TWI447521B - Manufacturing method of photospacer - Google Patents

Manufacturing method of photospacer Download PDF

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TWI447521B
TWI447521B TW098109829A TW98109829A TWI447521B TW I447521 B TWI447521 B TW I447521B TW 098109829 A TW098109829 A TW 098109829A TW 98109829 A TW98109829 A TW 98109829A TW I447521 B TWI447521 B TW I447521B
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photosensitive resin
film
substrate
photo
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TW098109829A
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TW200949445A (en
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Yuuichi Fukushige
Kazuhito Miyake
Kenta Yamazaki
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Fujifilm Corp
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  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

光間隔物之製法Method of making light spacers

本發明係關於感光性樹脂組成物、光間隔物及其形成方法、保護膜、著色圖案、顯示裝置用基板、以及顯示裝置。The present invention relates to a photosensitive resin composition, a photo spacer, a method for forming the same, a protective film, a colored pattern, a substrate for a display device, and a display device.

液晶顯示裝置係廣泛使用於顯示高畫質畫像的顯示裝置。A liquid crystal display device is widely used in a display device that displays a high-quality image.

液晶顯示裝置一般係在一對的基板(以下，亦稱為「顯示裝置用基板」)間，根據指定的配向配置能形成畫像顯示之液晶層，均勻地維持該基板間隔、亦即液晶層的厚度係為決定畫質的要素之一，為此配置了用以固定保持液晶層厚度的間隔物。該基板之間的厚度一般稱為「晶胞厚」，晶胞厚一般係為前述液晶層的厚度，換言之，表示對顯示領域的液晶施加電場之2片電極間的距離者。The liquid crystal display device is generally disposed between a pair of substrates (hereinafter also referred to as "display device substrate"), and a liquid crystal layer capable of forming an image display is arranged in accordance with a predetermined alignment, and the substrate interval, that is, the liquid crystal layer is uniformly maintained. The thickness is one of the elements determining the image quality, and a spacer for fixing the thickness of the liquid crystal layer is disposed for this purpose. The thickness between the substrates is generally referred to as "cell thickness", and the cell thickness is generally the thickness of the liquid crystal layer, in other words, the distance between two electrodes for applying an electric field to the liquid crystal in the display region.

顯示裝置用基板(例如，彩色濾光片基板、有源矩陣基板等)係在基板上形成著色圖案、保護膜等的構造物而構成的。此等之構造物之中，著色圖案、保護膜的形成方法係以使用感光性樹脂組成物且藉由微影術而形成的方法為主流。The display device substrate (for example, a color filter substrate or an active matrix substrate) is formed by forming a structure such as a colored pattern or a protective film on the substrate. Among these structures, a method of forming a colored pattern or a protective film is a method in which a photosensitive resin composition is used and formed by lithography.

又，關於間隔物在以往係藉由珠粒散布而形成的，但是在近年來係使用感光性樹脂組成物並藉由微影術，可形成位置精度高的間隔物。使用像這樣的感光性樹脂組成物而形成之間隔物係被稱為光間隔物。Further, the spacer is formed by scattering of beads in the related art. However, in recent years, a photosensitive resin composition is used and a spacer having a high positional accuracy can be formed by lithography. The spacer formed using such a photosensitive resin composition is called a photo spacer.

關於感光性樹脂組成物，從以往開始已有各種的檢討，例如，已揭示使用有乙烯性不飽和羧酸等與乙烯性不飽和化合物的共聚物及特定的光聚合引發劑之感光性樹脂組成物(例如，參照特開2007-86565號公報)。又，已揭示有由連結具有特定構造的脂肪族環狀烴基之構成單位、具有酸性官能基之構成單位與具有自由基聚合性基之構成單位的分子構造之脂肪族環狀烴基含有共聚物所構成的硬化性樹脂(例如，參照特開2002-293837號公報)。The photosensitive resin composition has been examined variously, and for example, a photosensitive resin composition using a copolymer of an ethylenically unsaturated carboxylic acid such as an ethylenically unsaturated carboxylic acid and a specific photopolymerization initiator has been disclosed. (For example, refer to Japanese Laid-Open Patent Publication No. 2007-86565). Further, an aliphatic cyclic hydrocarbon group-containing copolymer having a molecular structure in which a constituent unit of an aliphatic cyclic hydrocarbon group having a specific structure, a constituent unit having an acidic functional group, and a constituent unit having a radical polymerizable group are bonded is disclosed. A curable resin is formed (for example, see JP-A-2002-293837).

根據本發明的態樣，能提供提高曝光時的聚合硬化性、在低溫加熱或無加熱處理下的圖案構造物、保護膜的形成為可能之感光性樹脂組成物、使用它之光間隔物及其形成方法、保護膜、著色圖案、以及具備彼等之顯示裝置用基板、及具備該顯示裝置用基板之顯示裝置。前述感光性樹脂組成物係含有樹脂、具有下述構造部分(I)之聚合性化合物[構造部分(I)中，X係表示氫原子或甲基，*係表示結合鍵]、與光聚合引發劑的感光性樹脂組成物，前述聚合性化合物係較佳為在分子中具有2個或3個以上的構造部分(I)。According to the aspect of the present invention, it is possible to provide a photosensitive resin composition which is improved in polymerization hardenability at the time of exposure, a pattern structure under low-temperature heating or no heat treatment, a formation of a protective film, a photo spacer using the same, and The formation method, the protective film, the colored pattern, the substrate for a display device including the same, and the display device including the substrate for the display device. The photosensitive resin composition contains a resin and a polymerizable compound having the following structural part (I). In the structural part (I), X represents a hydrogen atom or a methyl group, * represents a bond, and photopolymerization is initiated. In the photosensitive resin composition of the agent, the polymerizable compound preferably has two or more structural portions (I) in the molecule.

發明所欲解決之課題Problem to be solved by the invention

在前述以往的感光性樹脂組成物中，一般的光聚合性單體係使用二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯等的具有乙烯性不飽和鍵之單體。In the conventional photosensitive resin composition, a monomer having an ethylenically unsaturated bond such as dipentaerythritol hexaacrylate or dipentaerythritol pentaacrylate is used as a general photopolymerizable single system.

然而，使用以往的感光性樹脂組成物而在基板上形成圖案構造物(例如，光間隔物、著色圖案等。以下相同)、形成保護膜之情形中，僅曝光的話聚合硬化未必就充分了，而且在曝光、顯像後施加高溫的加熱處理之必要情形很多。又，當要求精細度之光間隔物等的圖案構造物的形成時，在防止形狀偏移之點，一般係認為曝光之際的聚合反應快速係為所期望的。However, in the case where a conventional photosensitive resin composition is used to form a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) and a protective film is formed on the substrate, polymerization hardening is not necessarily sufficient only when exposed. Moreover, it is necessary to apply a high-temperature heat treatment after exposure and development. Further, when a pattern structure such as a fine photo spacer is required to be formed, it is generally considered that the polymerization reaction at the time of exposure is as fast as possible in order to prevent the shape from shifting.

本發明係有鑑於上述而完成的，以達成下述目的為課題。The present invention has been made in view of the above, and it is an object to achieve the following objects.

亦即，本發明係以提供在曝光時的聚合硬化性優異、能夠在低溫加熱處理或無加熱下得到圖案構造物、保護膜之感光性樹脂組成物為目的。In other words, the present invention has an object of providing a photosensitive resin composition which is excellent in polymerization hardenability at the time of exposure and which can obtain a pattern structure or a protective film under low-temperature heat treatment or without heating.

又，本發明係以提供具有均一性高的剖面形狀，且高度均一性優異之光間隔物及其製法為目的。Further, the present invention has an object of providing a photo spacer having a high cross-sectional shape with high uniformity and excellent uniformity of height and a method for producing the same.

又，本發明係以提供膜厚均一性優異之保護膜，或具有均一性高的剖面形狀，且膜厚均一性優異之著色圖案為目的。Further, the present invention has an object of providing a protective film having excellent film thickness uniformity or a colored pattern having a uniform cross-sectional shape and excellent film thickness uniformity.

又，本發明係以提供在使用於顯示裝置之際能夠抑制顯示不均之顯示裝置用基板、及顯示不均受到抑制之顯示裝置為目的。Moreover, the present invention has an object of providing a display device substrate capable of suppressing display unevenness and a display device having suppressed display unevenness when used in a display device.

解決課題之手段Means of solving problems

本發明係得到在分子中含有特定構造部分之聚合性化合物在提供光而進行之聚合反應為快速，所以成形性優異，而且與以往稱為所謂後烘烤之高溫加熱不同，例如在不滿200℃之低溫下加熱、或即使不進行加熱處理亦能提高硬化性的知見，且基於該知見而完成者。In the present invention, a polymerizable compound containing a specific structural moiety in a molecule is rapidly polymerized by providing light, and therefore it is excellent in moldability, and is different from high-temperature heating which is conventionally referred to as post-baking, for example, less than 200 ° C. It is known that the heating is performed at a low temperature or the curing property can be improved without performing heat treatment, and is completed based on the knowledge.

為達成前述課題之具體手段係如以下所示。The specific means for achieving the above problems are as follows.

<1>一種感光性樹脂組成物，其係含有樹脂、具有下述構造部分(I)之聚合性化合物、與光聚合引發劑之感光性樹脂組成物。下述構造部分(I)中，X係表示氫原子或甲基，「＊」係表示結合鍵。<1> A photosensitive resin composition containing a resin, a polymerizable compound having the following structural part (I), and a photosensitive resin composition with a photopolymerization initiator. In the following structural part (I), X represents a hydrogen atom or a methyl group, and "*" represents a bond.

<2>如前述<1>記載之感光性樹脂組成物，其中前述聚合性化合物係在分子中具有至少2個的前述構造部分(I)。The photosensitive resin composition of the above-mentioned <1>, wherein the polymerizable compound has at least two structural portions (I) in a molecule.

<3>如前述<1>或前述<2>記載之感光性樹脂組成物，其中前述聚合性化合物係具有連結含有前述構造部分(I)的2個基之對稱構造。The photosensitive resin composition of the above-mentioned <2>, wherein the polymerizable compound has a symmetrical structure in which two groups including the structural portion (I) are bonded.

<4>如前述<1>記載之感光性樹脂組成物，其中前述具有構造部分(I)之聚合性化合物係為下述構造式(II)所表示之聚合性化合物。The photosensitive resin composition of the structure (I) is a polymerizable compound represented by the following structural formula (II).

[式中，R係表示在2價烴基之碳-碳間含有至少1個醚鍵之連結基。X係表示氫原子、甲基]。[In the formula, R represents a linking group containing at least one ether bond between carbon and carbon of a divalent hydrocarbon group. X is a hydrogen atom or a methyl group.

<5>如前述<4>記載之感光性樹脂組成物，其係在前述構造式(II)中，R表示-CH2 -O-Ra -O-CH2 -，Ra 表示選自於由伸烷基部位、伸芳基部位、及組合此等的部位所構成群組之連結基。<5> The photosensitive resin composition according to <4> above, wherein in the above structural formula (II), R represents -CH 2 -OR a -O-CH 2 -, and R a is selected from the group consisting of alkylene The linking group of the group formed by the base portion, the aryl group, and the portion in which these are combined.

<6>如前述<1>~前述<5>項中任一項之感光性樹脂組成物，其中前述樹脂係在側鏈具有分枝及/或脂環構造、酸性基、以及乙烯性不飽和鍵。The photosensitive resin composition according to any one of the above-mentioned items, wherein the resin has a branching and/or alicyclic structure, an acidic group, and an ethylenic unsaturated group in a side chain. key.

<7>如前述<6>記載之感光性樹脂組成物，其中前述樹脂的酸價為20mgKOH/g以上。The photosensitive resin composition as described in the above <6>, wherein the acid value of the resin is 20 mgKOH/g or more.

<8>如前述<6>記載之感光性樹脂組成物，其中前述具有分枝及/或脂環構造之基係下述通式(3)所表示之基。The photosensitive resin composition of the above-mentioned <6>, wherein the base having a branched and/or alicyclic structure is a group represented by the following formula (3).

通式(3)中，X係表示2價的有機連結基，可無取代、亦可具有取代基。y係表示1或2，n係表示0~15的整數。In the formula (3), X represents a divalent organic linking group, and may be unsubstituted or may have a substituent. The y system represents 1 or 2, and the n system represents an integer of 0 to 15.

<9>一種光間隔物，其係使用如前述<1>~前述<8>項中任一項之感光性樹脂組成物而形成的。<9> A photo-resin formed by using the photosensitive resin composition according to any one of the above items <1> to <8>.

<10>一種光間隔物之製法，其係含有至少下述步驟(甲)~(丙)：<10> A method for producing a photo spacer, which comprises at least the following steps (A) to (C):

(甲)將前述<1>~前述<8>項中任一項之感光性樹脂組成物的被膜形成於基板上之形成步驟；(a) a step of forming a film of the photosensitive resin composition according to any one of the items <1> to <8> on the substrate;

(乙)曝光前述被膜的至少一部份之曝光步驟；(b) exposing at least a portion of the film to an exposure step;

(丙)顯像曝光後的前述被膜之顯像步驟。(c) a developing step of the above-mentioned film after development exposure.

<11>如前述<10>記載之光間隔物之製法，其中更具有加熱顯像後的前述被膜之加熱步驟，且在加熱時的最高溫度為40℃以上，145℃以下。<11> The method for producing a photo-spacer according to the above <10>, which further comprises the step of heating the film after heating and developing, and the maximum temperature during heating is 40° C. or higher and 145° C. or lower.

<12>一種保護膜，其係使用如前述<1>~前述<8>項中任一項之感光性樹脂組成物而形成的。<12> A protective film formed by using the photosensitive resin composition according to any one of the above items <1> to <8>.

<13>一種著色圖案，其係使用如前述<1>~前述<8>項中任一項之感光性樹脂組成物而形成的。<13> A coloring pattern formed by using the photosensitive resin composition according to any one of the above <1> to <8>.

<14>一種顯示裝置用基板，其係具備使用如前述<1>~前述<8>項中任一項之感光性樹脂組成物而形成的前述光間隔物、前述保護膜、及前述著色圖案之至少1者。The substrate for a display device, comprising the photo-spacer, the protective film, and the coloring pattern formed by using the photosensitive resin composition according to any one of the above items <1> to <8> At least one of them.

<15>一種顯示裝置，其係具備如前述<14>記載之顯示裝置用基板。<15> A display device comprising the substrate for a display device according to the above <14>.

實施發明之形態Form of implementing the invention

以下，詳細說明本發明的感光性樹脂組成物，進而詳述使用該感光性樹脂組成物之光間隔物及其形成方法、保護膜、著色圖案、顯示裝置用基板、以及顯示裝置。Hereinafter, the photosensitive resin composition of the present invention will be described in detail, and a photo spacer using the photosensitive resin composition, a method for forming the same, a protective film, a colored pattern, a substrate for a display device, and a display device will be described in detail.

《感光性樹脂組成物》"Photosensitive Resin Composition"

本發明的感光性樹脂組成物係至少使用樹脂、具有以下所示構造部分(I)之聚合性化合物、與光聚合引發劑而構成者。又，可按照需要，進一步使用其他成分來構成。The photosensitive resin composition of the present invention is composed of at least a resin, a polymerizable compound having the structural portion (I) shown below, and a photopolymerization initiator. Further, other components may be further used as needed.

一般使用感光性樹脂組成物以在基板上形成圖案構造物(例如，光間隔物、著色圖案等。以下同樣)、保護膜之情形中，因為僅曝光而會容易使得聚合硬化變得不充分，所以為了進一步加速聚合硬化，一般係在曝光、顯像後施加在高溫中的加熱處理。然而，一施加高溫的加熱處理，就會招來所形成的圖案構造物、保護膜的惡化，或基板上的已經設立的圖案構造物，保護膜係因重複施加的熱而惡化。例如，在具有著色圖案的彩色濾光片基板上形成光間隔物之情形中，會導致這樣所形成之光間隔物本身的惡化，又已經形成於基板上的著色圖案會因所賦予的更多的熱而惡化。相對於此，在本發明藉由前述構成感光性樹脂組成物，會加速曝光時的聚合進行，所以成形性優異，此外提高曝光時的聚合硬化性，即使在低溫加熱(例如145℃以下)、無加熱處理下，亦可形成有均一性的圖案構造物、保護膜。藉此，不僅可抑制圖案構造物、保護膜的形狀偏移，而且能有效地抑制這樣所形成的圖案構造物、保護膜所遭受到的惡化及基板上的已經設立的圖案構造物、保護膜因熱所重複遭受的惡化。In general, when a photosensitive resin composition is used to form a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) or a protective film on a substrate, polymerization hardening is likely to be insufficient because it is only exposed. Therefore, in order to further accelerate the polymerization hardening, it is generally applied to heat treatment at a high temperature after exposure and development. However, when a heat treatment is applied at a high temperature, the formed pattern structure, the deterioration of the protective film, or the already established pattern structure on the substrate, and the protective film are deteriorated by repeated application of heat. For example, in the case of forming a photo spacer on a color filter substrate having a colored pattern, the photo spacer itself thus formed may be deteriorated, and the colored pattern already formed on the substrate may be imparted by The heat is getting worse. On the other hand, in the present invention, since the composition of the photosensitive resin composition accelerates the polymerization during the exposure, the moldability is excellent, and the polymerization hardenability at the time of exposure is improved, and the mixture is heated at a low temperature (for example, 145 ° C or lower). A uniform pattern structure or a protective film can also be formed without heat treatment. Thereby, it is possible to suppress not only the pattern structure and the shape shift of the protective film, but also to effectively suppress the deterioration of the pattern structure and the protective film formed as described above, and the established pattern structure and protective film on the substrate. Deterioration due to repeated heat.

以下，說明樹脂、具有構造部分(I)之聚合性化合物、光聚合引發劑、及其他的成分。Hereinafter, a resin, a polymerizable compound having a structural portion (I), a photopolymerization initiator, and other components will be described.

<具有構造部分(I)之聚合性化合物><Polymerizable compound having a structural part (I)>

本發明的感光性樹脂組成物係含有具有下述構造部分(I)之聚合性化合物(以下，亦稱為「特定聚合性化合物」)的至少1種。聚合性化合物係受到來自後述之光聚合引發劑的自由基的作用並引起聚合反應而形成硬化膜者。關於由該特定聚合性化合物所引起的作用尚未明確，但是推測藉由具有下述構造部分(I)所示之構造，因而使得不飽和雙鍵部分在曝光時的反應進行加速，所以為聚合硬化性優異者。The photosensitive resin composition of the present invention contains at least one of a polymerizable compound having the following structural portion (I) (hereinafter also referred to as "specific polymerizable compound"). The polymerizable compound is a person who receives a radical from a photopolymerization initiator to be described later and causes a polymerization reaction to form a cured film. The effect by the specific polymerizable compound is not clear, but it is presumed that by having the structure shown in the following structural part (I), the reaction of the unsaturated double bond portion at the time of exposure is accelerated, so that it is polymer hardened. Excellent sex.

前述構造部分(I)中，X係表示氫原子或甲基，又，式中的「＊」係表示結合鍵。In the above structural portion (I), X represents a hydrogen atom or a methyl group, and "*" in the formula represents a bond.

本發明中的特定聚合性化合物若為前述具有構造部分(I)之化合物、則沒有特別地限制，可選擇本發明的感光性樹脂組成物的任意1種或2種以上而構成。The specific polymerizable compound in the present invention is not particularly limited as long as it is a compound having the structural portion (I), and any one or two or more kinds of the photosensitive resin compositions of the present invention can be selected.

具有構造部分(I)之化合物係可舉例如：具有1個構造部分(I)之化合物、2或3個以上的構造部分(I)係在各結合鍵(＊)間經由2價或3價以上的連結基而鍵結之化合物、及2個的構造部分(I)係以各結合鍵(＊)而直接鍵結之化合物。The compound having a structural moiety (I) may, for example, be a compound having one structural moiety (I), or two or more structural components (I) via a divalent or trivalent bond between each bonding bond (*). The compound which is bonded by the above-mentioned linking group, and the two structural parts (I) are compounds which are directly bonded by each bonding bond (*).

具有1個構造部分(I)之化合物係可舉例如：在構造部分(I)的結合鍵(＊)、例如在1價烴基之碳-碳間，鍵結含有至少1個醚鍵(-O-)之連結基的化合物。具有1個構造部分(I)之化合物的具體例係可舉例如下述的化合物。此外，下述的各具體例係表示「-X」為「-H」或「-CH3 」之化合物兩者。The compound having one structural moiety (I) may, for example, be a bond (*) in the structural moiety (I), for example, a carbon-carbon in a monovalent hydrocarbon group, and the bond contains at least one ether bond (-O) -) a compound of a linking group. Specific examples of the compound having one structural portion (I) include the following compounds. Further, specific examples of each of the following lines represent "-X" to "-H" or both compounds "-CH 3" of.

其中，從溶解性、黏度等的觀點，以構造部分(I)的結合鍵(＊)上鍵結有醚基、環氧乙烷基、醇基等之化合物為佳，特別是以醚、環氧乙烷基等為佳。Among them, from the viewpoints of solubility, viscosity, and the like, a compound having an ether group, an oxirane group, an alcohol group or the like bonded to the bond (*) of the structural moiety (I) is preferred, particularly an ether or a ring. An oxyethane group or the like is preferred.

前述2價或3價以上的連結基係可從多價的基之中任意地選擇，可舉例如：2價或3價以上的烴基、在2價或3價以上的烴基之碳-碳間含有1或2個以上的醚鍵(-O-)之基、-O-、-S-、酯鍵、醯胺基、胺基等、及組合此等之至少2者的2價基等。The above-mentioned divalent or trivalent or higher linking group may be arbitrarily selected from the polyvalent group, and examples thereof include a divalent or trivalent or higher hydrocarbon group and a carbon-carbon intermetallic group having a divalent or trivalent or higher hydrocarbon group. A group containing one or two or more ether bonds (-O-), -O-, -S-, an ester bond, a guanamine group, an amine group, and the like, and a divalent group or the like in which at least two of them are combined.

2價或3價以上的連結基的具體例係如下所示。但是，在本發明並不受限於此等。此外，具體例中的「＊」係表示結合鍵。Specific examples of the linking group of divalent or trivalent or higher are as follows. However, the invention is not limited thereto. Further, "*" in the specific example means a bond.

從曝光時的聚合進行快速且能進行良好的硬化、即使經低溫加熱與無加熱處理、以能形成有均一性之圖案構造物、保護膜的觀點，較佳係在分子內具有2或3個以上的前述構造部分(I)之特定聚合性化合物。It is preferable to carry out 2 or 3 molecules in the molecule from the viewpoint of rapid polymerization at the time of exposure and good hardening, and even if it is subjected to low-temperature heating and no heat treatment, and a uniform pattern structure or a protective film can be formed. The specific polymerizable compound of the above structural part (I).

