less. Further, when two or more R 222 are present, the R 222 may be different from each other. the same)
所述通式(a1-20)中,R220表示氫原子或甲基,較佳為甲基。 In the above formula (a1-20), R 220 represents a hydrogen atom or a methyl group, preferably a methyl group.
另外,R221表示單鍵或二價連結基。於為單鍵的情形時,可提高感度,進而可提高硬化膜的透明性,故較佳。R221的二價連結基可例示伸烷基,R221為伸烷基的具體例可列舉:亞甲基、伸乙基、伸丙基、伸異丙基、伸正丁基、伸異丁基、伸第三丁基、伸戊基、伸異戊基、伸新戊基、伸己基等。其中,R221較佳為單鍵、亞甲基、伸乙基。另外,所述二價連結基亦可具有取代基,取代基可列舉鹵素原子、羥基、烷氧基等。另外,a表示1~5的整數,就本發明的效果的觀點或製造容易的方面而言,a較佳為1或2,更佳為a為1。 Further, R 221 represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. Specific examples of the divalent linking group of R 221 may be an alkylene group, and R 221 is an alkylene group: methylene, ethyl, propyl, isopropyl, n-butyl, and isobutylene. Stretching the third butyl group, stretching the pentyl group, stretching the isoamyl group, stretching the neopentyl group, and stretching the hexyl group. Among them, R 221 is preferably a single bond, a methylene group or an ethyl group. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like. Further, a represents an integer of 1 to 5, and a is preferably 1 or 2, and more preferably a is 1 in terms of the effect of the present invention or the ease of production.
另外,關於苯環上的羥基的鍵結位置,於以與R221鍵結的碳原子為基準(1位)時,較佳為鍵結於4位。 Further, when the bonding position of the hydroxyl group on the benzene ring is based on the carbon atom bonded to R 221 (1 position), it is preferably bonded to the 4 position.
R222為鹵素原子或者碳數1~5的直鏈或分支鏈狀的烷基。具體可列舉:氟原子、氯原子、溴原子、甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、戊基、異戊基、新戊基等。其中,就製造容易的方面而言,較佳為氯原子、溴原子、甲基或乙基。 R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like. . Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred in terms of ease of production.
另外,b表示0或1~4的整數。 In addition, b represents an integer of 0 or 1 to 4.
<<<<可用於結構單元(a1-1-2)的酸分解性基>>>> <<<< Acid decomposable group available for structural unit (a1-1-2)>>>>
可用於所述結構單元(a1-1-2)的所述酸分解性基與可用於所述結構單元(a1-1-1)的酸分解性基同樣地可使用公知的基團,並無特別限定。酸分解性基中,就感光性樹脂組成物的基本物性、特別是感度或圖案形狀、感光性樹脂組成物的保存穩定性、接觸孔的形成性的觀點而言,較佳為具有經縮醛保護的保護酚性羥基的結構單元。進而,酸分解性基中,就感度的觀點而言,更佳為以所述通式(a1-10)所表示的縮醛的形式保護酚性羥基的保護酚性羥基。再者,於為以所述通式(a1-10)所表示的縮醛的形式保護酚性羥基的保護酚性羥基的情形時,保護酚性羥基總體成為-Ar-O-CR101R102(OR103)的結構。再者,Ar表示伸芳基。 The acid-decomposable group which can be used for the structural unit (a1-1-2) can be used in the same manner as the acid-decomposable group which can be used for the structural unit (a1-1-1), and Specially limited. In the acid-decomposable group, it is preferred to have an acetal from the viewpoint of basic physical properties of the photosensitive resin composition, particularly sensitivity or pattern shape, storage stability of the photosensitive resin composition, and formation of contact pores. Protected structural unit that protects phenolic hydroxyl groups. Further, in the acid-decomposable group, it is more preferable to protect the phenolic hydroxyl group from the phenolic hydroxyl group in the form of the acetal represented by the above formula (a1-10) from the viewpoint of sensitivity. Further, in the case of protecting the phenolic hydroxyl group in the form of the acetal represented by the above formula (a1-10), the protective phenolic hydroxyl group is generally -Ar-O-CR 101 R 102 The structure of (OR 103 ). Further, Ar represents an aryl group.
酚性羥基的縮醛酯結構的較佳例可例示:R101=R102=R103=甲基或R101=R102=甲基且R103=苄基的組合。 A preferred example of the acetal ester structure of the phenolic hydroxyl group is exemplified by a combination of R 101 = R 102 = R 103 = methyl or R 101 = R 102 = methyl and R 103 = benzyl.
另外,用於形成具有以縮醛的形式保護酚性羥基的保護酚性羥基的結構單元的自由基聚合性單體例如可列舉日本專利特開2011-215590號公報的段落編號0042中記載者。 In addition, the radically polymerizable monomer for forming a structural unit having a phenolic hydroxyl group which protects a phenolic hydroxyl group in the form of an acetal is described, for example, in Paragraph No. 0044 of JP-A-2011-215590.
該等中,就透明性的觀點而言,較佳為甲基丙烯酸-4-羥基苯酯的1-烷氧基烷基保護體、甲基丙烯酸-4-羥基苯酯的四氫吡喃基保護體。 Among these, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a tetrahydropyranyl group of 4-hydroxyphenyl methacrylate is preferred. Protector.
酚性羥基的縮醛保護基的具體例可列舉1-烷氧基烷基,例如可列舉:1-乙氧基乙基、1-甲氧基乙基、1-正丁氧基乙基、1-異丁氧基乙基、1-(2-氯乙氧基)乙基、1-(2-乙基己氧基)乙基、1-正丙氧基乙基、1-環己氧基乙基、1-(2-環己基乙氧基)乙基、1-苄 氧基乙基等,該等可單獨使用或組合使用兩種以上。 Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl, 1-methoxyethyl, and 1-n-butoxyethyl. 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyloxy Ethyl ethyl, 1-(2-cyclohexylethoxy)ethyl, 1-benzyl Ethoxyethyl or the like, these may be used alone or in combination of two or more.
用於形成所述結構單元(a1-1-2)的自由基聚合性單體可使用市售品,亦可使用藉由公知的方法所合成者。例如,可藉由使具有酚性羥基的化合物於酸觸媒的存在下與乙烯醚反應來進行合成。所述合成亦可使具有酚性羥基的單體與其他單體預先進行共聚合,其後於酸觸媒的存在下與乙烯醚反應。 A commercially available product may be used as the radical polymerizable monomer for forming the structural unit (a1-1-2), or may be synthesized by a known method. For example, the synthesis can be carried out by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The synthesis may also cause a monomer having a phenolic hydroxyl group to be copolymerized with another monomer in advance, and then reacted with a vinyl ether in the presence of an acid catalyst.
所述結構單元(a1-1-2)的較佳具體例可例示下述結構單元,但本發明不限定於該些結構單元。 The preferred specific examples of the structural unit (a1-1-2) may exemplify the following structural units, but the present invention is not limited to the structural units.
[化16]
<<<結構單元(a1-1)的較佳態樣>>> <<<The preferred aspect of structural unit (a1-1)>>>
於含有所述結構單元(a1-1)的聚合物實質上不含結構單元(a1-2)的情形時,於聚合物中,結構單元(a1-1)的含量較佳為20mol%(莫耳百分比)~100mol%,更佳為30mol%~90mol%。 In the case where the polymer containing the structural unit (a1-1) is substantially free of the structural unit (a1-2), the content of the structural unit (a1-1) in the polymer is preferably 20 mol% (Mo The percentage of the ear is ~100 mol%, more preferably 30 mol% to 90 mol%.
於含有所述結構單元(a1-1)的聚合物含有結構單元(a1-2)的情形時,於聚合物中,就感度的觀點而言,結構單元(a1-1)的含量較佳為3mol%~70mol%,更佳為10mol%~60mol%。另外,尤其於可用於所述結構單元(a1)的所述酸分解性基具有以縮醛的形式保護羧基的保護羧基的結構單元的情形時,較佳為20mol% ~50mol%。 In the case where the polymer containing the structural unit (a1-1) contains the structural unit (a1-2), the content of the structural unit (a1-1) is preferably in the polymer from the viewpoint of sensitivity. 3 mol% to 70 mol%, more preferably 10 mol% to 60 mol%. Further, in particular, in the case where the acid-decomposable group which can be used for the structural unit (a1) has a structural unit protecting a carboxyl group in the form of an acetal, it is preferably 20 mol%. ~50mol%.
所述結構單元(a1-1-1)與所述結構單元(a1-1-2)相比,有顯影較快的特徵。因此,於欲快速顯影的情形時,較佳為結構單元(a1-1-1)。反之於欲使顯影緩慢的情形時,較佳為使用結構單元(a1-1-2)。 The structural unit (a1-1-1) has a feature of faster development than the structural unit (a1-1-2). Therefore, in the case of rapid development, the structural unit (a1-1-1) is preferred. On the other hand, in the case where the development is to be slow, it is preferable to use the structural unit (a1-1-2).
<<(a1-2)具有交聯性基的結構單元>> <<(a1-2) Structural unit having a crosslinkable group>>
(A-1)聚合物成分含有具有交聯性基的結構單元(a1-2)。所述交聯性基只要為藉由加熱處理而引起硬化反應的基團,則並無特別限定。較佳的具有交聯性基的結構單元的態樣可列舉:含有選自由環氧基、氧雜環丁基、-NH-CH2-O-R(R為氫原子或碳數1~20的烷基)所表示的基團及乙烯性不飽和基所組成的組群中的至少一個的結構單元,較佳為選自環氧基、氧雜環丁基及-NH-CH2-O-R(R為氫原子或碳數1~20的烷基)所表示的基團中的至少一種。其中,本發明的感光性樹脂組成物較佳為(A-1)聚合物成分含有具有環氧基及氧雜環丁基中的至少一個的結構單元。更詳細而言,可列舉以下結構單元。 (A-1) The polymer component contains a structural unit (a1-2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which causes a curing reaction by heat treatment. Preferred examples of the structural unit having a crosslinkable group include an alkyl group selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R is a hydrogen atom or a carbon number of 1 to 20). The structural unit of at least one of the group represented by the group and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R). At least one of the groups represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In the photosensitive resin composition of the present invention, the polymer component (A-1) preferably contains a structural unit having at least one of an epoxy group and an oxetanyl group. More specifically, the following structural unit is mentioned.
<<<(a1-2-1)具有環氧基及/或氧雜環丁基的結構單元>>> <<<(a1-2-1) structural unit having an epoxy group and/or oxetanyl group>>>
所述(A-1)聚合物成分較佳為含有具有環氧基及/或氧雜環丁基的結構單元(以下亦稱為結構單元(a1-2-1))。 The (A-1) polymer component preferably contains a structural unit having an epoxy group and/or an oxetanyl group (hereinafter also referred to as a structural unit (a1-2-1)).
所述結構單元(a1-2-1)只要於一個結構單元中具有環氧基或氧雜環丁基的至少一個即可,可具有1個以上的環氧基及1個以 上的氧雜環丁基、2個以上的環氧基、或2個以上的氧雜環丁基,並無特別限定,較佳為具有合計1個~3個的環氧基及/或氧雜環丁基,更佳為具有合計1個或2個的環氧基及/或氧雜環丁基,進而佳為具有1個環氧基或氧雜環丁基。 The structural unit (a1-2-1) may have at least one of an epoxy group or an oxetanyl group in one structural unit, and may have one or more epoxy groups and one The above oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, and preferably have a total of one to three epoxy groups and/or oxygen. The heterocyclic butyl group preferably has one or two epoxy groups and/or oxetanyl groups in total, and further preferably has one epoxy group or oxetanyl group.
用於形成具有環氧基的結構單元的自由基聚合性單體的具體例例如可列舉:丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧丁酯、甲基丙烯酸-3,4-環氧丁酯、丙烯酸-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧環己基甲酯、α-乙基丙烯酸-3,4-環氧環己基甲酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、日本專利第4168443號公報的段落編號0031~段落編號0035中記載的含有脂環式環氧骨架的化合物等,將該些內容併入至本申請案說明書中。 Specific examples of the radical polymerizable monomer for forming a structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-n-propyl group. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl acrylate Ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidol Ether, p-vinylbenzyl glycidyl ether, the alicyclic epoxy skeleton-containing compound described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,184,843, etc., which are incorporated herein by reference. in.
用於形成具有氧雜環丁基的結構單元的自由基聚合性單體的具體例例如可列舉:日本專利特開2001-330953號公報的段落編號0011~段落編號0016中記載的具有氧雜環丁基的(甲基)丙烯酸酯、或日本專利特開2012-088459號公報的段落編號0027中記載的化合物等,將該些內容併入至本申請案說明書中。 Specific examples of the radical polymerizable monomer for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. The butyl (meth) acrylate or the compound described in Paragraph No. 0027 of JP-A-2012-088459 is incorporated herein by reference.
用於形成所述具有環氧基及/或氧雜環丁基的結構單元(a1-2-1)的自由基聚合性單體的具體例較佳為含有甲基丙烯酸酯結構的單體、含有丙烯酸酯結構的單體。 A specific example of the radical polymerizable monomer for forming the structural unit (a1-2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer having a methacrylate structure, A monomer containing an acrylate structure.
該等中,就提高共聚合反應性及硬化膜的各種特性的觀點而言,較佳為甲基丙烯酸縮水甘油酯、丙烯酸3,4-環氧環己基甲酯、甲基丙烯酸3,4-環氧環己基甲酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯及甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯。該些結構單元可單獨使用一種或組合使用兩種以上。 Among these, from the viewpoint of improving the copolymerization reactivity and various properties of the cured film, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and methacrylic acid 3,4- are preferred. Epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, acrylic acid (3-ethyloxetane-3-yl) Methyl ester and (3-ethyloxetan-3-yl)methyl methacrylate. These structural units may be used alone or in combination of two or more.
所述結構單元(a1-2-1)的較佳具體例可例示下述結構單元。再者,下述結構單元中,R表示氫原子或甲基。 A preferred specific example of the structural unit (a1-2-1) can exemplify the following structural unit. Further, in the following structural unit, R represents a hydrogen atom or a methyl group.
<<<(a1-2-2)具有乙烯性不飽和基的結構單元>>> <<<(a1-2-2) Structural unit having an ethylenically unsaturated group>>>
所述具有交聯性基的結構單元(a1-2)的一種可列舉具有乙烯性不飽和基的結構單元(a1-2-2)。所述結構單元(a1-2-2)較佳為於側鏈上具有乙烯性不飽和基的結構單元,更佳為於末端具有乙烯性不飽和基、且具有碳數3~16的側鏈的結構單元。 One of the structural units (a1-2) having a crosslinkable group may be a structural unit (a1-2-2) having an ethylenically unsaturated group. The structural unit (a1-2-2) is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal, and having a side chain having a carbon number of 3 to 16. Structural unit.
除此以外,關於結構單元(a1-2-2),可列舉日本專利特開2011-215580號公報的段落編號0072~段落編號0090的記載及日 本專利特開2008-256974的段落編號0013~段落編號0031中記載的化合物等作為較佳者,將該些內容併入至本申請案說明書中。 In addition, as for the structural unit (a1-2-2), the description and date of paragraph number 0072 to paragraph number 0090 of JP-A-2011-215580 can be cited. The compounds described in Paragraph No. 0013 to Paragraph No. 0031 of JP-A-2008-256974 are preferred, and the contents are incorporated into the specification of the present application.
<<<(a1-2-3)具有-NH-CH2-O-R(R為氫原子或碳數1~20的烷基)所表示的基團的結構單元>>> <<<(a1-2-3) Structural unit of a group represented by -NH-CH 2 -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>>
本發明中所用的(A-1)聚合物成分亦較佳為具有-NH-CH2-O-R(R為氫原子或碳數1~20的烷基)所表示的基團的結構單元(a1-2-3)。藉由含有結構單元(a1-2-3),可藉由緩慢的加熱處理來引起硬化反應,可獲得各種特性優異的硬化膜。此處,R較佳為碳數1~9的烷基,更佳為碳數1~4的烷基。另外,烷基可為直鏈、分支或環狀的烷基的任一種,較佳為直鏈或分支的烷基。結構單元(a1-2-3)更佳為具有下述通式(a2-30)所表示的基團的結構單元。 The (A-1) polymer component used in the present invention is also preferably a structural unit having a group represented by -NH-CH 2 -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) (a1) -2-3). By containing the structural unit (a1-2-3), a hardening reaction can be caused by a slow heat treatment, and a cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The structural unit (a1-2-3) is more preferably a structural unit having a group represented by the following formula (a2-30).
通式(a2-30)
(通式(a2-30)中,R1表示氫原子或甲基,R2表示氫原子或碳數1~20的烷基) (In the formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)
R2較佳為碳數1~9的烷基,更佳為碳數1~4的烷基。另外,烷基可為直鏈、分支或環狀的烷基的任一種,較佳為直鏈或分支的烷基。 R 2 is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.
R2的具體例可列舉:甲基、乙基、正丁基、異丁基、環己基及正己基。其中,較佳為異丁基、正丁基、甲基。 Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.
<<<具有交聯性基的結構單元(a1-2)的較佳態樣>>> <<<Preferred aspect of structural unit (a1-2) having crosslinkable group>>>
於含有所述結構單元(a1-2)的聚合物實質上不含結構單元(a1-1)的情形時,於聚合物中,結構單元(a1-2)的含量較佳為5mol%~90mol%,更佳為20mol%~80mol%。 In the case where the polymer containing the structural unit (a1-2) is substantially free of the structural unit (a1-1), the content of the structural unit (a1-2) is preferably from 5 mol% to 90 mol in the polymer. %, more preferably 20 mol% to 80 mol%.
於含有所述結構單元(a1-2)的聚合物含有所述結構單元(a1-1)的情形時,於聚合物中,就耐化學品性的觀點而言,結構單元(a1-2)的含量較佳為3mol%~70mol%,更佳為10mol%~60mol%。 In the case where the polymer containing the structural unit (a1-2) contains the structural unit (a1-1), in the polymer, from the viewpoint of chemical resistance, the structural unit (a1-2) The content is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.
本發明中,進而無論為哪一態樣,(A-1)聚合物成分的所有結構單元中,結構單元(a1-2)的含量均較佳為3mol%~70mol%,更佳為10mol%~60mol%。 In the present invention, in any of the structural units of the (A-1) polymer component, the content of the structural unit (a1-2) is preferably from 3 mol% to 70 mol%, more preferably 10 mol%. ~60mol%.
藉由設定為所述數值的範圍內,可形成各種特性優異的硬化膜。 By setting it as the said numerical value, the hardening film which is excellent in various characteristics can be formed.
<<(a1-3)其他結構單元>> <<(a1-3) Other structural units>>
本發明中,(A-1)聚合物成分除了含有所述結構單元(a1-1)及/或結構單元(a1-2)以外,亦可含有除此以外的其他結構單元 (a1-3)。結構單元(a1-3)亦可含有於所述聚合物(1)及/或聚合物(2)中。另外,亦可有別於所述聚合物(1)或聚合物(2)而另含有實質上不含結構單元(a1-1)及結構單元(a1-2)且含有其他結構單元(a1-3)的聚合物。 In the present invention, the polymer component (A-1) may contain other structural units other than the structural unit (a1-1) and/or the structural unit (a1-2). (a1-3). The structural unit (a1-3) may also be contained in the polymer (1) and/or the polymer (2). Further, it may be different from the polymer (1) or the polymer (2) and further contain substantially no structural unit (a1-1) and structural unit (a1-2) and contain other structural units (a1- 3) polymer.
形成其他結構單元(a1-3)的單體並無特別限制,例如可列舉:苯乙烯類、(甲基)丙烯酸烷基酯、(甲基)丙烯酸環狀烷基酯、(甲基)丙烯酸芳基酯、不飽和二羧酸二酯、雙環不飽和化合物類、馬來醯亞胺化合物類、不飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、不飽和二羧酸、不飽和二羧酸酐、其他不飽和化合物。另外,如後所述,亦可含有具有酸基的結構單元。形成其他結構單元(a1-3)的單體可單獨使用或組合使用兩種以上。 The monomer forming the other structural unit (a1-3) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and (meth)acrylic acid. Aryl ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid , unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as described later, a structural unit having an acid group may also be contained. The monomers forming the other structural unit (a1-3) may be used alone or in combination of two or more.
具體而言,結構單元(a1-3)可列舉來源於以下化合物的結構單元:苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、氯苯乙烯、乙烯基苯甲酸甲酯、乙烯基苯甲酸乙酯、4-羥基苯甲酸(3-甲基丙烯醯氧基丙基)酯、(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯醯基嗎啉、N-環己基馬來醯亞胺、丙烯腈、乙二醇單乙醯乙酸酯單(甲基)丙烯酸酯等。除此以外,可列舉日本專利特開2004-264623號公報的段落號0021~段落號0024中記載的化合物。 Specifically, the structural unit (a1-3) may be exemplified by structural units derived from styrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, methoxy group. Styrene, ethoxystyrene, chlorostyrene, methyl benzoate, ethyl vinyl benzoate, 4-hydroxypropenyl propyl 4-hydroxybenzoate, (methyl) Acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isodecyl (meth) acrylate, (meth) propylene hydrazino, N-cyclohexyl maleimide, acrylonitrile, ethylene Alcohol monoacetic acid acetate mono (meth) acrylate and the like. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.
另外,就電氣特性的觀點而言,其他結構單元(a1-3)較佳為苯乙烯類、具有脂肪族環式骨架的基團。具體可列舉:苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苄酯等。 Further, from the viewpoint of electrical characteristics, the other structural unit (a1-3) is preferably a styrene group or a group having an aliphatic cyclic skeleton. Specific examples thereof include styrene, methyl styrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isodecyl (meth)acrylate. , benzyl (meth) acrylate and the like.
進而,另外就密著性的觀點而言,其他結構單元(a1-3)較佳為(甲基)丙烯酸烷基酯。具體可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯等,更佳為(甲基)丙烯酸甲酯。 Further, from the viewpoint of adhesion, the other structural unit (a1-3) is preferably an alkyl (meth)acrylate. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate.
作為其他結構單元(a1-3),較佳為包含含有酸基的重複單元。藉由含有酸基,容易溶解於鹼性的顯影液中,本發明的效果得以更有效地發揮。本發明中所謂酸基,是指pKa小於7的質子解離性基。酸基通常是使用可形成酸基的單體以含酸基的結構單元的形式組入至聚合物中。藉由在聚合物中含有此種含酸基的結構單元,有容易溶解於鹼性的顯影液中的傾向。 As the other structural unit (a1-3), it is preferred to contain a repeating unit containing an acid group. The effect of the present invention can be more effectively exhibited by containing an acid group and easily dissolving in an alkaline developing solution. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer in the form of a structural unit containing an acid group using a monomer capable of forming an acid group. By containing such a structural unit containing an acid group in a polymer, it tends to be easily dissolved in an alkaline developing solution.
本發明中所用的酸基可例示:來源於羧酸基的酸基、來源於磺醯胺基的酸基、來源於膦酸基的酸基、來源於磺酸基的酸基、來源於酚性羥基的酸基、磺醯胺基、磺醯基醯亞胺基等,較佳為來源於羧酸基的酸基及/或來源於酚性羥基的酸基。 The acid group used in the present invention can be exemplified by an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, and a phenol derived from a phenol group. The acid group of the hydroxyl group, the sulfonylamino group, the sulfonyl fluorenylene group or the like is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group.
本發明中所用的含酸基的結構單元更佳為來源於苯乙烯的結構單元、或來源於乙烯系化合物的結構單元、來源於(甲基)丙烯酸及/或其酯的結構單元。例如可使用日本專利特開2012-88459號公 報的段落編號0021~段落編號0023及段落編號0029~段落編號0044中記載的化合物,將其內容併入至本申請案說明書中。其中,較佳為來源於對羥基苯乙烯、(甲基)丙烯酸、馬來酸、馬來酸酐的結構單元。 The acid group-containing structural unit used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth)acrylic acid and/or an ester thereof. For example, Japanese Patent Laid-Open No. 2012-88459 can be used. The compounds described in paragraph number 0021 to paragraph number 0023 and paragraph number 0029 to paragraph number 0044 are incorporated in the specification of the present application. Among them, a structural unit derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid or maleic anhydride is preferred.
關於含有酸基的重複單元的導入方法,可與(a1-1)結構單元及/或(a1-2)結構單元導入至相同的聚合物中,亦能以與(a1-1)結構單元及(a1-2)結構單元不同的聚合物的結構單元的形式導入。 The introduction method of the repeating unit containing an acid group can be introduced into the same polymer as (a1-1) structural unit and/or (a1-2) structural unit, and can also be combined with (a1-1) structural unit and (a1-2) Form introduction of structural units of polymers having different structural units.
此種聚合物較佳為於側鏈上具有羧基的樹脂。例如可列舉:如日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本專利特公昭58-12577號、日本專利特公昭54-25957號、日本專利特開昭59-53836號、日本專利特開昭59-71048號的各公報中記載般的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、丁烯酸共聚物、馬來酸共聚物、部分酯化馬來酸共聚物等、以及於側鏈具有羧基的酸性纖維素衍生物、於具有羥基的聚合物上加成酸酐而成者等,進而亦可列舉於側鏈上具有(甲基)丙烯醯基的高分子聚合物作為較佳者。 Such a polymer is preferably a resin having a carboxyl group in a side chain. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer, or a partially esterified horse as described in each of the publications of Japanese Laid-Open Patent Publication No. SHO 59-71048 An acid-based copolymer or the like, an acidic cellulose derivative having a carboxyl group in a side chain, an acid anhydride added to a polymer having a hydroxyl group, and the like, and further having a (meth)acryl fluorenyl group in a side chain. The polymer is preferred.
例如可列舉:(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸-2-羥基乙酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、日本專利特開平7-140654號公報中記載的(甲基)丙烯酸-2-羥基丙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸-2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯巨單體/甲基丙烯酸 苄酯/甲基丙烯酸共聚物、甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物、甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。 For example, benzyl (meth)acrylate/(meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, Japanese patent 2-Hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-benzene acrylate described in JP-A-7-140654 Oxypropyl propyl ester / polymethyl methacrylate macromonomer / methacrylic acid Benzyl ester/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polyphenylene Ethylene macromonomer / benzyl methacrylate / methacrylic acid copolymer.
除此以外,亦可使用日本專利特開平7-207211號公報、日本專利特開平8-259876號公報、日本專利特開平10-300922號公報、日本專利特開平11-140144號公報、日本專利特開平11-174224號公報、日本專利特開2000-56118號公報、日本專利特開2003-233179號公報、日本專利特開2009-52020號公報等中記載的公知的高分子化合物,將該些內容併入至本申請案說明書中。 In addition, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, Japanese Patent Laid-Open No. Hei 11-140144, and Japanese Patent No. A known polymer compound described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Incorporated into the specification of the present application.
該些聚合物可僅含有一種,亦可含有兩種以上。 These polymers may be contained alone or in combination of two or more.
該些聚合物亦可使用市售的SMA 1000P、SMA 2000P、SMA 3000P、SMA 1440F、SMA 17352P、SMA 2625P、SMA 3840F(以上為克雷威利(CrayValley)公司製造),亞如風(ARUFON)UC-3000、亞如風(ARUFON)UC-3510、亞如風(ARUFON)UC-3900、亞如風(ARUFON)UC-3910、亞如風(ARUFON)UC-3920、亞如風(ARUFON)UC-3080(以上為東亞合成(股)製造),莊克麗(Joncryl)690、莊克麗(Joncryl)678、莊克麗(Joncryl)67、莊克麗(Joncryl)586(以上為巴斯夫(BASF)製造)等。 These polymers can also be used with commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above is Cray Valley), and ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above is manufactured by East Asia Synthetic Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, BASF) and the like.
本發明中,尤其就感度的觀點而言,較佳為含有含羧基的結構單元、或含酚性羥基的結構單元。例如可使用日本專利特開2012-88459號公報的段落編號0021~段落編號0023及段落編號0029~段落編號0044中記載的化合物,將其內容併入至本申請 案說明書中。 In the present invention, in particular, from the viewpoint of sensitivity, a structural unit containing a carboxyl group or a structural unit containing a phenolic hydroxyl group is preferable. For example, the compounds described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the contents thereof are incorporated in the present application. In the case description.
含酸基的結構單元較佳為所有聚合物成分的結構單元的1mol%~80mol%,更佳為1mol%~50mol%,進而佳為5mol%~40mol%,尤佳為5mol%~30mol%,特佳為5mol%~25mol%。 The structural unit containing an acid group is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, even more preferably from 5 mol% to 40 mol%, even more preferably from 5 mol% to 30 mol%, of the structural unit of all the polymer components. It is particularly preferably from 5 mol% to 25 mol%.
以下列舉本發明的聚合物成分的較佳實施形態,但本發明不限定於該些實施形態。 Preferred embodiments of the polymer component of the present invention are listed below, but the present invention is not limited to the embodiments.
(第1實施形態) (First embodiment)
聚合物(1)更含有1種或2種以上的其他結構單元(a1-3)的態樣。 The polymer (1) further contains one or two or more kinds of other structural units (a1-3).
(第2實施形態) (Second embodiment)
聚合物(2)中的含有(a1-1)具有酸基經酸分解性基保護的基團的結構單元的聚合物更含有1種或2種以上的其他結構單元(a1-3)的態樣。 The polymer containing (a1-1) a structural unit having a group having an acid group which is protected by an acid-decomposable group in the polymer (2) further contains one or more kinds of other structural units (a1-3). kind.
(第3實施形態) (Third embodiment)
聚合物(2)中的含有(a1-2)具有交聯性基的結構單元的聚合物更含有1種或2種以上的其他結構單元(a1-3)的態樣。 The polymer containing (a1-2) a structural unit having a crosslinkable group in the polymer (2) further contains one or two or more kinds of other structural units (a1-3).
