TWI773813B - Photosensitive composition and photopolymerization initiator therefor - Google Patents
Photosensitive composition and photopolymerization initiator therefor Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C07—ORGANIC CHEMISTRY
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- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C07C2601/14—The ring being saturated
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
本發明提供一種抑制硬化後之黏性(發黏)而硬化性優異之感光性組合物、用於其之化合物及光聚合起始劑。 本發明之感光性組合物係含有(A)光聚合起始劑及(B)光聚合性化合物者，上述(A)光聚合起始劑包含下述式(1)：
Description
本發明係關於一種硬化性良好之感光性組合物、適宜用作感光性接著劑之感光性組合物、用於其之化合物及光聚合起始劑。The present invention relates to a photosensitive composition having good curability, a photosensitive composition suitable for use as a photosensitive adhesive, a compound used therefor, and a photopolymerization initiator.
於液晶顯示裝置之類之顯示裝置用面板中，絕緣膜或間隔件之類之材料需效率良好地使自背光源之類之光源發出之光透過。因此，使用藉由曝光而提供透明之硬化膜之感光性組合物以形成絕緣膜或間隔件之圖案。藉由選擇性地對此種感光性組合物進行曝光，可形成透明之硬化膜之圖案。In a panel for a display device such as a liquid crystal display device, a material such as an insulating film or a spacer needs to efficiently transmit light emitted from a light source such as a backlight. Therefore, the photosensitive composition which provides a transparent cured film by exposure is used to form the pattern of an insulating film or a spacer. By selectively exposing such a photosensitive composition, a pattern of a transparent cured film can be formed.
又，於顯示裝置用面板中，亦多有形成黑矩陣或黑間隔柱等經圖案化之遮光性膜之情況。針對此種用途，業界亦提出有各種用於形成遮光性膜之包含遮光劑與光聚合起始劑之感光性組合物。 用於形成遮光性膜之感光性組合物中含有遮光劑，故要求光聚合起始劑具有更高感度。Moreover, in the panel for display apparatuses, the patterned light-shielding film, such as a black matrix and a black spacer, is formed in many cases. For such use, various photosensitive compositions containing a light-shielding agent and a photopolymerization initiator for forming a light-shielding film have also been proposed in the industry. Since the photosensitive composition for forming a light-shielding film contains a light-shielding agent, the photopolymerization initiator is required to have a higher sensitivity.
例如關於含有感度優異之光聚合起始劑之感光性組合物，業界提出有一種含有肟酯化合物作為光聚合起始劑之感光性組合物，該肟酯化合物包含9位經取代之茀環作為主骨架(參照專利文獻1)。 [先前技術文獻] [專利文獻]For example, regarding a photosensitive composition containing a photopolymerization initiator with excellent sensitivity, the industry has proposed a photosensitive composition containing an oxime ester compound as a photopolymerization initiator, and the oxime ester compound contains a 9-substituted perylene ring as a Main skeleton (refer to Patent Document 1). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2016-218353號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-218353
[發明所欲解決之問題][Problems to be Solved by Invention]
然而，感光性組合物中含有之光聚合起始劑存在因空氣中之氧而失活之課題。 另一方面，就節約能源或減輕環境負荷之觀點而言，LED作為曝光用光源之使用推進。 業界要求於包含LED曝光之各種曝光條件(例如各種曝光波長)下硬化性均優異之感光性組合物。 本發明係鑒於上述先前技術課題而成者，目的在於提供一種抑制硬化後之黏性(發黏)而硬化性優異之感光性組合物，用於其之化合物及光聚合起始劑。 [解決問題之技術手段]However, the photopolymerization initiator contained in the photosensitive composition has a problem of being deactivated by oxygen in the air. On the other hand, from the viewpoint of saving energy or reducing environmental load, the use of LEDs as a light source for exposure is advancing. The industry requires a photosensitive composition with excellent curability under various exposure conditions (eg, various exposure wavelengths) including LED exposure. The present invention was made in view of the above-mentioned prior art problem, and an object of the present invention is to provide a photosensitive composition excellent in curability by suppressing stickiness (stickiness) after curing, a compound used for the photosensitive composition, and a photopolymerization initiator. [Technical means to solve problems]
本發明者等人發現，藉由使特定結構之肟酯系光聚合起始劑具有包含HX2 C-或H2 XC-所表示之基(X為鹵素原子)之取代基，可提高感光性組合物之硬化性(尤其是表面硬化性)，從而完成本發明。即，本發明如下所述。The inventors of the present invention have found that the photosensitivity can be improved by giving the oxime ester-based photopolymerization initiator of a specific structure a substituent containing a group represented by HX 2 C- or H 2 XC- (X is a halogen atom). The hardenability (especially the surface hardenability) of the composition has led to the completion of the present invention. That is, the present invention is as follows.
本發明之第1態樣係一種感光性組合物，其係含有(A)光聚合起始劑及(B)光聚合性化合物者，上述(A)光聚合起始劑包含下述式(1)： [化1]
本發明之第2態樣係一種化合物，其係由下述式(1)： [化2]
本發明之第3態樣係一種光聚合起始劑，其包含第2態樣之化合物。 [發明之效果]The third aspect of the present invention is a photopolymerization initiator comprising the compound of the second aspect. [Effect of invention]
本發明之感光性組合物於包含LED曝光之各種曝光條件(例如各種曝光波長)下均抑制硬化後之黏性(發黏)，硬化性優異。本發明之感光性組合物例如適宜用作感光性接著劑。 根據本發明，可提供一種適用於上述感光性組合物之化合物及光聚合起始劑。The photosensitive composition of this invention suppresses the stickiness (tackiness) after hardening under various exposure conditions (for example, various exposure wavelengths) including LED exposure, and is excellent in hardenability. The photosensitive composition of the present invention is suitably used, for example, as a photosensitive adhesive. According to the present invention, a compound and a photopolymerization initiator suitable for the above-mentioned photosensitive composition can be provided.
以下對本發明之實施態樣進行詳細說明，但本發明並不受下述實施態樣之任何限定，可於本發明之目的之範圍內適當施加變更而實施。 又，於本說明書中，只要無特別說明，則「～」表示以上至以下。Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, in this specification, unless otherwise specified, "-" represents the above to the following.
≪感光性組合物≫ 第1態樣之感光性組合物係含有(A)光聚合起始劑及(B)光聚合性化合物者，上述(A)光聚合起始劑包含上述式(1)所表示之化合物，且上述式(1)所表示之化合物滿足下述1)～3)中之至少一者(其中，X各自獨立為鹵素原子)。 1)n1為1以上且4以下之整數，Ra1 之至少一者為包含HX2 C-或H2 XC-所表示之基之取代基。 2)Ra4 為包含HX2 C-或H2 XC-所表示之基之取代基。 3)Ra5 為包含HX2 C-或H2 XC-所表示之基之取代基。 以下依序說明感光性組合物所含有之成分。≪Photosensitive composition≫ The photosensitive composition of the first aspect contains (A) a photopolymerization initiator and (B) a photopolymerizable compound, wherein the (A) photopolymerization initiator includes the above formula (1) The compound represented by the above formula (1) satisfies at least one of the following 1) to 3) (wherein X is each independently a halogen atom). 1) n1 is an integer of 1 or more and 4 or less, and at least one of R a1 is a substituent containing a group represented by HX 2 C- or H 2 XC-. 2) R a4 is a substituent containing a group represented by HX 2 C- or H 2 XC-. 3) R a5 is a substituent containing a group represented by HX 2 C- or H 2 XC-. The components contained in the photosensitive composition will be sequentially described below.
＜(A)光聚合起始劑＞ 感光性組合物含有包含上述式(1)所表示之化合物之(A)光聚合起始劑(以下亦稱為(A)成分)。 藉由使上述式(1)所表示之化合物滿足上述1)～3)中之至少一者，可提高感光性組合物之硬化性(尤其是表面硬化性)，其結果可減輕所形成之硬化物之表面之黏性(發黏)。<(A) Photopolymerization initiator> The photosensitive composition contains (A) a photopolymerization initiator (henceforth (A) component) containing the compound represented by the said formula (1). By making the compound represented by the above formula (1) satisfy at least one of the above 1) to 3), the curability (especially the surface curability) of the photosensitive composition can be improved, and as a result, the resulting hardening can be reduced The stickiness (tackiness) of the surface of an object.
於上述1)時，Ra1 中之至少一者為1價有機基，上述1價有機基中之至少一者可相當於包含HX2 C-或H2 XC-所表示之基之取代基。 於上述2)時，Ra4 為1價有機基，上述1價有機基可相當於包含HX2 C-或H2 XC-所表示之基之取代基。 於上述3)時，Ra5 為具有取代基之碳原子數1以上且20以下之脂肪族烴基或具有取代基之芳基，上述具有取代基之脂肪族烴基或上述具有取代基之芳基可相當於包含HX2 C-或H2 XC-所表示之基之取代基。In the above 1), at least one of R a1 is a monovalent organic group, and at least one of the above monovalent organic groups may correspond to a substituent including a group represented by HX 2 C- or H 2 XC-. In the above 2), R a4 is a monovalent organic group, and the above monovalent organic group may correspond to a substituent including a group represented by HX 2 C- or H 2 XC-. In the above 3), R a5 is a substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or substituted aryl group, and the above substituted aliphatic hydrocarbon group or the above substituted aryl group can be It corresponds to a substituent containing a group represented by HX 2 C- or H 2 XC-.
作為X所表示之鹵素原子，可列舉：氟原子、氯原子、溴原子等，較佳為氟原子。 作為包含HX2 C-或H2 XC-所表示之基之取代基，可列舉：包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、具有包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、具有包含HX2 C-或H2 XC-所表示之基之鹵化烷基的基等，更佳為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、或者具有包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的基。As a halogen atom represented by X, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, Preferably it is a fluorine atom. Examples of substituents containing a group represented by HX 2 C- or H 2 XC- include halogenated alkoxy groups containing a group represented by HX 2 C- or H 2 XC-, those containing HX 2 C- or H 2 XC- A halogenated alkoxy group represented by a group represented by 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC- A halogenated alkyl group, etc., more preferably a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, or a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- base base.
作為具有包含HX2 C-或H2 XC-所表示之基之鹵化烷基的基，可列舉：經包含HX2 C-或H2 XC-所表示之基之鹵化烷基取代之芳香族基(例如，苯基、萘基等)、經包含HX2 C-或H2 XC-所表示之基之鹵化烷基取代之環烷基(例如，環戊基、環己基等)等，較佳為經包含HX2 C-或H2 XC-所表示之基之鹵化烷基取代之芳香族基。Examples of the group having a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC- include an aromatic group substituted with a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC- (for example, phenyl, naphthyl, etc.), cycloalkyl (for example, cyclopentyl, cyclohexyl, etc.) substituted with a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, etc., preferably is an aromatic group substituted with a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-.
作為包含HX2
C-或H2
XC-所表示之基之鹵化烷基之具體例、及具有包含HX2
C-或H2
XC-所表示之基之鹵化烷基的基之具體例，例如可例示下述結構。 [化3]
作為具有包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的基，可列舉：經包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基取代之芳香族基(例如，苯基、萘基等)、經包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基取代之烷基(例如，甲基、乙基、正丙基、異丙基等)、經包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基取代之環烷基(例如，環戊基、環己基等)等，較佳為經包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基取代之芳香族基。Examples of the group having a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- include an aromatic substituted with a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- group (for example, phenyl, naphthyl, etc.), alkyl group (for example, methyl, ethyl, n - propyl , isopropyl group, etc.), cycloalkyl group substituted with halogenated alkoxy group (for example, cyclopentyl, cyclohexyl, etc.) containing a group represented by HX 2 C- or H 2 XC-, etc., preferably a group containing HX A halogenated alkoxy-substituted aromatic group of the group represented by 2 C- or H 2 XC-.
作為經包含HX2
C-或H2
XC-所表示之基之鹵化烷氧基取代之芳香族基，較佳為下述式(1-a)所表示之基。 [化4]
作為具有包含HX2
C-或H2
XC-所表示之基之鹵化烷氧基的基之具體例，例如可例示下述結構，但本發明並不限定於該等。 [化5]
於上述1)時，上述Ra1 較佳為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、或者具有包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的基， 於上述2)或3)時，上述Ra4 或Ra5 較佳為具有包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的基。In the above 1), the above R a1 is preferably a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, or a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- As for the alkoxy group, in the case of the above 2) or 3), the above R a4 or R a5 is preferably a group having a halogenated alkoxy group including a group represented by HX 2 C- or H 2 XC-.
式(1)中，Ra1 為氫原子、硝基、或1價有機基。Ra1 鍵結於式(1)中之茀環上之與鍵結於-(CO)n2 -所表示之基之6員芳香環不同的6員芳香環。式(1)中，Ra1 於茀環上之鍵結位置並無特別限定。於式(1)所表示之化合物具有1個以上之Ra1 之情形時，就式(1)所表示之化合物容易合成等而言，較佳為1個以上之Ra1 中之一者鍵結於茀環中之2位。於Ra1 為複數個之情形時，複數個Ra1 可相同亦可不同。In formula (1), R a1 is a hydrogen atom, a nitro group, or a monovalent organic group. The 6-membered aromatic ring that R a1 is bonded to the perylene ring in the formula (1) is different from the 6-membered aromatic ring bonded to the group represented by -(CO) n2- . In formula (1), the bonding position of R a1 on the indium ring is not particularly limited. When the compound represented by the formula (1) has one or more R a1 , the compound represented by the formula (1) is preferably bonded to one of the one or more R a1 in view of the ease of synthesis of the compound represented by the formula (1). 2 in the ring. When R a1 is plural, the plural R a1 may be the same or different.
於Ra1 為1價有機基之情形時，Ra1 於無損本發明之目的之範圍內無特別限定，可自各種有機基中適當選擇，如上所述，於上述1)時，Ra1 中之至少一者為1價有機基，上述1價有機基中之至少一者為包含HX2 C-或H2 XC-所表示之基之取代基。作為Ra1 為1價有機基之情形時之適宜例，可列舉：上述包含HX2 C-或H2 XC-所表示之基之取代基、烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、經1個或2個有機基取代之胺基、𠰌啉-1-基、及哌𠯤-1-基等。 Ra1 中之至少一者為包含HX2 C-或H2 XC-所表示之基之取代基之情形時之包含HX2 C-或H2 XC-所表示之基之取代基之具體例及較佳例如上所述。When R a1 is a monovalent organic group, R a1 is not particularly limited as long as it does not impair the purpose of the present invention, and can be appropriately selected from various organic groups. As described above, in the above 1), among R a1 At least one of them is a monovalent organic group, and at least one of the above-mentioned monovalent organic groups is a substituent containing a group represented by HX 2 C- or H 2 XC-. Preferable examples when R a1 is a monovalent organic group include substituents including the above-mentioned group represented by HX 2 C- or H 2 XC-, an alkyl group, an alkoxy group, a cycloalkyl group, and a cycloalkane group. Oxy group, saturated aliphatic alkyl group, alkoxycarbonyl group, saturated aliphatic alkyl group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted Substituent phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic, optionally substituted The heterocyclic carbonyl group, the amino group substituted by one or two organic groups, the 𠰌line-1-yl, and the pipe𠯤-1-yl, etc. Specific examples and _ _ Preferred examples are as described above.
於Ra1 為烷基之情形時，烷基之碳原子數較佳為1以上且20以下，更佳為1以上且6以下。又，於Ra1 為烷基之情形時，可為直鏈亦可為支鏈。作為Ra1 為烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於Ra1 為烷基之情形時，烷基可於碳鏈中包含醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。When R a1 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Moreover, when R a1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R a1 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-octyl Decyl, and isodecyl, etc. In addition, when R a1 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.
