TW201445248A - Photosensitive resin composition, cured product and method for manufacturing the same, manufacturing method of resin pattern, liquid crystal display device, organic EL display device, and touch panel display device - Google Patents
Photosensitive resin composition, cured product and method for manufacturing the same, manufacturing method of resin pattern, liquid crystal display device, organic EL display device, and touch panel 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上述感光性樹脂組成物硬化而成的硬化物及其製造方法、使用上述感光性樹脂組成物的樹脂圖案製造方法、使上述感光性組成物硬化而成的硬化膜、以及使用上述硬化膜的各種圖像顯示裝置。 The present invention relates to a photosensitive resin composition (hereinafter sometimes referred to simply as "the composition of the present invention"). Further, the present invention relates to a cured product obtained by curing the photosensitive resin composition, a method for producing the same, a method for producing a resin pattern using the photosensitive resin composition, and a curing method for curing the photosensitive composition. A film, and various image display devices using the above-described cured film.
更詳細而言，本發明是有關於一種適合於形成液晶顯示裝置、有機電致發光(Electroluminescence，EL)顯示裝置、觸控面板顯示裝置、積體電路元件、固體攝影元件等的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 flat portion of an electronic component suitable for forming a liquid crystal display device, an organic electroluminescence (EL) display device, a touch panel display device, an integrated circuit device, a solid-state imaging device, and the like. A photosensitive resin composition for a film, a protective film or an interlayer insulating film, and a method for producing a cured film using the same.
藉由固體攝影元件或液晶顯示裝置的發展，而開始廣泛進行利用有機原材料(樹脂)來製作微透鏡、光波導、抗反射膜等光學構件。 With the development of a solid-state imaging device or a liquid crystal display device, an optical member such as a microlens, an optical waveguide, or an antireflection film is widely produced by using an organic material (resin).
為了使該些光學構件的折射率變高，而正在研究添加氧化鈦等金屬氧化物粒子(參照下述專利文獻1)。 In order to increase the refractive index of these optical members, metal oxide particles such as titanium oxide have been studied (see Patent Document 1 below).
另外，作為先前的負型感光性樹脂組成物，已知有專利文獻2~專利文獻5中所記載的感光性樹脂組成物。 In addition, the photosensitive resin composition described in Patent Document 2 to Patent Document 5 is known as a conventional negative photosensitive resin composition.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2006-98985號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-98985
[專利文獻2]日本專利特開2011-127096號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-127096
[專利文獻3]日本專利特開2009-179678號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-179678
[專利文獻4]日本專利特開2008-185683號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-185683
[專利文獻5]韓國公開專利第10-2012-0121850號公報 [Patent Document 5] Korean Laid-Open Patent Publication No. 10-2012-0121850
為了實現高折射率化，必須將感光性樹脂組成物中的金屬氧化物粒子含量加以高濃度化。當含有許多金屬氧化物粒子時，於顯影後容易產生殘渣，因該殘渣含有金屬氧化物粒子，故無法藉由後續步驟的氧灰化等方法來去除的情況多。尤其，當用作觸控面板用絕緣膜的情況下，塗佈有氧化銦錫(Indium Tin Oxide，ITO)的基板上的殘渣的產生已成為問題。因此，期望一種顯影後的殘渣得到抑制、且不會對霧度等其他性能造成不良影響的殘渣改良方法。 In order to achieve a high refractive index, it is necessary to increase the content of the metal oxide particles in the photosensitive resin composition. When a large amount of metal oxide particles are contained, residue is likely to be generated after development, and since the residue contains metal oxide particles, it cannot be removed by a method such as oxygen ashing in a subsequent step. In particular, when used as an insulating film for a touch panel, generation of residue on a substrate coated with indium tin oxide (ITO) has become a problem. Therefore, it is desirable to have a residue improving method in which the residue after development is suppressed without adversely affecting other properties such as haze.
本發明是解決上述課題的發明，即，其目的在於提供一種基板上，特別是ITO基板上的顯影後的殘渣的產生得到抑制的含有金屬氧化物粒子的感光性樹脂組成物。本發明的進一步的目的在於提供一種使用上述感光性樹脂組成物的硬化物及其製造方法、樹脂圖案製造方法、以及具有上述硬化物的液晶顯示裝置、有機EL顯示裝置、及觸控面板顯示裝置。 The present invention has been made to solve the above problems, and an object of the invention is to provide a photosensitive resin composition containing metal oxide particles which is suppressed on the substrate, in particular, the generation of residue after development on the ITO substrate. A further object of the present invention is to provide a cured product using the photosensitive resin composition, a method for producing the same, a method for producing a resin pattern, a liquid crystal display device having the cured product, an organic EL display device, and a touch panel display device .
本發明的上述課題藉由以下的<1>、<8>、<9>、<11>、<12>、<14>~<16>中所記載的手段來解決。以下一併記載作為較佳的實施形態的<2>~<7>、<10>及<13>。 The above problems of the present invention are solved by the means described in the following <1>, <8>, <9>, <11>, <12>, <14> to <16>. <2> to <7>, <10>, and <13> which are preferred embodiments are described below.
<1>一種感光性樹脂組成物，其特徵在於包括：(成分A)含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分、(成分B)光酸產生劑、(成分C)金屬氧化物粒子、(成分D)溶劑、(成分E)分散劑、以及(成分F)聚氧伸烷基取代苯醚界面活性劑，(1)具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物，(2)具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物； <1> A photosensitive resin composition comprising: (Component A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (Component B) photoacid generation Agent, (Component C) metal oxide particles, (Component D) solvent, (Component E) dispersant, and (Component F) polyoxyalkylene-substituted phenyl ether surfactant, (1) having (a1) acid a constituent unit of a group protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, and (2) a constituent unit having a group (a1) having an acid group-protected group protected by an acid-decomposable group a polymer, and a polymer having (a2) a structural unit containing a crosslinkable group;
<2>如<1>所述的感光性樹脂組成物，其中上述聚氧伸烷基取代苯醚界面活性劑的分子中的苯環的數量的合計為1~4的範圍； The photosensitive resin composition as described in <1>, wherein the total number of the benzene rings in the molecule of the polyoxyalkylene-substituted phenyl ether surfactant is in the range of 1 to 4;
<3>如<1>或<2>所述的感光性樹脂組成物，其中上述聚氧伸烷基取代苯醚界面活性劑的親水親油平衡(Hydrophile-Lipophile Balance，HLB)值為12~16的範圍； <3> The photosensitive resin composition according to <1> or <2>, wherein the polyoxyalkylene-substituted phenyl ether surfactant has a Hydrophile-Lipophile Balance (HLB) value of 12~ The scope of 16;
<4>如<1>至<3>中任一項所述的感光性樹脂組成物，其除(成分F)聚氧伸烷基取代苯醚界面活性劑以外，更包括(成分G)氟系界面活性劑、及/或矽酮系界面活性劑； The photosensitive resin composition as described in any one of <1> to <3>, in addition to (component F) polyoxyalkylene-substituted phenyl ether surfactant, further comprises (component G) fluorine a surfactant, and/or an anthrone-based surfactant;
<5>如<1>至<4>中任一項所述的感光性樹脂組成物，其中上述成分C為氧化鈦粒子或氧化鋯粒子； The photosensitive resin composition as described in any one of <1> which the said component C is a titanium oxide particle or a zirconia particle;
<6>如<1>至<5>中任一項所述的感光性樹脂組成物，其更包括(成分H)具有2個以上的氮原子的雜環化合物； The photosensitive resin composition of any one of <1> to <5> further comprising (component H) a heterocyclic compound having two or more nitrogen atoms;
<7>如<1>至<6>中任一項所述的感光性樹脂組成物，其更包括(成分I)交聯劑； The photosensitive resin composition according to any one of <1> to <6> which further comprises (Component I) a crosslinking agent;
<8>一種硬化物的製造方法，其特徵在於：至少依次包括步驟(a)~步驟(c)，(a)將如<1>至<7>中任一項所述的感光性樹脂組成物塗佈於基板上的塗佈步驟、(b)自所塗佈的樹脂組成物中去除溶劑的溶劑去除步驟、以及(c)對去除了溶劑的樹脂組成物進行熱處理的熱處理步驟； <8> A method for producing a cured product, comprising: at least step (a) to step (c), (a) comprising the photosensitive resin according to any one of <1> to <7> a coating step of coating the substrate on the substrate, (b) a solvent removing step of removing the solvent from the applied resin composition, and (c) a heat treatment step of heat-treating the solvent-removed resin composition;
<9>一種樹脂圖案製造方法，其特徵在於：至少依次包括步驟(1)~步驟(5)，(1)將如<1>至<7>中任一項所述的感光性樹脂組成物塗 佈於基板上的塗佈步驟、(2)自所塗佈的樹脂組成物中去除溶劑的溶劑去除步驟、(3)利用光化射線將去除了溶劑的樹脂組成物曝光成圖案狀的曝光步驟、(4)利用水性顯影液對經曝光的樹脂組成物進行顯影的顯影步驟、以及(5)對經顯影的樹脂組成物進行熱處理的熱處理步驟； (9) A photosensitive resin composition according to any one of <1> to <7>, wherein the photosensitive resin composition according to any one of <1> to <7>, Paint a coating step on the substrate, (2) a solvent removal step of removing the solvent from the applied resin composition, and (3) an exposure step of exposing the solvent-removed resin composition to a pattern by actinic rays And (4) a developing step of developing the exposed resin composition with an aqueous developing solution, and (5) a heat treatment step of subjecting the developed resin composition to heat treatment;
<10>如<9>所述的樹脂圖案製造方法，其中上述基板的表面的全部或一部分為選自由玻璃、SiO、ITO、氧化銦鋅(Indium Zinc Oxide，IZO)、金屬膜、及金屬氧化物膜所組成的群組中的至少1種。 <10> The resin pattern manufacturing method according to <9>, wherein all or a part of the surface of the substrate is selected from the group consisting of glass, SiO, ITO, indium zinc oxide (IZO), metal film, and metal oxide. At least one of the group consisting of the film.
<11>一種硬化物，其藉由如<8>所述的硬化物的製造方法、或者如<9>或<10>所述的樹脂圖案製造方法而獲得。 <11> A cured product obtained by the method for producing a cured product according to <8> or the method for producing a resin pattern according to <9> or <10>.
<12>一種硬化膜，其是使如<1>至<7>中任一項所述的感光性樹脂組成物硬化而形成。 <12> A cured film formed by curing the photosensitive resin composition according to any one of <1> to <7>.
<13>如<12>所述的硬化膜，其為層間絕緣膜。 <13> The cured film according to <12> which is an interlayer insulating film.
<14>一種液晶顯示裝置，其包括如<12>或<13>所述的硬化膜。 <14> A liquid crystal display device comprising the cured film according to <12> or <13>.
<15>一種有機電致發光(EL)顯示裝置，其包括如<12>或<13>所述的硬化膜。 <15> An organic electroluminescence (EL) display device comprising the cured film according to <12> or <13>.
<16>一種觸控面板顯示裝置，其包括如<12>或<13>所述的硬化膜。 <16> A touch panel display device comprising the cured film according to <12> or <13>.
根據本發明，可提供一種基板上，特別是ITO基板上的顯影後的殘渣的產生得到抑制的含有金屬氧化物粒子的感光性樹脂組成物。進而，根據本發明，可提供一種使用上述感光性樹脂組成物的硬化物及其製造方法、樹脂圖案的製造方法、以及具有上述硬化物的液晶顯示裝置、有機EL顯示裝置、及觸控面板顯示裝置。 According to the present invention, it is possible to provide a photosensitive resin composition containing metal oxide particles which is suppressed on the substrate, in particular, the generation of residue after development on the ITO substrate. Further, according to the present invention, it is possible to provide a cured product using the photosensitive resin composition, a method for producing the same, a method for producing a resin pattern, and a liquid crystal display device, an organic EL display device, and a touch panel display having the cured product. Device.
1、16‧‧‧TFT(薄膜電晶體) 1,16‧‧‧TFT (thin film transistor)
2‧‧‧配線 2‧‧‧Wiring
3、8‧‧‧絕緣膜 3,8‧‧‧Insulation film
4‧‧‧平坦化膜 4‧‧‧Flat film
5‧‧‧第一電極 5‧‧‧First electrode
6、14、15‧‧‧玻璃基板 6, 14, 15‧ ‧ glass substrate
7、18‧‧‧接觸孔 7, 18‧‧‧ contact holes
10‧‧‧液晶顯示裝置 10‧‧‧Liquid crystal display device
12‧‧‧背光單元 12‧‧‧Backlight unit
17‧‧‧硬化膜 17‧‧‧ hardened film
19‧‧‧ITO透明電極 19‧‧‧ITO transparent electrode
20‧‧‧液晶 20‧‧‧LCD
22‧‧‧彩色濾光片 22‧‧‧Color filters
30‧‧‧靜電電容型輸入裝置 30‧‧‧Electrostatic type input device
31‧‧‧前面板 31‧‧‧ front panel
32‧‧‧遮罩層 32‧‧‧mask layer
33‧‧‧第一透明電極圖案 33‧‧‧First transparent electrode pattern
33a‧‧‧墊部分 33a‧‧‧Pie section
33b‧‧‧連接部分 33b‧‧‧Connected section
34‧‧‧第二透明電極圖案 34‧‧‧Second transparent electrode pattern
35‧‧‧絕緣層 35‧‧‧Insulation
36‧‧‧導電性要素 36‧‧‧Electrical elements
37‧‧‧透明保護層 37‧‧‧Transparent protective layer
38‧‧‧開口部 38‧‧‧ openings
圖1表示液晶顯示裝置的一例的構成概念圖。表示液晶顯示裝置中的主動矩陣基板的示意剖面圖，且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. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, and having a cured film 17 as an interlayer insulating film.
圖2表示有機EL顯示裝置的一例的構成概念圖。表示底部發光型的有機EL顯示裝置中的基板的示意剖面圖，且具有平坦化膜4。 FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and having a planarization film 4.
圖3是表示靜電電容型輸入裝置的構成的剖面圖。 3 is a cross-sectional view showing the configuration of a capacitance type input device.
圖4是表示前面板的一例的說明圖。 4 is an explanatory view showing an example of a front panel.
圖5是表示第一透明電極圖案及第二透明電極圖案的一例的說明圖。 FIG. 5 is an explanatory view showing an example of a first transparent electrode pattern and a second transparent electrode pattern.
以下，對本發明的內容進行詳細說明。以下所記載的構成要件的說明有時基於本發明的具有代表性的實施形態來進行， 但本發明並不限定於此種實施形態。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention. However, the present invention is not limited to such an embodiment.
再者，於本申請案說明書中，「~」是以包含其前後所記載的數值作為下限值及上限值的含義來使用。 In addition, in the specification of the present application, "~" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit.
另外，於本發明中，亦將「(成分A)含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分」等簡稱為「成分A」等，亦將「(a1)含有酸基由酸分解性基保護的基的構成單元」等簡稱為「構成單元(a1)」等。 In addition, in the present invention, "(Component A) contains a polymer component which satisfies at least one of the following (1) and the following (2)", etc., simply as "Component A", etc. (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, and the like is simply referred to as "constituting unit (a1)" or the like.
進而，於本說明書中的基(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(原子團)，並且亦包含具有取代基的基(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)，亦包含具有取代基的烷基(經取代的烷基)。 Further, in the description 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).
於本發明中，「質量份」及「質量%」的含義分別與「重量份」及「重量%」相同。 In the present invention, the meanings of "parts by mass" and "% by mass" are the same as "parts by weight" and "% by weight", respectively.
本發明的感光性樹脂組成物(以下，亦簡稱為「樹脂組成物」)的特徵在於包括：(成分A)含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分、(成分B)光酸產生劑、(成分C)金屬氧化物粒子、(成分D)溶劑、(成分E)分散劑、以及(成分F)聚氧伸烷基取代苯醚界面活性劑。 The photosensitive resin composition of the present invention (hereinafter also referred to simply as "resin composition") is characterized in that (component A) contains a polymer which satisfies at least one of the following (1) and (2) below. Component, (Component B) photoacid generator, (Component C) metal oxide particles, (Component D) solvent, (Component E) dispersant, and (Component F) polyoxyalkylene substituted phenyl ether surfactant .
(1)具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物， (2)具有(a1)含有酸基由酸分解性基保護的基的構成單元 的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物。 (1) a polymer having (a1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit containing a crosslinkable group, (2) a constituent unit having (a1) a group having an acid group protected by an acid-decomposable group The polymer and the polymer having (a2) a structural unit containing a crosslinkable group.
本發明的感光性樹脂組成物可適宜地用作正型抗蝕劑組成物。 The photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
本發明的感光性樹脂組成物較佳為具有藉由熱而硬化的性質的樹脂組成物。 The photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
另外，本發明的感光性樹脂組成物較佳為正型感光性樹脂組成物，更佳為化學增幅型的正型感光性樹脂組成物(化學增幅正型感光性樹脂組成物)。 In addition, the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, and more preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
本發明的感光性樹脂組成物較佳為不含1,2-醌二疊氮化合物作為感應光化射線的光酸產生劑。1,2-醌二疊氮化合物雖然藉由逐步型光化學反應而生成羧基，但其量子產率必定為1以下。 The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator for inducing actinic rays. Although the 1,2-quinonediazide compound generates a carboxyl group by a stepwise photochemical reaction, its quantum yield must be 1 or less.
相對於此，本發明中所使用的(成分B)光酸產生劑因感應光化射線而生成的酸作為觸媒而對成分A中的受到保護的酸基的脫保護發揮作用，故藉由1個光量子的作用所生成的酸有助於多個脫保護反應，量子產率超過1，例如變成如10的幾乘方般大的值，作為所謂的化學增幅的結果，可獲得高感度。 On the other hand, the (component B) photoacid generator used in the present invention acts as a catalyst for the deprotection of the protected acid group in the component A by the acid generated by the actinic ray. The acid generated by the action of one photon contributes to a plurality of deprotection reactions, and the quantum yield exceeds 1, for example, a value as large as several of 10, and as a result of the so-called chemical amplification, high sensitivity can be obtained.
進而，本發明的感光性樹脂組成物較佳為微透鏡、光波導、抗反射膜、發光二極體(Light Emitting Diode，LED)用密封材及LED用晶片塗佈材等的光學構件用樹脂組成物，或觸控面板中所使用的配線電極的視認性降低用樹脂組成物。再者，所謂觸控面板中所使用的配線電極的視認性降低用組成物，是指降低觸控面板中所使用的配線電極的視認性，即，使配線電極不易被看 到的構件用組成物，例如可列舉ITO(氧化銦錫)電極間的層間絕緣膜等，本發明的感光性樹脂組成物可適宜地用於該用途。 Furthermore, the photosensitive resin composition of the present invention is preferably a resin for optical members such as a microlens, an optical waveguide, an antireflection film, a sealing material for a light emitting diode (LED), and a wafer coating material for LED. The composition or the resin composition for reducing the visibility of the wiring electrode used in the touch panel. In addition, the composition for reducing the visibility of the wiring electrode used in the touch panel means reducing the visibility of the wiring electrode used in the touch panel, that is, making the wiring electrode difficult to be seen. The composition for the member to be obtained is, for example, an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photosensitive resin composition of the present invention can be suitably used for this purpose.
通常，若進行曝光，則藉由與光酸產生劑的作用，化學增幅正型感光性樹脂組成物所含有的聚合物所具有的脫離基脫離，並溶解於顯影液中，未曝光部作為圖案而形成。 In general, when exposed to light, the release group of the polymer contained in the chemically amplified positive photosensitive resin composition is desorbed by the action of the photoacid generator, and is dissolved in the developer, and the unexposed portion is used as a pattern. And formed.
當將含有金屬氧化物粒子、分散劑及包含脫離基及交聯基的聚合物的樹脂組成物用作正型感光性樹脂組成物時，如上所述，若以高濃度使用金屬氧化物粒子，則於顯影後容易產生殘渣，另外，因該殘渣含有金屬氧化物粒子，故存在難以藉由氧灰化等來去除這一問題。尤其存在於塗佈有ITO的基板上容易產生殘渣這一問題。 When a resin composition containing a metal oxide particle, a dispersing agent, and a polymer containing a leaving group and a crosslinking group is used as a positive photosensitive resin composition, as described above, when metal oxide particles are used at a high concentration, Further, since residue is likely to be generated after development, the residue contains metal oxide particles, so that it is difficult to remove it by oxygen ashing or the like. In particular, there is a problem in that a residue is likely to be generated on a substrate coated with ITO.
本發明者等進行詳細研究的結果，發現藉由製成含有成分A~成分E、及成分F的感光性樹脂組成物，而抑制基板上，特別是ITO基板上的顯影後的殘渣的產生，從而完成了本發明。 As a result of intensive studies, the present inventors have found that by producing a photosensitive resin composition containing the components A to E and the component F, it is possible to suppress the occurrence of residue after development on the substrate, particularly on the ITO substrate. The present invention has thus been completed.
以下，對本發明的組成物進行詳細說明。 Hereinafter, the composition of the present invention will be described in detail.
(成分A)含有滿足(1)及(2)的至少一個的聚合物的聚合物成分 (Component A) a polymer component containing a polymer satisfying at least one of (1) and (2)
本發明的感光性樹脂組成物包含(成分A)含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分。 The photosensitive resin composition of the present invention contains (Component A) a polymer component containing a polymer satisfying at least one of the following (1) and (2) below.
(1)具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物 (1) a polymer having (a1) a component having a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer comprising a component of a crosslinkable group
(2)具有(a1)含有酸基由酸分解性基保護的基的構成單元 的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物 (2) a constituent unit having (a1) a group having an acid group protected by an acid-decomposable group Polymer, and polymer having (a2) a structural unit containing a crosslinkable group
本發明的組成物可進而含有該些以外的聚合物。只要未特別說明，則本發明中的成分A是指除上述(1)及/或(2)以外，包含視需要而添加的其他聚合物的成分。 The composition of the present invention may further contain a polymer other than the above. Unless otherwise specified, the component A in the present invention means a component containing other polymers added as needed in addition to the above (1) and/or (2).
就硬化後的透明性(霧度)及未曝光部的殘膜率的觀點而言，本發明的感光性樹脂組成物較佳為含有滿足上述(1)的成分作為成分A。 The photosensitive resin composition of the present invention preferably contains a component satisfying the above (1) as the component A from the viewpoint of the transparency (haze) after curing and the residual film ratio of the unexposed portion.
另一方面，就分子設計的自由度的觀點而言，本發明的感光性樹脂組成物較佳為含有滿足上述(2)的成分作為成分A。 On the other hand, the photosensitive resin composition of the present invention preferably contains a component satisfying the above (2) as the component A from the viewpoint of the degree of freedom in molecular design.
再者，於含有滿足上述(1)的成分的情況下，亦可進而包含具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物、及/或具有(a2)含有交聯性基的構成單元的聚合物。 In addition, when the component satisfying the above (1) is contained, a polymer having (a1) a structural unit having a group having an acid group-protected group and/or (a2) may be further contained. A polymer of a constituent unit of a crosslinkable group.
另外，於含有滿足上述(2)的成分的情況下，當至少包含相當於具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物的成分時，亦作為相當於含有滿足上述(1)的成分的情況者。 In addition, when a component satisfying the above (2) is contained, at least a constituent unit having a group having an acid group-containing group protected by an acid group and (a2) a crosslinkable group is contained. In the case of the component of the polymer of the unit, it is also equivalent to the case where the component satisfying the above (1) is contained.
成分A較佳為加成聚合型的樹脂，更佳為含有源自(甲基)丙烯酸及/或其酯的構成單元的聚合物。再者，亦可具有源自(甲基)丙烯酸及/或其酯的構成單元以外的構成單元，例如源自苯乙烯的構成單元、或源自乙烯基化合物的構成單元等。 Component A is preferably an addition polymerization type resin, and more preferably a polymer containing a constituent unit derived from (meth)acrylic acid and/or its ester. Further, it may have a constituent unit other than the constituent unit derived from (meth)acrylic acid and/or an ester thereof, for example, a constituent unit derived from styrene or a constituent unit derived from a vinyl compound.
再者，亦將「源自(甲基)丙烯酸及/或其酯的構成單元」稱為「丙烯酸系構成單元」。另外，「(甲基)丙烯酸」是指「甲基丙烯酸 及/或丙烯酸」。 In addition, the "constituting unit derived from (meth)acrylic acid and/or its ester" is also referred to as "acrylic constituent unit". In addition, "(meth)acrylic acid" means "methacrylic acid" And / or acrylic."
<構成單元(a1)> <constitution unit (a1)>
成分A包含至少具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物。藉由成分A包含具有構成單元(a1)的聚合物，可製成感度極高的感光性樹脂組成物。 Component A contains a polymer having at least (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group. By containing the polymer having the constituent unit (a1) as the component A, a photosensitive resin composition having an extremely high sensitivity can be obtained.
本發明中的「酸基由酸分解性基保護的基」可使用作為酸基及酸分解性基所公知的基，並無特別限定。作為具體的酸基，可較佳地列舉羧基、及酚性羥基。另外，作為酸分解性基，可使用比較容易藉由酸而分解的基(例如由後述的式(a1-10)所表示的基、四氫吡喃基、或四氫呋喃基等縮醛系官能基)、或比較難以藉由酸而分解的基(例如第三丁基等三級烷基、碳酸第三丁酯基等碳酸三級烷基酯基)。 In the present invention, the "acid group which is protected by an acid-decomposable group" can be used as a group known as an acid group or an acid-decomposable group, and is not particularly limited. As a specific acid group, a carboxyl group and a phenolic hydroxyl group are preferable. In addition, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, a group represented by the formula (a1-10) to be described later, an acetal functional group such as a tetrahydropyranyl group or a tetrahydrofuranyl group can be used. Or a group which is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl carbonate group such as a tertiary butyl group such as a third butyl group or a tertiary butyl carbonate group).
(a1)含有酸基由酸分解性基保護的基的構成單元較佳為含有羧基由酸分解性基保護的保護羧基的構成單元(亦稱為「含有由酸分解性基保護的保護羧基的構成單元」)、或含有酚性羥基由酸分解性基保護的保護酚性羥基的構成單元(亦稱為「含有由酸分解性基保護的保護酚性羥基的構成單元」)。 (a1) The structural unit containing a group in which an acid group is protected by an acid-decomposable group is preferably a constituent unit containing a protective carboxyl group in which a carboxyl group is protected by an acid-decomposable group (also referred to as "protecting a carboxyl group protected by an acid-decomposable group" The constituent unit ") or a constituent unit for protecting a phenolic hydroxyl group which is protected by an acid-decomposable group (also referred to as "a structural unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group").
以下，依次對含有由酸分解性基保護的保護羧基的構成單元(a1-1)、及含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)分別進行說明。 Hereinafter, the constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group and the constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group will be sequentially described.
<<(a1-1)含有由酸分解性基保護的保護羧基的構成單元>> <<(a1-1) A constituent unit containing a protected carboxyl group protected by an acid-decomposable group>>
上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)是含有羧基的構成單元的羧基具有以下將詳細說明的由酸分解性基保護的保護羧基的構成單元。 The structural unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is a structural unit in which a carboxyl group of a structural unit containing a carboxyl group has a protective carboxyl group protected by an acid-decomposable group, which will be described in detail below.
作為可用於上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的上述含有羧基的構成單元，可無特別限制地使用公知的構成單元。例如可列舉：源自不飽和單羧酸、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構成單元(a1-1-1)，或同時具有乙烯性不飽和基與源自酸酐的結構的構成單元(a1-1-2)。 As the structural unit containing a carboxyl group which can be used for the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group, a known structural unit can be used without particular limitation. For example, a constituent unit (a1-1-1) 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, or both A constituent unit (a1-1-2) having an ethylenically unsaturated group and an acid anhydride-derived structure.
以下，依次對可用作上述含有羧基的構成單元的(a1-1-1)源自分子中具有至少1個羧基的不飽和羧酸等的構成單元、及(a1-1-2)同時具有乙烯性不飽和基與源自酸酐的結構的構成單元分別進行說明。 In the following, (a1-1-1) which is used as the structural unit containing a carboxyl group, is derived from a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) The constituent units of the ethylenically unsaturated group and the structure derived from the acid anhydride will be separately described.
<<<(a1-1-1)源自分子中具有至少1個羧基的不飽和羧酸等的構成單元>>> <<<(a1-1-1) is a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>
作為上述源自分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)，可使用如以下所列舉的不飽和羧酸作為本發明中所使用的不飽和羧酸。即，作為不飽和單羧酸，例如可列舉：丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、肉桂酸、2-(甲基)丙烯醯氧基乙基丁二酸、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。另外，作為不飽和二羧酸，例如可列舉：順丁烯二酸、反丁烯二酸、衣康酸、檸康酸、 中康酸等。另外，用於獲得含有羧基的構成單元的不飽和多元羧酸亦可為其酸酐。具體而言，可列舉順丁烯二酸酐、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：丁二酸單(2-丙烯醯氧基乙基)酯、丁二酸單(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，作為不飽和羧酸，亦可使用丙烯酸-2-羧基乙酯、甲基丙烯酸-2-羧基乙酯、順丁烯二酸單烷基酯、反丁烯二酸單烷基酯、4-羧基苯乙烯等。 As the constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, an unsaturated carboxylic acid as exemplified below can be used as the unsaturated carboxylic acid used in the present invention. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(methyl)acryloxyethyl succinic acid, and 2-(A). Base) acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalate, and the like. Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and citraconic acid. Zhongkang acid and so on. Further, the unsaturated polycarboxylic acid used to obtain a structural unit containing 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-(meth)acryloxyalkyl)ester of a polyvalent carboxylic acid, and for example, succinic acid mono(2-propenyloxyethyl) ester may be mentioned. , succinic acid mono(2-methylpropenyloxyethyl) ester, phthalic acid mono(2-propenyloxyethyl) ester, phthalic acid mono(2-methylpropenyloxy) Ethyl) ester and the like. Further, the unsaturated polycarboxylic acid may also 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 group. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 may be used. - Carboxystyrene and the like.
其中，就顯影性的觀點而言，為了形成上述源自分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)，較佳為使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基丁二酸、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。 In view of the developability, in order to form the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, and 2 are preferably used. -(Meth)acryloxyethyl succinic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl)acryloxyethyl phthalate Further, an anhydride such as an unsaturated polycarboxylic acid, or the like, more preferably acrylic acid, methacrylic acid or 2-(meth)acryloxyethyl hexahydrophthalic acid.
上述源自分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)可單獨包含1種，亦可包含2種以上。 The constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.
<<<(a1-1-2)同時具有乙烯性不飽和基與源自酸酐的結構的構成單元>>> <<<(a1-1-2) constituent unit having both an ethylenically unsaturated group and an acid anhydride-derived structure>>>
同時具有乙烯性不飽和基與源自酸酐的結構的構成單元 (a1-1-2)較佳為源自使含有乙烯性不飽和基的構成單元中所存在的羥基與酸酐進行反應而獲得的單體的單元。 a constituent unit having both an ethylenically unsaturated group and an acid anhydride-derived structure (a1-1-2) is preferably a unit derived from a monomer obtained by reacting a hydroxyl group present in a constituent unit containing an ethylenically unsaturated group with an acid anhydride.
作為上述酸酐，可使用公知的酸酐，具體而言，可列舉：順丁烯二酸酐、丁二酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、氯菌酸酐等二元酸酐；苯偏三甲酸酐、焦蜜石酸酐、二苯基酮四羧酸酐、聯苯四羧酸酐等酸酐。該些酸酐之中，就顯影性的觀點而言，較佳為鄰苯二甲酸酐、四氫鄰苯二甲酸酐、或丁二酸酐。 As the acid anhydride, a known acid anhydride can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic acid. A dibasic acid anhydride such as formic anhydride or chloric anhydride; an acid anhydride such as benzene trimellitic anhydride, pyrogallic anhydride, diphenyl ketone tetracarboxylic anhydride or biphenyl tetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.
就顯影性的觀點而言，上述酸酐對於羥基的反應率較佳為10莫耳%~100莫耳%，更佳為30莫耳%~100莫耳%。 The reaction rate of the acid anhydride to the hydroxyl group is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, from the viewpoint of developability.
-可用於構成單元(a1-1)的酸分解性基- - an acid-decomposable group which can be used to constitute the unit (a1-1) -
作為可用於上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的上述酸分解性基，可使用上述酸分解性基。 The acid-decomposable group which can be used for the above-mentioned acid-decomposable group which is the structural unit (a1-1) which contains the protective carboxyl group which is protected by the acid-decomposable group can be used.
該些酸分解性基之中，就感光性樹脂組成物的基本物性，特別是感度或圖案形狀、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，較佳為羧基為由縮醛的形式保護的保護羧基。進而，酸分解性基之中，就感度的觀點而言，更佳為羧基為由以下述式(a1-10)所表示的縮醛的形式保護的保護羧基。再者，於羧基為由以下述式(a1-10)所表示的縮醛的形式保護的保護羧基的情況下，保護羧基的整體變成-(C=O)-O-CR101R102(OR103)的結構。 Among the acid-decomposable groups, the carboxyl group is preferably a carboxyl group from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the contact hole formation property, and the storage stability of the photosensitive resin composition. It is a protected carboxyl group protected by the form of acetal. Further, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected by an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity. Further, in the case where the carboxyl group is a protected carboxyl group protected by an acetal represented by the following formula (a1-10), the entire protected carboxyl group becomes -(C=O)-O-CR 101 R 102 (OR 103 ) structure.