(第4實施形態) (Fourth embodiment)
於所述第1實施形態~第3實施形態的任一者中,至少包含含有酸基的結構單元作為其他結構單元(a1-3)的態樣。 In any of the first to third embodiments, at least the structural unit containing an acid group is included as the other structural unit (a1-3).
(第5實施形態) (Fifth Embodiment)
有別於所述聚合物(1)或聚合物(2)而更含有實質上不含結構單元(a1-1)及結構單元(a1-2)且含有其他結構單元(a1-3) 的聚合物的態樣。 Different from the polymer (1) or the polymer (2), it further contains substantially no structural unit (a1-1) and structural unit (a1-2) and contains other structural units (a1-3). The aspect of the polymer.
(第6實施形態) (Sixth embodiment)
包含所述第1實施形態~第5實施形態的2個以上的組合的形態。 A form including two or more combinations of the first embodiment to the fifth embodiment.
於含有實質上不含(a1-1)及(a1-2)且含有其他結構單元(a1-3)的聚合物的態樣中,含有(a1-1)及/或(a1-2)的聚合物的合計量、與實質上不含(a1-1)及(a1-2)且含有其他結構單元(a1-3)的聚合物的合計量之重量比例較佳為99:1~5:95,更佳為97:3~30:70,進而佳為95:5~50:50。 In the aspect containing a polymer substantially containing no (a1-1) and (a1-2) and containing other structural unit (a1-3), (a1-1) and/or (a1-2) are contained. The weight ratio of the total amount of the polymer to the total amount of the polymer substantially not containing (a1-1) and (a1-2) and containing the other structural unit (a1-3) is preferably 99:1 to 5: 95, preferably 97:3~30:70, and then 95:5~50:50.
本發明的第1形態的組成物較佳為以組成物的固體成分的70質量%以上的比例而含有(A-1)聚合物成分。 The composition of the first aspect of the present invention preferably contains (A-1) a polymer component in a proportion of 70% by mass or more of the solid content of the composition.
<<(A-1)聚合物成分的分子量>> <<(A-1) Molecular Weight of Polymer Composition>>
(A-1)聚合物成分的分子量以聚苯乙烯換算重量平均分子量計,較佳為1,000~200,000,更佳為2,000~50,000的範圍。若為所述數值的範圍內,則各種特性良好。數量平均分子量與重量平均分子量之比(分散度)較佳為1.0~5.0,更佳為1.5~3.5。 The molecular weight of the polymer component (A-1) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the range of the numerical value, various characteristics are good. The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.
(A-1)聚合物成分的重量平均分子量及分散度是定義為由凝膠滲透層析法(Gel Permeation Chromatography,GPC)測定所得的聚苯乙烯換算值。本說明書中,聚合物成分的重量平均分子量(Mw)及數量平均分子量(Mn)例如可藉由使用HLC-8120(東曹(股)製造),使用TSK gel Multipore HXL-M(東曹(股)製造,7.8mm ID×30.0cm)作為管柱,且使用四氫呋喃 (Tetrahydrofuran,THF)作為洗滌液而求出。 (A-1) The weight average molecular weight and the degree of dispersion of the polymer component are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component can be, for example, by using HLC-8120 (manufactured by Tosoh Corporation), using TSK gel Multipore HXL-M (Dongcao) ), manufactured, 7.8mm ID × 30.0cm) as a column and using tetrahydrofuran (Tetrahydrofuran, THF) was obtained as a washing liquid.
<<(A-1)聚合物成分的製造方法>> <<(A-1) Method for Producing Polymer Component>>
另外,關於(A-1)聚合物成分的合成法,亦已知各種方法,若列舉一例,則可藉由以下方式來進行合成:於有機溶劑中,使用自由基聚合起始劑,使至少含有用於形成所述(a1-1)及所述(a1-3)所表示的結構單元的自由基聚合性單體的自由基聚合性單體混合物進行聚合。另外,亦可利用所謂的高分子反應來進行合成。 Further, various methods are also known for the synthesis method of the (A-1) polymer component. When an example is given, the synthesis can be carried out by using a radical polymerization initiator in an organic solvent to at least The radically polymerizable monomer mixture containing the radical polymerizable monomer for forming the structural unit represented by the above (a1-1) and the above (a1-3) is polymerized. Further, it is also possible to carry out the synthesis by a so-called polymer reaction.
另外,例如亦可使用季戊四醇四(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、α-甲基苯乙烯二聚物等分子量調整劑。 Further, for example, a molecular weight modifier such as pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate) or α-methylstyrene dimer may be used.
(A-1)聚合物較佳為相對於所有結構單元而含有50mol%以上的來源於(甲基)丙烯酸及/或其酯的結構單元,更佳為含有80mol%以上的來源於(甲基)丙烯酸及/或其酯的結構單元。 The polymer (A-1) preferably contains 50 mol% or more of a structural unit derived from (meth)acrylic acid and/or an ester thereof, and more preferably contains 80 mol% or more of a (meth)-based (meth) group. a structural unit of acrylic acid and/or its ester.
<(B-1)光酸產生劑> <(B-1) Photoacid generator>
本發明的感光性樹脂組成物含有(B-1)光酸產生劑。本發明中使用的光酸產生劑較佳為感應波長300nm以上、較佳為波長300nm~450nm的光化射線而產生酸的化合物,其化學結構並無限制。另外,關於不直接感應波長300nm以上的光化射線的光酸產生劑,只要為藉由與增感劑併用而感應波長300nm以上的光化射線、產生酸的化合物,則可與增感劑組合而較佳地使用。本發明中使用的光酸產生劑較佳為產生pKa為4以下的酸的光酸產生劑,更佳為產生pKa為3以下的酸的光酸產生劑,最佳為產生2 以下的酸的光酸產生劑。 The photosensitive resin composition of the present invention contains (B-1) a photoacid generator. The photoacid generator used in the present invention is preferably a compound which generates an acid by an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and its chemical structure is not limited. In addition, the photoacid generator which does not directly induce actinic rays having a wavelength of 300 nm or more can be combined with a sensitizer by using an actinic ray having a wavelength of 300 nm or more and a compound which generates an acid by using it together with a sensitizer. It is preferably used. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and preferably produces 2 The following acid photoacid generator.
光酸產生劑的例子可列舉:三氯甲基均三嗪類、鋶鹽或錪鹽、四級銨鹽類、重氮甲烷化合物、醯亞胺磺酸酯化合物及肟磺酸酯化合物等。該等中,就絕緣性的觀點而言,較佳為使用肟磺酸酯化合物及醯亞胺磺酸酯化合物,更佳為使用肟磺酸酯化合物。該些光酸產生劑可單獨使用一種或組合使用兩種以上。 Examples of the photoacid generator include trichloromethyls-triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, sulfhydryl sulfonate compounds, and sulfonate compounds. Among these, from the viewpoint of insulating properties, an oxime sulfonate compound and a quinone sulfinate compound are preferably used, and an oxime sulfonate compound is more preferably used. These photoacid generators may be used alone or in combination of two or more.
三氯甲基均三嗪類、二芳基錪鹽類、三芳基鋶鹽類(例如下述化合物)、四級銨鹽類及重氮甲烷衍生物的具體例可例示日本專利特開2011-221494號公報的段落編號0083~段落編號0088中記載的化合物,將該些內容併入至本申請案說明書中。 Specific examples of trichloromethyl-s-triazines, diarylsulfonium salts, triarylsulfonium salts (for example, the following compounds), quaternary ammonium salts, and diazomethane derivatives can be exemplified by Japanese Patent Laid-Open No. 2011- The compound described in Paragraph No. 0083 to Paragraph No. 0088 of 221494 is incorporated herein by reference.
肟磺酸酯化合物、即具有肟磺酸酯結構的化合物可較佳地例示含有下述通式(B1-1)所表示的肟磺酸酯結構的化合物。 The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably a compound containing an oxime sulfonate structure represented by the following formula (B1-1).
通式(B1-1)
(通式(B1-1)中,R21表示烷基或芳基。波線表示與其他基團的鍵) (In the formula (B1-1), R 21 represents an alkyl group or an aryl group. The wave line indicates a bond with another group)
通式(B1-1)中,任一基團可經取代,R21的烷基可為直鏈狀亦可為分支狀亦可為環狀。以下將對容許的取代基加以說明。 In the general formula (B1-1), any of the groups may be substituted, and the alkyl group of R 21 may be linear or branched or cyclic. The permissible substituents will be described below.
R21的烷基較佳為碳數1~10的直鏈狀或分支狀烷基。R21的烷基可經鹵素原子、碳數6~11的芳基、碳數1~10的烷氧基、或環烷基(包括7,7-二甲基-2-氧代降冰片基等橋聯式脂環基,較佳為雙環烷基等)取代。 The alkyl group of R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R 21 may be a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group). The bridged alicyclic group, preferably a bicycloalkyl group, etc., is substituted.
R21的芳基較佳為碳數6~11的芳基,更佳為苯基或萘基。R21的芳基可經低級烷基、烷氧基或鹵素原子取代。 The aryl group of R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
含有所述通式(B1-1)所表示的肟磺酸酯結構的所述化合物亦較佳為下述通式(B1-2)所表示的肟磺酸酯化合物。 The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is also preferably an oxime sulfonate compound represented by the following formula (B1-2).
通式(B1-2)[化22]
(式(B1-2)中,R42表示可經取代的烷基或芳基,X表示烷基、烷氧基或鹵素原子,m4表示0~3的整數,於m4為2或3時,多個X可相同亦可不同) (In the formula (B1-2), R 42 represents a substitutable alkyl group or aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, and m4 represents an integer of 0 to 3, and when m4 is 2 or 3, Multiple Xs can be the same or different)
R42的較佳範圍與所述R21的較佳範圍相同。 The preferred range of R 42 is the same as the preferred range of R 21 .
作為X的烷基較佳為碳數1~4的直鏈狀或分支狀烷基。另外,作為X的烷氧基較佳為碳數1~4的直鏈狀或分支狀烷氧基。另外,作為X的鹵素原子較佳為氯原子或氟原子。 The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. Further, the halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4較佳為0或1。所述通式(B1-2)中,尤佳為m4為1,X為甲基,X的取代位置為鄰位,且R42為碳數1~10的直鏈狀烷基、7,7-二甲基-2-氧代降冰片基甲基或對甲苯甲醯基的化合物。 M4 is preferably 0 or 1. In the above formula (B1-2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R 42 is a linear alkyl group having a carbon number of 1 to 10, 7, 7 a compound of dimethyl-2-oxo norbornylmethyl or p-tolylmethylhydrazine.
含有所述通式(B1-1)所表示的肟磺酸酯結構的化合物亦較佳為下述通式(B1-3)所表示的肟磺酸酯化合物。 The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is also preferably an oxime sulfonate compound represented by the following formula (B1-3).
通式(B1-3)
(式(B1-3)中,R43與式(B1-2)中的R42為相同含意,X1表示鹵素原子、羥基、碳數1~4的烷基、碳數1~4的烷氧基、氰基或硝基,n4表示0~5的整數) (In the formula (B1-3), R 43 has the same meaning as R 42 in the formula (B1-2), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Oxy, cyano or nitro, n4 represents an integer from 0 to 5)
所述通式(B1-3)中的R43較佳為甲基、乙基、正丙基、正丁基、正辛基、三氟甲基、五氟乙基、全氟正丙基、全氟正丁基、對甲苯基、4-氯苯基或五氟苯基,尤佳為正辛基。 R 43 in the formula (B1-3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, Perfluoro-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, especially preferably n-octyl.
X1較佳為碳數1~5的烷氧基,更佳為甲氧基。 X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.
n4較佳為0~2,尤佳為0~1。 N4 is preferably 0 to 2, and particularly preferably 0 to 1.
所述通式(B1-3)所表示的化合物的具體例及較佳的肟磺酸酯化合物的具體例可參照日本專利特開2012-163937號公報的段落編號0080~段落編號0082的記載,將其內容併入至本申請案說明書中。 Specific examples of the compound represented by the above formula (B1-3) and specific examples of the preferred oxime sulfonate compound can be referred to the description of paragraph number 0080 to paragraph number 0082 of JP-A-2012-163937. The contents thereof are incorporated into the specification of the present application.
含有所述通式(B1-1)所表示的肟磺酸酯結構的化合物亦較佳為下述通式(OS-1)所表示的化合物。 The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is also preferably a compound represented by the following formula (OS-1).
所述通式(OS-1)中,R101表示氫原子、烷基、烯基、烷氧基、烷氧基羰基、醯基、胺甲醯基、胺磺醯基、磺基、氰基、芳基或雜芳基。R102表示烷基或芳基。 In the above formula (OS-1), R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group or a cyano group. , aryl or heteroaryl. R 102 represents an alkyl group or an aryl group.
X101表示-O-、-S-、-NH-、-NR105-、-CH2-、-CR106H-或-CR105R107-,R105~R107表示烷基或芳基。 X 101 represents -O-, -S-, -NH-, -NR 105 -, -CH 2 -, -CR 106 H- or -CR 105 R 107 -, and R 105 to R 107 represent an alkyl group or an aryl group.
R121~R124分別獨立地表示氫原子、鹵素原子、烷基、烯基、烷氧基、胺基、烷氧基羰基、烷基羰基、芳基羰基、醯胺基、磺基、氰基或芳基。R121~R124中的2個亦可分別相互鍵結而形成環。 R 121 to R 124 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group or a cyano group. Or aryl. Two of R 121 to R 124 may be bonded to each other to form a ring.
R121~R124較佳為氫原子、鹵素原子及烷基,另外,亦另外可較佳地列舉R121~R124中的至少2個相互鍵結而形成芳基的態樣。其中,就感度的觀點而言,較佳為R121~R124均為氫原子的態樣。 R 121 to R 124 are preferably a hydrogen atom, a halogen atom or an alkyl group, and further preferably, a form in which at least two of R 121 to R 124 are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R 121 to R 124 are hydrogen atoms.
所述官能基均可進一步具有取代基。 The functional group may further have a substituent.
所述通式(OS-1)所表示的化合物例如較佳為日本專利特開2012-163937號公報的段落編號0087~段落編號0089中記載的通式(OS-2)所表示的化合物,將其內容併入至本申請案說明書中。 The compound represented by the above formula (OS-1) is preferably a compound represented by the formula (OS-2) described in Paragraph No. 0087 to Paragraph No. 0089 of JP-A-2012-163937. The content thereof is incorporated into the specification of the present application.
可較佳地用於本發明的所述通式(OS-1)所表示的化合物的具體例可列舉日本專利特開2011-221494號公報的段落編號0128~段落編號0132中記載的化合物(例示化合物b-1~例示化合物b-34),但本發明不限定於此。 Specific examples of the compound represented by the above formula (OS-1) which can be preferably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494. The compound b-1 to the exemplified compound b-34), but the present invention is not limited thereto.
本發明中,含有所述通式(B1-1)所表示的肟磺酸酯結構的化合物較佳為下述通式(OS-3)、下述通式(OS-4)或下述通式(OS-5)所表示的肟磺酸酯化合物。 In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (B1-1) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following An oxime sulfonate compound represented by the formula (OS-5).
(通式(OS-3)~通式(OS-5)中,R22、R25及R28分別獨立地表示烷基、芳基或雜芳基,R23、R26及R29分別獨立地表示氫原子、烷基、芳基或鹵素原子,R24、R27及R30分別獨立地表示鹵素原子、烷基、烷氧基、磺酸基、胺基磺醯基或烷氧基磺醯基,X1~X3分別獨立地表示氧原子或硫原子,n1~n3分別獨立地表示1或2,m1~m3分別獨立地表示0~6的整數) (In the general formula (OS-3) to (OS-5), R 22 , R 25 and R 28 each independently represent an alkyl group, an aryl group or a heteroaryl group, and R 23 , R 26 and R 29 are each independently The ground represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X 1 to X 3 each independently represents an oxygen atom or a sulfur atom, and n 1 to n 3 each independently represent 1 or 2, and m 1 to m 3 each independently represent an integer of 0 to 6)
關於所述通式(OS-3)~通式(OS-5),例如可參照日本專利特開2012-163937號公報的段落編號0098~段落編號0115的記載,將其內容併入至本申請案說明書中。 For the general formula (OS-3) to the general formula (OS-5), for example, the description of Paragraph No. 0098 to Paragraph No. 0115 of JP-A-2012-163937 can be referred to, and the contents thereof are incorporated in the present application. In the case description.
另外,含有所述通式(B1-1)所表示的肟磺酸酯結構的化合物例如尤佳為日本專利特開2012-163937號公報的段落編號0117中記載的通式(OS-6)~通式(OS-11)的任一個所表示的化合物,將其內容併入至本申請案說明書中。 In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1-1) is, for example, preferably the formula (OS-6) described in Paragraph No. 0117 of JP-A-2012-163937. A compound represented by any one of the formula (OS-11), the contents of which are incorporated in the specification of the present application.
所述通式(OS-6)~通式(OS-11)的較佳範圍與日本專利特開2011-221494號公報的段落編號0110~0112中記載的(OS-6) ~(OS-11)的較佳範圍相同,將其內容併入至本申請案說明書中。 The preferred range of the general formula (OS-6) to the general formula (OS-11) and the (OS-6) described in paragraphs 0110 to 0112 of JP-A-2011-221494 The preferred ranges of ~(OS-11) are the same, and the contents thereof are incorporated into the specification of the present application.
所述通式(OS-3)~所述通式(OS-5)所表示的肟磺酸酯化合物的具體例可列舉日本專利特開2011-221494號公報的段落編號0114~段落編號0120中記載的化合物,將其內容併入至本申請案說明書中。本發明不限定於該些化合物。 Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include paragraph number 0114 to paragraph number 0120 of JP-A-2011-221494. The compounds described are incorporated into the specification of the present application. The invention is not limited to these compounds.
含有所述通式(B1-1)所表示的肟磺酸酯結構的化合物亦較佳為下述通式(B1-4)所表示的肟磺酸酯化合物。 The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is also preferably an oxime sulfonate compound represented by the following formula (B1-4).
通式(B1-4)
(通式(B1-4)中,R1表示烷基或芳基,R2表示烷基、芳基或雜芳基。R3~R6分別表示氫原子、烷基、芳基、鹵素原子。其中,R3與R4、R4與R5或R5與R6亦可鍵結而形成脂環或芳香環。X表示-O-或-S-) (In the formula (B1-4), R 1 represents an alkyl group or an aryl group, and R 2 represents an alkyl group, an aryl group or a heteroaryl group. R 3 to R 6 each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom. Wherein R 3 and R 4 , R 4 and R 5 or R 5 and R 6 may also be bonded to form an alicyclic or aromatic ring. X represents -O- or -S-)
R1表示烷基或芳基。烷基較佳為具有分支結構的烷基或環狀結構的烷基。 R 1 represents an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure.
烷基的碳數較佳為3~10。尤其於烷基具有分支結構的情形 時,較佳為碳數3~6的烷基,於具有環狀結構的情形時,較佳為碳數5~7的烷基。 The alkyl group preferably has a carbon number of from 3 to 10. Especially in the case where the alkyl group has a branched structure In the case of having a cyclic structure, an alkyl group having 3 to 6 carbon atoms is preferred, and an alkyl group having 5 to 7 carbon atoms is preferred.
烷基例如可列舉:丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、戊基、異戊基、新戊基、1,1-二甲基丙基、己基、2-乙基己基、環己基、辛基等,較佳為異丙基、第三丁基、新戊基、環己基。 The alkyl group may, for example, be propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, 1,1-dimethylpropane. The group, the hexyl group, the 2-ethylhexyl group, the cyclohexyl group, the octyl group and the like are preferably an isopropyl group, a tert-butyl group, a neopentyl group or a cyclohexyl group.
芳基的碳數較佳為6~12,更佳為6~8,進而佳為6~7。所述芳基可列舉苯基、萘基等,較佳為苯基。 The carbon number of the aryl group is preferably from 6 to 12, more preferably from 6 to 8, and further preferably from 6 to 7. The aryl group may, for example, be a phenyl group or a naphthyl group, and is preferably a phenyl group.
R1所表示的烷基及芳基亦可具有取代基。取代基例如可列舉:鹵素原子(氟原子、氯原子、溴原子、碘原子)、直鏈、分支或環狀的烷基(例如甲基、乙基、丙基等)、烯基、炔基、芳基、醯基、烷氧基羰基、芳氧基羰基、胺甲醯基、氰基、羧基、羥基、烷氧基、芳氧基、烷硫基、芳硫基、雜環氧基、醯氧基、胺基、硝基、肼基、雜環基等。另外,亦可經該些基團進一步取代。較佳為鹵素原子、甲基。 The alkyl group and the aryl group represented by R 1 may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched or cyclic alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, and an alkynyl group. , aryl, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, cyano, carboxyl, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heterocyclooxy, Alkoxy group, amine group, nitro group, mercapto group, heterocyclic group and the like. In addition, it may be further substituted by these groups. A halogen atom or a methyl group is preferred.
本發明的感光性樹脂組成物就透明性的觀點而言,R1較佳為烷基,就兼具保存穩定性與感度的觀點而言,R1較佳為碳數3~6的具有分支結構的烷基、碳數5~7的環狀結構的烷基、或苯基,更佳為碳數3~6的具有分支結構的烷基、或碳數5~7的環狀結構的烷基。藉由採用此種大體積的基團(特別是大體積的烷基)作為R1,可進一步提高透明性。 The photosensitive resin composition of the present invention in terms of the viewpoint of transparency, R 1 is preferably an alkyl group, on both the storage stability and in terms of sense, R 1 is preferably branched having a carbon number of 3 to 6 The alkyl group of the structure, the alkyl group having a cyclic structure of 5 to 7 carbon atoms, or a phenyl group, more preferably an alkyl group having a branched structure of 3 to 6 carbon atoms or an alkane having a cyclic structure of 5 to 7 carbon atoms base. By using such a large volume group (especially a large volume of alkyl group) as R 1 , transparency can be further improved.
大體積的取代基中,較佳為異丙基、第三丁基、新戊基、環 己基,更佳為第三丁基、環己基。 Among the large volume substituents, preferred are isopropyl, tert-butyl, neopentyl, and ring. The hexyl group is more preferably a tributyl group or a cyclohexyl group.
R2表示烷基、芳基或雜芳基。R2所表示的烷基較佳為碳數1~10的直鏈、分支或環狀的烷基。所述烷基例如可列舉:甲基、乙基、丙基、異丙基、正丁基、第三丁基、戊基、新戊基、己基、環己基等,較佳為甲基。 R 2 represents an alkyl group, an aryl group or a heteroaryl group. The alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group or a cyclohexyl group, and is preferably a methyl group.
芳基較佳為碳數6~10的芳基。所述芳基可列舉:苯基、萘基、對甲苯甲醯基(對甲基苯基)等,較佳為苯基、對甲苯甲醯基。 The aryl group is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, a p-tolylmethyl group (p-methylphenyl group), and the like, and a phenyl group and a p-tolylmethyl group are preferable.
雜芳基例如可列舉:吡咯基、吲哚基、咔唑基、呋喃基、噻吩基等。 Examples of the heteroaryl group include a pyrrolyl group, a fluorenyl group, a carbazolyl group, a furyl group, a thienyl group and the like.
R2所表示的烷基、芳基及雜芳基亦可具有取代基。取代基與R1所表示的烷基及芳基可具有的取代基為相同含意。 The alkyl group, the aryl group and the heteroaryl group represented by R 2 may have a substituent. The substituent has the same meaning as the substituent which the alkyl group and the aryl group represented by R 1 may have.
R2較佳為烷基或芳基,更佳為芳基,進而佳為苯基。苯基的取代基較佳為甲基。 R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and further preferably a phenyl group. The substituent of the phenyl group is preferably a methyl group.
R3~R6分別表示氫原子、烷基、芳基或鹵素原子(氟原子、氯原子、溴原子、碘原子)。R3~R6所表示的烷基與R2所表示的烷基為相同含意,較佳範圍亦相同。另外,R3~R6所表示的芳基與R1所表示的芳基為相同含意,較佳範圍亦相同。 R 3 to R 6 each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). The alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same. Further, the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
R3~R6中,R3與R4、R4與R5或R5與R6亦可鍵結而形成環,關於環,較佳為形成脂環或芳香環,更佳為苯環。 In R 3 to R 6 , R 3 and R 4 , R 4 and R 5 or R 5 and R 6 may be bonded to form a ring, and the ring preferably forms an alicyclic or aromatic ring, more preferably a benzene ring. .
R3~R6較佳為氫原子、烷基、鹵素原子(氟原子、氯原子、溴原子)或者R3與R4、R4與R5或R5與R6鍵結而構成苯環,更 佳為氫原子、甲基、氟原子、氯原子、溴原子或者R3與R4、R4與R5或R5與R6鍵結而構成苯環。 R 3 to R 6 are preferably a hydrogen atom, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom or a bromine atom) or R 3 and R 4 , R 4 and R 5 or R 5 and R 6 are bonded to each other to form a benzene ring. More preferably, it is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or R 3 and R 4 , R 4 and R 5 or R 5 and R 6 are bonded to each other to form a benzene ring.
R3~R6的較佳態樣如下。 Preferred aspects of R 3 to R 6 are as follows.
(態樣1)至少2個為氫原子。 (Stage 1) At least two are hydrogen atoms.
(態樣2)烷基、芳基或鹵素原子的個數為1個以下。 (Section 2) The number of alkyl groups, aryl groups or halogen atoms is one or less.
(態樣3)R3與R4、R4與R5或R5與R6鍵結而構成苯環。 (Stage 3) R 3 and R 4 , R 4 and R 5 or R 5 and R 6 are bonded to each other to form a benzene ring.
(態樣4)滿足所述態樣1與態樣2的態樣及/或滿足所述態樣1與態樣3的態樣。 (Stage 4) The aspect of the aspect 1 and the aspect 2 is satisfied and/or the aspect of the aspect 1 and the aspect 3 is satisfied.
X表示-O-或-S-。 X represents -O- or -S-.
所述通式(B1-4)的具體例可列舉如下化合物,但本發明中不特別限定於此。再者,例示化合物中,Ts表示甲苯磺醯基(對甲苯磺醯基),Me表示甲基,Bu表示正丁基,Ph表示苯基。 Specific examples of the above formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. Further, in the exemplified compound, Ts represents a toluenesulfonyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.
[化27]
作為光酸產生劑而使用的醯亞胺磺酸酯化合物可較佳地使用具有下述通式(B1-5)所表示的結構的醯亞胺磺酸酯化合物。 As the liminium sulfonate compound to be used as the photoacid generator, a ruthenium sulfonate compound having a structure represented by the following formula (B1-5) can be preferably used.
[化28]
(通式(B1-5)中,R200表示碳原子數16以下的1價有機基。波線表示與其他基團的鍵) (In the formula (B1-5), R 200 represents a monovalent organic group having 16 or less carbon atoms. The wave line indicates a bond with another group)
R200表示碳原子數16以下的1價有機基。R200較佳為僅含有C、H、O、F。R200例如可列舉:甲基、三氟甲基、丙基、苯基、甲苯磺醯基等。 R 200 represents a monovalent organic group having 16 or less carbon atoms. R 200 preferably contains only C, H, O, F. Examples of R 200 include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a toluenesulfonyl group.
含有通式(B1-5)所表示的結構的化合物的較佳態樣為下述通式(I)所表示的醯亞胺磺酸酯化合物。 A preferred aspect of the compound containing the structure represented by the formula (B1-5) is an oximine sulfonate compound represented by the following formula (I).
通式(I)中,R1及R2分別表示下述通式(A)所表示的基或氫原子。R3表示可經鹵素原子、烷硫基及脂環式烴基的任1個以上取代的碳數1~18的脂肪族烴基;可經鹵素原子、烷硫基、烷 基及醯基的任1個以上取代的碳數6~20的芳基;可經鹵素原子及/或烷硫基取代的碳數7~20的芳烷基;10-樟腦基或下述通式(B)所表示的基。 In the formula (I), R 1 and R 2 each represent a group represented by the following formula (A) or a hydrogen atom. R 3 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted by any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group; any one which may pass through a halogen atom, an alkylthio group, an alkyl group and a fluorenyl group More than one substituted aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom and/or an alkylthio group; 10-camphoric group or represented by the following formula (B) base.
通式(A)中,X1表示氧原子或硫原子,Y1表示單鍵或碳數1~4的伸烷基,R4表示碳數1~12的烴基,R5表示碳數1~4的伸烷基,R6表示氫原子、可分支的碳數1~4的烷基、碳數3~10的脂環式烴基、雜環基或羥基。n表示0~5的整數,當n為2~5時,多個R5可相同亦可不同。 In the formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 4 represents a hydrocarbon group having 1 to 12 carbon atoms, and R 5 represents a carbon number of 1 to 2. The alkyl group of 4, R 6 represents a hydrogen atom, a branched alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a heterocyclic group or a hydroxyl group. n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R 5 's may be the same or different.
式中,X1表示氧原子或硫原子,Y1表示單鍵或碳數1~4的烷烴二基,R11表示碳數1~12的烴基,R12表示碳數1~4的烷烴二基,R13表示氫原子、或可具有分支的碳數1~4的烷基、碳數3~10的脂環式烴基、或雜環基,m表示0~5,當m為2~5時,多個R12可相同亦可不同。 In the formula, X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, R 11 represents a hydrocarbon group having 1 to 12 carbon atoms, and R 12 represents an alkane having 2 to 4 carbon atoms. Further, R 13 represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a heterocyclic group which may have a branch, m represents 0 to 5, and m is 2 to 5 In the meantime, a plurality of R 12 's may be the same or different.