於Ra1 為烷氧基之情形時，烷氧基之碳原子數較佳為1以上且20以下，更佳為1以上且6以下。又，於Ra1 為烷氧基之情形時，可為直鏈亦可為支鏈。作為Ra1 為烷氧基之情形時之具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基、異戊氧基、第二戊氧基、第三戊氧基、正己氧基、正庚氧基、正辛氧基、異辛氧基、第二辛氧基、第三辛氧基、正壬氧基、異壬氧基、正癸氧基、及異癸氧基等。又，於Ra1 為烷氧基之情形時，烷氧基可於碳鏈中包含醚鍵(-O-)。作為碳鏈中具有醚鍵之烷氧基之例，可列舉：甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙氧基乙氧基乙氧基、及甲氧基丙氧基等。When R a1 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when R a1 is an alkoxy group, it may be linear or branched. Specific examples when R a1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. In addition, when R a1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy , propoxyethoxyethoxy, and methoxypropoxy, etc.
於Ra1 為環烷基或環烷氧基之情形時，環烷基或環烷氧基之碳原子數較佳為3以上且10以下，更佳為3以上且6以下。作為Ra1 為環烷基之情形時之具體例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為Ra1 為環烷氧基之情形時之具體例，可列舉：環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基、及環辛氧基等。When R a1 is a cycloalkyl group or a cycloalkoxy group, the carbon number of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. As a specific example when R a1 is a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Specific examples when R a1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
於Ra1 為飽和脂肪族醯基或飽和脂肪族醯氧基之情形時，飽和脂肪族醯基或飽和脂肪族醯氧基之碳原子數較佳為2以上且21以下，更佳為2以上且7以下。作為Ra1 為飽和脂肪族醯基之情形時之具體例，可列舉：乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一碳醯基、正十二碳醯基、正十三碳醯基、正十四碳醯基、正十五碳醯基、及正十六碳醯基等。作為Ra1 為飽和脂肪族醯氧基之情形時之具體例，可列舉：乙醯氧基、丙醯氧基、正丁醯氧基、2-甲基丙醯氧基、正戊醯氧基、2,2-二甲基丙醯氧基、正己醯氧基、正庚醯氧基、正辛醯氧基、正壬醯氧基、正癸醯氧基、正十一碳醯氧基、正十二碳醯氧基、正十三碳醯氧基、正十四碳醯氧基、正十五碳醯氧基、及正十六碳醯氧基等。When R a1 is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the carbon number of the saturated aliphatic alkanoyl group or saturated aliphatic alkoxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples in the case where R a1 is a saturated aliphatic acid group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethyl group. Propyl radical, n-hexyl radical, n-heptyl radical, n-octyl radical, n-nonyl radical, n-decyl radical, n-decyl radical, n-dodecyl radical, n-tdecyl radical, n-tetradecyl radical Carbonyl, n-pentadecyl, and n-hexadecyl, etc. Specific examples when R a1 is a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, and n-pentanoyloxy , 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like.
於Ra1 為烷氧基羰基之情形時，烷氧基羰基之碳原子數較佳為2以上且20以下，更佳為2以上且7以下。作為Ra1 為烷氧基羰基之情形時之具體例，可列舉：甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、異丁氧基羰基、第二丁氧基羰基、第三丁氧基羰基、正戊氧基羰基、異戊氧基羰基、第二戊氧基羰基、第三戊氧基羰基、正己氧基羰基、正庚氧基羰基、正辛氧基羰基、異辛氧基羰基、第二辛氧基羰基、第三辛氧基羰基、正壬氧基羰基、異壬氧基羰基、正癸氧基羰基、及異癸氧基羰基等。When R a1 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R a1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second-butoxycarbonyl, third-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second-pentoxycarbonyl, third-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy ylcarbonyl, n-octoxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl, etc.
於Ra1 為苯基烷基之情形時，苯基烷基之碳原子數較佳為7以上且20以下，更佳為7以上且10以下。又，於Ra1 為萘基烷基之情形時，萘基烷基之碳原子數較佳為11以上且20以下，更佳為11以上且14以下。作為Ra1 為苯基烷基之情形時之具體例，可列舉：苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為Ra1 為萘基烷基之情形時之具體例，可列舉：α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。於Ra1 為苯基烷基或萘基烷基之情形時，Ra1 可於苯基或萘基上進而具有取代基。When R a1 is a phenylalkyl group, the carbon number of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Moreover, when R a1 is a naphthyl alkyl group, it is preferable that it is 11 or more and 20 or less, and, as for the carbon number of a naphthyl alkyl group, it is more preferable that it is 11 or more and 14 or less. Specific examples when R a1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R a1 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthalene base) ethyl. When R a1 is phenylalkyl or naphthylalkyl, R a1 may further have a substituent on phenyl or naphthyl.
於Ra1 為雜環基之情形時，雜環基為包含1個以上之N、S、O之5員或6員單環，或者為該由單環彼此、或由該單環與苯環縮合而成之雜環基。於雜環基為縮合環之情形時，環數至多為3。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、喹㗁啉、哌啶、哌𠯤、𠰌啉、哌啶、四氫吡喃、及四氫呋喃等。於Ra1 為雜環基之情形時，雜環基可進而具有取代基。When R a1 is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or the monocyclic ring or the monocyclic ring and the benzene ring. Heterocyclic group formed by condensation. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Linen, quinazoline, phthaloline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R a1 is a heterocyclic group, the heterocyclic group may further have a substituent.
於Ra1 為雜環基羰基之情形時，雜環基羰基所含之雜環基與Ra1 為雜環基之情形時相同。When R a1 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when R a1 is a heterocyclic group.
於Ra1 為經1個或2個有機基取代之胺基之情形時，作為有機基之適宜例，可列舉：碳原子數1以上且20以下之烷基、碳原子數3以上且10以下之環烷基、碳原子數2以上且21以下之飽和脂肪族醯基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳原子數7以上且20以下之苯基烷基、可具有取代基之萘基、可具有取代基之萘甲醯基、可具有取代基之碳原子數11以上且20以下之萘基烷基、及雜環基等。該等適宜之有機基之具體例與Ra1 相同。作為經1個或2個有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙胺基、正丙基胺基、二正丙胺基、異丙基胺基、正丁基胺基、二正丁胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。When R a1 is an amino group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. cycloalkyl group, saturated aliphatic aliphatic group with 2 or more and 21 or less carbon atoms, phenyl group which may have substituents, benzyl group which may have substituents, and carbon atoms which may have 7 or more and 20 carbon atoms The following phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthyl groups, optionally substituted naphthyl alkyl groups having 11 to 20 carbon atoms, and heterocyclic groups, etc. Specific examples of these suitable organic groups are the same as those of R a1 . Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc.
作為Ra1 所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基，可列舉：包含HX2 C-或H2 XC-所表示之基之取代基(例如，包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基)、碳原子數1以上且6以下之烷基、碳原子數1以上且6以下之烷氧基、碳原子數2以上且7以下之飽和脂肪族醯基、碳原子數2以上且7以下之烷氧基羰基、碳原子數2以上且7以下之飽和脂肪族醯氧基、具有碳原子數1以上且6以下之烷基之單烷基胺基、具有碳原子數1以上且6以下之烷基之二烷基胺基、𠰌啉-1-基、哌𠯤-1-基、鹵素、硝基、及氰基等。於Ra1 所含之苯基、萘基及雜環基進而具有取代基之情形時，該取代基之數量於無損本發明之目的之範圍內無限定，較佳為1以上且4以下。於Ra1 所含之苯基、萘基及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。As the substituent in the case where the phenyl group, naphthyl group, and heterocyclic group contained in R a1 further has a substituent, a substituent including a group represented by HX 2 C- or H 2 XC- (for example, including A halogenated alkoxy group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-), an alkyl group having 1 to 6 carbon atoms , Alkoxy group with 1 to 6 carbon atoms, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, 2 to 7 carbon atoms The following saturated aliphatic alkanoyloxy groups, monoalkylamine groups having an alkyl group having 1 to 6 carbon atoms, a dialkylamine group having an alkyl group having 1 to 6 carbon atoms, and quinoline- 1-yl, piperazine-1-yl, halogen, nitro, and cyano, etc. When a phenyl group, a naphthyl group, and a heterocyclic group contained in R a1 further have a substituent, the number of the substituent is not limited within a range that does not impair the purpose of the present invention, and is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R a1 have plural substituents, the plural substituents may be the same or different.
以上說明之基之中，若Ra1 為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、硝基或Ra11 -CO-所表示之基，則有感度提高之傾向，從而較佳。Ra11 於無損本發明之目的之範圍內無特別限定，可自各種有機基中選擇。關於適宜作為Ra11 之基之例，可列舉：包含HX2 C-或H2 XC-所表示之基之取代基、碳原子數1以上且20以下之烷基、可具有取代基之苯基、可具有取代基之萘基、及可具有取代基之雜環基。作為Ra11 ，於該等基之中，尤佳為具有包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的苯基、具有包含HX2 C-或H2 XC-所表示之基之鹵化烷基的苯基、2-甲基苯基、噻吩-2-基、及α-萘基。 又，若Ra1 為氫原子，則有透明性良好之傾向，從而較佳。再者，若Ra1 為氫原子且Ra4 為下述式(R4-2)所表示之基，則有透明性更良好之傾向。Among the groups described above, if R a1 is a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, A nitro group or a group represented by R a11 -CO- tends to increase the sensitivity, which is preferable. R a11 is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of suitable groups for R a11 include substituents including groups represented by HX 2 C- or H 2 XC-, alkyl groups having 1 to 20 carbon atoms, and optionally substituted phenyl groups. , a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As R a11 , among these groups, a phenyl group having a halogenated alkoxy group including a group represented by HX 2 C- or H 2 XC-, a phenyl group having a group including HX 2 C- or H 2 XC-, The halogenated alkyl group represented by the group is phenyl, 2-methylphenyl, thiophen-2-yl, and α-naphthyl. Moreover, when R a1 is a hydrogen atom, since transparency tends to be favorable, it is preferable. Furthermore, when R a1 is a hydrogen atom and R a4 is a group represented by the following formula (R4-2), the transparency tends to be more favorable.
以下可例示Ra11
-CO-所表示之基之較佳之具體例，但本發明並不限定於該等。下述式中，m3為0或1。 [化6]
式(1)中，Ra2 及Ra3 分別為可具有取代基之鏈狀烷基、可具有取代基之環狀有機基、或氫原子。Ra2 與Ra3 可相互鍵結而形成環。該等基之中，Ra2 及Ra3 較佳為可具有取代基之鏈狀烷基。於Ra2 及Ra3 為可具有取代基之鏈狀烷基之情形時，鏈狀烷基可為直鏈烷基亦可為支鏈烷基。In formula (1), R a2 and R a3 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R a2 and R a3 may be bonded to each other to form a ring. Among these groups, R a2 and R a3 are preferably chain alkyl groups which may have a substituent. When R a2 and R a3 are chain alkyl groups which may have substituents, the chain alkyl groups may be straight chain alkyl groups or branched chain alkyl groups.
於Ra2 及Ra3 為不具有取代基之鏈狀烷基之情形時，鏈狀烷基之碳原子數較佳為1以上且20以下，更佳為1以上且10以下，尤佳為1以上且6以下。作為Ra2 及Ra3 為鏈狀烷基之情形時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、正己基、正庚基、正辛基、異辛基、第二辛基、第三辛基、正壬基、異壬基、正癸基、及異癸基等。又，於Ra2 及Ra3 為烷基之情形時，烷基可於碳鏈中包含醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基之例，可列舉：甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、及甲氧基丙基等。When R a2 and R a3 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 more than 6 and less than 6. Specific examples when R a2 and R a3 are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary Butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, Isononyl, n-decyl, and isodecyl, etc. In addition, when R a2 and R a3 are alkyl groups, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.
於Ra2 及Ra3 為具有取代基之鏈狀烷基之情形時，鏈狀烷基之碳原子數較佳為1以上且20以下，更佳為1以上且10以下，尤佳為1以上且6以下。於該情形時，鏈狀烷基之碳原子數不包括取代基之碳原子數。具有取代基之鏈狀烷基較佳為直鏈狀。 烷基可具有之取代基於無損本發明之目的之範圍內無特別限定。作為取代基之適宜例，可列舉：氰基、鹵素原子、環狀有機基、及烷氧基羰基。作為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。該等之中，較佳為氟原子、氯原子、溴原子。作為環狀有機基，可列舉：環烷基、芳香族烴基、雜環基。作為環烷基之具體例，與Ra1 為環烷基之情形時之適宜例相同。作為芳香族烴基之具體例，可列舉：苯基、萘基、聯苯基、蒽基、及菲基等。作為雜環基之具體例，與Ra1 為雜環基之情形時之適宜例相同。於Ra1 為烷氧基羰基之情形時，烷氧基羰基所含之烷氧基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。烷氧基羰基所含之烷氧基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下。When R a2 and R a3 are chain alkyl groups having substituents, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 or more and 6 or less. In this case, the carbon number of the chain alkyl group does not include the carbon number of the substituent. The chain alkyl group having a substituent is preferably a straight chain. The substitution which the alkyl group may have is not particularly limited within a range that does not impair the purpose of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. Specific examples of the cycloalkyl group are the same as suitable examples when R a1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. Specific examples of the heterocyclic group are the same as suitable examples when R a1 is a heterocyclic group. When R a1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
於鏈狀烷基具有取代基之情形時，取代基之數量無特別限定。取代基之較佳數量根據鏈狀烷基之碳原子數而變化。取代基之數量典型而言為1以上且20以下，較佳為1以上且10以下，更佳為1以上且6以下。When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The preferable number of substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
於Ra2 及Ra3 為環狀有機基之情形時，環狀有機基可為脂環式基，亦可為芳香族基。作為環狀有機基，可列舉：脂肪族環狀烴基、芳香族烴基、雜環基。於Ra2 及Ra3 為環狀有機基之情形時，環狀有機基可具有之取代基與Ra2 及Ra3 為鏈狀烷基之情形時相同。When R a2 and R a3 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. As a cyclic organic group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. When R a2 and R a3 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as when R a2 and R a3 are chain alkyl groups.
於Ra2 及Ra3 為芳香族烴基之情形時，芳香族烴基較佳為苯基、或複數個苯環經由碳-碳鍵進行鍵結所形成之基、或複數個苯環進行縮合所形成之基。於芳香族烴基為苯基、或為複數個苯環進行鍵結或縮合所形成之基之情形時，芳香族烴基所含之苯環之環數並無特別限定，較佳為3以下，更佳為2以下，尤佳為1。作為芳香族烴基之較佳之具體例，可列舉：苯基、萘基、聯苯基、蒽基、及菲基等。When R a2 and R a3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by the bonding of a plurality of benzene rings through carbon-carbon bonds, or a condensation of a plurality of benzene rings. foundation. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more 2 or less is preferable, and 1 is more preferable. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.
於Ra2 及Ra3 為脂肪族環狀烴基之情形時，脂肪族環狀烴基可為單環式，亦可為多環式。脂肪族環狀烴基之碳原子數無特別限定，較佳為3以上且20以下，更佳為3以上且10以下。作為單環式之環狀烴基之例，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降𦯉基、異𦯉基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。When R a2 and R a3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norxyl, isoxyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, and adamantyl, etc.