此外，基於相同的觀點，較佳係在分子內具有2個構造部分(I)、鍵結含有構造部分(I)之相同的2個基之對稱構造、亦即含有連結2個構造部分(I)之連結基的分子構造全體係構成為對稱構造之化合物為佳。對稱構造的較佳化合物係可舉例如：下述構造式(II)所示之化合物。Further, based on the same viewpoint, it is preferable to have two structural parts (I) in the molecule, and the same two basic structures of the structure containing the structural part (I), that is, the two structural parts (I) The molecular structure of the linking group is preferably a compound having a symmetrical structure. Preferred compounds of the symmetrical structure include, for example, the compounds represented by the following structural formula (II).

在前述構造式(II)中，R係表示含2價烴基之基、或在2價烴基之碳-碳間含有至少1個醚鍵(-O-)之連結基，較佳為在2價烴基之碳-碳間含有至少1個醚鍵(-O-)之連結基。In the above structural formula (II), R represents a group containing a divalent hydrocarbon group or a linking group containing at least one ether bond (-O-) between carbon-carbons of a divalent hydrocarbon group, preferably at a valence of 2 The carbon-carbon of the hydrocarbon group contains a linking group of at least one ether bond (-O-).

R所表示的「含2價烴基之基」係可舉例如：僅以Cn H2n (n≧1)所示之烴基所構成的2價基，及以Cn H2n (n≧1)所示之烴基，與組合選自於醚鍵、酯鍵、醯胺基、胺基等之至少1個的2價基等。n的範圍係在1~8為適宜。"Divalent hydrocarbon group having the" system R for example can be represented as: only divalent group C n H 2n (n ≧ 1 ) of the hydrocarbon group shown constituted, and to C n H 2n (n ≧ 1 ) The hydrocarbon group shown is a combination of a divalent group selected from at least one of an ether bond, an ester bond, a guanamine group, and an amine group. The range of n is suitable from 1 to 8.

又，R所表示的「在2價烴基之碳-碳間含有至少1個醚鍵之連結基」若為含有配置於碳-碳間之1或2個以上的氧原子與碳原子及氫原子之2價基的話，沒有特別地限制，可舉例如：含有-(AL及/或AR)-O-(AL及/或AR)-、-(AL及/或AR)-O-(AL及/或AR)-O-、-(AL及/或AR)-O-(AL及/或AR)-O-(AL及/或AR)-之2價基為適宜。此外，AL表示伸烷基，AR表示伸芳基。In addition, the "linking group containing at least one ether bond between the carbon-carbon of the divalent hydrocarbon group" represented by R includes one or two or more oxygen atoms and carbon atoms and hydrogen atoms disposed between the carbon and carbon. The two-valent group is not particularly limited, and examples thereof include -(AL and/or AR)-O-(AL and/or AR)-, -(AL and/or AR)-O-(AL and / or AR) -O-, - (AL and / or AR) - O - (AL and / or AR) - O - (AL and / or AR) - the divalent group is suitable. Further, AL represents an alkylene group and AR represents an extended aryl group.

前述伸烷基(AL)係可為直鏈、分枝鏈中任一者，前述伸烷基及伸芳基(AR)係可為無取代、亦可為以取代基所取代的。經取代之情形的取代基係可舉例如：與在下述Ra 中所列舉的下述取代基為相同之基。The alkylene group (AL) may be any of a straight chain or a branched chain, and the alkylene group and the extended aryl group (AR) may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be the same group as the substituents listed below in R a .

R之中，從曝光時的聚合進行快速且能進行良好的硬化之點，較佳為含有2以上的氧原子之情形，更佳係-CH2 -O-Ra -O-CH2 -之情形。此處，Ra 係表示由伸烷基部位、伸芳基部位、及此等組合之部位所構成群組所選擇之連結基。在Ra 所示伸烷基部位的碳-碳鍵間，可更配置有1或2個以上的醚鍵。Among R, it is preferred that the polymerization at the time of exposure is rapid and can be well cured, and it is preferable to contain two or more oxygen atoms, and more preferably -CH 2 -OR a -O-CH 2 -. Here, R a represents a linking group selected from the group consisting of an alkyl group, an aryl group, and a combination thereof. Further, one or two or more ether bonds may be disposed between the carbon-carbon bonds of the alkyl group represented by R a .

前述Ra 所表示之伸烷基部位係沒有特別地限制，可無取代、亦可經取代基所取代的。經取代之情形的取代基係可舉例如：碳數1~8的烷基(例；甲基、乙基、丁基、己基、辛基)、羥基、鹵素基等的1價取代基。The alkylene moiety represented by the above R a is not particularly limited and may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be a monovalent substituent such as an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, butyl group, hexyl group or octyl group), a hydroxyl group or a halogen group.

伸烷基部位的具體例係可舉例如：亞甲基、伸乙基、伸丙基、伸丁基、2-羥丙基、2-甲基伸乙基、2-二甲基伸乙基、伸環己基等。Specific examples of the alkylene moiety include, for example, methylene, ethyl, propyl, butyl, 2-hydroxypropyl, 2-methylexylethyl, 2-dimethylexylethyl , stretching the ring and so on.

其中，前述伸烷基部位從溶劑溶解性、析出抑制之點，以碳數1~8的取代或無取代之伸烷基為佳，碳數1~6的取代或無取代之伸烷基為較佳。Wherein, the alkylene group is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms from the viewpoint of solvent solubility and precipitation inhibition. Preferably.

前述Ra 所表示之伸芳基部位係沒有特別地限制，可無取代、亦可經取代基所取代的。經取代之情形的取代基係可舉例如：與在前述伸烷基部位的情形為相同的取代基。The exoaryl moiety represented by the above R a is not particularly limited and may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be the same substituent as in the case of the alkylene moiety described above.

伸芳基部位的具體例係可舉例如伸苯基、伸萘基等。其中，伸芳基部位係從溶劑溶解性、析出抑制之點，以碳數6~10的取代或無取代之伸芳基為佳，碳數6~8的取代或無取代之伸芳基為較佳。Specific examples of the aryl group moiety include a phenyl group and a naphthyl group. Among them, the aryl group is preferably a solvent having a carbon number of 6 to 10 or an unsubstituted aryl group, and a substituted or unsubstituted aryl group having a carbon number of 6 to 8 is a solvent-soluble or precipitation-inhibiting point. Preferably.

又，伸烷基部位及伸芳基部位的組合部位係可舉例如：-C6 H4 -C(CH3 )2 -C6 H4 -、-(CH2 )2 -O-C6 H4 -C(CH3 )2 -C6 H4 -O-(CH2 )2 -、-(CH2 )3 -O-C6 H4 -C(CH3 )2 -C6 H4 -O-(CH2 )3 -等。Further, the combination of the alkyl group and the aryl group may be, for example, -C 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -, -(CH 2 ) 2 -OC 6 H 4 - C(CH 3 ) 2 -C 6 H 4 -O-(CH 2 ) 2 -, -(CH 2 ) 3 -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-(CH 2 ) 3 - wait.

前述R所表示之「-CH2 -O-Ra -O-CH2 -」的具體例係如下所示。但是，在本發明並不受限於此等。此外，具體例中的「＊」係表示結合鍵。Specific examples of "-CH 2 -OR a -O-CH 2 -" represented by the above R are as follows. However, the invention is not limited thereto. Further, "*" in the specific example means a bond.

再者，前述Ra 所表示之連結基從曝光時的聚合反應性為良好之點，以對稱構造為佳。對稱構造之連結基的具體例係可舉例如：上述的具體例(1)、(2)、(4)~(9)等的情形做為具體之例所列舉的。Further, the linking group represented by the above R a is preferably a symmetrical structure because the polymerization reactivity at the time of exposure is good. Specific examples of the linking group of the symmetrical structure include, for example, the specific examples (1), (2), (4), and (9) described above as specific examples.

本發明中特定聚合性化合物的分子量，以重量平均分子量計為100~3000為佳，100~2000為更佳，100~1500為特佳。特定聚合性化合物的分子量為100以上，從抑制昇華之點而言係為所期望的，為3000以下從溶解性之點而言係為所期望的。The molecular weight of the specific polymerizable compound in the present invention is preferably from 100 to 3,000 in terms of weight average molecular weight, more preferably from 100 to 2,000, and particularly preferably from 100 to 1,500. The molecular weight of the specific polymerizable compound is preferably 100 or more, and is desirably from the viewpoint of suppressing sublimation, and is preferably 3,000 or less from the viewpoint of solubility.

此外，重量平均分子量係以凝膠滲透層析法(GPC)來進行測定。關於GPC係詳細表示於後記之實施例的項目中。Further, the weight average molecular weight is measured by gel permeation chromatography (GPC). The GPC system is shown in detail in the item of the following example.

以下，顯示前述具有構造部分(I)之特定聚合性化合物的具體例[例示化合物(1)~(20)及(M-1)~(M-15)]。但是，在本發明並不受限於此等。Hereinafter, specific examples of the specific polymerizable compound having the structural portion (I) [exemplary compounds (1) to (20) and (M-1) to (M-15)] are shown. However, the invention is not limited thereto.

具有構造部分(I)之聚合性化合物(特定聚合性化合物)在感光性樹脂組成物中的含量，係相對於組成物的全固體成分，以1~60質量%為佳，10~55質量%為較佳。特定聚合性化合物的含量為1質量%以上，則曝光時的聚合硬化性係為良好，可形成抑制形狀偏移之圖案構造物、保護膜，且亦可避免經由像在低溫下的加熱處理或無加熱處理所形成之圖案構造物、保護膜的惡化或已經設立的圖案構造物、保護膜的惡化。又，為60質量%以下則對於液體的黏度、硬化物的硬度等的調整、曝光感度的調整等係為有效。The content of the polymerizable compound (specifically polymerizable compound) having the structural portion (I) in the photosensitive resin composition is preferably 1 to 60% by mass, and 10 to 55% by mass based on the total solid content of the composition. It is better. When the content of the specific polymerizable compound is 1% by mass or more, the polymer curable property at the time of exposure is good, and a pattern structure or a protective film which suppresses the shape shift can be formed, and heat treatment at a low temperature or There is no deterioration of the pattern structure formed by the heat treatment, the deterioration of the protective film, or the established pattern structure or the protective film. In addition, when it is 60% by mass or less, adjustment of the viscosity of the liquid, the hardness of the cured product, and the like, adjustment of the exposure sensitivity, and the like are effective.

在本發明的感光性樹脂組成物中，除了上述的特定聚合性化合物以外，亦可更含有具有乙烯性不飽和鍵之其他的聚合性化合物。其他的聚合性化合物係可由構成眾所周知的組成物之聚合性化合物中來選擇使用，可舉例如：特開2006-23696號公報的段落號碼[0010]~[0020]中記載之成分、與特開2006-64921號公報的段落號碼[0027]~[0053]中所記載之成分。In addition to the specific polymerizable compound described above, the photosensitive resin composition of the present invention may further contain another polymerizable compound having an ethylenically unsaturated bond. Other polymerizable compounds may be selected from the group of the polymerizable compounds constituting the well-known composition, and the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696, and The components described in paragraphs [0027] to [0053] of the publication No. 2006-64921.

在不損及本發明效果之範圍內可含有其他的聚合性化合物。Other polymerizable compounds may be contained within the range not impairing the effects of the present invention.

在本發明中，含有特定聚合性化合物之聚合性化合物的合計量、與後述之樹脂的合計量之質量比率[聚合性化合物的合計量/樹脂的合計量]，從顯像性、力學特性之觀點，以0.5~2.0為佳，0.6~1.8為較佳，0.7~1.5為特佳。質量比率在前述範圍内則能得到良好的顯像性，例如當形成光間隔物等時，能夠得到具有力學強度之光間隔物。In the present invention, the mass ratio of the total amount of the polymerizable compound containing the specific polymerizable compound to the total amount of the resin to be described later [the total amount of the polymerizable compound/the total amount of the resin) is based on the development property and the mechanical property. The viewpoint is preferably 0.5 to 2.0, 0.6 to 1.8 is preferred, and 0.7 to 1.5 is particularly preferred. When the mass ratio is within the above range, good developability can be obtained. For example, when a photo spacer or the like is formed, a photo spacer having mechanical strength can be obtained.

<樹脂><Resin>

本發明的感光性樹脂組成物係含有至少一種的樹脂。樹脂係沒有特別地限制，以對於鹼性水溶液顯示膨潤性之化合物為佳，以對於鹼性水溶液顯示溶解性之化合物為較佳。The photosensitive resin composition of the present invention contains at least one kind of resin. The resin is not particularly limited, and a compound which exhibits swelling properties with respect to an aqueous alkaline solution is preferred, and a compound which exhibits solubility in an aqueous alkaline solution is preferred.

對於鹼性水溶液顯示膨潤性或溶解性之樹脂係可舉例如：具有酸性基者為適宜，具體上以在環氧化合物導入乙烯性不飽和雙鍵與酸性基之化合物(環氧丙烯酸酯化合物)、於側鏈具有(甲基)丙烯醯基及酸性基之乙烯基共聚物、環氧丙烯酸酯化合物、與在側鏈具有(甲基)丙烯醯基及酸性基之乙烯基共聚物的混合物、馬來醯胺酸系共聚物等為佳。The resin which exhibits swellability or solubility in an alkaline aqueous solution is, for example, a compound having an acidic group, and specifically a compound (epoxy acrylate compound) in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. a vinyl copolymer having a (meth)acrylonyl group and an acidic group in a side chain, an epoxy acrylate compound, and a vinyl copolymer having a (meth)acrylonyl group and an acidic group in a side chain, A maleic acid-based copolymer or the like is preferred.

前述酸性基係沒有特別地限制，可視其目的來適當選擇，可舉例如：羧基、磺酸基、磷酸基等，此等之中，從原料的入手性等之觀點，以羧基為佳。The acidic group is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred from the viewpoint of the starting property of the raw material and the like.

樹脂在本發明之感光性樹脂組成物中的含量，係相對於感光性樹脂組成物的全固體成分，以5~70質量%為佳，10~50質量%為較佳。該含量為5質量%以上則能維持感光樹脂層的膜強度，且能良好地保持該感光樹脂層的表面黏著性，為70質量%以下則曝光感度係為良好。The content of the resin in the photosensitive resin composition of the present invention is preferably from 5 to 70% by mass, preferably from 10 to 50% by mass, based on the total solid content of the photosensitive resin composition. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the surface adhesiveness of the photosensitive resin layer can be favorably maintained. When the content is 70% by mass or less, the exposure sensitivity is good.

在本發明中的樹脂係從在聚合硬化後施加外力而變形之際的變形回復性為良好之點，較佳為含有在側鏈具有分枝及/或脂環構造、酸性基、以及乙烯性不飽和鍵之樹脂(以下，亦稱為「樹脂A」)的至少1種之情形。The resin in the present invention is excellent in deformation recovery property when deformed by applying an external force after polymerization hardening, and preferably contains a branching and/or alicyclic structure, an acidic group, and an ethyl group in a side chain. At least one of a resin having an unsaturated bond (hereinafter also referred to as "resin A").

樹脂A係具有酸性基而具備顯像性的同時，藉由具有乙烯性不飽和鍵，由於具備高的聚合反應性、且具有優異的液保存性及在乾膜的經時保存性，所以能賦予圖案構造物可控制成所期望的形狀及膜厚(高度等)的控制性。又，具有分枝及/或脂環構造，且可提高所形成之圖案構造物受到外力之際的壓縮彈性率、由壓縮變形的變形回復性。因此，在構成例如顯示裝置用的光間隔物等的圖案構造物上係為有用的。Resin A has an acidic group and has developability, and has an ethylenically unsaturated bond, and has high polymer reactivity, excellent liquid storage stability, and long-term storage stability of a dry film. The pattern structure can be controlled to have a desired shape and controllability of film thickness (height, etc.). Further, it has a branching and/or alicyclic structure, and can improve the compressive modulus of elasticity of the formed pattern structure when subjected to an external force, and the deformation recovery property by compression deformation. Therefore, it is useful for forming a pattern structure such as a photo spacer for a display device.

此處，分枝及/或脂環構造、酸性基、以及乙烯性不飽和鍵係可含有於分別不同的側鏈中，亦可組合一部份而含有於相同的側鏈中，也可以全部含有於相同的側鏈中。Here, the branching and/or alicyclic structure, the acidic group, and the ethylenically unsaturated bond may be contained in different side chains, or may be combined in one part and contained in the same side chain, or may be all Contained in the same side chain.

此外，在本說明書中，(甲基)丙烯醯基係表示丙烯醯基或甲基丙烯醯基，(甲基)丙烯酸酯係表示丙烯酸酯或甲基丙烯酸酯，(甲基)丙烯酸係表示丙烯酸或甲基丙烯酸，(甲基)丙烯醯胺係表示丙烯醯胺或甲基丙烯醯胺，(甲基)丙烯醯苯胺係表示丙烯醯苯胺或甲基丙烯醯苯胺。Further, in the present specification, the (meth)acrylonitrile group means an acryloyl group or a methacryloyl group, the (meth)acrylate means an acrylate or a methacrylate, and the (meth)acrylic means an acrylic acid. Or methacrylic acid, (meth) acrylamide refers to acrylamide or methacrylamide, and (meth) acryl anilide means acrylamide or methacrylamide.

(分枝及/或脂環構造)(branched and / or alicyclic structure)

樹脂A係在鍵結於樹脂主鏈之側鏈上，至少含有1種的分枝及/或脂環構造。分枝及/或脂環構造係可複數含有於樹脂A的側鏈中。又，分枝及/或脂環構造係可與酸性基及/或乙烯性不飽和鍵一起含有於樹脂A的側鏈中。Resin A is bonded to the side chain of the resin main chain and contains at least one type of branching and/or alicyclic structure. The branched and/or alicyclic structure may be plurally contained in the side chain of the resin A. Further, the branching and/or alicyclic structure may be contained in the side chain of the resin A together with the acidic group and/or the ethylenically unsaturated bond.

又，分枝及/或脂環構造係可直接鍵結於樹脂A的主鏈上，且可僅以分枝及/或脂環構造來構成樹脂A的側鏈，亦可透過2價的有機連結基鍵結於樹脂A的主鏈上，來構成具有分枝及/或脂環構造之基的樹脂A的側鏈。Further, the branching and/or alicyclic structure may be directly bonded to the main chain of the resin A, and may constitute a side chain of the resin A only by a branching and/or alicyclic structure, or may be a divalent organic substance. The linking group is bonded to the main chain of the resin A to form a side chain of the resin A having a branching and/or alicyclic structure.

前述2價的有機連結基較佳為選自於伸烷基、伸芳基、酯基、醯胺基、及醚基之一者或其組合。前述伸烷基係以總碳數1~20的伸烷基為佳，尤佳為1~10。具體上，可舉例如：亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸辛基、十二烯基、十八烯基等，此等係可具有分枝/環狀構造、官能基，尤佳為亞甲基、伸乙基、伸辛基。前述伸芳基係以總碳數6~20的伸芳基為佳，尤佳為6~12。具體上，可舉例如：伸苯基、伸聯苯基、萘基、蒽基等，此等係可具有分枝、官能基，尤佳為伸苯基、伸聯苯基。The divalent organic linking group is preferably selected from one of an alkylene group, an extended aryl group, an ester group, a decylamino group, and an ether group, or a combination thereof. The alkylene group is preferably an alkylene group having a total carbon number of from 1 to 20, particularly preferably from 1 to 10. Specifically, for example, a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecenyl group, an octadecyl group, etc., may be mentioned. Branch/ring structure, functional group, especially preferably methylene, ethyl, and octyl. The above-mentioned aryl group is preferably a aryl group having a total carbon number of 6 to 20, particularly preferably 6 to 12. Specifically, for example, a phenyl group, a phenylene group, a naphthyl group, a fluorenyl group or the like may be mentioned, and these may have a branch or a functional group, and more preferably a phenyl group or a phenyl group.

分枝及/或脂環構造係從顯像性、彈性回復率等的觀點，以能透過至少酯基(-COO-)鍵結於樹脂A之主鏈的形態為佳。該形態係分枝及/或脂環構造不限於僅透過酯基(-COO-)而鍵結於樹脂A之主鏈的形態，亦可為分枝及/或脂環構造為透過含有酯基(-COO-)之2價的連結基而鍵結於樹脂A之主鏈的形態。亦即，分枝及/或脂環構造與酯鏈之間、及/或酯鏈與樹脂A的主鏈之間，亦可含有其他的原子與其他的連結基。The branching and/or alicyclic structure is preferably a form capable of permeating at least an ester group (-COO-) to the main chain of the resin A from the viewpoints of developmental properties, elastic recovery ratio, and the like. The branching and/or alicyclic structure of the form is not limited to a form in which the main chain of the resin A is bonded only by the ester group (-COO-), and the branch and/or the alicyclic structure may be configured to transmit the ester group. The divalent linking group of (-COO-) is bonded to the main chain of the resin A. That is, between the branch and/or alicyclic structure and the ester chain, and/or between the ester chain and the main chain of the resin A, other atoms and other linking groups may be contained.

前述分枝構造係可舉例如碳原子數3~12個之分枝狀的烷基，例如以異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、2-甲基丁基、異己基、2-乙基己基、2-甲基己基、異戊基、第三戊基、3-辛基、第三辛基等為佳。此等之中，尤以異丙基、第二丁基、第三丁基、異戊基等為更佳，以異丙基、第二丁基、第三丁基等為特佳。The above branched structure may, for example, be a branched alkyl group having 3 to 12 carbon atoms, for example, an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, an isopentyl group or a neopentyl group. Further, 2-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, isopentyl, third amyl, 3-octyl, trioctyl or the like is preferred. Among these, an isopropyl group, a second butyl group, a tert-butyl group, an isopentyl group or the like is more preferable, and an isopropyl group, a second butyl group, a third butyl group or the like is particularly preferable.

前述脂環構造係可舉例如碳原子數5~20個的脂環式烴基，例如以環戊基、環己基、環庚基、環辛基、降基、異基、金剛烷基、三環癸基、二環戊烯基、二環戊基、三環戊烯基、及三環戊基等以及具有此等之基為佳。此等之中，尤以二環戊烯基、環己基、降基、異基、金剛烷基、三環癸基、三環戊烯基、三環戊基等為更佳，以二環戊烯基、環己基、降基、異基、三環戊烯基等為更佳，以二環戊烯基、三環戊烯基為特佳。The alicyclic structure may, for example, be an alicyclic hydrocarbon group having 5 to 20 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a lower group. Basis The base, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentyl group, tricyclopentenyl group, and tricyclopentyl group, and the like are preferred. Among these, especially dicyclopentenyl, cyclohexyl, and descending Basis More preferably, adamantyl, tricyclodecyl, tricyclopentenyl, tricyclopentyl or the like is dicyclopentenyl, cyclohexyl, or Basis More preferably, a tricyclopentenyl group or the like is preferable, and a dicyclopentenyl group or a tricyclopentenyl group is particularly preferred.