通式(B)中,Y2表示單鍵或碳數1~4的伸烷基,R7 表示碳數2~6的伸烷基、碳數2~6的鹵化伸烷基、碳數6~20的伸芳基或者碳數6~20的鹵化伸芳基,R8表示單鍵、碳數2~6的伸烷基、碳數2~6的鹵化伸烷基、碳數6~20的伸芳基或者碳數6~20的鹵化伸芳基,R9表示可分支的碳數1~18的烷基、可分支的碳數1~18的鹵化烷基、碳數6~20的芳基、碳數6~20的鹵化芳基、碳數7~20的芳烷基或者碳數7~20的鹵化芳烷基。a及b分別獨立地表示0或1,a及b的至少1者為1。 In the formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, and a carbon number of 6 ~20 of an aryl group or a halogenated aryl group having a carbon number of 6 to 20, R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, and a carbon number of 6 to 20 An aryl group or a halogenated aryl group having 6 to 20 carbon atoms, R 9 represents a branchable alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, and a carbon number of 6 to 20 An aryl group, a halogenated aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a halogenated aralkyl group having 7 to 20 carbon atoms. a and b each independently represent 0 or 1, and at least one of a and b is 1.
關於通式(I),例如可參考國際公開WO11/087011號公報的段落編號0019~段落編號0063的記載,將其內容併入至本說明書中。通式(I)所表示的化合物例如可例示以下化合物。另外,除以下所例示的化合物以外,亦可參考國際公開WO11/087011號公報的段落編號0065~段落編號0075的記載,將其內容併入至本說明書中。 For the general formula (I), for example, the description of Paragraph No. 0019 to Paragraph No. 0063 of International Publication WO11/087011 can be referred to, and the contents thereof are incorporated in the present specification. The compound represented by the formula (I) can, for example, be exemplified by the following compounds. Further, in addition to the compounds exemplified below, the description of Paragraph No. 0065 to Paragraph No. 0075 of International Publication WO11/087011 can be referred to, and the contents thereof are incorporated in the present specification.
本發明的感光性樹脂組成物中,相對於感光性樹脂組成物中的總固體成分100質量份,(B-1)光酸產生劑的含量較佳為0.1質量份~20質量份,更佳為0.5質量份~10質量份,進而佳為0.5質量份~5質量份。光酸產生劑可僅使用一種,亦可併用兩種以上。 In the photosensitive resin composition of the present invention, the content of the (B-1) photoacid generator is preferably from 0.1 part by mass to 20 parts by mass, more preferably 100 parts by mass based on the total solid content of the photosensitive resin composition. It is 0.5 parts by mass to 10 parts by mass, and more preferably 0.5 parts by mass to 5 parts by mass. The photoacid generator may be used singly or in combination of two or more.
<(C-1)溶劑> <(C-1) solvent>
本發明的感光性樹脂組成物含有(C-1)溶劑。本發明的感光性樹脂組成物較佳為製備成將本發明的必需成分及進一步的後述任意成分溶解於溶劑中的溶液。用於製備本發明的組成物的溶劑可使用將必需成分及任意成分均勻溶解、且不與各成分反應的溶劑。 The photosensitive resin composition of the present invention contains (C-1) a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and further optional components described later in a solvent. As the solvent for preparing the composition of the present invention, a solvent which uniformly dissolves an essential component and an optional component and does not react with each component can be used.
本發明的感光性樹脂組成物中使用的溶劑可使用公知的溶劑,可例示:乙二醇單烷基醚類、乙二醇二烷基醚類、乙二醇單烷基醚乙酸酯類、丙二醇單烷基醚類、丙二醇二烷基醚類、丙二醇單烷基醚乙酸酯類、二乙二醇二烷基醚類、二乙二醇單烷基醚乙酸酯類、二丙二醇單烷基醚類、二丙二醇二烷基醚類、二丙二醇單烷基醚乙酸酯類、酯類、酮類、醯胺類、內酯類等。另外,本發明的感光性樹脂組成物中使用的溶劑的具體例亦可列舉日本專利特開2011-221494號公報的段落編號0174~段落編號0178中記載的溶劑、日本專利特開2012-194290公報的段落編號0167~段落編號0168中記載的溶劑,將該些內容併入至本申請案說明書中。 A known solvent can be used as the solvent to be used in the photosensitive resin composition of the present invention, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetates. Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl groups Ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. Further, a specific example of the solvent to be used in the photosensitive resin composition of the present invention is a solvent described in Paragraph No. 0174 to Paragraph No. 0178 of JP-A-2011-221494, and JP-A-2012-194290. The solvent described in paragraph number 0167 to paragraph number 0168 is incorporated into the specification of the present application.
另外,該些溶劑中,視需要亦可進而添加苄基乙基醚、二己基醚、乙二醇單苯醚乙酸酯、二乙二醇單甲醚、二乙二醇單***、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苄醇、苯甲醚、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、碳酸伸乙酯、碳酸伸丙酯等溶劑。該些溶劑可單獨使用一種或混合使用兩種以上。本發明中可使用的溶劑較佳為單獨一種或併用兩種,更佳為併用兩種,進而佳為併用丙二醇單烷基醚乙酸酯類或二烷基醚類、二乙酸酯類與二乙二醇二烷基醚類,或者酯類與丁二醇烷基醚乙酸酯類。 Further, among these solvents, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and different Buddha may be further added as needed. Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethyl carbonate , a solvent such as propylene carbonate. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably one alone or two, more preferably two, and it is preferred to use propylene glycol monoalkyl ether acetate or dialkyl ether, diacetate and diethyl Diol dialkyl ethers, or esters and butanediol alkyl ether acetates.
另外,溶劑較佳為沸點為130℃以上且小於160℃的溶劑、沸點為160℃以上的溶劑、或該些溶劑的混合物。 Further, the solvent is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of such solvents.
沸點為130℃以上且小於160℃的溶劑可例示:丙二醇單甲醚乙酸酯(沸點146℃)、丙二醇單***乙酸酯(沸點158℃)、丙二醇甲基正丁基醚(沸點155℃)、丙二醇甲基正丙基醚(沸點131℃)。 The solvent having a boiling point of 130 ° C or more and less than 160 ° C can be exemplified by propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), propylene glycol methyl n-butyl ether (boiling point 155 ° C) ), propylene glycol methyl n-propyl ether (boiling point 131 ° C).
沸點為160℃以上的溶劑可例示:3-乙氧基丙酸乙酯(沸點170℃)、二乙二醇甲基乙基醚(沸點176℃)、丙二醇單甲醚丙酸酯(沸點160℃)、二丙二醇甲醚乙酸酯(沸點213℃)、3-甲氧基丁基醚乙酸酯(沸點171℃)、二乙二醇二乙基醚(沸點189℃)、二乙二醇二甲醚(沸點162℃)、丙二醇二乙酸酯(沸點190℃)、二乙二醇單***乙酸酯(沸點220℃)、二丙二醇二甲醚(沸點175℃)、1,3-丁二醇二乙酸酯(沸點232℃)。 The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160) °C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene Alcohol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1, 3 - Butanediol diacetate (boiling point 232 ° C).
相對於感光性樹脂組成物中的所有成分100質量份,本發明的感光性樹脂組成物中的溶劑的含量較佳為50質量份~95質量份,更佳為60質量份~90質量份。溶劑可僅使用一種,亦可使用兩種以上。於使用兩種以上的情形時,較佳為其合計量成為所述範圍。 The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, more preferably 60 parts by mass to 90 parts by mass, per 100 parts by mass of all the components in the photosensitive resin composition. The solvent may be used singly or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.
<(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物> <(S) a compound represented by the formula (1) and/or a compound represented by the formula (2)>
本發明的組成物包含通式(1)及/或下述通式(2)所表示的化合物(亦稱為(S)成分)。 The composition of the present invention contains a compound represented by the formula (1) and/or the following formula (2) (also referred to as a component (S)).
通式(1)
(通式(1)中,R1及R2分別獨立地表示碳數1~4的烷基,n表示0~2的整數。L1表示單鍵或2價的連結基。X1表示-S-或-NH-,R3表示1價的有機基) (In the formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L 1 represents a single bond or a divalent linking group. X 1 represents - S- or -NH-, R 3 represents a monovalent organic group)
R1及R2分別獨立地表示碳數1~4的烷基,較佳為碳數1~3的烷基,更佳為甲基或乙基。R1及R2較佳為表示同一基團。 R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. R 1 and R 2 preferably represent the same group.
n表示0~2的整數,較佳為0或1的整數,更佳為0。 n represents an integer of 0 to 2, preferably an integer of 0 or 1, more preferably 0.
L1表示單鍵或2價的連結基,較佳為2價的連結基。作為2價的連結基,例如可列舉伸烷基、伸芳基等,較佳為伸烷基。 L 1 represents a single bond or a divalent linking group, and is preferably a divalent linking group. Examples of the divalent linking group include an alkylene group and an extended aryl group, and an alkylene group is preferred.
作為伸烷基,較佳為碳數1~10的伸烷基,更加為碳數2~8的伸烷基,進而佳為碳數3~5的伸烷基。伸烷基可具有取代基,但較佳為未經取代。伸烷基的具體例包含:亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸環己基、伸庚基、伸辛基、伸壬基、伸癸基等。 The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 3 to 5 carbon atoms. The alkylene group may have a substituent, but is preferably unsubstituted. Specific examples of the alkylene group include: methylene, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, thiol, decyl Wait.
作為伸芳基,較佳為碳數6~20的伸芳基,更加為碳數6~10的伸芳基。具體而言,可列舉:伸苯基、伸萘基等。 As the aryl group, a aryl group having a carbon number of 6 to 20 is preferred, and an aryl group having a carbon number of 6 to 10 is more preferred. Specifically, a phenyl group, a naphthyl group, etc. are mentioned.
亦可使該些伸烷基及伸芳基含有醚系氧原子而成為伸烷氧基及伸芳氧基。 Further, the alkylene group and the extended aryl group may contain an ether oxygen atom to form an alkyleneoxy group and an extended aryloxy group.
X1表示-S-或-NH-,較佳為-NH-。 X 1 represents -S- or -NH-, preferably -NH-.
R3表示1價的有機基。1價的有機基例如可列舉:烷基、芳基、烷氧基、芳氧基、醯氧基、烷氧基羰氧基、芳氧基羰氧基等。其中,較佳為烷基、芳基。 R 3 represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group. Among them, an alkyl group or an aryl group is preferred.
作為烷基,較佳為碳數1~10的烷基,更加為碳數1~6的烷基。具體而言,可列舉:甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基、環己基、庚基、辛基、壬基、癸基等。 The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group and the like.
作為芳基,較佳為碳數6~20的芳基,更加為碳數6~10的芳基。具體而言,可列舉:苯基、萘基、蒽基等。 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group and the like.
作為烷氧基,較佳為碳數1~10的烷氧基,更加為碳數1~6的烷氧基。具體而言,可列舉:甲氧基、乙氧基、丙氧基、異丙 氧基、丁氧基、第三丁氧基、戊氧基等。 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms. Specifically, a methoxy group, an ethoxy group, a propoxy group, and an isopropyl group are mentioned. Oxyl, butoxy, tert-butoxy, pentyloxy and the like.
作為芳氧基,較佳為碳數6~30的芳氧基。具體而言,可列舉:苯氧基、2-甲基苯氧基、4-第三丁基苯氧基、3-硝基苯氧基、2-十四醯基胺基苯氧基等。 The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms. Specific examples thereof include a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, a 2-tetradecylaminophenoxy group, and the like.
作為醯氧基,較佳為甲醯氧基、碳數2~30的烷基羰氧基、碳數6~30的芳基羰氧基。具體而言,可列舉:乙醯氧基、三甲基乙醯氧基、硬質醯氧基、苯基醯氧基、對甲氧基苯基羰氧基等。 The decyloxy group is preferably a methoxycarbonyl group, an alkylcarbonyloxy group having 2 to 30 carbon atoms, or an arylcarbonyloxy group having 6 to 30 carbon atoms. Specific examples thereof include an ethoxycarbonyl group, a trimethylacetoxy group, a hard methoxy group, a phenyl decyloxy group, a p-methoxyphenylcarbonyloxy group, and the like.
作為烷氧基羰氧基,較佳為碳數2~30的烷氧基羰氧基。具體而言,可列舉:甲氧基羰氧基、乙氧基羰氧基、第三丁氧基羰氧基、正辛基羰氧基等。 The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms. Specific examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.
作為芳氧基羰氧基,較佳為碳數7~30的芳氧基羰氧基。具體而言,可列舉:苯氧基羰氧基、對甲氧基苯氧基羰氧基、對正十六烷氧基苯氧基羰氧基等。 The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms. Specific examples thereof include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-hexadecaneoxyphenoxycarbonyloxy group, and the like.
R3表示的1價的有機基可具有取代基。取代基例如可列舉:鹵素原子(氟原子、氯原子、溴原子、碘原子)、直鏈、分支或環狀的烷基(例如甲基、乙基、丙基等)、烯基、炔基、芳基、醯基、烷氧基羰基、芳氧基羰基、胺甲醯基、氰基、羧基、羥基、烷氧基、芳氧基、烷硫基、芳硫基、雜環氧基、醯氧基、胺基、硝基、肼基、雜環基等。另外,亦可經該些基團進一步取代。 The monovalent organic group represented by R 3 may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched or cyclic alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, and an alkynyl group. , aryl, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, cyano, carboxyl, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heterocyclooxy, Alkoxy group, amine group, nitro group, mercapto group, heterocyclic group and the like. In addition, it may be further substituted by these groups.
通式(2)[化34]
(通式(2)中,R5及R6分別獨立地表示碳數1~4的烷基,n表示0~2的整數。L2表示單鍵或2價的連結基。X2表示-S-或-NH-,A表示包含碳原子及氮原子的雜環) (In the formula (2), R 5 and R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L 2 represents a single bond or a divalent linking group. X 2 represents - S- or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom)
R5及R6分別獨立地表示碳數1~4的烷基,且與通式(1)中的R1及R2含義相同,較佳範圍亦相同。 R 5 and R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, and have the same meanings as R 1 and R 2 in the formula (1), and the preferred ranges are also the same.
n表示0~2的整數,且與通式(1)中的n含義相同,較佳範圍亦相同。 n represents an integer of 0 to 2, and has the same meaning as n in the general formula (1), and the preferred range is also the same.
L2表示單鍵或2價的連結基,且與通式(1)中的L1含義相同,較佳範圍亦相同。 L 2 represents a single bond or a divalent linking group, and has the same meaning as L 1 in the formula (1), and the preferred range is also the same.
X2表示-S-或-NH-,且與通式(1)中的X1含義相同,較佳範圍亦相同。 X 2 represents -S- or -NH- and has the same meaning as X 1 in the formula (1), and the preferred range is also the same.
A表示包含碳原子及氮原子的雜環。包含碳原子及氮原子的雜環可為芳香族性,亦可為非芳香族性,通常為芳香族雜環。包含碳原子及氮原子的雜環除氮原子以外亦可更含有氧原子、氮原子、硫原子等雜原子。而且,雜環可為單環、縮合環的任一者,但較佳為單環。雜環較佳為3員環~7員環,更佳為5員環或6員環。 A represents a hetero ring containing a carbon atom and a nitrogen atom. The hetero ring containing a carbon atom and a nitrogen atom may be aromatic or non-aromatic, and is usually an aromatic hetero ring. The hetero ring containing a carbon atom and a nitrogen atom may further contain a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom in addition to the nitrogen atom. Further, the heterocyclic ring may be either a monocyclic ring or a condensed ring, but is preferably a single ring. The heterocyclic ring is preferably a 3-membered ring to a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.
具體而言,可列舉:吡啶基、噻唑基、2-呋喃基(2-furyl group)、 噻吩基(thienyl group)、嘧啶基、苯并噻唑基、嗎啉基、吡咯基、吲哚基、咔唑基、呋喃基(furan group)、噻吩基(thiophene group)等。 Specific examples thereof include a pyridyl group, a thiazolyl group, and a 2-furyl group. A thienyl group, a pyrimidinyl group, a benzothiazolyl group, a morpholinyl group, a pyrrolyl group, a fluorenyl group, a carbazolyl group, a furan group, a thiophene group, and the like.
A所表示的包含碳原子及氮原子的雜環可具有取代基。取代基與通式(1)中的R3可具有的取代基含義相同。 The hetero ring containing a carbon atom and a nitrogen atom represented by A may have a substituent. The substituent has the same meaning as the substituent which R 3 in the formula (1) may have.
以下表示本發明中所使用的(S)成分的例示化合物,但本發明當然並不限定於該些化合物。式中,Me表示甲基,Et表示乙基。 The exemplified compounds of the component (S) used in the present invention are shown below, but the present invention is of course not limited to these compounds. In the formula, Me represents a methyl group and Et represents an ethyl group.
該些之中,較佳為(S-1)~(S-24),更佳為(S-1)~(S-8),進而佳為(S-1)~(S-2)。 Among these, it is preferably (S-1) to (S-24), more preferably (S-1) to (S-8), and further preferably (S-1) to (S-2).
作為通式(1)所表示的化合物及/或通式(2)所表示的化合物,更佳為通式(2)所表示的化合物。 The compound represented by the formula (1) and/or the compound represented by the formula (2) are more preferably a compound represented by the formula (2).
通式(1)所表示的化合物及/或通式(2)所表示的化合物的分子量較佳為1000以下,更佳為500以下,進而佳為400以下。下限並無特別限定,為100以上。藉由設為所述範圍,本發明的效果得以更有效的發揮。 The molecular weight of the compound represented by the formula (1) and/or the compound represented by the formula (2) is preferably 1,000 or less, more preferably 500 or less, still more preferably 400 or less. The lower limit is not particularly limited and is 100 or more. By setting it as the said range, the effect of this invention is exerted more effectively.
相對於感光性樹脂組成物的總固體成分,本發明的感光性樹脂組成物較佳為以0.1質量%~20質量%的比例含有(S)成分,更佳為以0.1質量%~10質量%的比例含有(S)成分,進而佳為以1質量%~10質量%的比例含有(S)成分,尤佳為以2質量%~5質量%的比例含有(S)成分。(S)成分可僅為一種,亦可為兩種以上。於(S)成分為兩種以上的情形時,較佳為其合計量為所述範圍。 The photosensitive resin composition of the present invention preferably contains the component (S) in an amount of 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass based on the total solid content of the photosensitive resin composition. The ratio (S) is preferably contained in the proportion of (S), and the (S) component is preferably contained in a ratio of from 1% by mass to 10% by mass, and particularly preferably (S) in an amount of from 2% by mass to 5% by mass. The (S) component may be one type or two or more types. When the (S) component is two or more, it is preferred that the total amount is the above range.
<其他成分> <Other ingredients>
本發明的感光性樹脂組成物中,除了所述成分以外,視需要可較佳地添加增感劑、交聯劑、鹼性化合物、界面活性劑、抗氧化劑。進而,本發明的感光性樹脂組成物中,可添加酸增殖劑、顯影促進劑、塑化劑、熱自由基產生劑、熱酸產生劑、紫外線吸收劑、增稠劑、及有機或無機的防沈澱劑等公知的添加劑。另外,該些化合物例如可使用日本專利特開2012-88459號公報的段落編號0201~段落編號0224中記載的化合物,將該些內容併入至本申請案說明書中。另外,亦可含有(S)成分以外的矽烷偶合劑,且亦可將(S)成分以外的矽烷偶合劑的調配量設為小於本發明的組成物的固體成分的0.1質量%。該些成分可分別僅使用一種,亦可使用兩種以上。 In the photosensitive resin composition of the present invention, a sensitizer, a crosslinking agent, a basic compound, a surfactant, and an antioxidant may be preferably added in addition to the above components. Further, in the photosensitive resin composition of the present invention, an acid growth agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a UV absorber, a thickener, and an organic or inorganic agent may be added. A known additive such as an anti-precipitant. Further, as the compounds, for example, the compounds described in Paragraph No. 0201 to Paragraph No. 0224 of JP-A-2012-88459 can be used, and the contents are incorporated in the specification of the present application. In addition, a decane coupling agent other than the component (S) may be contained, and the amount of the decane coupling agent other than the component (S) may be set to be less than 0.1% by mass of the solid content of the composition of the present invention. These components may be used alone or in combination of two or more.
<<增感劑>> <<sensitizer>>
本發明的感光性樹脂組成物為了於與光酸產生劑組合時促進其分解,較佳為含有增感劑。增感劑吸收光化射線而成為電子激 發狀態。成為電子激發狀態的增感劑與光酸產生劑接觸,產生電子移動、能量移動、發熱等作用。藉此,光酸產生劑發生化學變化而分解,生成酸。較佳的增感劑的例子可列舉:屬於以下的化合物類,且於350nm~450nm的波長範圍內的任一處具有吸收波長的化合物。 The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof when combined with a photoacid generator. Sensitizer absorbs actinic rays and becomes electron excited Status. The sensitizer that is in an electronically excited state is in contact with the photoacid generator, and functions to move electrons, move energy, and generate heat. Thereby, the photoacid generator chemically changes and decomposes to form an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength at any of the wavelength ranges of 350 nm to 450 nm.
多核芳香族類(例如芘、苝、聯三伸苯(triphenylene)、蒽、9,10-二丁氧基蒽、9,10-二乙氧基蒽、3,7-二甲氧基蒽、9,10-二丙氧基蒽)、氧雜蒽類(例如螢光素、曙紅、赤藻紅、若丹明B、孟加拉玫瑰紅)、氧雜蒽酮類(例如氧雜蒽酮、硫雜蒽酮、二甲基硫雜蒽酮、二乙基硫雜蒽酮)、花青類(例如硫雜羰花青、氧雜羰花青)、部花青類(例如部花青、羰部花青)、若丹菁(rhodacyanine)類、氧喏類、噻嗪類(例如硫堇、亞甲基藍、甲苯胺藍)、吖啶類(例如吖啶橙、氯黃素、吖啶黃素)、吖啶酮類(例如吖啶酮、10-丁基-2-氯吖啶酮)、蒽醌類(例如蒽醌)、方酸內鎓類(例如方酸內鎓)、苯乙烯基類、鹼性苯乙烯基類(例如2-[2-[4-(二甲基胺基)苯基]乙烯基]苯并噁唑)、香豆素類(例如7-二乙基胺基4-甲基香豆素、7-羥基4-甲基香豆素、2,3,6,7-四氫-9-甲基-1H,5H,11H[1]苯并吡喃并[6,7,8-ij]喹嗪-11-酮)。 Polynuclear aromatics (eg, ruthenium, osmium, triphenylene, ruthenium, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropoxyfluorene), xanthones (eg luciferin, eosin, red algae, rhodamine B, bengal rose), xanthones (eg xanthones, Xanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanines (eg, thiocarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, Carbonyl cyanine), rhodacyanine, oxindole, thiazide (eg thiopurine, methylene blue, toluidine blue), acridine (eg acridine orange, chloroflavin, acridine flavin) ), acridone (such as acridone, 10-butyl-2-chloroacridone), anthraquinones (such as hydrazine), squaric acid guanidines (such as squaric acid ylide), styryl Classes, basic styryl groups (eg 2-[2-[4-(dimethylamino)phenyl]vinyl]benzoxazole), coumarins (eg 7-diethylamino) 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyrano[6] , 7,8-ij] quinolizin-11-one).
該些增感劑中,較佳為多核芳香族類、吖啶酮類、苯乙烯基類、鹼性苯乙烯基類、香豆素類,更佳為多核芳香族類。多核芳香族類中,最佳為蒽衍生物。 Among these sensitizers, polynuclear aromatics, acridones, styrenes, basic styrenes, and coumarins are preferred, and polynuclear aromatics are more preferred. Among the polynuclear aromatics, the most preferred is an anthracene derivative.
於本發明的感光性樹脂組成物含有增感劑的情形時,相 對於感光性樹脂組成物中的總固體成分100質量份,增感劑的添加量較佳為0.001質量份~100質量份,更佳為0.1質量份~50質量份,進而佳為0.5質量份~20質量份。增感劑亦可併用兩種以上。 When the photosensitive resin composition of the present invention contains a sensitizer, the phase The amount of the sensitizer added is preferably from 0.001 part by mass to 100 parts by mass, more preferably from 0.1 part by mass to 50 parts by mass, even more preferably from 0.5 part by mass to 100 parts by mass of the total solid content in the photosensitive resin composition. 20 parts by mass. The sensitizer may be used in combination of two or more.
<<交聯劑>> <<Crosslinker>>
本發明的感光性樹脂組成物較佳為視需要而含有交聯劑。藉由添加交聯劑,可使由本發明的感光性樹脂組成物所得的硬化膜成為更強固的膜。 The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can be made into a stronger film by adding a crosslinking agent.
交聯劑只要藉由熱而引起交聯反應,則並無限制。例如可添加:以下將述的分子內具有2個以上的環氧基或氧雜環丁基的化合物、含烷氧基甲基的交聯劑、或具有至少1個乙烯性不飽和雙鍵的化合物、封閉異氰酸酯化合物等。 The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, a crosslinking group containing an alkoxymethyl group, or at least one ethylenically unsaturated double bond may be added as described below. a compound, a blocked isocyanate compound, or the like.
於本發明的感光性樹脂組成物含有交聯劑的情形時,相對於所述(A-1)聚合物成分的合計100質量份,交聯劑的添加量較佳為0.01質量份~50質量份,更佳為0.1質量份~30質量份,進而佳為0.5質量份~20質量份。藉由在該範圍內添加,可獲得機械強度及耐溶劑性優異的硬化膜。交聯劑亦可併用多種,該情形時將交聯劑全部合計而計算含量。 In the case where the photosensitive resin composition of the present invention contains a crosslinking agent, the amount of the crosslinking agent added is preferably from 0.01 part by mass to 50% by mass based on 100 parts by mass of the total of the (A-1) polymer component. The portion is more preferably 0.1 part by mass to 30 parts by mass, and further preferably 0.5 part by mass to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total amount of the crosslinking agents is totaled to calculate the content.
<<<分子內具有2個以上的環氧基或氧雜環丁基的化合物>>> <<<Compounds having two or more epoxy groups or oxetanyl groups in the molecule>>>
分子內具有2個以上的環氧基的化合物的具體例可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、 甲酚酚醛清漆型環氧樹脂、脂肪族環氧樹脂等。 Specific examples of the compound having two or more epoxy groups in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenol novolak type epoxy resin. A cresol novolac type epoxy resin, an aliphatic epoxy resin, or the like.
該等可作為市售品而獲取。例如可列舉:JER152、JER157S70、JER157S65、JER806、JER828、JER1007(三菱化學控股(Mitsubishi Chemical Holdings)(股)製造)等,日本專利特開2011-221494號公報的段落編號0189中記載的市售品等,除此以外,亦可列舉:代那考爾(Denacol)EX-611、代那考爾(Denacol)EX-612、代那考爾(Denacol)EX-614、代那考爾(Denacol)EX-614B、代那考爾(Denacol)EX-622、代那考爾(Denacol)EX-512、代那考爾(Denacol)EX-521、代那考爾(Denacol)EX-411、代那考爾(Denacol)EX-421、代那考爾(Denacol)EX-313、代那考爾(Denacol)EX-314、代那考爾(Denacol)EX-321、代那考爾(Denacol)EX-211、代那考爾(Denacol)EX-212、代那考爾(Denacol)EX-810、代那考爾(Denacol)EX-811、代那考爾(Denacol)EX-850、代那考爾(Denacol)EX-851、代那考爾(Denacol)EX-821、代那考爾(Denacol)EX-830、代那考爾(Denacol)EX-832、代那考爾(Denacol)EX-841、代那考爾(Denacol)EX-911、代那考爾(Denacol)EX-941、代那考爾(Denacol)EX-920、代那考爾(Denacol)EX-931、代那考爾(Denacol)EX-212L、代那考爾(Denacol)EX-214L、代那考爾(Denacol)EX-216L、代那考爾(Denacol)EX-321L、代那考爾(Denacol)EX-850L、代那考爾(Denacol)DLC-201、代那考爾(Denacol)DLC-203、代那考爾(Denacol)DLC-204、代那考爾 (Denacol)DLC-205、代那考爾(Denacol)DLC-206、代那考爾(Denacol)DLC-301、代那考爾(Denacol)DLC-402(以上為長瀨化成(Nagase Chemtex)製造),YH-300、YH-301、YH-302、YH-315、YH-324、YH-325(以上為新日鐵化學製造)等。該些市售品可單獨使用一種或組合使用兩種以上。 These can be obtained as a commercial item. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and the commercial products described in Paragraph No. 0189 of JP-A-2011-221494 Etc. In addition, there are also: Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Dina Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX -211, Denacol EX-212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Dinaco Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX- 841, Denacol EX-911, Denacol EX-941, Denacol E X-920, Denacol EX-931, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Dina Denacol EX-321L, Denacol EX-850L, Denacol DLC-201, Denacol DLC-203, Denacol DLC -204, Denarcourt (Denacol) DLC-205, Denacol DLC-206, Denacol DLC-301, Denacol DLC-402 (above manufactured by Nagase Chemtex) ), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above is Nippon Steel Chemical Manufacturing). These commercially available products may be used alone or in combination of two or more.
該等中,可更佳地列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂及脂肪族環氧樹脂,可尤佳地列舉雙酚A型環氧樹脂。 Among these, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and an aliphatic epoxy resin can be more preferably mentioned, and a bisphenol A type ring can be especially mentioned. Oxygen resin.