於Ra2 及Ra3 為雜環基之情形時，雜環基為包含1個以上之N、S、O之5員或6員單環，或者為該由單環彼此、或由該單環與苯環縮合而成之雜環基。於雜環基為縮合環之情形時，環數至多為3。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、㗁唑、異㗁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡𠯤、嘧啶、嗒𠯤、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚𠯤、苯并咪唑、苯并***、苯并㗁唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞𠯤、㖕啉、喹㗁啉、哌啶、哌𠯤、𠰌啉、哌啶、四氫吡喃、及四氫呋喃等。When R a2 and R a3 are heterocyclic groups, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or the monocyclic ring or the monocyclic ring. Heterocyclic group formed by condensation with benzene ring. When the heterocyclic group is a condensed ring, the number of rings is at most 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine, Beta, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline Linen, quinazoline, phthaloline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc.
Ra2 與Ra3 可相互鍵結而形成環。包含由Ra2 與Ra3 所形成之環之基較佳為亞環烷基。於Ra2 與Ra3 鍵結而形成亞環烷基之情形時，構成亞環烷基之環較佳為5員環或6員環，更佳為5員環。R a2 and R a3 may be bonded to each other to form a ring. The group comprising the ring formed by R a2 and R a3 is preferably a cycloalkylene group. When R a2 and R a3 are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.
於Ra2 與Ra3 鍵結所形成之基為亞環烷基之情形時，亞環烷基亦可與1個以上之其他環進行縮合。作為可與亞環烷基縮合之環之例，可列舉：苯環、萘環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、呋喃環、噻吩環、吡咯環、吡啶環、吡𠯤環、及嘧啶環等。When the group formed by the bonding of R a2 and R a3 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring which can be condensed with a cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine ring, and pyrimidine ring, etc.
以上說明之Ra2 及Ra3 之中，作為適宜之基之例，可列舉式-A1 -A2 所表示之基。式中，作為A1 ，可列舉直鏈伸烷基，作為A2 ，可列舉烷氧基、氰基、鹵素原子、鹵化烷基、環狀有機基、或烷氧基羰基。Among R a2 and R a3 described above, examples of suitable groups include groups represented by formula -A 1 -A 2 . In the formula, as A 1 , a straight-chain extended alkyl group is mentioned, and as A 2 , an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group is mentioned.
作為A1 之直鏈伸烷基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下。於A2 為烷氧基之情形時，烷氧基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。烷氧基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下。於A2 為鹵素原子之情形時，較佳為氟原子、氯原子、溴原子、碘原子，更佳為氟原子、氯原子、溴原子。於A2 為鹵化烷基之情形時，鹵化烷基所含之鹵素原子較佳為氟原子、氯原子、溴原子、碘原子，更佳為氟原子、氯原子、溴原子。鹵化烷基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。於A2 為環狀有機基之情形時，環狀有機基之例與Ra2 及Ra3 所具有之作為取代基之環狀有機基相同。於A2 為烷氧基羰基之情形時，烷氧基羰基之例與Ra2 及Ra3 所具有之作為取代基之烷氧基羰基相同。The number of carbon atoms of the linear alkyl group as A 1 is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A 2 is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A 2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, more preferably a fluorine atom, a chlorine atom, and a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A 2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R a2 and R a3 have as a substituent. When A 2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R a2 and R a3 have as a substituent.
作為Ra2 及Ra3 之適宜之具體例，可列舉：乙基、正丙基、正丁基、正己基、正庚基、及正辛基等烷基；2-甲氧基乙基、3-甲氧基正丙基、4-甲氧基正丁基、5-甲氧基正戊基、6-甲氧基正己基、7-甲氧基正庚基、8-甲氧基正辛基、2-乙氧基乙基、3-乙氧基正丙基、4-乙氧基正丁基、5-乙氧基正戊基、6-乙氧基正己基、7-乙氧基正庚基、及8-乙氧基正辛基等烷氧基烷基；2-氰基乙基、3-氰基正丙基、4-氰基正丁基、5-氰基正戊基、6-氰基正己基、7-氰基正庚基、及8-氰基正辛基等氰基烷基；2-苯基乙基、3-苯基正丙基、4-苯基正丁基、5-苯基正戊基、6-苯基正己基、7-苯基正庚基、及8-苯基正辛基等苯基烷基；2-環己基乙基、3-環己基正丙基、4-環己基正丁基、5-環己基正戊基、6-環己基正己基、7-環己基正庚基、8-環己基正辛基、2-環戊基乙基、3-環戊基正丙基、4-環戊基正丁基、5-環戊基正戊基、6-環戊基正己基、7-環戊基正庚基、及8-環戊基正辛基等環烷基烷基；2-甲氧基羰基乙基、3-甲氧基羰基正丙基、4-甲氧基羰基正丁基、5-甲氧基羰基正戊基、6-甲氧基羰基正己基、7-甲氧基羰基正庚基、8-甲氧基羰基正辛基、2-乙氧基羰基乙基、3-乙氧基羰基正丙基、4-乙氧基羰基正丁基、5-乙氧基羰基正戊基、6-乙氧基羰基正己基、7-乙氧基羰基正庚基、及8-乙氧基羰基正辛基等烷氧基羰基烷基；2-氯乙基、3-氯正丙基、4-氯正丁基、5-氯正戊基、6-氯正己基、7-氯正庚基、8-氯正辛基、2-溴乙基、3-溴正丙基、4-溴正丁基、5-溴正戊基、6-溴正己基、7-溴正庚基、8-溴正辛基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基等鹵化烷基。Suitable specific examples of R a2 and R a3 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3 -Methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl base, 2-ethoxyethyl, 3-ethoxyn-propyl, 4-ethoxyn-butyl, 5-ethoxyn-pentyl, 6-ethoxyn-hexyl, 7-ethoxy n-heptyl, and alkoxyalkyl groups such as 8-ethoxyn-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl , 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl cyanoalkyl groups; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-octyl Butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl and other phenylalkyl groups; 2-cyclohexylethyl, 3-cyclohexyl Hexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl , 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl Cycloalkylalkyl such as pentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl , 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4 - Ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl alkanes Oxycarbonylalkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-butyl Octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, Halogenated alkyl groups such as 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.
作為Ra2 及Ra3 ，宜為上述基中之乙基、正丙基、正丁基、正戊基、2-甲氧基乙基、2-氰基乙基、2-苯基乙基、2-環己基乙基、2-甲氧基羰基乙基、2-氯乙基、2-溴乙基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基。R a2 and R a3 are preferably ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5, 5,5-heptafluoro-n-pentyl.
如上所述，於Ra4 為1價有機基之情形時，於上述2)時，上述1價有機基為包含HX2 C-或H2 XC-所表示之基之取代基。 關於作為Ra4 之適宜之有機基之例，與Ra1 同樣地，可列舉：上述包含HX2 C-或H2 XC-所表示之基之取代基、烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、經1個或2個有機基取代之胺基、𠰌啉-1-基、及哌𠯤-1-基等。該等基之具體例與針對Ra1 所說明者相同。又，作為Ra4 ，亦較佳為環烷基烷基、芳香環上可具有取代基之苯氧基烷基、芳香環上可具有取代基之苯硫基烷基。苯氧基烷基及苯硫基烷基可具有之取代基與Ra1 所含之苯基可具有之取代基相同。As described above, when R a4 is a monovalent organic group, in the above 2), the monovalent organic group is a substituent containing a group represented by HX 2 C- or H 2 XC-. Examples of suitable organic groups for R a4 include, as in R a1 , substituents including the above-mentioned groups represented by HX 2 C- or H 2 XC-, alkyl groups, alkoxy groups, and cycloalkyl groups. , cycloalkoxy, saturated aliphatic alkoxy, alkoxycarbonyl, saturated aliphatic alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted benzyl , phenoxycarbonyl which may have substituents, benzyloxy which may have substituents, phenylalkyl which may have substituents, naphthyl which may have substituents, naphthyloxy which may have substituents, Naphthyl carboxyl group with substituent, naphthoxycarbonyl group with optional group, naphthyloxy group with optional group, naphthylalkyl group with optional group, heterocyclic group with optional group, optional Substituted heterocyclic carbonyl group, amine group substituted with one or two organic groups, 𠰌olin-1-yl, and pipe𠯤-1-yl, etc. Specific examples of these groups are the same as those described for R a1 . Moreover, as R a4 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R a1 may have.
有機基之中，作為Ra4 ，較佳為上述包含HX2 C-或H2 XC-所表示之基之取代基、烷基、環烷基、可具有取代基之苯基、或環烷基烷基、芳香環上可具有取代基之苯硫基烷基。作為烷基，較佳為碳原子數1以上且20以下之烷基，更佳為碳原子數1以上且8以下之烷基，尤佳為碳原子數1以上且4以下之烷基，最佳為甲基。可具有取代基之苯基之中，較佳為甲基苯基，更佳為2-甲基苯基。環烷基烷基所含之環烷基之碳原子數較佳為5以上且10以下，更佳為5以上且8以下，尤佳為5或6。環烷基烷基所含之伸烷基之碳原子數較佳為1以上且8以下，更佳為1以上且4以下，尤佳為2。環烷基烷基之中，較佳為環戊基乙基。芳香環上可具有取代基之苯硫基烷基所含之伸烷基之碳原子數較佳為1以上且8以下，更佳為1以上且4以下，尤佳為2。芳香環上可具有取代基之苯硫基烷基之中，較佳為2-(4-氯苯硫基)乙基。Among the organic groups, R a4 is preferably a substituent containing the above-mentioned group represented by HX 2 C- or H 2 XC-, an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, or a cycloalkyl group An alkyl group and a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, particularly preferably an alkyl group having 1 or more and 4 or less carbon atoms, most preferably Preferably methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the optionally substituted phenylthioalkyl group on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.
又，作為Ra4 ，亦較佳為-A3 -CO-O-A4 所表示之基。A3 為2價有機基，較佳為2價烴基，較佳為伸烷基。A4 為1價有機基，較佳為1價烴基。Moreover, as R a4 , a group represented by -A 3 -CO-OA 4 is also preferable. A 3 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A 4 is a monovalent organic group, preferably a monovalent hydrocarbon group.
於A3 為伸烷基之情形時，伸烷基可為直鏈狀亦可為支鏈狀，較佳為直鏈狀。於A3 為伸烷基之情形時，伸烷基之碳原子數較佳為1以上且10以下，更佳為1以上且6以下，尤佳為1以上且4以下。When A 3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A 3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less.
作為A4 之適宜例，可列舉：碳原子數1以上且10以下之烷基、碳原子數7以上且20以下之芳烷基、及碳原子數6以上且20以下之芳香族烴基。作為A4 之適宜之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、苯基、萘基、苄基、苯乙基、α-萘基甲基、及β-萘基甲基等。Suitable examples of A4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Suitable specific examples of A4 include methyl, ethyl, n - propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl , phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc.
作為-A3 -CO-O-A4 所表示之基之適宜之具體例，可列舉：2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-正丙氧基羰基乙基、2-正丁氧基羰基乙基、2-正戊氧基羰基乙基、2-正己氧基羰基乙基、2-苄氧基羰基乙基、2-苯氧基羰基乙基、3-甲氧基羰基正丙基、3-乙氧基羰基正丙基、3-正丙氧基羰基正丙基、3-正丁氧基羰基正丙基、3-正戊氧基羰基正丙基、3-正己氧基羰基正丙基、3-苄氧基羰基正丙基、及3-苯氧基羰基正丙基等。Suitable specific examples of the group represented by -A 3 -CO-OA 4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-Butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methyl Oxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, 3-phenoxycarbonyl-n-propyl and the like.
以上對Ra4
進行了說明，作為Ra4
，較佳為下述式(R4-1)或(R4-2)所表示之基。 [化7]
作為式(R4-1)中之關於Ra8 及Ra9 之有機基之例，可列舉：包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之苯甲醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基、可具有取代基之萘氧基、可具有取代基之萘甲醯基、可具有取代基之萘氧基羰基、可具有取代基之萘甲醯氧基、可具有取代基之萘基烷基、可具有取代基之雜環基、可具有取代基之雜環基羰基、經1個或2個有機基取代之胺基、𠰌啉-1-基、及哌𠯤-1-基等。 包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基之具體例及較佳例如上所述。 作為Ra8 ，較佳為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、烷基或苯基。於R7 為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、或烷基之情形時，其碳原子數較佳為1以上且10以下，更佳為1以上且5以下，尤佳為1以上且3以下。 於Ra8 與Ra9 鍵結而形成環之情形時，該環可為芳香族環，亦可為脂肪族環。作為Ra8 與Ra9 形成環時式(R4-1)所表示之基之適宜例，可列舉：萘-1-基或1,2,3,4-四氫萘-5-基等。上述式(R4-1)中，p為0以上且4以下之整數，較佳為0或1，更佳為0。Examples of the organic groups for R a8 and R a9 in the formula (R4-1) include halogenated alkoxy groups including groups represented by HX 2 C- or H 2 XC-, halogenated alkoxy groups including HX 2 C- or A halogenated alkyl group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic alkyl group, an alkoxycarbonyl group, a saturated aliphatic alkyl group, an optionally substituted group represented by H 2 XC- phenyl, optionally substituted phenoxy, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted Phenylalkyl, optionally substituted naphthyl, optionally substituted naphthoxy, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthyl Oxy group, optionally substituted naphthyl alkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, optionally substituted with 1 or 2 organic groups, amine group, picolin-1- Base, and piper 𠯤-1-base and so on. Specific examples and preferred examples of the halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- and the halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC- are as described above. R a8 is preferably a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, an alkyl group or a benzene base. When R 7 is a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, or an alkyl group, The number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. When R a8 and R a9 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. As a suitable example of the group represented by formula (R4-1) when R a8 and R a9 form a ring, naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, etc. are mentioned. In the above formula (R4-1), p is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.
上述式(R4-2)中，Ra10 為有機基。作為有機基，可列舉與針對Ra8 及Ra9 所說明之有機基相同之基。有機基之中，較佳為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、或烷基。包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、或烷基可為直鏈狀亦可為支鏈狀。包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、及烷基之碳原子數較佳為1以上且10以下，更佳為1以上且5以下，尤佳為1以上且3以下。作為Ra10 ，可較佳地例示：包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、甲基、乙基、丙基、異丙基、丁基等，該等之中，更佳為包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基、包含HX2 C-或H2 XC-所表示之基之鹵化烷基、甲基。In the above formula (R4-2), R a10 is an organic group. As an organic group, the same group as the organic group demonstrated about R a8 and R a9 is mentioned. Among the organic groups, a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, or an alkyl group are preferred . A halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, or an alkyl group may be linear or may be branched. The halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, the halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, and the alkyl group preferably have 1 carbon atoms It is 1 or more and 10 or less, More preferably, it is 1 or more and 5 or less, More preferably, it is 1 or more and 3 or less. Preferable examples of R a10 include halogenated alkoxy groups including a group represented by HX 2 C- or H 2 XC-, halogenated alkyl groups including a group represented by HX 2 C- or H 2 XC-, methyl halide group, ethyl, propyl, isopropyl, butyl, etc., among these, more preferably halogenated alkoxy containing a group represented by HX 2 C- or H 2 XC-, containing HX 2 C- or A halogenated alkyl group and a methyl group of the group represented by H 2 XC-.