[化1]
(式(a1-10)中，R101及R102分別獨立地表示氫原子、烷基或芳基，其中，排除R101與R102均為氫原子的情況。R103表示烷基或芳基。R101或R102與R103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, an alkyl group or an aryl group, wherein R 101 and R 102 are both a hydrogen atom. R 103 represents an alkyl group or an aryl group. R 101 or R 102 and R 103 may be bonded to form a cyclic ether)
上述式(a1-10)中，R101及R102分別獨立地表示氫原子、烷基或芳基，上述烷基可為直鏈狀、支鏈狀、環狀的任一種。此處，不存在R101及R102均表示氫原子的情況，R101及R102的至少一個表示烷基或芳基。 In the above formula (a1-10), R 101 and R 102 each independently represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, in the case where both R 101 and R 102 represent a hydrogen atom, at least one of R 101 and R 102 represents an alkyl group or an aryl group.
上述式(a1-10中)，R103表示烷基或芳基，上述烷基可為直鏈狀、支鏈狀、環狀的任一種。 In the above formula (a1-10), R 103 represents an alkyl group or an aryl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group.
於上述式(a1-10)中，當R101、R102及R103表示烷基時，上述烷基可為直鏈狀、支鏈狀或環狀的任一種。 In the above formula (a1-10), when R 101 , R 102 and R 103 represent an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic group.
作為上述直鏈狀或支鏈狀的烷基，較佳為碳數為1~12，更佳為碳數為1~6，進而更佳為碳數為1~4。具體而言，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 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. 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.
作為上述環狀烷基，較佳為碳數為3~12，更佳為碳數為4~8，進而更佳為碳數為4~6。作為上述環狀烷基，例如可列 舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降莰基、異莰基等。 The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and still more preferably a carbon number of 4 to 6. As the above cyclic alkyl group, for example, it can be listed Examples: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isodecyl and the like.
上述烷基亦可具有取代基，作為取代基，可例示鹵素原子、芳基、烷氧基。當具有鹵素原子作為取代基時，R101、R102、R103成為鹵代烷基，當具有芳基作為取代基時，R101、R102、R103成為芳烷基。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and 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 an aralkyl group.
作為上述鹵素原子，可例示氟原子、氯原子、溴原子、碘原子，該些鹵素原子之中，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 halogen atoms, a fluorine atom or a chlorine atom is preferred.
另外，作為上述芳基，較佳為碳數為6~20的芳基，更佳為碳數為6~12的芳基。具體而言，可例示苯基、α-甲基苯基、萘基等，作為由芳基取代的烷基整體，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 an aryl group having 6 to 12 carbon atoms. Specifically, a phenyl group, an α-methylphenyl group, a naphthyl group and the like can be illustrated, and as an alkyl group substituted with an aryl group, that is, an aralkyl group, a benzyl group, an α-methylbenzyl group, or a phenethyl group can be exemplified. , naphthylmethyl and the like.
作為上述烷氧基，較佳為碳數為1~6的烷氧基，更佳為碳數為1~4的烷氧基，進而更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 an alkoxy group having 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group.
另外，當上述烷基為環烷基時，上述環烷基可具有碳數為1~10的直鏈狀或支鏈狀的烷基作為取代基，當烷基為直鏈狀或支鏈狀的烷基時，可具有碳數為3~12的環烷基作為取代基。 Further, when the above alkyl group is a cycloalkyl group, the above cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and when the alkyl group is linear or branched The alkyl group may have a cycloalkyl group having a carbon number of 3 to 12 as a substituent.
該些取代基亦可由上述取代基進一步取代。 These substituents may also be further substituted by the above substituents.
上述式(a1-10)中，當R101、R102及R103表示芳基時，上述芳基較佳為碳數為6~12，更佳為碳數為6~10。上述芳基可具有取代基，作為上述取代基，可較佳地例示碳數為1~6的烷基。作為芳基，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 preferably has a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The above aryl group may have a substituent, and as the above substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
另外，R101、R102及R103可相互鍵結，並與該些所鍵結的碳原子一同形成環。作為R101與R102、R101與R103或R102與R103鍵結時的環結構，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 bonded carbon atoms. Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded to each other include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And tetrahydropyranyl and the like.
再者，上述式(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.
另外，上述式(a1-10)中，R103較佳為烷基。 Further, in the above formula (a1-10), R 103 is preferably an alkyl group.
用於形成含有由上述式(a1-10)所表示的保護羧基的構成單元的自由基聚合性單體可使用市售的自由基聚合性單體，亦可使用藉由公知的方法所合成的自由基聚合性單體。例如，可藉由日本專利特開2011-221494號公報的段落0037~段落0040中所記載的合成方法等來合成。 A commercially available radical polymerizable monomer can be used as the radical polymerizable monomer for forming a constituent unit containing the protective carboxyl group represented by the above formula (a1-10), or can be synthesized by a known method. A radical polymerizable monomer. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP-A-2011-221494.
上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)較佳為由下述式所表示的構成單元。 The constituent unit (a1-1) containing the protective carboxyl group protected by the acid-decomposable group is preferably a constituent unit represented by the following formula.
(式中，R1及R2分別獨立地表示氫原子、烷基或芳基，至少R1及R2的任一個為烷基或芳基，R3表示烷基或芳基，R1或R2與R3可連結而形成環狀醚，R4表示氫原子或碳數為1~4的烷基，X表示單鍵或伸芳基) (wherein 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 is an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, R 1 or R 2 and R 3 may be bonded to form a cyclic ether, and R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a single bond or an extended aryl group)
當R1及R2為烷基時，較佳為碳數為1~10的烷基。當R1及R2為芳基時，較佳為苯基。R1及R2較佳為分別獨立地為氫原子或碳數為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. When R 1 and R 2 are an aryl group, a phenyl group is preferred. R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R3表示烷基或芳基，較佳為碳數為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.
R4表示氫原子或碳數為1~4的烷基，烷基較佳為氫原子或甲基，更佳為甲基。 R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
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.
作為上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的較佳的具體例，可例示下述的構成單元。再者，R表示氫原子或甲基。 As a preferable specific example of the structural unit (a1-1) containing the protective carboxyl group protected by the acid-decomposable group, the following structural unit can be exemplified. Further, R represents a hydrogen atom or a methyl group.
<<(a1-2)含有由酸分解性基保護的保護酚性羥基的構成單元>> <<(a1-2) A constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group>>
上述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)是含有酚性羥基的構成單元具有以下將詳細說明的由酸分解性基保護的保護酚性羥基的構成單元。 The structural unit (a1-2) containing a phenolic hydroxyl group protected by an acid-decomposable group is a constituent unit containing a phenolic hydroxyl group and has a constituent unit for protecting a phenolic hydroxyl group protected by an acid-decomposable group, which will be described in detail below.
<<<(a1-2-1)含有酚性羥基的構成單元>>> <<<(a1-2-1) constituent unit containing phenolic hydroxyl group>>>
作為上述含有酚性羥基的構成單元，可列舉羥基苯乙烯系構成單元或酚醛清漆系的樹脂中的構成單元，該些構成單元之中，就感度的觀點而言，較佳為源自羥基苯乙烯或α-甲基羥基苯乙烯的構成單元。另外，作為含有酚性羥基的構成單元，就感度的觀點而言，由下述式(a1-20)所表示的構成單元亦較佳。 The constituent unit containing the phenolic hydroxyl group may be a constituent unit of a hydroxystyrene-based constituent unit or a novolac-based resin, and among these constituent units, from the viewpoint of sensitivity, it is preferably derived from hydroxybenzene. A constituent unit of ethylene or α-methylhydroxystyrene. In addition, as a constituent unit containing a phenolic hydroxyl group, a constituent unit represented by the following formula (a1-20) is also preferable from the viewpoint of sensitivity.
(式(a1-20)中，R220表示氫原子或甲基，R221表示單鍵或二價的連結基，R222表示鹵素原子或碳數為1~5的直鏈或支鏈狀的烷基，a表示1~5的整數，b表示0~4的整數，a+b為5以下。再者，當存在2個以上的R222時，該些R222可相互不同，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 chain having a carbon number of 1 to 5. The alkyl group, a represents an integer of 1 to 5, b represents an integer of 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 or may be the same. )
上述式(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表示單鍵或二價的連結基。當R221為單鍵時，可提昇感度，進而可提昇硬化膜的透明性，故較佳。作為R221的二價的連結基，可例示伸烷基，伸烷基的碳數較佳為1~12，更佳為1~8，進而更佳為1~6。作為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、伸乙基或伸丙基。另外，上述二價的連結基可具有取代基，作為取代基，可列舉鹵素原子、羥基、烷氧基等。另外，a表示1~5的整數，但就本發明的效果的觀點、或容易製造這一點而言，較佳為a為1或2，更佳為a為1。 Further, R 221 represents a single bond or a divalent linking group. When R 221 is a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. The divalent linking group of R 221 may, for example, be an alkylene group having a carbon number of preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 6. Specific examples of R 221 as an alkylene group include a methylene group, an exoethyl group, a propyl group, an isopropyl group, an exobutyl group, an exobutyl group, a thirylene group, and a pentyl group. Stretching isoamyl, stretching neopentyl, stretching hexyl and so on. Wherein R 221 is preferably a single bond, a methylene group, an extended ethyl group or a stretched propyl group. Further, the above-mentioned 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. However, in view of the effect of the present invention or ease of production, a is preferably 1 or 2, and more preferably a is 1.
另外，當將與R221進行鍵結的碳原子作為基準(1位)時，苯環中的羥基的鍵結位置較佳為鍵結於4位上。 Further, when a carbon atom bonded to R 221 is used as a reference (1 position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4 position.
R222分別獨立地表示鹵素原子或者碳數為1~5的直鏈或支鏈狀的烷基。具體而言，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，就容易製造這一點而言，較佳為氯原子、溴原子、甲基或乙基。 R 222 each independently represents 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 tert-butyl group, a pentyl group, an isopentyl group, and a new one. Amyl and so on. 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.
-可用於構成單元(a1-2)的酸分解性基- - an acid-decomposable group which can be used to constitute the unit (a1-2) -
作為可用於上述含有由酸分解性基保護的保護酚性羥基的構 成單元(a1-2)的上述酸分解性基，與可用於上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的上述酸分解性基同樣地，可使用公知的酸分解性基，並無特別限定。酸分解性基之中，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，較佳為含有第三丁基等三級烷基、或由縮醛保護的保護酚性羥基的構成單元。進而，酸分解性基之中，就感度的觀點而言，更佳為酚性羥基為由以上述式(a1-10)所表示的縮醛的形式保護的保護酚性羥基。再者，於酚性羥基為由以上述式(a1-10)所表示的縮醛的形式保護的保護酚性羥基的情況下，保護酚性羥基的整體變成-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 (a1-2) containing the phenolic hydroxyl group which is protected by the acid-decomposable group, and the constituent unit (a1) which can be used for the above-mentioned protective carboxyl group which is protected by the acid-decomposable group Similarly to the above-described acid-decomposable group, a known acid-decomposable group can be used, and it is not particularly limited. Among the acid-decomposable groups, the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores, preferably contain the third A constituent unit of a tertiary alkyl group such as a butyl group or a phenolic hydroxyl group protected by an acetal. Further, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a phenolic hydroxyl group protected by the acetal represented by the above formula (a1-10) from the viewpoint of sensitivity. Further, in the case where the phenolic hydroxyl group is a phenolic hydroxyl group protected by the acetal represented by the above formula (a1-10), the entirety of the protective phenolic hydroxyl group becomes -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=甲基的組合，或R101=R102=甲基且R103=苄基的組合，R101=氫原子、R102=甲基、R103=乙基的組合。 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 group, or a combination of R 101 = R 102 = methyl group and R 103 = benzyl group, R 101 = hydrogen A combination of an atom, R 102 = methyl, and R 103 = ethyl.
另外，作為用於形成含有酚性羥基由縮醛的形式保護的保護酚性羥基的構成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0042中所記載的自由基聚合性單體等。 In addition, as a radically polymerizable monomer which forms a structural unit which protects a phenolic hydroxyl group which has a phenolic hydroxyl group and is protected by the acetal, it is described, for example, as described in paragraph 0042 of JP-A-2011-215590. A radical polymerizable monomer or the like.
該些自由基聚合性單體之中，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 radically polymerizable monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or 4-hydroxyphenyl methacrylate is preferred. Tetrahydropyranyl protecting agent.
作為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，該些基可單獨使用1種、或將2種以上組合使用。 Specific examples of the acetal protecting group of the phenolic hydroxyl group include 1-alkoxy group. The alkyl group may, for example, be 1-ethoxyethyl, 1-methoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl or 1-(2-chloroethoxy). Ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyloxyethyl, 1-(2-cyclohexylethoxy)ethyl, 1 - benzyloxyethyl or the like, and these may be used alone or in combination of two or more.
用於形成上述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的自由基聚合性單體可使用市售的自由基聚合性單體，亦可使用藉由公知的方法所合成的自由基聚合性單體。例如，可藉由在酸觸媒的存在下使含有酚性羥基的化合物與乙烯基醚進行反應來合成。上述合成亦可事先使含有酚性羥基的單體與其他單體進行共聚，然後在酸觸媒的存在下與乙烯基醚進行反應。 A commercially available radical polymerizable monomer can be used as the radical polymerizable monomer for forming the structural unit (a1-2) containing the phenolic hydroxyl group which is protected by the acid-decomposable group, and a known one can be used. The free radical polymerizable monomer synthesized by the method. For example, it can be synthesized by reacting a compound containing a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be copolymerized with another monomer in advance, and then reacted with a vinyl ether in the presence of an acid catalyst.
作為上述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的較佳的具體例，可例示第三丁氧基苯乙烯、及下述的構成單元，但本發明並不限定於該些構成單元。下述具體例中，R表示氫原子或甲基。 A preferred specific example of the structural unit (a1-2) containing the protective phenolic hydroxyl group protected by the acid-decomposable group is exemplified by the third butoxystyrene and the following constituent units. It is not limited to these constituent units. In the following specific examples, R represents a hydrogen atom or a methyl group.
[化5]
作為含有酸基由酸分解性基保護的基的構成單元(a1)，可例示由下述式所表示的構成單元作為特佳的形態。 The structural unit (a1) which is a group which has an acid group which is protected by an acid-decomposable group is a particularly preferable form as a structural unit represented by the following formula.
(式中，R121表示氫原子或碳數為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為1~4的烷基) (wherein 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 an alkyl group having 1 to 4 carbon atoms; )
R121較佳為氫原子或甲基，更佳為甲基。 R 121 is preferably a hydrogen atom or a methyl group, more preferably 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.
-構成單元(a1)的較佳的形態- - a preferred form of the constituent unit (a1) -
當含有上述構成單元(a1)的聚合物實質上不含構成單元(a2)時，於含有構成單元(a1)的聚合物中，構成單元(a1)較佳為20莫耳%~100莫耳%，更佳為30莫耳%~90莫耳%。 When the polymer containing the above structural unit (a1) does not substantially contain the constituent unit (a2), the constituent unit (a1) is preferably 20 mol% to 100 mol in the polymer containing the constituent unit (a1). %, more preferably 30% by mole to 90% by mole.
當含有上述構成單元(a1)的聚合物含有下述構成單元(a2)時，就感度的觀點而言，於含有構成單元(a1)與構成單元(a2)的聚合物中，構成單元(a1)較佳為3莫耳%~70莫耳%，更佳為10莫耳%~60莫耳%。另外，尤其於上述構成單元(a1)為含有羧基由縮醛的形式保護的保護羧基的構成單元的情況下，較佳為20莫耳%~50莫耳%。 When the polymer containing the above-mentioned structural unit (a1) contains the following structural unit (a2), in terms of sensitivity, in the polymer containing the structural unit (a1) and the constituent unit (a2), the constituent unit (a1) It is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%. Further, in particular, when the structural unit (a1) is a constituent unit containing a protective carboxyl group in which a carboxyl group is protected by an acetal form, it is preferably 20 mol% to 50 mol%.
再者，於本發明中，當以莫耳比來規定「構成單元」的含量時，該「構成單元」的含義與「單體單元」相同。另外，於本發明中，該「單體單元」可藉由高分子反應等而於聚合後進行修飾。以下亦同樣如此。 Further, in the present invention, when the content of the "composition unit" is defined by the molar ratio, the meaning of the "constituting unit" is the same as that of the "single unit". Further, in the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same is true below.
與上述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)相比，上述含有由酸分解性基保護的保護羧基的構成單元(a1-1)具有顯影快這一特徵。因此，於欲快速顯影的情況下，較佳為含有由酸分解性基保護的保護羧基的構成單元(a1-1)。相反地，於欲使顯影變慢的情況下，較佳為使用含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)。 The constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group has a feature of faster development than the constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group. . Therefore, in the case of rapid development, it is preferably a constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group. On the other hand, in the case where the development is to be slowed down, it is preferred to use a constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group.
<(a2)含有交聯性基的構成單元> <(a2) constituent unit containing a crosslinkable group>
成分A含有聚合物，此聚合物具有含有交聯性基的構成單元(a2)。上述交聯性基只要是藉由加熱處理而產生硬化反應的基，則並無特別限定。作為較佳的含有交聯性基的構成單元的形態，可列舉含有選自由環氧基、氧雜環丁基、由-NH-CH2-O-R(R表示氫原子或碳數為1~20的烷基)所表示的基、及乙烯性不飽和基所組成的群組中的至少1個的構成單元，較佳為選自由環氧基、氧雜環丁基、及由-NH-CH2-O-R(R表示氫原子或碳數為1~20的烷基)所表示的基所組成的群組中的至少1種。其中，本發明的感光性樹脂組成物更佳為上述成分A包含含有環氧基及氧雜環丁基中的至少1個的構成單元。更詳細而言，可列舉以下者。 Component A contains a polymer having a structural unit (a2) containing a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which undergoes a curing reaction by heat treatment. The form of the preferable structural unit containing a crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R represents a hydrogen atom or a carbon number of 1 to 20). The constituent unit of at least one of the group represented by the alkyl group and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and a -NH-CH group. At least one of the groups consisting of 2- OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). In the photosensitive resin composition of the present invention, it is more preferable that the component A contains at least one of an epoxy group and an oxetanyl group. More specifically, the following are mentioned.
<<(a2-1)具有環氧基及/或氧雜環丁基的構成單元>> <<(a2-1) A constituent unit having an epoxy group and/or an oxetanyl group>>
成分A較佳為含有聚合物，此聚合物含有具有環氧基及/或氧雜環丁基的構成單元(構成單元(a2-1))。3員環的環狀醚基亦被稱為環氧基，4員環的環狀醚基亦被稱為氧雜環丁基。 Component A preferably contains a polymer containing a constituent unit having an epoxy group and/or an oxetanyl group (constituting unit (a2-1)). The cyclic ether group of the 3-membered ring is also referred to as an epoxy group, and the cyclic ether group of the 4-membered ring is also referred to as an oxetanyl group.
上述具有環氧基及/或氧雜環丁基的構成單元(a2-1)只要1個構成單元中具有至少1個環氧基或氧雜環丁基即可，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，但較佳為具有合計為1個~3個的環氧基及/或氧雜環丁基，更佳為具有合計為1個或2個的環氧基及/或氧雜環丁基，進而更佳為具有1個環氧基或氧雜環丁基。 The constituent unit (a2-1) having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more rings. The oxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, but preferably have a total of one to three. The epoxy group and/or oxetanyl group is more preferably an epoxy group and/or an oxetanyl group having a total of one or two, and more preferably an epoxy group or an oxocyclic group. Butyl.
作為用於形成具有環氧基的構成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-環氧基丁酯、甲基丙烯酸-3,4-環氧基丁酯、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0031~段落0035中所記載的含有脂環式環氧基骨架的化合物等，該些的內容可被編入至本申請案說明書中。 Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-positive propylene. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Cyclohexyl methyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinylbenzyl glycidyl ether, m-vinyl benzyl a glycidyl ether, a p-vinylbenzyl glycidyl ether, a compound containing an alicyclic epoxy group described in paragraphs 0031 to 0035 of Japanese Patent No. 4,164,843, and the like, the contents of which can be incorporated into In the specification of the present application.
作為用於形成具有氧雜環丁基的構成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0011~段落0016中所記載的具有氧雜環丁基的(甲基)丙烯酸酯等，該些的內容可被編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 paragraphs 0011 to 0016 of JP-A-2001-330953. Butyl (meth) acrylates and the like, the contents of which can be incorporated into the specification of the present application.
作為用於形成上述具有環氧基及/或氧雜環丁基的構成單元(a2-1)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。 Specific examples of the radical polymerizable monomer for forming the structural unit (a2-1) having an epoxy group and/or an oxetanyl group are preferably a monomer having a methacrylate structure and containing Monomer of acrylate structure.
該些之中，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、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。該些構成單元可單獨使用1種、或將2種以上組合使用。 Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid (3-ethyloxycyclohexane) are preferred. Butan-3-yl)methyl ester, and (3-ethyloxetan-3-yl)methyl methacrylate. These constituent units may be used alone or in combination of two or more.
作為具有環氧基及/或氧雜環丁基的構成單元(a2-1)的 較佳的具體例，可例示下述的構成單元。再者，R表示氫原子或甲基。 As a constituent unit (a2-1) having an epoxy group and/or an oxetanyl group Preferred specific examples include the following constituent units. Further, R represents a hydrogen atom or a methyl group.
<<(a2-2)具有乙烯性不飽和基的構成單元>> <<(a2-2) constituent unit having an ethylenically unsaturated group>>
作為上述含有交聯性基的構成單元(a2)的1種，可列舉具有乙烯性不飽和基的構成單元(a2-2)(以下，亦稱為「構成單元(a2-2)」)。作為上述具有乙烯性不飽和基的構成單元(a2-2)，較佳為側鏈上具有乙烯性不飽和基的構成單元，更佳為末端具有乙烯性不飽和基、且具有碳數為3~16的側鏈的構成單元。 One type of the structural unit (a2) containing the crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as "constituting unit (a2-2)"). The structural unit (a2-2) having an ethylenically unsaturated group 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 carbon number of 3 The constituent unit of the side chain of ~16.
此外，關於(a2-2)具有乙烯性不飽和基的構成單元，可參考日本專利特開2011-215580號公報的段落0072~段落0090的記載及日本專利特開2008-256974號公報的段落0013~段落0031的記載，該些的內容可被編入至本申請案說明書中。 In addition, as for the structural unit having an ethylenically unsaturated group (a2-2), the description of paragraphs 0072 to 0090 of JP-A-2011-215580 and paragraph 0013 of JP-A-2008-256974 can be referred to. ~ Paragraph 0031, the contents of which can be incorporated into the specification of the present application.
<<(a2-3)具有由-NH-CH2-O-R(R表示氫原子或碳數為1~20的烷基)所表示的基的構成單元>> <<(a2-3) A constituent unit having a group represented by -NH-CH 2 -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)>>
作為上述含有交聯性基的構成單元(a2)，具有由-NH-CH2-O-R(R表示氫原子或碳數為1~20的烷基)所表示的基的構成單元 (a2-3)亦較佳。藉由含有構成單元(a2-3)，可利用緩和的加熱處理產生硬化反應，而可獲得各種特性優異的硬化膜。此處，R較佳為碳數為1~20的烷基，更佳為碳數為1~9的烷基，進而更佳為碳數為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，但較佳為直鏈或分支的烷基。構成單元(a2-3)更佳為具有由下述式(a2-30)所表示的基的構成單元。 The structural unit (a2) containing the crosslinkable group has a constituent unit represented by -NH-CH 2 -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) (a2-3) ) is also preferred. By containing the constituent unit (a2-3), a hardening reaction can be generated by a gentle heat treatment, and a cured film excellent in various properties can be obtained. Here, R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still 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, but is preferably a linear or branched alkyl group. The constituent unit (a2-3) is more preferably a constituent unit having a group represented by the following formula (a2-30).
(式(a2-30)中，R31表示氫原子或甲基，R32表示碳數為1~20的烷基) (In the formula (a2-30), R 31 represents a hydrogen atom or a methyl group, and R 32 represents an alkyl group having 1 to 20 carbon atoms)
R32較佳為碳數為1~9的烷基，更佳為碳數為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，但較佳為直鏈或分支的烷基。 R 32 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, but is preferably a linear or branched alkyl group.
作為R32的具體例，可列舉：甲基、乙基、正丙基、異丙基、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 32 include a methyl group, an ethyl group, a n-propyl group, an isopropyl 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.
-構成單元(a2)的較佳的形態- - a preferred form of the constituent unit (a2) -
當含有上述構成單元(a2)的聚合物實質上不含構成單元(a1)時，於含有構成單元(a2)的聚合物中，構成單元(a2)較佳為5莫耳%~90莫耳%，更佳為20莫耳%~80莫耳%。 When the polymer containing the above structural unit (a2) contains substantially no constituent unit (a1), the constituent unit (a2) is preferably 5 mol% to 90 mol in the polymer containing the constituent unit (a2). %, more preferably 20% by mole to 80% by mole.
當含有上述構成單元(a2)的聚合物含有上述構成單元(a1)時，就耐化學品性的觀點而言，於含有構成單元(a1)與構成單元(a2)的聚合物中，構成單元(a2)較佳為3莫耳%~70莫耳%，更佳為10莫耳%~60莫耳%。 When the polymer containing the above-mentioned structural unit (a2) contains the above-mentioned structural unit (a1), the constituent unit is contained in the polymer containing the constituent unit (a1) and the constituent unit (a2) from the viewpoint of chemical resistance. (a2) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.
進而，於本發明中，不論何種形態，在成分A的所有構成單元中，較佳為含有3莫耳%~70莫耳%的構成單元(a2)，更佳為含有10莫耳%~60莫耳%的構成單元(a2)。 Further, in the present invention, in all the constituent units of the component A, it is preferable to contain 3 mol% to 70 mol% of the constituent unit (a2), and more preferably 10 mol%. 60 mol% of the constituent unit (a2).
若為上述數值的範圍內，則由感光性樹脂組成物所獲得的硬化膜的透明性及耐化學品性變得良好。 When it is in the range of the above numerical values, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.
<(a3)其他構成單元> <(a3) Other constituent units>
於本發明中，成分A除上述構成單元(a1)及/或構成單元(a2)以外，亦可具有該些以外的其他構成單元(a3)。該些構成單元亦可含有上述聚合物成分(1)及/或聚合物成分(2)。另外，除上述聚合物成分(1)或聚合物成分(2)以外，亦可具有實質上不含構成單元(a1)及構成單元(a2)而含有其他構成單元(a3)的聚合物成分。當除上述聚合物成分(1)或聚合物成分(2)以外，包含實質上不含構成單元(a1)及構成單元(a2)而含有其他構成單元(a3)的聚合物成分時，於所有聚合物成分中，聚合物成 分的調配量較佳為60質量%以下，更佳為40質量%以下，進而更佳為20質量%以下。另外，較佳為1質量%以上，更佳為5質量%以上。 In the present invention, the component A may have other constituent units (a3) other than the constituent unit (a1) and/or the constituent unit (a2). These constituent units may also contain the above polymer component (1) and/or polymer component (2). Further, in addition to the polymer component (1) or the polymer component (2), a polymer component containing substantially no constituent unit (a1) and a constituent unit (a2) and containing another constituent unit (a3) may be contained. When the polymer component (a1) and the structural unit (a2) are substantially contained in addition to the polymer component (1) or the polymer component (2), and the polymer component containing the other constituent unit (a3) is contained, Among the polymer components, the polymer The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less. Further, it is preferably 1% by mass or more, and more preferably 5% by mass or more.
作為成為其他構成單元(a3)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、順丁烯二醯亞胺化合物類、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，如後述般，亦可具有含有酸基的構成單元。成為其他構成單元(a3)的單體可單獨使用1種、或將2種以上組合使用。 The monomer to be used as the other constituent unit (a3) 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 two Carboxylic acid, unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as will be described later, it may have a constituent unit containing an acid group. The monomers which are the other constituent units (a3) may be used alone or in combination of two or more.
具體而言，其他構成單元(a3)可列舉由以下化合物等形成的構成單元：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、丙烯腈、乙二醇單乙醯乙酸單(甲基)丙烯酸酯。除此以外，可列舉日本專利特開2004-264623號公報的段落0021~段落0024中所記載的化合物。 Specific examples of the other constituent unit (a3) include constituent units formed of the following compounds: styrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, and 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, acrylonitrile, ethylene glycol monoacetic acid mono (meth) acrylate. In addition, the compound described in paragraphs 0021 to 0024 of JP-A-2004-264623 may be mentioned.
另外，作為其他構成單元(a3)，就電特性的觀點而言， 較佳為源自苯乙烯類、或具有脂肪族環式骨架的單體的構成單元。具體而言，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, as another constituent unit (a3), from the viewpoint of electrical characteristics, It is preferably a constituent unit derived from a styrene or a monomer having an aliphatic cyclic skeleton. Specific examples thereof include styrene, methyl styrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylic acid. Isodecyl ester, benzyl (meth)acrylate, and the like.
進而，作為其他構成單元(a3)，就密著性的觀點而言，較佳為源自(甲基)丙烯酸烷基酯的構成單元。具體而言，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。構成聚合物的構成單元中，上述構成單元(a3)的含有率較佳為60莫耳%以下，更佳為50莫耳%以下，進而更佳為40莫耳%以下。作為下限值，可為0莫耳%，但例如較佳為設為1莫耳%以上，更佳為設為5莫耳%以上。若為上述數值的範圍內，則由感光性樹脂組成物所獲得的硬化膜的各種特性變得良好。 Further, the other constituent unit (a3) is preferably a constituent unit derived from an alkyl (meth)acrylate from the viewpoint of adhesion. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. . In the constituent unit constituting the polymer, the content of the constituent unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. The lower limit value may be 0% by mole, but is preferably, for example, 1% by mole or more, and more preferably 5% by mole or more. When it is in the range of the above numerical values, various properties of the cured film obtained from the photosensitive resin composition become good.
成分A中所含有的聚合物較佳為具有含有酸基的構成單元作為其他構成單元(a3)。聚合物藉由含有酸基，而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。本發明中的酸基是指pKa小於10.5的質子解離性基。通常，使用可形成酸基的單體作為含有酸基的構成單元，而將酸基導入至聚合物中。藉由在聚合物中包含此種含有酸基的構成單元，而存在容易溶解於鹼性的顯影液中的傾向。 The polymer contained in the component A preferably has a structural unit containing an acid group as another constituent unit (a3). The polymer is easily dissolved in an alkaline developing solution by containing an acid group, and the effect of the present invention can be more effectively exhibited. The acid group in the present invention means a proton dissociative group having a pKa of less than 10.5. Usually, a monomer capable of forming an acid group is used as a constituent unit containing an acid group, and an acid group is introduced into the polymer. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution.
作為本發明中所使用的酸基，可例示羧酸基、磺醯胺基、膦酸基、磺酸基、酚性羥基、磺醯胺基、磺醯基醯亞胺基、及該些 酸基的酸酐基、以及將該些酸基加以中和而形成鹽結構的基等，較佳為羧酸基及/或酚性羥基。作為上述鹽，並無特別限制，可較佳地例示鹼金屬鹽、鹼土金屬鹽、及有機銨鹽。 The acid group used in the present invention may, for example, be a carboxylic acid group, a sulfonylamino group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, and the like. The acid group of the acid group and the group which neutralizes the acid groups to form a salt structure are preferably a carboxylic acid group and/or a phenolic hydroxyl group. The salt is not particularly limited, and an alkali metal salt, an alkaline earth metal salt, and an organic ammonium salt are preferably exemplified.
本發明中所使用的含有酸基的構成單元更佳為源自苯乙烯的構成單元、或源自乙烯基化合物的構成單元、源自(甲基)丙烯酸及/或其酯的構成單元。例如可使用日本專利特開2012-88459號公報的段落0021~段落0023及段落0029~段落0044中記載的化合物，該內容可被編入至本申請案說明書中。其中，較佳為源自對羥基苯乙烯、(甲基)丙烯酸、順丁烯二酸、順丁烯二酸酐的構成單元。 The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth)acrylic acid and/or an ester thereof. For example, the compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP-A-2012-88459 can be used, and the contents can be incorporated into the specification of the present application. Among them, a constituent unit derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid, or maleic anhydride is preferred.
於本發明中，除上述聚合物成分(1)或聚合物成分(2)以外，亦可包含實質上不含構成單元(a1)及構成單元(a2)而含有其他構成單元(a3)的聚合物。 In the present invention, in addition to the polymer component (1) or the polymer component (2), a polymerization containing substantially no constituent unit (a1) and a constituent unit (a2) and containing another constituent unit (a3) may be included. Things.