分子內具有2個以上的氧雜環丁基的化合物的具體例可使用:亞龍氧雜環丁烷(Aron Oxetane)OXT-121、亞龍氧雜環丁烷(Aron Oxetane)OXT-221、亞龍氧雜環丁烷(Aron Oxetane)OX-SQ、亞龍氧雜環丁烷(Aron Oxetane)PNOX(以上為東亞合成(股)製造)。 Specific examples of the compound having two or more oxetanyl groups in the molecule include: Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.).
另外,含有氧雜環丁基的化合物較佳為單獨使用或與含有環氧基的化合物混合使用。 Further, the oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.
另外,其他交聯劑亦可較佳地使用日本專利特開2012-8223號公報的段落編號0107~段落編號0108中記載的含烷氧基甲基的交聯劑、及具有至少1個乙烯性不飽和雙鍵的化合物等,將該些內容併入至本申請案說明書中。含烷氧基甲基的交聯劑較佳為烷氧基甲基化甘脲。 Further, the other crosslinking agent may preferably be an alkoxymethyl group-containing crosslinking agent described in Paragraph No. 0107 to Paragraph No. 0108 of JP-A-2012-8223, and having at least one ethylenic property. Compounds of unsaturated double bonds, etc., are incorporated into the specification of the present application. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.
<<<封閉異氰酸酯化合物>>> <<<Seal blocked isocyanate compound>>>
本發明的感光性樹脂組成物中,亦可較佳地採用封閉異氰酸 酯系化合物作為交聯劑。封閉異氰酸酯化合物只要為所述通式(S1)所表示的化合物以外的且具有封閉異氰酸酯基的化合物則並無特別限制,就硬化性的觀點而言,較佳為一分子內具有2個以上的封閉異氰酸酯基的化合物。 In the photosensitive resin composition of the present invention, it is also preferred to use blocked isocyanic acid. An ester compound is used as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound other than the compound represented by the above formula (S1) and has a blocked isocyanate group. From the viewpoint of curability, it is preferably two or more in one molecule. A compound that blocks an isocyanate group.
另外,封閉異氰酸酯化合物的骨架並無特別限定,只要於一分子中具有2個異氰酸酯基,則可為任意化合物,可為脂肪族、脂環族或芳香族的聚異氰酸酯,例如可較佳地使用:2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、異佛爾酮二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,3-三亞甲基二異氰酸酯、1,4-四亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、1,9-九亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己烷二異氰酸酯、2,2'-二乙基醚二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯、鄰二甲苯二異氰酸酯、間二甲苯二異氰酸酯、對二甲苯二異氰酸酯、亞甲基雙(環己基異氰酸酯)、環己烷-1,3-二亞甲基二異氰酸酯、環己烷-1,4-二亞甲基二異氰酸酯、1,5-萘二異氰酸酯、對苯二異氰酸酯、3,3'-亞甲基二甲苯-4,4'-二異氰酸酯、4,4'-二苯基醚二異氰酸酯、四氯苯二異氰酸酯、降冰片烷二異氰酸酯、氫化1,3-二甲苯二異氰酸酯、氫化1,4-二甲苯二異氰酸酯等異氰酸酯化合物及由該些化合物衍生的預聚物型的骨架的化合物。該等中,尤佳為甲苯二異氰酸酯(TDI)或二苯基甲烷二異氰酸酯(MDI)、六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)。 Further, the skeleton of the blocked isocyanate compound is not particularly limited, and may be any compound as long as it has two isocyanate groups in one molecule, and may be an aliphatic, alicyclic or aromatic polyisocyanate, and can be preferably used, for example. : 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetra Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1 , 10-methylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate , m-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene Diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'- Isocyanate compounds such as phenyl ether diisocyanate, tetrachlorobenzene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylene diisocyanate, hydrogenated 1,4-xylene diisocyanate, and prepolymers derived from the compounds a type of skeleton compound. Among these, it is especially preferably toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI).
本發明的感光性樹脂組成物中的封閉異氰酸酯化合物的母結構可列舉:縮二脲型、異三聚氰酸酯型、加合物型、二官能預聚物型等。 The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may, for example, be a biuret type, an isomeric cyanurate type, an adduct type or a difunctional prepolymer type.
形成所述封閉異氰酸酯化合物的封閉結構的封閉劑可列舉:肟化合物、內醯胺化合物、酚化合物、醇化合物、胺化合物、活性亞甲基化合物、吡唑化合物、硫醇化合物、咪唑系化合物、醯亞胺系化合物等。該等中,尤佳為選自肟化合物、內醯胺化合物、酚化合物、醇化合物、胺化合物、活性亞甲基化合物、吡唑化合物中的封閉劑。 Examples of the blocking agent for forming the closed structure of the blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, an imidazole compound, A quinone imine compound or the like. Among these, a blocking agent selected from the group consisting of an anthraquinone compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.
所述肟化合物可列舉肟及酮肟,具體可例示:丙酮肟(acetoxime)、甲醛肟(formaldoxime)、環己烷肟、甲基乙基酮肟、環己酮肟、二苯甲酮肟、丙酮肟等。 The hydrazine compound may be exemplified by hydrazine and ketoxime, and specific examples thereof include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, Acetone oxime and the like.
所述內醯胺化合物可例示ε-己內醯胺、γ-丁內醯胺等。 The indoleamine compound can be exemplified by ε-caprolactam, γ-butylide or the like.
所述酚化合物可例示:苯酚、萘酚、甲酚、二甲苯酚、鹵素取代苯酚等。 The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.
所述醇化合物可例示:甲醇、乙醇、丙醇、丁醇、環己醇、乙二醇單烷基醚、丙二醇單烷基醚、乳酸烷基酯等。 The alcohol compound may, for example, be methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether or alkyl lactate.
所述胺化合物可列舉一級胺及二級胺,可為芳香族胺、脂肪族胺、脂環族胺的任一種,可例示苯胺、二苯基胺、伸乙基亞胺、聚伸乙基亞胺等。 The amine compound may be exemplified by a primary amine and a secondary amine, and may be any of an aromatic amine, an aliphatic amine, and an alicyclic amine, and examples thereof include aniline, diphenylamine, ethylenimine, and polyethylene. Imine and the like.
所述活性亞甲基化合物可例示:丙二酸二乙酯、丙二酸二甲酯、乙醯乙酸乙酯、乙醯乙酸甲酯等。 The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate.
所述吡唑化合物可例示:吡唑、甲基吡唑、二甲基吡唑等。 The pyrazole compound can be exemplified by pyrazole, methylpyrazole, dimethylpyrazole and the like.
所述硫醇化合物可例示:烷基硫醇、芳基硫醇等。 The thiol compound can be exemplified by an alkyl thiol, an aryl thiol or the like.
本發明的感光性樹脂組成物中可使用的封閉異氰酸酯化合物可作為市售品而獲取,例如可較佳地使用:克羅奈特(Coronate)AP穩定(stable)M、克羅奈特(Coronate)2503、克羅奈特(Coronate)2515、克羅奈特(Coronate)2507、克羅奈特(Coronate)2513、克羅奈特(Coronate)2555、米利奧(Millionate)MS-50(以上為日本聚胺酯工業(股)製造),塔克奈特(Takenate)B-830、塔克奈特(Takenate)B-815N、塔克奈特(Takenate)B-820NSU、塔克奈特(Takenate)B-842N、塔克奈特(Takenate)B-846N、塔克奈特(Takenate)B-870N、塔克奈特(Takenate)B-874N、塔克奈特(Takenate)B-882N(以上為三井化學(股)製造),杜拉奈特(Duranate)17B-60PX、杜拉奈特(Duranate)17B-60P、杜拉奈特(Duranate)TPA-B80X、杜拉奈特(Duranate)TPA-B80E、杜拉奈特(Duranate)MF-B60X、杜拉奈特(Duranate)MF-B60B、杜拉奈特(Duranate)MF-K60X、杜拉奈特(Duranate)MF-K60B、杜拉奈特(Duranate)E402-B80B、杜拉奈特(Duranate)SBN-70D、杜拉奈特(Duranate)SBB-70P、杜拉奈特(Duranate)K6000(以上為旭化成化學(股)製造),德斯莫(Desmodule)BL1100、德斯莫(Desmodule)BL1265 MPA/X、德斯莫(Desmodule)BL3575/1、德斯莫(Desmodule)BL3272MPA、德斯莫(Desmodule)BL3370MPA、德斯莫(Desmodule)BL3475BA/SN、德斯莫 (Desmodule)BL5375MPA、德斯莫(Desmodule)VPLS2078/2、德斯莫(Desmodule)BL4265SN、德斯莫(Desmodule)PL340、德斯莫(Desmodule)PL350、蘇米度(Sumidule)BL3175(以上為住化拜耳胺酯(股)製造)等。 The blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercially available product, and for example, Coronate AP stable M, Croonate can be preferably used. 2503, Coronate 2515, Coronate 2507, Coronate 2513, Coronate 2555, Millionate MS-50 (above Made by Japan Polyurethane Industry Co., Ltd., Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B -842N, Takenate B-846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above Mitsui Chemical (manufacturing), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E , Duranate MF-B60X, Duranate MF-B60B, Duranate MF-K60X, Duranate MF-K60B, Durantite Duranate) E402-B80B, Duranate SBN-70D Duranate SBB-70P, Duranate K6000 (above is manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodule BL1100, Desmodule BL1265 MPA/X, Germany Desmodule BL3575/1, Desmodule BL3272MPA, Desmodule BL3370MPA, Desmodule BL3475BA/SN, Desmo (Desmodule) BL5375MPA, Desmodule VPLS2078/2, Desmodule BL4265SN, Desmodule PL340, Desmodule PL350, Sumidule BL3175 (above) Manufactured by Bayeramine (manufacturing) and the like.
<<鹼性化合物>> <<Alkaline compound>>
本發明的感光性樹脂組成物亦可含有鹼性化合物。鹼性化合物可自化學增幅抗蝕劑中所用者中任意選擇來使用。例如可列舉脂肪族胺、芳香族胺、雜環式胺、氫氧化四級銨、羧酸的四級銨鹽等。該等的具體例可列舉日本專利特開2011-221494號公報的段落編號0204~段落編號0207中記載的化合物,將該些內容併入至本申請案說明書中。 The photosensitive resin composition of the present invention may also contain a basic compound. The basic compound can be arbitrarily selected from those used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of such a compound include the compounds described in Paragraph No. 0204 to Paragraph No. 0207 of JP-A-2011-221494, the contents of which are incorporated herein by reference.
具體而言,脂肪族胺例如可列舉:三甲胺、二乙胺、三乙胺、二正丙胺、三正丙胺、二正戊胺、三正戊胺、二乙醇胺、三乙醇胺、二環己胺、二環己基甲胺等。 Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , dicyclohexylmethylamine, and the like.
芳香族胺例如可列舉:苯胺、苄胺、N,N-二甲基苯胺、二苯胺等。 Examples of the aromatic amine include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.
雜環式胺例如可列舉:吡啶、2-甲基吡啶、4-甲基吡啶、2-乙基吡啶、4-乙基吡啶、2-苯基吡啶、4-苯基吡啶、N-甲基-4-苯基吡啶、4-二甲基胺基吡啶、咪唑、苯并咪唑、4-甲基咪唑、2-苯基苯并咪唑、2,4,5-三苯基咪唑、煙鹼、煙鹼酸、煙鹼醯胺、喹啉、8-羥基喹啉、吡嗪、吡唑、噠嗪、嘌呤、吡咯啶、哌啶、哌嗪、嗎啉、4-甲基嗎啉、N-環己基-N'-[2-(4-嗎啉基)乙基]硫脲、1,5-二 氮雜雙環[4.3.0]-5-壬烯、1,8-二氮雜雙環[5.3.0]-7-十一烯等。 Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-methyl. 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, indole, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N- Cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-di Azabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.3.0]-7-undecene, and the like.
氫氧化四級銨例如可列舉:氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化苄基三甲基銨、氫氧化四正丁基銨、氫氧化四正己基銨等。 Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetrahydric hydroxide. N-hexyl ammonium and the like.
羧酸的四級銨鹽例如可列舉:乙酸四甲基銨、苯甲酸四甲基銨、乙酸四正丁基銨、苯甲酸四正丁基銨等。 Examples of the quaternary ammonium salt of a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
本發明中可使用的鹼性化合物可單獨使用一種,亦可併用兩種以上。 The basic compounds which can be used in the present invention may be used alone or in combination of two or more.
於本發明的感光性樹脂組成物含有鹼性化合物的情形時,相對於感光性樹脂組成物中的總固體成分100質量份,鹼性化合物的含量較佳為0.001質量份~3質量份,更佳為0.005質量份~1質量份。 When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is preferably 0.001 parts by mass to 3 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition. Preferably, it is 0.005 parts by mass to 1 part by mass.
<<界面活性劑>> <<Interfacial active agent>>
本發明的感光性樹脂組成物亦可含有界面活性劑。界面活性劑可使用陰離子系、陽離子系、非離子系或兩性的任一種,但較佳的界面活性劑為非離子界面活性劑。本發明的組成物中所用的界面活性劑例如可使用:日本專利特開2012-88459號公報的段落編號0201~段落編號0205中記載者、或日本專利特開2011-215580號公報的段落編號0185~段落編號0188中記載者,將該些記載併入至本申請案說明書中。 The photosensitive resin composition of the present invention may also contain a surfactant. The surfactant may be any of an anionic, cationic, nonionic or amphoteric, but a preferred surfactant is a nonionic surfactant. The surfactant used in the composition of the present invention can be, for example, those described in paragraph number 0201 to paragraph number 0205 of JP-A-2012-88459, or paragraph number 0185 of JP-A-2011-215580. The ones described in paragraph number 0188 are incorporated into the specification of the present application.
非離子系界面活性劑的例子可列舉:聚氧伸乙基高級烷基醚類、聚氧伸乙基高級烷基苯基醚類、聚氧乙二醇的高級脂肪酸二 酯類、矽酮系、氟系界面活性劑。另外,可由以下商品名而列舉:KP-341、X-22-822(信越化學工業(股)製造),波利弗洛(Polyflow)No.99C(共榮社化學(股)製造),艾福拓(Eftop)(三菱材料化成公司製造),美佳法(Megafac)(迪愛生(DIC)(股)製造)、弗拉德諾瓦克(Fluorad Novec)FC-4430(住友3M(股)製造),沙福隆(Surflon)S-242(AGC清美化學(AGC Seimi Chemicals)公司製造),寶理福斯(PolyFox)PF-6320(歐諾瓦(OMNOVA)公司製造),SH-8400(東麗-道康寧矽酮(Toray-Dow corning silicone)),福吉特(Ftergent)FTX-218G(尼奧斯(Neos)公司製造)等。 Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylidene higher alkylphenyl ethers, and higher fatty acid esters of polyoxyethylene glycol. An ester, an anthrone or a fluorine-based surfactant. In addition, it can be listed by the following product names: KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), Ai Eftop (manufactured by Mitsubishi Materials Chemical Co., Ltd.), Megafac (made by DiCai (DIC) Co., Ltd.), and Fluorad Novec FC-4430 (Sumitomo 3M (share) manufacturing) ), Surflon S-242 (made by AGC Seimi Chemicals), PolyFox PF-6320 (made by OMNOVA), SH-8400 (East) Toray-Dow corning silicone, Ftergent FTX-218G (manufactured by Neos), and the like.
另外,關於界面活性劑,可列舉含有下述通式(I-1-1)所表示的結構單元A及結構單元B、且利用以四氫呋喃(THF)作為溶劑的情形的凝膠滲透層析法所測定的聚苯乙烯換算的重量平均分子量(Mw)為1,000以上且10,000以下的共聚物作為較佳例。 In addition, the gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent is exemplified. A copolymer having a weight average molecular weight (Mw) in terms of polystyrene of 1,000 or more and 10,000 or less is preferably used.
通式(I-1-1)
(式(I-1-1)中,R401及R403分別獨立地表示氫原子或甲基,R402表示碳數1以上且4以下的直鏈伸烷基,R404表示氫原子或碳數1以上且4以下的烷基,L表示碳數3以上且6以下的伸烷基,p及q為表示聚合比的質量百分率,p表示10質量%以上且80質量%以下的數值,q表示20質量%以上且90質量%以下的數值,r表示1以上且18以下的整數,s表示1以上且10以下的整數) (In the formula (I-1-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R 404 represents a hydrogen atom or carbon. An alkyl group having 1 or more and 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less, q A numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.
所述L較佳為下述通式(I-1-2)所表示的分支伸烷基。通式(I-1-2)中的R405表示碳數1以上且4以下的烷基,就相容性及對被塗佈面的濡濕性的方面而言,較佳為碳數1以上且3以下的烷基,更佳為碳數2或3的烷基。p與q之和(p+q)較佳為p+q=100、即100質量%。 The L is preferably a branched alkyl group represented by the following formula (I-1-2). R 405 in the formula (I-1-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably has a carbon number of 1 or more in terms of compatibility and wettability to a surface to be coated. Further, an alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms. The sum of p and q (p+q) is preferably p+q=100, that is, 100% by mass.
通式(I-1-2)
所述共聚物的重量平均分子量(Mw)更佳為1,500以上且5,000以下。 The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
該些界面活性劑可單獨使用一種或混合使用兩種以上。 These surfactants may be used alone or in combination of two or more.
於本發明的感光性樹脂組成物含有界面活性劑的情形時,相 對於感光性樹脂組成物中的總固體成分100質量份,界面活性劑的添加量較佳為10質量份以下,更佳為0.001質量份~10質量份,進而佳為0.01質量份~3質量份。 When the photosensitive resin composition of the present invention contains a surfactant, the phase The amount of the surfactant added is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, even more preferably 0.01 parts by mass to 3 parts by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. .
<<抗氧化劑>> <<Antioxidants>>
本發明的感光性樹脂組成物亦可含有抗氧化劑。抗氧化劑可含有公知的抗氧化劑。藉由添加抗氧化劑,有可防止硬化膜的著色、或可減少由分解所致的膜厚減薄、另外耐熱透明性優異的優點。 The photosensitive resin composition of the present invention may also contain an antioxidant. The antioxidant may contain a well-known antioxidant. By adding an antioxidant, it is possible to prevent the coloration of the cured film, or to reduce the film thickness reduction by decomposition, and to have excellent heat-resistant transparency.
此種抗氧化劑例如可列舉:磷系抗氧化劑、醯胺類、醯肼類、受阻胺系抗氧化劑、硫系抗氧化劑、酚系抗氧化劑、抗壞血酸類、硫酸鋅、糖類、亞硝酸鹽、亞硫酸鹽、硫代硫酸鹽、羥基胺衍生物等。該等中,就硬化膜的著色、膜厚減薄的觀點而言,尤其較佳為酚系抗氧化劑、受阻胺系抗氧化劑、磷系抗氧化劑、醯胺系抗氧化劑、醯肼系抗氧化劑、硫系抗氧化劑,最佳為酚系抗氧化劑。該些抗氧化劑可單獨使用一種,亦可混合使用兩種以上。 Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, nitrites, and sub- Sulfate, thiosulfate, hydroxylamine derivative, and the like. Among these, from the viewpoint of coloring and thinning of the cured film, a phenolic antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, a guanamine antioxidant, and a lanthanide antioxidant are particularly preferable. A sulfur-based antioxidant, preferably a phenolic antioxidant. These antioxidants may be used alone or in combination of two or more.
具體例可列舉:日本專利特開2005-29515號公報的段落編號0026~段落編號0031中記載的化合物、日本專利特開2011-227106號公報的段落編號0106~段落編號0116中記載的化合物,將該些內容併入至本申請案說明書中。 Specific examples include the compound described in Paragraph No. 0026 to Paragraph No. 0031 of JP-A-2005-29515, and the compound described in Paragraph No. 0106 to Paragraph No. 0116 of JP-A-2011-227106. This content is incorporated into the specification of the present application.
較佳的市售品可列舉:艾迪科斯塔波(Adekastab)AO-60、艾迪科斯塔波(Adekastab)AO-20、艾迪科斯塔波(Adekastab)AO-80、艾迪科斯塔波(Adekastab)LA-52、艾迪科斯塔波 (Adekastab)LA-81、艾迪科斯塔波(Adekastab)AO-412S、艾迪科斯塔波(Adekastab)PEP-36、豔諾斯(Irganox)1035、豔諾斯(Irganox)1098、地奴彬(Tinuvin)144。 Preferred commercial products include: Adekastab AO-60, Adekastab AO-20, Adekastab AO-80, Eddie Costap (Adekastab) LA-52, Eddie Costabo (Adekastab) LA-81, Adekastab AO-412S, Adekastab PEP-36, Irganox 1035, Irganox 1098, Di Nubin (Tinuvin) 144.
於本發明的感光性樹脂組成物含有抗氧化劑的情形時,相對於感光性樹脂組成物中的總固體成分100質量份,抗氧化劑的含量較佳為0.1質量份~10質量份,更佳為0.2質量份~5質量份,尤佳為0.5質量份~4質量份。藉由設定為該範圍,可獲得所形成的膜的充分的透明性,且圖案形成時的感度亦變良好。 In the case where the photosensitive resin composition of the present invention contains an antioxidant, the content of the antioxidant is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 100 parts by mass of the total solid content of the photosensitive resin composition. 0.2 parts by mass to 5 parts by mass, particularly preferably 0.5 parts by mass to 4 parts by mass. By setting it as this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation also becomes favorable.
<<酸增殖劑>> <<acid proliferator>>
為了提高感度,本發明的感光性樹脂組成物可使用酸增殖劑。 In order to improve the sensitivity, an acid proliferating agent can be used as the photosensitive resin composition of the present invention.
本發明中可使用的酸增殖劑為可藉由酸觸媒反應而進一步產生酸、使反應體系內的酸濃度上升的化合物,且為於不存在酸的狀態下穩定地存在的化合物。 The acid-proliferating agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyst reaction and raise the acid concentration in the reaction system, and is a compound which is stably present in the absence of an acid.
此種酸增殖劑的具體例可列舉日本專利特開2011-221494的段落編號0226~段落編號0228中記載的酸增殖劑,將其內容併入至本申請案說明書中。 Specific examples of such an acid-proliferating agent include the acid-proliferating agent described in Paragraph No. 0226 to Paragraph No. 0228 of JP-A-2011-221494, the contents of which are incorporated herein by reference.
<<顯影促進劑>> <<Developing accelerator>>
本發明的感光性樹脂組成物可含有顯影促進劑。 The photosensitive resin composition of the present invention may contain a development accelerator.
顯影促進劑可參照日本專利特開2012-042837號公報的段落編號0171~段落編號0172中記載的顯影促進劑,將其內容併入至本申請案說明書中。 The development accelerator can be referred to the development accelerator described in Paragraph No. 0171 to Paragraph No. 0172 of JP-A-2012-042837, the contents of which are incorporated herein by reference.
顯影促進劑可單獨使用一種,亦可併用兩種以上。 The development accelerator may be used alone or in combination of two or more.
於本發明的感光性樹脂組成物含有顯影促進劑的情形時,就感度及殘膜率的觀點而言,相對於感光性組成物的總固體成分100質量份,顯影促進劑的添加量較佳為0質量份~30質量份,更佳為0.1質量份~20質量份,最佳為0.5質量份~10質量份。 When the photosensitive resin composition of the present invention contains a development accelerator, the amount of the development accelerator is preferably added to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. It is 0 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, most preferably 0.5 parts by mass to 10 parts by mass.
另外,其他添加劑亦可使用日本專利特開2012-8223號公報的段落編號0120~段落編號0121中記載的熱自由基產生劑、WO2011/136074A1中記載的含氮化合物及熱酸產生劑,將該些內容併入至本申請案說明書中。 In addition, as the other additive, the thermal radical generating agent described in Paragraph No. 0120 to Paragraph No. 0121 of JP-A-2012-8223, and the nitrogen-containing compound and the thermal acid generator described in WO2011/136074A1 may be used. These are incorporated into the specification of the present application.
[本發明的第2態樣] [Second aspect of the invention]
以下,對本發明的組成物的第2態樣加以說明。 Hereinafter, the second aspect of the composition of the present invention will be described.
本發明的組成物的特徵在於含有:(A-2)包含滿足下述(1)及(2)的至少一個的聚合物的聚合物成分,(1)含有(a2-1)具有酸基的結構單元、及(a2-2)具有交聯性基的結構單元的聚合物,(2)含有(a2-1)具有酸基的結構單元的聚合物、及含有(a2-2)具有交聯性基的結構單元的聚合物;(B-2)醌二疊氮化合物;(S)通式(1)所表示的化合物及/或通式(2)所表示的化合物;以及(C-2)溶劑。 The composition of the present invention is characterized by comprising (A-2) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (1) containing (a2-1) having an acid group. a structural unit, and (a2-2) a polymer having a structural unit having a crosslinkable group, (2) a polymer containing (a2-1) a structural unit having an acid group, and having (a2-2) a crosslinked group a polymer of a structural unit; (B-2) a quinonediazide compound; (S) a compound represented by the formula (1) and/or a compound represented by the formula (2); and (C-2) ) Solvent.
<(A-2)聚合物成分> <(A-2) polymer component>
本發明中所用的(A-2)聚合物成分包含以下聚合物的至少一種:含有(a2-1)具有酸基的結構單元及(a2-2)具有交聯性基的結構單元的聚合物、以及含有(a2-1)具有酸基的結構單元的聚合物及含有(a2-2)具有交聯性基的結構單元的聚合物。進而,(A-2)聚合物成分亦可含有該等以外的聚合物。 The (A-2) polymer component used in the present invention contains at least one of the following polymers: a polymer containing (a2-1) a structural unit having an acid group and (a2-2) a structural unit having a crosslinkable group. And a polymer containing (a2-1) a structural unit having an acid group and a polymer containing (a2-2) a structural unit having a crosslinkable group. Further, the (A-2) polymer component may contain a polymer other than the above.
<<(a2-1)具有酸基的結構單元>> <<(a2-1) Structural unit having an acid group>>
藉由在(A-2)聚合物成分中含有(a2-1)具有酸基的結構單元,容易溶解於鹼性的顯影液中,可更有效地發揮本發明的效果。酸基通常是使用可形成酸基的單體以具有酸基的結構單元的形式組入至聚合物中。藉由使此種具有酸基的結構單元含有於聚合物中,有容易溶解於鹼性的顯影液中的傾向。 By containing (a2-1) a structural unit having an acid group in the polymer component (A-2), it is easily dissolved in an alkaline developing solution, and the effect of the present invention can be more effectively exhibited. The acid group is usually incorporated into the polymer in the form of a structural unit having an acid group using a monomer capable of forming an acid group. When such a structural unit having an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution.
本發明中所用的酸基可例示:來源於羧酸基的酸基、來源於磺醯胺基的酸基、來源於膦酸基的酸基、來源於磺酸基的酸基、來源於酚性羥基的酸基、磺醯胺基、磺醯基醯亞胺基等,較佳為來源於羧酸基的酸基及/或來源於酚性羥基的酸基。本發明中所用的含酸基的結構單元尤其較佳為含羧基及/或酚性羥基的結構單元。 The acid group used in the present invention can be exemplified by an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, and a phenol derived from a phenol group. The acid group of the hydroxyl group, the sulfonylamino group, the sulfonyl fluorenylene group or the like is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group. The acid group-containing structural unit used in the present invention is particularly preferably a structural unit containing a carboxyl group and/or a phenolic hydroxyl group.
本發明中所用的含酸基的結構單元亦較佳為來源於苯乙烯的結構單元、或來源於乙烯系化合物的結構單元、來源於(甲基)丙烯酸及/或其酯的結構單元。例如可使用日本專利特開2012-88459號公報的段落編號0021~段落編號0023及段落編號0029~段落編號0044中記載的化合物,將其內容併入至本申請案說明書中。其 中,較佳為來源於對羥基苯乙烯、(甲基)丙烯酸、馬來酸、馬來酸酐的結構單元。 The acid group-containing structural unit used in the present invention is also preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth)acrylic acid and/or an ester thereof. For example, the compounds described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the contents thereof are incorporated into the specification of the present application. its Among them, a structural unit derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid or maleic anhydride is preferred.
就感度的觀點而言,本發明中尤其較佳為含有含羧基的重複單元或含酚性羥基的重複單元。例如可使用日本專利特開2012-88459號公報的段落編號0021~段落編號0023及段落編號0029~段落編號0044中記載的化合物,將其內容併入至本申請案說明書中。 From the viewpoint of sensitivity, in the present invention, it is particularly preferred to contain a repeating unit containing a carboxyl group or a repeating unit having a phenolic hydroxyl group. For example, the compounds described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the contents thereof are incorporated into the specification of the present application.
<<(a2-2)具有交聯性基的結構單元>> <<(a2-2) Structural unit having a crosslinkable group>>
另外,(a2-2)具有交聯性基的結構單元較佳為含有具有選自由環氧基、氧雜環丁基、-NH-CH2-O-R(R為氫原子或碳數1~20的烷基)所表示的基團、乙烯性不飽和基所組成的組群中的至少一個的結構單元。 Further, the structural unit having a crosslinkable group (a2-2) preferably contains a group selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R is a hydrogen atom or a carbon number of 1 to 20). A structural unit of at least one of a group consisting of a group represented by an alkyl group and an ethylenically unsaturated group.
(a2-2)具有交聯性基的結構單元與上文所述的(A-1)聚合物中的(a1-2)具有交聯性基的結構單元為相同含意,除了調配量以外較佳範圍亦相同。 (a2-2) The structural unit having a crosslinkable group has the same meaning as the structural unit having a crosslinkable group of (a1-2) in the (A-1) polymer described above, except for the blending amount. The range is also the same.