上述式(R4-2)中，r為1以上且5以下之整數，較佳為1以上且3以下之整數，更佳為1或2。上述式(R4-2)中，s為0以上且(r＋3)以下，較佳為0以上且3以下之整數，更佳為0以上且2以下之整數，尤佳為0。上述式(R4-2)中，q為1以上且8以下之整數，較佳為1以上且5以下之整數，更佳為1以上且3以下之整數，尤佳為1或2。In the above formula (R4-2), r is an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (R4-2), s is 0 or more and (r+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, particularly preferably 0. In the above formula (R4-2), q is an integer of 1 or more and 8 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.
式(1)中，Ra5 為氫原子、可具有取代基之碳原子數1以上且20以下之脂肪族烴基、或可具有取代基之芳基。 其中，如上所述，於上述3)時，Ra5 為具有取代基之碳原子數1以上且20以下之脂肪族烴基或具有取代基之芳基，上述具有取代基之脂肪族烴基或上述具有取代基之芳基為包含HX2 C-或H2 XC-所表示之基之取代基。 Ra5 為包含HX2 C-或H2 XC-所表示之基之取代基之情形時之包含HX2 C-或H2 XC-所表示之基之取代基之具體例及較佳例如上所述。 作為Ra5 為脂肪族烴基之情形時可具有之取代基，可較佳地例示：苯基、萘基等。又，作為Ra1 為芳基之情形時可具有之取代基，可較佳地例示：碳原子數1以上且5以下之烷基、烷氧基、鹵素原子等。In formula (1), R a5 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group. Among them, as described above, in the above 3), R a5 is a substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituted aryl group, the above-mentioned substituted aliphatic hydrocarbon group or the above-mentioned substituted aliphatic hydrocarbon group The aryl group of the substituent is a substituent containing a group represented by HX 2 C- or H 2 XC-. When R a5 is a substituent containing a group represented by HX 2 C- or H 2 XC-, specific examples and preferred examples of the substituent containing a group represented by HX 2 C- or H 2 XC- are as described above. described. As a substituent which may have when R a5 is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group, etc. can be illustrated preferably. Moreover, as a substituent which may have when R a1 is an aryl group, an alkyl group with 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom, etc. can be illustrated preferably.
式(1)中，作為Ra5 ，可較佳地例示：包含HX2 C-或H2 XC-所表示之基之取代基、氫原子、甲基、乙基、正丙基、異丙基、正丁基、苯基、苄基、甲基苯基、萘基等，該等之中，更佳為包含HX2 C-或H2 XC-所表示之基之取代基、甲基或苯基。In the formula (1), as R a5 , a substituent including a group represented by HX 2 C- or H 2 XC-, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group can be preferably exemplified. , n-butyl, phenyl, benzyl, methylphenyl, naphthyl, etc., among these, more preferably a substituent containing a group represented by HX 2 C- or H 2 XC-, methyl or benzene base.
作為式(1)所表示之化合物之具體例，可例示下述化合物，但本發明並不限定於該等。 [化8]
作為(A)成分之光聚合起始劑之含量相對於感光性組合物中之溶劑以外之成分之質量之合計100質量份，較佳為0.001質量份以上且30質量份以下，更佳為0.1質量份以上且20質量份以下，進而較佳為0.5質量份以上且10質量份以下，尤佳為1質量份以上且5質量份以下。 又，作為(A)成分之光聚合起始劑之含量相對於(A)成分與(B)成分之總和，較佳為0.05質量%以上且50質量%以下，更佳為0.1質量%以上且30質量%以下，進而較佳為0.5質量%以上且20質量%以下。 (A)成分中之式(1)所表示之化合物可單獨使用，亦可使用2種以上。The content of the photopolymerization initiator as the component (A) is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass relative to 100 parts by mass in total of the mass of the components other than the solvent in the photosensitive composition The amount is not less than 20 parts by mass, more preferably not less than 0.5 parts by mass and not more than 10 parts by mass, and particularly preferably not less than 1 part by mass and not more than 5 parts by mass. Moreover, the content of the photopolymerization initiator as the component (A) is preferably 0.05 mass % or more and 50 mass % or less, more preferably 0.1 mass % or more, based on the sum of the (A) component and the (B) component. 30 mass % or less, and more preferably 0.5 mass % or more and 20 mass % or less. The compound represented by the formula (1) in the component (A) may be used alone, or two or more kinds may be used.
＜式(1)所表示之化合物之製造方法＞ 式(1)所表示之化合物之製造方法並無特別限定。式(1)所表示之化合物較佳為可藉由包括將下式(2)所表示之化合物所含之肟基(=N-OH)轉化為=N-O-CORa5
所表示之肟酯基之步驟的方法製造。Ra5
與式(1)中之Ra5
相同。 [化9]
將肟基(=N-OH)轉化為=N-O-CORa5 所表示之肟酯基之方法並無特別限定。典型而言，可列舉使肟基中之羥基與提供-CORa5 所表示之醯基之醯化劑反應之方法。作為醯化劑，可列舉：(Ra5 CO)2 O所表示之酸酐、或Ra5 COHal(Hal為鹵素原子)所表示之醯鹵。The method of converting an oxime group (=N-OH) into an oxime ester group represented by =NO-COR a5 is not particularly limited. Typically, a method of reacting a hydroxyl group in an oxime group with an acylation agent that provides an acylation group represented by -COR a5 is exemplified. The acid anhydride represented by (R a5 CO) 2 O, or the halide represented by R a5 COHal (Hal is a halogen atom) can be mentioned as the acylation agent.
於Ra5 為包含HX2 C-或H2 XC-所表示之基之取代基的上述3)之情形時，關於包含HX2 C-或H2 XC-所表示之基之取代基之導入方法，例如可藉由如下方式進行：藉由具有包含HX2 C-或H2 XC-所表示之基之取代基的酸酐或醯鹵與肟化合物(=N-OH)之任意之酯化反應而轉化為肟酯化合物。When R a5 is the above-mentioned 3) of a substituent containing a group represented by HX 2 C- or H 2 XC-, the method for introducing a substituent containing a group represented by HX 2 C- or H 2 XC- For example, it can be carried out in the following manner: by any esterification reaction of an acid anhydride or halide having a substituent containing a group represented by HX 2 C- or H 2 XC- and an oxime compound (=N-OH) Converted to oxime ester compounds.
通式(1)所表示之化合物於n2為0之情形時，例如可依據下述反應流程1而合成。於反應流程1中，使用下述式(1-1)所表示之茀衍生物作為原料。於Ra1 為硝基或1價有機基之情形時，式(1-1)所表示之茀衍生物可藉由周知方法於9位經Ra2 及Ra3 取代之茀衍生物中導入取代基Ra1 而獲得。When n2 is 0, the compound represented by the general formula (1) can be synthesized according to the following reaction scheme 1, for example. In Reaction Scheme 1, a fortium derivative represented by the following formula (1-1) was used as a raw material. When R a1 is a nitro group or a monovalent organic group, a substituent can be introduced into the fortium derivative substituted by R a2 and R a3 at the 9-position of the perylene derivative represented by the formula (1-1) by a known method. R a1 is obtained.
尤其於Ra1 為包含HX2 C-或H2 XC-所表示之基之取代基的上述1)之情形時，例如，使具有包含HX2 C-或H2 XC-所表示之基之取代基的烷基鹵化物或醯鹵於任意之路易斯酸(例如AlCl3 )觸媒之存在下，藉由夫里德耳-誇夫特(Friedel-Crafts)反應而與9位經Ra2 及Ra3 取代之茀衍生物進行反應，藉此可將作為包含HX2 C-或H2 XC-所表示之基之取代基的Ra1 導入至式(1)所表示之化合物中。In particular, when R a1 is the above-mentioned 1) as a substituent containing a group represented by HX 2 C- or H 2 XC-, for example, a substituent containing a group represented by HX 2 C- or H 2 XC- is used. In the presence of any Lewis acid (eg AlCl 3 ) catalyst, the alkyl halide or halide of the radical is reacted with the 9-position via R a2 and R a3 by Friedel-Crafts reaction. The substituted perylene derivative is reacted, whereby R a1 as a substituent containing a group represented by HX 2 C- or H 2 XC- can be introduced into the compound represented by the formula (1).
9位經Ra2 及Ra3 取代之茀衍生物例如於Ra2 及Ra3 為烷基之情形時，可如日本專利特開平06-234668號公報中所記載，使茀與烷基化劑於鹼金屬氫氧化物之存在下於非質子性極性有機溶劑中進行反應而獲得。又，藉由在茀之有機溶劑溶液中添加鹵化烷基之類之烷基化劑、鹼金屬氫氧化物之水溶液、及碘化四丁基銨或第三丁醇鉀之類之相間轉移觸媒進行烷基化反應，可獲得9,9-烷基取代茀。For example, in the case where R a2 and R a3 are alkyl groups, the fortium derivatives substituted at the 9-position by R a2 and R a3 can be described in Japanese Patent Laid-Open No. Hei 06-234668, wherein the fortium and the alkylating agent are used in It is obtained by reacting in an aprotic polar organic solvent in the presence of an alkali metal hydroxide. Also, by adding an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and an interphase transfer contact such as tetrabutylammonium iodide or potassium tertiary butoxide to the organic solvent solution Alkylation reaction can be carried out to obtain 9,9-alkyl substituted fortium.
藉由夫里德耳-誇夫特醯化反應於式(1-1)所表示之茀衍生物中導入-CO-Ra4 所表示之醯基，而獲得式(1-3)所表示之茀衍生物。 再者，如上所述，於Ra4 為包含HX2 C-或H2 XC-所表示之基之取代基的上述2)之情形時，Ra4 較佳為鹵化芳基，更佳為氟化芳基。 用以導入-CO-Ra4 所表示之醯基之醯化劑可為鹵化羰基化合物，亦可為酸酐。作為醯化劑，較佳為式(1-2)所表示之鹵化羰基化合物。式(1-2)中，Hal為鹵素原子。醯基於茀環上被導入之位置可藉由適當變更夫里德耳-誇夫特反應之條件、或對被醯化位置以外之位置實施保護及去保護等方法而選擇。The phenyl group represented by the formula (1-3) is obtained by introducing the acyl group represented by -CO-R a4 into the fluoride derivative represented by the formula (1-1) by the Friedel-Quaft hydration reaction derivative. Furthermore, as described above, when R a4 is the above-mentioned 2) of a substituent containing a group represented by HX 2 C- or H 2 XC-, R a4 is preferably a halogenated aryl group, more preferably a fluorinated group Aryl. The acylation agent for introducing the acylation group represented by -CO-R a4 may be a halogenated carbonyl compound or an acid anhydride. As an acylation agent, the halogenated carbonyl compound represented by formula (1-2) is preferable. In formula (1-2), Hal is a halogen atom. The introduced position on the acyl-based ring can be selected by appropriately changing the conditions of the Friedel-Quaft reaction, or by protecting and deprotecting positions other than the acyl-acrylated position.
繼而，將所獲得之式(1-3)所表示之茀衍生物中之-CO-Ra4 所表示之基轉化為-C(=N-OH)-Ra4 所表示之基，而獲得式(1-4)所表示之肟化合物。將-CO-Ra4 所表示之基轉化為-C(=N-OH)-Ra4 所表示之基之方法並無特別限定，較佳為利用羥胺之肟化。可使式(1-4)之肟化合物與下式(1-5)所表示之酸酐((Ra5 CO)2 O)或下述通式(1-6)所表示之醯鹵(Ra5 COHal，Hal為鹵素原子)反應而獲得下述式(1-7)所表示之化合物。Then, the group represented by -CO-R a4 in the obtained fluoride derivative represented by the formula (1-3) is converted into the group represented by -C(=N-OH)-R a4 to obtain the formula The oxime compound represented by (1-4). The method of converting the group represented by -CO-R a4 to the group represented by -C(=N-OH)-R a4 is not particularly limited, but oximation by hydroxylamine is preferable. The oxime compound of the formula (1-4) can be combined with an acid anhydride ((R a5 CO) 2 O) represented by the following formula (1-5) or an halide (R a5 ) represented by the following general formula (1-6) COHal, Hal is a halogen atom) reaction to obtain a compound represented by the following formula (1-7).
再者，於式(1-1)、(1-2)、(1-3)、(1-4)、(1-5)、(1-6)及(1-7)中，Ra1 、Ra2 、Ra3 、Ra4 及Ra5 與式(1)中相同。 其中，如上所述，於Ra4 為包含HX2 C-或H2 XC-所表示之基之取代基的上述2)之情形時，Ra4 較佳為鹵化芳基。 於上述2)之情形時，如上所述，較佳為將肟基(=N-OH)轉化為=N-O-CORa5 所表示之肟酯基後，使Ra4 之上述鹵化芳基之鹵素原子與包含HX2 C-或H2 XC-所表示之基之醇進行任意之芳香族親核取代反應，藉此製造上述式(1)所表示之化合物。Furthermore, in formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6) and (1-7), R a1 , R a2 , R a3 , R a4 and R a5 are the same as in formula (1). Among them, as described above, when R a4 is the above-mentioned 2) of a substituent containing a group represented by HX 2 C- or H 2 XC-, R a4 is preferably a halogenated aryl group. In the case of the above 2), as described above, after converting the oxime group (=N-OH) into the oxime ester group represented by =NO-COR a5 , the halogen atom of the above-mentioned halogenated aryl group of R a4 is preferably The compound represented by the above formula (1) is produced by subjecting it to an arbitrary aromatic nucleophilic substitution reaction with an alcohol containing a group represented by HX 2 C- or H 2 XC-.
又，於反應流程1中，式(1-2)、式(1-3)及式(1-4)各自所含之Ra1 、Ra4 及Ra5 可相同亦可不同。即，式(1-2)、式(1-3)及式(1-4)中之Ra1 、Ra4 及Ra5 於作為反應流程1所揭示之合成過程中可受到化學修飾。作為化學修飾之例，可列舉：酯化、醚化、醯化、醯胺化、鹵化、胺基中之氫原子被有機基之取代等，較佳為對Ra1 、Ra4 及Ra5 中之至少一者導入包含HX2 C-或H2 XC-所表示之基之鹵化烷氧基的醚化。Ra1 、Ra4 及Ra5 可接受之化學修飾並不限定於該等。Moreover, in Reaction Scheme 1, R a1 , R a4 and R a5 contained in each of formula (1-2), formula (1-3) and formula (1-4) may be the same or different. That is, R a1 , R a4 and R a5 in formula (1-2), formula (1-3) and formula (1-4) may be chemically modified during the synthesis process disclosed as Reaction Scheme 1 . Examples of chemical modification include: esterification, etherification, hydration, hydration, halogenation, substitution of a hydrogen atom in an amine group with an organic group, and the like, and preferably, among R a1 , R a4 and R a5 , At least one of them introduces etherification of a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-. The acceptable chemical modifications of R a1 , R a4 and R a5 are not limited to these.