作為此種聚合物，較佳為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號的各公報中所記載般的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物等、以及側鏈上具有羧基的酸性纖維素衍生物、於具有羥基的聚合物中加成酸酐而成者等，進而亦可列舉側鏈上具有(甲基)丙烯醯基的高分子聚合物作為較佳的聚合物。 As such a polymer, a resin having a carboxyl group in a side chain is preferred. 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 crotonic acid copolymer, a maleic acid copolymer, and a partial esterification as described in each of Japanese Laid-Open Patent Publication No. 59-71048 An acid-based cellulose derivative having a carboxyl group in a side chain, an acid anhydride derivative added to a polymer having a hydroxyl group, and the like, and a (meth) propylene having a side chain A mercapto-based polymer is preferred as the polymer.
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號公報中所記載的(甲基)丙烯酸2-羥基丙酯/聚苯乙烯大分子單體/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/聚甲基丙烯酸甲酯大分子單體/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/聚苯乙烯大分子單體/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/聚苯乙烯大分子單體/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 copolymer, Japanese patent 2-Hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxy acrylate, as described in Kaiping No. 7-140654 Propyl propyl ester / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / A methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.
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號公報等中所記載的公知的高分子化合物，該些的內容可被編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 JP-A-H07-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020, etc. The content can be incorporated into the specification of the application.
該些聚合物可僅含有1種，亦可含有2種以上。 These polymers may be contained alone or in combination of two or more.
作為該些聚合物，亦可使用市售的SMA 1000P、SMA 2000P、SMA 3000P、SMA 1440F、SMA 17352P、SMA 2625P、SMA 3840F(以上，沙多瑪(Sartomer)公司製造)，ARUFON UC-3000、ARUFON UC-3510、ARUFON UC-3900、ARUFON UC-3910、ARUFON UC-3920、ARUFON UC-3080(以上，東亞合成(股份) 製造)，JONCRYL 690、JONCRYL 678、JONCRYL 67、JONCRYL 586(以上，巴斯夫(BASF)公司製造)等。 As such polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, East Asia Synthesis (share) Manufacturing), JONCRYL 690, JONCRYL 678, JONCRYL 67, JONCRYL 586 (above, BASF).
於本發明中，就感度的觀點而言，特佳為含有具有羧基的構成單元、或具有酚性羥基的構成單元。例如可使用日本專利特開2012-88459號公報的段落0021~段落0023、及段落0029~段落0044中記載的化合物，該內容可被編入至本申請案說明書中。 In the present invention, from the viewpoint of sensitivity, a structural unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group is particularly preferable. For example, the compounds described in paragraphs 0021 to 0023 of the Japanese Patent Publication No. 2012-88459 and paragraphs 0029 to 0044 can be used, and the contents can be incorporated into the specification of the present application.
含有酸基的構成單元較佳為所有聚合物成分的構成單元的1莫耳%~80莫耳%，更佳為1莫耳%~50莫耳%，進而更佳為5莫耳%~40莫耳%，特佳為5莫耳%~30莫耳%，最佳為5莫耳%~20莫耳%。 The constituent unit containing an acid group is preferably 1 mol% to 80 mol%, more preferably 1 mol% to 50 mol%, and even more preferably 5 mol% to 40% of the constituent units of all the polymer components. Moer%, especially preferably 5 mol%~30 mol%, and most preferably 5 mol%~20 mol%.
以下，列舉本發明中的聚合物成分的較佳的實施形態，但本發明並不限定於該些實施形態。 Hereinafter, preferred embodiments of the polymer component in the present invention are listed, but the present invention is not limited to the embodiments.
-第1實施形態- - First embodiment -
聚合物成分(1)進而具有1種或2種以上的其他構成單元(a3)的形態。 The polymer component (1) further has one or two or more types of other constituent units (a3).
-第2實施形態- - Second embodiment -
聚合物成分(2)的具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物進而具有1種或2種以上的其他構成單元(a3)的形態。 In the polymer component (2), the polymer having (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group further has one or two or more kinds of other constituent units (a3).
-第3實施形態- - Third embodiment -
聚合物成分(2)的具有(a2)含有交聯性基的構成單元的聚合物進而具有1種或2種以上的其他構成單元(a3)的形態。 The polymer of the polymer component (2) having (a2) a structural unit containing a crosslinkable group further has one or two or more types of other constituent units (a3).
-第4實施形態- - Fourth embodiment -
於上述第1實施形態~第3實施形態的任一實施形態中，於任一種聚合物中具有至少含有酸基的構成單元作為其他構成單元(a3)的形態。 In any of the first to third embodiments, the polymer having at least an acid group as the other constituent unit (a3) is used in any of the polymers.
-第5實施形態- - Fifth embodiment -
除上述聚合物成分(1)或聚合物成分(2)以外，進而具有實質上不含構成單元(a1)及構成單元(a2)而含有其他構成單元(a3)的聚合物的形態。 In addition to the above polymer component (1) or polymer component (2), it further has a form of a polymer containing substantially no structural unit (a1) and structural unit (a2) and containing another structural unit (a3).
-第6實施形態- - Sixth embodiment -
包含上述第1實施形態~第5實施形態的2種以上的組合的形態。 The form of the combination of two or more types of the above-described first to fifth embodiments is included.
-成分A中的聚合物的分子量- - Molecular weight of the polymer in component A -
成分A中的聚合物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。若為上述數值的範圍內，則各種特性良好。數量平均分子量Mn與重量平均分子量Mw的比(分散度，Mw/Mn)較佳為1.0~5.0，更佳為1.5~3.5。 The molecular weight of the polymer in the component A 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 above numerical values, various characteristics are good. The ratio (dispersion, Mw/Mn) of the number average molecular weight Mn to the weight average molecular weight Mw is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.
-成分A中的聚合物的製造方法- - Method for producing a polymer in component A -
另外，關於成分A的聚合物的合成法，亦已知有各種方法，若列舉一例，則可藉由利用自由基聚合起始劑，使至少含有用於形成上述構成單元(a1)及上述構成單元(a3)的自由基聚合性單體的自由基聚合性單體混合物於有機溶劑中進行聚合來合成。 另外，亦可藉由所謂的高分子反應來合成。 Further, various methods are also known for the synthesis method of the polymer of the component A. For example, by using a radical polymerization initiator, at least the constituent unit (a1) and the above-mentioned constituents can be formed. The radically polymerizable monomer mixture of the radical polymerizable monomer of the unit (a3) is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.
相對於除成分C以外的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中的成分A的含量較佳為20質量%~99.9質量%，更佳為50質量%~98質量%，進而更佳為70質量%~95質量%。若含量為該範圍，則進行了顯影時的圖案形成性變得良好，另外，可獲得折射率更高的硬化物。再者，所謂感光性樹脂組成物的固體成分量，表示除溶劑等揮發性成分以外的量。 The content of the component A in the photosensitive resin composition of the present invention is preferably 20% by mass to 99.9% by mass, and more preferably 50% by mass to 98%, based on the total solid content of the photosensitive resin composition other than the component C. The mass%, and more preferably 70% by mass to 95% by mass. When the content is in this range, the pattern formation property at the time of development is improved, and a cured product having a higher refractive index can be obtained. In addition, the solid content of the photosensitive resin composition means an amount other than a volatile component such as a solvent.
(成分B)光酸產生劑 (ingredient B) photoacid generator
本發明的感光性樹脂組成物含有(成分B)光酸產生劑。作為本發明中所使用的光酸產生劑(亦稱為「成分B」)，較佳為感應波長為300nm以上，較佳為波長為300nm~450nm的光化射線而產生酸的化合物，但不受其化學結構限制。另外，關於不直接感應波長為300nm以上的光化射線的光酸產生劑，若為藉由與增感劑併用來感應波長為300nm以上的光化射線而產生酸的化合物，則亦可與增感劑組合後較佳地使用。作為本發明中所使用的光酸產生劑，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pKa為2以下的酸的光酸產生劑。另外，pKa較佳為-15以上。 The photosensitive resin composition of the present invention contains (Component B) a photoacid generator. The photoacid generator (also referred to as "component B") used in the present invention is preferably a compound having an inductive wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, to generate an acid, but not Limited by its chemical structure. In addition, a photoacid generator which does not directly induce an actinic ray having a wavelength of 300 nm or more can be used as a compound which generates an acid by using an actinic ray having a wavelength of 300 nm or more and a sensitizer. The sensitizer is preferably used after combination. 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 has a pKa of A photoacid generator of 2 or less acids. Further, the pKa is preferably -15 or more.
作為光酸產生劑的例子，可列舉：三氯甲基-對稱三嗪類、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。該些光酸產生劑之中，就絕緣性、感度的觀點而言，較佳為使用肟磺酸酯化合物。該些光酸產生劑 可單獨使用1種、或將2種以上組合使用。作為三氯甲基-對稱三嗪類、二芳基錪鹽類、三芳基鋶鹽類、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0083~段落0088中所記載的化合物，該些的內容可被編入至本申請案說明書中。 Examples of the photoacid generator include trichloromethyl-symmetric triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, sulfhydryl sulfonate compounds, and sulfonic acid. Ester compound and the like. Among these photoacid generators, an oxime sulfonate compound is preferably used from the viewpoint of insulation properties and sensitivity. Photoacid generator These may be used alone or in combination of two or more. Specific examples of the trichloromethyl-symmetric triazines, the diarylsulfonium salts, the triarylsulfonium salts, the quaternary ammonium salts, and the diazomethane derivatives can be exemplified by Japanese Patent Laid-Open No. 2011-221494. The compounds described in paragraphs 0083 to 0,088 of the publication, the contents of which are incorporated herein by reference.
作為肟磺酸酯化合物，即具有肟磺酸酯結構的化合物，可較佳地例示含有由下述式(B1)所表示的肟磺酸酯結構的化合物。 As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following formula (B1) can be preferably exemplified.
(式(B1)中，R21表示烷基或芳基，波狀線部分表示與其他基的鍵結部位) (In the formula (B1), R 21 represents an alkyl group or an aryl group, and a wavy line portion indicates a bonding site with another group)
任何基均可被取代，R21中的烷基可為直鏈狀，亦可為分支狀，亦可為環狀。以下說明所容許的取代基。 Any base may be substituted, R 21 the alkyl groups may be linear, may also be branched, it may also be cyclic. The substituents allowed are explained below.
作為R21的烷基，較佳為碳數為1~10的直鏈狀烷基或分支狀烷基。R21的烷基可由碳數為6~11的芳基、碳數為1~10的烷氧基、或環烷基(包含7，7-二甲基-2-側氧降莰基等橋環脂環式基，較佳為雙環烷基等)取代。 The alkyl group of R 21 is preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R 21 may be an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridge having 7,7-dimethyl-2-oxooxanyl group) The cycloalicyclic group is preferably a bicycloalkyl group or the like.
作為R21的芳基，較佳為碳數為6~11的芳基，更佳為苯基或 萘基。R21的芳基可由碳數為1~10的烷基、碳數為1~10的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 by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
含有由上述式(B1)所表示的肟磺酸酯結構的上述化合物為由下述式(B2)所表示的肟磺酸酯化合物亦較佳。 The above compound containing the oxime sulfonate structure represented by the above formula (B1) is preferably an oxime sulfonate compound represented by the following formula (B2).
(式(B2)中，R42表示烷基或芳基，X表示烷基、烷氧基或鹵素原子，m4表示0~3的整數，當m4為2或3時，多個X可相同，亦可不同) (In the formula (B2), R 42 represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same, Can also be different)
作為X的烷基較佳為碳數為1~4的直鏈狀烷基或分支狀烷基。 The alkyl group as X is preferably a linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms.
作為X的烷氧基較佳為碳數為1~4的直鏈狀烷氧基或分支狀烷氧基。 The alkoxy group as X is preferably a linear alkoxy group having a carbon number of 1 to 4 or a branched alkoxy group.
作為X的鹵素原子較佳為氯原子或氟原子。 The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4較佳為0或1。上述式(B2)中，特佳為m4為1，X為甲基，X的取代位置為鄰位，R42為碳數為1~10的直鏈狀烷基、7,7-二甲基-2-側氧降莰基甲基、或對甲苯甲醯基的化合物。 M4 is preferably 0 or 1. In the above formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, X is substituted at an ortho position, and R 42 is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethyl group. a compound of a 2-oxo-oxomethyl group or a p-tolylmethyl group.
含有由上述式(B1)所表示的肟磺酸酯結構的化合物為 由下述式(B3)所表示的肟磺酸酯化合物亦較佳。 The compound containing the oxime sulfonate structure represented by the above formula (B1) is The oxime sulfonate compound represented by the following formula (B3) is also preferable.
(式(B3)中，R43的含義與式(B2)中的R42相同，X1表示鹵素原子、羥基、碳數為1~4的烷基、碳數為1~4的烷氧基、氰基或硝基，n4表示0~5的整數) (In the formula (B3), R 43 has the same meaning as R 42 in the formula (B2), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. , cyano or nitro, n4 represents an integer from 0 to 5)
作為上述式(B3)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，特佳為正辛基。 R 43 in the above formula (B3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, or Fluorine-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.
X1較佳為碳數為1~5的烷氧基，更佳為甲氧基。 X 1 is preferably an alkoxy group having a carbon number of 1 to 5, more preferably a methoxy group.
n4較佳為0~2的整數，更佳為0或1。 N4 is preferably an integer of 0 to 2, more preferably 0 or 1.
作為由上述式(B3)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，可參考日本專利特開2012-163937號公報的段落0080~段落0082的記載，該內容可被編入至本申請案說明書中。 Specific examples of the compound represented by the above formula (B3) and specific examples of the preferred oxime sulfonate compound can be referred to the description of paragraphs 0080 to 0082 of JP-A-2012-163937. It is incorporated into the specification of this application.
作為含有由上述式(B1)所表示的肟磺酸酯結構的化合物，由下述式(OS-1)所表示的化合物亦較佳。 As the compound containing the oxime sulfonate structure represented by the above formula (B1), a compound represented by the following formula (OS-1) is also preferable.
[化12]
上述式(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、磺酸基、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 sulfonic acid group, a cyano group, or the like. 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 aromatic group. base.
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、磺酸基、氰基、或芳基。R121~R124中的2個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 sulfonic acid group or a cyanogen group. Base, or aryl. Two of R 121 to R 124 may be bonded to each other to form a ring.
作為R121~R124，較佳為分別獨立地為氫原子、鹵素原子、或烷基，另外，亦可較佳地列舉R121~R124中的至少2個相互鍵結而形成芳基的形態。其中，就感度的觀點而言，較佳為R121~R124均為氫原子的形態。 R 121 to R 124 are each independently a hydrogen atom, a halogen atom or an alkyl group, and preferably, at least two of R 121 to R 124 are bonded to each other to form an aryl group. form. Among them, from the viewpoint of sensitivity, it is preferred that R 121 to R 124 are each a hydrogen atom.
已述的官能基均可進一步具有取代基。 The functional groups described may each further have a substituent.
由上述式(OS-1)所表示的化合物較佳為例如日本專利特開2012-163937號公報的段落0087~段落0089中所記載的由式(OS-2)所表示的化合物，該內容可被編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) as described in paragraphs 0087 to 0089 of JP-A-2012-163937. It is incorporated into the specification of this application.
作為可適宜地用於本發明的由上述式(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0128~段落0132中所記載的化合物(例示化合物b-1~例示化合物b-34)，但本發明並不限定於此。 Specific examples of the compound represented by the above formula (OS-1) which can be suitably used in the present invention include the compounds (exemplified compounds) described in paragraphs 0128 to 0132 of JP-A-2011-221494. B-1 to exemplify the compound b-34), but the present invention is not limited thereto.
於本發明中，作為含有由上述式(B1)所表示的肟磺酸酯結構的化合物，較佳為由下述式(OS-3)、下述式(OS-4)或下述式(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) is preferably represented by the following formula (OS-3), the following formula (OS-4) or the following formula ( The oxime sulfonate compound represented by OS-5).
(式(OS-3)~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及m2分別獨立地表示0~6的整數，m3表示0~4的整數) (In the formula (OS-3) to the formula (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 represented. 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 alkoxysulfonyl group. X 1 to X 3 each independently represent an oxygen atom or a sulfur atom, and n 1 to n 3 each independently represent 1 or 2, and m 1 and m 2 each independently represent an integer of 0 to 6, and m 3 represents 0 to 4, respectively. Integer)
另外，含有由上述式(B1)所表示的肟磺酸酯結構的化合物特佳為例如日本專利特開2012-163937號公報的段落0117中所記載的由通式(OS-6)~通式(OS-11)的任一者所表示的化合物，該內容可被編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) is particularly preferably a compound of the formula (OS-6) as described in paragraph 0117 of JP-A-2012-163937. The compound represented by any of (OS-11) can be incorporated into the specification of the present application.
上述通式(OS-6)~通式(OS-11)中的較佳的範圍與日本專利特開2011-221494號公報的段落0110~段落0112中所記載的通式(OS-6)~通式(OS-11)的較佳的範圍相同。 The preferred range of the above formula (OS-6) to the formula (OS-11) and the formula (OS-6) described in paragraph 0110 to paragraph 0112 of JP-A-2011-221494 The preferred ranges of the general formula (OS-11) are the same.
作為由上述式(OS-3)~上述式(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0114~段落0120中所記載的化合物，但本發明並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 those described in paragraphs 0114 to 0120 of JP-A-2011-221494. A compound, but the invention is not limited to the compounds.
含有由上述式(B1)所表示的肟磺酸酯結構的化合物為由下述式(B1-4)所表示的肟磺酸酯化合物亦較佳。 The compound containing the oxime sulfonate structure represented by the above formula (B1) is preferably an oxime sulfonate compound represented by the following formula (B1-4).
(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 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。尤其當烷基具有分支結構時，較佳為碳數為3~6的烷基，當具有環狀結構時，較佳為碳數為5~7的烷基。作為烷基，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 preferably has a carbon number of from 3 to 10. In particular, when the alkyl group has a branched structure, it is preferably an alkyl group having 3 to 6 carbon atoms, and when it has a cyclic structure, it is preferably an alkyl group having 5 to 7 carbon atoms. Examples of the alkyl group include propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and 1,1-dimethyl Preference is given to propyl, hexyl, 2-ethylhexyl, cyclohexyl, octyl and the like, preferably isopropyl, tert-butyl, neopentyl or cyclohexyl.
芳基的碳數較佳為6~12，更佳為6~8，進而更佳為6~7。作為上述芳基，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, more 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可具有取代基。作為取代基，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，亦可由該些基進一步取代。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 the like. Alkynyl, aryl, decyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, cyano, carboxy, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heteroepoxy Base, decyloxy, amine, nitro, fluorenyl, heterocyclic, and the like. In addition, these groups may be further substituted. A halogen atom or a methyl group is preferred.
本發明的感光性樹脂組成物中，就透明性的觀點而言，R1較佳為烷基，就使保存穩定性與感度並存的觀點而言，R1較佳為碳數為3~6的具有分支結構的烷基、碳數為5~7的環狀結構 的烷基、或苯基，更佳為碳數為3~6的具有分支結構的烷基、或碳數為5~7的環狀結構的烷基。藉由採用此種體積大的基(特別是體積大的烷基)作為R1，而可進一步提昇透明性。 In the photosensitive resin composition of the present invention, R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 is preferably a carbon number of 3 to 6 from the viewpoint of storage stability and sensitivity. An alkyl group having a branched structure, an 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 having a carbon number of 3 to 6, or a carbon number of 5 to 7 The cyclic structure of the alkyl group. The transparency can be further improved by using such a bulky group (especially a bulky alkyl group) as R 1 .
體積大的取代基之中，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 bulky substituents, preferred are isopropyl, tert-butyl, neopentyl, cyclohexyl, and more preferred are tert-butyl or cyclohexyl.
R2表示烷基、芳基或雜芳基。作為R2所表示的烷基，較佳為碳數為1~10的直鏈、分支或環狀的烷基。作為上述烷基，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.
作為芳基，較佳為碳數為6~10的芳基。作為上述芳基，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。 As the aryl group, an aryl group having 6 to 10 carbon atoms is preferred. 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.
作為雜芳基，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、芳基及雜芳基可具有取代基。取代基的含義與R1所表示的烷基及芳基可具有的取代基相同。 The alkyl group, the aryl group and the heteroaryl group represented by R 2 may have a substituent. The meaning of the substituent is the same 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，進而更佳為苯基。作為苯基的取代基，較佳為甲基。 R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and even more 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所表示的烷基的含義與R2所表示的烷基相同，較佳的範圍亦相同。另外，R3~R6所表示的芳基的含義與R1所表示的芳基相同，較佳的範圍亦相同。 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 meaning of the alkyl group represented by R 3 to R 6 is the same as the alkyl group represented by R 2 , and the preferred range is also the same. Further, the meaning of the aryl group represented by R 3 to R 6 is the same as the aryl group represented by R 1 , and the preferred range is also the same.
R3~R6之中，R3與R4、R4與R5、或R5與R6可鍵結而形成環，作為環，較佳為形成脂環或芳香環，更佳為苯環。 Among 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 as the ring, an alicyclic or aromatic ring is preferred, and benzene is more preferred. 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 a combination of R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 . The benzene ring, more preferably a hydrogen atom, a methyl group, 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.
R3~R6的較佳的形態如下所示。 Preferred forms of R 3 to R 6 are as follows.
(形態1)至少2個為氫原子。 (Form 1) At least two are hydrogen atoms.
(形態2)烷基、芳基或鹵素原子的數量為1個以下。 (Form 2) The number of alkyl groups, aryl groups or halogen atoms is one or less.
(形態3)R3與R4、R4與R5、或R5與R6鍵結而構成苯環。 (Form 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.
(形態4)滿足上述形態1與形態2的形態、及/或滿足上述形態1與形態3的形態。 (Form 4) A form that satisfies the above-described Form 1 and Form 2, and/or a form that satisfies the above Form 1 and Form 3.
X表示-O-或-S-。 X represents -O- or -S-.
作為由上述式(B1-4)所表示的肟磺酸酯化合物的具體例，可列舉如下的化合物，但本發明並不特別限定於此。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 oxime sulfonate compound represented by 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15]
於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成分A 100質量份，(成分B)光酸產生劑較佳為使用0.1質量份~10質量份，更佳為使用0.5質量份~10質量份。另外，成分B可單獨使用1種，亦可併用2種以上。 In the photosensitive resin composition of the present invention, the photo-acid generator (component B) is preferably used in an amount of 0.1 part by mass to 10 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the component A in the photosensitive resin composition. 0.5 parts by mass to 10 parts by mass. In addition, the component B may be used alone or in combination of two or more.
(成分C)金屬氧化物粒子 (Component C) Metal oxide particles
本發明的樹脂組成物以調節折射率或透光性為目的，而含有金屬氧化物粒子。金屬氧化物粒子因透明性高、具有透光性，故可獲得折射率高、透明性優異的正型感光性樹脂組成物。 The resin composition of the present invention contains metal oxide particles for the purpose of adjusting the refractive index or light transmittance. Since the metal oxide particles have high transparency and light transmissivity, a positive photosensitive resin composition having a high refractive index and excellent transparency can be obtained.
成分C較佳為折射率高於包含除該粒子以外的材料的樹脂組成物的折射率者，具體而言，更佳為於具有400nm~750nm的波長的光中的折射率為1.50以上的粒子，進而更佳為折射率為1.70以上的粒子，特佳為折射率為1.90以上的粒子。折射率的上限並無特別限定，但就獲得容易性的觀點而言，較佳為3.00以下。 Component C preferably has a refractive index higher than that of a resin composition containing a material other than the particles, and more specifically, a particle having a refractive index of 1.50 or more in light having a wavelength of 400 nm to 750 nm. Further, it is more preferably a particle having a refractive index of 1.70 or more, and particularly preferably a particle having a refractive index of 1.90 or more. The upper limit of the refractive index is not particularly limited, but is preferably 3.00 or less from the viewpoint of availability.
此處，所謂於具有400nm~750nm的波長的光中的折射率為1.50以上，是指於具有上述範圍的波長的光中的平均折射率為1.50以上，無需於具有上述範圍的波長的所有光中的折射率為1.50以上。另外，平均折射率是將對於具有上述範圍的波長的各光的折射率的測定值的總和除以測定點的數量所得的值。 Here, the refractive index in the light having a wavelength of 400 nm to 750 nm is 1.50 or more, and the average refractive index in the light having the wavelength in the above range is 1.50 or more, and it is not necessary to use all the light having the wavelength in the above range. The refractive index in the medium is 1.50 or more. Further, the average refractive index is a value obtained by dividing the total of the measured values of the refractive indices of the respective lights having the wavelengths in the above range by the number of measurement points.
再者，本發明中的金屬氧化物粒子的金屬亦包含B、Si、Ge、As、Sb、Te等半金屬。 Further, the metal of the metal oxide particles in the present invention also contains a semimetal such as B, Si, Ge, As, Sb or Te.
作為折射率高的透光性金屬氧化物粒子，較佳為包含Be、Mg、Ca、Sr、Ba、Sc、Y、La、Ce、Gd、Tb、Dy、Yb、Lu、Ti、Zr、Hf、Nb、Mo、W、Zn、B、Al、Si、Ge、Sn、Pb、Sb、Bi、Te等原子的氧化物粒子，更佳為氧化鈦、鈦複合氧化物、氧化鋅、氧化鋯、銦/錫氧化物、銻/錫氧化物，進而更佳為氧化鈦、鈦複合氧化物、氧化鋯，特佳為氧化鈦、氧化鋯，最佳為氧化鈦。作為氧化鈦，尤其較佳為折射率高的金紅石型。為了賦予分散穩定性，亦可利用有機材料對該些金屬氧化物粒子的表面進行處理。 As the light-transmitting metal oxide particles having a high refractive index, it is preferable to contain Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf. Oxide particles of atoms such as Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc., more preferably titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, Indium/tin oxide, antimony/tin oxide, more preferably titanium oxide, titanium composite oxide, or zirconia, particularly preferably titanium oxide or zirconium oxide, and most preferably titanium oxide. As the titanium oxide, a rutile type having a high refractive index is particularly preferable. In order to impart dispersion stability, the surface of the metal oxide particles may be treated with an organic material.
就樹脂組成物的透明性的觀點而言，成分C的平均一次粒徑較佳為1nm~200nm，特佳為3nm~80nm。此處，利用電 子顯微鏡測定任意的200個粒子的粒徑，並將其算術平均作為粒子的平均一次粒徑。另外，當粒子的形狀並非球形時，將最長邊作為直徑。 The average primary particle diameter of the component C is preferably from 1 nm to 200 nm, particularly preferably from 3 nm to 80 nm, from the viewpoint of transparency of the resin composition. Here, use electricity The particle size of any 200 particles was measured by a submicroscope, and the arithmetic mean was taken as the average primary particle diameter of the particles. In addition, when the shape of the particles is not spherical, the longest side is taken as the diameter.
另外，成分C可單獨使用1種，亦可併用2種以上。 Further, the component C may be used singly or in combination of two or more.
本發明的樹脂組成物中的金屬氧化物粒子的含量只要考慮對藉由樹脂組成物所獲得的光學構件所要求的折射率或透光性等，而適宜決定即可，但相對於本發明的樹脂組成物的總固體成分，較佳為設為5質量%~80質量%，更佳為設為10質量%~70質量%，進而更佳為設為40質量%~65質量%。 The content of the metal oxide particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index or light transmittance required for the optical member obtained by the resin composition, but is equivalent to the present invention. The total solid content of the resin composition is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, still more preferably 40% by mass to 65% by mass.
於本發明中，粒子亦可作為如下的分散液來供於使用，上述分散液是藉由在適當的分散劑及溶劑中，使用球磨機、棒磨機等混合裝置進行混合．分散所製備的分散液。 In the present invention, the particles may also be used as a dispersion which is mixed by using a mixing device such as a ball mill or a rod mill in a suitable dispersant and solvent. The prepared dispersion was dispersed.
作為上述分散液的製備中所使用的溶劑，例如除後述的(成分D)溶劑以外，可列舉1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基-2-丙醇、1-戊醇、2-戊醇、3-戊醇、3-甲基-1-丁醇、2-甲基-2-丁醇、新戊醇、環戊醇、1-己醇、環己醇等醇類等。 The solvent to be used for the preparation of the above-mentioned dispersion liquid is, for example, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-, in addition to the solvent (component D) to be described later. 2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentyl alcohol, cyclopentanol, 1- An alcohol such as hexanol or cyclohexanol.
該些溶劑可單獨使用1種、或將2種以上混合使用。 These solvents may be used alone or in combination of two or more.
(成分D)溶劑 (ingredient D) solvent
本發明的感光性樹脂組成物含有(成分D)溶劑。本發明的感光性樹脂組成物較佳為作為使本發明的必需成分、及後述的任意的成分溶解於(成分D)溶劑中而成的溶液來製備。 The photosensitive resin composition of the present invention contains (Component D) a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and an optional component described below in a solvent of (Component D).
作為本發明的感光性樹脂組成物中所使用的溶劑，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，作為本發明的感光性樹脂組成物中所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0174~段落0178中所記載的溶劑、日本專利特開2012-194290號公報的段落0167~段落0168中所記載的溶劑，該些的內容可被編入至本申請案說明書中。 As the solvent used in the photosensitive resin composition of the present invention, a public can be used. The known solvent can be exemplified by ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, Propylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, diethylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether, dipropylene glycol dialkyl ether, dipropylene glycol single Alkyl ether acetates, esters, ketones, guanamines, lactones, and the like. In addition, as a specific example of the solvent used in the photosensitive resin composition of the present invention, a solvent described in paragraphs 0174 to 0178 of JP-A-2011-221494, Japanese Patent Laid-Open No. 2012- The solvent described in paragraphs 0167 to 0168 of the Japanese Patent Publication No. 194290, the contents of which are incorporated herein by reference.
另外，視需要亦可向該些溶劑中進一步添加苄基***、二己醚、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、順丁烯二酸二乙酯、碳酸乙烯酯、碳酸丙烯酯等溶劑。 In addition, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone may be further added to the solvents as needed. , caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, A solvent such as propylene carbonate.
該些溶劑可單獨使用1種、或將2種以上混合使用。可用於本發明的溶劑較佳為單獨使用1種、或併用2種。 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 used singly or in combination of two.
另外，作為成分D，較佳為沸點為130℃以上、未滿160℃的溶劑，沸點為160℃以上的溶劑，或該些的混合物。 Further, as the component D, a solvent having a boiling point of 130 ° C or higher and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture thereof is preferable.
作為沸點為130℃以上、未滿160℃的溶劑，可例示：丙二醇單甲醚乙酸酯(沸點為146℃)、丙二醇單***乙酸酯(沸點為158℃)、丙二醇甲基-正丁醚(沸點為155℃)、丙二醇甲基-正丙 醚(沸點為131℃)。 The solvent having a boiling point of 130 ° C or higher 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-positive C Ether (boiling point 131 ° C).
作為沸點為160℃以上的溶劑，可例示：3-乙氧基丙酸乙酯(沸點為170℃)、二乙二醇甲基乙基醚(沸點為176℃)、丙二醇單甲醚丙酸酯(沸點為160℃)、二丙二醇甲醚乙酸酯(沸點為213℃)、3-甲氧基丁醚乙酸酯(沸點為171℃)、二乙二醇二乙基醚(沸點為189℃)、二乙二醇二甲醚(沸點為162℃)、丙二醇二乙酸酯(沸點為190℃)、二乙二醇單***乙酸酯(沸點為220℃)、二丙二醇二甲醚(沸點為175℃)、1,3-丁二醇二乙酸酯(沸點為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), and propylene glycol monomethyl ether propionic acid. Ester (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 glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol Ether (boiling point 175 ° C), 1,3-butanediol diacetate (boiling point 232 ° C).
該些之中，作為溶劑，較佳為丙二醇單烷基醚乙酸酯類，特佳為丙二醇單甲醚乙酸酯。 Among these, as a solvent, a propylene glycol monoalkyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is especially preferable.
相對於感光性樹脂組成物100質量份，本發明的感光性樹脂組成物中的(成分D)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。 The content of the (Component D) solvent in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, and more preferably 60 parts by mass to 90 parts by mass, based on 100 parts by mass of the photosensitive resin composition.
(成分E)分散劑 (ingredient E) dispersant
本發明的感光性樹脂組成物含有(成分E)分散劑。藉由含有分散劑，而可進一步提昇成分C於樹脂組成物中的分散性。 The photosensitive resin composition of the present invention contains (Component E) a dispersant. The dispersibility of the component C in the resin composition can be further enhanced by containing a dispersing agent.
作為分散劑，可使用公知的分散劑，例如可適宜選擇公知的顏料分散劑來使用。 As the dispersing agent, a known dispersing agent can be used, and for example, a known pigment dispersing agent can be appropriately selected and used.
另外，作為分散劑，可較佳地使用高分子分散劑。再者，所謂高分子分散劑，是指分子量(重量平均分子量)為1,000以上的分散劑。 Further, as the dispersing agent, a polymer dispersing agent can be preferably used. In addition, the polymer dispersing agent means a dispersing agent having a molecular weight (weight average molecular weight) of 1,000 or more.