<<(a2-3)其他結構單元>> <<(a2-3) Other structural units>>
進而,(A-2)聚合物成分中,亦可與所述結構單元(a2-1)及所述結構單元(a2-2)一起而含有所述結構單元(a2-1)及所述結構單元(a2-2)以外的結構單元(a2-3)。 Further, in the polymer component (A-2), the structural unit (a2-1) and the structure may be contained together with the structural unit (a2-1) and the structural unit (a2-2). Structural unit (a2-3) other than unit (a2-2).
形成結構單元(a2-3)的單體只要為所述結構單元(a2-1)及結構單元(a2-2)以外的不飽和化合物,則並無特別限制。 The monomer forming the structural unit (a2-3) is not particularly limited as long as it is an unsaturated compound other than the structural unit (a2-1) and the structural unit (a2-2).
例如可列舉:苯乙烯類、(甲基)丙烯酸烷基酯、(甲基)丙烯酸 環狀烷基酯、(甲基)丙烯酸芳基酯、不飽和二羧酸二酯、雙環不飽和化合物類、馬來醯亞胺化合物類、不飽和芳香族化合物、共軛二烯系化合物、其他不飽和化合物。形成結構單元(a2-3)的單體可單獨使用或組合使用兩種以上。 For example, styrene, alkyl (meth)acrylate, (meth)acrylic acid a cyclic alkyl ester, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, a bicyclic unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, Other unsaturated compounds. The monomers forming the structural unit (a2-3) may be used alone or in combination of two or more.
(A-2)聚合物成分的所有結構單元中,較佳為含有3mol%~70mol%的結構單元(a2-1),更佳為含有10mol%~60mol%,進而佳為含有15mol%~50mol%。 (A-2) All structural units of the polymer component preferably contain 3 mol% to 70 mol% of the structural unit (a2-1), more preferably 10 mol% to 60 mol%, and even more preferably 15 mol% to 50 mol. %.
(A-2)聚合物成分的所有結構單元中,較佳為含有3mol%~70mol%的結構單元(a2-2),更佳為含有10mol%~60mol%,進而佳為含有15mol%~40mol%。 (A-2) All structural units of the polymer component preferably contain 3 mol% to 70 mol% of the structural unit (a2-2), more preferably 10 mol% to 60 mol%, and even more preferably 15 mol% to 40 mol. %.
(A-2)聚合物成分的所有結構單元中,較佳為含有1mol%~80mol%的結構單元(a2-3),更佳為含有5mol%~50mol%,進而佳為含有8mol%~30mol%。 (A-2) All structural units of the polymer component preferably contain 1 mol% to 80 mol% of the structural unit (a2-3), more preferably 5 mol% to 50 mol%, and even more preferably 8 mol% to 30 mol. %.
本發明的第2形態的組成物較佳為以組成物的固體成分的70質量%以上的比例而含有(A-2)聚合物成分。 The composition of the second aspect of the present invention preferably contains the polymer component (A-2) in a proportion of 70% by mass or more of the solid content of the composition.
<(B-2)醌二疊氮化合物> <(B-2) 醌diazide compound>
本發明的組成物中所用的醌二疊氮化合物可使用藉由光化射線的照射而產生羧酸的1,2-醌二疊氮化合物。1,2-醌二疊氮化合物可使用:酚性化合物或醇性化合物(以下稱為「母核」)與1,2-萘醌二疊氮磺醯鹵的縮合物。該些化合物的具體例例如可參照日本專利特開2012-088459號公報的段落編號0075~段落編號0078的記載,將其內容併入至本申請案說明書中。 As the quinonediazide compound used in the composition of the present invention, a 1,2-quinonediazide compound which generates a carboxylic acid by irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used. Specific examples of such a compound can be referred to, for example, the description of Paragraph No. 0075 to Paragraph No. 0078 of JP-A-2012-088459, the contents of which are incorporated herein by reference.
於酚性化合物或醇性化合物(母核)與1,2-萘醌二疊氮磺醯鹵的縮合反應中,可使用相對於酚性化合物或醇性化合物中的OH基數而相當於較佳為30mol%~85mol%、更佳為50mol%~70mol%的1,2-萘醌二疊氮磺醯鹵。縮合反應可藉由公知的方法來實施。 In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) with a 1,2-naphthoquinonediazidesulfonium halide, the number of OH groups in the phenolic compound or the alcoholic compound can be used to be preferably equivalent. It is 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonium halide. The condensation reaction can be carried out by a known method.
另外,1,2-醌二疊氮化合物亦可較佳地使用將所述例示的母核的酯鍵變更為醯胺鍵的1,2-萘醌二疊氮磺醯胺類、例如2,3,4-三胺基二苯甲酮-1,2-萘醌二疊氮-4-磺醯胺等。另外,亦可使用4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚(1.0莫耳)與1,2-萘醌二疊氮-5-磺醯氯(3.0莫耳)的縮合物、1,1,1-三(對羥基苯基)乙烷(1.0莫耳)與1,2-萘醌二疊氮-5-磺醯氯(2.0莫耳)的縮合物、2,3,4,4'-四羥基二苯甲酮(1.0莫耳)與1,2-萘醌二疊氮-5-磺酸酯(2.44莫耳)的縮合物等。 Further, as the 1,2-quinonediazide compound, a 1,2-naphthoquinonediazidesulfonamide which changes the ester bond of the exemplified parent core to a guanamine bond, for example, 2 can also be preferably used. 3,4-Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide and the like. Alternatively, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1 may also be used. a condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (3.0 mol), 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone a condensate of diazide-5-sulfonyl chloride (2.0 mol), 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5 a condensate of a sulfonate (2.44 mole) or the like.
該些醌二疊氮化合物可單獨使用或組合使用兩種以上。相對於所述感光性樹脂組成物中的總固體成分100質量份,本發明的感光性樹脂組成物中的醌二疊氮化合物的調配量較佳為1質量份~50質量份,更佳為2質量份~40質量份,進而佳為10質量份~25質量份。 These quinonediazide compounds may be used alone or in combination of two or more. The amount of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably from 1 part by mass to 50 parts by mass, more preferably from 100 parts by mass of the total solid content in the photosensitive resin composition. 2 parts by mass to 40 parts by mass, and more preferably 10 parts by mass to 25 parts by mass.
藉由將(B-2)醌二疊氮化合物的調配量設定為所述範圍,光化射線的照射部分與未照射部分於成為顯影液的鹼性水溶液中的溶解度之差大,圖案化性能變良好,另外所得的硬化膜的耐溶劑性變良好。 By setting the blending amount of the (B-2) quinonediazide compound to the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion in the alkaline aqueous solution to be the developing solution is large, and the patterning property is obtained. It became good, and the solvent resistance of the obtained cured film became favorable.
<(S)成分> <(S) component>
本發明的第2形態的組成物含有與上文所述的第1形態的組成物中的(S)成分相同的(S)成分,較佳範圍亦相同。 The composition of the second aspect of the present invention contains the same component (S) as the component (S) in the composition of the first embodiment described above, and the preferred range is also the same.
相對於第2形態的感光性樹脂組成物的總質量,(S)成分較佳為以0.1質量%~20質量%的比例而含有,更佳為以0.1質量%~10質量%的比例而含有,進而佳為以1質量%~10質量%的比例而含有,尤佳為以2質量%~5質量%的比例而含有。(S)成分可僅為一種,亦可為兩種以上。於(S)成分為兩種以上的情形時,較佳為其合計量成為所述範圍。 The (S) component is preferably contained in a ratio of 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, based on the total mass of the photosensitive resin composition of the second embodiment. Further, it is preferably contained in a proportion of from 1% by mass to 10% by mass, and more preferably from 2% by mass to 5% by mass. The (S) component may be one type or two or more types. When the (S) component is two or more, it is preferred that the total amount thereof is in the above range.
<(C-2)溶劑> <(C-2) Solvent>
本發明的感光性樹脂組成物含有溶劑。本發明的感光性樹脂組成物中使用的溶劑可使用上文所述的第1態樣的(C-1)溶劑,較佳範圍亦相同。 The photosensitive resin composition of the present invention contains a solvent. The solvent used in the photosensitive resin composition of the present invention can be the (C-1) solvent of the first aspect described above, and the preferred range is also the same.
相對於感光性樹脂組成物中的所有成分100質量份,本發明的感光性樹脂組成物中的溶劑的含量較佳為50質量份~95質量份,更佳為60質量份~90質量份。溶劑可僅使用一種,亦可使用兩種以上。於使用兩種以上的情形時,較佳為其合計量成為所述範圍。 The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, more preferably 60 parts by mass to 90 parts by mass, per 100 parts by mass of all the components in the photosensitive resin composition. The solvent may be used singly or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.
<其他成分> <Other ingredients>
本發明的組成物除了所述成分以外,可於不損及本發明的效果的範圍內,視需要而較佳地添加交聯劑、鹼性化合物、界面活性劑、抗氧化劑。進而,本發明的感光性樹脂組成物中,可添加 顯影促進劑、塑化劑、熱自由基產生劑、熱酸產生劑、紫外線吸收劑、增稠劑、及有機或無機的防沈澱劑等公知的添加劑。該些成分與上文所述的第1態樣相同,較佳範圍亦相同。另外,亦可含有(S)成分以外的矽烷偶合劑,且亦可將(S)成分以外的矽烷偶合劑的調配量設為小於本發明的組成物的固體成分的0.1質量%。該些成分可分別僅使用一種,亦可使用兩種以上。 In addition to the above components, the composition of the present invention may preferably contain a crosslinking agent, a basic compound, a surfactant, and an antioxidant as needed within the range not impairing the effects of the present invention. Further, in the photosensitive resin composition of the present invention, it is possible to add A known additive such as a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a UV absorber, a thickener, and an organic or inorganic anti-precipitation agent. These components are the same as the first aspect described above, and the preferred ranges are also the same. In addition, a decane coupling agent other than the component (S) may be contained, and the amount of the decane coupling agent other than the component (S) may be set to be less than 0.1% by mass of the solid content of the composition of the present invention. These components may be used alone or in combination of two or more.
[本發明的組成物的第3態樣] [The third aspect of the composition of the present invention]
本發明的第3態樣的組成物的特徵在於含有:(A-3)聚合性單體;(B-3)光聚合起始劑;(A-4)包含滿足下述(1)及(2)的至少一個的聚合物的聚合物成分,(1)含有(a4-1)具有酸基的結構單元、及(a4-2)具有交聯性基的結構單元的聚合物,(2)含有(a4-1)具有酸基的結構單元的聚合物、及含有(a4-2)具有交聯性基的結構單元的聚合物;(S)通式(1)及/或通式(2)所表示的化合物;以及(C-3)溶劑。 The composition of the third aspect of the present invention is characterized by comprising: (A-3) a polymerizable monomer; (B-3) a photopolymerization initiator; (A-4) comprising the following (1) and ( 2) a polymer component of at least one polymer, (1) a polymer comprising (a4-1) a structural unit having an acid group, and (a4-2) a structural unit having a crosslinkable group, (2) a polymer containing (a4-1) a structural unit having an acid group, and a polymer containing (a4-2) a structural unit having a crosslinkable group; (S) a general formula (1) and/or a general formula (2) ) a compound represented; and (C-3) a solvent.
(A-3)聚合性單體 (A-3) Polymerizable monomer
本發明中所用的聚合性單體可適當地選定使用適用於此種組成物的單體,其中較佳為使用乙烯性不飽和化合物。 The polymerizable monomer used in the present invention can be appropriately selected and used as a monomer suitable for such a composition, and among them, an ethylenically unsaturated compound is preferably used.
乙烯性不飽和化合物為具有至少一個乙烯性不飽和雙鍵的聚 合性化合物。乙烯性不飽和化合物的例子可列舉:不飽和羧酸(例如丙烯酸、甲基丙烯酸、衣康酸、丁烯酸、異丁烯酸、馬來酸等)或其酯類、醯胺類,較佳可使用不飽和羧酸與脂肪族多元醇化合物的酯、不飽和羧酸與脂肪族多元胺化合物的醯胺類。 An ethylenically unsaturated compound is a polymer having at least one ethylenically unsaturated double bond Synthetic compound. Examples of the ethylenically unsaturated compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof, guanamines, preferably. An ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound is used.
例如可列舉日本專利特開2006-23696號公報的段落0011中記載的成分、或日本專利特開2006-64921號公報的段落0031~段落0047中記載的成分,將該些記載併入至本申請案說明書中。 For example, the components described in paragraph 0011 of JP-A-2006-23696, or the components described in paragraphs 0031 to 0047 of JP-A-2006-64921, the contents of which are incorporated herein by reference. In the case description.
另外,使用異氰酸酯與羥基的加成反應所製造的胺基甲酸酯加成聚合性化合物亦較佳,日本專利特開昭51-37193號公報、日本專利特公平2-32293號公報、日本專利特公平2-16765號公報中記載般的丙烯酸胺基甲酸酯類,或日本專利特公昭58-49860號公報、日本專利特公昭56-17654號公報、日本專利特公昭62-39417號公報、日本專利特公昭62-39418號公報中記載的具有環氧乙烷骨架的胺基甲酸酯化合物類亦較佳,將該些記載併入至本申請案說明書中。 Further, a urethane addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also preferred. Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 56-196760, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39417 A urethane compound having an oxirane skeleton described in Japanese Patent Publication No. Sho 62-39418 is also preferred, and the description is incorporated into the specification of the present application.
其他例可列舉:日本專利特開昭48-64183號公報、日本專利特公昭49-43191號公報、日本專利特公昭52-30490號公報的各公報中記載般的聚酯丙烯酸酯類,使環氧樹脂與(甲基)丙烯酸反應所得的環氧丙烯酸酯類等多官能的丙烯酸酯或甲基丙烯酸酯,將該些記載併入至本申請案說明書中。進而,亦可使用「日本接著協會雜誌」(vol.20、No.7、300頁~308頁(1984年))中作為光硬化性單體及寡聚物而介紹的化合物。 Other examples include polyester acrylates as described in each of the publications of Japanese Laid-Open Patent Publication No. SHO-49-64183, Japanese Patent Publication No. SHO-49-43191, and Japanese Patent Publication No. Sho 52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an oxygen resin with (meth)acrylic acid is incorporated in the specification of the present application. Further, a compound which is described as a photocurable monomer and an oligomer in "Japanese Association of Associations" (vol. 20, No. 7, pp. 300-308 (1984)) can also be used.
關於該些乙烯性不飽和化合物,其結構、單獨使用或併用、添加量等使用方法的詳細情況可根據最終的感材(sensitive material)的性能設計而任意設定。例如可根據如下觀點來選擇。 Regarding the ethylenically unsaturated compound, the details of the structure, the use alone or in combination, the amount of addition, and the like can be arbitrarily set according to the performance design of the final sensitive material. For example, it can be selected according to the following points.
聚合性單體較佳為多官能,更佳為3官能以上,進而佳為4官能以上。上限並不特別存在,10官能以下較為實際。進而,藉由併用官能數不同及/或聚合性基不同(例如丙烯酸酯、甲基丙烯酸酯、苯乙烯化合物、乙烯醚化合物)的化合物來調節力學特性亦有效。 The polymerizable monomer is preferably polyfunctional, more preferably trifunctional or more, and still more preferably tetrafunctional or higher. The upper limit is not particularly present, and the 10-functional or less is more practical. Further, it is also effective to adjust the mechanical properties by using a compound having a different number of functional groups and/or a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound).
另外,就調整顯影性的觀點而言,含羧基的聚合性化合物亦較佳。於該情形時,藉由樹脂與(C-3)成分的交聯,可提高力學特性,因而較佳。 Further, from the viewpoint of adjusting the developability, a carboxyl group-containing polymerizable compound is also preferable. In this case, it is preferred to improve the mechanical properties by crosslinking the resin with the component (C-3).
進而,就與基板的密著性、與自由基聚合起始劑的相容性等的觀點而言,亦較佳為含有環氧乙烷(EO(Ethylene Oxide))改質體、胺基甲酸酯鍵。 Further, from the viewpoints of adhesion to a substrate, compatibility with a radical polymerization initiator, and the like, it is also preferable to contain an ethylene oxide (EO (Ethylene Oxide) modified body, an amine group A). Acid ester bond.
根據以上的觀點,較佳為季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三((甲基)丙烯醯氧基乙基)異三聚氰酸酯、季戊四醇四(甲基)丙烯酸酯EO改質體、二季戊四醇六(甲基)丙烯酸酯EO改質體等,以及作為市售品的卡亞拉得(KAYARAD)DPHA(日本化藥(股)製造),NK酯(NK Ester)A-TMMT、NK酯(NK Ester)A-TMPT、NK酯(NK Ester)A-TMM-3、NK寡聚(NK Oligo)UA-32P、NK寡聚(NK Oligo)UA-7200(以上為新 中村化學工業(股)製造),亞羅尼斯(Aronix)M-305、亞羅尼斯(Aronix)M-306、亞羅尼斯(Aronix)M-309、亞羅尼斯(Aronix)M-450、亞羅尼斯(Aronix)M-402、TO-1382(以上為東亞合成(股)製造),V#802(大阪有機化學工業(股)製造)。 From the above viewpoints, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris((A) are preferred. Alkenyloxyethyl)isophthalocyanate, pentaerythritol tetra(meth)acrylate EO modified body, dipentaerythritol hexa(meth)acrylate EO modified body, and the like, and commercially available products KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-TMMT, NK Ester A-TMPT, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (above new) Nakamura Chemical Industry Co., Ltd., Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Asia Aronix M-402, TO-1382 (above is manufactured by East Asia Synthetic Co., Ltd.), V#802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
本發明中應用的聚合性單體較佳為下述式(A-3-1)所表示的化合物。 The polymerizable monomer to be used in the present invention is preferably a compound represented by the following formula (A-3-1).
式(A-3-1)
式(A-3-1)中,L表示二價以上的連結基。連結基並無特別限定,可列舉伸烷基、羰基、亞胺基、醚基(-O-)、硫醚基(-S-)或該等的組合。連結基的碳數並無特別限定,較佳為2~24,更佳為2~12。其中,較佳為所述碳數的分支伸烷基。 In the formula (A-3-1), L represents a divalent or higher linking group. The linking group is not particularly limited, and examples thereof include an alkyl group, a carbonyl group, an imido group, an ether group (-O-), a thioether group (-S-), or a combination thereof. The carbon number of the linking group is not particularly limited, but is preferably 2 to 24, more preferably 2 to 12. Among them, a branched alkyl group having a carbon number is preferred.
式(A-3-1)中,A表示聚合性官能基。聚合性官能基較佳為乙烯基或含乙烯基的基團。含乙烯基的基團可列舉:丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、乙烯基苯基等。 In the formula (A-3-1), A represents a polymerizable functional group. The polymerizable functional group is preferably a vinyl group or a vinyl group-containing group. Examples of the vinyl group-containing group include an acryloyl group, a methacryloyl group, an acryloxy group, a methacryloxy group, a vinyl phenyl group, and the like.
式(A-3-1)中,Ra表示取代基。取代基並無特別限定,可列舉:烷基(較佳為碳數1~21)、烯基(較佳為碳數2~12)、芳基(較佳為碳數6~24)等。該些取代基亦可進一步具有取代基,可具有的取代基可列舉:羥基、烷氧基(較佳為碳數1~6)、羧基、 醯基(較佳為碳數1~6)等。 In the formula (A-3-1), Ra represents a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 21 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), and an aryl group (preferably having 6 to 24 carbon atoms). These substituents may further have a substituent, and examples of the substituent which may be exemplified are a hydroxyl group, an alkoxy group (preferably having a carbon number of 1 to 6), a carboxyl group, and the like. Sulfhydryl (preferably carbon number 1 to 6) and the like.
式(A-3-1)中,na表示1~10的整數,較佳為3~8。nb表示0~9的整數,較佳為2~7。na+nb為10以下,較佳為2~8。於na、nb為2以上時,其所規定的多個結構部位亦可互不相同。 In the formula (A-3-1), na represents an integer of 1 to 10, preferably 3 to 8. Nb represents an integer of 0 to 9, preferably 2 to 7. Na+nb is 10 or less, preferably 2 to 8. When na and nb are 2 or more, the plurality of structural portions defined by the plurality of structures may be different from each other.
相對於所述(A-3)聚合物成分的合計100質量份,聚合性單體的含量較佳為5質量份~60質量份,更佳為10質量份~50質量份,進而佳為15質量份~45質量份。 The content of the polymerizable monomer is preferably from 5 parts by mass to 60 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, even more preferably from 15 parts by mass to the total of the (A-3) polymer component. Parts by mass to 45 parts by mass.
相對於總固體成分,本發明的感光性樹脂組成物較佳為以5質量%~60質量%的比例而含有聚合性單體,更佳為以10質量%~50質量%的比例含有,進而佳為以15質量%~45質量%的比例含有。聚合性單體可僅使用一種,亦可使用兩種以上。於使用兩種以上的情形時,較佳為其合計量成為所述範圍。 The photosensitive resin composition of the present invention preferably contains a polymerizable monomer in a proportion of from 5% by mass to 60% by mass, more preferably from 10% by mass to 50% by mass, based on the total solid content. Jia is contained in a ratio of 15% by mass to 45% by mass. The polymerizable monomer may be used alone or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.
(B-3)光聚合起始劑 (B-3) Photopolymerization initiator
本發明中可使用的光聚合起始劑為藉由光化射線而感光,引發、促進所述聚合性單體的聚合的化合物。 The photopolymerization initiator which can be used in the present invention is a compound which is photosensitive by actinic rays, which initiates and promotes polymerization of the polymerizable monomer.
本發明中可使用的光聚合起始劑較佳為藉由光化射線而感光,引發、促進所述乙烯性不飽和化合物的聚合的化合物。 The photopolymerization initiator which can be used in the present invention is preferably a compound which is photosensitive by actinic rays, which initiates and promotes polymerization of the ethylenically unsaturated compound.
本發明中所謂「放射線」,只要為可藉由其照射而賦予可由成分B-3產生起始種的能量的活性能量線,則並無特別限制,廣泛地包含α射線、γ射線、X射線、紫外線(UV)、可見光線、電子束等。 In the present invention, the "radiation" is not particularly limited as long as it is an energy source capable of imparting energy to the starting species by the component B-3 by irradiation, and broadly includes α rays, γ rays, and X rays. , ultraviolet (UV), visible light, electron beam, etc.
光聚合起始劑為感應較佳為波長300nm以上、更佳為波長300nm~450nm的光化射線,引發、促進所述(A-3)聚合性單體的聚合的化合物。另外,關於不直接感應波長300nm以上的光化射線的光聚合起始劑,亦只要為藉由與增感劑併用而感應波長300nm以上的光化射線的化合物,則可與增感劑組合而較佳地使用。 The photopolymerization initiator is a compound which induces and accelerates the polymerization of the (A-3) polymerizable monomer, preferably an actinic ray having a wavelength of 300 nm or more, more preferably 300 nm to 450 nm. In addition, the photopolymerization initiator which does not directly induce actinic rays having a wavelength of 300 nm or more can be combined with a sensitizer as long as it is a compound which induces actinic rays having a wavelength of 300 nm or more by using in combination with a sensitizer. It is preferably used.
光聚合起始劑例如可列舉:肟酯化合物、有機鹵化化合 物、氧基二唑化合物、羰基化合物、縮酮化合物、安息香化合物、吖啶化合物、有機過氧化化合物、偶氮化合物、香豆素化合物、疊氮化合物、茂金屬化合物、六芳基聯咪唑化合物、有機硼酸化合物、二磺酸化合物、α胺基酮化合物、鎓鹽化合物、醯基膦(氧化物)化合物。該等中,就感度的方面而言,較佳為肟酯化合物、α胺基酮化合物、六芳基聯咪唑化合物,更佳為肟酯化合物或α胺基酮化合物。 The photopolymerization initiator may, for example, be an oxime ester compound or an organic halogenated compound. , oxydiazole compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxidation compound, azo compound, coumarin compound, azide compound, metallocene compound, hexaarylbiimidazole compound An organoboric acid compound, a disulfonic acid compound, an alpha aminoketone compound, a phosphonium salt compound, or a mercaptophosphine (oxide) compound. Among these, from the viewpoint of sensitivity, an oxime ester compound, an α-aminoketone compound, and a hexaarylbiimidazole compound are preferable, and an oxime ester compound or an α-aminoketone compound is more preferable.
該些化合物的具體例例如可參照日本專利特開2011-186398公報的段落編號0061~段落編號0073的記載,將其內容併入至本申請案說明書中。 Specific examples of such compounds can be found in the description of Paragraph No. 0061 to Paragraph No. 0073 of JP-A-2011-186398, the contents of which are incorporated herein by reference.
光聚合起始劑亦可使用市售品,例如可使用豔佳固(IRGACURE)OXE 01、豔佳固(IRGACURE)OXE 02(巴斯夫(BASF)製造)等。 Commercially available products can also be used as the photopolymerization initiator. For example, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), or the like can be used.
光聚合起始劑可使用一種或組合使用兩種以上。另外,於使用對曝光波長不具有吸收的起始劑的情形時,必須使用增感 劑。 The photopolymerization initiator may be used alone or in combination of two or more. In addition, when using an initiator that does not absorb the exposure wavelength, sensitization must be used. Agent.
相對於所述(A-3)聚合物成分的合計100質量份,本發明的感光性樹脂組成物中的光聚合起始劑的含量較佳為0.5重量份~30重量份,更佳為2重量份~20重量份。 The content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably from 0.5 part by weight to 30 parts by weight, more preferably 2, based on 100 parts by mass of the total of the (A-3) polymer component. Parts by weight to 20 parts by weight.
相對於總固體成分,本發明的感光性樹脂組成物較佳為以0.5質量%~30質量%的比例而含有光聚合起始劑,更佳為以2質量%~20質量%的比例含有。 The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator in a proportion of 0.5% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, based on the total solid content.
(A-4)聚合物成分 (A-4) Polymer composition
本發明中所用的(A-4)聚合物成分含有以下聚合物的至少一種:含有(a4-1)具有酸基的結構單元及(a4-2)具有交聯性基的重複單元的聚合物、以及含有(a4-1)具有酸基的結構單元的聚合物及含有(a4-2)具有交聯性基的結構單元的聚合物。進而,亦可於(A-4)聚合物成分中,與所述結構單元(a4-1)及所述結構單元(a4-2)一起而含有所述結構單元(a4-1)及所述結構單元(a4-2)以外的結構單元(a4-3)。 The (A-4) polymer component used in the present invention contains at least one of the following polymers: a polymer containing (a4-1) a structural unit having an acid group and (a4-2) a repeating unit having a crosslinkable group. And a polymer containing (a4-1) a structural unit having an acid group and a polymer containing (a4-2) a structural unit having a crosslinkable group. Further, in the polymer component (A-4), the structural unit (a4-1) and the structural unit (a4-1) and the structural unit (a4-2) may be contained together Structural unit (a4-3) other than the structural unit (a4-2).
(A-4)聚合物所含的(a4-1)具有酸基的結構單元可採用與上文所述的第2態樣的(A-2)聚合物成分中所述的(a2-1)具有酸基的結構單元相同者,較佳範圍亦相同。 (A-4) The structural unit having an acid group (a4-1) contained in the polymer may be as described in the (A-2) polymer component of the second aspect described above (a2-1) The structural units having an acid group are the same, and the preferred ranges are also the same.
(A-4)聚合物所含的(a4-2)具有交聯性基的結構單元可採用與上文所述的第2態樣的(A-2)聚合物成分中所述的(a2-2)具有交聯性基的結構單元相同者,較佳範圍亦相同。 (A-4) The structural unit having a crosslinkable group (a4-2) contained in the polymer may be as described in the (A-2) polymer component of the second aspect described above (a2) -2) The structural units having a crosslinkable group are the same, and the preferred ranges are also the same.
(A-4)聚合物所含的結構單元(a4-3)例如可採用與上文所 述的第2態樣的(A-2)聚合物成分中所述的(a2-3)其他結構單元相同者,較佳範圍亦相同。 (A-4) The structural unit (a4-3) contained in the polymer can be, for example, the above The (a2-3) other structural unit described in the (A-2) polymer component of the second aspect described above is the same, and the preferred range is also the same.
本發明的組成物較佳為以組成物的固體成分的30質量%以上的比例而含有(A-4)聚合物成分。 The composition of the present invention preferably contains the polymer component (A-4) in a proportion of 30% by mass or more of the solid content of the composition.
<(C-3)溶劑> <(C-3) Solvent>
本發明的感光性樹脂組成物含有溶劑。本發明的感光性樹脂組成物較佳為以將本發明的各成分溶解於溶劑中的溶液的形式製備。 The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared in the form of a solution in which each component of the present invention is dissolved in a solvent.
本發明的感光性樹脂組成物中使用的溶劑可使用公知的溶劑、例如上文所述的第1態樣的(C-1)溶劑。 The solvent used in the photosensitive resin composition of the present invention can be a known solvent, for example, the (C-1) solvent of the first aspect described above.
相對於感光性樹脂組成物中的總成分100質量份,本發明的感光性樹脂組成物中的溶劑的含量較佳為50質量份~95質量份,更佳為60質量份~90質量份。溶劑可僅使用一種,亦可使用兩種以上。於使用兩種以上的情形時,較佳為其合計量成為所述範圍。 The content of the solvent in the photosensitive resin composition of the present invention is preferably from 50 parts by mass to 95 parts by mass, more preferably from 60 parts by mass to 90 parts by mass, per 100 parts by mass of the total component of the photosensitive resin composition. The solvent may be used singly or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.
<(S)成分> <(S) component>
本發明的組成物含有上文所述的(S)成分。第2態樣中所用的(S)成分可使用上文所述的第1態樣的(S)成分,較佳範圍亦相同。 The composition of the present invention contains the component (S) described above. The (S) component used in the second aspect can be used as the (S) component of the first aspect described above, and the preferred range is also the same.