[反應流程1] [化10]
式(1)所表示之化合物於n2為1之情形時，例如可依據下述反應流程2而合成。於反應流程2中，使用下述式(2-1)所表示之茀衍生物作為原料。式(2-1)所表示之茀衍生物係採用與反應流程1相同之方法，藉由夫里德耳-誇夫特反應於式(1-1)所表示之化合物中導入-CO-CH2 -Ra4 所表示之醯基而獲得。 再者，如上所述，於Ra4 為包含HX2 C-或H2 XC-所表示之基之取代基的上述2)之情形時，Ra4 較佳為鹵化芳基。 作為醯化劑，較佳為式(1-8)：Hal-CO-CH2 -Ra4 所表示之羧醯鹵。繼而，將式(2-1)所表示之化合物中之存在於Ra4 與羰基之間之亞甲基進行肟化，而獲得下式(2-3)所表示之酮肟化合物。將亞甲基進行肟化之方法並無特別限定，較佳為於鹽酸之存在下與下述通式(2-2)所表示之亞硝酸酯(RONO，R為碳數1以上且6以下之烷基)反應之方法。繼而，可使下述式(2-3)所表示之酮肟化合物與下述式(2-4)所表示之酸酐((Ra5 CO)2 O)或下述通式(2-5)所表示之醯鹵(Ra5 COHal，Hal為鹵素原子)反應，而獲得下述式(2-6)所表示之化合物。再者，下述式(2-1)、(2-3)、(2-4)、(2-5)及(2-6)中，Ra1 、Ra2 、Ra3 、Ra4 、及Ra5 與通式(1)中相同。 其中，如上所述，於Ra4 為包含HX2 C-或H2 XC-所表示之基之取代基的上述2)之情形時，Ra4 較佳為鹵化芳基。 於上述2)之情形時，如上所述，較佳為將肟基(=N-OH)轉化為=N-O-CORa5 所表示之肟酯基後，使Ra4 之上述鹵化芳基之鹵素原子與包含HX2 C-或H2 XC-所表示之基之醇進行任意之芳香族親核取代反應，藉此製造上述式(1)所表示之化合物。When n2 is 1, the compound represented by the formula (1) can be synthesized according to the following reaction scheme 2, for example. In Reaction Scheme 2, a fortium derivative represented by the following formula (2-1) was used as a raw material. The fluoride derivative represented by the formula (2-1) adopts the same method as the reaction scheme 1, and introduces -CO-CH 2 into the compound represented by the formula (1-1) by Friedel-Quaft reaction. -R a4 represented by the acyl group obtained. Furthermore, as described above, when R a4 is the above-mentioned 2) of a substituent containing a group represented by HX 2 C- or H 2 XC-, R a4 is preferably a halogenated aryl group. As the halide agent, a carboxyhalide halide represented by the formula (1-8): Hal-CO-CH 2 -R a4 is preferred. Next, in the compound represented by the formula (2-1), the methylene group existing between R a4 and the carbonyl group is oximation to obtain a ketoxime compound represented by the following formula (2-3). The method for oximation of the methylene group is not particularly limited, but it is preferably a nitrite (RONO, R is 1 or more and 6 or less carbon atoms) represented by the following general formula (2-2) in the presence of hydrochloric acid. The method of the alkyl) reaction. Then, the ketoxime compound represented by the following formula (2-3) and the acid anhydride ((R a5 CO) 2 O) represented by the following formula (2-4) or the following general formula (2-5) can be used The represented halide (R a5 COHal, where Hal is a halogen atom) is reacted to obtain a compound represented by the following formula (2-6). Furthermore, in the following formulae (2-1), (2-3), (2-4), (2-5) and (2-6), R a1 , R a2 , R a3 , R a4 , and R a5 is the same as in the general formula (1). Among them, as described above, when R a4 is the above-mentioned 2) of a substituent containing a group represented by HX 2 C- or H 2 XC-, R a4 is preferably a halogenated aryl group. In the case of the above 2), as described above, after converting the oxime group (=N-OH) into the oxime ester group represented by =NO-COR a5 , the halogen atom of the above-mentioned halogenated aryl group of R a4 is preferably The compound represented by the above formula (1) is produced by subjecting it to an arbitrary aromatic nucleophilic substitution reaction with an alcohol containing a group represented by HX 2 C- or H 2 XC-.
於n2為1之情形時，存在可進一步減少使用含有式(1)所表示之化合物之感光性組合物所形成之圖案中有異物之情況的傾向。 又，於反應流程2中，式(1-8)、式(2-1)及式(2-3)各自所含之Ra4 可相同亦可不同。即，式(1-8)、式(2-1)及式(2-3)中之Ra4 於作為反應流程2所揭示之合成過程中可受到化學修飾。作為化學修飾之例，可列舉：酯化、醚化、醯化、醯胺化、鹵化、胺基中之氫原子被有機基取代等。Ra4 可接受之化學修飾並不限定於該等。When n2 is 1, there exists a tendency to further reduce the case where the foreign material exists in the pattern formed using the photosensitive composition containing the compound represented by Formula (1). Moreover, in Reaction Scheme 2, R a4 contained in each of formula (1-8), formula (2-1) and formula (2-3) may be the same or different. That is, R a4 in formula (1-8), formula (2-1) and formula (2-3) may be chemically modified during the synthesis process disclosed as Reaction Scheme 2. Examples of chemical modification include esterification, etherification, amidation, amidation, halogenation, substitution of a hydrogen atom in an amine group with an organic group, and the like. The acceptable chemical modifications of R a4 are not limited to these.
[反應流程2] [化11]
＜化合物及光聚合起始劑＞ 本發明亦為關於以上說明之式(1)所表示之化合物、及包含上述化合物之光聚合起始劑者。 即，第2態樣之化合物為以上說明之式(1)所表示之化合物。 第3態樣之光聚合起始劑包含以上說明之式(1)所表示之化合物。<Compound and Photopolymerization Initiator> The present invention also relates to the compound represented by the above-described formula (1) and the photopolymerization initiator containing the above-mentioned compound. That is, the compound of the second aspect is the compound represented by the above-described formula (1). The photopolymerization initiator of the third aspect contains the compound represented by the formula (1) described above.
＜其他光聚合起始劑＞ (A)光聚合起始劑亦可包含上述式(1)所表示之化合物以外之其他光聚合起始劑(以下亦稱為(A')成分)。(A)光聚合起始劑中之上述式(1)所表示之化合物之含量例如為1質量%以上99質量%以下，較佳為10質量%以上且80質量%以下，更佳為20質量%以上且60質量%以下，進而較佳為30質量%以上且50質量%以下。 於(A)光聚合起始劑包含上述式(1)所表示之化合物以外之其他光聚合起始劑之情形時，光聚合起始劑亦可組合包含2種以上之其他光聚合起始劑。<Other photopolymerization initiators> (A) The photopolymerization initiators may contain other photopolymerization initiators (hereinafter also referred to as (A') components) other than the compound represented by the above formula (1). (A) The content of the compound represented by the above formula (1) in the photopolymerization initiator is, for example, 1 mass % or more and 99 mass % or less, preferably 10 mass % or more and 80 mass % or less, more preferably 20 mass % % or more and 60 mass % or less, more preferably 30 mass % or more and 50 mass % or less. When (A) the photopolymerization initiator contains other photopolymerization initiators other than the compound represented by the above formula (1), the photopolymerization initiator may also contain two or more other photopolymerization initiators in combination .
上述式(1)所表示之化合物以外之其他光聚合起始劑可使用先前公知之任意之光聚合起始劑。 作為上述式(1)所表示之化合物以外之任意之光聚合起始劑之具體例，可列舉： 包含下述式(3)： [化12]
1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(4-二甲基胺基苯基)酮、2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-𠰌啉基苯基)-丁烷-1-酮、4-苯甲醯基-4'-甲基二甲基硫醚、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸丁酯、4-二甲基胺基苯甲酸2-乙基己酯、4-二甲基胺基苯甲酸2-異戊酯、苯偶醯-β-甲氧基乙基縮醛、苯偶醯二甲基縮酮、鄰苯甲醯基苯甲酸甲酯、2,4-二乙基9-氧硫𠮿
上述式(3)中，作為關於R11 及R12 之烷基，可列舉碳原子數1以上且12以下(較佳為碳原子數1以上且8以下，更佳為碳原子數1以上且4以下)之烷基。 作為關於R11 及R12 之環烷基，可列舉碳原子數5以上且12以下之環烷基，例如可列舉：環戊基、環己基等。 作為關於R11 及R12 之芳基，可列舉可具有鹵素原子、烷基、烷氧基等取代基之碳原子數6以上且12以下之芳基，可列舉：苯基、萘基等。 作為關於R11 及R12 之脂肪族醯基，可列舉可具有鹵素原子、烷氧基等取代基之碳原子數2以上且12以下(較佳為碳原子數2以上且8以下，更佳為碳原子數2以上且6以下)之脂肪族醯基，可列舉：乙醯基、丙醯基、丁醯基、戊醯基、己醯基、庚醯基、辛醯基、壬醯基、癸醯基等。 作為關於R11 及R12 之芳香族醯基，可列舉可具有鹵素原子、烷基、烷氧基等取代基之碳原子數6以上且12以下之芳香族醯基，可列舉：苯甲醯基、α-萘甲醯基、β-萘甲醯基等。In the above formula (3), examples of the alkyl group for R 11 and R 12 include 1 or more and 12 or less carbon atoms (preferably, 1 or more and 8 or less carbon atoms, more preferably 1 or more and 12 carbon atoms). 4 or less). As a cycloalkyl group about R<11> and R< 12 >, the cycloalkyl group with a carbon number of 5 or more and 12 or less is mentioned, for example, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Examples of the aryl group for R 11 and R 12 include aryl groups having 6 to 12 carbon atoms which may have substituents such as halogen atoms, alkyl groups, and alkoxy groups, and examples thereof include phenyl, naphthyl, and the like. Examples of the aliphatic acyl group for R 11 and R 12 include 2 or more and 12 or less carbon atoms (preferably, 2 or more and 8 or less, more preferably carbon atoms) which may have substituents such as halogen atoms and alkoxy groups. The aliphatic aryl group having 2 or more and 6 or less carbon atoms) includes acetyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Wait. Examples of the aromatic aryl group for R 11 and R 12 include aromatic aryl groups having 6 to 12 carbon atoms, which may have substituents such as halogen atoms, alkyl groups, and alkoxy groups, and examples thereof include benzyl base, α-naphthoyl group, β-naphthoyl group, etc.
作為包含上述式(3)所表示之結構部分之醯基氧化膦系光聚合起始劑，可列舉：2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦等。Examples of the acylphosphine oxide-based photopolymerization initiator containing the moiety represented by the above formula (3) include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2, 4,6-Trimethylbenzyl)phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, etc.
感光性組合物中之光聚合起始劑(A)之含量於無損本發明之目的之範圍內無特別限定。光聚合起始劑(A)之含量相對於感光性組合物之固形物成分之質量，較佳為0.1質量%以上且30質量%以下，更佳為0.3質量%以上且15質量%以下，進而較佳為0.5質量%以上且10質量%以下，尤佳為0.8質量%以上且5質量%以下。藉由使用該範圍內之量之光聚合起始劑(A)，容易獲得期望由使用光聚合起始劑(A)產生之效果。The content of the photopolymerization initiator (A) in the photosensitive composition is not particularly limited within a range that does not impair the purpose of the present invention. The content of the photopolymerization initiator (A) is preferably 0.1 mass % or more and 30 mass % or less, more preferably 0.3 mass % or more and 15 mass % or less, with respect to the mass of the solid content of the photosensitive composition, and further 0.5 mass % or more and 10 mass % or less are preferable, and 0.8 mass % or more and 5 mass % or less are especially preferable. By using the photopolymerization initiator (A) in an amount within this range, the effect expected to be produced by the use of the photopolymerization initiator (A) is easily obtained.
＜(B)光聚合性化合物＞ 作為第1態樣之感光性組合物所含有之(B)光聚合性化合物(以下亦稱為(B)成分)，並無特別限定，可使用先前公知之光聚合性化合物。其中，較佳為具有乙烯性不飽和基之樹脂或單體，可將該等組合使用。藉由組合使用具有乙烯性不飽和基之樹脂與具有乙烯性不飽和基之單體，可提高感光性組合物之硬化性，容易形成圖案。於第1態樣中，更佳為具有乙烯性不飽和基之單體。<(B) Photopolymerizable compound> The (B) photopolymerizable compound (hereinafter also referred to as (B) component) contained in the photosensitive composition of the first aspect is not particularly limited, and conventionally known ones can be used. Photopolymerizable compounds. Among them, resins or monomers having an ethylenically unsaturated group are preferred, and these can be used in combination. By using a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group in combination, the curability of the photosensitive composition can be improved and patterning can be facilitated. In the first aspect, a monomer having an ethylenically unsaturated group is more preferred.
[具有乙烯性不飽和基之樹脂] 作為具有乙烯性不飽和基之樹脂，可列舉：由(甲基)丙烯酸、反丁烯二酸、順丁烯二酸、反丁烯二酸單甲酯、反丁烯二酸單乙酯、(甲基)丙烯酸2-羥基乙酯、乙二醇單甲醚(甲基)丙烯酸酯、乙二醇單***(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、(甲基)丙烯醯胺、丙烯腈、甲基丙烯腈、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、酚酞基環氧二丙烯酸酯等聚合而成之低聚物類；使由多元醇類與一元酸或多元酸縮合而成之聚酯預聚物再與(甲基)丙烯酸進行反應而獲得之聚酯(甲基)丙烯酸酯；使多元醇與具有2個異氰酸基之化合物反應後再與(甲基)丙烯酸反應而獲得之聚(甲基)丙烯酸胺基甲酸酯；使雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚或甲酚酚醛清漆型環氧樹脂、可溶酚醛型環氧樹脂、三苯酚甲烷型環氧樹脂、聚羧酸聚縮水甘油酯、多元醇聚縮水甘油酯、脂肪族或脂環式環氧樹脂、胺環氧樹脂、二羥基苯型環氧樹脂等環氧樹脂與(甲基)丙烯酸進行反應而獲得之環氧(甲基)丙烯酸酯樹脂等。可較佳地使用進而使環氧(甲基)丙烯酸酯樹脂與多元酸酐反應獲得之樹脂。再者，於本說明書中，「(甲基)丙烯酸」意指「丙烯酸或甲基丙烯酸」。[Resin having an ethylenically unsaturated group] Examples of the resin having an ethylenically unsaturated group include (meth)acrylic acid, fumaric acid, maleic acid, and monomethyl fumarate , Monoethyl fumarate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, glycerol (methyl) ) acrylate, (meth)acrylamide, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropane Tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6- Oligomers formed by the polymerization of hexanediol di(meth)acrylate, phenolphthalein-based epoxy diacrylate, etc.; Polyester (meth)acrylate obtained by reacting (meth)acrylic acid; poly(meth)acrylate obtained by reacting polyol with a compound having two isocyanate groups and then reacting with (meth)acrylic acid Acrylic urethane; make bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol or cresol novolac epoxy resin, resol novolac epoxy resin , triphenol methane type epoxy resin, polycarboxylate polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin and other epoxy resins Epoxy (meth)acrylate resin etc. obtained by reacting with (meth)acrylic acid. A resin obtained by further reacting an epoxy (meth)acrylate resin and a polybasic acid anhydride can be preferably used. In addition, in this specification, "(meth)acrylic acid" means "acrylic acid or methacrylic acid".
又，作為具有乙烯性不飽和基之樹脂，可較佳地使用藉由使環氧化合物與含不飽和基之羧酸化合物之反應物進而與多元酸酐反應而獲得之樹脂。Moreover, as resin which has an ethylenically unsaturated group, the resin obtained by making the reactant of an epoxy compound and an unsaturated-group containing carboxylic compound further react with a polybasic acid anhydride can be used suitably.