作為分散劑，可使用多種化合物，具體而言，例如可列 舉：(甲基)丙烯酸系(共)聚合物Polyflow No.75、No.90、No.95(共榮社化學(股份)製造)，W001(裕商(股份)製造)等陽離子系界面活性劑；聚氧乙烯月桂醚、聚氧乙烯硬脂醚、聚氧乙烯油醚、聚氧乙烯辛基苯醚、聚氧乙烯壬基苯醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖脂肪酸酯等非離子系界面活性劑；W004、W005、W017(裕商(股份)製造)等陰離子系界面活性劑；EFKA-46、EFKA-47、EFKA-47EA、EFKA Polymer 100、EFKA Polymer 400、EFKA Polymer 401、EFKA Polymer 450(均為汽巴精化(Ciba Specialty Chemicals)公司製造)，Disperse Aid 6、Disperse Aid 8、Disperse Aid 15、Disperse Aid 9100(均為聖諾普科(San Nopco)(股份)製造)等高分子分散劑；Solsperse3000、5000、9000、12000、13240、13940、17000、24000、26000、28000等各種Solsperse分散劑(路博潤(Lubrizol)(股份)製造)；Adeka Pluronic L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、L121、P-123(艾迪科(ADEKA)(股份)製造)及IONET S-20(三洋化成工業(股份)製造)，DISPERBYK 101、103、106、108、109、111、112、116、130、140、142、162、163、164、166、167、170、171、174、176、180、182、2000、2001、2050、2150(畢克化學(BYK-Chemie)公司製造)。此外，可列舉丙烯酸系共聚物等在分子末端或側鏈上具有極性基的寡聚物或聚合物。 As the dispersing agent, a plurality of compounds can be used, specifically, for example, The cationic interface activity of (meth)acrylic (co)polymers Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) Agent; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as distearate and sorbitan fatty acid ester; anionic surfactants such as W004, W005, W017 (manufactured by Yushang); EFKA-46, EFKA-47, EFKA- 47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (both Polymer dispersant for San Nopco (manufactured by San Nopco); various Solsperse dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 (Lubrizol ) (manufacturing of shares); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by ADEKA (share)) and IONET S-20 (made by Sanyo Chemical Industry Co., Ltd.), DISPERBYK 101, 103 , 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 Manufactured by BYK-Chemie). Further, an oligomer or polymer having a polar group at a molecular terminal or a side chain such as an acrylic copolymer may be mentioned.
分散劑可單獨使用1種，亦可併用2種以上。 The dispersing agent may be used alone or in combination of two or more.
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中的分散劑的含量較佳為5質量%~70質量%的範圍，更佳為10質量%~50質量%的範圍。 The content of the dispersant in the photosensitive resin composition of the present invention is preferably in the range of 5 mass% to 70 mass%, more preferably 10 mass% to 50 mass%, based on the total solid content of the photosensitive resin composition. range.
(成分F)聚氧伸烷基取代苯醚界面活性劑 (Component F) polyoxyalkylene substituted phenyl ether surfactant
本發明的感光性樹脂組成物含有(成分F)聚氧伸烷基取代苯醚界面活性劑。藉由含有成分F，顯影後的殘渣的產生得到抑制。尤其，於ITO基板上顯著的顯影後的殘渣的產生得到抑制。 The photosensitive resin composition of the present invention contains (Component F) a polyoxyalkylene-substituted phenyl ether surfactant. By containing the component F, the generation of the residue after development is suppressed. In particular, the occurrence of significant residue after development on the ITO substrate was suppressed.
作為成分F，較佳為由以下的式(F)所表示的化合物。 The component F is preferably a compound represented by the following formula (F).
(式(F)中，R表示伸烷基，n表示1~50的整數，R'表示一價的取代基，m表示1~5的整數，當m為2以上時，存在多個的R'彼此可相同，亦可不同，當n為2以上時，存在多個的R彼此可相同，亦可不同) (In the formula (F), R represents an alkylene group, n represents an integer of 1 to 50, R' represents a monovalent substituent, m represents an integer of 1 to 5, and when m is 2 or more, a plurality of R are present. 'They may be the same or different from each other. When n is 2 or more, a plurality of Rs may be the same or different)
式(F)中，R表示伸烷基。即，(RO)表示伸烷氧基。作為R，較佳為碳數為2~8的伸烷基，更佳為碳數為2~6的伸烷基，進而更佳為碳數為2~4的伸烷基，特佳為伸乙基或伸丙基。 In the formula (F), R represents an alkylene group. That is, (RO) represents an alkoxy group. R is preferably an alkylene group having a carbon number of 2 to 8, more preferably an alkylene group having a carbon number of 2 to 6, more preferably an alkylene group having a carbon number of 2 to 4, particularly preferably Ethyl or propyl.
式(F)中，R'表示一價的取代基。作為R'，可例示鹵素原子、 烷基、芳基、烯基、羥基、烷氧基、芳氧基，上述取代基可被進一步取代。R'的總碳數較佳為1~50，更佳為1~20。 In the formula (F), R' represents a monovalent substituent. As R', a halogen atom can be exemplified, The alkyl group, the aryl group, the alkenyl group, the hydroxyl group, the alkoxy group, the aryloxy group, and the above substituents may be further substituted. The total carbon number of R' is preferably from 1 to 50, more preferably from 1 to 20.
成分F可如聚氧伸烷基烷基苯醚般，取代有脂肪族烴基作為R'，但較佳為R'為含有芳香族烴基的一價的基。 Component F may be substituted with an aliphatic hydrocarbon group as R' as in the case of a polyoxyalkylene alkyl phenyl ether, but R' is preferably a monovalent group containing an aromatic hydrocarbon group.
成分F更佳為由以下的式(F-1)所表示的化合物。 The component F is more preferably a compound represented by the following formula (F-1).
(式(F-1)中，R表示伸烷基，X表示單鍵、或二價的連結基，Q表示烷基，x表示0~5的整數，m表示0~5的整數，n表示1~50的整數，當x為2以上時，存在多個的Q彼此可相同，亦可不同，當m為2以上時，存在多個的X及Q彼此可相同，亦可不同，當n為2以上時，存在多個的R彼此可相同，亦可不同) (In the formula (F-1), R represents an alkylene group, X represents a single bond or a divalent linking group, Q represents an alkyl group, x represents an integer of 0 to 5, m represents an integer of 0 to 5, and n represents An integer of 1 to 50, when x is 2 or more, a plurality of Qs may be the same or different, and when m is 2 or more, a plurality of X and Q may be the same or different, and when n is When it is 2 or more, a plurality of Rs may be the same or different from each other)
式(F-1)中，R表示伸烷基。即，(RO)表示伸烷氧基。作為R，較佳為碳數為2~8的伸烷基，更佳為碳數為2~6的伸烷基，進而更佳為碳數為2~4的伸烷基，特佳為伸乙基或伸丙基。即，特佳為具有含有伸乙氧基或伸丙氧基作為重複單元的聚伸烷氧基。再者，當具有2種以上的伸烷氧基時，例如當具有多個伸乙氧基與多個伸丙氧基時，聚伸乙氧基與聚伸丙氧基可成為嵌段 共聚物，亦可為無規共聚物，另外，亦可存在嵌段共聚物的部分與無規共聚物的部分這兩者，並無特別限定。 In the formula (F-1), R represents an alkylene group. That is, (RO) represents an alkoxy group. R is preferably an alkylene group having a carbon number of 2 to 8, more preferably an alkylene group having a carbon number of 2 to 6, more preferably an alkylene group having a carbon number of 2 to 4, particularly preferably Ethyl or propyl. That is, it is particularly preferred to have a polyalkyleneoxy group having a ethoxymethyl group or a propenyloxy group as a repeating unit. Further, when there are two or more kinds of alkoxy groups, for example, when having a plurality of ethoxy groups and a plurality of propoxy groups, the ethoxy group and the poly(propoxy group) may become a block. The copolymer may be a random copolymer, and may be a part of the block copolymer and a part of the random copolymer, and is not particularly limited.
式(F-1)中，X表示單鍵或二價的連結基，作為二價的連結基，較佳為二價的烴基，較佳為碳數為1~8的伸烷基(烷烴二基)、碳數為2~8的烯烴二基，更佳為碳數為1~4的伸烷基、碳數為2~4的烯烴二基。X特佳為碳數為1~4的伸烷基或碳數為2~4的烯烴二基。上述伸烷基及烯烴二基可為直鏈狀，亦可為分支狀。 In the formula (F-1), X represents a single bond or a divalent linking group, and as the divalent linking group, a divalent hydrocarbon group is preferred, and an alkylene group having 1 to 8 carbon atoms (alkane II) is preferred. The olefin diyl group having a carbon number of 2 to 8, more preferably an alkylene group having a carbon number of 1 to 4 and an olefin diyl group having a carbon number of 2 to 4. X is particularly preferably an alkylene group having a carbon number of 1 to 4 or an olefin diyl group having a carbon number of 2 to 4. The alkylene group and the olefin diyl group may be linear or branched.
式(F-1)中，Q為對於苯環的取代基，較佳為碳數為1~6的烷基，更佳為碳數為1~4，進而更佳為甲基、乙基、丙基或丁基。 In the formula (F-1), Q is a substituent for the benzene ring, preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group. Propyl or butyl.
式(F-1)中，作為取代於伸烷氧基所鍵結的苯環上的基(-X-Ph-Qx)，可例示：苯基(-Ph)、苄基(-CH2-Ph)、2-苯基丙烷-2-基(-C(CH3)2-Ph)、苯乙烯基(-CH=CH-Ph)、1-苯基乙基(-CH(CH3)-Ph)。再者，所謂Ph，表示苯環，於一價的情況下表示苯基，於二價的情況下表示伸苯基。 In the formula (F-1), as a group (-X-Ph-Qx) substituted on the benzene ring to which the alkoxy group is bonded, a phenyl group (-Ph) or a benzyl group (-CH 2 -) can be exemplified. Ph), 2-phenylpropan-2-yl (-C(CH 3 ) 2 -Ph), styryl (-CH=CH-Ph), 1-phenylethyl (-CH(CH 3 )- Ph). Further, Ph denotes a benzene ring, which means a phenyl group in the case of monovalent, and a phenyl group in the case of divalent.
式(F-1)中，x表示0~5的整數，較佳為0~3的整數，更佳為0~2的整數，進而更佳為0或1，特佳為0。 In the formula (F-1), x represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
式(F-1)中，m表示0~5的整數，較佳為1~5的整數，更佳為1~4，進而更佳為1~3。 In the formula (F-1), m represents an integer of 0 to 5, preferably an integer of 1 to 5, more preferably 1 to 4, still more preferably 1 to 3.
式(F-1)中，n表示1~50的整數，更佳為3~40的整數，進而更佳為5~35的整數，特佳為8~30的整數。 In the formula (F-1), n represents an integer of 1 to 50, more preferably an integer of 3 to 40, more preferably an integer of 5 to 35, and particularly preferably an integer of 8 to 30.
由式(F-1)所表示的化合物更佳為由下述式(F-2)所表示的化合物。 The compound represented by the formula (F-1) is more preferably a compound represented by the following formula (F-2).
(式(F-2)中，R1~R4分別獨立地表示氫原子或碳數為1~4的烷基，n1及n2分別獨立地表示0~50的整數，n1+n2表示1~50的整數，m表示1~5的整數。但是，排除R1與R2相同的情況) (In the formula (F-2), R 1 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 and n2 each independently represent an integer of 0 to 50, and n1+n2 represents 1~. An integer of 50, m represents an integer from 1 to 5. However, the case where R 1 and R 2 are excluded is excluded)
式(F-2)中，R1及R2分別獨立地表示氫原子或碳數為1~4的烷基，但排除R1與R2相同的情況。當R1與R2相同時，單一的伸烷氧基重複，因此作為n2=0，以n1表示重複單元的總數。R1及R2為氫原子或碳數為1~4的烷基，較佳為氫原子或碳數為1~2的烷基，更佳為氫原子或甲基。即，由式(F-1)所表示的化合物特佳為具有伸乙氧基、伸丙氧基、或伸乙氧基與伸丙氧基。 In the formula (F-2), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the case where R 1 and R 2 are the same is excluded. When R 1 and R 2 are the same, a single alkoxy group repeats, so as n2 = 0, the total number of repeating units is represented by n1. R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group. That is, the compound represented by the formula (F-1) is particularly preferably having an extended ethoxy group, a propenoxy group, or an ethoxy group and a propoxy group.
再者，當具有多個伸乙氧基與伸丙氧基時，聚伸乙氧基與聚伸丙氧基可成為嵌段共聚物，亦可為無規共聚物，另外，亦可存在嵌段共聚物的部分與無規共聚物的部分這兩者，並無特別限定。 Furthermore, when having a plurality of ethoxylated and propenoxyoxy groups, the poly(ethyleneoxy) group and the poly(extended propoxy group) may be a block copolymer, or may be a random copolymer, or may be embedded. The portion of the segment copolymer and the portion of the random copolymer are not particularly limited.
式(F-2)中，R3及R4分別獨立地表示氫原子或碳數為1~4的烷基，較佳為氫原子或碳數為1~2的烷基，更佳為氫原子 或甲基。更佳為R3及R4均為甲基、或一者為氫原子且另一者為甲基，特佳為一者為氫原子，另一者為甲基。 In the formula (F-2), R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably hydrogen. Atom or methyl. More preferably, both R 3 and R 4 are a methyl group, or one of them is a hydrogen atom and the other is a methyl group, and particularly preferably one is a hydrogen atom and the other is a methyl group.
式(F-2)中，n1及2分別獨立地表示0~50的整數，n1+n2表示1~50的整數。n1+n2較佳為3~40的整數，更佳為5~35的整數，進而更佳為8~30的整數。 In the formula (F-2), n1 and 2 each independently represent an integer of 0 to 50, and n1+n2 represents an integer of 1 to 50. N1+n2 is preferably an integer of 3 to 40, more preferably an integer of 5 to 35, and still more preferably an integer of 8 to 30.
式(F-2)中，m表示1~5的整數，更佳為1~4的整數，進而更佳為1~3的整數。 In the formula (F-2), m represents an integer of 1 to 5, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 3.
於本發明中，成分F的1分子中的苯環的數量的合計較佳為1~4的範圍。若苯環的數量的合計為上述範圍內，則可抑制殘渣的產生，故較佳。 In the present invention, the total number of benzene rings in one molecule of the component F is preferably in the range of 1 to 4. When the total amount of the benzene rings is within the above range, the generation of the residue can be suppressed, which is preferable.
於本發明中，成分F的親水親油平衡(Hydrophile-Lipophile Balance，HLB)值較佳為5~18，更佳為8~16，特佳為12~16。若HLB值為上述範圍內，則殘渣的產生進一步得到抑制，故較佳。 In the present invention, the Hydrophile-Lipophile Balance (HLB) value of the component F is preferably from 5 to 18, more preferably from 8 to 16, and particularly preferably from 12 to 16. When the HLB value is within the above range, the generation of the residue is further suppressed, which is preferable.
此處，HLB值是親水親油平衡(hydrophile-lipophile balance)的略稱，且為顯現界面活性劑所達成的效果的指標之一，HLB值越大，親水性變得越高。HLB值可根據其分子結構來算出，於本發明中，HLB值較佳為藉由格里芬法(Griffin method)來算出。 Here, the HLB value is an abbreviation for the hydrophilic-lipophile balance, and is one of the indexes for exhibiting the effect achieved by the surfactant. The larger the HLB value, the higher the hydrophilicity. The HLB value can be calculated from the molecular structure. In the present invention, the HLB value is preferably calculated by the Griffin method.
於格里芬法中，HLB值由下式來定義。 In the Griffin method, the HLB value is defined by the following formula.
HLB值=20×親水部的式量(分子量)的總和/分子量 HLB value = 20 × sum of molecular weight (molecular weight) of hydrophilic portion / molecular weight
例如，若親水部僅為聚氧伸烷基結構，則HLB值變成如下式般。 For example, if the hydrophilic portion is only a polyoxyalkylene structure, the HLB value becomes as follows.
HLB值=20×(聚氧伸烷基部分的式量的總和)/分子量 HLB value = 20 × (sum of the formula amount of the polyoxyalkylene moiety) / molecular weight
作為成分F，可使用合成品，另外，亦可使用市售品，並無特別限定。 As the component F, a synthetic product can be used, and a commercially available product can also be used, and it is not particularly limited.
作為已上市的製品，可列舉：Pionin D-6112、Pionin D-6115、Pionin D-6112-W、Pionin D-6108-W、Pionin D-6115X、Pionin D-6120X、D-6414、Pionin D-6512、Pionin D-6310、Pionin D-6315、Pionin D-6320(以上，竹本油脂(股份)製造)，Newcol CMP6、Newcol CMP-11、Newcol 610、Newcol 710、Newcol 710-F、Newcol 2609、Newcol 2600-FB(以上，日本乳化劑(股份)製造)。該些之中，較佳為Pionin D-6112-W、Pionin D-6512。 As products already on the market, Pionin D-6112, Pionin D-6115, Pionin D-6112-W, Pionin D-6108-W, Pionin D-6115X, Pionin D-6120X, D-6414, Pionin D- 6512, Pionin D-6310, Pionin D-6315, Pionin D-6320 (above, manufactured by Takeshi Oil & Fats Co., Ltd.), Newcol CMP6, Newcol CMP-11, Newcol 610, Newcol 710, Newcol 710-F, Newcol 2609, Newcol 2600-FB (above, manufactured by Japan Emulsifier (share)). Among these, Pionin D-6112-W and Pionin D-6512 are preferable.
於本發明中，成分F可單獨使用1種，亦可併用2種以上。 In the present invention, the component F may be used singly or in combination of two or more.
相對於固體成分100質量份，成分F於感光性樹脂組成物中的含量較佳為0.1質量份~10質量份，更佳為0.2質量份~5質量份，進而更佳為0.5質量份~3質量份。若成分F的含量為上述範圍內，則殘渣的產生進一步得到抑制，故較佳。 The content of the component F in the photosensitive resin composition is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.2 part by mass to 5 parts by mass, even more preferably from 0.5 part by mass to 3 parts by mass per 100 parts by mass of the solid component. Parts by mass. When the content of the component F is within the above range, the generation of the residue is further suppressed, which is preferable.
再者，成分F只要添加至感光性樹脂組成物中即可，其添加時期並無特別限定，與在金屬氧化物粒子的分散步驟中添加 相比，較佳為在將金屬氧化物粒子的分散物與其他成分混合的步驟中添加。 In addition, the component F may be added to the photosensitive resin composition, and the addition timing thereof is not particularly limited, and is added to the dispersion step of the metal oxide particles. In contrast, it is preferably added in the step of mixing the dispersion of the metal oxide particles with other components.
(成分G)氟系界面活性劑、及/或矽酮系界面活性劑 (Component G) fluorine-based surfactant, and/or anthrone-based surfactant
本發明的感光性樹脂組成物較佳為進而含有(成分G)氟系界面活性劑、及/或矽酮系界面活性劑。藉由含有成分G，顯影後的殘渣的產生進一步得到抑制，故較佳。 The photosensitive resin composition of the present invention preferably further contains (Component G) a fluorine-based surfactant and/or an anthrone-based surfactant. Since the component G is contained, the generation of the residue after development is further suppressed, which is preferable.
再者，可含有氟系界面活性劑及矽酮系界面活性劑的任一者，亦可含有兩者，並無特別限定，但就經濟的觀點而言，較佳為含有氟系界面活性劑或矽酮系界面活性劑，就殘渣的產生進一步得到抑制的觀點而言，更佳為含有氟系界面活性劑。 Further, the fluorine-based surfactant and the fluorenone-based surfactant may be contained, and may be contained, and are not particularly limited. However, from the viewpoint of economy, it is preferred to contain a fluorine-based surfactant. The ketone-based surfactant is more preferably a fluorine-based surfactant from the viewpoint of further suppressing the generation of the residue.
另外，氟系界面活性劑及矽酮系界面活性劑較佳為寡聚物或聚合物，重量平均分子量較佳為1,000以上，更佳為3,000以上。 Further, the fluorine-based surfactant and the anthrone-based surfactant are preferably oligomers or polymers, and the weight average molecular weight is preferably 1,000 or more, and more preferably 3,000 or more.
以下，分別進行說明。 Hereinafter, each description will be made.
<氟系界面活性劑> <Fluorine surfactant>
作為氟系界面活性劑，較佳為含有氟的非離子性界面活性劑，較佳為含有全氟烷基(CnF2n+1-，n為正的整數)。 The fluorine-based surfactant is preferably a fluorine-containing nonionic surfactant, and preferably contains a perfluoroalkyl group (C n F 2n+1 -, n is a positive integer).
氟系界面活性劑中的氟含有率合適的是3質量%~40質量%，更佳為5質量%~30質量%，特佳為7質量%~25質量%。就抑制殘渣的產生這一點而言，氟含有率為該範圍內的氟系界面活性劑有效果，於感光性樹脂組成物中的溶解性亦良好。 The fluorine content in the fluorine-based surfactant is suitably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. In terms of suppressing the generation of the residue, the fluorine content is effective in the fluorine-based surfactant in the range, and the solubility in the photosensitive resin composition is also good.
作為氟系界面活性劑，例如可列舉：MEGAFACE F-171、MEGAFACE F-172、MEGAFACE F-173、MEGAFACE F-176、MEGAFACE F-177、MEGAFACE F-141、MEGAFACE F-142、MEGAFACE F-143、MEGAFACE F-144、MEGAFACE R-30、MEGAFACE F-437、MEGAFACE F-475、MEGAFACE F-479、MEGAFACE F-482、MEGAFACE F-554、MEGAFACE F-780、MEGAFACE F-781(以上，迪愛生(DIC)(股份)製造)，Fluorad FC430、Fluorad FC431、Fluorad FC171(以上，住友3M(股份)製造)，Surflon S-382，Surflon SC-101，Surflon SC-103，Surflon SC-104，Surflon SC-105，Surflon SC1068，Surflon SC-381，Surflon SC-383，Surflon S393，Surflon KH-40(以上，旭硝子(股份)製造)等。 Examples of the fluorine-based surfactant include MEGAFACE F-171, MEGAFACE F-172, MEGAFACE F-173, and MEGAFACE. F-176, MEGAFACE F-177, MEGAFACE F-141, MEGAFACE F-142, MEGAFACE F-143, MEGAFACE F-144, MEGAFACE R-30, MEGAFACE F-437, MEGAFACE F-475, MEGAFACE F-479, MEGAFACE F-482, MEGAFACE F-554, MEGAFACE F-780, MEGAFACE F-781 (above, manufactured by Di Aisheng (DIC) (share)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (share) manufacturing) , Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, Asahi Glass) (shares) manufacturing) and so on.
<矽酮系界面活性劑> <Anthrone-based surfactant>
作為矽酮系界面活性劑的較佳例，可列舉含有多個二甲基矽烷氧基單元作為重複單元、且於化合物鏈的末端及/或側鏈上具有取代基者。於含有二甲基矽烷氧基作為重複單元的化合物鏈中亦可含有二甲基矽烷氧基以外的構成單元。取代基可相同，亦可不同，較佳為存在多個取代基。作為較佳的取代基的例子，可列舉包含聚醚基、烷基、芳基、芳氧基、丙烯醯基、甲基丙烯醯基、乙烯基、芳基、肉桂醯基、環氧基、氧雜環丁基、羥基、氟烷基、聚氧伸烷基、羧基、胺基等的基。 Preferable examples of the anthrone-based surfactant include a plurality of dimethyl alkoxy units as a repeating unit and a substituent at a terminal and/or a side chain of the compound chain. The compound chain containing a dimethyl decyloxy group as a repeating unit may also contain a structural unit other than a dimethyl decyloxy group. The substituents may be the same or different, and it is preferred to have a plurality of substituents. Examples of preferred substituents include a polyether group, an alkyl group, an aryl group, an aryloxy group, an alkylene group, a methacryl group, a vinyl group, an aryl group, a cinnamyl group, an epoxy group, and the like. a group such as an oxetanyl group, a hydroxyl group, a fluoroalkyl group, a polyoxyalkylene group, a carboxyl group, an amine group or the like.
分子量並無特別限制，但較佳為10萬以下，更佳為5萬以下，進而更佳為1,000~30,000，特佳為1,000~20,000。 The molecular weight is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000.
矽酮系界面活性劑的矽酮原子含量並無特別限制，但較 佳為18.0質量%以上，特佳為25.0質量%~37.8質量%，最佳為30.0質量%~37.0質量%。 The content of the fluorenone atom of the anthrone-based surfactant is not particularly limited, but Preferably, it is 18.0% by mass or more, particularly preferably 25.0% by mass to 37.8% by mass, and most preferably 30.0% by mass to 37.0% by mass.
作為較佳的矽酮系界面活性劑的例子，可列舉：信越化學工業(股份)製造的X-22-174DX、X-22-2426、X-22-164B、X22-164C、X-22-170DX、X-22-176D、X-22-1821(以上為商品名)；智索(Chisso)(股份)製造的FM-0725、FM-7725、FM-4421、FM-5521、FM-6621、FM-1121(以上為商品名)；蓋勒斯特(Gelest)製造的DMS-U22、RMS-033、RMS-083、UMS-182、DMS-H21、DMS-H31、HMS-301、FMS121、FMS123、FMS131、FMS141、FMS221(以上為商品名)；東麗．道康寧(Toray Dow Corning)(股份)製造的SH200、DC11PA、SH28PA、ST80PA、ST86PA、ST97PA、SH550、SH710、L7604、FZ-2105、FZ2123、FZ2162、FZ-2191、FZ2203、FZ-2207、FZ-3704、FZ-3736、FZ-3501、FZ-3789、L-77、L-720、L-7001、L-7002、L-7604、Y-7006、SS-2801、SS-2802、SS-2803、SS-2804、SS-2805(以上為商品名)；日本邁圖高新材料(Momentive Performance Materials Japan)製造的TSF400、TSF401、TSF410、TSF433、TSF4450、TSF4460(以上為商品名)等；但並不限定於該些例子。 Examples of preferred anthrone-based surfactants include X-22-174DX, X-22-2426, X-22-164B, X22-164C, and X-22- manufactured by Shin-Etsu Chemical Co., Ltd. 170DX, X-22-176D, X-22-1821 (above); FM-0725, FM-7725, FM-4421, FM-5521, FM-6621 manufactured by Chisso FM-1121 (above trade name); DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123 manufactured by Gelest , FMS131, FMS141, FMS221 (above is the trade name); Toray. SH200, DC11PA, SH28PA, ST80PA, ST86PA, ST97PA, SH550, SH710, L7604, FZ-2105, FZ2123, FZ2162, FZ-2191, FZ2203, FZ-2207, FZ-3704 manufactured by Toray Dow Corning (share) , FZ-3736, FZ-3501, FZ-3789, L-77, L-720, L-7001, L-7002, L-7604, Y-7006, SS-2801, SS-2802, SS-2803, SS -2804, SS-2805 (the above is a product name); TSF400, TSF401, TSF410, TSF433, TSF4450, TSF4460 (the above are trade names) manufactured by Momentive Performance Materials Japan, etc.; but not limited to These examples.
成分G可單獨使用1種，亦可併用2種以上。 The component G may be used alone or in combination of two or more.
相對於感光性樹脂組成物的固體成分，成分G於感光性樹脂組成物中的含量較佳為0.001質量%~1質量%，更佳為0.01質量%~0.5質量%，進而更佳為0.02質量%~0.3質量%。若成分G的 含量為上述範圍內，則對於基板的潤濕擴展性變得良好，可抑制由塗佈面的異物所產生的塌凹或由液體回流等所引起的不均的產生。另外，對於顯影液的潤濕性亦變得良好，可獲得均勻且良好的畫素圖案，故較佳。 The content of the component G in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and still more preferably 0.02% by mass based on the solid content of the photosensitive resin composition. %~0.3% by mass. If component G When the content is within the above range, the wettability to the substrate becomes good, and the occurrence of unevenness due to foreign matter on the coated surface or the occurrence of unevenness due to liquid reflux or the like can be suppressed. Further, the wettability of the developer is also good, and a uniform and good pixel pattern can be obtained, which is preferable.
另外，於本發明中，成分F與成分G的含量的比以質量比計，較佳為成分F：成分G=10：0.001~10：5，更佳為10：0.1~10：2。 Further, in the present invention, the ratio of the content of the component F to the component G is preferably a component F: a component G = 10: 0.001 to 10:5, more preferably 10: 0.1 to 10:2.
藉由將成分F與成分G的含有比設為上述範圍內，而達成利用成分G的良好的塗佈面狀的形成、成分F對於金屬氧化物粒子的充分的吸附、及朝與基板的液體界面上的充分的配向，且殘渣得到抑制，故較佳。 By setting the content ratio of the component F to the component G within the above range, formation of a favorable coating surface using the component G, sufficient adsorption of the component F on the metal oxide particles, and liquid toward the substrate are achieved. It is preferred to have sufficient alignment at the interface and to suppress the residue.
(成分H)具有2個以上的氮原子的雜環化合物 (Component H) a heterocyclic compound having two or more nitrogen atoms
本發明的感光性樹脂組成物較佳為含有(成分H)具有2個以上的氮原子的雜環化合物。推斷因成分H吸附於金屬氧化物粒子的表面，故產生金屬氧化物粒子彼此的靜電排斥或立體排斥，尤其防止塗佈組成物並進行了乾燥時的金屬氧化物的凝聚，因此霧度變小。以下，亦將成分H稱為「特定表面改質劑」。 The photosensitive resin composition of the present invention preferably contains a heterocyclic compound having two or more nitrogen atoms (component H). It is estimated that the component H is adsorbed on the surface of the metal oxide particles, so that electrostatic repulsion or steric repulsion of the metal oxide particles occurs, and in particular, aggregation of the metal oxide when the composition is applied and dried is performed, so that the haze becomes small. . Hereinafter, the component H is also referred to as a "specific surface modifier."
作為成分H，除具有2個以上的氮原子以外，並無特別限制，但較佳為具有2個以上的氮原子作為雜環的環員的雜環化合物，更佳為具有於1位、3位上至少含有氮原子的雜環結構的化合物，進而更佳為具有於1位、3位上至少含有氮原子的5員雜環結構或6員雜環結構的化合物。若為上述形態，則可獲得金屬氧化物粒子 的分散性更優異、霧度更小的硬化物。 The component H is not particularly limited as long as it has two or more nitrogen atoms, but is preferably a heterocyclic compound having two or more nitrogen atoms as a ring member of a hetero ring, and more preferably has one or three. The compound having a heterocyclic structure containing at least a nitrogen atom is more preferably a compound having a 5-membered heterocyclic ring structure or a 6-membered heterocyclic ring structure containing at least a nitrogen atom at the 1-position and the 3-position. If it is in the above form, metal oxide particles can be obtained. A hardened material that is more dispersible and has a lower haze.
再者，所謂「於1位、3位上至少含有氮原子的雜環結構」，只要是於雜環中氮原子鍵結於碳原子的兩側的結構即可，亦可不是正式的命名法中的雜環上的1位及3位。 In addition, the "heterocyclic structure containing at least a nitrogen atom at the 1st position and the 3rd position" may be a structure in which a nitrogen atom is bonded to both sides of a carbon atom in the hetero ring, and may not be an official nomenclature. 1 and 3 positions on the heterocyclic ring.
成分H中的雜環的環員較佳為至少包含碳原子及氮原子，可進而含有氧原子或硫原子作為環員，但特佳為包含碳原子及氮原子。 The ring member of the hetero ring in the component H preferably contains at least a carbon atom and a nitrogen atom, and further contains an oxygen atom or a sulfur atom as a ring member, but particularly preferably contains a carbon atom and a nitrogen atom.
成分H所具有的氮原子的數量為2個以上，較佳為2個~6個，更佳為2個~4個。另外，成分H較佳為具有2個~4個氮原子作為雜環的環員，更佳為具有2個或3個氮原子作為雜環的環員，進而更佳為具有2個氮原子作為雜環的環員。 The number of nitrogen atoms in the component H is two or more, preferably two to six, and more preferably two to four. Further, the component H is preferably a ring member having 2 to 4 nitrogen atoms as a hetero ring, more preferably a ring member having 2 or 3 nitrogen atoms as a hetero ring, and more preferably having 2 nitrogen atoms as a ring member. A ring of heterocyclic rings.
成分H中的雜環可為飽和雜環，亦可為不飽和雜環，亦可為芳香族雜環。 The heterocyclic ring in the component H may be a saturated heterocyclic ring, an unsaturated heterocyclic ring or an aromatic heterocyclic ring.
另外，成分H中的雜環可進而與其他環進行縮合。另外，作為上述其他環，並非僅為雜環，可為脂肪族環，亦可為芳香環。 Further, the heterocyclic ring in the component H can be further condensed with other rings. Further, the other ring is not limited to a hetero ring, and may be an aliphatic ring or an aromatic ring.