相對於感光性樹脂組成物的總質量,(S)成分較佳為以0.1質量%~20質量%的比例而含有,更佳為以0.1質量%~10質量%的比例而含有,進而佳為以1質量%~10質量%的比例而含有,尤 佳為以2質量%~5質量%的比例而含有。(S)成分可僅為一種,亦可為兩種以上。於(S)成分為兩種以上的情形時,較佳為其合計量成為所述範圍。 The (S) component is preferably contained in a proportion of 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass based on the total mass of the photosensitive resin composition, and further preferably Contained in a ratio of 1% by mass to 10% by mass, especially It is contained in a ratio of 2% by mass to 5% by mass. The (S) component may be one type or two or more types. When the (S) component is two or more, it is preferred that the total amount thereof is in the above range.
<其他成分> <Other ingredients>
本發明的感光性樹脂組成物除了所述成分以外,可視需要而較佳地添加界面活性劑、聚合抑制劑等。 In addition to the above components, the photosensitive resin composition of the present invention may preferably be added with a surfactant, a polymerization inhibitor or the like as needed.
界面活性劑可使用與上文所述的第1態樣的界面活性劑相同的化合物,較佳範圍亦相同。 As the surfactant, the same compound as the surfactant of the first aspect described above can be used, and the preferred range is also the same.
所述聚合抑制劑例如可使用日本專利特開2008-250074號公報的段落編號0101~段落編號0102中記載的熱聚合抑制劑,將該些內容併入至本申請案說明書中。另外,亦可含有(S)成分以外的矽烷偶合劑,且亦可將(S)成分以外的矽烷偶合劑的調配量設為小於本發明的組成物的固體成分的0.1質量%。該些成分可分別僅使用一種,亦可使用兩種以上。 The polymerization inhibitor can be, for example, a thermal polymerization inhibitor described in Paragraph No. 0101 to Paragraph No. 0102 of JP-A-2008-250074, which is incorporated herein by reference. In addition, a decane coupling agent other than the component (S) may be contained, and the amount of the decane coupling agent other than the component (S) may be set to be less than 0.1% by mass of the solid content of the composition of the present invention. These components may be used alone or in combination of two or more.
<感光性樹脂組成物的製備方法> <Method for Preparing Photosensitive Resin Composition>
將各成分以既定的比例且利用任意的方法混合,攪拌溶解而製備感光性樹脂組成物。例如,亦可製成將成分分別預先溶解於溶劑中的溶液後,將該些溶液以既定的比例混合而製備樹脂組成物。如以上般製備的組成物溶液亦可於使用例如孔徑0.2μm的過濾器等進行過濾後加以使用。 Each component was mixed at a predetermined ratio by an arbitrary method, and stirred and dissolved to prepare a photosensitive resin composition. For example, a solution in which components are previously dissolved in a solvent may be prepared, and these solutions may be mixed in a predetermined ratio to prepare a resin composition. The composition solution prepared as above can also be used after being filtered using, for example, a filter having a pore size of 0.2 μm.
<本發明的第1態樣的硬化膜的製造方法> <Method for Producing Cured Film According to First Aspect of the Present Invention>
本發明的第1態樣的硬化膜的製造方法較佳為包括以下的 (1-1)~(5-1)的步驟。 The method for producing a cured film according to the first aspect of the present invention preferably includes the following Steps of (1-1)~(5-1).
(1-1)將本發明的第1態樣的感光性樹脂組成物塗佈於基板上的步驟;(2-1)自所塗佈的感光性樹脂組成物中去除溶劑的步驟;(3-1)藉由光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟;(4-1)藉由水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟;(5-1)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 (1-1) a step of applying the photosensitive resin composition of the first aspect of the present invention to a substrate; (2-1) a step of removing a solvent from the applied photosensitive resin composition; (3) -1) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4-1) a step of developing the exposed photosensitive resin composition by an aqueous developing solution; (5- 1) A post-baking step of thermally curing the developed photosensitive resin composition.
以下依序對各步驟加以說明。 The steps are described in order below.
於(1-1)的塗佈步驟中,較佳為將本發明的感光性樹脂組成物塗佈於基板上而製成含有溶劑的濕潤膜。較佳為於將感光性樹脂組成物塗佈於基板上之前,進行鹼清洗或電漿清洗等基板的清洗,更佳為進一步於基板清洗後利用六甲基二矽氮烷對基板表面進行處理。藉由進行該處理,有感光性樹脂組成物對基板的密著性提高的傾向。利用六甲基二矽氮烷對基板表面進行處理的方法並無特別限定,例如可列舉將基板暴露在六甲基二矽氮烷蒸氣中的方法等。 In the coating step of (1-1), it is preferred to apply the photosensitive resin composition of the present invention to a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to further treat the surface of the substrate with hexamethyldioxane after the substrate cleaning. . By performing this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldioxane vapor.
所述基板可列舉無機基板、樹脂、樹脂複合材料等。 Examples of the substrate include an inorganic substrate, a resin, a resin composite material, and the like.
無機基板例如可列舉:玻璃、石英、矽酮、氮化矽,及於該些材料的基板上蒸鍍有鉬、鈦、鋁、銅等的複合基板。 Examples of the inorganic substrate include glass, quartz, anthrone, and tantalum nitride, and composite substrates of molybdenum, titanium, aluminum, copper, and the like are deposited on the substrates of the materials.
關於樹脂,可列舉包含以下樹脂的基板:聚對苯二甲酸丁二酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚苯乙烯、聚碳酸酯、聚碸、聚醚碸、聚芳酯、烯丙基二甘醇碳酸酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚苯并唑、聚苯硫醚、聚環烯烴、降冰片烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸系樹脂、環氧樹脂、矽酮樹脂、離子聚合物樹脂、氰酸酯樹脂、交聯富馬酸二酯、環狀聚烯烴、芳香族醚、馬來醯亞胺-烯烴、纖維素、環硫化合物等合成樹脂。 The resin may, for example, be a substrate comprising the following resins: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, poly Carbonate, polyfluorene, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimide, polyamidimide, polyether quinone, polybenzoxazole, Polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorene ketone resin, ionic polymer resin, cyanate resin, and A synthetic resin such as a bifuranic acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.
該些基板很少以所述形態直接使用,通常視最終產品的形態不同而形成例如TFT元件般的多層積層結構。 These substrates are rarely used in the form described above, and a multilayer laminated structure such as a TFT element is usually formed depending on the form of the final product.
對基板的塗佈方法並無特別限定,例如可使用:狹縫塗佈法、噴霧法、輥塗佈法、旋轉塗佈法、流延塗佈法、狹縫及旋轉法等方法。 The method of applying the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit, and a spin method can be used.
於狹縫塗佈法的情況下,較佳為將基板與狹縫模具的相對移動速度設為50mm/sec~120mm/sec。 In the case of the slit coating method, the relative moving speed of the substrate and the slit die is preferably 50 mm/sec to 120 mm/sec.
塗佈時的濕潤膜厚並無特別限定,能以與用途相對應的膜厚來塗佈,但通常於0.5μm~10μm的範圍內使用。 The thickness of the wet film at the time of application is not particularly limited, and it can be applied to a film thickness corresponding to the application, but is usually used in the range of 0.5 μm to 10 μm.
進而,亦可於在基板上塗佈本發明中所用的組成物之前,應用日本專利特開2009-145395號公報中記載般的所謂預濕(pre-wet)法。 Further, a so-called pre-wet method as described in JP-A-2009-145395 may be applied before the composition used in the present invention is applied onto a substrate.
於(2-1)的溶劑去除步驟中,藉由減壓(真空)及/或加熱等自所塗佈的所述膜中去除溶劑,於基板上形成乾燥塗膜。 溶劑去除步驟的加熱條件較佳為70℃~130℃下30秒鐘~300秒鐘左右。於溫度及時間為所述範圍的情形時,有圖案的密著性更良好、且可進一步減少殘渣的傾向。 In the solvent removal step of (2-1), the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition in the solvent removal step is preferably from about 30 seconds to about 300 seconds at 70 ° C to 130 ° C. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the tendency of the residue can be further reduced.
於(3-1)的曝光步驟中,對設有塗膜的基板照射既定圖案的光化射線。於該步驟中,光酸產生劑分解而產生酸。藉由所產生的酸的觸媒作用,將塗膜成分中所含的酸分解性基水解,生成羧基或酚性羥基。 In the exposure step of (3-1), the substrate provided with the coating film is irradiated with actinic rays of a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to form a carboxyl group or a phenolic hydroxyl group.
利用光化射線的曝光用光源可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、發光二極體(Light Emitting Diode,LED)光源、準分子雷射產生裝置等,可較佳地使用i射線(365nm)、h射線(405nm)、g射線(436nm)等具有300nm以上且450nm以下的波長的光化射線。另外,視需要亦可通過長波長截止濾波器、短波長截止濾波器、帶通濾波器般的分光濾波器來調整照射光。曝光量較佳為1mJ/cm2~500mJ/cm2。 The light source for exposure using actinic rays can use a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, etc., and can preferably use i. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as ray (365 nm), h-ray (405 nm), or g-ray (436 nm). Further, the illumination light may be adjusted by a long wavelength cut filter, a short wavelength cut filter, or a band pass filter like a spectral filter as needed. The exposure amount is preferably from 1 mJ/cm 2 to 500 mJ/cm 2 .
曝光裝置可使用:鏡面投影對準機(mirror projection aligner)、步進機(stepper)、掃描器(scanner)、近接式(proximity)、接觸式(contact)、微透鏡陣列(microlens array)、透鏡掃描器(lens scanner)、雷射曝光等各種方式的曝光機。 Exposure devices can be used: mirror projection aligner, stepper, scanner, proximity, contact, microlens array, lens Various types of exposure machines such as a lens scanner and laser exposure.
於生成酸觸媒的區域中,為了使所述水解反應加快,可進行曝光後加熱處理(曝光後烘烤(Post Exposure Bake),以下亦稱為「PEB」)。藉由PEB,可促進由酸分解性基生成羧基或酚性羥基。進行PEB的情形的溫度較佳為30℃以上、130℃以下,更佳為40℃ 以上、110℃以下,尤佳為50℃以上、100℃以下。 In the region where the acid catalyst is formed, in order to accelerate the hydrolysis reaction, post-exposure heat treatment (Post Exposure Bake, hereinafter also referred to as "PEB") may be performed. By the PEB, the formation of a carboxyl group or a phenolic hydroxyl group by an acid-decomposable group can be promoted. The temperature in the case of performing PEB is preferably 30 ° C or more and 130 ° C or less, more preferably 40 ° C. Above 110 ° C, more preferably 50 ° C or more, 100 ° C or less.
其中,本發明的酸分解性基的酸分解的活化能量低,容易因由曝光所致的來源於酸產生劑的酸而分解,生成羧基或酚性羥基,故未必一定要進行PEB,亦可藉由顯影來形成正型圖像。 In particular, the acid decomposition of the acid-decomposable group of the present invention has a low activation energy, and is easily decomposed by an acid derived from an acid generator due to exposure to form a carboxyl group or a phenolic hydroxyl group. Therefore, PEB may not necessarily be carried out. A positive image is formed by development.
於(4-1)的顯影步驟中,使用鹼性顯影液對具有游離的羧基或酚性羥基的共聚物進行顯影。藉由將含有容易溶解於鹼性顯影液中的具有羧基或酚性羥基的樹脂組成物的曝光部區域去除,而形成正型圖像。 In the developing step of (4-1), a copolymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. A positive image is formed by removing an exposed portion region containing a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.
顯影步驟中使用的顯影液中,較佳為含有鹼性化合物的水溶液。鹼性化合物例如可使用:氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物類;碳酸鈉、碳酸鉀、碳酸銫等鹼金屬碳酸鹽類;重碳酸鈉、重碳酸鉀等鹼金屬重碳酸鹽類;氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化二乙基二甲基銨等氫氧化四烷基銨類;膽鹼等氫氧化(羥基烷基)三烷基銨類;矽酸鈉、偏矽酸鈉等矽酸鹽類;乙胺、丙胺、二乙胺、三乙胺等烷基胺類;二甲基乙醇胺、三乙醇胺等醇胺類;1,8-二氮雜雙環-[5.4.0]-7-十一烯、1,5-二氮雜雙環-[4.3.0]-5-壬烯等脂環式胺類。 The developing solution used in the developing step is preferably an aqueous solution containing a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate, potassium carbonate or cesium carbonate; or a base such as sodium bicarbonate or potassium bicarbonate; Metal bicarbonate; tetramethylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or diethyldimethylammonium hydroxide a hydroxy acid (hydroxyalkyl) trialkylammonium such as choline; a citrate such as sodium citrate or sodium metasilicate; an alkylamine such as ethylamine, propylamine, diethylamine or triethylamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5- An alicyclic amine such as a terpene.
該等中,較佳為氫氧化鈉、氫氧化鉀、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、膽鹼(氫氧化-2-羥基乙基三甲基銨)。 Among these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (hydrogen hydroxide-2) are preferred. -hydroxyethyltrimethylammonium).
另外,亦可將於所述鹼類的水溶液中添加適當量的甲醇或乙 醇等水溶性有機溶劑或者界面活性劑而成的水溶液用作顯影液。 In addition, an appropriate amount of methanol or B may be added to the aqueous solution of the base. An aqueous solution obtained by using a water-soluble organic solvent such as an alcohol or a surfactant is used as a developing solution.
顯影液的pH值較佳為10.0~14.0。 The pH of the developer is preferably from 10.0 to 14.0.
顯影時間較佳為30秒鐘~500秒鐘,另外,顯影的方法可為覆液法(puddle method)、噴淋法、浸漬法等的任一種。 The development time is preferably from 30 seconds to 500 seconds, and the development method may be any one of a puddle method, a shower method, and a dipping method.
於顯影後,亦可進行淋洗步驟。於淋洗步驟中,藉由利用純水等清洗顯影後的基板,而進行所附著的顯影液去除、顯影殘渣去除。淋洗方法可使用公知的方法。例如可列舉噴淋淋洗或浸漬淋洗等。 After the development, a rinsing step can also be performed. In the elution step, the developed developer is removed by washing the developed substrate with pure water or the like, and the developed developer is removed and the development residue is removed. A known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned.
於(5-1)的後烘烤步驟中,對所得的正型圖像進行加熱,使酸分解性基進行熱分解而生成羧基或酚性羥基,與交聯性基、交聯劑等交聯,藉此可形成硬化膜。該加熱較佳為使用加熱板或烘箱等加熱裝置,於既定的溫度、例如180℃~250℃下進行既定時間的加熱處理,例如若為加熱板上則進行5分鐘~90分鐘的加熱處理,若為烘箱則進行30分鐘~120分鐘的加熱處理。藉由如此般進行交聯反應,可形成耐熱性、硬度等更優異的保護膜或層間絕緣膜。另外,於進行加熱處理時,藉由在氮氣環境下進行,可進一步提高透明性。 In the post-baking step of (5-1), the obtained positive image is heated to thermally decompose the acid-decomposable group to form a carboxyl group or a phenolic hydroxyl group, and to crosslink the crosslinking group or the crosslinking agent. Thereby, a cured film can be formed. The heating is preferably performed by a heating means such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C for a predetermined period of time. For example, if it is a hot plate, heat treatment is performed for 5 minutes to 90 minutes. If it is an oven, heat it for 30 minutes to 120 minutes. By performing the crosslinking reaction as described above, it is possible to form a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness. Further, when the heat treatment is performed, the transparency can be further improved by performing in a nitrogen atmosphere.
於後烘烤之前,亦可於在相對較低的溫度下進行烘烤之後進行後烘烤(追加中烘烤步驟)。於進行中烘烤的情形時,較佳為於90℃~150℃下加熱1分鐘~60分鐘後,於200℃以上的高溫下進行後烘烤。另外,亦可將中烘烤、後烘烤分為三階段以上的多階段來進行加熱。藉由設置此種中烘烤、後烘烤,可調整圖案的錐 角。該些烘烤的加熱可使用加熱板、烘箱、紅外線加熱器等公知的加熱方法。 Post-baking may also be performed after baking at a relatively low temperature before the post-baking (additional baking step). In the case of in-process baking, it is preferably heated at 90 ° C to 150 ° C for 1 minute to 60 minutes, and then post-baked at a high temperature of 200 ° C or higher. In addition, the middle baking and the post baking may be divided into three stages or more in multiple stages for heating. The pattern can be adjusted by setting such a baking and post baking angle. For the heating of these baking, a known heating method such as a hot plate, an oven, or an infrared heater can be used.
再者,可於後烘烤之前,藉由光化射線對形成有圖案的基板進行全面再曝光(後曝光)後,進行後烘烤,藉此由存在於未曝光部分中的光酸產生劑產生酸,作為促進交聯步驟的觸媒而發揮功能,從而可促進膜的硬化反應。包括後曝光步驟的情形的較佳曝光量較佳為100mJ/cm2~3,000mJ/cm2,尤佳為100mJ/cm2~500mJ/cm2。 Furthermore, after the post-baking, the substrate on which the pattern is formed is subjected to full re-exposure (post-exposure) by actinic rays, and post-baking is performed, whereby the photoacid generator present in the unexposed portion is formed. The acid is generated and functions as a catalyst for promoting the crosslinking step, thereby promoting the hardening reaction of the film. The preferred exposure amount in the case of including the post-exposure step is preferably from 100 mJ/cm 2 to 3,000 mJ/cm 2 , particularly preferably from 100 mJ/cm 2 to 500 mJ/cm 2 .
進而,亦可將由本發明的感光性樹脂組成物所得的硬化膜用作乾式蝕刻抗蝕劑。於將藉由後烘烤步驟進行熱硬化所得的硬化膜用作乾式蝕刻抗蝕劑的情形時,關於蝕刻處理,可進行灰化、電漿蝕刻、臭氧蝕刻等乾式蝕刻處理。 Further, the cured film obtained from the photosensitive resin composition of the present invention may be used as a dry etching resist. In the case where a cured film obtained by thermal curing by a post-baking step is used as a dry etching resist, a dry etching treatment such as ashing, plasma etching, or ozone etching may be performed on the etching treatment.
<本發明的第2態樣的硬化膜的製造方法> <Method for Producing Cured Film According to Second Aspect of the Present Invention>
本發明的第2態樣的硬化膜的製造方法較佳為包括以下的(1-2)~(5-2)的步驟。 The method for producing a cured film according to the second aspect of the present invention preferably includes the following steps (1-2) to (5-2).
(1-2)將本發明的第2態樣的感光性樹脂組成物塗佈於基板上的步驟;(2-2)自所塗佈的感光性樹脂組成物中去除溶劑的步驟;(3-2)藉由光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟;(4-2)藉由水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟; (5-2)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 (1-2) a step of applying a photosensitive resin composition of a second aspect of the present invention to a substrate; (2-2) a step of removing a solvent from the applied photosensitive resin composition; (3) -2) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4-2) a step of developing the exposed photosensitive resin composition by an aqueous developing solution; (5-2) A post-baking step of thermally curing the developed photosensitive resin composition.
本發明的硬化膜的製造方法的各步驟(1-2)~步驟(5-2)可分別與上文所述的第1態樣的硬化膜的製造方法的(1-1)~(5-1)的步驟同樣地進行,較佳條件亦相同。 (1-1) to (5) of each of the steps (1-2) to (5-2) of the method for producing a cured film of the present invention, respectively, and the method for producing a cured film of the first aspect described above. The steps of -1) are carried out in the same manner, and the preferred conditions are also the same.
由本發明的組成物所得的硬化膜亦可用作蝕刻抗蝕劑。 The cured film obtained from the composition of the present invention can also be used as an etching resist.
[本發明的第3態樣的硬化膜的製造方法] [Method for Producing Cured Film of Third Aspect of the Present Invention]
本發明的第3態樣的硬化膜的製造方法較佳為包括以下的(1-3)~(5-3)的步驟。 The method for producing a cured film according to the third aspect of the present invention preferably includes the following steps (1-3) to (5-3).
(1-3)將本發明的第3態樣的感光性樹脂組成物塗佈於基板上的步驟;(2-3)自所塗佈的感光性樹脂組成物中去除溶劑的步驟;(3-3)藉由活性放射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟;(4-3)藉由水性顯影液等對經曝光的感光性樹脂組成物進行顯影的步驟;(5-3)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 (1-3) a step of applying a photosensitive resin composition of a third aspect of the present invention to a substrate; (2-3) a step of removing a solvent from the applied photosensitive resin composition; (3) -3) a step of exposing the solvent-removed photosensitive resin composition by active radiation; (4-3) a step of developing the exposed photosensitive resin composition by an aqueous developing solution or the like; (5- 3) A post-baking step of thermally curing the developed photosensitive resin composition.
以下依序對各步驟加以說明。 The steps are described in order below.
於(1-3)的塗佈步驟中,將感光性樹脂組成物塗佈於基板上。 In the coating step of (1-3), the photosensitive resin composition is applied onto a substrate.
關於感光性樹脂組成物的製備,例如亦可製成將所述含有成 分分別預先溶解於溶劑中的溶液後,將該些溶液以既定的比例混合而製備樹脂組成物。如以上般製備的組成物溶液亦可於使用例如孔徑0.2μm的過濾器等進行過濾後供於使用。 For the preparation of the photosensitive resin composition, for example, the inclusion may be made into After separately dissolving the solutions previously dissolved in the solvent, the solutions were mixed in a predetermined ratio to prepare a resin composition. The composition solution prepared as above can also be used after being filtered using, for example, a filter having a pore size of 0.2 μm.
於(1-3)的塗佈步驟中,可使用上文所述的(1-1)步驟中記載的基板,另外,可使用上文所述的(1-1)步驟中記載的塗佈方法。 In the coating step of (1-3), the substrate described in the above (1-1) step may be used, and the coating described in the above (1-1) step may be used. method.
於(2-3)的溶劑去除步驟中,較佳為藉由減壓及/或加熱自所塗佈的感光性樹脂組成物中去除溶劑,於基板上形成乾燥塗膜。(2-3)溶劑去除步驟的加熱條件亦視各成分的種類或調配比而不同,較佳為80℃~130℃下30秒鐘~120秒鐘左右。 In the solvent removal step of (2-3), it is preferred to remove the solvent from the applied photosensitive resin composition by pressure reduction and/or heating to form a dried coating film on the substrate. (2-3) The heating conditions in the solvent removal step differ depending on the type of each component or the mixing ratio, and it is preferably from about 30 to about 120 seconds at 80 to 130 °C.
於(3-3)的曝光步驟中,較佳為對所得的塗膜以既定的圖案狀照射波長300nm以上且450nm以下的光化射線。於該步驟中,聚合性單體(聚合性化合物)藉由聚合起始劑的作用而聚合硬化。 In the exposure step of (3-3), it is preferred that the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less in a predetermined pattern. In this step, the polymerizable monomer (polymerizable compound) is polymerized and hardened by the action of a polymerization initiator.
關於利用光化射線的曝光,可使用與上文所述的第1態樣的硬化膜的製造方法中的曝光步驟的說明中列舉的光化射線。另外,視需要亦可通過長波長截止濾波器、短波長截止濾波器、帶通濾波器般的分光濾波器來調整照射光。 Regarding the exposure by actinic rays, the actinic rays listed in the description of the exposure step in the method for producing a cured film according to the first aspect described above can be used. Further, the illumination light may be adjusted by a long wavelength cut filter, a short wavelength cut filter, or a band pass filter like a spectral filter as needed.
於(4-3)的顯影步驟中,較佳為使用鹼性顯影液來進行顯影。藉由將含有具有酸基的樹脂組成物的未曝光部區域去除,而形成負型圖像。 In the developing step of (4-3), it is preferred to carry out development using an alkaline developing solution. A negative image is formed by removing an unexposed portion region containing a resin composition having an acid group.
顯影步驟中使用的顯影液中,較佳為含有鹼性化合物。鹼性 化合物例如可使用上文所述的第1態樣的硬化膜的製造方法中的顯影步驟的說明中列舉的鹼性化合物。 The developer used in the developing step preferably contains a basic compound. Alkaline As the compound, for example, the basic compound exemplified in the description of the development step in the method for producing a cured film of the first aspect described above can be used.
顯影液的pH值較佳為10.0~14.0。顯影時間較佳為30秒鐘~180秒鐘,另外,顯影的方法可為覆液法、浸漬法等的任一種。顯影後,可進行30秒鐘~90秒鐘的流水清洗而形成所需的圖案。顯影後,亦可與上文所述的第1態樣的硬化膜的製造方法同樣地進行淋洗步驟。 The pH of the developer is preferably from 10.0 to 14.0. The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a liquid coating method and a dipping method. After development, it can be washed with running water for 30 seconds to 90 seconds to form a desired pattern. After the development, the rinsing step may be performed in the same manner as the method for producing the cured film of the first aspect described above.
於(5-3)的後烘烤步驟中,對所得的負型圖像進行加熱,藉此將殘存的溶劑成分去除,視需要促進樹脂的交聯,藉此可形成硬化膜。該加熱較佳為加熱至150℃以上的高溫,更佳為加熱至180℃~250℃,尤佳為加熱至200℃~240℃。加熱時間可根據加熱溫度等而適當設定,較佳為設定為10分鐘~120分鐘的範圍內,亦可與上文所述的第1態樣的硬化膜的製造方法同樣地實施中烘烤。 In the post-baking step of (5-3), the obtained negative image is heated, thereby removing the remaining solvent component, and if necessary, promoting crosslinking of the resin, whereby a cured film can be formed. The heating is preferably carried out to a high temperature of 150 ° C or higher, more preferably to 180 ° C to 250 ° C, and particularly preferably to 200 ° C to 240 ° C. The heating time can be appropriately set depending on the heating temperature and the like, and is preferably set to be in the range of 10 minutes to 120 minutes, and may be baked in the same manner as in the method for producing a cured film according to the first aspect described above.
若於後烘烤步驟之前增加對顯影圖案整個面照射光化射線、較佳為紫外線的步驟(後曝光步驟),則可藉由光化射線照射而促進交聯反應。進而,由本發明的感光性樹脂組成物所得的硬化膜亦可用作乾式蝕刻抗蝕劑。 If the step of irradiating the entire surface of the developing pattern with actinic rays, preferably ultraviolet rays, is added before the post-baking step (post-exposure step), the crosslinking reaction can be promoted by irradiation with actinic rays. Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
於將藉由(5-3)的後烘烤步驟進行熱硬化所得的硬化膜用作乾式蝕刻抗蝕劑的情形時,關於蝕刻處理,可進行灰化、電漿蝕刻、臭氧蝕刻等乾式蝕刻處理。 In the case where a cured film obtained by thermal hardening by the post-baking step of (5-3) is used as a dry etching resist, dry etching such as ashing, plasma etching, ozone etching, or the like may be performed on the etching treatment. deal with.
[硬化膜] [hardened film]
本發明的硬化膜是使上文所述的本發明的第1態樣~第3態樣的感光性樹脂組成物硬化所得的硬化膜。 The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the first aspect to the third aspect of the present invention described above.
本發明的硬化膜可較佳地用作層間絕緣膜。另外,本發明的硬化膜較佳為藉由上文所述的本發明的第1態樣~第3態樣的硬化膜的形成方法所得的硬化膜。 The cured film of the present invention can be preferably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film according to the first aspect to the third aspect of the present invention described above.
藉由本發明的感光性樹脂組成物,可獲得絕緣性優異、且即便於高溫下經烘烤的情形時亦具有高的透明性的層間絕緣膜。使用本發明的感光性樹脂組成物而成的層間絕緣膜具有高的透明性,且硬化膜物性優異,故於液晶顯示裝置或有機EL顯示裝置的用途中有用。 According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulating properties and has high transparency even when baked at a high temperature can be obtained. The interlayer insulating film which is obtained by using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and thus is useful for use in a liquid crystal display device or an organic EL display device.
[液晶顯示裝置] [Liquid Crystal Display Device]
本發明的液晶顯示裝置的特徵在於具備本發明的硬化膜。 A liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention.
本發明的液晶顯示裝置只要具有使用所述本發明的感光性樹脂組成物所形成的平坦化膜或層間絕緣膜,除此以外,並無特別限制,可列舉採用各種結構的公知的液晶顯示裝置。 The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and a known liquid crystal display device having various configurations is exemplified. .
例如,本發明的液晶顯示裝置所具備的薄膜電晶體(Thin-Film Transistor,TFT)的具體例可列舉:非晶矽-TFT、低溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電氣特性優異,故可與該些TFT組合而較佳地使用。 Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
另外,本發明的液晶顯示裝置可取的液晶驅動方式可列舉:扭轉向列(Twisted Nematic,TN)方式、垂直配向(Vertical Alignment,VA)方式、共面切換(In-Plane-Switching,IPS)方 式、邊緣場切換(Fringe Field Switching,FFS)方式、光學補償彎曲(Optical Compensated Bend,OCB)方式等。 Further, examples of the liquid crystal driving method that can be obtained by the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (IPS) method. Formula, Fringe Field Switching (FFS) method, Optical Compensated Bend (OCB) method, etc.
關於面板構成,於彩色濾光片陣列(Color Filter on Array,COA)方式的液晶顯示裝置中亦可使用本發明的硬化膜,例如,可用作日本專利特開2005-284291的有機絕緣膜(115)或日本專利特開2005-346054的有機絕緣膜(212)。另外,本發明的液晶顯示裝置可取的液晶配向膜的具體配向方式可列舉摩擦配向法、光配向方等。另外,亦可藉由日本專利特開2003-149647號公報或日本專利特開2011-257734號公報中記載的聚合物穩定配向(Polymer Sustained Alignment,PSA)技術來進行聚合物配向支持。 Regarding the panel structure, the cured film of the present invention can also be used in a color filter on Array (COA) type liquid crystal display device, for example, as an organic insulating film of Japanese Patent Laid-Open Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054. Further, a specific alignment method of the liquid crystal alignment film which can be obtained by the liquid crystal display device of the present invention includes a rubbing alignment method, a light alignment method, and the like. Further, the polymer alignment support can be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.