其中，較佳為下述通式(b1)所表示之化合物。該通式(b1)所表示之化合物其本身由於光硬化性較高而較佳。 [化13]
上述通式(b1)中，X表示下述通式(b2)所表示之基。 [化14]
上述通式(b2)中，R1b
分別獨立表示氫原子、碳原子數1以上且6以下之烴基、或鹵素原子，R2b
分別獨立表示氫原子或甲基，W表示單鍵、或下述結構式(b3)所表示之基。再者，於通式(b2)及結構式(b3)中，「＊」意指2價基之鍵結鍵之末端。 [化15]
上述通式(b1)中，Y表示自二羧酸酐去除酸酐基(-CO-O-CO-)而獲得之殘基。作為二羧酸酐之例，可列舉：順丁烯二酸酐、琥珀酸酐、伊康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯橋酸酐、甲基四氫鄰苯二甲酸酐、戊二酸酐等。In the above general formula (b1), Y represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylendene. base tetrahydrophthalic anhydride, chloro bridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.
又，上述通式(b1)中，Z表示自四羧酸二酐去除2個酸酐基而獲得之殘基。作為四羧酸二酐之例，可列舉：均苯四甲酸二酐、二苯甲酮四羧酸二酐、聯苯四羧酸二酐、聯苯醚四羧酸二酐等。進而，上述通式(b1)中，b表示0以上且20以下之整數。Moreover, in the said general formula (b1), Z represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. As an example of a tetracarboxylic dianhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, a biphenyl ether tetracarboxylic dianhydride, etc. are mentioned. Furthermore, in the said general formula (b1), b represents the integer of 0 or more and 20 or less.
具有乙烯性不飽和基之樹脂之酸值以樹脂固形物成分計，較佳為10 mgKOH/g以上且150 mgKOH/g以下，更佳為70 mgKOH/g以上且110 mgKOH/g以下。藉由將酸值設為10 mgKOH/g以上，可獲得於顯影液中之充分之溶解性，因此較佳。又，藉由將酸值設為150 mgKOH/g以下，可獲得充分之硬化性，可使表面性變得良好，因此較佳。The acid value of the resin having an ethylenically unsaturated group is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 110 mgKOH/g or less, in terms of resin solid content. By setting the acid value to be 10 mgKOH/g or more, sufficient solubility in the developer can be obtained, which is preferable. Moreover, by setting an acid value to be 150 mgKOH/g or less, sufficient hardenability can be obtained and surface properties can be improved, which is preferable.
又，具有乙烯性不飽和基之樹脂之質量平均分子量較佳為1000以上且40000以下，更佳為2000以上且30000以下。藉由將質量平均分子量設為1000以上，可獲得良好之耐熱性、膜強度，因此較佳。又，藉由將質量平均分子量設為40000以下，可獲得良好之顯影性，因此較佳。Moreover, the mass average molecular weight of the resin which has an ethylenically unsaturated group becomes like this. Preferably it is 1000 or more and 40000 or less, More preferably, it is 2000 or more and 30000 or less. Since favorable heat resistance and film strength can be obtained by making a mass average molecular weight into 1000 or more, it is preferable. Moreover, since favorable developability can be obtained by making a mass average molecular weight into 40000 or less, it is preferable.
[具有乙烯性不飽和基之單體] 具有乙烯性不飽和基之單體有單官能單體與多官能單體。以下依序說明單官能單體及多官能單體。[Monomer having an ethylenically unsaturated group] The monomer having an ethylenically unsaturated group includes a monofunctional monomer and a polyfunctional monomer. The monofunctional monomer and the polyfunctional monomer will be described in order below.
作為單官能單體，可列舉：(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、(甲基)丙烯酸、反丁烯二酸、順丁烯二酸、順丁烯二酸酐、伊康酸、伊康酸酐、檸康酸、檸康酸酐、丁烯酸、2-丙烯醯胺-2-甲基丙磺酸、第三丁基丙烯醯胺磺酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基-2-羥基丙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、二甲胺基(甲基)丙烯酸乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、鄰苯二甲酸衍生物之半(甲基)丙烯酸酯等。該等單官能單體可單獨使用或將2種以上組合使用。As a monofunctional monomer, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, butyric acid Acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-(meth)acrylate -Hydroxybutyl ester, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylic acid ester, tetrahydrofurfuryl (meth)acrylate, ethyl dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, ( 2,2,3,3-tetrafluoropropyl meth)acrylate, hemi(meth)acrylate of phthalic acid derivatives, etc. These monofunctional monomers may be used alone or in combination of two or more.
作為多官能單體，可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、碳數1以上且5以下之環氧烷改性新戊二醇二丙烯酸酯(其中，環氧丙烷改性新戊二醇二丙烯酸酯)、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚縮水甘油醚聚(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯(即為甲苯二異氰酸酯)、三甲基六亞甲基二異氰酸酯與六亞甲基二異氰酸酯與(甲基)丙烯酸2-羥基乙酯之反應物、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多元醇與N-羥甲基(甲基)丙烯醯胺之縮合物等多官能單體、或三丙烯醯基縮甲醛等。該等多官能單體可單獨使用或將2種以上組合使用。As a polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, Acrylates, polypropylene glycol di(meth)acrylates, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylates, alkylene oxides modified with 1 or more and 5 or less carbon atoms Pentylene glycol diacrylate (among them, propylene oxide modified neopentyl glycol diacrylate), 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acrylooxydiethoxybenzene) propyl) propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate , ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, triglyceride Acrylates, glycerol polyglycidyl ether poly(meth)acrylates, urethane (meth)acrylates (i.e. toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate Reactants with 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyol and N-methylol (methyl) ) polyfunctional monomers such as condensates of acrylamide, or triacrylamide-based formals, and the like. These polyfunctional monomers may be used alone or in combination of two or more.
作為(B)成分之光聚合性化合物之含量相對於感光性組合物去除下述溶劑後之成分之合計100質量份，較佳為10質量份以上且99.9質量份以下，更佳為80質量份以上且99.5質量份以下，進而較佳為90質量份以上且99質量份以下。藉由將(B)成分之含量設為相對於去除下述溶劑後之成分之合計100質量份為10質量份以上，使用感光性組合物可形成硬化性良好且不發黏之膜。 於第1態樣中，(B)成分較佳為包含多官能單體，多官能單體更佳為2官能或3官能單體，進而較佳為2官能單體。(B)成分中之多官能單體之比率較佳為50質量%以上，更佳為85質量%以上，進而較佳為90質量%以上且100質量%以下。The content of the photopolymerizable compound as the component (B) is preferably 10 parts by mass or more and 99.9 parts by mass or less, more preferably 80 parts by mass with respect to 100 parts by mass in total of the photosensitive composition after removing the following solvent It is more than 99.5 mass parts, and more preferably, it is 90 mass parts or more and 99 mass parts or less. By making content of (B) component 10 mass parts or more with respect to the total 100 mass parts of components which remove|eliminate the following solvent, the hardenability is favorable and the film which does not stick can be formed using the photosensitive composition. In the first aspect, the component (B) preferably contains a polyfunctional monomer, and the polyfunctional monomer is more preferably a bifunctional or trifunctional monomer, and more preferably a bifunctional monomer. (B) The ratio of the polyfunctional monomer in a component becomes like this. Preferably it is 50 mass % or more, More preferably, it is 85 mass % or more, More preferably, it is 90 mass % or more and 100 mass % or less.
＜(C)增感劑＞ 感光性組合物可含有亦可不含有(C)增感劑，但較佳為含有(C)增感劑。 藉由使感光性組合物一併含有上述包含式(1)所表示之化合物之(A)光聚合起始劑與(C)增感劑，感光性組合物即便於LED曝光下亦能夠良好地硬化。 認為其原因在於增感劑特別容易使式(1)所表示之化合物感度增加。<(C) Sensitizer> The photosensitive composition may or may not contain the (C) sensitizer, but preferably contains the (C) sensitizer. By making the photosensitive composition contain the (A) photopolymerization initiator and (C) sensitizer containing the compound represented by the above-mentioned formula (1) together, the photosensitive composition can be satisfactorily exposed to LED. hardening. The reason for this is considered to be that the sensitizer is particularly likely to increase the sensitivity of the compound represented by the formula (1).
作為(C)增感劑，可無特別限制地使用先前於感光性組合物中使用之用以使光聚合起始劑增感之化合物。As the (C) sensitizer, a compound previously used in a photosensitive composition for sensitizing a photopolymerization initiator can be used without particular limitation.
作為(C)增感劑，較佳為具有選自由烷氧基、取代羰氧基及側氧基(＝O)所組成之群中之1種以上作為取代基之化合物。作為該具有取代基之化合物，較佳為縮合多環式芳香族烴化合物或縮合多環式芳香族雜環化合物。 縮合多環式芳香族烴化合物或縮合多環式芳香族雜環化合物亦可具有烷氧基、取代羰氧基及側氧基(＝O)以外之取代基，作為該取代基之例，可列舉：碳原子數1以上且20以下之烷基、碳原子數1以上且20以下之鹵化烷基、碳原子數2以上且20以下之烷氧基烷基、碳原子數2以上且20以下之脂肪族醯基、碳原子數7～11之芳香族醯基(芳醯基)、氰基、硝基、亞硝基、鹵素原子、羥基、及巰基等。The (C) sensitizer is preferably a compound having, as a substituent, one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and a pendant oxy group (=O). The compound having the substituent is preferably a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound. The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have substituents other than alkoxy group, substituted carbonyloxy group and pendant oxy group (=O). Examples include: alkyl groups with 1 to 20 carbon atoms, halogenated alkyl groups with 1 to 20 carbon atoms, alkoxyalkyl groups with 2 to 20 carbon atoms, and 2 to 20 carbon atoms. aliphatic acyl group, aromatic acyl group (aryl group) having 7 to 11 carbon atoms, cyano group, nitro group, nitroso group, halogen atom, hydroxyl group, and mercapto group, etc.
烷氧基可為直鏈狀亦可為支鏈狀。烷氧基之碳原子數並無特別限定，較佳為1以上且20以下，更佳為1以上且12以下，尤佳為1以上且6以下。 作為烷氧基之適宜例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、2-乙基己基、正壬氧基、及正癸氧基等。The alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 6 or less. Suitable examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyl, n-nonyloxy, n-decyloxy and the like.
取代羰氧基為-O-CO-A所表示之基。只要(C)增感劑具有所需之增感作用，A並無特別限定，可為各種有機基。作為A，較佳為碳原子數1以上且20以下之烷基、碳原子數6以上且10以下之芳基、碳原子數1以上且20以下之烷氧基、碳原子數6以上且10以下之芳氧基。Substituted carbonyloxy is a group represented by -O-CO-A. A is not particularly limited as long as the (C) sensitizer has a desired sensitizing effect, and various organic groups may be used. As A, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 6 to 10 The following aryloxy groups.
芳基或芳氧基可具有1個或複數個取代基。只要無損本發明之目的，取代基之種類無特別限定。於芳基或芳氧基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 作為取代基之適宜例，可列舉：碳原子數1以上且6以下之烷氧基、碳原子數1以上且6以下之烷氧基、碳原子數6以上且10以下之芳氧基、碳原子數6以上且10以下之芳氧基、碳原子數2以上且7以下之脂肪族醯基、碳原子數7以上且11以下之芳香族醯基(芳醯基)、氰基、硝基、亞硝基、鹵素原子、羥基、及巰基等。The aryl group or aryloxy group may have one or a plurality of substituents. The kind of the substituent is not particularly limited as long as the object of the present invention is not impaired. When an aryl group or an aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different. Suitable examples of the substituent include: an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a carbon Aryloxy group with 6 or more and 10 or less atoms, aliphatic aryl group with 2 or more and 7 or less carbon atoms, aromatic aryl group with 7 or more and 11 or less carbon atoms (aryl group), cyano group, nitro group , nitroso group, halogen atom, hydroxyl group, and mercapto group, etc.
於A為烷基或烷氧基之情形時，該等基可為直鏈狀亦可為支鏈狀。 作為烷基之適宜例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、及2-乙基己基等。 作為芳基之適宜例，可列舉：苯基、鄰甲苯基、間甲苯基、對甲苯基、α-萘基、β-萘基等。 作為烷氧基之適宜例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、及2-乙基己氧基等。When A is an alkyl group or an alkoxy group, these groups may be linear or branched. Suitable examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl group, and 2-ethylhexyl, etc. Suitable examples of the aryl group include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, an α-naphthyl group, a β-naphthyl group, and the like. Suitable examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy and the like.
於經選自由烷氧基、取代羰氧基及側氧基(＝O)所組成之群中之1種以上取代之縮合多環式芳香族烴化合物或縮合多環式芳香族雜環化合物中，只要可獲得所需之增感作用，構成縮合環之環數無特別限定。環數較佳為2以上，更佳為3以上，尤佳為3以上且6以下，最佳為3或4。 再者，只要縮合多環式芳香族烴化合物或縮合多環式芳香族雜環化合物具有芳香族性，則形成縮合多環之單環未必必須為芳香環。In a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound substituted with at least one selected from the group consisting of alkoxy, substituted carbonyloxy, and pendant oxy (=O) , as long as the desired sensitization effect can be obtained, the number of rings constituting the condensed ring is not particularly limited. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 or more and 6 or less, and most preferably 3 or 4. Furthermore, as long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the monocyclic ring forming the condensed polycyclic ring does not necessarily have to be an aromatic ring.