再者，具有分枝及/或脂環構造之基係以具有下述通式(3)所示之基所構成的形態為佳。Further, it is preferred that the base having a branched and/or alicyclic structure is constituted by a group having a group represented by the following formula (3).

通式(3)中，X係表示2價的有機連結基，可無取代、亦可具有取代基。y係表示1或2，n係表示0~15的整數。In the formula (3), X represents a divalent organic linking group, and may be unsubstituted or may have a substituent. The y system represents 1 or 2, and the n system represents an integer of 0 to 15.

前述2價的有機連結基係為選自於伸烷基、伸芳基、酯基、醯胺基、及醚基之一者或其組合為佳，此等係亦可具有取代基。The divalent organic linking group is preferably one selected from the group consisting of an alkylene group, an extended aryl group, an ester group, a decylamino group, and an ether group, or a combination thereof, and these may have a substituent.

前述伸烷基係以總碳數1~20的伸烷基為佳，尤佳為1~10的伸烷基。具體上，可舉例如亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸辛基、十二烯基、十八烯基等的基，此等係可具有分枝/環狀構造、官能基，尤佳為亞甲基、伸乙基、伸辛基。The alkylene group is preferably an alkylene group having a total carbon number of 1 to 20, particularly preferably an alkylene group having 1 to 10 carbon atoms. Specifically, for example, a group such as a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecenyl group, an octadecyl group or the like may be mentioned. It has a branched/annular structure and a functional group, and is particularly preferably a methylene group, an ethyl group, and an extended octyl group.

前述伸芳基係以總碳數6~20的伸芳基為佳，尤佳為6~12的伸芳基。具體上，可舉例如伸苯基、伸聯苯基、萘基、蒽基等，此等係可具有分枝、官能基，尤佳為伸苯基、伸聯苯基。The above-mentioned aryl group is preferably an extended aryl group having a total carbon number of 6 to 20, and particularly preferably an extended aryl group of 6 to 12. Specifically, for example, a phenyl group, a phenylene group, a naphthyl group, a fluorenyl group or the like may be mentioned, and these may have a branch or a functional group, and more preferably a phenyl group or a phenyl group.

經取代之情形的取代基，可舉例如具有烷基、羥基、胺基、鹵素基、芳香環基、脂環構造之基等。The substituent in the case of substitution may, for example, be an alkyl group, a hydroxyl group, an amine group, a halogen group, an aromatic ring group or a alicyclic structure.

在樹脂A的合成中，用以將分枝及/或脂環構造導入側鏈用的單體係可舉例如：苯乙烯類、(甲基)丙烯酸酯類、乙烯基醚類、乙烯基酯類、(甲基)丙烯醯胺類等，以(甲基)丙烯酸酯類、乙烯基酯類、(甲基)丙烯醯胺類為佳，以(甲基)丙烯酸酯類為較佳。In the synthesis of the resin A, a single system for introducing a branching and/or alicyclic structure into a side chain may, for example, be a styrene, a (meth) acrylate, a vinyl ether or a vinyl ester. The (meth) acrylates, vinyl esters, and (meth) acrylamides are preferred, and (meth) acrylates are preferred.

在樹脂A的合成中，用以將分枝構造導入側鏈之具體單體係可舉例如：(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸第三戊酯、(甲基)丙烯酸第二異戊酯、(甲基)丙烯酸2-辛酯、(甲基)丙烯酸3-辛酯、(甲基)丙烯酸第三辛酯等，其中，尤以(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、甲基丙烯酸第三丁酯等為佳，以甲基丙烯酸異丙酯、甲基丙烯酸第三丁酯等為較佳。In the synthesis of the resin A, a specific single system for introducing the branched structure into the side chain may, for example, be isopropyl (meth)acrylate, isobutyl (meth)acrylate, or (meth)acrylic acid second. Butyl ester, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, third amyl (meth)acrylate, second isoamyl (meth)acrylate, 2-(meth)acrylate Octyl ester, 3-octyl (meth)acrylate, and third octyl (meth)acrylate, among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, methacrylic acid Tributyl ester or the like is preferred, and isopropyl methacrylate, butyl methacrylate or the like is preferred.

在樹脂A的合成中，用以導入脂環構造於側鏈用的單體係可舉例如具有碳原子數5~20個之脂環式烴基的(甲基)丙烯酸酯。具體之例可舉例如：(甲基)丙烯酸(雙環[2.2.1]庚基-2)酯、(甲基)丙烯酸1-金剛烷酯、(甲基)丙烯酸2-金剛烷酯、(甲基)丙烯酸3-甲基-1-金剛烷酯、(甲基)丙烯酸3,5-二甲基-1-金剛烷酯、(甲基)丙烯酸3-乙基金剛烷酯、(甲基)丙烯酸3-甲基-5-乙基-1-金剛烷酯、(甲基)丙烯酸3,5,8-三乙基-1-金剛烷酯、(甲基)丙烯酸3,5-二甲基-8-乙基-1-金剛烷酯、(甲基)丙烯酸2-甲基-2-金剛烷酯、(甲基)丙烯酸2-乙基-2-金剛烷酯、(甲基)丙烯酸3-羥基-1-金剛烷酯、(甲基)丙烯酸八氫-4,7-烷基茚-5-酯、(甲基)丙烯酸八氫-4,7-烷基茚-1-基甲酯、(甲基)丙烯酸1-酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸3-羥基-2,6,6-三甲基-雙環[3.1.1]庚酯、(甲基)丙烯酸3,7,7-三甲基-4-羥基-雙環[4.1.0]庚酯、(甲基)丙烯酸(降)酯、(甲基)丙烯酸異酯、(甲基)丙烯酸小茴香酯、(甲基)丙烯酸2,2,5-三甲基環己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸三環戊烯酯等。In the synthesis of the resin A, a single system for introducing an alicyclic structure to a side chain may, for example, be a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2) ester, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (A) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, (methyl) 3-methyl-5-ethyl-1-adamantyl acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl (meth)acrylate -8-ethyl-1-adamantyl ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylic acid 3 -hydroxy-1-adamantyl ester, octahydro-4,7-(meth)acrylate Alkyl oxime-5-ester, octahydro-4,7-(meth)acrylate Alkyl inden-1-yl methyl ester, (meth)acrylic acid 1- Ester, tricyclodecyl (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7 (meth)acrylic acid -trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (meth)acrylic acid (decreasing) Ester, (meth)acrylic acid Ester, fenyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, ( Tricyclopentenyl ester of methyl) acrylate.

此等(甲基)丙烯酸酯之中，從體積越大的官能基壓縮彈性率、變形回復性越良好之點，以(甲基)丙烯酸環己酯、(甲基)丙烯酸(降)酯、(甲基)丙烯酸異酯、(甲基)丙烯酸1-金剛烷酯、(甲基)丙烯酸2-金剛烷酯、(甲基)丙烯酸小茴香酯、(甲基)丙烯酸1-酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸三環戊烯酯等為佳，以(甲基)丙烯酸環己酯、(甲基)丙烯酸(降)酯、(甲基)丙烯酸異酯、(甲基)丙烯酸2-金剛烷酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸三環戊烯酯為特佳。Among these (meth) acrylates, the higher the volume of the functional group, the better the compression modulus and the recovery property of the deformation, and the cyclohexyl (meth)acrylate and the (meth)acrylic acid (lower) Ester, (meth)acrylic acid Ester, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenyl (meth)acrylate, 1-(meth)acrylate Ester, tricyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentenyl (meth)acrylate, etc., preferably cyclohexyl (meth)acrylate, (methyl) Acrylic (lower) Ester, (meth)acrylic acid The ester, 2-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and tricyclopentenyl (meth)acrylate are particularly preferred.

又，在樹脂A的合成中，將脂環構造導入於側鏈用的單體係可舉例如下述通式(4)或(5)所示之化合物。此處，在通式(4)、(5)中，X係表示2價的有機連結基，R係表示氫原子或甲基，y係表示1或2，n係表示0~15。通式(4)、(5)之中，尤以y=1或2、n=0~8為佳，較佳為y=1或2、n=0~4(更佳為n=0~2)。通式(4)或(5)所示之化合物的較佳具體例係可舉例如下述化合物D-1~D-11、T-1~T-12。In the synthesis of the resin A, the single system for introducing the alicyclic structure into the side chain may, for example, be a compound represented by the following formula (4) or (5). Here, in the general formulae (4) and (5), X represents a divalent organic linking group, R represents a hydrogen atom or a methyl group, y represents 1 or 2, and n represents 0-15. Among the general formulae (4) and (5), y=1 or 2 and n=0 to 8 are preferable, and y=1 or 2 and n=0 to 4 (more preferably n=0). 2). Preferable specific examples of the compound represented by the formula (4) or (5) include the following compounds D-1 to D-11 and T-1 to T-12.

其中，從變形回復率之點，以下述通式(4)所示之化合物為佳。Among them, from the point of the deformation recovery rate, a compound represented by the following formula (4) is preferred.

在前述通式(4)~(5)中，X所示之2價的有機連結基係可無取代、亦可具有取代基，與前述通式(3)中的X所示之2價的有機連結基同義，較佳態樣亦為相同。In the above formulae (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and may be a divalent group represented by X in the above formula (3). The organic linking group is synonymous, and the preferred aspect is also the same.

在樹脂A的合成中，將脂環構造導入於側鏈用的單體係可使用適宜製造者，亦可使用市售品。In the synthesis of the resin A, a single system for introducing the alicyclic structure into the side chain can be used as a suitable manufacturer, and a commercially available product can also be used.

前述市售品係可舉例如日立化成工業(股)製；FA-511A、FA-512A(S)、FA-512M、FA-513A、FA-513M、TCPD-A、TCPD-M、H-TCPD-A、H-TCPD-M、TOE-A、TOE-M、H-TOE-A、H-TOE-M等。此等之中，從顯像性優異、變形回復率優異之點而言，以FA-512A(S)、512M為佳。The commercially available product may, for example, be manufactured by Hitachi Chemical Co., Ltd.; FA-511A, FA-512A(S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD -A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M, and the like. Among these, FA-512A (S) and 512 M are preferable from the viewpoint of excellent developability and excellent deformation recovery.

(酸性基)(acid base)

樹脂A係在鍵結於主鏈之側鏈上，具有至少1種的酸性基。酸性基係可複數含有於側鏈中。又，酸性基係可與前述分枝及/或脂環構造、以及在與主鏈之間透過酯基所配置的乙烯性不飽和鍵一起含有於在樹脂A的側鏈中。Resin A has at least one acidic group bonded to the side chain bonded to the main chain. The acidic group may be plurally contained in the side chain. Further, the acidic group may be contained in the side chain of the resin A together with the branching and/or alicyclic structure and the ethylenically unsaturated bond disposed between the main chain and the ester group.

又，前述酸性基係可直接鍵結於樹脂A的主鏈上而僅以酸性基來構成樹脂A的側鏈，亦可透過2價的有機連結基鍵結於樹脂A的主鏈上，而構成為具有酸性基之基的樹脂A的側鏈。此處，關於2價的有機連結基係可舉例如在前述分枝及/或脂環構造的説明中所例示之2價的有機連結基，較佳範圍亦為相同。Further, the acidic group may be directly bonded to the main chain of the resin A to form a side chain of the resin A only by an acidic group, or may be bonded to the main chain of the resin A through a divalent organic linking group. A side chain of the resin A which is constituted by a group having an acidic group. Here, the divalent organic linking group may be, for example, a divalent organic linking group exemplified in the description of the branching and/or alicyclic structure, and the preferred range is also the same.

前述酸性基係沒有特別地限制，可從眾所周知者之中來適當選擇，可舉例如：羧基、磺酸基、磺醯胺基、磷酸基、酚性羥基等。此等之中，從顯像性、及硬化膜的耐水性為優異之點，以羧基、酚性羥基為佳。The acidic group is not particularly limited, and may be appropriately selected from among those skilled in the art, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfonylamino group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, a carboxyl group and a phenolic hydroxyl group are preferred from the viewpoints of excellent development properties and water resistance of the cured film.

在樹脂A的合成中，導入前述酸性基用的單體之具體例係可從眾所周知者之中來適當選擇，可舉例如：(甲基)丙烯酸、乙烯基安息香酸、馬來酸、馬來酸單烷基酯、富馬酸、衣康酸、丁烯酸、桂皮酸、山梨酸、α-氰基桂皮酸、丙烯酸二聚物、具有羥基之單體與環狀酸酐的加成反應物、ω-羧基-聚己酸內酯單(甲基)丙烯酸酯等。此等係可使用適宜製造者，亦可使用市售品。In the synthesis of the resin A, a specific example of the monomer for introducing the acidic group described above can be appropriately selected from known ones, and examples thereof include (meth)acrylic acid, vinylbenzoic acid, maleic acid, and Malay. Addition reaction of acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano cinnamic acid, acrylic acid dimer, monomer having hydroxyl group and cyclic acid anhydride , ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. These may be used by a suitable manufacturer or a commercially available product.

前述具有羥基之單體與環狀酸酐的加成反應物中所使用的具有羥基之單體，可舉例如：2-羥乙基(甲基)丙烯酸酯等。前述環狀酸酐係可舉例如：馬來酸酐、苯二甲酸酐、環己烷二羧酸酐等。The monomer having a hydroxyl group used in the addition reaction of the monomer having a hydroxyl group and the cyclic acid anhydride may, for example, be 2-hydroxyethyl (meth)acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride.

單體的市售品係可舉例如：東亞合成化學工業(股)製；ARONIX M-5300、ARONIX M-5400、ARONIX M-5500、ARONIX M-5600、新中村化學工業(股)製；NK ESTER CB-1、NK ESTER CBX-1、共榮社油脂化學工業(股)製；HOA-MP、HOA-MS、大阪有機化學工業(股)製；VISCOAT#2100等。此等之中，從顯像性優異、低成本之點，以(甲基)丙烯酸等為佳。Commercially available monomers include, for example, East Asian Synthetic Chemical Industry Co., Ltd.; ARONIX M-5300, ARONIX M-5400, ARONIX M-5500, ARONIX M-5600, and New Nakamura Chemical Industry Co., Ltd.; NK ESTER CB-1, NK ESTER CBX-1, Kyoeisha Oil Chemical Industry Co., Ltd.; HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd.; VISCOAT #2100. Among these, (meth)acrylic acid or the like is preferred from the viewpoint of excellent developability and low cost.

(乙烯性不飽和鍵)(ethylenically unsaturated bond)

樹脂A係在側鏈含有至少1種的乙烯性不飽和鍵。在樹脂A中，乙烯性不飽和鍵較佳係透過酯基配置在與主鏈之間。該乙烯性不飽和鍵係可複數含有於側鏈中。又，乙烯性不飽和鍵係可與前述分枝及/或脂環構造、以及/或前述酸性基一起含有於樹脂A的側鏈中。Resin A contains at least one kind of ethylenically unsaturated bond in a side chain. In the resin A, the ethylenically unsaturated bond is preferably disposed between the main chain through the ester group. The ethylenically unsaturated bond may be plurally contained in the side chain. Further, the ethylenically unsaturated bond may be contained in the side chain of the resin A together with the above-mentioned branching and/or alicyclic structure and/or the aforementioned acidic group.

又，乙烯性不飽和鍵係可透過至少1個酯基(-COO-)鍵結於與樹脂A的主鏈之間，亦可僅以乙烯性不飽和鍵與酯基來構成樹脂A的側鏈。又，在樹脂A的主鏈與酯基之間、及/或在酯基與乙烯性不飽和鍵之間，可更具有2價的有機連結基，乙烯性不飽和鍵係亦可構成「在與主鏈之間具有透過酯基所配置的乙烯性不飽和鍵之基」的樹脂A之側鏈。此處，關於2價的有機連結基，可舉例如在分枝及/或脂環構造的説明中所例示之2價的有機連結基，較佳範圍亦為相同。Further, the ethylenically unsaturated bond may be bonded to the main chain of the resin A through at least one ester group (-COO-), or may form the side of the resin A only by an ethylenically unsaturated bond and an ester group. chain. Further, a divalent organic linking group may be further provided between the main chain of the resin A and the ester group, and/or between the ester group and the ethylenically unsaturated bond, and the ethylenically unsaturated bond may also constitute A side chain of the resin A having a group having an ethylenically unsaturated bond disposed through the ester group with the main chain. Here, the divalent organic linking group may, for example, be a divalent organic linking group exemplified in the description of the branching and/or alicyclic structure, and the preferred range is also the same.

又，乙烯性不飽和鍵係較佳為導入(甲基)丙烯醯基而配置的。Further, the ethylenically unsaturated bond is preferably disposed by introducing a (meth)acrylonitrile group.

在樹脂A的合成中，將(甲基)丙烯醯基導入於側鏈之方法係可從眾所周知的方法之中來適當選擇，可舉例如：將具有環氧基之(甲基)丙烯酸酯附加於具有酸性基之重複單位的方法、將具有異氰酸酯基之(甲基)丙烯酸酯附加於具有羥基之重複單位的方法、將具有羥基之(甲基)丙烯酸酯附加於具有異氰酸酯基之重複單位的方法等。In the synthesis of the resin A, a method of introducing a (meth) acrylonitrile group into a side chain can be appropriately selected from known methods, and for example, a (meth) acrylate having an epoxy group may be added. a method of adding a repeating unit having an acidic group, a method of attaching a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and attaching a (meth) acrylate having a hydroxyl group to a repeating unit having an isocyanate group. Method, etc.

其中，尤以在具有酸性基之重複單位上，附加具有環氧基之(甲基)丙烯酸酯的方法為最容易製造，從低成本之點而言為佳。Among them, a method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group is particularly easy to manufacture, and it is preferable from the viewpoint of low cost.

前述具有環氧基之(甲基)丙烯酸酯係沒有特別地限制，例如以下述構造式(A)所示之化合物及下述構造式(B)所示之化合物為佳。The (meth) acrylate having an epoxy group is not particularly limited, and for example, a compound represented by the following structural formula (A) and a compound represented by the following structural formula (B) are preferred.

前述構造式(A)中，R1 係表示氫原子或甲基。L1 係表示有機基。In the above structural formula (A), R 1 represents a hydrogen atom or a methyl group. L 1 represents an organic group.

前述構造式(B)中，R2 係表示氫原子或甲基。L2 係表示有機基。W係表示4~7員環的脂肪族烴基。In the above structural formula (B), R 2 represents a hydrogen atom or a methyl group. L 2 represents an organic group. The W system represents an aliphatic hydrocarbon group of a 4 to 7 membered ring.

前述構造式(A)所示之化合物及構造式(B)所示之化合物之中，以構造式(A)所示之化合物比構造式(B)要更好。在前述構造式(A)及(B)中，L1 及L2 係各自獨立為碳數1~4之伸烷基者為較佳。Among the compounds represented by the above structural formula (A) and the compounds represented by the structural formula (B), the compound represented by the structural formula (A) is more preferable than the structural formula (B). In the above structural formulae (A) and (B), it is preferred that each of L 1 and L 2 is independently an alkyl group having 1 to 4 carbon atoms.

前述構造式(A)所示之化合物或構造式(B)所示之化合物係沒有特別地限制，可舉例如以下之例示化合物(1)~(10)。The compound represented by the above structural formula (A) or the compound represented by the structural formula (B) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (10).

~~其他的單體~~~~Other monomers~~

在本發明的樹脂A中，可使用其他的單體導入其他的基。In the resin A of the present invention, other monomers may be introduced into other groups.

前述其他的單體係沒有特別地限制，可舉例如：(甲基)丙烯酸酯、苯乙烯、具有乙烯基醚基、二元酸酐基、乙烯基酯基、烴烯基等的單體等。The other single system described above is not particularly limited, and examples thereof include (meth) acrylate, styrene, and a monomer having a vinyl ether group, a dibasic acid anhydride group, a vinyl ester group, or a hydrocarbon alkenyl group.

前述乙烯基醚基係沒有特別地限制，可舉例如：丁基乙烯基醚基等。The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group and the like.

前述二元酸酐基係沒有特別地限制，可舉例如：馬來酸酐基、衣康酸酐基等。The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.

前述乙烯基酯基係沒有特別地限制，可舉例如：乙酸乙烯酯基等。The vinyl ester group is not particularly limited, and examples thereof include a vinyl acetate group and the like.

前述烴烯基係沒有特別地限制，可舉例如：丁二烯基、異戊二烯基等。The hydrocarbon alkenyl group is not particularly limited, and examples thereof include a butadienyl group and a prenyl group.

在前述樹脂A中的其他單體之含有率係組成比為1~40質量%為佳，2~30質量%為更佳。The content ratio of the other monomer in the resin A is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass.

樹脂A的具體例係可舉例如：下述構造所示之化合物(例示化合物P-1~P-56)。Specific examples of the resin A include, for example, compounds represented by the following structures (exemplary compounds P-1 to P-56).

又，例示化合物中的x、y、及z係表示各重複單位的組成比(質量比)，以後述的較佳範圍所構成之形態為適宜。又，各例示化合物的重量平均分子量亦以後述的較佳範圍所構成之形態為適宜。Further, x, y, and z in the exemplified compound indicate the composition ratio (mass ratio) of each repeating unit, and the form constituting the preferred range described later is suitable. Further, the weight average molecular weight of each of the exemplified compounds is also preferably in the form of a preferred range described later.

~合成法~~Synthesis method~

樹脂A係可由單體的(共)聚合反應之步驟、與導入乙烯性不飽和基之步驟的二階段步驟來進行合成。The resin A can be synthesized by a step of (co)polymerization of a monomer and a two-stage step of a step of introducing an ethylenically unsaturated group.

首先，(共)聚合反應係可由各種的單體(共)聚合反應來製作，沒有特別地限制，可從眾所周知者之中來適當選擇。例如，關於聚合的活性種，可適當選擇自由基聚合、陽離子聚合、陰離子聚合、配位聚合等。此等之中，從合成為容易，低成本之點而言，以自由基聚合為佳。又，關於聚合方法亦沒有特別地限制，可從眾所周知者之中來適當選擇。例如，可適當選擇整體聚合法、懸浮聚合法、乳化聚合法、溶液聚合法等。此等之中，尤以溶液聚合法係為所更為期望的。First, the (co)polymerization reaction can be produced by various monomer (co)polymerization reactions, and is not particularly limited, and can be appropriately selected from among those skilled in the art. For example, as the active species to be polymerized, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, or the like can be appropriately selected. Among these, from the viewpoint of easy synthesis and low cost, radical polymerization is preferred. Further, the polymerization method is not particularly limited, and can be appropriately selected from among those skilled in the art. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like can be appropriately selected. Among these, the solution polymerization method is particularly desirable.