另外,本發明的感光性樹脂組成物及本發明的硬化膜不限定於所述用途,可用於各種用途中。例如,除了平坦化膜或層間絕緣膜以外,亦可較佳地用於彩色濾光片的保護膜、或用以將液晶顯示裝置中的液晶層保持於一定厚度的間隔件(spacer)或於固體攝像元件中設置於彩色濾光片上的微透鏡等。 Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the planarization film or the interlayer insulating film, a protective film for a color filter or a spacer for holding a liquid crystal layer in a liquid crystal display device at a certain thickness or A microlens or the like provided on a color filter in a solid-state image sensor.
圖1為表示主動式矩陣方式的液晶顯示裝置10的一例的概念性剖面圖。該彩色液晶顯示裝置10為於背面上具有背光單元12的液晶面板,且液晶面板中,配置有與於貼附有偏光膜的2片玻璃基板14、玻璃基板15之間配置的所有畫素相對應的TFT 16的元件。形成於玻璃基板上的各元件通過形成於硬化膜17中的接觸孔18,而配線形成畫素電極的氧化銦錫(Indium Tin Oxide,ITO) 透明電極19。於ITO透明電極19上,設有液晶20的層及配置有黑色矩陣的紅綠藍(Red Green Blue,RGB)彩色濾光片22。 FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and all the pixel phases disposed between the two glass substrates 14 and the glass substrate 15 to which the polarizing film is attached are disposed in the liquid crystal panel. Corresponding components of the TFT 16. Each element formed on the glass substrate passes through the contact hole 18 formed in the cured film 17, and is wired to form indium tin oxide (ITO) of the pixel electrode. Transparent electrode 19. On the ITO transparent electrode 19, a layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are provided.
背光的光源並無特別限定,可使用公知的光源。例如可列舉白色LED、藍色/紅色/綠色等的多色LED、螢光燈(冷陰極管)、有機EL等。 The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue/red/green, a fluorescent lamp (cold cathode tube), an organic EL, or the like can be given.
另外,液晶顯示裝置可設定為三維(Three Dimensions,3D)(立體視)型,亦可設定為觸控面板型。進而亦可設定為可撓型,可用作日本專利特開2011-145686號公報中記載的第2層間絕緣膜(48)、或日本專利特開2009-258758號公報中記載的層間絕緣膜(520)。 In addition, the liquid crystal display device can be set to a three-dimensional (3D) (stereoscopic) type, or can be set to a touch panel type. In addition, the second interlayer insulating film (48) described in Japanese Laid-Open Patent Publication No. 2011-145686, or the interlayer insulating film described in Japanese Laid-Open Patent Publication No. 2009-258758 ( 520).
進而,即便為靜態驅動方式的液晶顯示裝置,藉由應用本發明亦可顯示設計性高的圖案。作為一例,可將本發明用作如日本專利特開2001-125086號公報中所記載般的聚合物網路型液晶的絕緣膜。 Further, even in the static drive type liquid crystal display device, a design pattern can be displayed by applying the present invention. As an example, the present invention can be used as an insulating film of a polymer network type liquid crystal as described in Japanese Laid-Open Patent Publication No. 2001-125086.
[有機EL顯示裝置] [Organic EL display device]
本發明的有機EL顯示裝置的特徵在於具備本發明的硬化膜。 The organic EL display device of the present invention is characterized by comprising the cured film of the present invention.
本發明的有機EL顯示裝置除了具有使用所述本發明的感光性樹脂組成物所形成的平坦化膜或層間絕緣膜以外,並無特別限制,可列舉採用各種結構的公知的各種有機EL顯示裝置或液晶顯示裝置。 The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic EL display devices having various configurations are exemplified. Or a liquid crystal display device.
例如,本發明的有機EL顯示裝置所具備的薄膜電晶體(Thin-Film Transistor,TFT)的具體例可列舉:非晶矽-TFT、低 溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電氣特性優異,故可與該些TFT組合而較佳地使用。 For example, specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT and low Warm polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
圖2為有機EL顯示裝置的一例的構成概念圖。其表示底部發光型的有機EL顯示裝置中的基板的示意性剖面圖,具有平坦化膜4。 FIG. 2 is a conceptual diagram showing an example of an organic EL display device. This is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
於玻璃基板6上形成底部閘極型的TFT 1,以覆蓋該TFT 1的狀態形成包含Si3N4的絕緣膜3。於絕緣膜3中形成此處省略圖示的接觸孔後,將經由該接觸孔而連接於TFT 1的配線2(高度1.0μm)形成於絕緣膜3上。配線2為用以將TFT 1間連接或將後續步驟中形成的有機EL元件與TFT 1連接的配線。 A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si 3 N 4 . After the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. The wiring 2 is a wiring for connecting the TFTs 1 or connecting the organic EL elements formed in the subsequent steps to the TFT 1.
進而,為了使因形成配線2所致的凹凸平坦化,以填埋由配線2所致的凹凸的狀態於絕緣膜3上形成平坦化膜4。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled.
於平坦化膜4上,形成底部發光型的有機EL元件。即,於平坦化膜4上,經由接觸孔7連接於配線2而形成包含ITO的第一電極5。另外,第一電極5相當於有機EL元件的陽極。 On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 including ITO is formed on the planarizing film 4 by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.
形成覆蓋第一電極5的邊緣的形狀的絕緣膜8,藉由設置該絕緣膜8,可防止第一電極5與其後續步驟中形成的第二電極之間的短路。 The insulating film 8 having a shape covering the edge of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.
進而,圖2中雖未圖示,但介隔所需的圖案而依序蒸鍍設置電洞傳輸層、有機發光層、電子傳輸層,繼而,於基板上方的整個面上形成包含Al的第二電極,使用密封用玻璃板及紫外線硬化型環氧樹脂進行貼合,由此進行密封,獲得對各有機EL元件連接 用以驅動該有機EL元件的TFT 1而成的主動式矩陣型的有機EL顯示裝置。 Further, although not shown in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by interposing a desired pattern, and then Al is formed on the entire upper surface of the substrate. The two electrodes are bonded together using a sealing glass plate and an ultraviolet curable epoxy resin, thereby sealing and obtaining connection to each organic EL element. An active matrix type organic EL display device for driving the TFT 1 of the organic EL element.
本發明的感光性樹脂組成物由於硬化性及硬化膜特性優異,故作為微機電系統(Microelectromechanical Systems,MEMS)元件的結構構件,將使用本發明的感光性樹脂組成物所形成的抗蝕劑圖案作為隔離壁,或作為機械驅動零件的一部分組入而使用。此種MEMS用元件例如可列舉:表面聲波(Surface Acoustic Wave,SAW)濾波器、體聲波(Bulk Acoustic Wave,BAW)濾波器、陀螺感測器(gyro sensor)、顯示器用微快門(microshutter)、影像感測器、電子紙、噴墨頭、生物晶片(biochip)、密封劑等零件。更具體的例子例示於日本專利特表2007-522531、日本專利特開2008-250200、日本專利特開2009-263544等中。 Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the photosensitive resin composition of the present invention is used as a structural member of a microelectromechanical systems (MEMS) device. Used as a partition or as part of a mechanically driven part. Examples of such MEMS devices include a surface acoustic wave (SAW) filter, a Bulk Acoustic Wave (BAW) filter, a gyro sensor, and a microshutter for a display. Image sensors, electronic paper, inkjet heads, biochips, sealants and more. More specific examples are exemplified in Japanese Patent Laid-Open No. 2007-522531, Japanese Patent Laid-Open No. 2008-250200, Japanese Patent Laid-Open No. 2009-263544, and the like.
本發明的感光性樹脂組成物由於平坦性或透明性優異,故例如亦可用於形成日本專利特開2011-107476號公報的圖2中記載的岸堤層(16)及平坦化膜(57)、日本專利特開2010-9793號公報的圖4(a)中記載的隔離壁(12)及平坦化膜(102)、日本專利特開2010-27591號公報的圖10中記載的岸堤層(221)及第3層間絕緣膜(216b)、日本專利特開2009-128577號公報的圖4(a)中記載的第2層間絕緣膜(125)及第3層間絕緣膜(126)、日本專利特開2010-182638號公報的圖3中記載的平坦化膜(12)及畫素分離絕緣膜(14)等。除此以外,亦可較佳地用於用以將液晶顯示裝置中的液晶層保持於一定厚度的間隔件,或傳真機 (facsimile)、電子影印機、固體攝像元件等的晶載彩色濾光片的成像光學系統或光纖連接器的微透鏡。 Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, it can be used, for example, to form the bank layer (16) and the planarizing film (57) shown in Fig. 2 of JP-A-2011-107476. The partition wall (12) and the flattening film (102) described in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793, and the bank layer described in Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577, Japan The planarizing film (12) and the pixel separating insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638. In addition, it can also be preferably used for a spacer for holding a liquid crystal layer in a liquid crystal display device at a certain thickness, or a facsimile machine. (facsimile), an imaging optical system of an on-chip color filter such as an electronic photocopier, a solid-state imaging device, or a microlens of an optical fiber connector.
[實施例] [Examples]
以下列舉實施例對本發明加以更具體說明。以下的實施例中所示的材料、使用量、比例、處理內容、處理順序等只要不偏離本發明的主旨,則可適當變更。因此,本發明的範圍不限定於以下所示的具體例。再者,只要無特別說明,則「份」、「%」為質量基準。 The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are the quality standards.
於以下的合成例中,以下的符號分別表示以下的化合物。 In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF:甲基丙烯酸-2-四氫呋喃酯(合成品) MATHF: 2-tetrahydrofuran methacrylate (synthetic)
MAEVE:甲基丙烯酸-1-乙氧基乙酯(和光純藥工業公司製造) MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PHSEVE:對羥基苯乙烯的1-乙氧基乙酯保護體 PHSEVE: 1-Ethyl Ethyl Ester Protector of p-Hydroxystyrene
OXE-30:甲基丙烯酸-3-乙基-3-氧雜環丁基甲酯(大阪有機化學工業公司製造) OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA:甲基丙烯酸縮水甘油酯(和光純藥工業公司製造) GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
NBMA:正丁氧基甲基丙烯醯胺(東京化成製造) NBMA: n-Butoxymethyl propylene decylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
HEMA:甲基丙烯酸羥基乙酯(和光純藥公司製造) HEMA: Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MAA:甲基丙烯酸(和光純藥工業公司製造) MAA: Methacrylic Acid (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA:甲基丙烯酸甲酯(和光純藥工業公司製造) MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
St:苯乙烯(和光純藥工業公司製造) St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)
DCPM:甲基丙烯酸二環戊酯 DCPM: Dicyclopentyl Methacrylate
V-601:二甲基-2,2'-偶氮雙(2-甲基丙酸酯)(和光純藥工業公司製造) V-601: dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65:2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥工業公司製造) V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
[第1實施例] [First Embodiment]
<MATHF的合成> <Synthesis of MATHF>
將甲基丙烯酸(86g,1mol)冷卻至15℃,添加樟腦磺酸(4.6g,0.02mol)。於該溶液中滴加2-二氫呋喃(71g,1mol,1.0當量)。攪拌1小時後,添加飽和碳酸氫鈉(500mL),利用乙酸乙酯(500mL)進行萃取,利用硫酸鎂加以乾燥後,將不溶物過濾後於40℃以下減壓濃縮,將殘渣的黃色油狀物減壓蒸餾,以無色油狀物的形式獲得沸點(bp.)為54℃/3.5mmHg~56℃/3.5mmHg餾分的甲基丙烯酸四氫-2H-呋喃-2-基酯(MATHF)125g(產率為80%)。 Methyl acrylate (86 g, 1 mol) was cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution was added dropwise 2-dihydrofuran (71 g, 1 mol, 1.0 eq.). After stirring for 1 hour, a saturated sodium hydrogencarbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate, and the insolubles were filtered and concentrated under reduced pressure at 40 ° C or less to give a yellow oily residue. Distillation under reduced pressure to obtain tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 ° C / 3.5 mmHg - 56 ° C / 3.5 mmHg in the form of a colorless oil. (Yield 80%).
<聚合物P-1的合成例> <Synthesis Example of Polymer P-1>
於三口燒瓶中加入PGMEA(丙二醇單甲基醚乙酸酯)(89g),於氮氣環境下升溫至90℃。於該溶液中用2小時滴加使MAA(成為所有單體成分中的9.5mol%的量)、MATHF(成為所有單體成分中的43mol%的量)、GMA(相當於所有單體成分中的47.5mol%)、V-65(相對於所有單體成分的合計量100mol%而相當於4mol%)於室溫下溶解於PGMEA(89g)中的溶液。滴加結束後攪拌2小時,使反應結束。藉此獲得聚合物P-1。再者,以溶劑以外的成分(稱為固體成分)的濃度成為40質量%的方式進行調整。 PGMEA (propylene glycol monomethyl ether acetate) (89 g) was added to a three-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. MAA (to be 9.5 mol% of all monomer components), MATHF (to be 43 mol% of all monomer components), and GMA (corresponding to all monomer components) were added dropwise to the solution over 2 hours. A solution of 47.5 mol%) and V-65 (corresponding to 100 mol% of all the monomer components and corresponding to 4 mol%) dissolved in PGMEA (89 g) at room temperature. After the completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, the polymer P-1 was obtained. In addition, the concentration of the component other than the solvent (referred to as a solid component) was adjusted to 40% by mass.
如下述表所示般變更單體種類等,合成其他聚合物。 The monomer type and the like were changed as shown in the following table to synthesize other polymers.
所述表中,表中未特別標註單位的數值是以mol%為單位。聚合起始劑及添加劑的數值為將單體成分設定為100mol%的情形的mol%。固體成分濃度是以單體質量/(單體質量+溶劑質量)×100(單位質量%)來表示。於使用V-601作為聚合起始劑的情況下,反應溫度為90℃,於使用V-65的情況下,將反應溫度設為70℃。 In the table, the numerical values of the units not specifically indicated in the table are in mol%. The numerical value of the polymerization initiator and the additive is mol% in the case where the monomer component is set to 100 mol%. The solid content concentration is represented by the monomer mass / (monomer mass + solvent mass) × 100 (unit mass %). In the case of using V-601 as a polymerization initiator, the reaction temperature was 90 ° C, and in the case of using V-65, the reaction temperature was 70 °C.
<感光性樹脂組成物的製備> <Preparation of photosensitive resin composition>
以成為下述表中記載的固體成分比的方式調配各成分,於溶劑(PGMEA:MEDG=1:1)中溶解混合直至固體成分濃度成為15%為止,利用口徑0.2μm的聚四氟乙烯製過濾器進行過濾,獲得各種實施例及比較例的感光性樹脂組成物。 The components were prepared so as to have a solid content ratio as described in the following table, and dissolved and mixed in a solvent (PGMEA: MEDG = 1:1) until the solid content concentration became 15%, and made of polytetrafluoroethylene having a diameter of 0.2 μm. The filter was filtered to obtain photosensitive resin compositions of various examples and comparative examples.
表示實施例及比較例中所用的各化合物的簡稱的詳細情況如下。 The details of the abbreviations of the respective compounds used in the examples and comparative examples are as follows.
(聚合性單體) (polymerizable monomer)
A-3-1:卡亞拉得(KAYARAD)DPHA(日本化藥(股)製造) A-3-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(光酸產生劑) (photoacid generator)
B-1-1:下述所示的結構(合成例將於後述) B-1-1: Structure shown below (synthesis example will be described later)
[化44]
B-1-2:下述所示的結構(合成例將於後述) B-1-2: Structure shown below (synthesis example will be described later)
B-1-3:下述所示的結構(依照日本專利特表2002-528451號公報的段落0108中記載的方法來合成) B-1-3: Structure shown below (synthesized according to the method described in paragraph 0108 of JP-A-2002-528451)
B-1-4:PAG-103(商品名,下述所示的結構,巴斯夫(BASF)公司製造) B-1-4: PAG-103 (trade name, structure shown below, manufactured by BASF)
B-1-5:GSID-26-1,三芳基鋶鹽(巴斯夫(BASF)公司製造) B-1-5: GSID-26-1, triarylsulfonium salt (BASF)
B-1-6:艾迪科歐普托瑪(Adeka Optomer)SPO-82(艾迪科(ADEKA)製造) B-1-6: Adeka Optomer SPO-82 (made by ADEKA)
(醌二疊氮化合物) (醌 叠 azide compound)
B-2-1:4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚(1.0莫耳)與1,2-萘醌二疊氮-5-磺醯氯(3.0莫耳)的縮合 物 B-2-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and Condensation of 1,2-naphthoquinonediazide-5-sulfonyl chloride (3.0 mol) Object
B-2-2:1,1,1-三(對羥基苯基)乙烷(1.0莫耳)與1,2-萘醌二疊氮-5-磺醯氯(2.0莫耳)的縮合物 B-2-2: condensate of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)
B-2-3:2,3,4,4'-四羥基二苯甲酮(1.0莫耳)與1,2-萘醌二疊氮-5-磺酸酯(2.44莫耳)的縮合物 B-2-3: condensate of 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonate (2.44 mol)
(光聚合起始劑) (photopolymerization initiator)
B-3-1:豔佳固(IRGACURE)OXE 01(巴斯夫(BASF)製造) B-3-1: IRGACURE OXE 01 (Manufactured by BASF)
((S)成分) ((S) component)
S-1:下述所示結構,分子量341.48 S-1: structure shown below, molecular weight 341.48
S-2:下述所示結構,分子量366.57 S-2: structure shown below, molecular weight 366.57
S-9:下述所示結構,分子量269.46(合成例將於後述) S-9: the structure shown below, molecular weight 269.46 (synthesis example will be described later)
S-14:下述所示結構,分子量252.41(合成例將於後述) S-14: structure shown below, molecular weight 252.41 (synthesis example will be described later)
S-15:下述所示結構,分子量314.48 S-15: Structure shown below, molecular weight 314.48
S-16:下述所示結構,分子量264.49 S-16: Structure shown below, molecular weight 264.49
[化55]
S'-11:3-縮水甘油氧基丙基甲基二甲氧基矽烷(信越化學公司製造,KBM-402) S'-11: 3-glycidoxypropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-402)
S'-12:3-巰基丙基三甲氧基矽烷(信越化學公司製造,KBM-803) S'-12: 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
[化57](CH 3 O) 3 SiC 3 H 6 SH (CH 3 O) 3 SiC 3 H 6 SH
S'-13:3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學KBM-503) S'-13: 3-methacryloxypropyltrimethoxydecane (Shin-Etsu Chemical KBM-503)
S'-14:3-縮水甘油氧基丙基三甲氧基矽烷(信越化學 KBM-403) S'-14: 3-glycidoxypropyltrimethoxydecane (Shin-Etsu Chemical) KBM-403)
S'-15:下述結構的化合物 S'-15: a compound of the following structure
S'-16:下述結構的化合物 S'-16: a compound of the following structure
S'-17:下述結構的化合物 S'-17: a compound of the following structure
(增感劑) (sensitizer)
DBA:9,10-二丁氧基蒽(川崎化成公司製造) DBA: 9,10-dibutoxy oxime (manufactured by Kawasaki Chemical Co., Ltd.)
(鹼性化合物) (alkaline compound)
H-1:下述結構的化合物 H-1: a compound of the following structure
(界面活性劑) (surfactant)
W-1:下述結構式所示的含有全氟烷基的非離子界面活性劑(F-554,迪愛生(DIC)製造) W-1: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by Diane Health (DIC))
(溶劑) (solvent)
MEDG(二乙二醇乙基甲基醚):海索夫(Hisolve)EDM(東邦化學工業公司製造) MEDG (diethylene glycol ethyl methyl ether): Hisolve EDM (manufactured by Toho Chemical Industry Co., Ltd.)
PGMEA(丙二醇單甲基醚乙酸酯):(昭和電工公司製造) PGMEA (propylene glycol monomethyl ether acetate): (manufactured by Showa Denko)
(其他添加劑) (other additives)
F-1:JER828(三菱化學控股(Mitsubishi Chemical Holdings)(股)製造) F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)
F-2:JER1007(三菱化學控股(Mitsubishi Chemical Holdings)(股)製造) F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)
F-3:JER157S65(三菱化學控股(Mitsubishi Chemical Holdings)(股)製造) F-3: JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)
J-1:艾迪科斯塔波(Adekastab)AO-60(艾迪科(股)製造) J-1: Adekastab AO-60 (made by Eddy Co.)
J-2:豔諾斯(Irganox)1035(巴斯夫(BASF)製造) J-2: Irganox 1035 (made by BASF)
J-3:豔諾斯(Irganox)1098(巴斯夫(BASF)製造) J-3: Irganox 1098 (made by BASF)
<B-1-1的合成> <Synthesis of B-1-1>
於2-萘酚(10g)、氯苯(30mL)的懸浮溶液中添加氯化鋁(10.6g)、2-氯丙醯氯(10.1g),將混合液加熱至40℃並反應2小時。於冰浴冷卻下,於反應液中滴加4N的HCl水溶液(60mL),添加乙酸乙酯(50mL)進行分液。於有機層中添加碳酸鉀(19.2g),於40℃下反應1小時後,添加2N的HCl水溶液(60mL)進行分液,將有機層濃縮後,利用二異丙醚(10mL)將結晶再製漿,進行過濾、乾燥而獲得酮化合物(6.5g)。 Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C and reacted for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction mixture under ice-cooling, and ethyl acetate (50 mL) was added. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous HCl solution (60 mL) was added to the mixture, and the organic layer was concentrated, and then crystallised from diisopropyl ether (10 mL) Pulping, filtration, and drying gave a ketone compound (6.5 g).
於所得的酮化合物(3.0g)、甲醇(30mL)的懸浮溶液中添加乙酸(7.3g)、50質量%羥基胺水溶液(8.0g),進行加熱回流。放置冷卻後,添加水(50mL),將析出的結晶過濾,進行冷甲醇清洗後加以乾燥,獲得肟化合物(2.4g)。 Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated under reflux. After standing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g).
使所得的肟化合物(1.8g)溶解於丙酮(20mL)中,於冰浴冷卻下添加三乙胺(1.5g)、對甲苯磺醯氯(2.4g),升溫至室溫並反應1小時。於反應液中添加水(50mL),將析出的結晶過濾後,利用甲醇(20mL)進行再製漿,進行過濾、乾燥而獲得B-1-1的化合物(所述結構)(2.3g)。 The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was warmed to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then repulped with methanol (20 mL), filtered, and dried to obtain a compound (the structure) (2.3 g) of B-1-1.
再者,B-1-1的1H-核磁共振(Nuclear Magnetic Resonance,NMR)光譜(300MHz,CDCl3)為δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6(dd,1H),7.4(dd,1H),7.3(d,2H),7.1(d,1H),5.6(q,1H),2.4(s,3H),1.7(d,3H)。 Furthermore, the 1 H-nuclear magnetic resonance (NMR) spectrum of B-1-1 (300 MHz, CDCl 3 ) is δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H). ), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H) , 1.7 (d, 3H).
<B-1-2的合成> <Synthesis of B-1-2>
使1-胺基-2-萘酚鹽酸鹽(東京化成製造)4.0g懸浮於N-甲基吡咯啶酮(和光純藥製造)16g中,添加碳酸氫鈉(和光純藥製造)3.4g後,滴加4,4'-二甲基-3-氧代戊酸甲酯(和光純藥製造)4.9g,並在氮氣環境下以120℃加熱2小時。放置冷卻後,將水、乙酸乙酯添加至反應混合液中並進行分液,利用硫酸鎂對有機相進行乾燥,並進行過濾、濃縮而獲得粗製B-1-2A。對粗製B-1-2A進行矽膠管柱層析精製,從而獲得1.7g中間物B-1-2A。 4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), and sodium hydrogencarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Thereafter, 4.9 g of methyl 4,4'-dimethyl-3-oxopentanoate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and heated at 120 ° C for 2 hours under a nitrogen atmosphere. After standing to cool, water and ethyl acetate were added to the reaction mixture and liquid separation was carried out, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-1-2A. The crude B-1-2A was subjected to silica gel column chromatography purification to obtain 1.7 g of intermediate B-1-2A.
將B-1-2A(1.7g)與對二甲苯(6mL)混合,添加對甲苯磺酸一水合物(和光純藥製造)0.23g並以140℃加熱2小時。放置冷卻後,將水、乙酸乙酯添加至反應混合液中並進行分液,利用硫酸鎂對有機相進行乾燥後,進行過濾、濃縮而獲得粗製B-1-2B。 B-1-2A (1.7 g) was mixed with p-xylene (6 mL), and 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C for 2 hours. After standing to cool, water and ethyl acetate were added to the reaction mixture, and liquid separation was carried out, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-1-2B.
將THF(2mL)與粗製B-1-2B的總量混合,於冰浴冷卻下滴 加2M鹽酸/THF溶液6.0mL,繼而滴加亞硝酸異戊酯(和光純藥製造)(0.84g),升溫至室溫為止後攪拌2小時。將水、乙酸乙酯添加至所得的反應混合物中並進行分液,利用水對有機層進行清洗後,利用硫酸鎂進行乾燥,並進行過濾、濃縮而獲得中間物粗製B-1-2C。 Mix THF (2 mL) with the total amount of crude B-1-2B and drop in an ice bath 6.0 mL of a 2 M hydrochloric acid/THF solution was added, followed by dropwise addition of isoamyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g), and the mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture, and the organic layer was washed with water, dried with magnesium sulfate, filtered, and concentrated to obtain a crude B-1-2C intermediate.
將中間物粗製B-1-2C的總量與丙酮(10mL)混合,於冰浴冷卻下添加三乙胺(和光純藥製造)(1.2g)、對甲苯磺醯氯(東京化成製造)(1.4g)後,升溫至室溫為止並攪拌1小時。將水、乙酸乙酯添加至所得的反應混合液中並進行分液,利用硫酸鎂對有機相進行乾燥後,進行過濾、濃縮而獲得粗製B-1-2。利用冷卻甲醇對粗製B-1-2進行再製漿後,進行過濾、乾燥而獲得B-1-2(1.2g)。 The total amount of the crude intermediate B-1-2C was mixed with acetone (10 mL), and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added under ice cooling. After 1.4 g), the mixture was stirred at room temperature for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture, and liquid separation was carried out, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-1-2. The crude B-1-2 was repulped with cooling methanol, filtered, and dried to obtain B-1-2 (1.2 g).
再者,B-1-2的1H-NMR光譜(300MHz,CDCl3)為δ=8.5-8.4(m,1H),8.0-7.9(m,4H),7.7-7.6(m,2H),7.6-7.5(m,1H)7.4(d,2H),2.4(s,3H),1.4(s,9H)。 Further, the 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B-1-2 was δ=8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 (m, 2H), 7.6-7.5 (m, 1H) 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).
<S-9的合成> <Synthesis of S-9>
於具備回流冷卻器、滴液漏斗及溫度計的1L燒瓶中加入異硫氰酸甲酯73.1g(1.0mol)、2-乙基己酸錫(II)0.9g(0.0023mol)、甲苯316.1g,加熱至70℃。向其中滴加γ-巰基丙基三甲氧基矽烷243.2g(1.02mol),其後於110℃下進行3小時加熱攪拌。藉由紅外線(Infrared,IR)測定確認來源於原料的異硫氰酸酯基的吸收峰值消失,且存在來源於二硫胺基甲酸酯鍵的吸收峰值, 使反應結束。然後,減壓蒸餾去除反應溶液而去除甲苯,藉此獲得淡黃色透明液體。利用1H-NMR光譜進行鑒定。 73.1 g (1.0 mol) of methyl isothiocyanate, 0.9 g (0.0023 mol) of tin (II) 2-ethylhexanoate, and 316.1 g of toluene were placed in a 1 L flask equipped with a reflux condenser, a dropping funnel and a thermometer. Heat to 70 ° C. 243.2 g (1.02 mol) of γ-mercaptopropyltrimethoxydecane was added dropwise thereto, followed by heating and stirring at 110 ° C for 3 hours. It was confirmed by infrared (IR) measurement that the absorption peak of the isothiocyanate group derived from the raw material disappeared, and the absorption peak derived from the dithiocarbamate bond was present to complete the reaction. Then, the reaction solution was distilled off under reduced pressure to remove toluene, whereby a pale yellow transparent liquid was obtained. Identification was carried out by using 1 H-NMR spectrum.
<S-14的合成> <Synthesis of S-14>
於具備回流冷卻器、滴液漏斗及溫度計的1L燒瓶中加入異硫氰酸甲酯73.1g(1.0mol)、甲苯316.1g,加熱至70℃。向其中滴加γ-胺基丙基三甲氧基矽烷225.4g(1.02mol),其後於110℃下進行3小時加熱攪拌。藉由IR測定確認來源於原料的異硫氰酸酯基的吸收峰值消失,且存在來源於硫脲鍵的吸收峰值,使反應結束。然後,減壓蒸餾去除反應溶液而去除甲苯,藉此獲得淡黃色透明液體。利用1H-NMR光譜進行鑒定。 73.1 g (1.0 mol) of methyl isothiocyanate and 316.1 g of toluene were placed in a 1 L flask equipped with a reflux condenser, a dropping funnel and a thermometer, and the mixture was heated to 70 °C. 225.4 g (1.02 mol) of γ-aminopropyltrimethoxydecane was added dropwise thereto, followed by heating and stirring at 110 ° C for 3 hours. It was confirmed by IR measurement that the absorption peak of the isothiocyanate group derived from the raw material disappeared, and the absorption peak derived from the thiourea bond was present to complete the reaction. Then, the reaction solution was distilled off under reduced pressure to remove toluene, whereby a pale yellow transparent liquid was obtained. Identification was carried out by using 1 H-NMR spectrum.