作為縮合多環式芳香族烴化合物或縮合多環式芳香族雜環化合物所含之縮合多環之適宜例，可列舉：苊環、菲環、蒽環、稠四苯環、𠮿
作為宜用作(C)增感劑之包含蒽環之化合物之具體例，可列舉：9,10-雙(乙醯氧基)蒽、9,10-雙(丙醯氧基)蒽、9,10-雙(正丙基羰氧基)蒽、9,10-雙(異丙基羰氧基)蒽、9,10-雙(正丁基羰氧基)蒽、9,10-雙(異丁基羰氧基)蒽、9,10-雙(正戊基羰氧基)蒽、9,10-雙(正己基羰氧基)蒽、9,10-雙(正庚基羰氧基)蒽、9,10-雙(2-乙基己醯氧基)蒽、9,10-雙(正辛基羰氧基)蒽、9,10-雙(正壬基羰氧基)蒽、9,10-雙(正癸基羰氧基)蒽、9,10-雙(苯甲醯氧基)蒽、9,10-雙(4-甲基苯甲醯氧基)蒽、9,10-雙(2-萘甲醯氧基)蒽、2-甲基-9,10-雙(乙醯氧基)蒽、2-甲基-9,10-雙(丙醯氧基)蒽、2-甲基-9,10-雙(正丙基羰氧基)蒽、2-甲基-9,10-雙(異丙基羰氧基)蒽、2-甲基-9,10-雙(正丁基羰氧基)蒽、2-甲基-9,10-雙(異丁基羰氧基)蒽、2-甲基-9,10-雙(正戊基羰氧基)蒽、2-甲基-9,10-雙(正己基羰氧基)蒽、2-甲基-9,10-雙(苯甲醯氧基)蒽、2-甲基-9,10-雙(4-甲基苯甲醯氧基)蒽、2-甲基-9,10-雙(2-萘甲醯氧基)蒽、1-甲基-9,10-雙(乙醯氧基)蒽、1-甲基-9,10-雙(丙醯氧基)蒽、1-甲基-9,10-雙(正丙基羰氧基)蒽、1-甲基-9,10-雙(異丙基羰氧基)蒽、1-甲基-9,10-雙(正丁基羰氧基)蒽、1-甲基-9,10-雙(異丁基羰氧基)蒽、1-甲基-9,10-雙(正戊基羰氧基)蒽、1-甲基-9,10-雙(正己基羰氧基)蒽、1-甲基-9,10-雙(苯甲醯氧基)蒽、1-甲基-9,10-雙(4-甲基苯甲醯氧基)蒽、1-甲基-9,10-雙(2-萘甲醯氧基)蒽、2-乙基-9,10-雙(乙醯氧基)蒽、2-乙基-9,10-雙(丙醯氧基)蒽、2-乙基-9,10-雙(正丙基羰氧基)蒽、2-乙基-9,10-雙(異丁基羰氧基)蒽、2-乙基-9,10-雙(正丁基羰氧基)蒽、2-乙基-9,10-雙(異丁基羰氧基)蒽、2-乙基-9,10-雙(正戊基羰氧基)蒽、2-乙基-9,10-雙(正己基羰氧基)蒽、2-乙基-9,10-雙(苯甲醯氧基)蒽、2-乙基-9,10-雙(4-乙基苯甲醯氧基)蒽、2-乙基-9,10-雙(2-萘甲醯氧基)蒽、1-乙基-9,10-雙(乙醯氧基)蒽、1-乙基-9,10-雙(丙醯氧基)蒽、1-乙基-9,10-雙(正丙基羰氧基)蒽、1-乙基-9,10-雙(異丙基羰氧基)蒽、1-乙基-9,10-雙(正丁基羰氧基)蒽、1-乙基-9,10-雙(異丁基羰氧基)蒽、1-乙基-9,10-雙(正戊基羰氧基)蒽、1-乙基-9,10-雙(正己基羰氧基)蒽、1-乙基-9,10-雙(苯甲醯氧基)蒽、1-乙基-9,10-雙(4-乙基苯甲醯氧基)蒽、1-乙基-9,10-雙(2-萘甲醯氧基)蒽、1-(第三丁基)-9,10-雙(正丙基羰氧基)蒽、1-(第三丁基)-9,10-雙(異丙基羰氧基)蒽、1-(第三丁基)-9,10-雙(正丁基羰氧基)蒽、1-(第三丁基)-9,10-雙(異丁基羰氧基)蒽、1-(第三丁基)-9,10-雙(正戊基羰氧基)蒽、1-(第三丁基)-9,10-雙(正己基羰氧基)蒽、1-(第三丁基)-9,10-雙(苯甲醯氧基)蒽、1-(第三丁基)-9,10-雙(4-(第三丁基)-苯甲醯氧基)蒽、1-(第三丁基)-9,10-雙(2-萘甲醯氧基)蒽、2-(第三丁基)-9,10-雙(正丙基羰氧基)蒽、2-(第三丁基)-9,10-雙(異丙基羰氧基)蒽、2-(第三丁基)-9,10-雙(正丁基羰氧基)蒽、2-(第三丁基)-9,10-雙(異丁基羰氧基)蒽、2-(第三丁基)-9,10-雙(正戊基羰氧基)蒽、2-(第三丁基)-9,10-雙(正己基羰氧基)蒽、2-(第三丁基)-9,10-雙(苯甲醯氧基)蒽、2-(第三丁基)-9,10-雙(4-(第三丁基)-苯甲醯氧基)蒽、2-(第三丁基)-9,10-雙(2-萘甲醯氧基)蒽、2-戊基-9,10-雙(正丙基羰氧基)蒽、2-戊基-9,10-雙(異丙基羰氧基)蒽、2-戊基-9,10-雙(正丁基羰氧基)蒽、2-戊基-9,10-雙(異丁基羰氧基)蒽、2-戊基-9,10-雙(正戊基羰氧基)蒽、2-戊基-9,10-雙(正己基羰氧基)蒽、2-戊基-9,10-雙(苯甲醯氧基)蒽、2-戊基-9,10-雙(4-(第三丁基)-苯甲醯氧基)蒽、及2-戊基-9,10-雙(2-萘甲醯氧基)蒽等。Specific examples of the compound containing an anthracene ring suitable for use as the (C) sensitizer include 9,10-bis(acetoxy)anthracene, 9,10-bis(propionoxy)anthracene, 9,10-bis(acetoxy)anthracene, 9,10-bis(acetoxy)anthracene, ,10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis( Isobutylcarbonyloxy)anthracene, 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(n-heptylcarbonyloxy)anthracene ) anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10-bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n-decylcarbonyloxy)anthracene, 9,10-bis(benzyloxy)anthracene, 9,10-bis(4-methylbenzyloxy)anthracene, 9,10 -Bis(2-naphthyloxy)anthracene, 2-methyl-9,10-bis(acetyloxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2 -Methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-methyl-9,10-bis( n-Butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2 -Methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-methyl-9,10-bis(benzyloxy)anthracene, 2-methyl-9,10-bis(4- Methylbenzyloxy)anthracene, 2-methyl-9,10-bis(2-naphthyloxy)anthracene, 1-methyl-9,10-bis(acetyloxy)anthracene, 1 -Methyl-9,10-bis(propionyloxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isopropyl) ylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-methyl Alkyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9,10-bis(benzyloxy) anthracene oxy) anthracene, 1-methyl-9,10-bis(4-methylbenzyloxy)anthracene, 1-methyl-9,10-bis(2-naphthyloxy)anthracene, 2 -Ethyl-9,10-bis(acetyloxy)anthracene, 2-ethyl-9,10-bis(propyloxy)anthracene, 2-ethyl-9,10-bis(n-propylcarbonyl) oxy) anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-ethyl- 9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-hexylcarbonyloxy) yl)anthracene, 2-ethyl-9,10-bis(benzyloxy)anthracene, 2-ethyl-9,10-bis(4-ethylbenzyloxy)anthracene, 2-ethyl -9,10-bis(2-naphthyloxy)anthracene, 1-ethyl-9,10-bis(acetyloxy)anthracene, 1-ethyl- 9,10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isopropylcarbonyloxy) ) anthracene, 1-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-ethyl-9, 10-bis(n-pentylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(benzyloxy)anthracene , 1-ethyl-9,10-bis(4-ethylbenzyloxy)anthracene, 1-ethyl-9,10-bis(2-naphthyloxy)anthracene, 1-(third Butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(tert-butyl) )-9,10-bis(n-butylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 1-(tert-butyl)- 9,10-bis(n-pentylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10 -Bis(benzyloxy)anthracene, 1-(tert-butyl)-9,10-bis(4-(tert-butyl)-benzyloxy)anthracene, 1-(tert-butyl) )-9,10-bis(2-naphthoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 2-(tert-butyl) -9,10-bis(isopropylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(tert-butyl)-9 ,10-bis(isobutylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10 -Bis(n-hexylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(benzyloxy)anthracene, 2-(tert-butyl)-9,10-bis(4 -(tert-butyl)-benzyloxy)anthracene, 2-(tert-butyl)-9,10-bis(2-naphthyloxy)anthracene, 2-pentyl-9,10- Bis(n-propylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyloxy)anthracene , 2-pentyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9,10- Bis(n-hexylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(benzyloxy)anthracene, 2-pentyl-9,10-bis(4-(tert-butyl)-benzene carboxyloxy)anthracene, 2-pentyl-9,10-bis(2-naphthyloxy)anthracene, and the like.
又，經鹵素原子取代之蒽化合物亦適宜作為(C)增感劑。作為鹵素原子，可列舉：氟原子、氯原子、溴原子或碘原子。In addition, an anthracene compound substituted with a halogen atom is also suitable as the (C) sensitizer. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.
作為宜用作(C)增感劑之經鹵素原子取代之蒽化合物之具體例，可列舉：2-氯-9,10-雙(乙醯氧基)蒽、2-氯-9,10-雙(丙醯氧基)蒽、2-氯-9,10-雙(正丙基羰氧基)蒽、2-氯-9,10-雙(異丙基羰氧基)蒽、2-氯-9,10-雙(正丁基羰氧基)蒽、2-氯-9,10-雙(異丁基羰氧基)蒽、2-氯-9,10-雙(正戊基羰氧基)蒽、2-氯-9,10-雙(正己基羰氧基)蒽、2-氯-9,10-雙(苯甲醯氧基)蒽、2-氯-9,10-雙(4-甲基苯甲醯氧基)蒽、2-氯-9,10-雙(2-萘甲醯氧基)蒽、1-氯-9,10-雙(乙醯氧基)蒽、1-氯-9,10-雙(丙醯氧基)蒽、1-氯-9,10-雙(正丙基羰氧基)蒽、1-氯-9,10-雙(異丙基羰氧基)蒽、1-氯-9,10-雙(正丁基羰氧基)蒽、1-氯-9,10-雙(異丁基羰氧基)蒽、1-氯-9,10-雙(正戊基羰氧基)蒽、1-氯-9,10-雙(正己基羰氧基)蒽、1-氯-9,10-雙(苯甲醯氧基)蒽、1-氯-9,10-雙(4-甲基苯甲醯氧基)蒽、1-氯-9,10-雙(2-萘甲醯氧基)蒽、2-氟-9,10-雙(乙醯氧基)蒽、2-氟-9,10-雙(丙醯氧基)蒽、2-氟-9,10-雙(正丙基羰氧基)蒽、2-氟-9,10-雙(異丙基羰氧基)蒽、2-氟-9,10-雙(正丁基羰氧基)蒽、2-氟-9,10-雙(異丁基羰氧基)蒽、2-氟-9,10-雙(正戊基羰氧基)蒽、2-氟-9,10-雙(正己基羰氧基)蒽、2-氟-9,10-雙(苯甲醯氧基)蒽、2-氟-9,10-雙(4-甲基苯甲醯氧基)蒽、2-氟-9,10-雙(2-萘甲醯氧基)蒽、1-氟-9,10-雙(乙醯氧基)蒽、1-氟-9,10-雙(丙醯氧基)蒽、1-氟-9,10-雙(正丙基羰氧基)蒽、1-氟-9,10-雙(異丙基羰氧基)蒽、1-氟-9,10-雙(正丁基羰氧基)蒽、1-氟-9,10-雙(異丁基羰氧基)蒽、1-氟-9,10-雙(正戊基羰氧基)蒽、1-氟-9,10-雙(正己基羰氧基)蒽、1-氟-9,10-雙(苯甲醯氧基)蒽、1-氟-9,10-雙(4-甲基苯甲醯氧基)蒽、1-氟-9,10-雙(2-萘甲醯氧基)蒽、2-溴-9,10-雙(乙醯氧基)蒽、2-溴-9,10-雙(丙醯氧基)蒽、2-溴-9,10-雙(正丙基羰氧基)蒽、2-溴-9,10-雙(異丙基羰氧基)蒽、2-溴-9,10-雙(正丁基羰氧基)蒽、2-溴-9,10-雙(異丁基羰氧基)蒽、2-溴-9,10-雙(正戊基羰氧基)蒽、2-溴-9,10-雙(正己基羰氧基)蒽、2-溴-9,10-雙(苯甲醯氧基)蒽、2-溴-9,10-雙(4-甲基苯甲醯氧基)蒽、2-溴-9,10-雙(2-萘甲醯氧基)蒽、1-溴-9,10-雙(乙醯氧基)蒽、1-溴-9,10-雙(丙醯氧基)蒽、1-溴-9,10-雙(正丙基羰氧基)蒽、1-溴-9,10-雙(異丙基羰氧基)蒽、1-溴-9,10-雙(正丁基羰氧基)蒽、1-溴-9,10-雙(異丁基羰氧基)蒽、1-溴-9,10-雙(正戊基羰氧基)蒽、1-溴-9,10-雙(正己基羰氧基)蒽、1-溴-9,10-雙(苯甲醯氧基)蒽、1-溴-9,10-雙(4-甲基苯甲醯氧基)蒽、及1-溴-9,10-雙(2-萘甲醯氧基)蒽等。Specific examples of halogen-substituted anthracene compounds suitable for use as (C) sensitizers include 2-chloro-9,10-bis(acetyloxy)anthracene, 2-chloro-9,10- Bis(propionyloxy)anthracene, 2-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-chloro -9,10-bis(n-butylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-pentylcarbonyloxy) base) anthracene, 2-chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-chloro-9,10-bis(benzyloxy)anthracene, 2-chloro-9,10-bis( 4-methylbenzyloxy)anthracene, 2-chloro-9,10-bis(2-naphthyloxy)anthracene, 1-chloro-9,10-bis(acetoxy)anthracene, 1 -Chloro-9,10-bis(propionyloxy)anthracene, 1-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isopropylcarbonyloxy) base) anthracene, 1-chloro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 1-chloro-9,10- Bis(n-pentylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-chloro-9,10-bis(benzyloxy)anthracene, 1-chloro -9,10-Bis(4-methylbenzyloxy)anthracene, 1-chloro-9,10-bis(2-naphthyloxy)anthracene, 2-fluoro-9,10-bis(ethyl) Anthracene, 2-Fluoro-9,10-bis(propionyloxy)anthracene, 2-Fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, Bis(isopropylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(isobutylcarbonyloxy)anthracene, 2 -Fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(benzyloxy)anthracene base) anthracene, 2-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 2-fluoro-9,10-bis(2-naphthyloxy)anthracene, 1-fluoro- 9,10-Bis(acetyloxy)anthracene, 1-Fluoro-9,10-bis(propionyloxy)anthracene, 1-Fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 1 -Fluoro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isobutyl) Carbonyloxy)anthracene, 1-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-fluoro-9,10 -Bis(benzyloxy)anthracene, 1-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 1-fluoro-9,10-bis(2-naphthyloxy)anthracene ) anthracene, 2-bromo-9,10-bis(acetyloxy)anthracene, 2-bromo-9,10-bis(propionyloxy)anthracene, 2-bromo-9,10-bis(n-propyl) Carbonyloxy)anthracene, 2-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-butylcarbonyl) oxy)anthracene, 2-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-bromo-9,10 -Bis(n-hexylcarbonyloxy)anthracene, 2-bromo-9,10-bis(benzyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzyloxy)anthracene , 2-bromo-9,10-bis(2-naphthoyloxy)anthracene, 1-bromo-9,10-bis(acetyloxy)anthracene, 1-bromo-9,10-bis(propionyloxy)anthracene oxy) anthracene, 1-bromo-9,10-bis(n-propylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 1-bromo-9,10 -Bis(n-butylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-Bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-bromo-9,10-bis(benzyloxy)anthracene, 1-bromo-9,10-bis(4-methyl) benzyloxy)anthracene, 1-bromo-9,10-bis(2-naphthyloxy)anthracene, and the like.