~碳數~~Core number~

樹脂A的主鏈之總碳數係從彈性係數(硬度)之點而言，以10以上為佳。其中，總碳數係以10~30為更佳，特佳為10~15。The total carbon number of the main chain of the resin A is preferably 10 or more from the viewpoint of the modulus of elasticity (hardness). Among them, the total carbon number is preferably 10 to 30, and particularly preferably 10 to 15.

~分子量~~Molecular weight~

樹脂A的分子量以重量平均分子量計為10,000~10萬為佳，12,000~60,000為更佳，15,000~45,000為特佳。重量平均分子量在前述範圍内，則從樹脂(較佳為共聚物)的製造適性、顯像性之點而言係為所期望的。又，藉由溶融黏度的降低所形成之形狀係從不易塌陷之點而言，又從不易變成交聯不良之點而言、從顯像中沒有間隔物形狀的殘渣之點而言為佳。The molecular weight of the resin A is preferably 10,000 to 100,000 in terms of weight average molecular weight, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of the production suitability and developability of the resin (preferably a copolymer). Further, the shape formed by the decrease in the melt viscosity is preferably from the point where the collapse is not likely to occur, and the point at which the residue of the spacer is not visible in the development is preferable.

重量平均分子量係利用凝膠滲透層析法(GPC)來測定。關於GPC係詳細表示於後記之實施例的項目中。The weight average molecular weight is determined by gel permeation chromatography (GPC). The GPC system is shown in detail in the item of the following example.

~玻璃轉移溫度~~ glass transfer temperature ~

樹脂A的玻璃轉移溫度(Tg)係以40~180℃為佳，45~140℃為較佳，50~130℃為特佳。玻璃轉移溫度(Tg)在前述的較佳範圍内，則能得到具有良好的顯像性、力學強度之間隔物。The glass transition temperature (Tg) of the resin A is preferably 40 to 180 ° C, preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the above preferred range, a spacer having good developability and mechanical strength can be obtained.

~酸價~~acid price~

樹脂A的酸價係因取得之分子構造而變動較佳的範圍，惟一般係20mgKOH/g以上為佳，40mgKOH/g以上為較佳，50~130mgKOH/g為特佳。酸價在前述較佳範圍内，則能得到具有良好的顯像性、力學強度之間隔物。The acid value of the resin A is preferably in a range which is preferably changed by the molecular structure obtained, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and particularly preferably 50 to 130 mgKOH/g. When the acid value is within the above preferred range, a spacer having good developability and mechanical strength can be obtained.

~Tg~~Tg~

前述樹脂A係從能得到具有良好的顯像性、力學強度之間隔物之點，以玻璃轉移溫度(Tg)為40~180℃，且重量平均分子量為10,000~100,000為佳，Tg為45~140℃(更佳為50~130℃)，且重量平均分子量為12,000~60,000(更佳為15,000~45,000)為佳。The resin A is preferably a glass transition temperature (Tg) of 40 to 180 ° C and a weight average molecular weight of 10,000 to 100,000, and a Tg of 45 to a point at which a spacer having good developability and mechanical strength can be obtained. It is preferably 140 ° C (more preferably 50 to 130 ° C) and has a weight average molecular weight of 12,000 to 60,000 (more preferably 15,000 to 45,000).

再者，前述樹脂A的較佳例更佳係前述的較佳分子量、玻璃轉移溫度(Tg)、及酸價的組合。Further, a preferred example of the above resin A is more preferably a combination of the above preferred molecular weight, glass transition temperature (Tg), and acid value.

在本發明中樹脂A的較佳形態，以分枝及/或脂環構造、酸性基、與(較佳為在與主鏈之間透過酯基而配置的)乙烯性不飽和鍵為分別具有於其他的重複單位(共聚合單位)之3元共聚合以上的共聚物，從形成圖案構造物(例如彩色濾光片用的間隔物)時的變形回復率、顯像殘渣、網狀組織之觀點而言為佳。In the present invention, a preferred embodiment of the resin A has a branching and/or alicyclic structure, an acidic group, and an ethylenically unsaturated bond (preferably disposed between the main chain and the ester group). Copolymerization of the above copolymer in the other three repeating units (copolymerization units), deformation recovery rate, development residue, and network structure when forming a pattern structure (for example, a spacer for a color filter) It is better from a point of view.

具體上，前述樹脂A係至少含有：具有分枝及/或脂環構造之重複單位：X(x莫耳%)、具有酸性基之重複單位：Y(y莫耳%)、與具有(較佳為在主鏈之間透過酯基而配置的)乙烯性不飽和鍵之重複單位：Z(z莫耳%)之3元共聚合以上的共聚物為佳。再者，亦可按照需要含有其他的重複單位：L(1莫耳%)。Specifically, the resin A contains at least: a repeating unit having a branching and/or alicyclic structure: X (x mole %), a repeating unit having an acidic group: Y (y mole %), and having Preferably, the repeating unit of the ethylenically unsaturated bond which is disposed between the main chain and the ester group is a copolymer of 3 or more of Z (z mole %). Furthermore, other repeating units: L (1 mol%) may be contained as needed.

如此之共聚物係例如使具有分枝及/或脂環構造之單體、具有酸性基之單體、具有乙烯性不飽和鍵之單體、與按照需要的其他單體共聚合而可得到。其中，從以體積大的官能基能使壓縮彈性率、變形回復性變得良好之點而言，使前述通式(4)所示之單體共聚合來做為至少具有前述分枝及/或脂環構造之單體，且導入具有分枝及/或脂環構造之基而成之共聚物的情形為佳。此時，樹脂A係在主鏈具有來目前述通式(4)所示單體之構成單位。Such a copolymer is obtained, for example, by copolymerizing a monomer having a branched and/or alicyclic structure, a monomer having an acidic group, a monomer having an ethylenically unsaturated bond, and other monomers as needed. In particular, the monomer represented by the above formula (4) is copolymerized to have at least the aforementioned branch and/or from the viewpoint that the compressive modulus and the recovery property of the functional group having a large volume can be improved. It is preferred that the monomer of the alicyclic structure is introduced into a copolymer having a branching and/or alicyclic structure. At this time, the resin A has a constituent unit of the monomer represented by the above-described general formula (4) in the main chain.

關於前述樹脂A為共聚物之情形中的共聚合組成比，係可考量玻璃轉移溫度與酸價來決定。雖然無法一概而論，惟可在下述的範圍。The copolymerization composition ratio in the case where the aforementioned resin A is a copolymer can be determined by considering the glass transition temperature and the acid value. Although it cannot be generalized, it can be in the scope below.

樹脂A中具有分枝及/或脂環構造之重複單位的組成比(x)係以10~70莫耳%為佳，15~65莫耳%為更佳，20~60莫耳%為特佳。組成比(x)在前述範圍内，則能得到良好的顯像性，同時畫像部的顯像液耐性亦為良好。The composition ratio (x) of the repeating unit having the branching and/or alicyclic structure in the resin A is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and 20 to 60 mol% is special. good. When the composition ratio (x) is within the above range, good developability can be obtained, and the development liquid resistance of the image portion is also good.

樹脂A中具有酸性基之重複單位的組成比(y)係以5~70莫耳%為佳，10~60莫耳%為更佳，20~50莫耳%為特佳。組成比(y)在前述範圍内，則能得到良好的硬化性、顯像性。The composition ratio (y) of the repeating unit having an acidic group in the resin A is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%. When the composition ratio (y) is within the above range, good hardenability and developability can be obtained.

樹脂A中具有乙烯性不飽和鍵之重複單位的組成比(z)係以10~70莫耳%為佳，20~70莫耳%為更佳，30~70莫耳%為特佳。組成比(z)在前述範圍内，則顔料分散性為優異，同時感度及聚合硬化性為良好，在調液後的液保存性、及塗布後的乾膜狀態下經長期保持之際的經時安定性變得良好。The composition ratio (z) of the repeating unit having an ethylenically unsaturated bond in the resin A is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, and particularly preferably 30 to 70 mol%. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, and the sensitivity and the polymerization hardenability are good, and the liquid storage property after liquid adjustment and the dry film state after coating are maintained for a long period of time. The stability is getting good.

再者，樹脂A係組成比(x)為10~70莫耳%(更佳為15~65莫耳%、特佳為20~50莫耳%)，組成比(y)為5~70莫耳%(更佳為10~60莫耳%、特佳為30~70莫耳%)，組成比(z)係10~70莫耳%(更佳為20~70莫耳%、特佳為30~70莫耳%)之情形為佳。Further, the resin A composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly preferably 20 to 50 mol%), and the composition ratio (y) is 5 to 70 m. Ear % (more preferably 10~60 mol%, especially good 30~70 mol%), composition ratio (z) is 10~70 mol% (more preferably 20~70 mol%, especially good The case of 30~70 mol%) is better.

以上，說明樹脂A的較佳形態，本發明的感光性樹脂組成物的較佳形態係以前述樹脂為樹脂A的較佳形態，且前述聚合性化合物為前述構造式(I)所示之特定聚合性化合物中的具體化合物之例示化合物(3)、例示化合物(10)、例示化合物(M-5)、例示化合物(M-6)、例示化合物(M-7)、例示化合物(M-8)、例示化合物(M-14)等進行組合之態樣為佳。本發明的感光性樹脂組成物係像這樣構成，則本發明的效果係能更有效果地表現。In the above, a preferred embodiment of the resin A is described. In a preferred embodiment of the photosensitive resin composition of the present invention, the resin is preferably a resin A, and the polymerizable compound is specific to the structural formula (I). Exemplary compounds (3), exemplified compounds (10), exemplified compounds (M-5), exemplified compounds (M-6), exemplified compounds (M-7), and exemplified compounds (M-8) of the specific compound in the polymerizable compound The combination of the exemplary compound (M-14) and the like is preferred. When the photosensitive resin composition of the present invention is configured as described above, the effects of the present invention can be more effectively expressed.

本發明的感光性樹脂組成物含有前述樹脂A之情形中，樹脂A在感光性樹脂組成物中的含有比例係相對於組成物中的全樹脂量(質量)，以5~50質量%為佳，10~40質量%為較佳。In the case where the photosensitive resin composition of the present invention contains the resin A, the content ratio of the resin A in the photosensitive resin composition is preferably 5 to 50% by mass based on the total resin amount (mass) in the composition. 10 to 40% by mass is preferred.

樹脂A係亦可與其他的樹脂併用，以樹脂A單獨構成之情形為佳。The resin A may be used in combination with other resins, and it is preferable to use the resin A alone.

<光聚合引發劑><Photopolymerization initiator>

本發明的感光性樹脂組成物至少含有1種的光聚合引發劑。The photosensitive resin composition of the present invention contains at least one type of photopolymerization initiator.

本發明中的光聚合引發劑係沒有特別地限定，可使用眾所周知的光聚合引發劑。眾所周知的光聚合引發劑係可舉例如：特開2006-23696號公報的段落號碼[0010]~[0020]、特開2006-64921號公報的段落號碼[0027]~[0053]中記載之引發劑。眾所周知的光聚合引發劑之例從感度之點而言，係以上述以外的胺基苯乙酮系化合物、醯基氧化膦系化合物、肟酯系化合物為適宜。The photopolymerization initiator in the present invention is not particularly limited, and a well-known photopolymerization initiator can be used. The known photopolymerization initiators are, for example, those described in paragraph numbers [0010] to [0020] of JP-A-2006-23696, and paragraph numbers [0027] to [0053] of JP-A-2006-64921. Agent. In the case of a known photopolymerization initiator, an aminoacetophenone-based compound, a mercaptophosphine oxide-based compound, or an oxime ester-based compound other than the above is preferable.

胺基苯乙酮系化合物的具體例係可舉例如IRGACURE(Irg)907(汽巴特殊化學品(股)製)等。醯基氧化膦系化合物的具體例係可舉例如DAROCUR TPO、Irgacure(Irg)819(以上，汽巴特殊化學品(股)製)等。又，肟酯系化合物的具體例係可舉例如IRGACURE(Irg)OXE01、CGI242等(以上，汽巴特殊化學品(股)製)。以下，表示此等引發劑的構造。Specific examples of the aminoacetophenone-based compound include, for example, IRGACURE (Irg) 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Specific examples of the fluorenyl phosphine oxide-based compound include, for example, DAROCUR TPO and Irgacure (Irg) 819 (above, Ciba Specialty Chemicals Co., Ltd.). Further, specific examples of the oxime ester-based compound include, for example, IRGACURE (Irg) OXE01, CGI242, and the like (above, Ciba Specialty Chemicals Co., Ltd.). Hereinafter, the structure of these initiators is shown.

光聚合引發劑在感光性樹脂組成物中的總量係相對於感光性樹脂組成物的全固體成分，以0.5~25質量%為佳，1~20質量%為較佳。The total amount of the photopolymerization initiator in the photosensitive resin composition is preferably from 0.5 to 25% by mass, preferably from 1 to 20% by mass, based on the total solid content of the photosensitive resin composition.

<微粒><microparticle>

本發明中的感光性樹脂組成物係從樹脂、聚合性化合物、光聚合引發劑以及力學強度之點而言，至少含有1種的微粒為佳。The photosensitive resin composition of the present invention preferably contains at least one kind of fine particles from the viewpoints of a resin, a polymerizable compound, a photopolymerization initiator, and a mechanical strength.

微粒係沒有特別地限制，可按照目的來進行適當選擇，例如以特開2003-302639號公報[0035]~[0041]中記載之體質顔料為佳，其中從能得到具有良好的顯像性、力學強度的光間隔物之點而言，以膠態矽石為佳。The fine particles are not particularly limited, and can be appropriately selected according to the purpose. For example, the extender pigments described in JP-A-2003-302639 [0035] to [0041] are preferred, and good development properties can be obtained. In terms of the optical spacer of the mechanical strength, colloidal vermiculite is preferred.

前述微粒的平均粒徑係從在形成容易承受光間隔物等的外力之構造的情形中可得到較高的力學強度之點，以5~50nm為佳，10~40nm為較佳，15~30nm為特佳。The average particle diameter of the fine particles is a point at which a high mechanical strength can be obtained in a structure in which an external force which easily absorbs a photo spacer or the like is formed, preferably 5 to 50 nm, preferably 10 to 40 nm, and 15 to 30 nm. It is especially good.

前述微粒在感光性樹脂組成物(形成光間隔物時在光間隔物(或構成該之感光性樹脂層)中的含量，從提高力學強度之觀點(例如，能得到具有較高的力學強度之光間隔物的觀點)而言，相對於感光性樹脂組成物中的全固體成分(質量)，以5~50質量%為佳，10~40質量%為較佳，15~30質量%為特佳。The content of the fine particles in the photosensitive resin composition (the photo spacer (or the photosensitive resin layer constituting the photosensitive spacer) is increased from the viewpoint of improving the mechanical strength (for example, a high mechanical strength can be obtained). The viewpoint of the photo-spacer is preferably 5 to 50% by mass, preferably 10 to 40% by mass, and 15 to 30% by mass based on the total solid content (mass) of the photosensitive resin composition. good.

<其他><Other>

本發明中的感光性樹脂組成物係除了樹脂、特定聚合性化合物、光聚合引發劑、及按照需要所含有的微粒以外，亦可按照需要含有光聚合起始助劑等的其他成分。In addition to the resin, the specific polymerizable compound, the photopolymerization initiator, and the fine particles contained as needed, the photosensitive resin composition of the present invention may contain other components such as a photopolymerization initiation aid as needed.

感光性樹脂組成物係可併用光聚合起始助劑做為其他的添加成分。光聚合起始助劑由於係促進藉由光聚合引發劑而起始聚合之聚合性化合物的聚合，所以可與光聚合引發劑來組合使用。光聚合起始助劑係使用胺系化合物的至少1種為佳。The photosensitive resin composition can be used in combination with a photopolymerization initiation aid as another additive component. The photopolymerization initiation aid can be used in combination with a photopolymerization initiator because it promotes polymerization of a polymerizable compound which initiates polymerization by a photopolymerization initiator. The photopolymerization initiation aid is preferably at least one of an amine compound.

前述胺系化合物係可舉例如：三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基安息香酸甲酯、4-二甲基胺基安息香酸乙酯、4-二甲基胺基安息香酸異戊酯、安息香酸2-二甲基胺基乙酯、4-二甲基胺基安息香酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯基酮(通稱米其勒酮)、4,4’-雙(二乙基胺基)二苯基酮、4,4’-雙(乙基甲基胺基)二苯基酮等，其中尤以4,4’-雙(二乙基胺基)二苯基酮為佳。又，可複數組合胺系、其他的光聚合起始助劑來使用。The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylamino benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4 , 4'-bis(dimethylamino)diphenyl ketone (commonly known as Michlerone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-double (B More preferably, 4,4'-bis(diethylamino)diphenyl ketone is preferred. Further, a combination of an amine-based or other photopolymerization initiation aid may be used in combination.

上述以外之其他光聚合起始助劑係可舉例如：烷氧基蒽系化合物、氧硫 系化合物、香豆素系化合物等。前述烷氧基蒽系化合物係可舉例如：9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽等。前述氧硫 系化合物係可舉例如：2-異丙硫基醌、4-異丙硫基醯、2,4-二乙硫基醌、2,4-二氯氧硫 、1-氯-4-丙氧硫基醌等。Other photopolymerization initiation assistants other than the above may, for example, be an alkoxy ruthenium compound or oxygen sulphur A compound, a coumarin compound, or the like. The alkoxy oxime-based compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-B. Base-9,10-diethoxyanthracene, and the like. Oxygen and sulfur The compound is, for example, 2-isopropylthio Bismuth, 4-isopropylthio Bismuth, 2,4-diethylthio Bismuth, 2,4-dichlorooxysulfide 1-chloro-4-propoxythio Hey.

又，亦可使用市售者做為光聚合起始助劑。市售的光聚合起始助劑係可舉例如：商品名「EAB-F」(保土谷化學工業(股)製)等。Further, a commercially available person can also be used as a photopolymerization starting aid. The commercially available photopolymerization starter is, for example, a product name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.).

光聚合起始助劑在感光性樹脂組成物中的含量係相對於上述的光聚合引發劑1質量份，以0.6質量份以上、20質量份以下為佳，1質量份以上、15質量份以下為更佳，特別是以1.5質量份以上、15質量份以下為佳。The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.6 parts by mass or more and 20 parts by mass or less, and 1 part by mass or more and 15 parts by mass or less, based on 1 part by mass of the photopolymerization initiator. More preferably, it is preferably 1.5 parts by mass or more and 15 parts by mass or less.

又，其他的成分係可由構成眾所周知之組成物的成分中來選擇使用，可舉例如特開2006-23696號公報的段落號碼[0010]~[0020]、特開2006-64921號公報的段落號碼[0027]~[0053]中記載之成分。Further, the other components may be selected and used as a component constituting a well-known composition, and the paragraph numbers of [0010] to [0020] and JP-A-2006-64921 of JP-A-2006-23696, for example, may be used. [0027] The components described in [0053].

本發明的感光性樹脂組成物係除了適於使用於後述之光間隔物、著色圖案、保護膜的形成以外，亦可適當使用於圖案分隔牆(例如，黑底等)、配向控制用突起等、其他的圖案構造物、被膜的形成。The photosensitive resin composition of the present invention can be suitably used for forming a photo spacer, a colored pattern, or a protective film, which will be described later, and can be suitably used for a pattern partition wall (for example, a black matrix or the like), an alignment control protrusion, or the like. , other pattern structures, and the formation of a film.

《光間隔物及其形成方法》"Photo spacers and their formation methods"

本發明的光間隔物係使用先前所述之本發明的感光性樹脂組成物而形成者。關於感光性樹脂組成物的詳細及較佳態樣係如前所述者。The photo spacer of the present invention is formed by using the photosensitive resin composition of the present invention described above. The details and preferred aspects of the photosensitive resin composition are as described above.

本發明的光間隔物由於係使用本發明的感光性樹脂組成物而構成的，所以具有均一性高的剖面形狀，且能抑制高度偏移。再者，本發明的感光性樹脂組成物在含有樹脂A之情形中，能得到具有做為光間隔物必要之高壓縮彈性率、變形回復性的光間隔物。Since the photo-spacer of the present invention is formed by using the photosensitive resin composition of the present invention, it has a cross-sectional shape with high uniformity and can suppress height shift. Further, in the case where the photosensitive resin composition of the present invention contains the resin A, a photo spacer having a high compression modulus and deformation recovery property which is necessary for the photo spacer can be obtained.

此處，就本發明中光間隔物等的圖案構造物為具有「均一的剖面形狀」之狀態來加以說明。Here, in the present invention, the pattern structure such as the photo spacer is described as having a "uniform cross-sectional shape".

圖案構造物為具有「均一的剖面形狀」之狀態，係在基板内的複數處(較佳為3處以上)中，以圖案構造物的剖面形狀接近於矩形之形狀的狀態為佳。前述「接近於矩形之形狀」係平行於基板法線方向，且以從圖案構造物的基板法線方向與緊密的邊緣(為圓柱狀構造物之情形係邊緣的接線)成正交的平面切斷該圖案構造物時的切剖面中，相當於圖案構造物側面之線與相當於圖案構造物下面之線所形成的角度(以下，亦稱為「錐形角度」)為80°以上、100°以下之形狀為較佳。In the state in which the pattern structure has a "uniform cross-sectional shape", it is preferable that the cross-sectional shape of the pattern structure is close to the shape of a rectangle in a plurality of places (preferably three or more) in the substrate. The above-mentioned "a shape close to a rectangle" is parallel to the normal direction of the substrate, and is cut in a plane perpendicular to the normal direction of the substrate of the pattern structure and the tight edge (the wiring of the edge of the cylindrical structure). In the cross section when the pattern structure is broken, the angle formed by the line corresponding to the side surface of the pattern structure and the line corresponding to the lower surface of the pattern structure (hereinafter also referred to as "taper angle") is 80° or more, 100. A shape below ° is preferred.

此處，前述圖案構造物下面係在圖案構造物的面之中，所謂與形成該圖案構造物之基底的接觸面。又，前述圖案構造物側面係在圖案構造物的面之中，所謂的不為前述圖案構造物下面、不為圖案構造物上面(與前述圖案構造物下面相對的(例如平行的)面，且不與前述下地接觸之面)的該面。Here, the pattern structure is placed under the surface of the pattern structure, and is a contact surface with the base on which the pattern structure is formed. Further, the side surface of the pattern structure is formed on the surface of the pattern structure, and is not the lower surface of the pattern structure, and is not the upper surface of the pattern structure (the (for example, parallel) surface facing the lower surface of the pattern structure, and The face that is not in contact with the aforementioned lower ground).