成分A亦可具有雜環的環員以外的氮原子，雜環的環員以外的氮原子的數量較佳為0個~3個，較佳為0個~2個，進而更佳為0個或1個，特佳為不具有雜環的環員以外的氮原子。 The component A may have a nitrogen atom other than the ring member of the hetero ring, and the number of nitrogen atoms other than the ring member of the hetero ring is preferably 0 to 3, preferably 0 to 2, and more preferably 0. Or one, particularly preferably a nitrogen atom other than a ring member having no hetero ring.
作為成分H所具有的雜環結構的具體例，可較佳地列舉選自由咪唑結構、苯并咪唑結構、1,2,4-***結構、4,5-二氫-1,2,4-***結構、四唑結構、2-咪唑啉結構、4-咪唑啉結構(2,3-二氫咪唑結構)、咪唑啶結構、嘧啶結構、喹噁啉結構、嘌呤結構、喋啶 結構、及呸啶結構所組成的群組中的環結構，可更佳地列舉選自由咪唑結構、苯并咪唑結構、1,2,4-***結構、4,5-二氫-1,2,4-***結構、四唑結構、2-咪唑啉結構、4-咪唑啉結構、咪唑啶結構、及嘧啶結構所組成的群組中的環結構，可特佳地列舉苯并咪唑結構或咪唑啶結構。若為上述形態，則可獲得金屬氧化物粒子的分散性更優異、霧度更小的硬化物。 Specific examples of the heterocyclic structure of the component H are preferably selected from the group consisting of an imidazole structure, a benzimidazole structure, a 1,2,4-triazole structure, and 4,5-dihydro-1,2,4. - triazole structure, tetrazole structure, 2-imidazoline structure, 4-imidazoline structure (2,3-dihydroimidazole structure), imidazolium structure, pyrimidine structure, quinoxaline structure, oxime structure, acridine The ring structure in the group consisting of the structure and the acridine structure may be more preferably selected from the group consisting of an imidazole structure, a benzimidazole structure, a 1,2,4-triazole structure, and 4,5-dihydro-1. The ring structure in the group consisting of a 2,4-triazole structure, a tetrazole structure, a 2-imidazoline structure, a 4-imidazoline structure, an imidazolium structure, and a pyrimidine structure, particularly preferably a benzimidazole structure Or imidazolium structure. According to the above aspect, a cured product having more excellent dispersibility of metal oxide particles and a smaller haze can be obtained.
成分H較佳為具有巰基(-SH)或硫酮基(=S)。若為上述形態，則可獲得金屬氧化物粒子的分散性更優異、霧度更小的硬化物。 Component H preferably has a mercapto group (-SH) or a thioketone group (=S). According to the above aspect, a cured product having more excellent dispersibility of metal oxide particles and a smaller haze can be obtained.
另外，作為成分H，較佳為由下述式(1)所表示的化合物。 Further, the component H is preferably a compound represented by the following formula (1).
(式(1)中，R1及R2分別獨立地表示氫原子、鹵素原子或一價的有機基，R1與R2可鍵結而為二價的有機基，R3及R4分別獨立地表示氫原子或一價的有機基，L1表示形成5員環或6員環的二價的連結基，R3或R4與L1可鍵結而形成環，另外，當存在 由虛線所記載的含氮雙鍵時，虛線的鍵結表示不存在R2及R4，當不存在由虛線所記載的含氮雙鍵時，虛線的鍵結表示存在R2及R4) (In the formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and R 1 and R 2 may be bonded to form a divalent organic group, and R 3 and R 4 respectively Independently representing a hydrogen atom or a monovalent organic group, L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and R 3 or R 4 may be bonded to L 1 to form a ring, and when present, In the nitrogen-containing double bond described by the broken line, the dotted bond indicates the absence of R 2 and R 4 , and when there is no nitrogen-containing double bond as indicated by the broken line, the dotted bond indicates the presence of R 2 and R 4 )
作為R1~R4中的一價的有機基，可列舉烷基(包含環烷基、雙環烷基、三環烷基)、烯基(包含環烯基、雙環烯基)、炔基、芳基、雜環(heterocyclic ring)基(亦稱為雜環(heterocycle)基)、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、雜環氧基、醯氧基、胺甲醯氧基、烷氧基羰氧基、芳氧基羰氧基、胺基(包含烷基胺基、芳基胺基、雜環胺基)、銨基、醯基胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺磺醯基胺基、烷基磺醯基胺基及芳基磺醯基胺基、巰基、烷硫基、芳硫基、雜環硫基、烷基二硫基、芳基二硫基、雜環二硫基、胺磺醯基、磺酸基、烷基亞磺醯基及芳基亞磺醯基、烷基磺醯基及芳基磺醯基、醯基、芳氧基羰基、烷氧基羰基、胺甲醯基、芳基偶氮基及雜環偶氮基、醯亞胺基、膦基、氧膦基、氧膦基氧基、氧膦基胺基、膦醯基、矽烷基、肼基、脲基、硫脲基、硼酸基(-B(OH)2)、磷酸根基(-OPO(OH)2)、硫酸根基(-OSO3H)、其他公知的取代基作為例子。另外，上述基可進一步由取代基取代。 Examples of the monovalent organic group in R 1 to R 4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group, a bicycloalkenyl group), and an alkynyl group. An aryl group, a heterocyclic ring group (also known as a heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a heterocyclic oxy group, an anthracene group Oxyl, amine methyl methoxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine (including alkylamino, arylamino, heterocyclic amine), ammonium, mercaptoamine , aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminesulfonylamino group, alkylsulfonylamino group and arylsulfonylamino group, mercapto group, alkylthio group, Arylthio, heterocyclic thio, alkyldithio, aryldithio, heterocyclic dithio, sulfonyl, sulfonate, alkylsulfinyl and arylsulfinyl, Alkylsulfonyl and arylsulfonyl, anthracenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, arylazo and heterocyclic azo, fluorenylene, phosphino, Phosphine, phosphinyloxy, phosphinylamino, phosphinium, Alkyl group, a hydrazino group, a urea group, a thiourea group, a boronic acid group (-B (OH) 2), phosphate (-OPO (OH) 2), sulfate (-OSO 3 H), other well known substituent groups as example. Further, the above group may be further substituted with a substituent.
R1及R2較佳為分別獨立地為氫原子、鹵素原子、烷基、烯基、芳基、或巰基，更佳為氫原子、鹵素原子、烷基(較佳為碳數炭為1~20，更佳為碳數為1~8，進而更佳為碳數為1~4)、烯基(較佳為碳數為2~20，更佳為碳數為2~8，進而更佳為碳數為2~4)、芳基(較佳為碳數為6~20，更佳為碳數為6~16， 進而更佳為碳數為6~10)、或巰基。另外，上述烷基、烯基及芳基可進一步由取代基取代，例如可為烷基由芳基取代的芳烷基。 R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group or a fluorenyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group (preferably a carbon number of carbon 1). ~20, more preferably a carbon number of 1 to 8, and more preferably a carbon number of 1 to 4), an alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 8, and further more Preferably, the carbon number is 2 to 4), the aryl group (preferably, the carbon number is 6 to 20, more preferably the carbon number is 6 to 16, and more preferably the carbon number is 6 to 10), or the sulfhydryl group. Further, the above alkyl group, alkenyl group and aryl group may be further substituted by a substituent, for example, an aralkyl group in which an alkyl group is substituted with an aryl group.
R3及R4較佳為分別獨立地為氫原子、烷基、烯基、炔基、芳基、或雜環基，更佳為氫原子、烷基(較佳為碳數炭為1~20，更佳為碳數為1~8，進而更佳為碳數為1~4)、烯基(較佳為碳數為2~20，更佳為碳數為2~12，進而更佳為碳數為2~6)、炔基(較佳為碳數為2~20，更佳為碳數為2~12，進而更佳為碳數為2~6)、芳基(較佳為碳數為6~20，更佳為碳數為6~16，進而更佳為碳數為6~10)、或雜環基。另外，上述烷基、烯基、炔基、芳基、雜環基可進一步由取代基取代，例如可為烷基由芳基取代的芳烷基。 R 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, more preferably a hydrogen atom or an alkyl group (preferably a carbon number of carbon 1). 20, more preferably a carbon number of 1 to 8, and more preferably a carbon number of 1 to 4), an alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, and thus more preferably The carbon number is 2 to 6), the alkynyl group (preferably, the carbon number is 2 to 20, more preferably the carbon number is 2 to 12, and more preferably the carbon number is 2 to 6), and the aryl group is preferably The carbon number is 6 to 20, more preferably 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms, or a heterocyclic group. Further, the above alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group may be further substituted by a substituent, and for example, an aralkyl group in which an alkyl group is substituted with an aryl group.
作為R1及R2中的一價的有機基，該些基之中，特佳為巰基。 As the monovalent organic group in R 1 and R 2 , among these groups, a mercapto group is particularly preferable.
另外，R1及R2中的一價的有機基的碳數較佳為0~20，更佳為0~8，特佳為0。 Further, the carbon number of the monovalent organic group in R 1 and R 2 is preferably 0 to 20, more preferably 0 to 8, and particularly preferably 0.
另外，作為R1與R2鍵結所形成的二價的有機基，可列舉側氧基、硫酮基、亞烷基等作為例子。該些基之中，特佳為硫酮基。 Further, examples of the divalent organic group formed by bonding R 1 and R 2 include a pendant oxy group, a thioke group, an alkylene group and the like. Among these groups, a thioketone group is particularly preferred.
R1及R2特佳為分別獨立地為氫原子或巰基，另外，當R1與R2鍵結而形成二價的有機基時，特佳為硫酮基。 R 1 and R 2 are particularly preferably each independently a hydrogen atom or a fluorenyl group, and when R 1 and R 2 are bonded to form a divalent organic group, a thioketone group is particularly preferred.
作為R3及R4中的一價的有機基，較佳為烷基或芳基，更佳為嗎啉基甲基或苯基。另外，上述烷基或芳基可由取代基取代。 As the monovalent organic group in R 3 and R 4 , an alkyl group or an aryl group is preferred, and a morpholinylmethyl group or a phenyl group is more preferred. Further, the above alkyl group or aryl group may be substituted with a substituent.
R3及R4中的一價的有機基的碳數較佳為0~20，更佳為1~10，進而更佳為4~8。 The carbon number of the monovalent organic group in R 3 and R 4 is preferably from 0 to 20, more preferably from 1 to 10, still more preferably from 4 to 8.
R3及R4較佳為分別獨立地為氫原子、烷基或芳基，更佳為氫原子、嗎啉基甲基或苯基，進而更佳為氫原子或苯基。 R 3 and R 4 are each independently a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a morpholinylmethyl group or a phenyl group, and still more preferably a hydrogen atom or a phenyl group.
L1表示形成5員環或6員環的二價的連結基，其與式(1)中的碳原子及2個氮原子一同形成雜環。 L 1 represents a divalent linking group which forms a 5-membered ring or a 6-membered ring, and forms a hetero ring together with the carbon atom and two nitrogen atoms in the formula (1).
作為二價的連結基，只要是與式(1)中的碳原子及2個氮原子一同形成5員雜環或6員雜環的基，則並無特別限制，但其環員較佳為由碳原子及/或氮原子所形成的基，更佳為形成上述雜環結構的具體例的基。其中，特佳為形成苯并咪唑結構的基，即1,2-伸苯基，或形成咪唑啶結構的基，即1,2-伸乙基。 The divalent linking group is not particularly limited as long as it forms a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with the carbon atom and two nitrogen atoms in the formula (1), but the ring member is preferably a ring member. The group formed of a carbon atom and/or a nitrogen atom is more preferably a group forming a specific example of the above heterocyclic ring structure. Among them, a group which forms a benzimidazole structure, that is, a 1,2-phenyl group, or a group which forms an imidazole pyridine structure, that is, a 1,2-extended ethyl group, is particularly preferred.
進而，作為成分H，更佳為由下述式(1-1)或式(1-2)所表示的化合物。 Further, the component H is more preferably a compound represented by the following formula (1-1) or formula (1-2).
(式(1-1)及式(1-2)中，R6~R8分別獨立地表示氫原子或一價的有機基，L2及L3分別獨立地表示形成5員環或6員環的 二價的連結基，R6與L2可鍵結而形成環，R7或R8與L3可鍵結而形成環) (In the formulae (1-1) and (1-2), R 6 to R 8 each independently represent a hydrogen atom or a monovalent organic group, and L 2 and L 3 each independently represent a 5-membered ring or 6 members. a divalent linking group of the ring, R 6 and L 2 may be bonded to form a ring, and R 7 or R 8 may be bonded to L 3 to form a ring)
式(1-1)或式(1-2)中的R6~R8的含義與上述式(1)中的R3及R4相同，較佳的形態亦相同。 R 6 to R 8 in the formula (1-1) or the formula (1-2) have the same meanings as those of R 3 and R 4 in the above formula (1), and preferred embodiments are also the same.
另外，式(1-1)或式(1-2)中的L2及L3的含義與上述式(1)中的L1相同，較佳的形態亦相同。 Further, L 2 and L 3 in the formula (1-1) or the formula (1-2) have the same meanings as L 1 in the above formula (1), and preferred embodiments are also the same.
以下表示成分H的較佳的具體例(h-1~h-11)。但是，於本發明中，並不受該些具體例限制。 Preferred specific examples (h-1 to h-11) of the component H are shown below. However, in the present invention, it is not limited by these specific examples.
該些之中，較佳為h-3~h-11，更佳為h-3、h-5、h-6或h-9，特佳為h-5或h-9。 Among these, it is preferably h-3 to h-11, more preferably h-3, h-5, h-6 or h-9, and particularly preferably h-5 or h-9.
另外，成分H可單獨使用1種，亦可併用2種以上。 Further, the component H may be used alone or in combination of two or more.
相對於本發明的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中的成分H的含量較佳為0.1質量%~20質量%，更佳為0.5質量%~15質量%，進而更佳為0.5質量%~10質量%。若為上述範圍，則可獲得金屬氧化物粒子的分散性更優異、霧度更小的硬化物。 The content of the component H in the photosensitive resin composition of the present invention is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.5% by mass to 15% by mass, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.5 mass% - 10 mass%. When it is in the above range, a cured product in which the dispersibility of the metal oxide particles is more excellent and the haze is smaller can be obtained.
<其他成分> <Other ingredients>
於本發明的感光性樹脂組成物中，除上述成分以外，視需要可較佳地添加(成分I)交聯劑、(成分J)抗氧化劑、(成分K)增感劑、(成分L)烷氧基矽烷化合物、(成分M)鹼性化合物、(成分N)其他界面活性劑。進而，於本發明的感光性樹脂組成物中，可添加紫外線吸收劑、金屬鈍化劑、或酸增殖劑、顯影促進劑、塑化劑、熱自由基產生劑、熱酸產生劑、增黏劑、及有機或無機的防沈澱劑等公知的添加劑。另外，作為該些化合物，亦可參考例如日本專利特開2012-88459號公報的段落0201~段落0224的記載，該些的內容可被編入至本申請案說明書中。 In the photosensitive resin composition of the present invention, in addition to the above components, (Component I) crosslinking agent, (Component J) antioxidant, (Component K) sensitizer, (Component L) may be preferably added. Alkoxydecane compound, (Component M) basic compound, (Component N) other surfactant. Further, in the photosensitive resin composition of the present invention, an ultraviolet absorber, a metal deactivator, or an acid multiplier, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, or a tackifier may be added. And known additives such as organic or inorganic anti-precipitation agents. Further, as such a compound, for example, the descriptions of paragraphs 0201 to 0224 of JP-A-2012-88459 can be referred to, and the contents can be incorporated into the specification of the present application.
(成分I)交聯劑 (ingredient I) crosslinker
本發明的感光性樹脂組成物較佳為視需要而含有(成分I)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獲得的硬化膜變成更牢固的膜。 The photosensitive resin composition of the present invention preferably contains (Component I) 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.
作為交聯劑，只要是藉由熱而產生交聯反應者，則並無限制(但是，成分A除外)。即，可適宜地使用熱交聯劑作為交聯劑。例如，可添加以下所述的分子內具有2個以上的環氧基或氧雜環丁基的化合物、含有烷氧基甲基的交聯劑、具有至少1個乙烯性不飽和雙鍵的化合物、或封閉型異氰酸酯化合物等。 The crosslinking agent is not limited as long as it is a crosslinking reaction by heat (however, the component A is excluded). That is, a thermal crosslinking agent can be suitably used as a crosslinking agent. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, a crosslinking agent containing an alkoxymethyl group, and a compound having at least one ethylenically unsaturated double bond may be added as described below. Or a blocked isocyanate compound or the like.
相對於感光性樹脂組成物的總固體成分100質量份，本發明的感光性樹脂組成物中的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，進而更佳為0.5質量份~20質量份。藉由在該範圍內進行添加，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，於此情況下，計算所有交聯劑的合計含量。 The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 30 parts by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. The parts by mass are more preferably 0.5 parts 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 content of all the crosslinking agents is calculated.
<分子內具有2個以上的環氧基或氧雜環丁基的化合物> <Compound having two or more epoxy groups or oxetanyl groups in the molecule>
作為分子內具有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, a phenol novolak type epoxy resin, and a cresol novolak type ring. Oxygen resin, aliphatic epoxy resin, and the like.
該些化合物可作為市售品而獲得。例如可列舉JER152、JER157S70、JER157S65、JER806、JER828、JER1007(三菱化學控股(Mitsubishi Chemical Holdings)(股份)製造)等，日本專利特開2011-221494號公報的段落0189中所記載的市售品等，除此以外，亦可列舉ADEKA RESIN EP-4000S、ADEKA RESIN EP-4003S、ADEKA RESIN EP-4010S、ADEKA RESIN EP-4011S(以 上，艾迪科(股份)製造)，NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上，艾迪科(股份)製造)，Denacol EX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、DLC-301、DLC-402(以上，長瀨化成(Nagase chemteX)(股份)製造)，YH-300、YH-301、YH-302、YH-315、YH-324、YH-325(以上，新日鐵化學(股份)製造)等。 These compounds are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and commercially available products described in paragraph 0189 of JP-A-2011-221494 In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (also , Eddie (manufacturing), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by Eddie Co., Ltd.), Denacol EX-611 , EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX -212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931 , EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above) , manufactured by Nagase chemteX (shares), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemical Co., Ltd.) .
該些可單獨使用1種、或將2種以上組合使用。 These may be used alone or in combination of two or more.
該些之中，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，可特佳地列舉雙酚A型環氧樹脂。 Among these, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac 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.
作為分子內具有2個以上的氧雜環丁基的化合物的具體例，可使用ARONE OXETANE OXT-121、OXT-221、OX-SQ、PNOX(以上，東亞合成(股份)製造)。 Specific examples of the compound having two or more oxetanyl groups in the molecule include ARONE OXETANE OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei 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，作為其他交聯劑，亦可較佳地使用日本專利特開2012-8223號公報的段落0107~段落0108中所記載的含有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。 作為含有烷氧基甲基的交聯劑，較佳為烷氧基甲基化甘脲。 Further, as the other crosslinking agent, an alkoxymethyl group-containing crosslinking agent described in paragraphs 0107 to 0108 of JP-A-2012-8223, and at least one ethylene may be preferably used. A compound of a sexually unsaturated double bond or the like. As the crosslinking agent containing an alkoxymethyl group, an alkoxymethylated glycoluril is preferred.
<封閉型異氰酸酯化合物> <Blocked isocyanate compound>
於本發明的感光性樹脂組成物中，亦可較佳地採用封閉型異氰酸酯系化合物作為交聯劑。封閉型異氰酸酯化合物只要是具有封閉型異氰酸酯基的化合物，則並無特別限制，但就硬化性的觀點而言，較佳為1分子內具有2個以上的封閉型異氰酸酯基的化合物。 In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also preferably be used as the crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group. From the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferred.
再者，本發明中的封閉型異氰酸酯基是指可藉由熱而生成異氰酸酯基的基，例如，可較佳地例示使封閉劑與異氰酸酯基進行反應來保護異氰酸酯基的基。另外，上述封閉型異氰酸酯基較佳為可藉由90℃~250℃的熱而生成異氰酸酯基的基。 In addition, the blocked isocyanate group in the present invention means a group which can form an isocyanate group by heat, and for example, a group which blocks a blocking agent and an isocyanate group to protect an isocyanate group can be preferably exemplified. Further, the blocked isocyanate group is preferably a group capable of forming an isocyanate group by heat of from 90 ° C to 250 ° C.
另外，作為封閉型異氰酸酯化合物，其骨架並無特別限定，只要是1分子中具有2個異氰酸酯基的化合物，則可為任何化合物，可為脂肪族、脂環族或芳香族的聚異氰酸酯，例如可適宜地使用：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***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'-二苯醚二異氰酸酯、四氯伸苯基二異氰酸酯、降莰烷二異氰酸酯、氫化1,3-伸茬基二異氰酸酯、氫化1,4-伸茬基二異氰酸酯等異氰酸酯化合物及自該些化合物衍生出的預聚物型的骨架的化合物。該些之中，特佳為甲苯二異氰酸酯(Tolylene Diisocyanate，TDI)或二苯基甲烷二異氰酸酯(Diphenyl Methane Diisocyanate，MDI)、六亞甲基二異氰酸酯(Hexamethylene Diisocyanate，HDI)、異佛爾酮二異氰酸酯(Isophorone Diisocyanate，IPDI)。 Further, the blocked isocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups in one molecule, and may be any compound, and may be an aliphatic, alicyclic or aromatic polyisocyanate, for example. It can be suitably used: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1 , 4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene Diisocyanate, 1,10-decethylene 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-di Methyl diiso Cyanate ester, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorine Isocyanate compounds such as phenyl diisocyanate, norbornane diisocyanate, hydrogenated 1,3-decyl diisocyanate, hydrogenated 1,4-decyl diisocyanate, and a prepolymer type skeleton derived from the compounds Compound. Among them, particularly preferred is Tolylene Diisocyanate (TDI) or Diphenyl Methane Diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Isophorone II. Isocyanate Diisocyanate (IPDI).
作為本發明的感光性樹脂組成物中的封閉型異氰酸酯化合物的母結構，可列舉：縮二脲型、異氰脲酸酯型(Isocyanurate)、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 isocyanurate type, an adduct type or a difunctional prepolymer type.
作為形成上述封閉型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。該些之中，特佳為選自肟化合物、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 a ruthenium compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. a compound, a quinone imine compound, or the like. Among these, a blocking agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.
作為上述肟化合物，可列舉醛肟、及酮肟，具體而言，可例示：丙酮肟、甲醛肟、環己烷肟、甲基乙基酮肟、環己酮肟、二苯基酮肟、丙酮肟等。 Examples of the hydrazine compound include aldoxime and ketoxime. Specific examples thereof include acetone oxime, formaldehyde oxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and diphenyl ketone oxime. Acetone oxime and the like.
作為上述內醯胺化合物，可例示：ε-己內醯胺、γ-丁內醯胺等。 The above-mentioned indoleamine compound may, for example, be ε-caprolactam or γ-butylidene.
作為上述酚化合物，可例示：苯酚、萘酚、甲酚、二甲酚、鹵素取代苯酚等。 The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.
作為上述醇化合物，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.
作為上述胺化合物，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、乙烯亞胺、聚乙烯亞胺等。 Examples of the amine compound include 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, ethyleneimine, and polyethyleneimine. Wait.
作為上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.
作為上述吡唑化合物，可例示：吡唑、甲基吡唑、二甲基吡唑等。 The pyrazole compound may, for example, be pyrazole, methylpyrazole or dimethylpyrazole.
作為上述硫醇化合物，可例示：烷基硫醇、芳基硫醇等。 The thiol compound may, for example, be an alkyl mercaptan or an aryl thiol.
可用於本發明的感光性樹脂組成物的封閉型異氰酸酯化合物可作為市售品而獲得，例如可較佳地使用：Coronate AP Stable M、Coronate2503、2515、2507、2513、2555、Millionate MS-50(以上，日本聚氨酯工業(Nippon Polyurethane Industry)(股份)製造)，Takenate B-830、B-815N、B-820NSU、B-842N、B-846N、B-870N、B-874N、B-882N(以上，三井化學(股份)製造)，Duranate17B-60PX、17B-60P、TPA-B80X、TPA-B80E、MF-B60X、MF-B60B、MF-K60X、MF-K60B、E402-B80B、SBN-70D、SBB-70P、K6000(以上，旭化成化學(Asahi Kasei Chemicals)(股份)製造)，Desmodur BL1100、BL1265 MPA/X、BL3575/1、BL3272MPA、 BL3370MPA、BL3475BA/SN、BL5375MPA、VPLS2078/2、BL4265SN、PL340、PL350、Sumidur BL3175(以上，住化拜爾聚氨脂(Sumika Bayer Urethane)(股份)製造)等。 A blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercial product, and for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (for example) can be preferably used. Above, manufactured by Nippon Polyurethane Industry (shares), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above , manufactured by Mitsui Chemicals Co., Ltd., Duranate17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB -70P, K6000 (above, manufactured by Asahi Kasei Chemicals (share)), Desmodur BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane (share)).
(成分J)抗氧化劑 (ingredient J) antioxidant
本發明的感光性樹脂組成物較佳為含有抗氧化劑。可含有公知的抗氧化劑作為抗氧化劑。藉由添加抗氧化劑，具有如下的優點：可防止硬化膜的著色、或可減少由分解所引起的膜厚減少，另外，耐熱透明性優異。 The photosensitive resin composition of the present invention preferably contains an antioxidant. A known antioxidant can be contained as an antioxidant. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or reduction in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
作為此種抗氧化劑，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、羥胺衍生物等。該些抗氧化劑之中，就硬化膜的著色、膜厚減少的觀點而言，特佳為酚系抗氧化劑、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1種，亦可混合2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, sugars, and nitrites. , sulfite, thiosulfate, hydroxylamine derivatives, and the like. Among these antioxidants, phenol-based antioxidants, guanamine-based antioxidants, lanthanide-based antioxidants, and sulfur-based antioxidants are preferred as the phenol from the viewpoint of color reduction and film thickness reduction of the cured film. It is an antioxidant. These antioxidants may be used alone or in combination of two or more.
作為具體例，可列舉日本專利特開2005-29515號公報的段落0026~段落0031中所記載的化合物，該些的內容可被編入至本申請案說明書中。 Specific examples thereof include the compounds described in paragraph 0026 to paragraph 0031 of JP-A-2005-29515, the contents of which are incorporated herein by reference.
作為酚系抗氧化劑的市售品，例如可列舉：Adekastab AO-15、Adekastab AO-18、Adekastab AO-20、Adekastab AO-23、Adekastab AO-30、Adekastab AO-37、Adekastab AO-40、Adekastab AO-50、Adekastab AO-51、Adekastab AO-60、Adekastab AO-70、Adekastab AO-80、Adekastab AO-330、Adekastab AO-412S、Adekastab AO-503、Adekastab A-611、Adekastab A-612、Adekastab A-613、Adekastab PEP-4C、Adekastab PEP-8、Adekastab PEP-8W、Adekastab PEP-24G、Adekastab PEP-36、Adekastab PEP-36Z、Adekastab HP-10、Adekastab 2112、Adekastab 260、Adekastab 522A、Adekastab 1178、Adekastab 1500、Adekastab C、Adekastab 135A、Adekastab 3010、Adekastab TPP、Adekastab CDA-1、Adekastab CDA-6、Adekastab ZS-27、Adekastab ZS-90、Adekastab ZS-91(以上，艾迪科(股份)製造)，Irganox 245FF、Irganox 1010FF、Irganox 1010、Irganox MD1024、Irganox 1035FF、Irganox 1035、Irganox 1098、Irganox 1330、Irganox 1520L、Irganox 3114、Irganox 1726、Irgafos 168、Irgamod 295(巴斯夫公司製造)，Tinuvin405(巴斯夫公司製造)等。其中，可適宜地使用Adekastab AO-60、Adekastab AO-80、Irganox 1726、Irganox 1035、Irganox 1098、Tinuvin405。 As a commercial item of a phenolic antioxidant, Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab are mentioned, for example. AO-50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A-613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1 Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (above, manufactured by Eddy Co., Ltd.), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (manufactured by BASF Corporation), Tinuvin 405 (manufactured by BASF Corporation), and the like. Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098, Tinuvin 405 can be suitably used.
相對於感光性樹脂組成物的總固體成分，抗氧化劑的含量較佳為0.1質量%~10質量%，更佳為0.2質量%~5質量%，特佳為0.5質量%~4質量%。藉由設為該範圍內，所形成的膜可獲得充分的透明性、且圖案形成時的感度亦變得良好。 The content of the antioxidant is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 5% by mass, even more preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, the film formed can obtain sufficient transparency, and the sensitivity at the time of pattern formation also becomes favorable.
另外，亦可將「高分子添加劑的新進展」(日刊工業新聞社(股份))中所記載的各種紫外線吸收劑、或金屬鈍化劑等作為抗氧化劑以外的添加劑，添加至本發明的感光性樹脂組成物中。 In addition, various ultraviolet absorbers, metal passivators, and the like described in "New Development of Polymer Additives" (Japanese Journal of Industry News, Inc.) may be added as additives other than antioxidants to the photosensitivity of the present invention. In the resin composition.
(成分K)增感劑 (ingredient K) sensitizer
本發明的感光性樹脂組成物較佳為在與(成分B)光酸產生劑的組合中含有增感劑，以促進光酸產生劑的分解。增感劑吸收光化射線或放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，而產生電子移動、能量移動、發熱等作用。藉此，光酸產生劑產生化學變化而分解，並生成酸。作為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的波長區域的任一者中具有吸收波長的化合物。 The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the (component B) photoacid generator to promote decomposition of the photoacid generator. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. 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 generates a chemical change to decompose and generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of wavelength regions of 350 nm to 450 nm.
多核芳香族類(例如芘、苝、聯伸三苯、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)、二苯并哌喃(xanthene)類(例如螢光黃(fluorescein)、曙紅、赤藻紅(erythrosine)、玫瑰紅B(Rhodamine B)、孟加拉玫紅(Rose Bengal))、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(rodacyanine)類、氧雜菁類、噻嗪類(例如噻嚀、亞甲藍、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)、方酸內鎓鹽類(例如方酸內鎓鹽)、苯乙烯基類、鹼性苯乙烯基類(例如2-{2-[4-(二甲胺基)苯基]乙烯基}苯并噁唑)、香豆素類(例如7-二乙胺基-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]苯并吡喃並[6,7,8-ij]喹嗪-11-酮)。 Polynuclear aromatics (eg, ruthenium, osmium, tert-triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Dipropoxyfluorene), xanthene (eg, fluorescein, eosin, erythrosine, Rhodamine B, Rose Bengal) ), xanthone (such as xanthone, thioxanthone, dimethylthiazinone, diethyl thianonanone), cyanine (such as thiacarbocyanine, oxacarbonyl) Cyanine), merocyanines (eg, merocyanine, carbocyanine), rodacyanine, oxophthalenes, thiazides (eg, thiazide, methylene blue, toluidine blue), Acridines (eg acridine orange, chloroflavin, acriflavine), acridone (eg acridone, 10-butyl-2-chloroacridone), anthraquinones (eg hydrazine) , succinic acid ylide (such as squaric acid ylide), styryl, basic styrenic (such as 2-{2-[4-(dimethylamino)phenyl]vinyl}benzene And oxazole), coumarins (eg 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-9 -methyl-1H, 5H, 11 H[1]benzopyrano[6,7,8-ij]quinolizin-11-one).
該些增感劑之中，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。多核芳香族類之中，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.
相對於感光性樹脂組成物的光酸產生劑100質量份，本發明的感光性樹脂組成物中的增感劑的添加量較佳為0質量份~1,000質量份，更佳為10質量份~500質量份，進而更佳為50質量份~200質量份。 The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably from 0 part by mass to 1,000 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the photoacid generator of the photosensitive resin composition. 500 parts by mass, and more preferably 50 parts by mass to 200 parts by mass.
另外，增感劑可單獨使用1種，亦可併用2種以上。 Further, the sensitizer may be used alone or in combination of two or more.
(成分L)烷氧基矽烷化合物 (Component L) alkoxydecane compound
本發明的感光性樹脂組成物可含有(成分L)烷氧基矽烷化合物。若使用烷氧基矽烷化合物，則可提昇由本發明的感光性樹脂組成物所形成的膜與基板的密著性、或可調整由本發明的感光性樹脂組成物所形成的膜的性質。可用於本發明的感光性樹脂組成物的(成分L)烷氧基矽烷化合物較佳為提昇成為基材的無機物(例如矽、氧化矽、氮化矽等矽化合物，金、銅、鉬、鈦、鋁等金屬)與絕緣膜的密著性的化合物。具體而言，公知的矽烷偶合劑等亦有效。 The photosensitive resin composition of the present invention may contain (component L) alkoxydecane compound. When an alkoxy decane compound is used, the adhesion of the film formed by the photosensitive resin composition of this invention to a board|substrate, or the film of the photosensitive resin composition of this invention can be adjusted. The (component L) alkoxydecane compound which can be used in the photosensitive resin composition of the present invention is preferably an inorganic substance which is promoted as a substrate (for example, an antimony compound such as antimony, cerium oxide or tantalum nitride, gold, copper, molybdenum or titanium). A compound such as a metal such as aluminum or the like which is in close contact with an insulating film. Specifically, a known decane coupling agent or the like is also effective.