<密著性評價> <Adhesion evaluation>
於形成有Mo(鉬)薄膜的玻璃基板上旋塗塗佈各感光性樹脂組成物後,於90℃下於加熱板上進行120秒種預烘烤而使溶劑揮發,形成膜厚3.0μm的感光性樹脂組成物層。繼而,使用超高壓水銀燈以累計照射量成為300mJ/cm2(能量強度:20mW/cm2,i射線)的方式進行曝光,其後,將該基板於烘箱中於230℃下加熱30分鐘,獲得硬化膜。 After each photosensitive resin composition was spin-coated on a glass substrate on which a Mo (molybdenum) film was formed, it was prebaked on a hot plate at 90 ° C for 120 seconds to volatilize the solvent to form a film thickness of 3.0 μm. A photosensitive resin composition layer. Then, the ultrahigh pressure mercury lamp was used for exposure so that the cumulative irradiation amount was 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray), and thereafter, the substrate was heated in an oven at 230 ° C for 30 minutes to obtain Hardened film.
繼而,對硬化膜使用切割刀(cutter),以1mm的間隔縱橫切入切口,使用透明膠帶(scotch tape)進行膠帶剝離試驗(100格交叉切割法:依據日本工業標準(Japanese Industrial Standards,JIS)5600)。根據轉印至膠帶背面上的硬化膜的面積來評價硬化膜與基板之間的密著性。將其結果示於下述表中。數值越大則與基底基板的密著性越高,6分、5分或4分為實用水準。 Then, a cutter was used for the cured film, and the slit was cut vertically and horizontally at intervals of 1 mm, and the tape peeling test was performed using a scotch tape (100-frame cross-cut method: according to Japanese Industrial Standards (JIS) 5600 ). The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred onto the back surface of the tape. The results are shown in the following table. The larger the value, the higher the adhesion to the base substrate, and the 6 points, 5 minutes, or 4 are classified into practical levels.
6:轉印的面積小於1% 6: The transfer area is less than 1%
5:轉印的面積為1%以上、小於5% 5: The transfer area is 1% or more and less than 5%.
4:轉印的面積為5%以上、小於10% 4: The transfer area is 5% or more and less than 10%.
3:轉印的面積為10%以上、小於30% 3: The transfer area is 10% or more and less than 30%.
2:轉印的面積為30%以上、小於50%50%以上 2: The transfer area is 30% or more, less than 50% and 50% or more.
1:轉印的面積為50%以上 1: The transfer area is 50% or more
<烘烤後錐角評價> <Evaluation of cone angle after baking>
使用狹縫塗布機,以乾燥膜厚成為3μm的方式,於將形成有Mo(鉬)薄膜的玻璃基板成膜而得的基板(10cm×10cm)上塗佈 各感光性樹脂組成物後,於90℃下於加熱板上進行2分鐘預烘烤而使溶劑揮發。然後,隔著可再現10μm孔(1:3)的遮罩,使用超高壓水銀燈以累計照射量40mJ/cm2(照度:20mW/cm2,i射線)進行曝光,其後,藉由鹼顯影液(2.38質量%的TMAH水溶液)以23℃進行60秒顯影後,藉由超純水進行1分鐘淋洗。繼而,使用加熱板,於230℃下進行30分鐘烘烤。 The photosensitive resin composition was applied onto a substrate (10 cm × 10 cm) obtained by forming a glass substrate on which a Mo (molybdenum) film was formed by using a slit coater so that the dried film thickness was 3 μm. The solvent was volatilized by prebaking on a hot plate at 90 ° C for 2 minutes. Then, through a mask capable of reproducing a hole of 10 μm (1:3), exposure was performed using an ultrahigh pressure mercury lamp at a cumulative irradiation amount of 40 mJ/cm 2 (illuminance: 20 mW/cm 2 , i-ray), and thereafter, by alkali development. The solution (2.38 mass% of TMAH aqueous solution) was developed at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 1 minute. Then, using a hot plate, baking was performed at 230 ° C for 30 minutes.
將所得的基板割斷,自正橫向對所述孔形進行掃描式電子顯微鏡(Scanning Electron Microscope,SEM)觀察,將基板界面部與孔壁面所成的角作為錐角來進行測定。將其結果示於下述表中。就高解析性的觀點而言,較佳為3分以上。 The obtained substrate was cut, and the hole shape was observed by a scanning electron microscope (SEM) from the lateral direction, and the angle formed by the substrate interface portion and the hole wall surface was measured as a taper angle. The results are shown in the following table. From the viewpoint of high resolution, it is preferably 3 or more.
5:錐角超過80度 5: cone angle exceeds 80 degrees
4:錐角超過60度、小於80度 4: The cone angle exceeds 60 degrees and is less than 80 degrees
3:錐角超過40度、小於60度 3: the cone angle exceeds 40 degrees and is less than 60 degrees
2:錐角超過20度、小於40度 2: the taper angle exceeds 20 degrees and is less than 40 degrees
1:錐角小於20度 1: cone angle is less than 20 degrees
<感度的評價> <Evaluation of sensitivity>
將玻璃基板(伊格爾(EAGLE)XG,0.7mm厚(康寧(Corning)公司製造))於六甲基二矽氮烷(HMDS)蒸氣下暴露30秒鐘,旋塗塗佈各感光性樹脂組成物後,於90℃下於加熱板上進行120秒鐘預烘烤而使溶劑揮發,形成膜厚為3.0μm的感光性樹脂組成物層。 A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin was spin-coated. After the composition, the mixture was prebaked on a hot plate at 90 ° C for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.
繼而,對所得的感光性樹脂組成物層使用佳能(Canon)(股) 製造的MPA 5500CF(高壓水銀燈),介隔既定的遮罩進行曝光。繼而,利用鹼顯影液(0.4%的氫氧化四甲基銨水溶液)於23℃下對曝光後的感光性樹脂組成物層進行60秒鐘顯影後,利用超純水淋洗20秒鐘。將藉由該些操作而解析5μm的孔時的最適i射線曝光量(Eopt)作為感度。 Then, using the obtained photosensitive resin composition layer, Canon (share) The manufactured MPA 5500CF (high pressure mercury lamp) is exposed to a predetermined mask. Then, the exposed photosensitive resin composition layer was developed by an alkali developer (0.4% aqueous tetramethylammonium hydroxide solution) at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 20 seconds. The optimum i-ray exposure amount (Eopt) when the 5 μm hole was analyzed by these operations was taken as the sensitivity.
5:小於20mJ/cm2 5: less than 20mJ/cm 2
4:20mJ/cm2以上、小於40mJ/cm2 4:20 mJ/cm 2 or more and less than 40 mJ/cm 2
3:40mJ/cm2以上、小於80mJ/cm2 3: 40 mJ/cm 2 or more and less than 80 mJ/cm 2
2:80mJ/cm2以上、小於160mJ/cm2 2: 80 mJ/cm 2 or more and less than 160 mJ/cm 2
1:160mJ/cm2以上 1:160mJ/cm 2 or more
如所述結果所表明般,得知含有(S)成分的實施例1~實施例69中,密著性優異,錐角亦高。而且得知,感度亦良好。另一方面,得知不含(S)成分的比較例1~比較例11的密著性及錐角均比實施例差。 As shown by the results, it was found that in Examples 1 to 69 containing the (S) component, the adhesion was excellent and the taper angle was also high. And I know that the sensitivity is also good. On the other hand, it was found that the adhesion and the taper angle of Comparative Example 1 to Comparative Example 11 which did not contain the (S) component were inferior to those of the Examples.
[第1實施例] [First Embodiment]
<實施例101> <Example 101>
於日本專利第3321003號公報的圖1所記載的主動式矩陣型液晶顯示裝置中,如以下般形成硬化膜17作為層間絕緣膜,從而獲得實施例101的液晶顯示裝置。即,使用實施例1的感光性樹脂組成物形成硬化膜17作為層間絕緣膜。 In the active matrix liquid crystal display device of FIG. 1 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film as follows, whereby the liquid crystal display device of the example 101 is obtained. That is, the cured film 17 was formed using the photosensitive resin composition of Example 1 as an interlayer insulating film.
即,作為提高日本專利第3321003號公報的0058段落的基板與層間絕緣17的濡濕性的前處理,將基板於六甲基二矽氮烷(HMDS)蒸氣下暴露30秒鐘,然後,旋塗塗佈實施例1的感光性樹脂組成物後,於90℃下於加熱板上進行2分鐘預烘烤而使溶劑揮發,形成膜厚為3μm的感光性樹脂組成物層。繼而,對所得的感光性樹脂組成物層使用佳能(Canon)(股)製造的MPA 5500CF (高壓水銀燈),介隔10μmΦ的孔狀圖案的遮罩、並以成為40mJ/cm2(能量強度:20mW/cm2,i射線)的方式進行曝光。並且,利用鹼顯影液(0.4%的氫氧化四甲基銨水溶液)對曝光後的感光性樹脂組成物層進行23℃/60秒鐘覆液式顯影後,藉由超純水淋洗20秒鐘。繼而,使用超高壓水銀燈以累計照射量成為300mJ/cm2(能量強度:20mW/cm2,i射線)的方式進行整面曝光,其後,將該基板於烘箱中於230℃下加熱30分鐘而獲得硬化膜。 That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then spin-coated. After the photosensitive resin composition of Example 1 was applied, it was prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, the obtained photosensitive resin composition layer was made of MPA 5500CF (high-pressure mercury lamp) manufactured by Canon Co., Ltd., and a mask of a hole pattern of 10 μm Φ was interposed so as to be 40 mJ/cm 2 (energy intensity: Exposure was carried out in a manner of 20 mW/cm 2 , i-ray). Further, the exposed photosensitive resin composition layer was subjected to a liquid-repellent development at 23 ° C for 60 seconds using an alkali developing solution (0.4% aqueous tetramethylammonium hydroxide solution), and then rinsed with ultrapure water for 20 seconds. bell. Then, the entire surface exposure was performed using an ultrahigh pressure mercury lamp so that the cumulative irradiation amount was 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray), and thereafter, the substrate was heated in an oven at 230 ° C for 30 minutes. A cured film is obtained.
塗佈所述感光性樹脂組成物時的塗佈性良好,於曝光、顯影、煅燒後所得的硬化膜中,未確認到皺褶或龜裂的產生。 The coating property at the time of applying the photosensitive resin composition was good, and no occurrence of wrinkles or cracks was observed in the cured film obtained after exposure, development, and firing.
對所得的液晶顯示裝置施加驅動電壓,結果顯示出良好的顯示特性,得知其為可靠性高的液晶顯示裝置。 When a driving voltage was applied to the obtained liquid crystal display device, it was found to have good display characteristics, and it was found to be a highly reliable liquid crystal display device.
<實施例102> <Example 102>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便將曝光裝置自佳能(Canon)(股)製造的MPA 5500CF(高壓水銀燈)變更為尼康(Nikon)(股)製造的FX-803M(gh-Line步進機),液晶顯示裝置的性能亦與實施例101同樣良好。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the exposure apparatus is changed from MPA 5500CF (high-pressure mercury lamp) manufactured by Canon (Canon) to FX-803M (gh-Line stepper) manufactured by Nikon, the performance of the liquid crystal display device It was also as good as Example 101.
<實施例103> <Example 103>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便將曝光裝置自佳能(Canon)(股)製造的MPA 5500CF(高壓水銀燈)變更為使用V科技股份有限公司(V-Technology)製造的「AEGIS」(波長355nm脈衝寬度6nsec),液晶顯示裝置的性能亦與實施例101同樣良好。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the exposure apparatus is changed from MPA 5500CF (high-pressure mercury lamp) manufactured by Canon (share) to "AEGIS" (wavelength 355 nm pulse width 6nsec) manufactured by V-Technology, liquid crystal display The performance of the device was also as good as in Example 101.
<實施例104> <Example 104>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便於省略基板的前處理即六甲基二矽氮烷(HMDS)處理而塗佈實施例1的感光性樹脂組成物時,所獲得的硬化膜亦為無圖案的缺損或剝落的良好狀態。而且液晶顯示裝置的性能亦與實施例101同樣良好。認為其原因在於本發明的組成物與基板的密著性優異。就提高生產性的觀點而言,亦較佳為省略所述基板的前處理的步驟。 The same liquid crystal display device was obtained only by changing the following process from Example 101. In other words, even when the photosensitive resin composition of Example 1 is applied by hexamethyldiazepine (HMDS) treatment, which is a pretreatment of the substrate, the cured film obtained is also excellent in pattern-free defects or peeling. status. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate. From the viewpoint of improving productivity, it is also preferred to omit the step of pre-processing of the substrate.
<實施例105> <Example 105>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便於預烘烤後導入減壓乾燥步驟(蒸氣壓縮蒸餾(Vapor Compression Distillation,VCD)),所獲得的硬化膜亦為無圖案的缺損或剝落的良好狀態。而且液晶顯示裝置的性能亦與實施例101同樣良好。就對應於組成物的固體成分濃度或膜厚而抑制塗佈不均的觀點而言,亦較佳為導入減壓乾燥步驟。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even after the pre-baking, a vacuum drying step (Vapor Compression Distillation (VCD)) is introduced, the obtained cured film is in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. From the viewpoint of suppressing coating unevenness in accordance with the solid content concentration or film thickness of the composition, it is also preferred to introduce a vacuum drying step.
<實施例106> <Example 106>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便於遮罩曝光後至顯影步驟之間導入PEB步驟,所獲得的硬化膜亦為無圖案的缺損或剝落的良好狀態。而且液晶顯示裝置的性能亦與實施例101同樣良好。就提高尺寸穩定性的觀點而言,亦較佳為導入PEB步驟。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the PEB step is introduced between the exposure of the mask and the development step, the obtained cured film is in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. From the standpoint of improving dimensional stability, it is also preferred to introduce the PEB step.
<實施例107> <Example 107>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便將鹼顯影液自0.4%的氫氧化四甲基銨水溶液變更為2.38%的氫氧化四甲基銨水溶液,所獲得的硬化膜亦為無圖案的缺損或剝落的良好狀態。而且液晶顯示裝置的性能亦與實施例101同樣良好。認為其原因在於本發明的組成物與基板的密著性優異。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the alkali developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 2.38% aqueous solution of tetramethylammonium hydroxide, the obtained cured film was in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.
<實施例108> <Example 108>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便將鹼顯影方法自覆液式顯影變更為噴淋顯影,所獲得的硬化膜亦為無圖案的缺損或剝落的良好狀態。而且液晶顯示裝置的性能亦與實施例101同樣良好。認為其原因在於本發明的組成物與基板的密著性優異。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the alkali development method is changed from the overcoat development to the shower development, the obtained cured film is in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.
<實施例109> <Example 109>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,即便將鹼顯影液自0.4%的氫氧化四甲基銨水溶液變更為0.04%的KOH水溶液,所獲得的硬化膜亦為無圖案的缺損或剝落的良好狀態。而且液晶顯示裝置的性能亦與實施例101同樣良好。認為其原因在於本發明的組成物與基板的密著性優異。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the alkali developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 0.04% aqueous KOH solution, the obtained cured film was in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.
<實施例110> <Example 110>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,省略顯影、淋洗後的整面曝光的步驟,於烘箱中以230℃加熱30分鐘而獲得硬化膜。所獲得液晶顯示裝置的性能與實施例101同樣良好。認為其原因在於本發明的組成物的耐化學品性 優異。就提高生產性的觀點而言,亦較佳為省略整面曝光的步驟。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, the step of the entire surface exposure after development and rinsing was omitted, and the film was heated at 230 ° C for 30 minutes in an oven to obtain a cured film. The performance of the obtained liquid crystal display device was as good as that of Example 101. The reason is considered to be the chemical resistance of the composition of the present invention. Excellent. From the viewpoint of improving productivity, it is also preferred to omit the step of the entire surface exposure.
<實施例111> <Example 111>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,於整面曝光的步驟與烘箱中的230℃/30分鐘加熱步驟之間追加於100℃下於加熱板上加熱3分鐘的步驟。所獲得的液晶顯示裝置的性能與實施例101同樣良好。就使孔狀圖案的形狀整齊的觀點而言,亦較佳為追加所述步驟。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, a step of heating on a hot plate at 100 ° C for 3 minutes was added between the step of exposing the entire surface and the heating step of 230 ° C / 30 minutes in the oven. The performance of the obtained liquid crystal display device was as good as that of Example 101. It is also preferable to add the above steps from the viewpoint of aligning the shape of the hole pattern.
<實施例112> <Example 112>
僅自實施例101變更以下的製程而獲得同樣的液晶顯示裝置。即,於顯影、淋洗的步驟與整面曝光的步驟之間追加於100℃下於加熱板上加熱3分鐘的步驟。所獲得的液晶顯示裝置的性能與實施例101同樣良好。就使孔狀圖案的形狀整齊的觀點而言,亦較佳為追加所述步驟。 The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, a step of heating on a hot plate at 100 ° C for 3 minutes was added between the steps of development, rinsing, and the entire surface exposure. The performance of the obtained liquid crystal display device was as good as that of Example 101. It is also preferable to add the above steps from the viewpoint of aligning the shape of the hole pattern.
利用以下方法來製作使用薄膜電晶體(TFT)的有機EL顯示裝置(參照圖2)。 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
於玻璃基板6上形成底部閘極型的TFT 1,以覆蓋該TFT 1的狀態形成包含Si3N4的絕緣膜3。繼而,於該絕緣膜3中形成此處省略圖示的接觸孔後,將經由該接觸孔而連接於TFT 1的配線2(高度為1.0μm)形成於絕緣膜3上。該配線2為用以將TFT 1間連接、或將後續步驟中形成的有機EL元件與TFT 1連接的配線。 A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si 3 N 4 . Then, after the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is a wiring for connecting the TFTs 1 or connecting the organic EL elements formed in the subsequent steps to the TFT 1.
進而,為了使因形成配線2所致的凹凸平坦化,以填埋由配線2所致的凹凸的狀態於絕緣膜3上形成平坦化膜4。於絕緣 膜3上的平坦化膜4的形成是將實施例1的感光性樹脂組成物旋塗塗佈於基板上,於加熱板上進行預烘烤(90℃/120秒)後,自遮罩上方使用高壓水銀燈照射45mJ/cm2(能量強度:20mW/cm2)的i射線(365nm)後,利用鹼水溶液(0.4%的TMAH水溶液)進行顯影而形成圖案,使用超高壓水銀燈以累計照射量成為300mJ/cm2(能量強度:20mW/cm2,i射線)的方式進行整面曝光,進行230℃/30分鐘的加熱處理。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled. The planarization film 4 on the insulating film 3 is formed by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking on a hot plate (90 ° C / 120 seconds), and self-masking. The i-ray (365 nm) of 45 mJ/cm 2 (energy intensity: 20 mW/cm 2 ) was irradiated with a high-pressure mercury lamp above the cover, and then developed by an aqueous alkali solution (0.4% aqueous TMAH solution) to form a pattern, and the ultrahigh pressure mercury lamp was used for total irradiation. The amount was 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray), and the entire surface was exposed, and heat treatment was performed at 230 ° C for 30 minutes.
塗佈感光性樹脂組成物時的塗佈性良好,於曝光、顯影、煅燒後所得的硬化膜中,未確認到皺褶或龜裂的產生。進而,配線2的平均階差為500nm,所製作的平坦化膜4的膜厚為2,000nm。 When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed in the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.
繼而,於所得的平坦化膜4上形成底部發光型的有機EL元件。首先,於平坦化膜4上,經由接觸孔7連接於配線2而形成包含ITO的第一電極5。其後,塗佈抗蝕劑並進行預烘烤,介隔所需圖案的遮罩進行曝光,並進行顯影。將該抗蝕劑圖案作為遮罩,藉由使用ITO蝕刻劑的濕式蝕刻進行圖案加工。其後,使用抗蝕劑剝離液(去除液(Remover)100,AZ電子材料公司製造)於50℃下將所述抗蝕劑圖案剝離。如此所得的第一電極5相當於有機EL元件的陽極。 Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 containing ITO is formed on the planarizing film 4 via the contact hole 7 and connected to the wiring 2. Thereafter, the resist is applied and pre-baked, and a mask which is interposed with a desired pattern is exposed and developed. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled off at 50 ° C using a resist stripper (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.
繼而,形成覆蓋第一電極5的邊緣的形狀的絕緣膜8。關於絕緣膜8,使用實施例1的感光性樹脂組成物,利用與上文所述相同的方法來形成絕緣膜8。藉由設置該絕緣膜8,可防止第一電極5與其後續步驟中形成的第二電極之間的短路。 Then, an insulating film 8 covering the shape of the edge of the first electrode 5 is formed. With regard to the insulating film 8, the insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 1. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.
進而,於真空蒸鍍裝置內,介隔所需的圖案遮罩依序蒸鍍設置電洞傳輸層、有機發光層、電子傳輸層。繼而,於基板上方的整個面上形成包含Al的第二電極。將所得的所述基板自蒸鍍機中取出,使用密封用玻璃板及紫外線硬化型環氧樹脂進行貼合,藉此進行密封。 Further, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially depositing a desired pattern mask. Then, a second electrode containing Al is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine, and bonded by using a sealing glass plate and an ultraviolet curable epoxy resin.
如以上般獲得對各有機EL元件連接用以驅動該有機EL元件的TFT1而成的主動式矩陣型的有機EL顯示裝置。經由驅動電路施加電壓,結果顯示出良好的顯示特性,得知其為可靠性高的有機EL顯示裝置。 An active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements is obtained as described above. When a voltage was applied via the drive circuit, it was found to have good display characteristics, and it was found to be a highly reliable organic EL display device.
[第2實施例] [Second Embodiment]
<實施例113> <Example 113>
與所述第1實施例同樣地,使用實施例40的感光性樹脂組成物而獲得液晶顯示裝置。對所得的液晶顯示裝置施加驅動電壓,結果顯示出良好的顯示特性,得知其為可靠性高的液晶顯示裝置。 A liquid crystal display device was obtained using the photosensitive resin composition of Example 40 in the same manner as in the first embodiment. When a driving voltage was applied to the obtained liquid crystal display device, it was found to have good display characteristics, and it was found to be a highly reliable liquid crystal display device.
而且,與所述第1實施例同樣地,使用實施例40的感光性樹脂組成物製作使用薄膜電晶體(TFT)的有機EL顯示裝置。經由驅動電路施加電壓,結果顯示出良好的顯示特性,得知其為可靠性高的有機EL顯示裝置。 Further, in the same manner as in the first embodiment, an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 40. When a voltage was applied via the drive circuit, it was found to have good display characteristics, and it was found to be a highly reliable organic EL display device.
[第3實施例] [Third embodiment]
<實施例114> <Example 114>
與所述第1實施例同樣地,使用實施例51的感光性樹脂組成物而獲得液晶顯示裝置。對所得的液晶顯示裝置施加驅動電壓, 結果顯示出良好的顯示特性,得知其為可靠性高的液晶顯示裝置。 In the same manner as in the first embodiment, a liquid crystal display device was obtained using the photosensitive resin composition of Example 51. Applying a driving voltage to the obtained liquid crystal display device, As a result, good display characteristics were exhibited, and it was found to be a highly reliable liquid crystal display device.
而且,與所述第1實施例同樣地,使用實施例51的感光性樹脂組成物製作使用薄膜電晶體(TFT)的有機EL顯示裝置。經由驅動電路施加電壓,結果顯示出良好的顯示特性,得知其為可靠性高的有機EL顯示裝置。 Further, in the same manner as in the first embodiment, an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 51. When a voltage was applied via the drive circuit, it was found to have good display characteristics, and it was found to be a highly reliable organic EL display device.
1‧‧‧TFT(薄膜電晶體) 1‧‧‧TFT (thin film transistor)
2‧‧‧配線 2‧‧‧Wiring
3‧‧‧絕緣膜 3‧‧‧Insulation film
4‧‧‧平坦化膜 4‧‧‧Flat film
5‧‧‧第一電極 5‧‧‧First electrode
6‧‧‧玻璃基板 6‧‧‧ glass substrate
7‧‧‧接觸孔 7‧‧‧Contact hole
8‧‧‧絕緣膜 8‧‧‧Insulation film
Claims (18)
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JP2013198395 | 2013-09-25 |
Publications (1)
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TW201520695A true TW201520695A (en) | 2015-06-01 |
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TW103132697A TW201520695A (en) | 2013-09-25 | 2014-09-23 | Photo-sensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device and organic EL display device |
Country Status (5)
Country | Link |
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JP (1) | JP6182613B2 (en) |
KR (1) | KR101823424B1 (en) |
CN (1) | CN105579908B (en) |
TW (1) | TW201520695A (en) |
WO (1) | WO2015046296A1 (en) |
Cited By (2)
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TWI795461B (en) * | 2017-11-09 | 2023-03-11 | 日商富士軟片股份有限公司 | Solid-state imaging device, composition for foming organic layer |
TWI830850B (en) * | 2019-12-30 | 2024-02-01 | 奇美實業股份有限公司 | Chemically amplified positive photosensitive resin composition and uses thereof |
Families Citing this family (12)
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JP6309755B2 (en) * | 2013-12-25 | 2018-04-11 | 東京応化工業株式会社 | Photosensitive resin composition |
KR20160102532A (en) * | 2014-03-05 | 2016-08-30 | 후지필름 가부시키가이샤 | Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device and touch panel display device |
JP6388640B2 (en) * | 2014-03-17 | 2018-09-12 | 旭化成株式会社 | Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device |
JP6470615B2 (en) * | 2015-03-31 | 2019-02-13 | 東京応化工業株式会社 | Photosensitive resin composition, pattern forming method, color filter, and display device |
JP6794653B2 (en) * | 2016-04-21 | 2020-12-02 | Hdマイクロシステムズ株式会社 | Positive photosensitive resin composition |
JP6667361B2 (en) * | 2016-05-06 | 2020-03-18 | 東京応化工業株式会社 | Chemically amplified positive photosensitive resin composition |
JP6508446B1 (en) * | 2017-06-30 | 2019-05-08 | 住友ベークライト株式会社 | Photosensitive resin composition, resin film and electronic device |
JP2020076945A (en) * | 2018-09-21 | 2020-05-21 | 旭化成株式会社 | Photosensitive resin composition |
JP7071300B2 (en) * | 2019-01-21 | 2022-05-18 | 信越化学工業株式会社 | Resin composition, resin film, semiconductor laminate, method for manufacturing semiconductor laminate, and method for manufacturing semiconductor device |
CN114207525A (en) * | 2019-08-02 | 2022-03-18 | 富士胶片株式会社 | Photosensitive transfer member, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel |
JP7107297B2 (en) * | 2019-11-01 | 2022-07-27 | 信越化学工業株式会社 | Organosilicon compound, active energy ray-curable composition and coated article |
CN114846053A (en) * | 2019-12-13 | 2022-08-02 | 琳得科株式会社 | Resin composition and resin sheet |
Family Cites Families (9)
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JP2652093B2 (en) * | 1991-09-12 | 1997-09-10 | 富士写真フイルム株式会社 | Photosensitive composition |
JP5281357B2 (en) * | 2008-10-23 | 2013-09-04 | 新日鉄住金化学株式会社 | Photosensitive resin composition for black resist and color filter light-shielding film |
JP5343570B2 (en) * | 2009-01-13 | 2013-11-13 | 信越化学工業株式会社 | Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same |
JP2011128359A (en) * | 2009-12-17 | 2011-06-30 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, cured film using the same and electronic component |
JP5495991B2 (en) * | 2010-07-12 | 2014-05-21 | 富士フイルム株式会社 | Colored photosensitive resin composition, cured film and method for producing the same, color filter, and display device |
JP5419952B2 (en) * | 2011-12-02 | 2014-02-19 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition |
JP5814144B2 (en) * | 2012-01-30 | 2015-11-17 | 富士フイルム株式会社 | Photosensitive resin composition and method for producing pattern using the same |
CN104870565B (en) * | 2012-12-21 | 2019-04-26 | 日立化成杜邦微***股份有限公司 | Polyimide precursor resin composition |
WO2014199800A1 (en) * | 2013-06-12 | 2014-12-18 | Jsr株式会社 | Resin composition, photosensitive resin composition, insulating film and method for producing same, and electronic component |
-
2014
- 2014-09-23 TW TW103132697A patent/TW201520695A/en unknown
- 2014-09-25 WO PCT/JP2014/075367 patent/WO2015046296A1/en active Application Filing
- 2014-09-25 CN CN201480052307.4A patent/CN105579908B/en active Active
- 2014-09-25 KR KR1020167007159A patent/KR101823424B1/en active IP Right Grant
- 2014-09-25 JP JP2015539294A patent/JP6182613B2/en active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI795461B (en) * | 2017-11-09 | 2023-03-11 | 日商富士軟片股份有限公司 | Solid-state imaging device, composition for foming organic layer |
TWI830850B (en) * | 2019-12-30 | 2024-02-01 | 奇美實業股份有限公司 | Chemically amplified positive photosensitive resin composition and uses thereof |
Also Published As
Publication number | Publication date |
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KR101823424B1 (en) | 2018-01-30 |
CN105579908B (en) | 2019-08-27 |
JP6182613B2 (en) | 2017-08-16 |
WO2015046296A1 (en) | 2015-04-02 |
KR20160045109A (en) | 2016-04-26 |
JPWO2015046296A1 (en) | 2017-03-09 |
CN105579908A (en) | 2016-05-11 |
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