本發明的光間隔物若為使用本發明的感光性樹脂組成物之方法，可以任何的方法來形成，藉由使用含有以下所示步驟(甲)~(丙)的方法(本發明的光間隔物之製法)可最適宜的形成。The photo spacer of the present invention can be formed by any method by using the photosensitive resin composition of the present invention by using a method comprising the steps (A) to (c) shown below (the photointerval of the present invention). The method of preparation of matter can be most suitably formed.

本發明的光間隔物之製法係設置有以下步驟而構成的：(甲)在基板上形成先前所述之本發明感光性樹脂組成物的被膜之形成步驟(以下，亦稱為「被膜形成步驟」)、(乙)曝光前述被膜之至少一部份的曝光步驟(以下，亦稱為「曝光步驟」)、與(丙)顯像曝光後的前述被膜之顯像步驟(以下，亦稱為「顯像步驟」)，可按照需要設置(丁)加熱顯像後的前述被膜之加熱步驟(以下，亦稱為「被膜加熱步驟」)、及其他的步驟而構成的。The method for producing a photo spacer of the present invention comprises the steps of: (a) forming a film of the photosensitive resin composition of the present invention described above on a substrate (hereinafter, also referred to as "film formation step" And (b) an exposure step (hereinafter, also referred to as "exposure step") of exposing at least a portion of the film, and a development step of the film after exposure to (c) exposure (hereinafter also referred to as In the "development step", a heating step (hereinafter also referred to as "film heating step") of the film after heating and development, and other steps may be provided as needed.

(甲)被膜形成步驟(A) film formation step

被膜形成步驟係在基板上形成先前所述之本發明的感光性樹脂組成物的被膜。可形成感光性樹脂層為被膜之該感光性樹脂層係可經由後述之曝光步驟、顯像步驟等的其他步驟，而構成能均勻地保持晶胞厚之光間隔物。藉由使用本發明的光間隔物，特別是在因晶胞厚的變動而容易產生顯示不均之顯示裝置(特別是液晶顯示裝置)的畫像中，能有效地消除顯示不均。The film forming step is a film on which a photosensitive resin composition of the present invention described above is formed on a substrate. The photosensitive resin layer in which the photosensitive resin layer is formed as a film can be formed into a photo spacer capable of uniformly maintaining a cell thickness by other steps such as an exposure step and a development step which will be described later. By using the photo spacer of the present invention, particularly in an image of a display device (particularly a liquid crystal display device) which is liable to cause display unevenness due to variations in cell thickness, display unevenness can be effectively eliminated.

在基板上形成感光性樹脂層之方法，可適當舉例如：(a)塗布至少含有先前所述之樹脂、聚合性化合物、及光聚合引發劑之感光性樹脂組成物的塗布法、及(b)使用具有前述感光性樹脂層之感光性轉印材料，且藉由加熱及/或加壓而積層、轉印感光性樹脂層之轉印法。A method of forming a photosensitive resin layer on a substrate, for example, (a) a coating method of applying a photosensitive resin composition containing at least a resin, a polymerizable compound, and a photopolymerization initiator described above, and (b) A transfer method in which a photosensitive transfer material having the photosensitive resin layer is used and a photosensitive resin layer is laminated and transferred by heating and/or pressurization.

(a)塗布法(a) Coating method

感光性樹脂組成物的塗布係可藉由眾所周知的塗布法，例如：旋塗法、簾塗法、狹縫塗布法、浸漬塗布法、刮刀塗布法、輥塗法、金屬棒材塗布法、凹版印刷塗布法、或使用美國專利第2681294號說明書中記載之沸騰床(popper)之擠壓模塑塗布法等來進行。其中，尤以藉由特開2004-89851號公報、特開2004-17043號公報、特開2003-170098號公報、特開2003-164787號公報、特開2003-10767號公報、特開2002-79163號公報、特開2001-310147號公報等中記載之狹縫噴嘴或狹縫塗布機之方法為適宜。The coating of the photosensitive resin composition can be carried out by a well-known coating method such as spin coating, curtain coating, slit coating, dip coating, blade coating, roll coating, metal bar coating, gravure It is carried out by a printing coating method or an extrusion molding method using a popper described in the specification of U.S. Patent No. 2,681,294. In particular, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002- A method of a slit nozzle or a slit coater described in JP-A-2001-310147 or the like is suitable.

(b)轉印法(b) Transfer method

轉印係使用感光性轉印材料，使用例如加熱及/或加壓之輥或平板將在暫時支持體上形成膜狀之感光性樹脂層藉由進行壓延或加熱壓延來貼合至所期望的基板面之後，剝離暫時支持體藉以將感光性樹脂層轉印至基板上。具體上，可舉例如特開平7-110575號公報、特開平11-77942號公報、特開2000-334836號公報、特開2002-148794號公報中記載之層合機及積層方法，從低異物之觀點而言，以使用特開平7-110575號公報中記載之方法者為佳。The transfer system uses a photosensitive transfer material, and the photosensitive resin layer formed into a film shape on the temporary support is bonded to a desired one by calendering or heating calendering using, for example, a heated or/or pressurized roll or flat plate. After the substrate surface, the temporary support is peeled off to transfer the photosensitive resin layer onto the substrate. Specifically, a laminator and a lamination method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In view of the above, it is preferred to use the method described in Japanese Laid-Open Patent Publication No. H7-110575.

形成感光性樹脂層之情形中，可在感光性樹脂層與暫時支持體之間更設置有氧遮斷層(以下，亦稱為「氧遮斷膜」或「中間層」)。藉此，可提昇曝光感度。又，為了提高轉印性，亦可設置具有緩衝性之熱可塑性樹脂層。In the case of forming the photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as "oxygen interrupting film" or "intermediate layer") may be further provided between the photosensitive resin layer and the temporary support. Thereby, the exposure sensitivity can be improved. Moreover, in order to improve transferability, a thermoplastic resin layer having a cushioning property may be provided.

關於構成感光性轉印材料之暫時支持體、氧遮斷層、熱可塑性樹脂層、其他的層、與該感光性轉印材料的製作方法，係可應用特開2006-23696號公報的段落號碼[0024]~[0030]中記載之構成、製作方法。The temporary support, the oxygen barrier layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material, and the method for producing the photosensitive transfer material can be applied to the paragraph number of JP-A-2006-23696 [ The structure and production method described in 0024]~[0030].

以(a)塗布法、(b)轉印法來一起形成感光性樹脂層之情形中，其層厚係以0.5~10.0μm為佳，1~6μm為較佳。層厚在前述範圍則能在製造時的塗布形成之際防止針孔的發生，且顯像去除未曝光部不需要長時間即可進行。In the case where the photosensitive resin layer is formed together by the (a) coating method and the (b) transfer method, the layer thickness is preferably 0.5 to 10.0 μm, and preferably 1 to 6 μm. When the layer thickness is in the above range, the occurrence of pinholes can be prevented at the time of coating formation at the time of production, and the development of the unexposed portions without development does not require a long time.

形成感光性樹脂層之基板係可舉例如：透明基板(例如玻璃基板、塑膠基板)、附有透明導電膜(例如ITO膜)之基板、附有彩色濾光片之基板(亦稱為彩色濾光片基板)、附有驅動元件(例如，薄膜電晶體[TFT])之驅動基板等。基板的厚度係一般以700~1200μm為較佳。Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also referred to as a color filter). A light sheet substrate), a drive substrate to which a driving element (for example, a thin film transistor [TFT]) is attached, or the like. The thickness of the substrate is generally preferably from 700 to 1200 μm.

(乙)曝光步驟、(丙)顯像步驟(b) exposure step, (c) development step

在曝光步驟中係將在前述被膜形成步驟中所形成之被膜的至少一部份曝光，以形成潜像。在隨後的顯像步驟中，係將在前述曝光步驟中曝光之被膜進行顯像，可形成所期望的形狀之間隔物圖案。At least a portion of the film formed in the film forming step described above is exposed in the exposure step to form a latent image. In the subsequent development step, the film exposed in the aforementioned exposure step is developed to form a spacer pattern of a desired shape.

此等步驟的具體例係可舉例如特開2006-64921號公報的段落號碼[0071]~[0077]中記載之形成例、與特開2006-23696號公報的段落號碼[0040]~[0051]中記載之步驟等來做為本發明中的合適之例。Specific examples of such steps include, for example, the formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and the paragraph numbers [0040] to [0051] of JP-A-2006-23696. The steps and the like described in the above are taken as suitable examples in the present invention.

本發明的光間隔物之製法亦可設置後述之(丁)被膜加熱步驟，可藉由使在前述曝光中的曝光量增加等，不設置被膜加熱步驟(以下，亦稱為「無加熱步驟」)，亦可形成具有均一性高的剖面形狀及優異的高度均一性之光間隔物。The photo spacer of the present invention may be provided with a heating process of a film described later, and the film heating step may not be provided by increasing the exposure amount during the exposure (hereinafter, also referred to as "no heating step"). It is also possible to form a photo spacer having a uniform cross-sectional shape and excellent height uniformity.

藉由「無加熱步驟」，可更有效地抑制所形成之光間隔物的惡化、已經形成之圖案構造物(著色圖案等)與保護膜的惡化。By the "no heating step", deterioration of the formed photo spacer, deterioration of the already formed pattern structure (coloring pattern, etc.), and the protective film can be more effectively suppressed.

為「無加熱步驟」情形之曝光量係以1~500mJ/cm2 為佳，10~300mJ/cm2 為佳。The exposure amount in the case of "no heating step" is preferably 1 to 500 mJ/cm 2 and preferably 10 to 300 mJ/cm 2 .

(丁)被膜加熱步驟(D) film heating step

本發明的光間隔物之製法係亦可在前述顯像步驟的顯像後，設置加熱被膜之被膜加熱步驟。藉由加熱，可更促進被膜的硬化，而得到具有高強度之光間隔物。又，感光性樹脂組成物含有前述樹脂A之情形中，能得到壓縮彈性率、變形回復性更為良好的光間隔物。The photo spacer of the present invention can also be provided with a film heating step of heating the film after the development of the developing step. By heating, the hardening of the film can be further promoted, and a photo spacer having high strength can be obtained. Further, in the case where the photosensitive resin composition contains the resin A, a photo spacer having a higher compression modulus and deformation recovery property can be obtained.

此處，在加熱的最高溫度係因加熱時間而有所不同，在40℃~145℃為佳，40℃~140℃為更佳。最高溫度在40℃~145℃的範圍内則能更有效地抑制所形成之光間隔物的惡化、已經形成之圖案構造物(著色圖案等)與保護膜的惡化。Here, the maximum temperature at the heating varies depending on the heating time, preferably 40 ° C to 145 ° C, and more preferably 40 ° C to 140 ° C. When the maximum temperature is in the range of 40 ° C to 145 ° C, deterioration of the formed photo spacer, deterioration of the formed pattern structure (coloring pattern, etc.), and the protective film can be more effectively suppressed.

其中，在加熱中的最高溫度係以80℃~140℃，加熱時間係以0.1小時~3.0小時(尤佳為0.2小時~1小時)為更佳。Among them, the maximum temperature during heating is 80 ° C to 140 ° C, and the heating time is preferably 0.1 to 3.0 hours (particularly 0.2 to 1 hour).

如上所述，可在基板上製作具備光間隔物之顯示裝置用基板。光間隔物較佳係形成於在基板上形成之黑底等的黑色遮光部上、TFT等的驅動元件上。又，亦可在黑底等的黑色遮光部、TFT等的驅動元件與光間隔物之間存在有ITO等的透明導電層(透明電極)、聚醯亞胺等的配向膜。As described above, a substrate for a display device including a photo spacer can be fabricated on a substrate. The photo spacer is preferably formed on a black light-shielding portion such as a black matrix formed on a substrate, or a driving element such as a TFT. In addition, a transparent conductive layer (transparent electrode) such as ITO or an alignment film such as polyimide may be present between a black light-shielding portion such as a black matrix or a driving element such as a TFT and a photo spacer.

例如，光間隔物設置於黑色遮光部、驅動元件之上的情形中，可以被覆預先配設於該基板之黑色遮光部(黑底等)、驅動元件的方式，將例如感光性轉印材料的感光性樹脂層積層於支持體面，進行剝離轉印而形成感光性樹脂層之後，對其施加曝光、顯像、加熱處理等來形成光間隔物，而可製作顯示裝置用基板。For example, in the case where the photo spacer is provided on the black light-shielding portion or the driving element, a black light-shielding portion (black matrix or the like) of the substrate and a driving element may be coated in advance, for example, a photosensitive transfer material may be used. After the photosensitive resin layer is laminated on the support surface, and the photosensitive resin layer is formed by peeling and transferring, exposure, development, heat treatment, or the like is applied thereto to form a photo spacer, whereby a substrate for a display device can be produced.

本發明的顯示裝置用基板中可更按照需要，設置紅色(R)、藍色(B)、綠色(G)3色等的著色像素。In the substrate for a display device of the present invention, colored pixels of three colors of red (R), blue (B), and green (G) can be provided as needed.

本發明的光間隔物係可在形成含有黑底等的黑色遮蔽部及著色像素等的著色部之彩色濾光片之後而形成。The photo spacer of the present invention can be formed after forming a color filter including a black mask portion such as a black matrix or a colored portion such as a color pixel.

前述黑色遮蔽部及著色部與光間隔物係可任意組合：塗布感光性樹脂組成物之塗布法、與使用具有由感光性樹脂組成物所構成之感光性樹脂層的轉印材料之轉印法而形成的。The black masking portion, the coloring portion, and the photo spacer may be arbitrarily combined: a coating method of applying a photosensitive resin composition, and a transfer method using a transfer material having a photosensitive resin layer composed of a photosensitive resin composition. And formed.

前述黑色遮蔽部及著色部以及前述光間隔物係可分別由感光性樹脂組成物而形成的，具體上例如藉由將液體之前述感光性樹脂組成物直接塗布於基板上，以形成感光性樹脂層之後，進行曝光、顯像，將前述黑色遮蔽部及著色部形成為圖案狀，隨後，使用藉由將設置其他液體之前述感光性樹脂組成物於與前述基板為不同之其他基板(暫時支持體)上以形成感光性樹脂層所製作之轉印材料，並在使該轉印材料黏附於形成前述黑色遮蔽部及著色部之前述基板來轉印感光性樹脂層之後，藉由進行曝光、顯像，而可將光間隔物形成為圖案狀。The black shielding portion, the colored portion, and the photo spacer may be formed of a photosensitive resin composition, and specifically, the photosensitive resin composition of the liquid is directly applied onto the substrate to form a photosensitive resin. After the layer, exposure and development are performed, and the black shielding portion and the colored portion are formed into a pattern, and then the photosensitive resin composition containing the other liquid is used on the other substrate different from the substrate (temporary support) a transfer material produced by forming a photosensitive resin layer, and after the transfer material is adhered to the substrate on which the black shielding portion and the colored portion are formed, and the photosensitive resin layer is transferred, exposure is performed. Development, the photo spacer can be formed into a pattern.

藉由如此，可製作設置光間隔物之彩色濾光片。By doing so, a color filter in which a photo spacer is provided can be produced.

《保護膜》Protective film

本發明的保護膜係使用先前所述之本發明的感光性樹脂組成物而形成者。The protective film of the present invention is formed by using the photosensitive resin composition of the present invention described above.

本發明的保護膜由於係使用本發明的感光性樹脂組成物而構成的，所以即使在以較低的加熱溫度或無加熱處理而形成之情形中，膜厚均一性亦為優異。Since the protective film of the present invention is formed by using the photosensitive resin composition of the present invention, even when it is formed at a low heating temperature or without heat treatment, the film thickness uniformity is excellent.

本發明的保護膜若使用本發明的感光性樹脂組成物之方法，可以任一方法來形成，可以與前述之本發明的光間隔物之製法相同的方法來形成。此處，在沒有對保護膜實施圖案化之情形，亦即在形成保護膜為所謂的貝它(beta)膜之情形下，前述(乙)曝光步驟中係以全面曝光被膜之方法為適宜。The protective film of the present invention can be formed by any method using the method of the photosensitive resin composition of the present invention, and can be formed in the same manner as the above-described method for producing a photo spacer of the present invention. Here, in the case where the protective film is not patterned, that is, in the case where the protective film is formed into a so-called beta film, the above-described (b) exposure step is preferably a method of uniformly exposing the film.

《著色圖案》Coloring Pattern

本發明的著色圖案係使用先前所述之本發明的感光性樹脂組成物而形成者。此處，感光性樹脂組成物係除了先前所述之各成分之外，更含有著色劑之至少1種的形態為適宜。The colored pattern of the present invention is formed by using the photosensitive resin composition of the present invention described above. Here, the photosensitive resin composition is preferably in a form containing at least one of a coloring agent in addition to the components described above.

前述著色劑係沒有特別地限制，可從眾所周知的著色劑之中來適當選擇。眾所周知的著色劑係具體上可舉例如：特開2005-17716號公報[0038]~[0054]中記載之顔料及染料、與特開2004-361447號公報[0068]~[0072]中記載之顔料、特開2005-17521號公報[0080]~[0088]中記載之著色劑等。The coloring agent is not particularly limited and can be appropriately selected from among known coloring agents. The pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and those described in JP-A-2004-361447 [0068] to [0072] are specifically mentioned. A coloring agent or the like described in JP-A-2005-17521 [0080] to [0088].

本發明的著色圖案由於係使用本發明的感光性樹脂組成物而構成的，所以即使在較低的加熱溫度或無加熱處理而形成之情形中，亦具有均一性高的剖面形狀，且膜厚均一性亦為優異。Since the colored pattern of the present invention is formed by using the photosensitive resin composition of the present invention, even in the case of forming at a low heating temperature or without heat treatment, a cross-sectional shape having high uniformity and a film thickness are obtained. Uniformity is also excellent.

此外，本發明的著色圖案為使用具有複數色的著色圖案之彩色濾光片為一要素之情形，至少一色的著色圖案可為使用本發明的感光性樹脂組成物而形成的。Further, the coloring pattern of the present invention is a case where a color filter having a coloring pattern of a plurality of colors is used as one element, and at least one coloring pattern can be formed using the photosensitive resin composition of the present invention.

本發明的著色圖案若為使用本發明的感光性樹脂組成物之方法，可以任一的方法來形成，例如可藉由與前述之本發明光間隔物之製法為相同的方法而形成。The colored pattern of the present invention can be formed by any method using the photosensitive resin composition of the present invention, and can be formed, for example, by the same method as the above-described method for producing a photo spacer of the present invention.

《顯示裝置用基板》"Substrate for display device"

本發明的顯示裝置用基板係具備先前所述之本發明的光間隔物、本發明的保護膜、及由本發明的著色圖案所選出之1或2個以上而構成的。The substrate for a display device of the present invention comprises the above-described photo spacer of the present invention, the protective film of the present invention, and one or more selected from the colored pattern of the present invention.

本發明的顯示裝置用基板由於具備使用本發明的感光性樹脂組成物而形成之剖面形狀及膜厚(高度)均一性為良好的圖案構造物(本發明的光間隔物、本發明的保護膜、及本發明的著色圖案之至少1者)，所以使用於顯示裝置能夠在畫像顯示之際抑制顯示不均。The substrate for a display device of the present invention has a cross-sectional shape and uniformity of film thickness (height) formed by using the photosensitive resin composition of the present invention (the photo spacer of the present invention, the protective film of the present invention) Further, at least one of the color patterns of the present invention is used in the display device to suppress display unevenness when the image is displayed.

此處，所謂的顯示裝置用基板係指構成顯示裝置用的一對支持體之中的至少一者。顯示裝置用基板的具體例係因顯示元件、顯示裝置的構成而有所不同，可舉例如：具備著色圖案(以下，亦稱為「著色像素」)之彩色濾光片基板、具備驅動手段之附有驅動手段的基板(例如，無源矩陣基板、有源矩陣基板等)、具備離隔壁之附有離隔壁的基板(例如，具備黑底之附有黑底的基板等)、具備著色圖案與驅動手段兩者的彩色濾光片陣列(on array)基板、沒有設置圖案構造物、被膜之玻璃基板等。Here, the substrate for a display device refers to at least one of a pair of supports constituting the display device. The specific example of the display device substrate differs depending on the configuration of the display device and the display device, and may be, for example, a color filter substrate having a colored pattern (hereinafter also referred to as "colored pixel") and a driving means. A substrate (for example, a passive matrix substrate or an active matrix substrate) with a driving means, a substrate having a partition wall attached to the partition wall (for example, a substrate having a black matrix with a black matrix), and a colored pattern A color filter array (on array) substrate and a driving method, a glass substrate on which no pattern structure or film is provided, or the like.

前述彩色濾光片基板之前述著色圖案群(著色像素群)係可由不相呈現不同顏色之2色的像素所構成者，亦可由3色的像素、4色以上的像素所構成者。例如在3色之情形中，以紅(R)、綠(G)及青(B)的3種色相所構成的。配置RGB3色的像素群之情形中，以鑲嵌型、三角形型等的配置為佳，配置4色以上的像素群之情形中無論是哪種配置均可。彩色濾光片基板的製作係例如可在形成2色以上的像素群之後以先前所述的方式形成黑底，相反地亦可在形成黑底之後以形成像素群的方式來形成。關於RGB像素的形成，可參照特開2004-347831號公報等。The coloring pattern group (colored pixel group) of the color filter substrate may be composed of pixels of two colors that do not appear to be different colors, or may be composed of pixels of three colors or pixels of four or more colors. For example, in the case of three colors, it is composed of three kinds of hue of red (R), green (G), and cyan (B). In the case of arranging a pixel group of RGB three colors, it is preferable to arrange it in a mosaic type or a triangular type, and it is possible to arrange any of the four or more pixel groups. The color filter substrate can be formed, for example, by forming a pixel group of two or more colors in a manner as described above, or conversely, forming a pixel group after forming a black matrix. For the formation of RGB pixels, JP-A-2004-347831 and the like can be referred to.

《顯示元件》Display component

可使用先前所述之本發明的顯示裝置用基板來形成顯示元件。The display element can be formed using the substrate for a display device of the present invention described previously.

顯示元件之1者係可舉例如：在至少一者為透光性之一對支持體(包含顯示裝置用基板)之間，至少具備液晶層與液晶驅動手段(包含無源矩陣驅動方式及有源矩陣驅動方式)之液晶顯示元件。In one of the display elements, for example, at least one of the light-transmitting pair of supports (including a substrate for a display device) includes at least a liquid crystal layer and a liquid crystal driving means (including a passive matrix driving method and The liquid crystal display element of the source matrix driving method).