作為矽烷偶合劑，例如可列舉：γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三烷氧基矽烷、γ-縮水甘油氧基丙基烷基二烷氧基矽烷、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧基丙基烷基二烷氧基矽烷、γ-氯丙基三烷氧基矽烷、γ-巰基丙基三烷氧基矽烷、β-(3,4-環氧環己基)乙基 三烷氧基矽烷、乙烯基三烷氧基矽烷。該些之中，更佳為γ-縮水甘油氧基丙基三烷氧基矽烷或γ-甲基丙烯醯氧基丙基三烷氧基矽烷，進而更佳為γ-縮水甘油氧基丙基三烷氧基矽烷，特佳為3-縮水甘油氧基丙基三甲氧基矽烷。該些矽烷偶合劑可單獨使用1種、或將2種以上組合使用。 Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidol. Oxypropyl propyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl Trilutoxy decane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyl Trialkoxydecane, vinyl trialkoxydecane. More preferably, it is γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and more preferably γ-glycidoxypropyl. Trialkoxydecane, particularly preferably 3-glycidoxypropyltrimethoxydecane. These decane coupling agents may be used alone or in combination of two or more.
另外，亦可較佳地採用由下述式所表示的化合物。 Further, a compound represented by the following formula can also be preferably used.
(R1)4-n-Si-(OR2)n (R 1 ) 4-n -Si-(OR 2 ) n
式中，R1為不具有反應性基的碳數為1~20的烴基，R2為碳數為1~3的烷基或苯基，n為1~3的整數。再者，當n為2或3時，存在多個的R2彼此可相同，亦可不同，但就合成上的觀點而言，較佳為相同。另外，當n為1或2時，存在多個的R1彼此可相同，亦可不同，但就合成上的觀點而言，較佳為相同。 In the formula, R 1 is a hydrocarbon group having 1 to 20 carbon atoms which does not have a reactive group, R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3. Further, when n is 2 or 3, a plurality of R 2 's may be the same or different from each other, but from the viewpoint of synthesis, they are preferably the same. Further, when n is 1 or 2, a plurality of R 1 's may be the same or different from each other, but from the viewpoint of synthesis, they are preferably the same.
作為具體例，可列舉以下的化合物。再者，Ph表示苯基。 Specific examples thereof include the following compounds. Further, Ph represents a phenyl group.
[化22]
[化23]
本發明的感光性樹脂組成物中的(成分L)烷氧基矽烷化合物並不特別限定於該些烷氧基矽烷化合物，可使用公知的烷氧基矽烷化合物。 The (component L) alkoxydecane compound in the photosensitive resin composition of the present invention is not particularly limited to the alkoxydecane compounds, and a known alkoxydecane compound can be used.
相對於感光性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烷氧基矽烷化合物的含量較佳為0.1質量份~30質量份，更佳為0.5質量份~20質量份。 The content of the alkoxydecane compound in the photosensitive resin composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably 0.5 part by mass, per 100 parts by mass of the total solid content of the photosensitive composition. 20 parts by mass.
(成分M)鹼性化合物 (ingredient M) basic compound
本發明的感光性樹脂組成物可含有(成分M)鹼性化合物。作為(成分M)鹼性化合物，可自化學增幅抗蝕劑中所使用的鹼性化合物中任意地選擇來使用。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。作為該些的具體例，可列舉日本專利特開2011-221494號公報的段落0204~段落0207中所記載的化合物。 The photosensitive resin composition of the present invention may contain (Component M) a basic compound. The (component M) basic compound can be arbitrarily selected from the basic compounds 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 the above include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-221494.
具體而言，作為脂肪族胺，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。 Specifically, examples of the aliphatic amine include trimethylamine and diethyl Amine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.
作為芳香族胺，例如可列舉：苯胺、苄基胺、N,N-二甲基苯胺、二苯基胺等。 Examples of the aromatic amine include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.
作為雜環式胺，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、菸鹼、菸鹼酸、菸鹼醯胺、喹啉、8-羥基喹啉(8-oxyquinoline)、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-methyl Basomomorpholine, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8 -Diazabicyclo[5.3.0]-7-undecene.
作為氫氧化四級銨，例如可列舉：氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四-正丁基銨、氫氧化四-正己基銨等。 Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
作為羧酸的四級銨鹽，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 the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
可用於本發明的鹼性化合物可單獨使用1種，亦可併用2種以上。 The basic compound which can be used in the present invention may be used alone or in combination of two or more.
相對於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。 The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 part by mass to 3 parts by mass, more preferably 0.005 part by mass to 1 part by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. Parts by mass.
(成分N)其他界面活性劑 (ingredient N) other surfactants
本發明的感光性樹脂組成物除上述成分F及成分G以外，可進而含有(成分N)其他界面活性劑。 The photosensitive resin composition of the present invention may further contain (Component N) another surfactant in addition to the above component F and component G.
作為(成分N)其他界面活性劑，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系界面活性劑。作為本發明的組成物中所使用的其他界面活性劑，例如可使用日本專利特開2012-88459號公報的段落0201~段落0205中所記載的界面活性劑、或日本專利特開2011-215580號公報的段落0185~段落0188中所記載的界面活性劑，該些記載可被編入至本申請案說明書中。 As the (component N) other surfactant, any of anionic, cationic, nonionic or amphoteric may be used, but a preferred surfactant is a nonionic surfactant. As the other surfactant to be used in the composition of the present invention, for example, the surfactant described in paragraph 0201 to paragraph 0205 of JP-A-2012-88459, or Japanese Patent Laid-Open No. 2011-215580 can be used. The surfactants described in paragraphs 0185 to 0188 of the publication can be incorporated into the specification of the present application.
作為非離子系界面活性劑的例子，可列舉：聚氧乙烯高級烷基醚類、聚氧乙烯二醇的高級脂肪酸二酯類。 Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers and higher fatty acid diesters of polyoxyethylene glycol.
其他界面活性劑可單獨使用1種、或將2種以上混合使用。 The other surfactants may be used alone or in combination of two or more.
於本發明的感光性樹脂組成部中，當將成分F的含量設為100質量份時，其他界面活性劑的含量較佳為未滿100質量份，更佳為未滿50質量份，進而更佳為未滿25質量份，特佳為未滿10質量份。 In the photosensitive resin component of the present invention, when the content of the component F is 100 parts by mass, the content of the other surfactant is preferably less than 100 parts by mass, more preferably less than 50 parts by mass, and further more Jia is less than 25 parts by mass, and particularly preferably less than 10 parts by mass.
[酸增殖劑] [acid proliferator]
為了提昇感度，本發明的感光性樹脂組成物可使用酸增殖劑。 In order to enhance the sensitivity, an acid proliferating agent can be used as the photosensitive resin composition of the present invention.
可用於本發明的酸增殖劑是可藉由酸觸媒反應而進一步產生酸並使反應系統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 multiplying 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 stably exists in the absence of an acid.
作為此種酸增殖劑的具體例，可列舉日本專利特開 2011-221494號公報的段落0226~段落0228中所記載的酸增殖劑，該內容可被編入至本申請案說明書中。 Specific examples of such an acid proliferating agent include Japanese Patent Laid-Open The acid multiplying agent described in paragraphs 0226 to 0228 of JP-A-2011-221494 can be incorporated into the specification of the present application.
就曝光部與未曝光部的溶解對比度的觀點而言，相對於光酸產生劑100質量份，將酸增殖劑於感光性組成物中的含量較佳為設為10質量份~1,000質量份，更佳為設為20質量份~500質量份。 The content of the acid-proliferating agent in the photosensitive composition is preferably from 10 parts by mass to 1,000 parts by mass based on 100 parts by mass of the photo-acid generator, from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. More preferably, it is set to 20 mass parts - 500 mass parts.
[顯影促進劑] [development 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.
作為顯影促進劑，可使用具有顯影促進效果的任意的化合物，但較佳為具有選自由羧基、酚性羥基、及伸烷氧基所組成的群組中的至少一種結構的化合物，更佳為具有羧基或酚性羥基的化合物，最佳為具有酚性羥基的化合物。 As the development accelerator, any compound having a development promoting effect can be used, but a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyloxy group is preferable, and more preferably The compound having a carboxyl group or a phenolic hydroxyl group is preferably a compound having a phenolic hydroxyl group.
作為顯影促進劑，可參考日本專利特開2012-042837號公報的段落0171~段落0172的記載，該內容可被編入至本申請案說明書中。 As a development accelerator, the description of paragraphs 0171 to 0172 of JP-A-2012-042837 can be referred to, and the content can be incorporated into the specification of the present application.
顯影促進劑可單獨使用1種，亦可併用2種以上。 The development accelerator may be used alone or in combination of two or more.
就感度與殘膜率的觀點而言，相對於感光性組成物的總固體成分100質量份，本發明的感光性樹脂組成物中的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。 From the viewpoint of the sensitivity and the residual film ratio, the amount of the development accelerator added to the photosensitive resin composition of the present invention is preferably from 0 to 30 mass% per 100 parts by mass of the total solid content of the photosensitive composition. The portion is more preferably 0.1 part by mass to 20 parts by mass, most preferably 0.5 part by mass to 10 parts by mass.
另外，顯影促進劑的分子量較佳為100~2,000，更佳為150~1,500，進而更佳為150~1,000。 Further, the molecular weight of the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, still more preferably from 150 to 1,000.
[塑化劑] [Plasticizer]
本發明的樹脂組成物可含有塑化劑。 The resin composition of the present invention may contain a plasticizer.
作為塑化劑，例如可列舉：鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、鄰苯二甲酸二-十二酯、聚乙二醇、甘油、二甲基甘油鄰苯二甲酸酯、酒石酸二丁酯、己二酸二辛酯、三乙醯基甘油等。 Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, di-dodecyl phthalate, polyethylene glycol, glycerin, and dimethyl glycerol phthalate. An acid ester, dibutyl tartrate, dioctyl adipate, triethylene glyceryl, and the like.
相對於成分A的含量100質量份，本發明的樹脂組成物中的塑化劑的含量較佳為0.1質量份~30質量份，更佳為1質量份~10質量份。 The content of the plasticizer in the resin composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 10 parts by mass, per 100 parts by mass of the component A.
另外，亦可使用日本專利特開2012-8223號公報的段落0120~段落0121中所記載的熱自由基產生劑、國際公開第2011/136074號中所記載的含氮化合物及熱酸產生劑作為其他添加劑，該些的內容可被編入至本申請案說明書中。 In addition, the thermal radical generating agent described in paragraph 0120 to paragraph 0121 of JP-A-2012-8223, and the nitrogen-containing compound and the thermal acid generator described in International Publication No. 2011/136074 can be used as the hot radical generating agent. Other additives, the contents of which can be incorporated into the specification of the present application.
<感光性樹脂組成物的製備方法> <Method for Preparing Photosensitive Resin Composition>
以規定的比例且以任意的方法將各成分混合，然後進行攪拌溶解來製備感光性樹脂組成物。例如，亦可事先使成分分別溶解於溶劑中而製成溶液後，以規定的比例將該些溶液混合來製備樹脂組成物。以上述方式製備的組成物溶液亦可於例如使用孔徑為0.2μm的過濾器等進行過濾後，供於使用。 The components are mixed at a predetermined ratio and in an arbitrary manner, and then stirred and dissolved to prepare a photosensitive resin composition. For example, the components may be prepared by dissolving the components in a solvent in advance to prepare a solution, and then mixing the solutions at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be used after being filtered, for example, using a filter having a pore size of 0.2 μm or the like.
再者，於本發明中，特佳為事先製備含有(成分C)金屬氧化物粒子、(成分D)溶劑、及(成分E)分散劑的金屬氧化物粒子分散物，然後添加金屬氧化物粒子分散物與成分A、成分D及成分F、以及任意的成分來製備感光性樹脂組成物。 Further, in the present invention, it is particularly preferred to prepare a metal oxide particle dispersion containing (Component C) metal oxide particles, (Component D) solvent, and (Component E) dispersant in advance, and then adding metal oxide particles. A photosensitive resin composition was prepared from the dispersion, component A, component D, and component F, and arbitrary components.
(硬化膜的製造方法) (Method for producing cured film)
其次，對本發明的硬化膜的製造方法進行說明。 Next, a method of producing the cured film of the present invention will be described.
本發明的硬化膜的製造方法較佳為包括以下的(1)~(5)的步驟。 The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1)將本發明的感光性樹脂組成物塗佈於基板上的塗佈步驟；(2)自所塗佈的樹脂組成物中去除溶劑的溶劑去除步驟；(3)利用光化射線將去除了溶劑的樹脂組成物曝光成圖案狀的曝光步驟；(4)利用水性顯影液對經曝光的樹脂組成物進行顯影的顯影步驟；以及(5)對經顯影的樹脂組成物進行熱處理的熱處理步驟。 (1) a coating step of applying the photosensitive resin composition of the present invention onto a substrate; (2) a solvent removing step of removing a solvent from the applied resin composition; (3) removing by using actinic rays a step of exposing the resin composition of the solvent to a pattern; (4) a developing step of developing the exposed resin composition with an aqueous developing solution; and (5) a heat treatment step of heat-treating the developed resin composition .
以下依次對各步驟進行說明。 Each step will be described in order below.
於(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。較佳為在將感光性樹樹脂組成物塗佈於基板上前進行鹼清洗或電漿清洗等基板的清洗，更佳為於基板清洗後進而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，感光性樹脂組成物對於基板的密著性提昇。作為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，例如可列舉事先使基板曝露於六甲基二矽氮烷蒸氣中的方法等。 In the coating step of (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. Preferably, the substrate is cleaned by a substrate such as alkali cleaning or plasma cleaning before the photosensitive resin composition is applied onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiazane after the substrate is cleaned. . By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is 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 in advance.
作為上述基板，可列舉：無機基板，樹脂，樹脂複合材料， ITO，Cu基板，聚對苯二甲酸乙二酯、三乙酸纖維素(Cellulose Triacetate，TAC)等的塑膠基板。 Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. ITO, Cu substrate, plastic substrate such as polyethylene terephthalate or Cellulose Triacetate (TAC).
作為無機基板，例如可列舉：玻璃，石英，矽酮，氮化矽，以及於如該些般的基板上蒸鍍鉬、鈦、鋁、銅等而成的複合基板。 Examples of the inorganic substrate include glass, quartz, anthrone, tantalum nitride, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on the substrate.
作為樹脂，可列舉包含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、降莰烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸樹脂、環氧樹脂、矽酮樹脂、離子聚合物樹脂、氰酸酯樹脂、交聯反丁烯二酸二酯樹脂、環狀聚烯烴、芳香族醚樹脂、順丁烯二醯亞胺-烯烴樹脂、纖維素、環硫樹脂(episulfide resin)等合成樹脂的基板。 Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and polyfluorene. , polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimide, polyamidimide, polyether phthalimide, polybenzoxazole, polyphenylene sulfide, Polycyclic olefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, crosslinked fumaric acid A substrate of a synthetic resin such as a diester resin, a cyclic polyolefin, an aromatic ether resin, a maleimide-olefin resin, a cellulose, or an episulfide resin.
該些基板直接以上述形態使用的情況少，通常為根據最終製品的形態，例如形成有如薄膜電晶體(Thin Film Transistor，TFT)元件般的多層積層構造的情況。 These substrates are used as they are in the above-described form, and it is usually a case where a multilayer laminated structure such as a thin film transistor (TFT) element is formed depending on the form of the final product.
該些之中，於本發明中，較佳為基板的表面的全部或一部分為選自由玻璃、SiO、ITO、IZO、金屬膜、及金屬氧化物膜所組成的群組中的至少1種，特佳為基板的表面的全部或一部分為ITO。 In the above, in the present invention, it is preferable that all or a part of the surface of the substrate is at least one selected from the group consisting of glass, SiO, ITO, IZO, a metal film, and a metal oxide film. It is particularly preferred that all or part of the surface of the substrate be ITO.
本發明者等人進行努力研究的結果，發現當基板的表面的全部或一部分為ITO(氧化銦錫，Indium Tin Oxide)時，ITO上的 顯影殘渣的產生特別顯著。本發明的感光性樹脂組成物具有即便當基板的表面的全部或一部分為ITO時，亦可抑制顯影殘渣的產生這一極其顯著的效果。 As a result of intensive studies, the inventors of the present invention found that when all or a part of the surface of the substrate is ITO (Indium Tin Oxide), it is on ITO. The generation of development residue is particularly remarkable. The photosensitive resin composition of the present invention has an extremely remarkable effect of suppressing the occurrence of development residue even when all or a part of the surface of the substrate is ITO.
朝基板上塗佈的方法並無特別限定，例如可使用：狹縫塗佈法、噴霧法、輥塗法、旋轉塗佈法、流延塗佈法、狹縫及旋轉(slit and spin)法等方法。進而，亦可應用如日本專利特開2009-145395號公報中所記載般的所謂的預濕(prewet)法。 The method of applying onto 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. And other methods. Further, a so-called prewet method as described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.
塗佈膜厚並無特別限定，能夠以對應於用途的膜厚進行塗佈，但較佳為於0.5μm~10μm的範圍內使用。 The coating film thickness is not particularly limited, and can be applied in a film thickness corresponding to the application, but is preferably used in the range of 0.5 μm to 10 μm.
於(2)的溶劑去除步驟中，較佳為藉由減壓(真空)及/或加熱而自所應用的上述膜中去除溶劑，從而於基板上形成乾燥塗膜。溶劑去除步驟的加熱條件較佳為於70℃~130℃下加熱30秒~300秒左右。當溫度與時間為上述範圍時，圖案的密著性良好、且亦可減少殘渣。 In the solvent removal step of (2), it is preferred to remove the solvent from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition of the solvent removal step is preferably from 70 ° C to 130 ° C for about 30 seconds to 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is good and the residue can be reduced.
於(3)的曝光步驟中，較佳為隔著具有規定的圖案的遮罩對設置有塗膜的基板照射光化射線。於該步驟中，光酸產生劑分解並產生酸。塗膜成分中所含有的酸分解性基因所產生的酸的觸媒作用而水解，從而生成酸基(例如羧基或酚性羥基)。 In the exposure step of (3), it is preferred that the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator decomposes and produces an acid. The acid generated by the acid-decomposable gene contained in the coating component is hydrolyzed to form an acid group (for example, a carboxyl group or a phenolic hydroxyl group).
作為利用光化射線的曝光光源，可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、LED光源、準分子雷射產生裝置等，可較佳地使用g射線(436nm)、i射線(365nm)、h射線(405nm)等具有波長300nm以上、450nm以下的波長的光化射線。 另外，視需要亦可通過如長波長截止濾波器、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。 As the exposure light source using actinic rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generating device, or the like can be used, and g-ray (436 nm) and i-ray (365 nm can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as h-ray (405 nm). Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.
作為曝光裝置，可使用鏡面投影對準曝光器(mirror projection aligner)，步進機，掃描器，近接式、接觸式、微透鏡陣列式、雷射曝光式等各種方式的曝光機。 As the exposure device, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity type, a contact type, a microlens array type, and a laser exposure type can be used.
於生成有酸觸媒的區域中，為了加快上述水解反應，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，可促進來自酸分解性基的羧基或酚性羥基的生成。進行PEB時的溫度較佳為30℃以上、130℃以下，更佳為40℃以上、110℃以下，特佳為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. The formation of a carboxyl group or a phenolic hydroxyl group derived from an acid-decomposable group can be promoted by PEB. The temperature at the time of PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 100° C. or lower.
但是，本發明中的酸分解性基由於酸分解的活化能低，容易因由曝光所產生的源自酸產生劑的酸而分解，並產生酸基(例如羧基或酚性羥基)，因此並非一定要進行PEB，亦可藉由顯影而形成正像(positive image)。 However, the acid-decomposable group in the present invention has low activation energy due to acid decomposition, is easily decomposed by an acid derived from an acid generator generated by exposure, and generates an acid group (for example, a carboxyl group or a phenolic hydroxyl group), and thus is not necessarily To perform PEB, a positive image can also be formed by development.
於(4)的顯影步驟中，較佳為使用鹼性顯影液對具有已游離的酸基(例如羧基或酚性羥基)的共聚物進行顯影。將包含具有容易溶解於鹼性顯影液中的酸基(例如羧基或酚性羥基)的樹脂組成物的曝光部區域去除，藉此形成正像。 In the developing step of (4), it is preferred to develop a copolymer having a free acid group (e.g., a carboxyl group or a phenolic hydroxyl group) using an alkaline developing solution. The exposed portion region containing the resin composition having an acid group (for example, a carboxyl group or a phenolic hydroxyl group) which is easily dissolved in the alkaline developing solution is removed, thereby forming a positive image.
較佳為於顯影步驟中所使用的顯影液中含有鹼性化合物。作為鹼性化合物，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、氫氧化膽鹼等氫氧化銨類；矽酸鈉、偏矽酸鈉等的水溶液。另外，亦可將向上述鹼類的水溶液中添加適量的甲醇或乙醇等水溶性有機溶劑或界面活性劑而成的水溶液用作顯影液。 It is preferred that the developer used in the developing step contains 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 or potassium carbonate; or an alkali metal such as sodium bicarbonate or potassium bicarbonate can be used. Bicarbonate; tetramethylammonium hydroxide, hydrogen tetraoxide Ammonium hydroxide such as ethylammonium or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkali may be used as the developing solution.
作為較佳的顯影液，可列舉：氫氧化四乙基銨的0.4質量%水溶液、0.5質量%水溶液、0.7質量%水溶液、或2.38質量%水溶液。 As a preferable developing solution, a 0.4 mass% aqueous solution of tetraethylammonium hydroxide, a 0.5 mass% aqueous solution, a 0.7 mass% aqueous solution, or a 2.38 mass% aqueous solution can be mentioned.
顯影液的pH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~500秒，另外，顯影的方法可為覆液法、浸漬法等任一種方法。顯影後，可進行30秒~300秒流水清洗，而形成所期望的圖案。 The development time is preferably from 30 seconds to 500 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 water for 30 seconds to 300 seconds to form a desired pattern.
於顯影後，亦可進行淋洗步驟。於淋洗步驟中，利用純水等清洗顯影後的基板，藉此將所附著的顯影液去除，並將顯影殘渣去除。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 substrate is washed with pure water or the like, whereby the adhered 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)的熱處理步驟(後烘烤)中，藉由對所獲得的正像進行加熱，而可使酸分解性基進行熱分解而生成酸基(例如羧基或酚性羥基)，並與交聯性基、交聯劑等進行交聯，藉此形成硬化膜。該加熱較佳為使用加熱板或烘箱等加熱裝置，於規定的溫度，例如180℃~250℃下，以規定的時間，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。藉由進行交聯反應，而可形成耐熱性、硬度等優異的保護膜或層間絕緣膜。另外，當進行加熱處理時，亦可於氮氣環境下進行，藉此提昇透明性。當使用塑膠基板時，較佳 為於80℃~140℃下進行5分鐘~120分鐘的加熱處理。 In the heat treatment step (post-baking) of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to form an acid group (for example, a carboxyl group or a phenolic hydroxyl group), and A crosslinkable group, a crosslinking agent, or the like is crosslinked to form a cured film. The heating is preferably performed by using 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. In the case of an oven, heat treatment is performed for 30 minutes to 120 minutes. By performing a crosslinking reaction, a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. Further, when the heat treatment is performed, it can also be carried out under a nitrogen atmosphere, thereby improving transparency. When using a plastic substrate, it is preferred It is heated at 80 ° C ~ 140 ° C for 5 minutes to 120 minutes.
亦可於熱處理步驟(後烘烤)前、以比較低的溫度進行烘烤後進行熱處理步驟(中間烘烤步驟的追加)。當進行中間烘烤時，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，亦可將中間烘烤、後烘烤分成3個階段以上的多階段來進行加熱。藉由此種中間烘烤、後烘烤的設計，可調整圖案的錐角。該些加熱可使用加熱板、烘箱、紅外線加熱器等公知的加熱方法。 The heat treatment step (addition of the intermediate baking step) may be performed after baking at a relatively low temperature before the heat treatment step (post-baking). When the intermediate baking is performed, 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. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. With this intermediate baking and post-baking design, the taper angle of the pattern can be adjusted. A known heating method such as a hot plate, an oven, or an infrared heater can be used for the heating.
再者，可於後烘烤之前，利用光化射線對形成有圖案的基板進行全面再曝光(後曝光)，然後進行後烘烤，藉此自存在於未曝光部分中的光酸產生劑產生酸，並使其作為促進交聯步驟的觸媒發揮功能，從而可促進膜的硬化反應。作為包含後曝光步驟時的較佳的曝光量，較佳為100mJ/cm2~3,000mJ/cm2，特佳為100mJ/cm2~500mJ/cm2。 Furthermore, the patterned substrate can be fully re-exposed (post-exposure) with actinic rays before post-baking, and then post-baked, whereby photoacid generators are present from the unexposed portions. The acid acts 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 100 mJ/cm 2 to 3,000 mJ/cm 2 , particularly preferably 100 mJ/cm 2 to 500 mJ/cm 2 .
進而，自本發明的感光性樹脂組成物所獲得的硬化膜亦可用作乾蝕刻抗蝕劑(dry etching resist)。當將藉由熱處理步驟進行熱硬化而獲得的硬化膜用作乾蝕刻抗蝕劑時，可進行灰化、電漿蝕刻、臭氧蝕刻等乾蝕刻處理作為蝕刻處理。 Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. When a cured film obtained by thermally hardening by a heat treatment step is used as a dry etching resist, a dry etching treatment such as ashing, plasma etching, or ozone etching may be performed as an etching treatment.
(硬化膜) (hardened film)
本發明的硬化膜是使本發明的感光性樹脂組成物硬化而獲得的硬化膜。 The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
本發明的硬化膜可適宜地用作層間絕緣膜。另外，本發明的 硬化膜較佳為藉由本發明的硬化膜的形成方法所獲得的硬化膜。 The cured film of the present invention can be suitably used as an interlayer insulating film. In addition, the present invention The cured film is preferably a cured film obtained by the method for forming a cured film of the present invention.
藉由本發明的感光性樹脂組成物，而可獲得絕緣性優異、即便於高溫下進行了烘烤時亦具有高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透明性，且硬化膜物性優異，因此對於有機EL顯示裝置或液晶顯示裝置的用途有用。 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 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 an organic EL display device or a liquid crystal display device.
(硬化物及其製造方法) (hardened material and its manufacturing method)
本發明的硬化物是使本發明的感光性樹脂組成物硬化而獲得的硬化物，如上所述，其形狀可不為膜，只要是任意的形狀即可。 The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention, and as described above, the shape may not be a film, and may be any shape.
本發明的硬化物的製造方法並無特別限制，但較佳為至少依次包括以下的步驟(a)~步驟(c)：(a)將本發明的感光性樹脂組成物塗佈於基板上的塗佈步驟；(b)自所塗佈的樹脂組成物中去除溶劑的溶劑去除步驟；以及(c)對去除了溶劑的樹脂組成物進行熱處理的熱處理步驟。 The method for producing the cured product of the present invention is not particularly limited, but preferably includes at least the following steps (a) to (c): (a) applying the photosensitive resin composition of the present invention onto a substrate a coating step; (b) a solvent removal step of removing the solvent from the applied resin composition; and (c) a heat treatment step of heat-treating the solvent-removed resin composition.
步驟(a)及步驟(b)的含義分別與上述塗佈步驟及上述溶劑去除步驟相同，較佳的形態亦相同。 The meanings of the steps (a) and (b) are the same as those of the coating step and the solvent removal step, respectively, and the preferred embodiments are also the same.
除進行熱處理的對象為藉由步驟(b)所獲得的去除了溶劑的樹脂組成物以外，步驟(c)為與上述熱處理步驟相同的步驟，上述熱處理步驟中的加熱溫度、加熱時間、加熱方法等的較佳的形態亦同樣較佳。 The step (c) is the same step as the above heat treatment step except for the resin composition from which the solvent is removed by the step (b), the heating temperature, the heating time, and the heating method in the heat treatment step. The preferred form of the same is also preferred.
本發明的硬化物或硬化膜可適宜地用作微透鏡、光波導、抗反射膜、LED用密封材及LED用晶片塗佈材等光學構件，或觸控面板中所使用的配線電極的視認性降低用硬化物。 The cured product or the cured film of the present invention can be suitably used as an optical member such as a microlens, an optical waveguide, an antireflection film, an LED sealing material, and a wafer coating material for LED, or a wiring electrode used in a touch panel. Reduce the hardness of the product.
另外，本發明的硬化物或硬化膜例如可適宜地用於如後所述的液晶顯示裝置或有機EL裝置等中的平坦化膜或層間絕緣膜、彩色濾光片的保護膜、用以將液晶顯示裝置中的液晶層的厚度保持為固定的間隔片、微機電系統(Micro Electro Mechanical Systems，MEMS)元件的構造構件等。 In addition, the cured product or the cured film of the present invention can be suitably used, for example, in a flattening film or an interlayer insulating film, a protective film of a color filter, or the like in a liquid crystal display device or an organic EL device as described later. The thickness of the liquid crystal layer in the liquid crystal display device is maintained as a fixed spacer, a structural member of a micro electro mechanical system (MEMS) device, or the like.
(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.
作為本發明的液晶顯示裝置，除具有使用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，可列舉採用各種構造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 structures can be cited.
例如，作為本發明的液晶顯示裝置所具備的TFT(Thin-Film Transistor)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特性優異，因此可與該些TFT組合後較佳地使用。 Specific examples of the TFT (Thin-Film Transistor) 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，作為本發明的液晶顯示裝置可採用的液晶驅動方式，可列舉：扭曲向列(Twisted Nematic，TN)方式、垂直配向(Vertical Alignment，VA)方式、面內切換(In-Plane-Switching，IPS)方式、邊緣場切換(Fringe Field Switching，FFS)方式、光學補償彎曲(Optically Compensated Bend，OCB)方式等。 Further, examples of the liquid crystal driving method which can be employed in 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 (In-Plane-Switching, IPS) mode, Fringe Field Switching (FFS) mode, Optically Compensated Bend (OCB) mode, etc.
於面板構成中，即便是彩色濾光片陣列(Color Filter on Array，COA)方式的液晶顯示裝置，亦可使用本發明的硬化膜，例如可用作日本專利特開2005-284291號公報中所記載的有機絕緣膜(115)、或日本專利特開2005-346054號公報中所記載的有機絕緣膜(212)。 In the panel structure, the cured film of the present invention can be used in a liquid crystal display device of a color filter on Array (COA) type, and can be used, for example, in Japanese Laid-Open Patent Publication No. 2005-284291. The organic insulating film (212) described in Japanese Laid-Open Patent Publication No. 2005-346054, or the organic insulating film (212).
另外，作為本發明的液晶顯示裝置可採用的液晶配向膜的具體的配向方式，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號公報中所記載的聚合物穩定配向(Polymer Sustained Alignment，PSA)技術而得到聚合物配向支撐。 In addition, as a specific alignment method of the liquid crystal alignment film which can be used for the liquid crystal display device of the present invention, a rubbing alignment method, a light alignment method, and the like can be given. Further, the polymer alignment support can be obtained 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並不限定於上述用途，可用於各種用途。例如，除平坦化膜或層間絕緣膜以外，亦可適宜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的厚度保持為固定的間隔片、或固體攝影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 which is suitably used for a color filter, or a spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device to be fixed, or a solid-state imaging element A microlens or the like disposed on a color filter.
圖1是表示主動矩陣方式的液晶顯示裝置10的一例的概念剖面圖。該彩色液晶顯示裝置10為背面具有背光單元12的液晶面板，液晶面板配置有與配置在貼附有偏光膜的2片玻璃基板14、玻璃基板15之間的所有畫素相對應的TFT16的元件。在形成於玻璃基板上的各元件中，藉由形成於硬化膜17中的接觸孔18而配線有形成畫素電極的ITO透明電極19。於ITO透明電極19上設置有液晶20的層、及配置有黑色矩陣的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 the liquid crystal panel is provided with elements of the TFT 16 corresponding to all the pixels disposed between the two glass substrates 14 and the glass substrate 15 to which the polarizing film is attached. . Among the elements formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired by a contact hole 18 formed in the cured film 17. a layer in which the liquid crystal 20 is provided on the ITO transparent electrode 19, and an RGB color filter in which a black matrix is disposed twenty two.
作為背光源的光源，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 as the backlight is not particularly limited, and a known light source can be used. For example, white LED, blue. red. Multicolor LEDs such as green, fluorescent lamps (cold cathode tubes), organic EL, etc.
另外，液晶顯示裝置亦可製成3D(立體視)型的裝置、或觸控面板型的裝置。進而，亦可設定成可撓型，並可用作日本專利特開2011-145686號公報中所記載的第2相間絕緣膜(48)、或日本專利特開2009-258758號公報中所記載的相間絕緣膜(520)。 Further, the liquid crystal display device can also be a 3D (stereoscopic) type device or a touch panel type device. Further, it can be set to a flexible type, and can be used as the second interphase insulating film (48) described in Japanese Laid-Open Patent Publication No. 2011-145686, or as described in Japanese Laid-Open Patent Publication No. 2009-258758. Interphase insulating film (520).
(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.
作為本發明的有機EL顯示裝置，除具有使用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，可列舉採用各種構造的公知的各種有機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 structures are exemplified. Or a liquid crystal display device.
例如，作為本發明的有機EL顯示裝置所具備的TFT(Thin-Film Transistor)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特性優異，因此可與該些TFT組合後較佳地使用。 Specific examples of the TFT (Thin-Film Transistor) included in the organic EL 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.
圖2是有機EL顯示裝置的一例的構成概念圖。表示底部發光型的有機EL顯示裝置中的基板的示意剖面圖，且具有平坦化膜4。 FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and having a planarization film 4.
於玻璃基板6上形成底閘極型的TFT1，並在覆蓋該TFT1的 狀態下形成包含Si3N4的絕緣膜3。於絕緣膜3上形成此處省略了圖示的接觸孔後，經由該接觸孔而在絕緣膜3上形成連接於TFT1的配線2(高度為1.0μm)。配線2是用以將TFT1間、或將其後的步驟中形成的有機EL元件與TFT1加以連接的線。 A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si 3 N 4 is formed in a state of covering the TFT 1. After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.
進而，為了使由配線2的形成所產生的凹凸平坦化，於埋入由配線2所產生的凹凸的狀態下，在絕緣膜3上形成平坦化層4。 Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.
於平坦化膜4上形成底部發光型的有機EL元件。即，使包含ITO的第一電極5經由接觸孔7連接於配線2而形成在平坦化膜4上。另外，第一電極5相當於有機EL元件的陽極。 A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Further, the first electrode 5 corresponds to the anode of the organic EL element.
形成覆蓋第一電極5的周緣的形狀的絕緣膜8，藉由設置該絕緣膜8，可防止第一電極5與其後的步驟中所形成的第二電極之間的短路。 The insulating film 8 having a shape covering the periphery 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，雖然圖2中未圖示，但隔著所期望的圖案遮罩而依次進行蒸鍍來設置電洞傳輸層、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，然後藉由使用紫外線硬化型環氧樹脂而與密封用玻璃板進行貼合來密封，而獲得於各有機EL元件上連接用以對其進行驅動的TFT1而成的主動矩陣型的有機EL顯示裝置。 Further, although not shown in FIG. 2, the hole transport layer, the organic light-emitting layer, and the electron transport layer are sequentially formed by vapor deposition through a desired pattern mask, and then formed on the entire upper surface of the substrate. The second electrode of Al is sealed by bonding with a glass plate for sealing by using an ultraviolet curable epoxy resin, and an active matrix obtained by connecting TFT1 for driving the organic EL elements to be driven is obtained. Type organic EL display device.
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，因此將使用本發明的感光性樹脂組成物所形成的抗蝕劑圖案製成隔離壁來作為MEMS元件的構造構件、或作為機械驅動零件的一部分加以組裝後使用。作為此種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、陀螺儀感測器(gyro sensor)、顯示器用微快門、影像感測器、電子紙、噴墨頭、生物晶片、密封劑等零件。更具體的例子於日本專利特表2007-522531號公報、日本專利特開2008-250200號公報、日本專利特開2009-263544號公報等中有例示。 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 partition wall as a structural member of a MEMS element or as a mechanical member. A part of the drive parts is assembled and used. As such a component for MEMS, for example, List: Surface Acoustic Wave (SAW) filter, Bulk Acoustic Wave (BAW) filter, gyro sensor, micro-shutter for display, image sensor, electronic paper, spray Ink heads, biochips, sealants and other parts. More specific examples are exemplified in Japanese Patent Laid-Open Publication No. 2007-522531, Japanese Patent Laid-Open Publication No. 2008-250200, and Japanese Patent Laid-Open No. 2009-263544.
本發明的感光性樹脂組成物由於平坦性或透明性優異，因此亦可用於形成例如日本專利特開2011-107476號公報的圖2中所記載的堆積層(16)及平坦化膜(57)、日本專利特開2010-9793號公報的圖4(a)中所記載的隔離壁(12)及平坦化膜(102)、日本專利特開2010-27591號公報的圖10中所記載的堆積層(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)中所記載的第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中所記載的平坦化膜(12)及畫素分離絕緣膜(14)等。 The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used to form a buildup layer (16) and a planarization film (57) as 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 stacking shown in Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The layer (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 The planarizing film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.
另外，本發明的感光性樹脂組成物由於透明性或折射率優異，因此適宜用作微透鏡或稜鏡用的構件、光導出用的構件。例如可用作顯示器用的平板的背光單元中所使用的稜鏡用的構件、或稜鏡與導光板的接合用的構件。另外，例如亦可用作有機EL顯示器的光導出效率的改善用的構件。 Further, since the photosensitive resin composition of the present invention is excellent in transparency and refractive index, it is suitably used as a member for microlenses or enamel, and a member for light extraction. For example, it can be used as a member for use in a backlight unit of a flat panel for a display, or a member for bonding a crucible and a light guide plate. Further, for example, it can also be used as a member for improving the light extraction efficiency of an organic EL display.
(觸控面板顯示裝置) (touch panel display device)
本發明的觸控面板顯示裝置具有使本發明的感光性樹脂組成 物硬化而成的硬化物。另外，本發明的觸控面板具有使本發明的感光性樹脂組成物硬化而成的硬化物。 The touch panel display device of the present invention has a photosensitive resin composition of the present invention A hardened material that hardens. Further, the touch panel of the present invention has a cured product obtained by curing the photosensitive resin composition of the present invention.
本發明的靜電電容型輸入裝置的特徵在於具有使本發明的本發明的感光性樹脂組成物硬化而成的硬化物。 The capacitance type input device of the present invention is characterized by having a cured product obtained by curing the photosensitive resin composition of the present invention.
本發明的靜電電容型輸入裝置較佳為具有前面板，並於上述前面板的非接觸側至少具有下述(1)~下述(5)的要素，且下述(4)為本發明的熱處理物。 The capacitance type input device of the present invention preferably has a front panel, and has at least the following elements (1) to (5) on the non-contact side of the front panel, and the following (4) is the present invention. Heat treated material.
(1)遮罩層 (1) mask layer
(2)多個墊部分經由連接部分而於第一方向上延伸所形成的多個第一透明電極圖案 (2) a plurality of first transparent electrode patterns formed by the plurality of pad portions extending in the first direction via the connection portion
(3)與上述第一透明電極圖案電性絕緣、且包含在與上述第一方向交叉的方向上延伸所形成的多個墊部分的多個第二透明電極圖案 (3) a plurality of second transparent electrode patterns electrically insulated from the first transparent electrode pattern and including a plurality of pad portions formed to extend in a direction crossing the first direction
(4)將上述第一透明電極圖案與上述第二透明電極圖案電性絕緣的絕緣層 (4) an insulating layer electrically insulating the first transparent electrode pattern from the second transparent electrode pattern
(5)與上述第一透明電極圖案及上述第二透明電極圖案的至少一者電性連接、且與上述第一透明電極圖案及上述第二透明電極圖案不同的導電性要素(conductive element) (5) a conductive element that is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and that is different from the first transparent electrode pattern and the second transparent electrode pattern
本發明的靜電電容型輸入裝置較佳為以覆蓋上述(1)~上述(5)的要素的全部或一部分的方式進而設置透明保護層，更佳為上述透明保護層為本發明的硬化膜。 The capacitance type input device of the present invention preferably further includes a transparent protective layer so as to cover all or a part of the elements (1) to (5), and more preferably the transparent protective layer is a cured film of the present invention.
首先，對靜電電容型輸入裝置的構成進行說明。圖3是 表示靜電電容型輸入裝置的構成的剖面圖。於圖3中，靜電電容型輸入裝置30包括：前面板31、遮罩層32、第一透明電極圖案33、第二透明電極圖案34、絕緣層35、導電性要素36、及透明保護層37。 First, the configuration of the capacitance type input device will be described. Figure 3 is A cross-sectional view showing the configuration of a capacitive input device. In FIG. 3, the capacitive input device 30 includes a front panel 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, a conductive element 36, and a transparent protective layer 37. .
前面板31由玻璃基板等透光性基板構成，可使用以康寧(Corning)公司的大猩猩玻璃(Gorilla Glass)為代表的強化玻璃等。另外，於圖3中，將前面板31的設置有各要素之側稱為非接觸面。於本發明的靜電電容型輸入裝置30中，使手指等與前面板31的接觸面(非接觸面的相反面)接觸等來進行輸入。以下，有時將前面板稱為「基材」。 The front panel 31 is made of a light-transmissive substrate such as a glass substrate, and tempered glass such as Gorilla Glass of Corning Co., Ltd. can be used. In addition, in FIG. 3, the side of the front panel 31 in which each element is provided is called a non-contact surface. In the capacitance type input device 30 of the present invention, a finger or the like is brought into contact with a contact surface (opposite surface of the non-contact surface) of the front panel 31, and the like. Hereinafter, the front panel may be referred to as a "substrate".
另外，於前面板31的非接觸面上設置有遮罩層32。遮罩層32是形成於觸控面板前面板的非接觸側的顯示區域周圍的邊框狀的圖案，其為了使引線等不被看到而形成。 Further, a mask layer 32 is provided on the non-contact surface of the front panel 31. The mask layer 32 is a frame-like pattern formed around the display area on the non-contact side of the front panel of the touch panel, and is formed in order to prevent the lead wires or the like from being seen.
於本發明的靜電電容型輸入裝置中，如圖4所示，以覆蓋前面板31的一部分的區域(圖4中輸入面以外的區域)的方式設置有遮罩層32。進而，於前面板31中，如圖4所示，可於一部分中設置開口部38。於開口部38中，可設置利用按壓的機械式開關。 In the capacitance type input device of the present invention, as shown in FIG. 4, the mask layer 32 is provided so as to cover a portion of the front panel 31 (a region other than the input surface in FIG. 4). Further, in the front panel 31, as shown in FIG. 4, the opening 38 may be provided in a part. In the opening 38, a mechanical switch that uses pressing can be provided.
如圖5所示，於前面板31的接觸面上形成有多個第一透明電極圖案33、多個第二透明電極圖案34、及絕緣層35，上述多個第一透明電極圖案33是多個墊部分經由連接部分而於第一方向上延伸所形成者，上述多個第二透明電極圖案34是與第一透明電極圖案33電性絕緣、且包含在與第一方向交叉的方向上延伸所 形成的多個墊部分者，上述絕緣層35是使第一透明電極圖案33與第二透明電極圖案34電性絕緣者。上述第一透明電極圖案33、第二透明電極圖案34、及後述的導電性要素36例如可藉由ITO(Indium Tin Oxide)或IZO(Indium Zinc Oxide)等透光性的導電性金屬氧化膜來製作。作為此種金屬膜，可列舉：ITO膜；Al、Zn、Cu、Fe、Ni、Cr、Mo等的金屬膜；SiO2等的金屬氧化膜等。此時，各要素的膜厚可設為10nm~200nm。另外，因藉由煅燒來使非晶的ITO膜變成多晶的ITO膜，故亦可減少電阻。另外，上述第一透明電極圖案33、第二透明電極圖案34、及後述的導電性要素36亦可使用感光性轉印材料來製造，該感光性轉印材料具有使用上述導電性纖維的感光性樹脂組成物。此外，當藉由ITO等來形成第一導電性圖案等時，可參考日本專利第4506785號公報的段落0014~段落0016等。 As shown in FIG. 5, a plurality of first transparent electrode patterns 33, a plurality of second transparent electrode patterns 34, and an insulating layer 35 are formed on the contact surface of the front panel 31, and the plurality of first transparent electrode patterns 33 are The pad portion is formed to extend in the first direction via the connecting portion, the plurality of second transparent electrode patterns 34 being electrically insulated from the first transparent electrode pattern 33 and extending in a direction crossing the first direction In the plurality of pad portions formed, the insulating layer 35 electrically insulates the first transparent electrode pattern 33 from the second transparent electrode pattern 34. The first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later can be, for example, a translucent conductive metal oxide film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide). Production. Examples of such a metal film include an ITO film; a metal film of Al, Zn, Cu, Fe, Ni, Cr, Mo, or the like; a metal oxide film of SiO 2 or the like. In this case, the film thickness of each element can be set to 10 nm to 200 nm. Further, since the amorphous ITO film is formed into a polycrystalline ITO film by firing, the electric resistance can be reduced. Further, the first transparent electrode pattern 33, the second transparent electrode pattern 34, and a conductive element 36 to be described later may be produced using a photosensitive transfer material having photosensitivity using the above-mentioned conductive fiber. Resin composition. Further, when the first conductive pattern or the like is formed by ITO or the like, reference is made to paragraphs 0014 to 0016 of Japanese Patent No. 4,506,785 and the like.
另外，第一透明電極圖案33及第二透明電極圖案34的至少一者可橫跨前面板31的非接觸面、及遮罩層32的與前面板31為相反側的面這兩個區域來設置。於圖3中，表示第二透明電極圖案橫跨前面板31的非接觸面、及遮罩層32的與前面板31為相反側的面這兩個區域來設置的圖。 Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 may extend across the non-contact surface of the front panel 31 and the surface of the mask layer 32 opposite to the front panel 31. Settings. FIG. 3 shows a view in which the second transparent electrode pattern is provided across the non-contact surface of the front panel 31 and the surface of the mask layer 32 opposite to the front panel 31.
使用圖5對第一透明電極圖案33及第二透明電極圖案34進行說明。圖5是表示本發明中的第一透明電極圖案及第二透明電極圖案的一例的說明圖。如圖5所示，第一透明電極圖案33是墊部分33a經由連接部分33b而於第一方向上延伸來形成。另 外，第二透明電極圖案34藉由絕緣層35而與第一透明電極圖案33電性絕緣、且包含在與第一方向交叉的方向(圖5中的第二方向)上延伸所形成的多個墊部分。此處，當形成第一透明電極圖案33時，可將上述墊部分33a與連接部分33b作為一體來製作，亦可僅製作連接部分33b，而將墊部分33a與第二透明電極圖案34作為一體來製作(圖案化)。當將墊部分33a與第二透明電極圖案34作為一體來製作(圖案化)時，如圖5所示，以如下方式形成各層：連接部分33b的一部分與墊部分33a的一部分相連結、且第一透明電極圖案33與第二透明電極圖案34藉由絕緣層35而電性絕緣。 The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. 5. FIG. 5 is an explanatory view showing an example of a first transparent electrode pattern and a second transparent electrode pattern in the present invention. As shown in FIG. 5, the first transparent electrode pattern 33 is formed by the pad portion 33a extending in the first direction via the connection portion 33b. another In addition, the second transparent electrode pattern 34 is electrically insulated from the first transparent electrode pattern 33 by the insulating layer 35, and is formed by extending in a direction crossing the first direction (the second direction in FIG. 5). Pad part. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be integrally formed, or only the connection portion 33b may be formed, and the pad portion 33a and the second transparent electrode pattern 34 may be integrated. To make (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, each layer is formed in such a manner that a part of the connection portion 33b is connected to a part of the pad portion 33a, and The transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by the insulating layer 35.
於圖3中，在遮罩層32的與前面板31為相反側的面側設置有導電性要素36。導電性要素36是與第一透明電極圖案33及第二透明電極圖案34的至少一者電性連接、且與第一透明電極圖案33及第二透明電極圖案34不同的要素。於圖3中，表示導電性要素36與第二透明電極圖案34連接的圖。 In FIG. 3, the conductive element 36 is provided on the surface side of the mask layer 32 opposite to the front panel 31. The conductive element 36 is an element that is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 and that is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34 . FIG. 3 shows a diagram in which the conductive element 36 is connected to the second transparent electrode pattern 34.
另外，於圖3中，以將各構成要素全部覆蓋的方式設置有透明保護層37。透明保護層37能夠以僅覆蓋各構成要素的一部分的方式構成。絕緣層35與透明保護層37可為相同的材料，亦可為不同的材料。 In addition, in FIG. 3, the transparent protective layer 37 is provided so that all the components may be covered. The transparent protective layer 37 can be configured to cover only a part of each constituent element. The insulating layer 35 and the transparent protective layer 37 may be the same material or different materials.
<靜電電容型輸入裝置、及具備靜電電容型輸入裝置的觸控面板顯示裝置> <Electrostatic capacitance type input device and touch panel display device including capacitance type input device>
藉由本發明的製造方法所獲得的靜電電容型輸入裝置、及具 備該靜電電容型輸入裝置作為構成要素的觸控面板顯示裝置可應用「最新觸控面板技術」(2009年7月6日發行，技術時代(Techno Times)(股份))、三谷雄二監修，「觸控面板的技術與開發」、CMC出版(2004,12)，平板顯示器國際論壇2009(FPD International 2009 Forum)T-11講演教材，賽普拉斯半導體公司(Cypress Semiconductor Corporation)應用指南AN2292等中所揭示的構成。 Electrostatic capacitance type input device and device obtained by the manufacturing method of the present invention The touch panel display device with the capacitive input device as a component can be applied with "the latest touch panel technology" (released on July 6, 2009, Techno Times (share)), and repaired by Mitani Yuji. Touch panel technology and development", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 lecture materials, Cypress Semiconductor Corporation application guide AN2292, etc. The disclosed composition.
<觸控面板及其製造方法> <Touch panel and method of manufacturing the same>
本發明的觸控面板是絕緣層的全部或一部分包含本發明的樹脂組成物的熱處理物(硬化物)的觸控面板。另外，本發明的觸控面板較佳為至少具有透明基板、ITO電極及絕緣層。 The touch panel of the present invention is a touch panel in which all or a part of the insulating layer contains a heat-treated product (cured material) of the resin composition of the present invention. Further, the touch panel of the present invention preferably has at least a transparent substrate, an ITO electrode, and an insulating layer.
本發明的觸控面板顯示裝置較佳為具有本發明的觸控面板的觸控面板顯示裝置。 The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.
另外，本發明的觸控面板的製造方法是具有透明基板、ITO電極及絕緣層的觸控面板的製造方法，較佳為包括如下步驟：以與ITO電極接觸的方式，利用噴墨塗佈方式塗佈本發明的噴墨塗佈用感光性樹脂組成物的步驟；於上述樹脂組成物上載置具有規定形狀的開口圖案的遮罩、且進行活性能量線照射來進行曝光的步驟；對曝光後的樹脂組成物進行顯影的步驟；以及對顯影後的樹脂組成物進行加熱來製造絕緣層的步驟。 In addition, the method for manufacturing a touch panel of the present invention is a method for manufacturing a touch panel having a transparent substrate, an ITO electrode, and an insulating layer, and preferably includes the following steps: using an inkjet coating method in contact with the ITO electrode a step of applying the photosensitive resin composition for inkjet coating of the present invention; a step of depositing a mask having an opening pattern having a predetermined shape on the resin composition, and performing exposure with an active energy ray; and performing exposure a step of developing the resin composition; and heating the resin composition after development to produce an insulating layer.
作為本發明的觸控面板中的透明基板，可較佳地列舉：玻璃基板、石英基板、透明樹脂基板等。 The transparent substrate in the touch panel of the present invention may preferably be a glass substrate, a quartz substrate, a transparent resin substrate or the like.
上述以與ITO電極接觸的方式，利用噴墨塗佈方式塗佈本發 明的噴墨塗佈用感光性樹脂組成物的步驟中的噴墨塗佈可與上述塗佈步驟同樣地進行，較佳的形態亦相同。另外，於上述步驟中，只要所塗佈的本發明的感光性樹脂組成物的至少一部分與ITO電極接觸即可。 The above method is applied by inkjet coating in such a manner as to be in contact with the ITO electrode. The inkjet coating in the step of the photosensitive resin composition for inkjet coating can be carried out in the same manner as the above-described coating step, and the preferred embodiment is also the same. Further, in the above step, at least a part of the applied photosensitive resin composition of the present invention may be brought into contact with the ITO electrode.
上述於樹脂組成物上載置具有規定形狀的開口圖案的遮罩、且進行活性能量線照射來進行曝光的步驟，對曝光後的樹脂組成物進行顯影的步驟可與上述曝光步驟同樣地進行，較佳的形態亦相同。 In the step of depositing a mask having an opening pattern having a predetermined shape on the resin composition and performing exposure by active energy ray irradiation, the step of developing the exposed resin composition may be performed in the same manner as the above-described exposure step. The best form is the same.
上述對顯影後的樹脂組成物進行加熱來製造絕緣層的步驟可與上述熱處理步驟同樣地進行，較佳的形態亦相同。 The step of heating the resin composition after development to produce an insulating layer can be carried out in the same manner as the above-described heat treatment step, and the preferred embodiment is also the same.
另外，作為本發明的觸控面板中的ITO電極圖案的一例，可較佳地列舉上述圖5所示的圖案。 Moreover, as an example of the ITO electrode pattern in the touch panel of the present invention, the pattern shown in FIG. 5 described above can be preferably used.
[實施例] [Examples]
以下，列舉實施例來更具體地說明本發明。只要不脫離本發明的主旨，則以下的實施例中所示的材料、使用量、比例、處理內容、處理程序等可適宜變更。因此，本發明的範圍並不限定於以下所示的具體例。再者，只要事先無特別說明，則「份」、「%」為質量基準。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.
於以下的合成例及實施例中，以下的符號分別表示以下的化合物。 In the following synthesis examples and examples, the following symbols represent the following compounds, respectively.
MATHF：甲基丙烯酸四氫呋喃-2-基酯(合成品) MATHF: tetrahydrofuran-2-yl methacrylate (synthetic)
MAEVE：甲基丙烯酸1-乙氧基乙酯(和光純藥工業(股份) 製造) MAEVE: 1-ethoxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.) Manufacturing)
MACHOE：甲基丙烯酸1-(環己氧基)乙酯(合成品) MACHOE: 1-(cyclohexyloxy)ethyl methacrylate (synthetic)
MATHP：甲基丙烯酸四氫-2H-吡喃-2-基酯(新中村化學工業(股份)製造) MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
GMA：甲基丙烯酸縮水甘油酯(和光純藥工業(股份)製造) GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30：甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯(大阪有機化學工業(股份)製造) OXE-30: (3-ethyloxetane-3-yl)methyl methacrylate (Manufactured by Osaka Organic Chemical Industry Co., Ltd.)
NBMA：正丁氧基甲基丙烯醯胺(三菱麗陽(股份)製造) NBMA: n-butoxymethyl acrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)
MAA：甲基丙烯酸(和光純藥工業(股份)製造) MAA: Methacrylic acid (made by Wako Pure Chemical Industries, Ltd.)
HEMA：甲基丙烯酸2-羥基乙酯(和光純藥工業(股份)製造) HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA：甲基丙烯酸甲酯(和光純藥工業(股份)製造) MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
St：苯乙烯(和光純藥工業(股份)製造) St: Styrene (made by Wako Pure Chemical Industries, Ltd.)
DCPM：甲基丙烯酸二環戊酯(日立化成工業(股份)製造) DCPM: Dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
V-601：二甲基-2,2'-偶氮雙(丙酸2-甲酯)(和光純藥工業(股份)製造) V-601: dimethyl-2,2'-azobis(2-methyl propionate) (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(股份)製造) V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
MEDG：二乙二醇乙基甲醚(東邦化學工業(股份)製造，Hisolve EDM) MEDG: Diethylene glycol ethyl methyl ether (Manufactured by Toho Chemical Industry Co., Ltd., Hisolve EDM)
PGMEA：乙酸甲氧基丙酯(昭和電工(股份)製造) PGMEA: methoxypropyl acetate (manufactured by Showa Denko (share))
EEP：3-乙氧基丙酸乙酯(三協化學(股份)製造) EEP: 3-ethoxypropionate ethyl ester (manufactured by Sanxie Chemical Co., Ltd.)
<MATHF的合成> <Synthesis of MATHF>
先將甲基丙烯酸(86g，1mol)冷卻至15℃，然後添加樟腦磺酸(4.6g，0.02mol)。向該溶液中滴加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)，並利用乙酸乙酯(500mL)進行萃取，利用硫酸鎂進行乾燥後，將不溶物過濾，然後於40℃以下進行減壓濃縮，對殘渣的黃色油狀物進行減壓蒸餾，而獲得作為無色油狀物的沸點(bp.)54℃~56℃/3.5mmHg餾分的甲基丙烯酸四氫呋喃-2-基酯(MATHF)125g(產率為80%)。 Methacrylic acid (86 g, 1 mol) was first cooled to 15 ° C, then 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, saturated sodium hydrogencarbonate (500 mL) was added, and extracted with ethyl acetate (500 mL). After drying over magnesium sulfate, the insolubles were filtered, and then concentrated under reduced pressure at 40 ° C or less. The yellow oil was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 ° C to 56 ° C / 3.5 mmHg as a colorless oil. %).
再者，除將2-二氫呋喃變更成相對應的化合物以外，以與上述MATHF相同的方法合成MACHOE。 Further, MACHOE was synthesized in the same manner as the above MATHF except that 2-dihydrofuran was changed to the corresponding compound.
[聚合物A-1的合成] [Synthesis of Polymer A-1]
向三口燒瓶中加入MEDG(89g)，於氮氣環境下升溫至90℃。歷時2小時向該溶液中滴加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100mol%，相當於4mol%)並使該些溶解。滴加結束後攪拌2小時，然後使反應結束。藉此獲得聚合物A-1。再者，將MEDG與其他成分的合計量的比設為70：30。即，製備固體成分濃度為30%的聚合物溶液。 MEDG (89 g) was added to a three-necked flask, and the mixture was heated to 90 ° C under a nitrogen atmosphere. MAA (amount of 9.5 mol% of all monomer components), MATHF (amount of 43 mol% of all monomer components), and GMA (corresponding to all monomer components) were added dropwise to the solution over 2 hours. 47.5 mol%), V-65 (100 mol% based on the total of all monomer components, equivalent to 4 mol%) and dissolved. After the completion of the dropwise addition, the mixture was stirred for 2 hours, and then the reaction was completed. Thereby, the polymer A-1 was obtained. Further, the ratio of the total amount of MEDG to other components was 70:30. Namely, a polymer solution having a solid concentration of 30% was prepared.
(聚合物A-2~聚合物A-10的合成) (Synthesis of Polymer A-2~Polymer A-10)
如下述表所示般變更所使用的單體的種類、聚合起始劑等， 而合成其他聚合物。再者，表中「-」表示未使用符合的成分。 Change the type of monomer used, polymerization initiator, etc. as shown in the following table. And synthesize other polymers. Furthermore, the "-" in the table indicates that the matching component is not used.
上述表中的未特別附加單位的數值將mol%作為單位。另外，聚合起始劑的數值是將單體成分設為100mol%時的mol%。 The values of the units not particularly attached in the above table are expressed in mol%. Further, the numerical value of the polymerization initiator is mol% when the monomer component is 100 mol%.
固體成分濃度可藉由以下的式子來算出。 The solid content concentration can be calculated by the following formula.
固體成分濃度：單體質量/(單體質量+溶劑質量)×100(單位：質量%) Solid content concentration: monomer mass / (monomer mass + solvent mass) × 100 (unit: mass%)
另外，當使用V-601作為起始劑時，將反應溫度設為90℃， 當使用V-65作為起始劑時，將反應溫度設為70℃。 In addition, when V-601 was used as the initiator, the reaction temperature was set to 90 ° C. When V-65 was used as the initiator, the reaction temperature was set to 70 °C.
(實施例1) (Example 1)
<分散液D1的製備> <Preparation of Dispersion D1>
將下述組成的分散液加以調合，並使其與氧化鋯珠(0.3mmφ)17,000份混合，然後使用塗料振盪機(Paint Shaker)進行12小時分散。濾取氧化鋯珠(0.3mmφ)，而獲得分散液D1。 The dispersion of the following composition was blended, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and then dispersed for 12 hours using a paint shaker (Paint Shaker). The zirconia beads (0.3 mmφ) were collected by filtration to obtain a dispersion D1.
．二氧化鈦(石原產業(股份)製造，商品名：TTO-51(A)，平均一次粒徑：10nm~30nm)：1,875份 . Titanium dioxide (manufactured by Ishihara Industry Co., Ltd., trade name: TTO-51 (A), average primary particle size: 10 nm to 30 nm): 1,875
．DISPERBYK-111(日本畢克化學(BYK-Chemie Japan)(股份)製造)30%PGMEA溶液：2,200份 . DISPERBYK-111 (made by BYK-Chemie Japan (stock)) 30% PGMEA solution: 2,200 parts
．溶劑(PGMEA)：3,425份 . Solvent (PGMEA): 3,425
<感光性樹脂組成物的製備> <Preparation of photosensitive resin composition>
以下述組成進行調配、混合而製成均勻的溶液後，使用具有0.2μm的孔徑的聚乙烯製過濾器進行過濾，而製成實施例1的感光性樹脂組成物。使用所獲得的感光性樹脂組成物，進行後述的各種評價。將評價結果示於後述的表3中。 The mixture was prepared and mixed to obtain a uniform solution, and then filtered using a polyethylene filter having a pore diameter of 0.2 μm to prepare a photosensitive resin composition of Example 1. Various evaluations to be described later were carried out using the obtained photosensitive resin composition. The evaluation results are shown in Table 3 which will be described later.
．PGMEA：51.8份 . PGMEA: 51.8 parts
．EEP：142.4份 . EEP: 142.4 copies
．下述化合物(鹼性化合物，東洋化成工業(股份)製造，CMTU)：0.02份 . The following compounds (basic compound, manufactured by Toyo Chemical Co., Ltd., CMTU): 0.02 parts
．聚合物A-1的30%MEDG溶液：100.0份 . 30% MEDG solution of polymer A-1: 100.0 parts
．光酸產生劑B-1(下述化合物)：1.9份 . Photoacid generator B-1 (compounds below): 1.9 parts
．交聯劑I-1(下述化合物)：6.8份 . Crosslinker I-1 (compounds below): 6.8 parts
．3-縮水甘油氧基丙基三甲氧基矽烷(KBM-403，信越化學工業(股份)製造)：1.7份 . 3-glycidoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1.7 parts
．Irganox1726(抗氧化劑，巴斯夫公司製造)：3.0份 . Irganox 1726 (antioxidant, manufactured by BASF): 3.0 parts
．G-1(氟系界面活性劑，F-554，迪愛生(股份)製造)：0.08份 . G-1 (fluorine-based surfactant, F-554, manufactured by Di Aisheng (share)): 0.08 parts
．分散液D1：181.7份 . Dispersion D1: 181.7 parts
．Pionin D-6414(竹本油脂(股份)製造)：2.2份 . Pionin D-6414 (manufactured by Takemoto Oil Co., Ltd.): 2.2 parts
．特定表面改質劑H-1：1.0份 . Specific surface modifier H-1: 1.0 parts
(其他實施例及比較例) (Other embodiments and comparative examples)
除變更成下述表中所示的聚合物、光酸產生劑、增感劑、界面活性劑、特定表面改質劑以外，與實施例1同樣地分別製備感光性樹脂組成物。再者，於實施例67~實施例71、實施例73~實施例77、實施例79~實施例83、及實施例85~實施例89中，進而追加1.9份的增感劑K-1。 A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer, the photoacid generator, the sensitizer, the surfactant, and the specific surface modifier were changed as shown in the following Table. Further, in Examples 67 to 71, Examples 73 to 77, Examples 79 to 83, and Examples 85 to 89, 1.9 parts of the sensitizer K-1 was further added.
表示實施例及比較例中所使用的各化合物的略號的詳 細情況如下所示。 The details of the abbreviations of the compounds used in the examples and comparative examples are shown. The details are as follows.
(成分A)聚合物 (ingredient A) polymer
A-1~A-10：根據上述合成例所合成的聚合物 A-1~A-10: a polymer synthesized according to the above synthesis example
A-11：Joncryl67(巴斯夫公司製造) A-11: Joncryl67 (manufactured by BASF Corporation)
(成分B)光酸產生劑 (ingredient B) photoacid generator
B-1：下述所示的結構(合成例將後述) B-1: Structure shown below (synthesis example will be described later)
B-2：下述所示的結構(合成例將後述) B-2: Structure shown below (synthesis example will be described later)
B-3：下述所示的結構(根據日本專利特表2002-528451 號公報的段落0108中所記載的方法合成) B-3: Structure shown below (according to Japanese Patent Special Table 2002-528451 Synthesized by the method described in paragraph 0108 of the bulletin)
B-4：PAG-103(商品名，下述所示的結構，巴斯夫公司製造) B-4: PAG-103 (trade name, structure shown below, manufactured by BASF Corporation)
B-5：GSID-26-1，三芳基鋶鹽(巴斯夫公司製造) B-5: GSID-26-1, triarylsulfonium salt (manufactured by BASF Corporation)
[化29]
<B-1的合成> <Synthesis of B-1>
向2-萘酚(10g)、氯苯(30mL)的懸濁溶液中添加氯化鋁(10.6g)、2-氯丙醯氯(10.1g)，將混合液加熱至40℃後反應2小時。於冰浴冷卻下，向反應液中滴加4N的HCl水溶液(60mL)，然後添加乙酸乙酯(50mL)來進行分液。向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)來進行分液，將有機層濃縮後，利用二異丙醚(10mL)將結晶再漿料化(reslurry)，然後進行過濾、乾燥而獲得酮化合物(6.5g)。 To a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added, and the mixture was heated to 40 ° C and reacted for 2 hours. . Under ice cooling, a 4N aqueous HCl solution (60 mL) was added dropwise, and ethyl acetate (50 mL) was added to the mixture. 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 carry out liquid separation. The organic layer was concentrated, and then crystallised from diisopropyl ether (10 mL). It was reslurryed, and then filtered and dried to obtain a ketone compound (6.5 g).