在該液晶顯示元件之情形中，顯示裝置用基板係可做為具有複數個的RGB像素群，且構成該像素群之各像素係彼此以黑底隔離像素之彩色濾光片基板來使用。該彩色濾光片基板中由於設置有剖面形狀及膜厚(高度)均一性為良好的圖案構造物，所以具備該彩色濾光片基板之液晶顯示元件能有效地抑制：起因於彩色濾光片基板與對向基板之間的晶胞間距(晶胞厚)的變動，因液晶材料偏在、因低溫發泡等所引起的顏色不均等的顯示不均的發生。藉此，所製作之液晶顯示元件係能顯示顯明的畫像。In the case of the liquid crystal display device, the substrate for a display device can be used as a color filter substrate having a plurality of RGB pixel groups and each of the pixels constituting the pixel group is separated from each other by a black matrix. Since the color filter substrate is provided with a pattern structure having a uniform cross-sectional shape and uniformity of film thickness (height), the liquid crystal display element including the color filter substrate can be effectively suppressed: resulting from a color filter The variation in the cell pitch (cell thickness) between the substrate and the counter substrate occurs due to unevenness in color unevenness due to partial deviation of the liquid crystal material or low-temperature foaming. Thereby, the liquid crystal display element produced can display a clear image.

又，液晶顯示元件的更詳細態樣係可舉例如：在至少一者為透光性之一對支持體(包含液晶顯示裝置用基板)之間，至少具備液晶層與液晶驅動手段，前述液晶驅動手段具有有源元件(例如TFT)，且一對的基板間係由光間隔物規定成指定寬度而構成者。In a more detailed aspect of the liquid crystal display device, for example, at least one of the light-transmitting pair of supports (including a substrate for a liquid crystal display device) includes at least a liquid crystal layer and a liquid crystal driving means, and the liquid crystal The driving means has an active element (for example, a TFT), and a pair of substrates are formed by defining a predetermined width of the photo spacer.

《顯示裝置》Display device

本發明的顯示裝置係具備上述的顯示裝置用基板者。The display device of the present invention includes the above-described substrate for a display device.

本發明的顯示裝置由於具備設置有剖面形狀及膜厚(高度)均一性為良好的圖案構造物之本發明的顯示裝置用基板，所以能抑制顯示不均。Since the display device of the present invention includes the substrate for a display device of the present invention having a cross-sectional shape and a uniform pattern thickness (height) uniformity, it is possible to suppress display unevenness.

顯示裝置係可舉例如：液晶顯示裝置、電漿顯示顯示裝置、EL顯示裝置、CRT顯示裝置等的顯示裝置等。關於顯示裝置的定義與各顯示裝置的説明，係記載於例如「電子顯示裝置(佐佐木昭夫著、工業(股)調查會1990年發行)」、「顯示裝置(伊吹順章著、產業圖書(股)平成元年發行)」等中。The display device may be, for example, a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. The definition of the display device and the description of each display device are described in, for example, "Electronic display device (sasaki Sasaki, Industrial (stock) survey society issued in 1990)", "display device (Ibuki Shunzhang, industrial book (share) ) issued in the first year of Heisei).

在顯示裝置之中，以液晶顯示裝置為佳。Among the display devices, a liquid crystal display device is preferred.

液晶顯示裝置係例如以光間隔物將彼此相對所對向配置之一對基板間規定成指定的寬度，且在規定的間隙中封入(封入部位係稱為液晶層)液晶材料而構成的，液晶層的厚度(晶胞厚)係保持為所期望的均一厚度。The liquid crystal display device is configured by, for example, arranging a liquid crystal material with a predetermined width between one of the opposing surfaces of the optical spacer, and enclosing the liquid crystal layer (the sealed portion is referred to as a liquid crystal layer) in a predetermined gap. The thickness of the layer (cell thickness) is maintained to a desired uniform thickness.

在液晶顯示裝置中的液晶顯示模式係可舉例如STN型、TN型、GH型、ECB型、鐵電性液晶、反鐵電性液晶、VA型、IPS型、OCB型、ASM型、其他各種者為適宜。其中，在本發明的液晶顯示裝置中，從能最有效果地表現出本發明的效果之觀點而言，以不易因液晶胞之晶胞厚的變動而引起顯示不均的顯示模式為所期望的，構成晶胞厚為2~4μm之VA型顯示模式、IPS型顯示模式、OCB型顯示模式者為佳。The liquid crystal display mode in the liquid crystal display device may be, for example, an STN type, a TN type, a GH type, an ECB type, a ferroelectric liquid crystal, an antiferroelectric liquid crystal, a VA type, an IPS type, an OCB type, an ASM type, or the like. It is suitable. In the liquid crystal display device of the present invention, the display mode in which display unevenness is unlikely to occur due to fluctuations in the cell thickness of the liquid crystal cell is desired from the viewpoint of exhibiting the effect of the present invention most effectively. It is preferable to form a VA type display mode, an IPS type display mode, or an OCB type display mode in which the cell thickness is 2 to 4 μm.

又，可使用於本發明之液晶係可舉例如向列液晶、膽甾醇液晶、層列液晶、鐵電液晶。Further, the liquid crystal used in the present invention may, for example, be a nematic liquid crystal, a cholesteric liquid crystal, a smectic liquid crystal or a ferroelectric liquid crystal.

液晶顯示裝置的基本構成態樣係可舉例如：(a)透過光間隔物，使具備薄膜電晶體(TFT)等的驅動元件與像素電極(導電層)配列形成之驅動側基板、與對向電極(導電層)之對向基板成對向配置，且在其間隙部封入液晶材料而構成者；(b)透過光間隔物，使具備驅動基板、與對向電極(導電層)之對向基板成對向配置，且在其間隙部封入液晶材料而構成者，本發明的液晶顯示裝置係可適於使用於各種的液晶顯示機器。In the basic configuration of the liquid crystal display device, for example, (a) a light-transmitting spacer is used, and a driving side substrate including a driving element such as a thin film transistor (TFT) and a pixel electrode (conductive layer) is arranged and aligned. The electrode (conductive layer) is disposed opposite to the opposite substrate, and the liquid crystal material is sealed in the gap portion; (b) the light-transmitting spacer is provided to have the driving substrate and the counter electrode (conductive layer) facing each other The liquid crystal display device of the present invention can be suitably used for various liquid crystal display devices in which the substrates are arranged in opposite directions and a liquid crystal material is sealed in the gap portions.

關於液晶顯示裝置係在例如「次世代液晶顯示技術(内田龍男編集、側工業調查會、1994年發行)」中有記載。在本發明的液晶顯示裝置中，除了具備本發明的液晶顯示元件以外，沒有特別地限制，可以例如前述「次世代液晶顯示技術」中記載之各種方式來構成液晶顯示裝置。其中，特別是在構成彩色TFT方式的液晶顯示裝置上為有效。關於彩色TFT方式的液晶顯示裝置係在例如「彩色TFT液晶顯示(共立出版(股)、1996年發行)」有記載。The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Side Industry Survey, issued in 1994)". In addition to the liquid crystal display element of the present invention, the liquid crystal display device of the present invention is not particularly limited, and the liquid crystal display device can be configured, for example, in various forms described in the "second-generation liquid crystal display technology". Among them, it is effective particularly in a liquid crystal display device constituting a color TFT system. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)".

液晶顯示裝置係除了具備先前所述之光間隔物、著色圖案、保護膜、液晶顯示裝置用基板、液晶顯示元件以外，一般可使用電極基板、偏光薄膜、相位差薄膜、背光、光間隔物、視野角補償薄膜、抗反射薄膜、光擴散薄膜、防眩薄膜等的各式各樣的構件來構成。關於此等的構件係在例如「’94液晶顯示周邊材料、化學品的市場(島健太郎、CMC(股)、1994年發行)」、「2003液晶相關市場的現狀與將來展望(下卷)(表良吉、富士CHIMERA(股)總研、2003等發行)」中有記載。本專利申請係主張2008年3月31日申請的日本專利申請第2008-092583號、及日本專利申請第2008-092584號為優先權之利益者，此等之申請專利的揭示全部係引用於本文。The liquid crystal display device can generally use an electrode substrate, a polarizing film, a retardation film, a backlight, a photo spacer, and the like, in addition to the above-described photo spacer, coloring pattern, protective film, substrate for liquid crystal display device, and liquid crystal display device. A wide variety of members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film are used. These components are, for example, "'94 Liquid Crystal Display Peripherals, Chemicals Markets (Island Kentaro, CMC (shares), issued in 1994)", "2003 Liquid Crystal Related Market Status and Future Outlook (Volume 2)" It is described in "Bian Liangji, Fuji Chimera (share) general research, 2003, etc.). Japanese Patent Application No. 2008-092583, filed on March 31, 2008, and Japanese Patent Application No. 2008-092584, the priority of each of which is incorporated herein by reference. .

實施例Example

以下，根據實施例更具體地說明本發明，惟本發明係只要不超過其主旨，則不受限於以下的實施例。此外，若沒有特別地限制，「份」為質量基準。Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. In addition, "parts" are quality standards unless otherwise specified.

此外，重量平均分子量係以凝膠滲透層析法(GPC)而測定的。GPC係使用HLC-8020GPC(東曹(股)製)，管柱係使用3根的TSKgel、Supermultipore HZ-H(東曹(股)製、4.6mmID×15cm)，洗提液係使用THF(四氫呋喃)。又，條件係以試料濃度為0.045mg/mL、流速為0.35mL/min、試樣注入量為10μL、測定溫度為40℃，使用IR檢出器來進行的。又，檢量線係由東曹(股)製「標準試料TSK standard,polystyrene」；「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、「正丙基苯」的8種試樣來製作的。Further, the weight average molecular weight was measured by gel permeation chromatography (GPC). The GPC system uses HLC-8020GPC (manufactured by Tosoh Corporation), and the column system uses three TSKgels, Supermultipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm), and the eluent is THF (tetrahydrofuran). ). Further, the conditions were carried out using an IR detector with a sample concentration of 0.045 mg/mL, a flow rate of 0.35 mL/min, a sample injection amount of 10 μL, and a measurement temperature of 40 °C. In addition, the calibration line is made of Tosoh Corporation's "standard sample TSK standard, polystyrene"; "F-40", "F-20", "F-4", "F-1", "A-5000" Eight samples of "A-2500", "A-1000", and "n-propylbenzene" were produced.

<樹脂A的合成><Synthesis of Resin A>

首先進行先前所述的樹脂A之中做為具體例所舉例的例示化合物P-52、P-51、P-53、P-46、及P-47的合成，來做為感光性樹脂組成物中所使用的樹脂。此外，在本實施例中所使用的其他樹脂A亦可藉由變更對應之單體的類似方法來合成。First, the synthesis of the exemplified compounds P-52, P-51, P-53, P-46, and P-47 exemplified as the specific examples of the resin A described above is carried out as a photosensitive resin composition. The resin used in the process. Further, the other resin A used in the present embodiment can also be synthesized by a similar method of changing the corresponding monomer.

(例示化合物P-52的合成)(Synthesis of Compound P-52)

在反應容器中，預先加入1-甲氧基-2-丙醇(MFG、日本EMULSION(股)製)7.48份，昇溫至90℃，將由苯乙烯(St)3.1份、甲基丙烯酸三環戊烯酯(日立化成工業(股)製的TCPD-M；x)4.28份、甲基丙烯酸(MAA；y)11.7份、偶氮系聚合引發劑(和光純藥(股)製、V-601)2.08份、及1-甲氧基-2-丙醇55.2份所構成之混合溶液，在氮氣雰圍氣下，花2小時滴下至90℃的反應容器中。滴下後，使其反應4小時，以得到丙烯酸樹脂溶液。In the reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by EMULSION, Japan) was added in advance, and the temperature was raised to 90 ° C, and 3.1 parts of styrene (St) and tricyclopentyl methacrylate were added. Ester ester (TCPD-M manufactured by Hitachi Chemical Co., Ltd.; x) 4.28 parts, methacrylic acid (MAA; y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical Co., Ltd., V-601) A mixed solution of 2.08 parts and 55.2 parts of 1-methoxy-2-propanol was dropped into a reaction vessel at 90 ° C for 2 hours under a nitrogen atmosphere. After dropping, it was allowed to react for 4 hours to obtain an acrylic resin solution.

接著，在前述丙烯酸樹脂溶液中，加入氫醌單甲基醚0.15份、及溴化四乙基銨0.34份之後，花2小時滴下甲基丙烯酸縮水甘油酯(GLM，東京化成工業(股)製)26.4份(GLM-MAA；z)。滴下後，一邊吹拂空氣、一邊在90℃下使其反應4小時之後，以形成固體成分濃度為45%的方式，添加溶媒1-甲氧基-2-丙基乙酸酯(MMPGAc、戴西爾化學工業(股)製)來進行調製，以得到在具有不飽和基之先前所述的例示化合物P-51中加入來自苯乙烯之構造單位的例示化合物P-52(樹脂A)的樹脂溶液(固體成分酸價；76.0mgKOH/g、Mw；25,000、1-甲氧基-2-丙醇/1-甲氧基-2-丙基乙酸酯45%溶液)(x；y；z；St=30mol%；27mol%；37mol%；6mol%)。Next, 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide were added to the acrylic resin solution, and then glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped for 2 hours. ) 26.4 parts (GLM-MAA; z). After dropping, the reaction was carried out at 90 ° C for 4 hours while blowing air, and then the solvent 1-methoxy-2-propyl acetate (MMPGAc, Daisy) was added so as to form a solid concentration of 45%. Prepared by the Chemical Industry Co., Ltd. to obtain a resin solution of the exemplified compound P-52 (Resin A) containing a structural unit derived from styrene in the previously described exemplified compound P-51 having an unsaturated group. (solid content acid value; 76.0 mg KOH / g, Mw; 25,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) (x; y; z; St = 30 mol%; 27 mol%; 37 mol%; 6 mol%).

此處，GLM-MAA係顯示甲基丙烯酸縮水甘油酯與甲基丙烯酸鍵結者(以下相同)。Here, GLM-MAA shows that glycidyl methacrylate is bonded to methacrylic acid (the same applies hereinafter).

此外，例示化合物P-52的分子量Mw係表示重量平均分子量，重量平均分子量的測定係使用凝膠滲透層析法(GPC法)來進行(以下相同)。Further, the molecular weight Mw of the exemplified compound P-52 represents a weight average molecular weight, and the measurement of the weight average molecular weight is carried out by gel permeation chromatography (GPC method) (the same applies hereinafter).

(例示化合物P-51的合成)(Synthesis of Compound P-51)

在前述例示化合物P-52的合成中，除了不使用苯乙烯、使例示化合物P-51中的x；y；z為34mol%；27mol%；39mol%、變更TCPD-M(x)、甲基丙烯酸(y)、及GLM-MAA(z)的添加量以外，藉由與前述例示化合物P-52的合成為相同的方法來進行合成，以得到具有不飽和基之例示化合物P-51(樹脂A)的樹脂溶液(固體成分酸價；72.5mgKOH/g、Mw；22,000、1-甲氧基-2-丙醇/1-甲氧基-2-丙基乙酸酯45%溶液)。In the synthesis of the aforementioned exemplified compound P-52, except that styrene was not used, x; y; z in the exemplified compound P-51 was 34 mol%; 27 mol%; 39 mol%, changed TCPD-M (x), methyl group In addition to the addition amount of the acrylic acid (y) and GLM-MAA (z), the synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain an exemplified compound P-51 having an unsaturated group (resin Resin solution of A) (solid content acid value; 72.5 mg KOH/g, Mw; 22,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(例示化合物P-53的合成)(Exemplified synthesis of compound P-53)

在前述例示化合物P-52的合成中，除了不使用苯乙烯、以二環戊烯基氧基乙基甲基丙烯酸酯(日立化成工業(股)製的FANCRYL FA-512M)取代甲基丙烯酸三環戊烯酯、使例示化合物P-53中的x；y；z為46.2mol%；24.3mol%；29.5mol%、且變更FA-512M(x)、甲基丙烯酸(y)、GLM-MAA(z)的添加量以外，藉由與前述例示化合物P-52的合成為相同的方法來進行合成，以得到具有不飽和基之例示化合物P-53(樹脂A)的樹脂溶液(固體成分酸價；71.2mgKOH/g、Mw；25,500、1-甲氧基-2-丙醇/1-甲氧基-2-丙基乙酸酯45%溶液)。In the synthesis of the above-exemplified compound P-52, methacrylic acid was replaced by dicyclopentenyloxyethyl methacrylate (FANCRYL FA-512M manufactured by Hitachi Chemical Co., Ltd.) without using styrene. Cyclopentene ester, such that x; y; z in the exemplified compound P-53 is 46.2 mol%; 24.3 mol%; 29.5 mol%, and the change of FA-512M (x), methacrylic acid (y), GLM-MAA In addition to the addition amount of (z), the synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain a resin solution (solid component acid) of the exemplified compound P-53 (resin A) having an unsaturated group. Price; 71.2 mg KOH/g, Mw; 25,500, 1-methoxy-2-propanol/1-methoxy-2-propyl acetate 45% solution).

(例示化合物P-46的合成)(Synthesis of Compound P-46)

在前述例示化合物P-52的合成中，除了以ADMA(出光興產(股)製)取代甲基丙烯酸三環戊烯酯、使在例示化合物P-1中加入來自苯乙烯之構造單位的組成x；y；z；St為30mol%；24mol%；38mol%；8mol%、變更ADMA(x)、甲基丙烯酸(y)、GLM-MAA(z)、及苯乙烯的添加量以外，藉由與前述例示化合物P-52的合成為相同的方法來進行合成，以得到在具有不飽和基之例示化合物P-1中加入來自苯乙烯之構造單位的例示化合物P-46(樹脂A)的樹脂溶液(固體成分酸價；74.1mgKOH/g、Mw；29,000、1-甲氧基-2-丙醇/1-甲氧基-2-丙基乙酸酯45%溶液)。In the synthesis of the above-exemplified compound P-52, in place of the substitution of ADMA (manufactured by Idemitsu Kosan Co., Ltd.) for tricyclopentenyl methacrylate, the composition of the structural unit derived from styrene is added to the exemplified compound P-1. x; y; z; St is 30 mol%; 24 mol%; 38 mol%; 8 mol%, by changing the addition amount of ADMA (x), methacrylic acid (y), GLM-MAA (z), and styrene, by The synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain a resin in which an exemplary compound P-46 (resin A) derived from a structural unit of styrene was added to the exemplified compound P-1 having an unsaturated group. Solution (solid content acid value; 74.1 mg KOH/g, Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(例示化合物P-47的合成)(Synthesis of Compound P-47)

在前述例示化合物P-52的合成中，除了以甲基丙烯酸異基(IBXMA，和光純藥工業(股)製)取代甲基丙烯酸三環戊烯酯、使在例示化合物P-2中加入來自苯乙烯之構造單位的組成x；y；z；St為34mol%；24mol%；36mol%；6mol%、變更IBXMA(x)、甲基丙烯酸(y)、GLM-MAA(z)、及苯乙烯的添加量以外，藉由與例示化合物P-52的合成為相同的方法來進行合成，以得到在具有不飽和基之例示化合物P-2中加入來自苯乙烯之構造單位的例示化合物P-47(樹脂A)的樹脂溶液(固體成分酸價；72.9mgKOH/g、Mw；29,000、1-甲氧基-2-丙醇/1-甲氧基-2-丙基乙酸酯45%溶液)。In the synthesis of the aforementioned exemplified compound P-52, except for methacrylic acid The base (IBXMA, manufactured by Wako Pure Chemical Industries, Ltd.) is substituted for tricyclopentenyl methacrylate, and the composition of the structural unit derived from styrene is added to the exemplified compound P-2. x; y; z; St is 34 mol% ; 24 mol%; 36 mol%; 6 mol%, modified IBXMA (x), methacrylic acid (y), GLM-MAA (z), and styrene added, by the same as the synthesis of the exemplified compound P-52 A method of synthesizing to obtain a resin solution of an exemplary compound P-47 (resin A) containing a structural unit derived from styrene in an exemplary compound P-2 having an unsaturated group (solid content acid value; 72.9 mgKOH/g) Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

[實施例1]：塗布法[Example 1]: Coating method

<彩色濾光片基板的製作><Production of Color Filter Substrate>

根據特開2005-3861號公報的段落號碼[0084]~[0095]中記載之方法，製作具有黑底、R(紅色)像素、G(綠色)像素、B(藍色)像素之彩色濾光片(以下，將其稱為彩色濾光片基板)。此處，彩色濾光片基板的基板尺寸為550mm×650mm。Color filter having black matrix, R (red) pixel, G (green) pixel, and B (blue) pixel is prepared according to the method described in paragraphs [0084] to [0095] of JP-A-2005-3861 A sheet (hereinafter, referred to as a color filter substrate). Here, the substrate size of the color filter substrate is 550 mm × 650 mm.

接著，在所得到彩色濾光片基板的R像素、G像素、及B像素以及黑底之上，再藉由濺鍍ITO(Indium Tin Oxide，氧化銦錫)的透明電極而形成的。Next, on the R pixel, the G pixel, the B pixel, and the black matrix of the obtained color filter substrate, a transparent electrode of ITO (Indium Tin Oxide) was sputtered.

<光間隔物的形成><Formation of photo spacers>

在上述所製作之ITO透明電極濺鍍形成的彩色濾光片基板之ITO透明電極上，以旋轉器，狹縫塗布由下述表1所示之配方(實施例1中為配方1)所構成之感光性樹脂層用塗布液。繼而，使用真空乾燥機VCD(東京應化公司製)以30秒鐘使溶媒的一部份乾燥至塗布膜沒有流動性之後，在90℃的加熱板上預烘烤3分鐘，以形成膜厚5.2μm的感光性樹脂層(被膜形成步驟)。The ITO transparent electrode of the color filter substrate formed by sputtering the ITO transparent electrode prepared above was formed by a spinner and slit coating by the formulation shown in Table 1 below (Formulation 1 in Example 1). A coating liquid for a photosensitive resin layer. Then, using a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.), a part of the solvent was dried for 30 seconds until the coating film had no fluidity, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film thickness. 5.2 μm photosensitive resin layer (film formation step).

繼續，使用具有超高壓水銀燈之近接型曝光機(日立高科技電子工程(股)製)，在遮罩(具有直徑15μm的圓形圖案之石英曝光遮罩)、與該遮罩和感光性樹脂層成相對向方式所配置之彩色濾光片基板為呈現約略平行垂直的豎立狀態下，將遮罩面與感光性樹脂層的表面之間的距離設為100μm，透過該遮罩，以在365nm中的強度為250W/m2 透過紫外透過濾光片(UV-35、東芝玻璃(股)製)來照射紫外線(曝光量200mJ/cm2 ；曝光步驟)。Continuing, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (a quartz exposure mask having a circular pattern of 15 μm in diameter), a mask and a photosensitive resin The color filter substrate disposed in the opposite direction is in an upright state that is approximately parallel and perpendicular, and the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and the mask is passed through the mask at 365 nm. The intensity was 250 W/m 2 and was irradiated with ultraviolet rays through an ultraviolet transmission filter (UV-35, manufactured by Toshiba Glass Co., Ltd.) (exposure amount: 200 mJ/cm 2 ; exposure step).

接著，使用碳酸Na系顯像液(含有0.38莫耳/升的碳酸氫鈉、0.47莫耳/升的碳酸鈉、5%的二丁基萘磺酸鈉、陰離子界面活性劑、消泡劑、及安定劑；商品名：T-CD1(富士軟片(股)製)以純水稀釋成10倍之稀釋液)，在29℃下30秒鐘，以圓錐型噴嘴壓力0.15MPa進行淋浴顯像，以形成圖案影像(顯像步驟)。繼而，使用洗淨劑(含有磷酸鹽‧矽酸鹽‧非離子界面活性劑‧消泡劑‧安定劑；商品名：T-SD3(富士軟片(股)製))以純水稀釋成10倍之稀釋液，在33℃下20秒鐘，以圓錐型噴嘴壓力0.02MPa進行淋浴且吹拂，進行所形成之圖案影像周邊的殘渣去除，以形成圓柱狀的間隔物圖案在300μm×300μm中為1根間隔物所間隔的。Next, a Na carbonate-based developing solution (containing 0.38 mol/liter sodium hydrogencarbonate, 0.47 mol/liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, And stabilizer; trade name: T-CD1 (Fuji film (manufactured by Fujifilm)) diluted with pure water to a 10-fold dilution), at 29 ° C for 30 seconds, with a cone nozzle pressure of 0.15MPa for shower imaging, To form a pattern image (development step). Then, using a detergent (containing phosphate ‧ citrate ‧ nonionic surfactant ‧ defoamer ‧ stabilizer; trade name: T-SD3 (Fuji film (stock))) diluted 10 times with pure water The diluted solution was showered at 33 ° C for 20 seconds at a conical nozzle pressure of 0.02 MPa, and the residue around the formed pattern image was removed to form a cylindrical spacer pattern of 300 μm × 300 μm. The root spacers are spaced apart.

接著，藉由將設置有間隔物圖案之彩色濾光片基板在140℃下60分鐘、進行加熱處理(加熱步驟)，以在彩色濾光片基板上製作光間隔物。此處，就所得之光間隔物1000個，使用三次元表面構造解析顯微鏡(製造商；ZYGOCorporation、型式：New View 5022)，測定從ITO透明電極上面(與基板成平行的2個面之中，選離基板之側的面)至光間隔物之最高位置的距離(以下，該距離亦稱為「光間隔物的高度」)，並將平均值作為光間隔物的平均高度。Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment (heating step) at 140 ° C for 60 minutes to form a photo spacer on the color filter substrate. Here, 1000 pieces of the obtained photo spacers were measured using a three-dimensional surface structure analysis microscope (manufacturer; ZYGO Corporation, type: New View 5022), and the upper surface of the ITO transparent electrode (the two surfaces parallel to the substrate, The distance from the side of the substrate to the highest position of the photo spacer (hereinafter, this distance is also referred to as "the height of the photo spacer") is used, and the average value is taken as the average height of the photo spacer.

又，所得之光間隔物的底面積計測係使用SEM照相來進行的。其結果係直徑為15.1μm、平均高度為4.7μm的圓柱形狀。Further, the measurement of the bottom area of the obtained photo spacer was carried out using SEM photographing. The result was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm.

<液晶顯示裝置的製作><Production of Liquid Crystal Display Device>

另外，準備玻璃基板作為對向基板，且在上述所得之彩色濾光片基板的透明電極上及對向基板上分別施加PVA模式用的圖案化，更於其上設置由聚醯亞胺所形成的配向膜。Further, a glass substrate is prepared as a counter substrate, and a pattern for PVA mode is applied to each of the transparent electrode and the counter substrate of the color filter substrate obtained above, and a polyimide film is formed thereon. Alignment membrane.

隨後，以圍繞彩色濾光片之像素群的方式在相當於設置於周圍的黑底外框之位置，藉由分配器方式塗布紫外線硬化樹脂的密封劑，滴下PVA模式用液晶，與對向基板貼合之後，UV照射所貼合的基板後，進行熱處理以使得密封劑硬化。在如此所得之液晶胞的兩面上，貼附SANRITZ(股)製的偏光板HLC2-2518。Then, the sealing agent for the ultraviolet curable resin is applied by a dispenser method so as to surround the pixel group surrounding the color filter, and the liquid crystal for PVA mode is dropped and the counter substrate After the bonding, after the irradiated substrate is irradiated with UV, heat treatment is performed to harden the sealant. On both sides of the thus obtained liquid crystal cell, a polarizing plate HLC2-2518 manufactured by SANRITZ Co., Ltd. was attached.

接著，使用FR1112H(STONELEY電氣(股)製的基片型LED)為紅色(R)LED、使用DG1112H(STONELEY電氣(股)製的基片型LED)為綠色(G)LED、使用DB1112H(STONELEY電氣(股)製的基片型LED)為藍色(B)LED以構成側光方式的背光，將前述偏光板配置於在所設置的液晶胞之背面側，以形成液晶顯示裝置。Next, FR1112H (a substrate type LED made by STONELEY Electric Co., Ltd.) was used as a red (R) LED, and DG1112H (a substrate type LED made by STONELEY Electric Co., Ltd.) was used as a green (G) LED, and DB1112H (STONELEY) was used. The substrate type LED made of electric (share) is a blue (B) LED to constitute a backlight of the side light type, and the polarizing plate is disposed on the back side of the liquid crystal cell to be formed to form a liquid crystal display device.

<評價><evaluation>

就所得之光間隔物、液晶顯示裝置進行下述的評價。測定評價的結果係表示於下述表2。The following evaluation was performed about the obtained photo spacer and liquid crystal display device. The results of the measurement evaluation are shown in Table 2 below.

(光間隔物的剖面形狀)(cross-sectional shape of the photo spacer)

用與基板法線方向平行的平面切斷上述<光間隔物的形成>中所得之加熱處理後的光間隔物，且藉由掃瞄型電子顯微鏡觀察其切剖面的形狀。觀察係針對基板周邊部及基板中央部的共計5處來進行，並按照下述基準來評價光間隔物的剖面形狀。The heat-treated photo spacer obtained in the above-mentioned <formation of photo spacers> was cut by a plane parallel to the normal direction of the substrate, and the shape of the cross section was observed by a scanning electron microscope. The observation was performed on a total of five locations on the peripheral portion of the substrate and the central portion of the substrate, and the cross-sectional shape of the photo spacer was evaluated in accordance with the following criteria.

~評價基準~~ Evaluation benchmark ~

A；在全部的5處中，形成具有錐形角度45°以上、90°以下的剖面形狀之光間隔物。A; In all five places, a photo spacer having a cross-sectional shape having a taper angle of 45° or more and 90° or less is formed.

B；在全部的5處中，雖然形成具有錐形角度45°以上、95°以下的剖面形狀之光間隔物，但是與上述A相比，從錐形角度為大者稍微有點多之點而言變差。B; in all of the five places, although a light spacer having a cross-sectional shape having a taper angle of 45° or more and 95° or less is formed, compared with the above A, the angle from the taper is slightly larger. The words are getting worse.

C；在全部的5處中，形成具有錐形角度40°以上、100°以下的剖面形狀之光間隔物，但是與上述A及B相比，從錐形角度大者為更多之點而言變差。C; a photo spacer having a cross-sectional shape having a taper angle of 40° or more and 100° or less is formed in all five places, but the angle from the taper angle is larger than the above-mentioned A and B. The words are getting worse.

D；在5處的1~4處中，形成錐形角度不在40°以上、100°以下的範圍之光間隔物。D; at 1 to 4 places of 5, a photo spacer having a taper angle not in the range of 40° or more and 100° or less is formed.

E；在全部的5處中，形成錐形角度不在40°以上、100°以下的範圍之光間隔物。E; a photo spacer having a taper angle not in the range of 40° or more and 100° or less is formed in all five places.

(光間隔物的高度均一性)(high uniformity of photo spacers)

從在上述<光間隔物的形成>所測定之光間隔物1000個分之高度的結果，算出最大值與最小值之差異，並按照下述基準來進行評價。高度均一性係表示值的差異越小均一性越優異。The difference between the maximum value and the minimum value was calculated from the results of the height of 1000 parts of the photo-spacer measured by the above-mentioned <formation of photo spacers>, and evaluated according to the following criteria. The degree of homogeneity indicates that the smaller the difference in values, the more excellent the uniformity.

~評價基準~~ Evaluation benchmark ~

A：光間隔物之高度的最大值與最小值之差異為低於0.2μm。A: The difference between the maximum value and the minimum value of the height of the photo spacer is less than 0.2 μm.

B：光間隔物之高度的最大值與最小值之差異為0.2μm以上、低於0.3μm。B: The difference between the maximum value and the minimum value of the height of the photo spacer is 0.2 μm or more and less than 0.3 μm.

C：光間隔物之高度的最大值與最小值之差異為0.3μm以上、低於0.4μm。C: The difference between the maximum value and the minimum value of the height of the photo spacer is 0.3 μm or more and less than 0.4 μm.

D：光間隔物之高度的最大值與最小值之差異為0.4μm以上、低於0.5μm。D: The difference between the maximum value and the minimum value of the height of the photo spacer is 0.4 μm or more and less than 0.5 μm.

E：光間隔物之高度的最大值與最小值之差異為0.5μm以上。E: The difference between the maximum value and the minimum value of the height of the photo spacer is 0.5 μm or more.

(加熱處理條件的評價)(Evaluation of heat treatment conditions)

根據以下的順序，來進行加熱處理條件的評價。The evaluation of the heat treatment conditions was carried out in the following order.

首先，除了將曝光量變更為250mJ/cm2 來進行曝光以外，以與上述<光間隔物的形成>同樣進行，進行至殘渣處理後、加熱處理前的操作，以製作具有間隔物圖案之評價用試樣。First, in the same manner as the above-mentioned <formation of photo spacers>, the exposure to the amount of exposure was changed to 250 mJ/cm 2 , and the operation after the residue treatment and before the heat treatment was performed to prepare an evaluation having a spacer pattern. Use the sample.

就所得之評價用試樣，評價沒有加熱處理時、及使加熱溫度種種變化來進行加熱處理(加熱處理時間固定為60分鐘)時的光間隔物之剖面形狀及光間隔物之高度均一性。光間隔物的剖面形狀及光間隔物的高度均一性的評價方法係如前所述。With respect to the obtained sample for evaluation, the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer when the heat treatment was performed without changing the heating temperature and the heat treatment was performed (the heat treatment time was fixed to 60 minutes) was evaluated. The method for evaluating the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer is as described above.

基於光間隔物的剖面形狀及光間隔物的高度均一性的評價結果，按照下述基準來進行加熱處理條件的評價。Based on the evaluation results of the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer, the evaluation of the heat treatment conditions was performed in accordance with the following criteria.

此外，在下述評價基準中，所謂具有「均一性優異的剖面形狀」之狀態，在前述光間隔物的剖面形狀的評價基準中係指A、B、或C之狀態。又，在下述基準中，所謂具有「優異的高度均一性」之狀態，在前述光間隔物的高度均一性的評價基準中係指A、B、或C之狀態。In addition, in the following evaluation criteria, the state in which the "cross-sectional shape excellent in uniformity" refers to the state of A, B, or C in the evaluation criteria of the cross-sectional shape of the photo spacer. In addition, in the following criteria, the state of "high degree of uniformity" means the state of A, B, or C in the evaluation criteria of the height uniformity of the photo spacer.

~評價基準~~ Evaluation benchmark ~

A；沒有加熱處理，得到了剖面形狀的均一性及高度均一性優異的間隔物圖案。A; without a heat treatment, a spacer pattern having excellent cross-sectional shape uniformity and high uniformity was obtained.

B；加熱溫度為低於80℃，得到的剖面形狀的均一性及高度均一性優異的間隔物圖案。B; a heating agent having a uniformity of cross-sectional shape and a spacer pattern excellent in height uniformity, which is lower than 80 °C.

C；加熱溫度為80℃以上、低於150℃，得到了剖面形狀的均一性及高度均一性優異的間隔物圖案。C; The heating temperature is 80 ° C or more and less than 150 ° C, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained.

D；加熱溫度為150℃以上、低於200℃，得到了剖面形狀的均一性及高度均一性優異的間隔物圖案。D; The heating temperature is 150 ° C or more and less than 200 ° C, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained.

E；加熱溫度為200℃以上，得到了剖面形狀的均一性及高度均一性優異的間隔物圖案。E; The heating temperature is 200 ° C or more, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained.

(變形回復率)(deformation recovery rate)

對於所得之光間隔物，藉由微小硬度計(DUH-W201、島津製作所(股)製)如下述般進行測定、評價。測定係採用50μmψ的圓錘台壓子，以最大荷重50mN、保持時間5秒，依照負荷-除荷試驗法來進行。從該測定值按照下述式來求得變形回復率[%]，並根據下述評價基準來進行評價。測定係在22±1℃、50%RH的環境下來進行。The obtained photo-spacer was measured and evaluated by a microhardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was carried out by using a 50 μm crucible round hammer press with a maximum load of 50 mN and a holding time of 5 seconds in accordance with the load-loading test method. From the measured values, the deformation recovery ratio [%] was determined according to the following formula, and the evaluation was performed based on the following evaluation criteria. The measurement was carried out in an environment of 22 ± 1 ° C and 50% RH.

變形回復率(%)Deformation recovery rate (%)

=(荷重開放後的回復量[μm]/荷重時的變形量[μm])×100= (the amount of recovery after the load is opened [μm] / the amount of deformation at the load [μm]) × 100

~評價基準~~ Evaluation benchmark ~

A：變形回復率為90%以上。A: The deformation recovery rate is 90% or more.

B：變形回復率為87%以上、低於90%。B: The deformation recovery rate is 87% or more and less than 90%.

C：變形回復率為85%以上、低於87%。C: The deformation recovery rate is 85% or more and less than 87%.

D：變形回復率為80%以上、低於85%。D: The deformation recovery rate is 80% or more and less than 85%.

E：變形回復率為75%以上、低於80%。E: The deformation recovery rate is 75% or more and less than 80%.

F：變形回復率為低於75%。F: The deformation recovery rate is less than 75%.

(液晶顯示裝置的顯示不均)(The display of the liquid crystal display device is uneven)

就上述所製作的液晶顯示裝置，以目視觀察輸入灰階的測試信號時的灰階顯示，並依照下述評價基準來評價顯示不均的有無發生。評價結果係表示於下述表2。In the liquid crystal display device produced as described above, the gray scale display when the test signal of the gray scale was input was visually observed, and the presence or absence of display unevenness was evaluated in accordance with the following evaluation criteria. The evaluation results are shown in Table 2 below.

~評價基準~~ Evaluation benchmark ~

A：沒有顯示不均，得到了非常良好的顯示畫像。A: No unevenness was displayed, and a very good display image was obtained.

B：雖然在玻璃基板的邊緣部分稍微有點不均，但是對於顯示部沒有影響且顯示畫像為良好。B: Although the edge portion of the glass substrate was slightly uneven, it did not affect the display portion and the display image was good.

C：在顯示部觀察到稍微有點不均，但是在實用上的許容範圍内。C: A slight unevenness was observed on the display unit, but it was within the practical tolerance range.

D：在顯示部觀察到不均。D: Unevenness was observed on the display unit.

[實施例2~13]：塗布法[Examples 2 to 13]: Coating method

在實施例1中，除了將聚合性化合物的種類變更為如下述表2所示的以外，以與實施例1同樣地方式，製作光間隔物及液晶顯示裝置。就所得之光間隔物及液晶顯示裝置，進行與實施例1同樣的評價。評價結果係表示於下述表2。In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in the first embodiment except that the type of the polymerizable compound was changed as shown in the following Table 2. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

[實施例14~18]：塗布法[Examples 14 to 18]: Coating method

在實施例1中，除了將聚合性化合物與樹脂的種類變更為如下述表2所示的以外，以與實施例1同樣地方式，製作光間隔物及液晶顯示裝置。In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in the first embodiment except that the type of the polymerizable compound and the resin were changed as shown in the following Table 2.

此外，感光性樹脂組成物的配方在實施例14~17係前述配方1，在實施例18係前述配方2。又，就所得之光間隔物及液晶顯示裝置，進行與實施例1同樣的評價。評價結果係表示於下述表2。Further, the formulation of the photosensitive resin composition was the same as the above-mentioned Formulation 1 in Examples 14 to 17, and the above Formulation 2 in Example 18. Moreover, the same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

[實施例19]：塗布法[Example 19]: Coating method

在實施例1中，除了將感光性樹脂組成物的配方變更為表1中的配方4以外，以與實施例1同樣地方式，製作光間隔物及液晶顯示裝置。就所得之光間隔物及液晶顯示裝置，進行與實施例1同樣的評價。評價結果係表示於下述表2。In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the formulation of the photosensitive resin composition was changed to the formulation 4 in Table 1. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

[實施例20]：轉印法[Example 20]: Transfer method

在實施例1中，除了藉由將感光性樹脂層用塗布液的配方取代為配方1～配方3、將感光性樹脂層用塗布液的塗布取代為進行使用以下所示之間隔物用感光性轉印薄膜的轉印，來形成感光性樹脂層以外，以與實施例1同樣的方式，來製作光間隔物及液晶顯示裝置。所得之光間隔物係圓柱形狀。就所得之光間隔物及液晶顯示裝置，進行與實施例1同樣的評價。評價結果係表示於下述表2。In the first embodiment, the formulation for the photosensitive resin layer is replaced by the formulation of the coating liquid for the photosensitive resin layer, and the coating liquid for the photosensitive resin layer is replaced by the coating for the use of the spacer shown below. A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the transfer film was transferred to form a photosensitive resin layer. The resulting photo spacer is cylindrical in shape. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

<間隔物用感光性轉印薄膜的製作><Production of Photosensitive Transfer Film for Spacer>

將由下述配方A所構成之熱可塑性樹脂層用塗布液塗布於厚度75μm的聚對苯二甲酸乙二酯薄膜暫時支持體(PET暫時支持體)上，並使其乾燥，以形成乾燥層厚為15.0μm的熱可塑性樹脂層。The coating liquid for a thermoplastic resin layer composed of the following Formula A was applied onto a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, and dried to form a dry layer thickness. It is a thermoplastic resin layer of 15.0 μm.

~熱可塑性樹脂層用塗布液的配方A~~Formulation A of coating liquid for thermoplastic resin layer~

‧甲基丙烯酸甲酯/丙烯酸2-乙基己酯/甲基丙烯酸苄酯/甲基丙烯酸共聚物　25.0份‧Methyl methacrylate/2-ethylhexyl acrylate/Benzyl methacrylate/methacrylic acid copolymer 25.0 parts

(=55/11.7/4.5/28.8[莫耳比]、重量平均分子量90,000)(=55/11.7/4.5/28.8 [Morby], weight average molecular weight 90,000)

‧苯乙烯/丙烯酸共聚物　58.4份‧ Styrene / Acrylic Copolymer 58.4

(=63/37[莫耳比]、重量平均分子量8,000)(=63/37 [Morbi], weight average molecular weight 8,000)

‧2,2-雙[4-(甲基丙烯醯氧基聚乙氧基)苯基]丙烷　39.0份‧2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane 39.0 parts

‧下述界面活性劑1　10.0份‧The following surfactants 1 10.0 parts

‧甲醇　90.0份‧Methanol 90.0 parts

‧1-甲氧基-2-丙醇　51.0份‧1-methoxy-2-propanol 51.0 parts

‧甲基乙基酮　700份‧ methyl ethyl ketone 700 parts

＊界面活性劑1* surfactant 1

‧下述構造物1　30%‧The following structures 1 30%

‧甲基乙基酮　70%‧ methyl ethyl ketone 70%

接著，將由下述配方B所構成之中間層用塗布液塗布於所形成之熱可塑性樹脂層上，並使其乾燥，以積層乾燥層厚為1.5μm的中間層。Next, the coating liquid for an intermediate layer composed of the following Formula B was applied onto the formed thermoplastic resin layer, and dried to laminate an intermediate layer having a layer thickness of 1.5 μm.

~中間層用塗布液的配方B~~ Formulation of coating solution for intermediate layer B~

‧聚乙烯醇　3.22份‧ polyvinyl alcohol 3.22 parts

(PVA-205(皂化率80%)、可藥麗(股)製)(PVA-205 (saponification rate 80%), can be made by Pharmacy (share))

‧聚乙烯基吡咯啶酮　1.49份‧ polyvinylpyrrolidone 1.49 parts

(PVPK-30、ISB‧日本股份有限公司製)(PVPK-30, ISB‧ Japan Co., Ltd.)

‧甲醇　42.3份‧Methanol 42.3 parts

‧蒸餾水　524份‧ distilled water 524

接著，再在所形成之中間層上塗布由前述表1所示之配方3所構成的感光性樹脂層用塗布液，並使其乾燥，以積層乾燥層厚為5.0μm的感光性樹脂層。Then, the coating liquid for a photosensitive resin layer composed of the formulation 3 shown in Table 1 above was applied to the formed intermediate layer, and dried to laminate a photosensitive resin layer having a layer thickness of 5.0 μm.

如以上進行，構成PET暫時支持體/熱可塑性樹脂層/中間層/感光性樹脂層的積層構造(3層的合計層厚；21.5μm)之後，再對感光性樹脂層的表面加熱、加壓貼附做為覆蓋薄膜之厚度12μm的聚丙烯製薄膜，以得到間隔物用感光性轉印薄膜。As described above, the laminated structure of the PET temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer (the total thickness of the three layers; 21.5 μm) is formed, and then the surface of the photosensitive resin layer is heated and pressurized. A polypropylene film as a cover film having a thickness of 12 μm was attached to obtain a photosensitive transfer film for a spacer.

<光間隔物的製作><Production of Photo spacers>

剝離所得之間隔物用感光性轉印薄膜的覆蓋薄膜，將露出之感光性樹脂層的表面重疊至濺鍍形成與實施例1同樣製作之ITO透明電極而成的彩色濾光片基板之ITO透明電極上，並使用層合機LamicII型[日立工業(股)製]，在線壓100N/cm、130℃的加壓、加熱條件下，以搬送速度2m/分使其貼合。隨後，將PET暫時支持體在與熱可塑性樹脂層之界面剝離除去，並使感光性樹脂層與熱可塑性樹脂層及中間層一同被轉印(被膜形成步驟)。The obtained spacer was peeled off with a cover film of a photosensitive transfer film, and the surface of the exposed photosensitive resin layer was superposed on the ITO transparent of the color filter substrate formed by sputtering the ITO transparent electrode formed in the same manner as in Example 1. On the electrode, a laminator type Lamic II type [manufactured by Hitachi Industrial Co., Ltd.] was used, and under pressure and heating conditions of 100 N/cm and 130 ° C were applied, and the bonding speed was 2 m/min. Subsequently, the PET temporary support is peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin layer is transferred together with the thermoplastic resin layer and the intermediate layer (film formation step).