向所獲得的酮化合物(3.0g)、甲醇(30mL)的懸濁溶液中添加乙酸(7.3g)、50質量%羥胺水溶液(8.0g)，並進行加熱回流。放置冷卻後，添加水(50mL)，對所析出的結晶進行過濾， 利用冷甲醇進行清洗後，加以乾燥而獲得肟化合物(2.4g)。 To a suspension solution of the obtained ketone compound (3.0 g) and methanol (30 mL), acetic acid (7.3 g) and a 50% by mass aqueous hydroxylamine solution (8.0 g) were added, and the mixture was heated under reflux. After standing to cool, water (50 mL) was added, and the precipitated crystal was filtered. After washing with cold methanol, it was dried to obtain a hydrazine compound (2.4 g).
使所獲得的肟化合物(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(25℃)後反應1小時。向反應液中添加水(50mL)，對所析出的結晶進行過濾後，利用甲醇(20mL)再漿料化，然後進行過濾、乾燥而獲得B-1的化合物(上述結構)(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 temperature was raised to room temperature (25 ° C). The reaction was carried out for 1 hour. Water (50 mL) was added to the reaction mixture, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), followed by filtration and drying to obtain a compound (the above structure) (2.3 g) of B-1.
再者，B-1的1H-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)。 Further, the 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B-1 was 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-2的合成> <Synthesis of B-2>
使1-胺基-2-萘酚鹽酸鹽(東京化成工業(股份)製造)4.0g懸濁於N-甲基吡咯啶酮(和光純藥工業(股份)製造)16g中，添加碳酸氫鈉(和光純藥工業(股份)製造)3.4g後，滴加4,4-二甲基-3-側氧戊酸甲酯(和光純藥工業(股份)製造)4.9g，並於氮氣環境下以120℃進行2小時加熱。放置冷卻後，向反應混合液中添加水、乙酸乙酯來進行分液，利用硫酸鎂對有機相(organic phase)進行乾燥後，進行過濾、濃縮而獲得粗B-2A。利用矽膠管柱層析法對粗B-2A進行精製，而獲得1.7g的中間物B-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 hydrogen carbonate was added thereto. After 3.4 g of sodium (manufactured by Wako Pure Chemical Industries, Ltd.), methyl 4.9 g of 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to a nitrogen atmosphere. The mixture was heated at 120 ° C for 2 hours. After standing to cool, water and ethyl acetate were added to the reaction mixture to carry out liquid separation, and the organic phase was dried with magnesium sulfate, followed by filtration and concentration to obtain crude B-2A. The crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-2A.
將B-2A(1.7g)與對二甲苯(6mL)混合，添加對甲苯磺酸一水合物(和光純藥工業(股份)製造)0.23g並於140℃下進行2小時加熱。放置冷卻後，向反應混合液中添加水、乙酸乙酯來進行分液，利用硫酸鎂對有機相進行乾燥後，進行過濾、濃縮而獲 得粗B-2B。 B-2A (1.7 g) and p-xylene (6 mL) were mixed, 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 to carry out liquid separation, and the organic phase was dried with magnesium sulfate, filtered, and concentrated. Get thick B-2B.
將THF(2mL)與所有粗B-2B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(和光純藥工業(股份)製造)(0.84g)，昇溫至室溫為止後攪拌2小時。向所獲得的反應混合物中添加水、乙酸乙酯來進行分液，利用水對有機層進行清洗後，利用硫酸鎂進行乾燥，然後進行過濾、濃縮而獲得中間物粗B-2C。 THF (2 mL) was mixed with all the crude B-2B, and 6.0 mL of 2M hydrochloric acid/THF solution was added dropwise thereto under ice-cooling, followed by dropwise addition of isoamyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g). After the temperature was raised to room temperature, the mixture was stirred for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture to carry out liquid separation, and the organic layer was washed with water, dried with magnesium sulfate, filtered, and concentrated to obtain an intermediate crude B-2C.
將所有中間物粗B-2C與丙酮(10mL)混合，於冰浴冷卻下添加三乙胺(和光純藥工業(股份)製造)(1.2g)、對甲苯磺醯氯(東京化成工業(股份)製造)(1.4g)後，昇溫至室溫為止並攪拌1小時。向所獲得的反應混合液中添加水、乙酸乙酯來進行分液，利用硫酸鎂對有機相進行乾燥後，進行過濾、濃縮而獲得粗B-2。利用冷甲醇將粗B-2再漿料化後，進行過濾、乾燥而獲得B-2(1.2g)。 All the intermediates, crude B-2C, were mixed with acetone (10 mL), and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonium chloride (Tokyo Chemical Industry Co., Ltd.) were added under ice cooling. After the production (1.4 g), the mixture was heated to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to carry out liquid separation, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-2. The crude B-2 was reslurryed with cold methanol, filtered, and dried to obtain B-2 (1.2 g).
再者，B-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-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).
(成分F)界面活性劑 (ingredient F) surfactant
F-1：Pionin D-6414(竹本油脂(股份)製造) F-1: Pionin D-6414 (manufactured by Takemoto Oil Co., Ltd.)
F-2：Pionin D-6112(竹本油脂(股份)製造) F-2: Pionin D-6112 (manufactured by Takemoto Oil Co., Ltd.)
F-3：Pionin D-6115(竹本油脂(股份)製造) F-3: Pionin D-6115 (manufactured by Takemoto Oil Co., Ltd.)
F-4：Pionin D-6112-W(竹本油脂(股份)製造) F-4: Pionin D-6112-W (made by Takemoto Oil Co., Ltd.)
F-5：Pionin D-6108-W(竹本油脂(股份)製造) F-5: Pionin D-6108-W (made by Takemoto Oil & Fats Co., Ltd.)
F-6：Pionin D-6512(竹本油脂(股份)製造) F-6: Pionin D-6512 (made by Takemoto Oil & Fats Co., Ltd.)
F-7：Newcol CMP-6(聚氧乙烯4-枯基苯醚，日本乳化劑(股份)製造) F-7: Newcol CMP-6 (polyoxyethylene 4-cumylphenyl ether, manufactured by Japan Emulsifier (share))
F-8：Newcol CMP-11(聚氧乙烯4-枯基苯醚，日本乳化劑(股份)製造) F-8: Newcol CMP-11 (polyoxyethylene 4-cumylphenyl ether, manufactured by Japan Emulsifier (share))
F-9：Newcol 1006(日本乳化劑(股份)製造) F-9: Newcol 1006 (manufactured by Japan Emulsifier (Stock))
F-10：Newcol 1020(日本乳化劑(股份)製造) F-10: Newcol 1020 (made by Japan Emulsifier (Stock))
F-11：Epan 450(第一工業製藥(股份)製造) F-11: Epan 450 (Manufactured by First Industrial Pharmaceuticals Co., Ltd.)
將上述F-1~上述F-11的結構、環氧烷加成莫耳數的合計、及HLB值示於以下的表中。再者，HLB值是藉由格里芬法所測定的值。 The structure of the above F-1 to F-11, the total of the alkylene oxide addition mole numbers, and the HLB value are shown in the following table. Further, the HLB value is a value measured by the Griffin method.
(成分G)氟系界面活性劑、矽酮系界面活性劑 (Component G) Fluorine-based surfactant, anthrone-based surfactant
G-1：Megafac F-554(氟系界面活性劑．迪愛生(股份)製造) G-1: Megafac F-554 (fluorine-based surfactant. Manufactured by Di Aisheng (share))
G-2：X-22-822(矽酮系界面活性劑．信越化學工業(股份)製造) G-2: X-22-822 (anthrone-based surfactant. manufactured by Shin-Etsu Chemical Co., Ltd.)
(成分H)具有2個以上的氮原子的雜環化合物(特定表面改質劑) (Component H) a heterocyclic compound (specific surface modifier) having two or more nitrogen atoms
H-1：下述化合物 H-1: the following compounds
H-2：下述化合物 H-2: the following compounds
H-3：下述化合物 H-3: the following compounds
H-4：下述化合物 H-4: the following compounds
H-5：下述化合物 H-5: the following compounds
[化30]
(成分K)增感劑 (ingredient K) sensitizer
K-1：DBA(9,10-二丁氧基蒽，川崎化成工業(股份)製造) K-1: DBA (9,10-dibutoxy oxime, manufactured by Kawasaki Chemical Industry Co., Ltd.)
(成分I)交聯劑(熱交聯劑) (ingredient I) crosslinker (thermal crosslinker)
I-1：jER828(三菱化學控股(股份)製造) I-1: jER828 (Mitsubishi Chemical Holdings (share) manufacturing)
I-2：jER157S65(三菱化學控股(股份)製造) I-2: jER157S65 (Mitsubishi Chemical Holdings (share) manufacturing)
I-3：jER1007(三菱化學控股(股份)製造) I-3: jER1007 (Mitsubishi Chemical Holdings (share) manufacturing)
(評價) (Evaluation)
<顯影後的殘渣評價> <Residue evaluation after development>
於在100mm×100mm的玻璃表面形成有ITO膜的玻璃基板(日本板硝子(股份)製造)上，利用旋轉塗佈機以膜厚變成2.0μm的方式塗佈所獲得的感光性樹脂組成物，並於90℃的加熱板上進行120秒乾燥(預烘烤)。 On the glass substrate (manufactured by Nippon Sheet Glass Co., Ltd.) having an ITO film formed on a glass surface of 100 mm × 100 mm, the obtained photosensitive resin composition was applied so as to have a film thickness of 2.0 μm by a spin coater. Drying (prebaking) was carried out on a hot plate at 90 ° C for 120 seconds.
其次，使用ghi射線高壓水銀燈曝光機，以照度20mW/cm2、200mJ/cm2隔著線與空間為1：1的帶有1%~60%灰階(gradation) 的遮罩進行曝光。 Next, using a ghi-ray high-pressure mercury lamp exposure machine, exposure was performed with a illuminance of 20 mW/cm 2 and 200 mJ/cm 2 with a line and space of 1:1 with a gradient of 1% to 60%.
繼而，於23℃下，利用0.5%的氫氧化四甲基銨(Tetramethyl Ammonium Hydroxide，TMAH)水溶液並藉由浸覆液法進行15秒顯影，進而利用超純水進行10秒淋洗。繼而，於220℃下加熱45分鐘而獲得評價基板。於暗室中在透過白色光下對所獲得的基板進行目視觀察。另外，利用掃描型電子顯微鏡(Scanning Electron Microscope，SEM)以15,000倍拍攝基板表面，並觀察殘渣的產生，藉此進行殘渣的評價。3以上為實用範圍。 Then, it was developed by a 0.5% aqueous solution of Tetramethyl Ammonium Hydroxide (TMAH) at 23 ° C for 15 seconds by a dip solution method, and further rinsed with ultrapure water for 10 seconds. Then, the evaluation substrate was obtained by heating at 220 ° C for 45 minutes. The obtained substrate was visually observed under a white light in a dark room. Further, the surface of the substrate was photographed by a scanning electron microscope (SEM) at 15,000 times, and the generation of the residue was observed, whereby the residue was evaluated. 3 or more is a practical range.
5：不論於目視觀察中還是於SEM觀察中均完全未觀察到殘渣。 5: No residue was observed at all in visual observation or in SEM observation.
4：於目視觀察中未觀察到殘渣，但於SEM觀察中在畫素周邊略微觀察到殘渣。 4: No residue was observed in the visual observation, but the residue was slightly observed around the pixels in the SEM observation.
3：於目視觀察中未觀察到殘渣，但於SEM觀察中在畫素周邊以外亦略微觀察到殘渣。 3: No residue was observed by visual observation, but the residue was slightly observed outside the periphery of the pixel in the SEM observation.
2：於目視觀察中略微觀察到殘渣。 2: The residue was slightly observed in visual observation.
1：於目視觀察中清楚地觀察到殘渣。 1: The residue was clearly observed in visual observation.
<霧度(透明性)的評價> <Evaluation of haze (transparency)>
於100mm×100mm的玻璃基板(商品名：XG，康寧公司製造)上，以乾燥膜厚變成1.5μm的方式塗佈所獲得的感光性樹脂組成物，並於80℃的加熱板上進行120秒乾燥(預烘烤)。進而，於220℃的烘箱中對塗佈膜實施15分鐘加熱處理(後烘烤)，針對後烘烤後的霧度，利用日本電色工業(股份)製造的NDH-5000， 使膜面向上，並依據塑膠製品試驗方法(JIS K7136．JIS K7361．ASTM D1003)來測定霧度(霧度值)。 The obtained photosensitive resin composition was applied to a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning Incorporated) so as to have a dry film thickness of 1.5 μm, and was applied to a hot plate at 80 ° C for 120 seconds. Dry (pre-bake). Further, the coating film was subjected to heat treatment (post-baking) in an oven at 220 ° C for 15 minutes, and the NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. was used for the haze after post-baking. The film was faced upward, and the haze (haze value) was measured in accordance with the plastic product test method (JIS K7136. JIS K7361.ASTM D1003).
再者，所謂霧度值，是指由擴散透過光對於全光線透過光的比例(%)所表示的值。霧度值越小，表示透明性越高。評價基準如下所示。3以上為實用範圍。 In addition, the haze value is a value represented by the ratio (%) of the diffused transmitted light to the total light transmitted light. The smaller the haze value, the higher the transparency. The evaluation criteria are as follows. 3 or more is a practical range.
5：霧度值未滿0.5%。 5: The haze value is less than 0.5%.
4：霧度值為0.5%以上、未滿0.7%。 4: The haze value is 0.5% or more and less than 0.7%.
3：霧度值為0.7%以上、未滿1.0%。 3: The haze value is 0.7% or more and less than 1.0%.
2：霧度值為1.0%以上、未滿2.0%。 2: The haze value is 1.0% or more and less than 2.0%.
1：霧度值為2.0%以上。 1: Haze value is 2.0% or more.
將結果示於以下的表中。 The results are shown in the table below.
如根據上述表所示的結果而明確般，本發明的感光性組成物的殘渣的去除性優異，霧度亦良好。相對於此，於比較例的感光性樹脂組成物中，產生了殘渣。 As is clear from the results shown in the above table, the photosensitive composition of the present invention has excellent residue removability and good haze. On the other hand, in the photosensitive resin composition of the comparative example, a residue was produced.
(實施例102) (Example 102)
於日本專利第3321003號公報的圖1中所記載的主動矩陣型液晶顯示裝置中，以如下方式形成硬化膜17作為層間絕緣膜，而獲得實施例102的液晶顯示裝置。即，將實施例1的感光性樹脂組成物旋塗於基板上，於加熱板上進行預烘烤(90℃/120秒)後，使用高壓水銀燈自遮罩上照射45mJ/cm2(照度為20mW/cm2)的i射線(365nm)，然後利用鹼性水溶液進行顯影而形成圖案，並於230℃下進行30分鐘的加熱處理，而形成硬化膜17作為層間絕緣膜。 In the active matrix liquid crystal display device described in FIG. 1 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film in the following manner, and the liquid crystal display device of the example 102 is obtained. That is, the photosensitive resin composition of Example 1 was spin-coated on a substrate, prebaked on a hot plate (90 ° C / 120 seconds), and then irradiated with a high-pressure mercury lamp at a surface of 45 mJ/cm 2 (the illuminance was The i-ray (365 nm) of 20 mW/cm 2 ) was developed by an aqueous alkaline solution to form a pattern, and heat-treated at 230 ° C for 30 minutes to form a cured film 17 as an interlayer insulating film.
對所獲得的液晶顯示裝置施加驅動電壓的結果，可知其為顯示良好的顯示特性、且可靠性高的液晶顯示裝置。 As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited high display characteristics and high reliability.
(實施例103) (Example 103)
藉由以下的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上形成底閘極型的TFT1，並在覆蓋該TFT1的狀態下形成包含Si3N4的絕緣膜3。繼而，於該絕緣膜3上形成此處省略了圖示的接觸孔後，經由該接觸孔而於絕緣膜3上形成連接於TFT1的配線2(高度為1.0μm)。該配線2是用以將TFT1間、或將其後的步驟中形成的有機EL元件與TFT1加以連接的線。 A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si 3 N 4 is formed in a state of covering the TFT 1. Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. This wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.
進而，為了使由配線2的形成所產生的凹凸平坦化，於埋入由配線2所產生的凹凸的狀態下，朝絕緣膜3上形成平坦化膜4。朝絕緣膜3上的平坦化膜4的形成是將實施例4的感光性樹脂組成物旋塗於基板上，在加熱板上進行預烘烤(90℃/120秒)後，使用高壓水銀燈自遮罩上照射45mJ/cm2(照度為20mW/cm2)的i射線(365nm)，然後利用鹼性水溶液進行顯影而形成圖案，並於230℃下進行30分鐘的加熱處理。 Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The planarization film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 4 on a substrate, and pre-baking (90 ° C / 120 seconds) on a hot plate, using a high-pressure mercury lamp. The mask was irradiated with i-rays (365 nm) of 45 mJ/cm 2 (illuminance of 20 mW/cm 2 ), developed with an alkaline aqueous solution to form a pattern, and heat-treated 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、煅燒後所獲得的硬化膜中，未發現皺褶或裂痕的產生。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 wrinkles or cracks were 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，於所獲得的平坦化膜4上形成底部發光型的有機EL元件。首先，使包含ITO的第一電極5經由接觸孔7連接於配線2而形成在平坦化膜4上。其後，塗佈抗蝕劑，並進行預烘烤，隔著所期望的圖案的遮罩進行曝光，然後進行顯影。將該抗蝕劑圖案作為遮罩，藉由使用ITO蝕刻劑的濕式蝕刻來進行圖案加工。其後，於50℃下，使用抗蝕劑剝離液(Remover 100，安智電子材料(AZ Electronic Materials)公司製造)將上述抗蝕劑圖案剝離。以上述方式獲得的第一電極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 connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Thereafter, the resist is applied, pre-baked, exposed through a mask of a desired pattern, and then 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 obtained in the above manner corresponds to the anode of the organic EL element.
繼而，形成覆蓋第一電極5的周緣的形狀的絕緣膜8。將實施例4的感光性樹脂組成物用於絕緣膜8，以與上述相同的方法形成絕緣膜8。藉由設置該絕緣膜8，可防止第一電極5與其後的步驟中所形成的第二電極之間的短路。 Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The photosensitive resin composition of Example 4 was used for the insulating film 8, and the insulating film 8 was formed in the same manner as described above. 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，隔著所期望的圖案遮罩而依次進行蒸鍍來設置電洞傳輸層、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。自蒸鍍機中取出所獲得的上述基板，藉由使用紫外線硬化型環氧樹脂與密封用玻璃板進行貼合來密封。 Further, in the vacuum vapor deposition apparatus, vapor deposition is sequentially performed through a desired pattern mask to provide a hole transport layer, an organic light-emitting layer, and an electron transport layer. 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 sealed by bonding with an ultraviolet curable epoxy resin and a sealing glass plate.
如以上般，獲得於各有機EL元件上連接用以對其進行驅動的TFT1而成的主動矩陣型的有機EL顯示裝置。經由驅動電路而施加電壓的結果，可知其為顯現良好的顯示特性、且可靠性高的有機EL顯示裝置。 As described above, an active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. As a result of applying a voltage via the drive circuit, it is understood that the organic EL display device exhibits excellent display characteristics and high reliability.
(實施例104) (Example 104)
藉由以下所述的方法，並使用本發明的高折射率的感光性樹脂組成物來製作觸控面板顯示裝置。 A touch panel display device was produced by the method described below and using the high refractive index photosensitive resin composition of the present invention.
<第一透明電極圖案的形成> <Formation of First Transparent Electrode Pattern>
[透明電極層的形成] [Formation of Transparent Electrode Layer]
將事先形成有遮罩層的強化處理玻璃(300mm×400mm×0.7mm)的前面板導入至真空室內，使用SnO2含有率為10質量%的ITO靶材(銦：錫=95：5(莫耳比))，藉由直流(Direct Current，DC)磁控濺鍍(條件：基材的溫度為250℃，氬壓力為0.13Pa，氧壓力為0.01Pa)來形成厚度為40nm的ITO薄膜，而獲得形成有透明電極層的前面板。ITO薄膜的表面電阻為80Ω/□。 The front panel of the tempered glass (300 mm × 400 mm × 0.7 mm) in which the mask layer was formed in advance was introduced into a vacuum chamber, and an ITO target having a SnO 2 content of 10% by mass (indium: tin = 95: 5 (Mo) was used. Ear ratio)), by direct current (DC) magnetron sputtering (condition: substrate temperature is 250 ° C, argon pressure is 0.13 Pa, oxygen pressure is 0.01 Pa) to form an ITO film with a thickness of 40 nm, A front panel formed with a transparent electrode layer was obtained. The surface resistance of the ITO film was 80 Ω/□.
繼而，將市售的蝕刻抗蝕劑塗佈於ITO上並進行乾燥，而形成蝕刻抗蝕劑層。將曝光遮罩(具有透明電極圖案的石英曝 光遮罩)面與蝕刻抗蝕劑層之間的距離設定為100μm，以50mJ/cm2的曝光量(i射線)進行圖案曝光後，藉由專用的顯影液來進行顯影，進而於130℃下進行30分鐘的後烘烤處理，而獲得形成有透明電極層與蝕刻用光硬化性樹脂層圖案的前面板。 Then, a commercially available etching resist was applied onto ITO and dried to form an etch resist layer. The distance between the surface of the exposure mask (the quartz exposure mask having the transparent electrode pattern) and the etching resist layer was set to 100 μm, and after pattern exposure with an exposure amount (i-ray) of 50 mJ/cm 2 , The developing solution was subjected to development, and further subjected to a post-baking treatment at 130 ° C for 30 minutes to obtain a front plate on which a transparent electrode layer and an etching photocurable resin layer pattern were formed.
使形成有透明電極層與蝕刻用光硬化性樹脂層圖案的前面板浸漬於加入有ITO蝕刻劑(鹽酸、氯化鉀水溶液。液溫為30℃)的蝕刻槽中，進行100秒處理，將未由蝕刻抗蝕劑層覆蓋而露出的區域的透明電極層溶解去除，而獲得附有帶有蝕刻抗蝕劑層圖案的透明電極層圖案的前面板。 The front plate on which the transparent electrode layer and the etching photocurable resin layer pattern were formed was immersed in an etching bath to which an ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature: 30 ° C) was added, and treated for 100 seconds. The transparent electrode layer of the region not exposed by the etching of the resist layer is dissolved and removed, and a front panel having a pattern of a transparent electrode layer with an etching resist layer pattern is obtained.
繼而，使附有帶有蝕刻抗蝕劑層圖案的透明電極層圖案的前面板浸漬於專用的抗蝕劑剝離液中，將蝕刻用光硬化性樹脂層去除，而獲得形成有遮罩層與第一透明電極圖案的前面板。 Then, the front panel with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, and the etching photocurable resin layer is removed to obtain a mask layer and The front panel of the first transparent electrode pattern.
[絕緣層的形成] [Formation of insulating layer]
將實施例6的感光性樹脂組成物塗佈於形成有遮罩層與第一透明電極圖案的前面板上並進行乾燥(膜厚為1μm，90℃、120秒)，而獲得感光性樹脂組成物層。將曝光遮罩(具有絕緣層用圖案的石英曝光遮罩)面與感光性樹脂組成物層之間的距離設定為30μm，以50mJ/cm2的曝光量(i射線)進行圖案曝光。 The photosensitive resin composition of Example 6 was applied onto a front surface plate on which a mask layer and a first transparent electrode pattern were formed, and dried (film thickness: 1 μm, 90 ° C, 120 seconds) to obtain a photosensitive resin composition. Layer of matter. The distance between the surface of the exposure mask (the quartz exposure mask having the pattern for the insulating layer) and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed at an exposure amount (i-ray) of 50 mJ/cm 2 .
繼而，於23℃下，利用2.38質量%的氫氧化四甲基銨水溶液並藉由浸覆液法進行15秒顯影，進而利用超純水進行10秒淋洗。繼而，於220℃下進行45分鐘的後烘烤處理，而獲得形成有遮罩層、第一透明電極圖案、絕緣層圖案的前面板。 Then, it was developed by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 15 seconds by a dip solution method, and further rinsed with ultrapure water for 10 seconds. Then, a post-baking treatment was performed at 220 ° C for 45 minutes to obtain a front panel on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.
<第二透明電極圖案的形成> <Formation of Second Transparent Electrode Pattern>
[透明電極層的形成] [Formation of Transparent Electrode Layer]
對以與上述第一透明電極圖案的形成相同的方式形成至絕緣層圖案為止的前面板進行DC磁控濺鍍處理(條件：基材的溫度為50℃，氬壓力為0.13Pa，氧壓力為0.01Pa)，形成厚度為80nm的ITO薄膜，而獲得形成有透明電極層的前面板。ITO薄膜的表面電阻為110Ω/□。 A DC magnetron sputtering treatment was performed on the front panel formed to the insulating layer pattern in the same manner as the formation of the first transparent electrode pattern (condition: substrate temperature was 50 ° C, argon pressure was 0.13 Pa, and oxygen pressure was 0.01 Pa), an ITO film having a thickness of 80 nm was formed, and a front panel on which a transparent electrode layer was formed was obtained. The surface resistance of the ITO film was 110 Ω/□.
以與第一透明電極圖案的形成相同的方式，使用市售的蝕刻抗蝕劑獲得形成有第一透明電極圖案、利用實施例6的感光性樹脂組成物所形成的絕緣層圖案、透明電極層、蝕刻抗蝕劑圖案的前面板(後烘烤處理；130℃、30分鐘)。 In the same manner as the formation of the first transparent electrode pattern, a commercially available etching resist was used to obtain an insulating layer pattern formed by using the photosensitive resin composition of Example 6 and a transparent electrode layer formed using the first transparent electrode pattern. The front panel of the resist pattern was etched (post-baking treatment; 130 ° C, 30 minutes).
進而，以與第一透明電極圖案的形成相同的方式進行蝕刻，而去除蝕刻抗蝕劑層，藉此獲得形成有遮罩層、第一透明電極圖案、使用實施例6的感光性樹脂組成物所形成的絕緣層圖案、第二透明電極圖案的前面板。 Further, etching is performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer is removed, whereby the photosensitive resin composition using the mask layer, the first transparent electrode pattern, and the use example 6 is obtained. The formed insulating layer pattern and the front panel of the second transparent electrode pattern.
<與第一透明電極圖案及第二透明電極圖案不同的導電性要素的形成> <Formation of a conductive element different from the first transparent electrode pattern and the second transparent electrode pattern>
以與上述第一透明電極圖案、及第二透明電極圖案的形成相同的方式，對形成有第一透明電極圖案、利用實施例6的感光性樹脂組成物所形成的絕緣層圖案、第二透明電極圖案的前面板進行DC磁控濺鍍處理，而獲得形成有厚度為200nm的鋁(Al)薄膜的前面板。 In the same manner as the formation of the first transparent electrode pattern and the second transparent electrode pattern, the first transparent electrode pattern, the insulating layer pattern formed by the photosensitive resin composition of Example 6, and the second transparent layer are formed. The front panel of the electrode pattern was subjected to DC magnetron sputtering treatment to obtain a front panel formed with an aluminum (Al) film having a thickness of 200 nm.
以與上述第一透明電極圖案、及第二透明電極圖案的形成相同的方式，使用市售的蝕刻抗蝕劑獲得形成有第一透明電極圖案、利用實施例6的感光性樹脂組成物所形成的絕緣層圖案、第二透明電極圖案、蝕刻抗蝕劑圖案的前面板(後烘烤處理；130℃、30分鐘)。 In the same manner as the formation of the first transparent electrode pattern and the second transparent electrode pattern, a commercially available etching resist was used to obtain a first transparent electrode pattern, and the photosensitive resin composition of Example 6 was used. The insulating layer pattern, the second transparent electrode pattern, and the front panel of the etching resist pattern (post-baking treatment; 130 ° C, 30 minutes).
進而，以與第一透明電極圖案的形成相同的方式進行蝕刻(30℃、50秒)，而將蝕刻抗蝕劑層去除(45℃、200秒)，藉此獲得形成有遮罩層、第一透明電極圖案、利用實施例6的感光性樹脂組成物所形成的絕緣層圖案、第二透明電極圖案、與第一透明電極圖案及第二透明電極圖案不同的導電性要素的前面板。 Further, etching (30 ° C, 50 seconds) is performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer is removed (45 ° C, 200 seconds), thereby obtaining a mask layer, A transparent electrode pattern, an insulating layer pattern formed by the photosensitive resin composition of Example 6, a second transparent electrode pattern, and a front panel of a conductive element different from the first transparent electrode pattern and the second transparent electrode pattern.
<透明保護層的形成> <Formation of transparent protective layer>
在以與絕緣層的形成相同的方式形成至與上述第一透明電極圖案及第二透明電極圖案不同的導電性要素為止的前面板上，塗佈實施例6的感光性樹脂組成物並進行乾燥(膜厚為1μm，90℃、120秒)，而獲得感光性樹脂組成物膜。進而，不隔著曝光遮罩而以50mJ/cm2的曝光量(i射線)進行前面曝光，然後進行顯影、後曝光(1,000mJ/cm2)、後烘烤處理，而獲得以如下方式積層利用實施例6的感光性樹脂組成物所形成的絕緣層(透明保護層)的前面板，該方式是將遮罩層、第一透明電極圖案、利用實施例6的感光性樹脂組成物所形成的絕緣層圖案、第二透明電極圖案、與第一透明電極圖案及第二透明電極圖案不同的導電性要素全部覆蓋的方式。 The photosensitive resin composition of Example 6 was applied and dried on a front plate formed to form a conductive element different from the first transparent electrode pattern and the second transparent electrode pattern in the same manner as the formation of the insulating layer. (The film thickness was 1 μm, 90 ° C, 120 seconds), and a photosensitive resin composition film was obtained. Further, the front exposure was performed at an exposure amount (i-ray) of 50 mJ/cm 2 without interposing the exposure mask, followed by development, post-exposure (1,000 mJ/cm 2 ), and post-baking treatment, thereby obtaining a laminate in the following manner. The front panel of the insulating layer (transparent protective layer) formed of the photosensitive resin composition of Example 6, which is formed by using the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 6. The insulating layer pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern and the second transparent electrode pattern are all covered.
<圖像顯示裝置(觸控面板)的製作> <Production of Image Display Device (Touch Panel)>
於藉由日本專利特開2009-47936號公報中記載的方法所製造的液晶顯示元件上貼合先前製造的前面板，利用公知的方法製作具備靜電電容型輸入裝置作為構成要素的圖像顯示裝置。 A front panel manufactured by a method is bonded to a liquid crystal display device manufactured by the method described in JP-A-2009-47936, and an image display device including a capacitance type input device as a constituent element is produced by a known method. .
<前面板、及圖像顯示裝置的評價> <Evaluation of front panel and image display device>
第一透明電極圖案、第二透明電極圖案、及與兩者不同的導電性要素各自的導電性不存在問題，另一方面，第一透明電極圖案與第二透明電極圖案之間具有絕緣性，作為觸控面板，獲得了良好的顯示特性。進而，第一透明電極圖案及第二透明電極圖案不易被視認，獲得了顯示特性優異的圖像顯示裝置。 The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the two have no problem in conductivity, and the first transparent electrode pattern and the second transparent electrode pattern have insulation properties. As a touch panel, good display characteristics are obtained. Further, the first transparent electrode pattern and the second transparent electrode pattern are not easily visible, and an image display device having excellent display characteristics is obtained.
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
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| JP4084712B2 (en) * | 2003-06-23 | 2008-04-30 | 松下電器産業株式会社 | Pattern formation method |
| JP5340623B2 (en) * | 2008-03-31 | 2013-11-13 | 富士フイルム株式会社 | Photosensitive resin composition, light-shielding color filter, method for producing the same, and solid-state imaging device |
| JP5015891B2 (en) * | 2008-10-02 | 2012-08-29 | 信越化学工業株式会社 | Metal oxide-containing film forming composition, metal oxide-containing film forming substrate, and pattern forming method |
| JP5744694B2 (en) * | 2011-10-06 | 2015-07-08 | 富士フイルム株式会社 | Positive photosensitive resin composition, method for producing cured product, method for producing resin pattern, cured product, and optical member |
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