繼續，使用具有超高壓水銀燈之近接型曝光機(日立高科技電子工程(股)製)，在遮罩(具有畫像圖案之石英曝光遮罩)、與該遮罩和熱可塑性樹脂層成相對向配置之彩色濾光片基板為大略平行垂直豎立之狀態下，使遮罩面與感光性樹脂層接近中間層之側的表面之間的距離為100μm，並透過遮罩從熱可塑性樹脂層側以曝光量90mJ/cm2 來進行近接曝光(曝光步驟)。Continuing, a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultra-high pressure mercury lamp is used, and a mask (a quartz exposure mask having an image pattern) is opposed to the mask and the thermoplastic resin layer. The color filter substrate is disposed in a state of being substantially parallel and vertically erected, and a distance between the surface of the mask and the surface of the photosensitive resin layer on the side close to the intermediate layer is 100 μm, and is transmitted through the mask from the side of the thermoplastic resin layer. The exposure amount was 90 mJ/cm 2 to perform the proximity exposure (exposure step).

接著，將三乙醇胺系顯像液(含有三乙醇胺30%，商品名：T-PD2(富士軟片(股)製)以純水稀釋成12倍(以T-PD2為1份與純水為11份的比例來混合)之稀釋液)在30℃下50秒鐘，且以扁平噴嘴壓力0.04MPa進行淋浴顯像，以去除熱可塑性樹脂層與中間層。繼而，對該玻璃基板的上面吹拂空氣使其液切之後，藉由淋浴純水且吹拂10秒鐘，進行純水淋浴洗淨，並吹拂空氣以減少基板上的液體。繼續，使用碳酸Na系顯像液(0.38莫耳/升的碳酸氫鈉、0.47莫耳/升的碳酸鈉、5%的二丁基萘磺酸鈉、陰離子界面活性劑、消泡劑、及安定劑含有；商品名：T-CD1(富士軟片(股)製)用純水稀釋成10倍之稀釋液)，在29℃下30秒鐘，以圓錐型噴嘴壓力0.15MPa進行淋浴顯像，以形成圖案影像(顯像步驟)。Next, a triethanolamine-based developing solution (containing 30% of triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Co., Ltd.) was diluted to 12 times with pure water (1 part with T-PD2 and 11 with pure water) The proportion of the mixture was mixed) at 30 ° C for 50 seconds, and shower development was carried out at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Then, the air was blown on the upper surface of the glass substrate to be liquid-cut, and then pure water was showered for 10 seconds by showering, and pure water shower was washed, and air was blown to reduce the liquid on the substrate. Continuing, using a Na-carbonic acid imaging solution (0.38 mol/L sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and The stabilizer is contained; the product name: T-CD1 (manufactured by Fujifilm Co., Ltd.) diluted with pure water to a 10-fold dilution), and subjected to shower development at a cone nozzle pressure of 0.15 MPa at 30 ° C for 30 seconds. To form a pattern image (development step).

接著，使用以純水稀釋洗淨劑(含有磷酸鹽‧矽酸鹽‧非離子界面活性劑‧消泡劑‧安定劑；商品名：T-SD3(富士軟片(股)製))成10倍之稀釋液，在33℃下20秒鐘、以圓錐型噴嘴壓力0.02MPa淋浴且吹拂，進行所形成之圖案影像的周邊殘渣去除，使圓柱狀的間隔物圖案在300μm×300μm為1根的間隔物間隔所形成的。Next, use a detergent diluted with pure water (containing phosphate ‧ citrate ‧ nonionic surfactant ‧ defoamer ‧ stabilizer; trade name: T-SD3 (Fuji film)) 10 times The diluted solution was showered at 33 ° C for 20 seconds at a conical nozzle pressure of 0.02 MPa, and the surrounding residue of the formed pattern image was removed, and the columnar spacer pattern was set at an interval of 300 μm × 300 μm. The space formed by the object.

接著，藉由將設置間隔物圖案而成之彩色濾光片基板在130℃下，進行加熱處理60分鐘(被膜加熱步驟)，以在彩色濾光片基板上製作光間隔物。所得之光間隔物係直徑為15.1μm、平均高度為4.7μm的圓柱形狀。Next, the color filter substrate in which the spacer pattern was formed was subjected to heat treatment at 130 ° C for 60 minutes (film heating step) to form a photo spacer on the color filter substrate. The obtained photo spacer was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm.

而且，使用製作光間隔物之彩色濾光片基板，與實施例1同樣地，製作PVA模式液晶顯示裝置。Further, a PVA mode liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which a photo spacer was formed.

[比較例1][Comparative Example 1]

在實施例1中，除了將聚合性化合物變更為下述的比較化合物W-1以外，以與實施例1同樣地方式，製作光間隔物及液晶顯示裝置。就光間隔物及液晶顯示裝置，進行與實施例1同樣的評價。評價結果係表示於下述表2。In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the polymerizable compound was changed to the comparative compound W-1 described below. The same evaluation as in Example 1 was carried out for the photo spacer and the liquid crystal display device. The evaluation results are shown in Table 2 below.

[比較例2][Comparative Example 2]

在實施例1中，除了藉由將感光性樹脂組成物的組成變更為配方5、將聚合性化合物變更為DPHA(二季戊四醇六丙烯酸酯)以外，以與實施例1同樣地方式，製作光間隔物及液晶顯示裝置。就光間隔物及液晶顯示裝置，進行與實施例1同樣的評價。評價結果係表示於下述表2。In Example 1, a light interval was produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed to Formulation 5 and the polymerizable compound was changed to DPHA (dipentaerythritol hexaacrylate). And liquid crystal display device. The same evaluation as in Example 1 was carried out for the photo spacer and the liquid crystal display device. The evaluation results are shown in Table 2 below.

如前述表2所示，實施例的光間隔物係剖面形狀的均一性高，且能抑制高度偏移。又，在具備所得光間隔物之液晶顯示裝置係能抑制顯示不均。As shown in the above Table 2, the photo spacer of the embodiment has high uniformity in cross-sectional shape and can suppress height shift. Further, the liquid crystal display device including the obtained photo spacer can suppress display unevenness.

[實施例21][Example 21]

<保護膜的形成><Formation of Protective Film>

在實施例8中的彩色濾光片基板的製作中，於黑底、R像素、G像素、及B像素形成後，再在黑底及各像素上塗布由前述配方1所構成之感光性樹脂組成物，不透過遮罩來進行曝光(全面曝光)、加熱處理，以形成保護膜。此處，塗布、曝光、加熱處理的條件係除了不透過遮罩進行曝光以外，係與在實施例8之光間隔物的形成中的塗布、曝光、加熱處理的條件相同。In the production of the color filter substrate of the eighth embodiment, after the black matrix, the R pixel, the G pixel, and the B pixel are formed, the photosensitive resin composed of the above formulation 1 is applied to the black matrix and each pixel. The composition is exposed (overall exposure) and heat-treated without passing through a mask to form a protective film. Here, the conditions of the coating, the exposure, and the heat treatment are the same as those of the coating, exposure, and heat treatment in the formation of the photo spacer of Example 8, except that the exposure is not performed through the mask.

接著，再在所得之保護層上濺鍍ITO(Indium Tin Oxide)的透明電極而形成。Next, a transparent electrode of ITO (Indium Tin Oxide) was sputtered on the obtained protective layer to form.

<光間隔物的形成><Formation of photo spacers>

在上述所形成之ITO透明電極上，除了使用在比較例2所使用的感光性樹脂組成物作為感光性樹脂組成物以外，藉由與實施例1同樣的方法來形成光間隔物。On the ITO transparent electrode formed above, a photo spacer was formed in the same manner as in Example 1 except that the photosensitive resin composition used in Comparative Example 2 was used as the photosensitive resin composition.

<液晶顯示裝置的製作及評價><Production and evaluation of liquid crystal display device>

接著，使用形成前述光間隔物之彩色濾光片基板，藉由與實施例1同樣的方法來製作液晶顯示裝置。Next, a liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which the photo spacers were formed.

就所得之保護膜及液晶顯示裝置，以與實施例1同樣的方法來進行評價。此外，膜厚均一性的評價係藉由與實施例1之「光間隔物的高度均一性」的同樣方法來進行。評價結果係表示於表3。The obtained protective film and liquid crystal display device were evaluated in the same manner as in Example 1. Further, the evaluation of the film thickness uniformity was carried out in the same manner as in "the height uniformity of the photo spacer" of Example 1. The evaluation results are shown in Table 3.

[比較例3][Comparative Example 3]

在實施例21中，除了將聚合性化合物變更為前述比較化合物W-1以外，以與實施例21同樣的方式，製作保護膜、光間隔物、及液晶顯示裝置，並進行同樣的評價。評價結果係表示於下述表3。In the same manner as in Example 21 except that the polymerizable compound was changed to the comparative compound W-1, a protective film, a photo spacer, and a liquid crystal display device were produced, and the same evaluation was carried out. The evaluation results are shown in Table 3 below.

[實施例22][Example 22]

<著色圖案的形成><Formation of Colored Pattern>

在實施例8中的彩色濾光片基板的製作中，除了藉由下述方法形成R像素以外，以與實施例8同樣的方式製作彩色濾光片基板。In the production of the color filter substrate of Example 8, a color filter substrate was produced in the same manner as in Example 8 except that the R pixel was formed by the following method.

亦即，再在前述配方1中添加顏料紅254(19.4份)及顏料紅177(4.83份)，以調製R像素用感光性樹脂組成物。In other words, Pigment Red 254 (19.4 parts) and Pigment Red 177 (4.83 parts) were added to the above-mentioned Formulation 1 to prepare a photosensitive resin composition for R pixels.

除了使用所調製的R像素用感光性樹脂組成物及使用R像素用光罩作為光罩以外，藉由與實施例1之光間隔物的形成同樣的方法，來形成R像素。R pixels were formed by the same method as the formation of the photo spacers of Example 1, except that the photosensitive resin composition for R pixels to be prepared and the photomask for R pixels were used as the photomask.

在形成所製作彩色濾光片基板的R像素、G像素、及B像素後，再在各像素上藉由濺鍍以形成ITO(Indium Tin Oxide，氧化銦錫)的透明電極。After the R pixel, the G pixel, and the B pixel of the color filter substrate to be formed are formed, a transparent electrode of ITO (Indium Tin Oxide) is formed by sputtering on each pixel.

<光間隔物的形成><Formation of photo spacers>

除了在上述所形成之ITO透明電極上，使用在比較例2所用之感光性樹脂組成物作為感光性樹脂組成物以外，藉由與實施例1同樣的方法，來形成光間隔物。A photo spacer was formed in the same manner as in Example 1 except that the photosensitive resin composition used in Comparative Example 2 was used as the photosensitive resin composition on the ITO transparent electrode formed as described above.

<液晶顯示裝置的製作及評價><Production and evaluation of liquid crystal display device>

接著，使用形成前述光間隔物之彩色濾光片基板，藉由與實施例1同樣的方法來製作液晶顯示裝置。Next, a liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which the photo spacers were formed.

就所得之保護膜及液晶顯示裝置，依照與實施例1同樣的方法來進行評價。此外，膜厚均一性的評價係藉由與實施例1之「光間隔物的高度均一性」同樣的方法來進行。評價結果係表示於表3。The obtained protective film and liquid crystal display device were evaluated in the same manner as in Example 1. Further, the evaluation of the film thickness uniformity was carried out by the same method as the "height uniformity of the photo spacer" of Example 1. The evaluation results are shown in Table 3.

[比較例4][Comparative Example 4]

在實施例22中，除了將聚合性化合物變更為前述比較化合物W-1以外，以與實施例22同樣的方式，製作著色圖案、光間隔物、及液晶顯示裝置，並進行同樣的評價。評價結果係表示於下述表3。In the same manner as in Example 22 except that the polymerizable compound was changed to the above-mentioned comparative compound W-1, a colored pattern, a photo spacer, and a liquid crystal display device were produced, and the same evaluation was carried out. The evaluation results are shown in Table 3 below.

如前述表3所示，在使用本發明的感光性樹脂組成物形成保護膜及著色圖案之情形中，亦能得到與形成光間隔物之情形同樣良好的結果。As shown in the above Table 3, in the case where the protective film and the colored pattern were formed using the photosensitive resin composition of the present invention, the same results as in the case of forming the photo spacer were obtained.

根據本發明，能提供曝光時的聚合硬化性優異、在低溫加熱處理或無加熱下能形成圖案構造物、保護膜之感光性樹脂組成物。According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in polymerization hardenability at the time of exposure and which can form a pattern structure or a protective film under low-temperature heat treatment or without heating.

又，根據本發明，能提供具有均一性高的剖面形狀，且高度均一性優異之光間隔物及其製法。Moreover, according to the present invention, it is possible to provide a photo spacer having a high cross-sectional shape with high uniformity and excellent uniformity of height and a method for producing the same.

又，根據本發明，能提供膜厚均一性優異之保護膜，或具有均一性高的剖面形狀且膜厚均一性優異之著色圖案。Moreover, according to the present invention, it is possible to provide a protective film having excellent film thickness uniformity or a colored pattern having a uniform cross-sectional shape and excellent film thickness uniformity.

又，根據本發明，能提供在使用於顯示裝置之際能抑制顯示不均之顯示裝置用基板、及能抑制顯示不均之顯示裝置。Moreover, according to the present invention, it is possible to provide a display device substrate capable of suppressing display unevenness when used in a display device, and a display device capable of suppressing display unevenness.

本發明之具體態樣的前述記述係以記述與説明之目的而提供者。不應企圖將本發明限定於所揭示的、相同的形態中，或不應僅限定於其所包括之範圍者。該態樣係為了最適宜地說明本發明的概念或其實際的應用而選定者，因此，應該能適用於該業者的其他人所企圖之特定的用途，可為各種的態樣與各種的變形方式，而可為該業者之其他人理解本發明的。The above description of specific aspects of the invention is provided for the purposes of illustration and description. The invention is not intended to be limited to the scope of the invention disclosed, or the scope of the invention. This aspect is selected to best illustrate the concepts of the present invention or its actual application, and therefore should be applicable to the particular use sought by others of the industry, and can be varied and varied. The manner in which the invention can be understood by others of the industry.

記述於本說明書之全部的期刊與專利申請、以及技術標準，特別是在彼等個別的期刊與專利申請、以及技術標準作為引用文獻而且個別指定編入之情形中，係將關於與該引用文獻相同的限定範圍編入本說明書中。上述本發明的較佳實施態樣的詳細內容，當然可為該業者根據其企圖應用之態樣，來自由的變更成各式各樣的應用形態。本發明的範圍係根據下述專利申請專利範圍及其相等者來決定者。All journals and patent applications and technical standards described in this specification, especially in the case where their individual journals and patent applications, and technical standards are cited and individually specified, will be the same as the cited documents. The limited scope is incorporated in this specification. The details of the preferred embodiment of the present invention described above may of course be changed to a variety of application forms according to the manner in which the applicant applies. The scope of the invention is determined by the scope of the following patent claims and their equivalents.

Claims (8)

一種光間隔物之製法，其特徵係至少含有下述步驟(甲)~(丁)：(甲)在基板上形成含有樹脂、具有下述構造部分(I)之聚合性化合物、與光聚合引發劑之感光性樹脂組成物的被膜之形成步驟， 〔構造部分(I)中，X係表示氫原子或甲基，＊係表示結合鍵〕；(乙)曝光前述被膜的至少一部份之曝光步驟；(丙)顯像曝光後的前述被膜之顯像步驟；(丁)加熱顯像後的前述被膜之加熱步驟；且在前述步驟(丁)之加熱時的最高溫度為40℃以上145℃以下。A method for producing a photo spacer, characterized in that it comprises at least the following steps (A) to (d): (a) forming a polymerizable compound containing a resin, having the following structural portion (I) on a substrate, and photopolymerization initiation a step of forming a film of the photosensitive resin composition of the agent, [In the structural part (I), X represents a hydrogen atom or a methyl group, * represents a bonding bond]; (B) an exposure step of exposing at least a part of the film; (c) the film after exposure exposure a developing step; (d) heating step of the film after heating and development; and a maximum temperature at the time of heating in the above step (d) is 40° C. or higher and 145° C. or lower. 如申請專利範圍第1項之光間隔物之製法，其中前述聚合性化合物係在分子中具有至少2個前述構造部分(I)。 The method for producing a photo spacer according to claim 1, wherein the polymerizable compound has at least two of the aforementioned structural portions (I) in the molecule. 如申請專利範圍第1項之光間隔物之製法，其中前述聚合性化合物係具有連結含有前述構造部分(I)的2個基之對稱構造。 The method for producing a photo-spacer according to the first aspect of the invention, wherein the polymerizable compound has a symmetrical structure in which two groups including the structural portion (I) are bonded. 如申請專利範圍第1項之光間隔物之製法，其中前述具有構造部分(I)之聚合性化合物係為下述構造式(Ⅱ)所表示之聚合性化合物， 〔式中，R係表示在2價烴基之碳-碳間含有至少1個醚鍵之連結基，X係表示氫原子、甲基〕。The method for producing a photo-spacer according to the first aspect of the invention, wherein the polymerizable compound having the structural portion (I) is a polymerizable compound represented by the following structural formula (II), [In the formula, R represents a linking group containing at least one ether bond between carbon and carbon of a divalent hydrocarbon group, and X represents a hydrogen atom or a methyl group]. 如申請專利範圍第4項之光間隔物之製法，其中在前述構造式(Ⅱ)中，R係表示-CH2 -O-Ra -O-CH2 -，Ra 係表示選自於由伸烷基部位、伸芳基部位、及組合此等的部位所構成群組之連結基。The method for preparing a photo spacer according to claim 4, wherein in the above structural formula (II), R represents -CH 2 -OR a -O-CH 2 -, and R a represents a selected from alkyl The linking group of the group, the aryl group, and the group in which these are combined. 如申請專利範圍第1項之光間隔物之製法，其中前述樹脂係在側鏈具有具有分枝及/或脂環構造之基、酸性基、以及乙烯性不飽和鍵。 The method of producing a photo-spacer according to claim 1, wherein the resin has a branch having a branching and/or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in the side chain. 如申請專利範圍第6項之光間隔物之製法，其中前述樹脂的酸價為20mgKOH/g以上。 The method for producing a photo spacer according to claim 6, wherein the acid value of the resin is 20 mgKOH/g or more. 如申請專利範圍第6項之光間隔物之製法，其中前述具有分枝及/或脂環構造之基係下述通式(3)所表示之基， 〔通式(3)中，X’係表示2價的有機連結基，可無取代、亦可具有取代基，y係表示1或2，n係表示0~15的整數〕。The method for producing a photo spacer according to claim 6, wherein the base having the branched and/or alicyclic structure is a group represented by the following formula (3), In the general formula (3), X' represents a divalent organic linking group, and may be unsubstituted or may have a substituent, and y represents 1 or 2, and n represents an integer of 0 to 15].
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5423004B2 (en) * 2009-01-08 2014-02-19 東レ株式会社 Negative photosensitive resin composition and touch panel material using the same
KR101805224B1 (en) * 2010-05-03 2017-12-05 바스프 에스이 Color filter for low temperature applications
CN102692661B (en) * 2011-03-24 2016-01-06 Jsr株式会社 The manufacture method of colored filter, colored filter and liquid crystal display cells
JP5835014B2 (en) * 2011-03-31 2015-12-24 Jsr株式会社 Pixel pattern forming method and color filter manufacturing method
JP5742051B2 (en) * 2011-04-08 2015-07-01 岡本化学工業株式会社 Photosensitive composition and lithographic printing plate precursor using the same
TW201303489A (en) * 2011-04-19 2013-01-16 Sumitomo Chemical Co Photosensitive resin composition
CN103717629B (en) * 2011-08-10 2016-05-18 大阪有机化学工业株式会社 Adamantane based polymer
JP2014048556A (en) * 2012-09-03 2014-03-17 Sumitomo Chemical Co Ltd Photosensitive resin composition
CN103838084B (en) * 2012-11-26 2020-06-16 住友化学株式会社 Photosensitive resin composition
WO2015178462A1 (en) * 2014-05-21 2015-11-26 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and method for forming circuit pattern
DE102015119939A1 (en) 2015-11-18 2017-05-18 ALTANA Aktiengesellschaft Crosslinkable polymeric materials for dielectric layers in electronic components
WO2019065687A1 (en) * 2017-09-26 2019-04-04 大阪有機化学工業株式会社 Photosensitive resin composition for forming photospacer, method for forming photospacer, substrate equipped with photospacer, and colour filter
US20220357657A1 (en) * 2019-09-27 2022-11-10 Altana Ag Composition for preparing a color filter

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005140993A (en) * 2003-11-06 2005-06-02 Sekisui Chem Co Ltd Photocurable resin composition, columnar spacer, particle spacer fixing agent and liquid crystal display element
WO2007113107A1 (en) * 2006-03-30 2007-10-11 Ciba Holding Inc. Photosensitive resist composition for color filters for use in electronic paper display devices
CN101114124A (en) * 2006-07-26 2008-01-30 富士胶片株式会社 Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device
JP2008052250A (en) * 2006-05-31 2008-03-06 Mitsubishi Chemicals Corp Thermosetting composition for protective film, cured object and liquid-crystal display
JP2008070822A (en) * 2006-09-15 2008-03-27 Fujifilm Corp Curable composition, color filter and method for producing the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01278523A (en) * 1988-04-28 1989-11-08 Kanegafuchi Chem Ind Co Ltd Resin composition and fiber-reinforced composite material consisting thereof
JP2005529200A (en) * 2002-05-03 2005-09-29 ディーエスエム アイピー アセッツ ビー．ブイ． Radiation curable resin composition and rapid prototyping method using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005140993A (en) * 2003-11-06 2005-06-02 Sekisui Chem Co Ltd Photocurable resin composition, columnar spacer, particle spacer fixing agent and liquid crystal display element
WO2007113107A1 (en) * 2006-03-30 2007-10-11 Ciba Holding Inc. Photosensitive resist composition for color filters for use in electronic paper display devices
JP2008052250A (en) * 2006-05-31 2008-03-06 Mitsubishi Chemicals Corp Thermosetting composition for protective film, cured object and liquid-crystal display
CN101114124A (en) * 2006-07-26 2008-01-30 富士胶片株式会社 Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device
JP2008070822A (en) * 2006-09-15 2008-03-27 Fujifilm Corp Curable composition, color filter and method for producing the same

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