進而，經烷氧基取代之蒽化合物亦適宜用作(C)增感劑。 作為宜用作(C)增感劑之經烷氧基取代之蒽化合物之具體例，可列舉：9,10-二甲氧基蒽、9,10-二乙氧基蒽、9,10-雙(正丙氧基)蒽、9,10-雙(正丁氧基)蒽、9,10-雙(正戊氧基)蒽、9,10-雙(異戊氧基氧基)蒽、9,10-雙(正己氧基)蒽、9,10-雙(正庚氧基)蒽、9,10-雙(正辛氧基)蒽、9,10-雙(2-乙基己氧基)蒽、9-甲氧基蒽、9-乙氧基蒽、9-(正丙氧基)蒽、9-(正丁氧基)蒽、9-(正戊氧基)蒽、9-(異戊氧基氧基)蒽、9-(正己氧基)蒽、9-(正庚氧基)蒽、9-(正辛氧基)蒽、9-(2-乙基己氧基)蒽、2-甲基-9,10-二甲氧基蒽、2-甲基-9,10-二乙氧基蒽、2-甲基-9,10-雙(正丙氧基)蒽、2-甲基-9,10-雙(正丁氧基)蒽、2-甲基-9,10-雙(正戊氧基)蒽、2-甲基-9,10-雙(異戊氧基氧基)蒽、2-甲基-9,10-雙(正己氧基)蒽、2-甲基-9,10-雙(正庚氧基)蒽、2-甲基-9,10-雙(正辛氧基)蒽、2-甲基-9,10-雙(2-乙基己氧基)蒽、2-乙基-9,10-二甲氧基蒽、2-乙基-9,10-二乙氧基蒽、2-乙基-9,10-雙(正丙氧基)蒽、2-乙基-9,10-雙(正丁氧基)蒽、2-乙基-9,10-雙(正戊氧基)蒽、2-乙基-9,10-雙(異戊氧基氧基)蒽、2-乙基-9,10-雙(正己氧基)蒽、2-乙基-9,10-雙(正庚氧基)蒽、2-乙基-9,10-雙(正辛氧基)蒽、2-乙基-9,10-雙(2-乙基己氧基)蒽、2-甲基-9-甲氧基蒽、2-甲基-9-乙氧基蒽、2-甲基-9-(正丙氧基)蒽、2-甲基-9-(正丁氧基)蒽、2-甲基-9-(正戊氧基)蒽、2-甲基-9-(異戊氧基氧基)蒽、2-甲基-9-(正己氧基)蒽、2-甲基-9-(正庚氧基)蒽、2-甲基-9-(正辛氧基)蒽、2-甲基-9-(2-乙基己氧基)蒽、2-乙基-9-甲氧基蒽、2-乙基-9-乙氧基蒽、2-乙基-9-(正丙氧基)蒽、2-乙基-9-(正丁氧基)蒽、2-乙基-9-(正戊氧基)蒽、2-乙基-9-(異戊氧基氧基)蒽、2-乙基-9-(正己氧基)蒽、2-乙基-9-(正庚氧基)蒽、2-乙基-9-(正辛氧基)蒽、2-乙基-9-(2-乙基己氧基)蒽、2-氯-9,10-二甲氧基蒽、2-氯-9,10-二乙氧基蒽、2-氯-9,10-雙(正丙氧基)蒽、2-氯-9,10-雙(正丁氧基)蒽、2-氯-9,10-雙(正戊氧基)蒽、2-氯-9,10-雙(異戊氧基氧基)蒽、2-氯-9,10-雙(正己氧基)蒽、2-氯-9,10-雙(正庚氧基)蒽、2-氯-9,10-雙(正辛氧基)蒽、2-氯-9,10-雙(2-乙基己氧基)蒽、2-溴-9,10-二甲氧基蒽、2-溴-9,10-二乙氧基蒽、2-溴-9,10-雙(正丙氧基)蒽、2-溴-9,10-雙(正丁氧基)蒽、2-溴-9,10-雙(正戊氧基)蒽、2-溴-9,10-雙(異戊氧基氧基)蒽、2-溴-9,10-雙(正己氧基)蒽、2-溴-9,10-雙(正庚氧基)蒽、2-溴-9,10-雙(正辛氧基)蒽、2-溴-9,10-雙(2-乙基己氧基)蒽、2-氯-9-甲氧基蒽、2-氯-9-乙氧基蒽、2-氯-9-(正丙氧基)蒽、2-氯-9-(正丁氧基)蒽、2-氯-9-(正戊氧基)蒽、2-氯-9-(異戊氧基氧基)蒽、2-氯-9-(正己氧基)蒽、2-氯-9-(正庚氧基)蒽、2-氯-9-(正辛氧基)蒽、2-氯-9-(2-乙基己氧基)蒽、2-溴-9-甲氧基蒽、2-溴-9-乙氧基蒽、2-溴-9-(正丙氧基)蒽、2-溴-9-(正丁氧基)蒽、2-溴-9-(正戊氧基)蒽、2-乙基-9-(異戊氧基氧基)蒽、2-溴-9-(正己氧基)蒽、2-溴-9-(正庚氧基)蒽、2-溴-9-(正辛氧基)蒽、及2-溴-9-(2-乙基己氧基)蒽等。Furthermore, an anthracene compound substituted by an alkoxy group is also suitably used as the (C) sensitizer. Specific examples of the alkoxy-substituted anthracene compound suitable for use as the (C) sensitizer include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10- Bis(n-propoxy)anthracene, 9,10-bis(n-butoxy)anthracene, 9,10-bis(n-pentoxy)anthracene, 9,10-bis(isoamyloxy)anthracene, 9,10-bis(n-hexyloxy)anthracene, 9,10-bis(n-heptyloxy)anthracene, 9,10-bis(n-octyloxy)anthracene, 9,10-bis(2-ethylhexyloxy) base) anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-(n-propoxy)anthracene, 9-(n-butoxy)anthracene, 9-(n-pentoxy)anthracene, 9- (Isopentoxyoxy)anthracene, 9-(n-hexyloxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy) Anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-bis(n-propoxy)anthracene, 2-Methyl-9,10-bis(n-butoxy)anthracene, 2-methyl-9,10-bis(n-pentoxy)anthracene, 2-methyl-9,10-bis(isoamyloxy)anthracene oxy)anthracene, 2-methyl-9,10-bis(n-hexyloxy)anthracene, 2-methyl-9,10-bis(n-heptyloxy)anthracene, 2-methyl-9,10- Bis(n-octyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 2-ethyl-9,10-bis(n-propoxy)anthracene, 2-ethyl-9,10-bis(n-butoxy)anthracene, 2-ethyl -9,10-bis(n-pentoxy)anthracene, 2-ethyl-9,10-bis(isoamyloxy)anthracene, 2-ethyl-9,10-bis(n-hexyloxy)anthracene , 2-ethyl-9,10-bis(n-heptyloxy)anthracene, 2-ethyl-9,10-bis(n-octyloxy)anthracene, 2-ethyl-9,10-bis(2- Ethylhexyloxy)anthracene, 2-methyl-9-methoxyanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl-9-(n-propoxy)anthracene, 2-methylanthracene Base-9-(n-butoxy)anthracene, 2-methyl-9-(n-pentoxy)anthracene, 2-methyl-9-(isoamyloxy)anthracene, 2-methyl-9 -(n-hexyloxy)anthracene, 2-methyl-9-(n-heptyloxy)anthracene, 2-methyl-9-(n-octyloxy)anthracene, 2-methyl-9-(2-ethyl) Hexyloxy)anthracene, 2-ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9-(n-propoxy)anthracene, 2-ethyl- 9-(n-Butoxy)anthracene, 2-ethyl-9-(n-pentoxy)anthracene, 2-ethyl-9-(isoamyloxy)anthracene, 2-ethyl-9-( n-hexyloxy)anthracene, 2-ethyl-9-(n-heptyloxy)anthracene, 2-ethyl-9-(n-octyloxy)anthracene, 2-ethyl-9-(2-ethylhexyloxy)anthracene base) anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis(n-propoxy)anthracene, 2 -Chloro-9, 10-Bis(n-butoxy)anthracene, 2-chloro-9,10-bis(n-pentoxy)anthracene, 2-chloro-9,10-bis(isoamyloxy)anthracene, 2-chloro -9,10-bis(n-hexyloxy)anthracene, 2-chloro-9,10-bis(n-heptyloxy)anthracene, 2-chloro-9,10-bis(n-octyloxy)anthracene, 2-chloro -9,10-Bis(2-ethylhexyloxy)anthracene, 2-bromo-9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo-9 ,10-bis(n-propoxy)anthracene, 2-bromo-9,10-bis(n-butoxy)anthracene, 2-bromo-9,10-bis(n-pentoxy)anthracene, 2-bromo- 9,10-bis(isoamyloxy)anthracene, 2-bromo-9,10-bis(n-hexyloxy)anthracene, 2-bromo-9,10-bis(n-heptoxy)anthracene, 2- Bromo-9,10-bis(n-octyloxy)anthracene, 2-bromo-9,10-bis(2-ethylhexyloxy)anthracene, 2-chloro-9-methoxyanthracene, 2-chloro- 9-ethoxyanthracene, 2-chloro-9-(n-propoxy)anthracene, 2-chloro-9-(n-butoxy)anthracene, 2-chloro-9-(n-pentoxy)anthracene, 2 -Chloro-9-(isoamyloxyoxy)anthracene, 2-chloro-9-(n-hexyloxy)anthracene, 2-chloro-9-(n-heptyloxy)anthracene, 2-chloro-9-(n-hexyloxy)anthracene Octyloxy)anthracene, 2-chloro-9-(2-ethylhexyloxy)anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9 -(n-Propoxy)anthracene, 2-bromo-9-(n-butoxy)anthracene, 2-bromo-9-(n-pentoxy)anthracene, 2-ethyl-9-(isoamyloxy)anthracene yl)anthracene, 2-bromo-9-(n-hexyloxy)anthracene, 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, and 2-bromo- 9-(2-ethylhexyloxy)anthracene, etc.
以上說明之蒽化合物之中，就易製造性與作為(C)增感劑之性能之方面而言，較佳為9,10-雙(乙醯氧基)蒽、9,10-雙(丙醯氧基)蒽、9,10-雙(正丙基羰氧基)蒽、9,10-雙(異丙基羰氧基)蒽、9,10-雙(正丁基羰氧基)蒽、9,10-雙(異丁基羰氧基)蒽、9,10-雙(正己醯氧基)蒽、9,10-雙(正庚醯氧基)蒽、9,10-雙(正辛醯氧基)蒽、9,10-雙(2-乙基己醯氧基)蒽、9,10-雙(正壬醯氧基)蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、及9,10-二丁氧基蒽。Among the anthracene compounds described above, 9,10-bis(acetoxy)anthracene, 9,10-bis(propane) are preferable in terms of ease of manufacture and performance as a (C) sensitizer Ethyloxy)anthracene, 9,10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene , 9,10-bis(isobutylcarbonyloxy)anthracene, 9,10-bis(n-hexyloxy)anthracene, 9,10-bis(n-heptyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene Octanoyloxy)anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9, 10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.
作為宜用作(C)增感劑之包含稠四苯環之化合物之具體例，可列舉： 2-甲基-5,11-二側氧基-6,12-雙(乙醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(丙醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正丙基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(異丙基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正丁基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(異丁基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正戊基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正己基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正庚基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(乙醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(丙醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正丙基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(異丙基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正丁基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(異丁基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正戊基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正己基羰氧基)稠四苯、及2-乙基-5,11-二側氧基-6,12-雙(正庚基羰氧基)稠四苯等烷基羰氧基取代稠四苯化合物； 2-甲基-5,11-二側氧基-6,12-雙(苯甲醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(鄰甲苯醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(間甲苯醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(對甲苯醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(α-萘甲醯氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(β-萘甲醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(苯甲醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(鄰甲苯醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(間甲苯醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(對甲苯醯氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(α-萘甲醯氧基)稠四苯、及2-乙基-5,11-二側氧基-6,12-雙(β-萘甲醯氧基)稠四苯等芳醯氧基取代稠四苯化合物； 2-甲基-5,11-二側氧基-6,12-雙(甲氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(乙氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正丙氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(異丙氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正丁氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(異丁氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正戊氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正己氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正庚氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(正辛氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(甲氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(乙氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正丙氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(異丙氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正丁氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(異丁氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正戊氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正己氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(正庚氧基羰氧基)稠四苯、及2-乙基-5,11-二側氧基-6,12-雙(正辛氧基羰氧基)稠四苯等烷氧基羰氧基取代稠四苯化合物；以及 2-甲基-5,11-二側氧基-6,12-雙(苯氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(鄰甲苯氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(間甲苯氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(對甲苯氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(α-萘氧基羰氧基)稠四苯、2-甲基-5,11-二側氧基-6,12-雙(β-萘氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(苯氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(鄰甲苯氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(間甲苯氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(對甲苯氧基羰氧基)稠四苯、2-乙基-5,11-二側氧基-6,12-雙(α-萘氧基羰氧基)稠四苯、及2-乙基-5,11-二側氧基-6,12-雙(β-萘氧基羰氧基)稠四苯等芳醯氧基羰氧基取代稠四苯化合物。Specific examples of the compound containing a condensed tetraphenyl ring suitable for use as the (C) sensitizer include: 2-methyl-5,11-dioxy-6,12-bis(acetoxy) Fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(propionyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12 -Bis(n-propylcarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(isopropylcarbonyloxy) fused tetraphenyl, 2-methyl- 5,11-Dioxy-6,12-bis(n-butylcarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(isobutylcarbonyl) oxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(n-pentylcarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy Base-6,12-bis(n-hexylcarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(n-heptylcarbonyloxy) fused tetraphenyl, 2 -Ethyl-5,11-dioxy-6,12-bis(acetoxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(propionyl) oxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(n-propylcarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy base-6,12-bis(isopropylcarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(n-butylcarbonyloxy) fused tetraphenyl, 2-Methyl-5,11-dioxy-6,12-bis(isobutylcarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis (n-pentylcarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(n-hexylcarbonyloxy) fused tetraphenyl, and 2-ethyl-5, 11-Di-oxy-6,12-bis(n-heptylcarbonyloxy) fused tetraphenyl and other alkylcarbonyloxy-substituted condensed tetraphenyl compounds; 2-Methyl-5,11-di-oxy-6 ,12-bis(benzyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(o-tolyloxy) fused tetraphenyl, 2-methyl- 5,11-Di-oxy-6,12-bis(m-tolyloxy) fused tetraphenyl, 2-methyl-5,11-di-oxy-6,12-bis(p-tolyloxy) ) fused tetraphenyl, 2-methyl-5,11-di-oxy-6,12-bis(α-naphthoyloxy) fused tetraphenyl, 2-methyl-5,11-di-oxy -6,12-bis(β-naphthyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(benzyloxy) fused tetraphenyl, 2 -Ethyl-5,11-dioxy-6,12-bis(o-tolyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(m- Tolyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(p-tolyloxy) fused tetraphenyl, 2-ethyl-5,11-dimension Oxy-6,12-bis(α-naphthoyloxy) Condensed tetraphenyl, and 2-ethyl-5,11-dioxy-6,12-bis(β-naphthyloxy) condensed tetraphenyl and other aryloxy-substituted condensed tetraphenyl compounds; 2-methyl Alkyl-5,11-dioxy-6,12-bis(methoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(ethoxy) carbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(n-propoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11- Di-oxy-6,12-bis(isopropoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-di-oxy-6,12-bis(n-butoxycarbonyloxy) ) Condensed tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(isobutoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxyl -6,12-bis(n-pentoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(n-hexyloxycarbonyloxy) fused tetraphenyl, 2-Methyl-5,11-dioxy-6,12-bis(n-heptoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12- Bis(n-octyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(methoxycarbonyloxy) fused tetraphenyl, 2-ethyl- 5,11-Dioxy-6,12-bis(ethoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(n-propoxy) Carbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(isopropoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-di Pendant oxy-6,12-bis(n-butoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(isobutoxycarbonyloxy) Condensed tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(n-pentoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy- 6,12-bis(n-hexyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(n-heptoxycarbonyloxy) fused tetraphenyl, and 2-ethyl-5,11-di-oxy-6,12-bis(n-octyloxycarbonyloxy) fused tetraphenyl and other alkoxycarbonyloxy-substituted fused tetraphenyl compounds; and 2-methyl- 5,11-Dioxy-6,12-bis(phenoxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(o-tolyloxy) Carbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(m-tolyloxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-di Pendant oxy-6,12-bis(p-tolyloxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(α-naphthyloxycarbonyloxy) ) fused tetraphenyl, 2-methyl-5,11-dioxy-6,12-bis(β-naphthyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy Base-6,12-bis(phenoxycarbonyloxy) fused tetraphenyl, 2-ethyl- 5,11-Dioxy-6,12-bis(o-tolyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(m-tolyloxy) ylcarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxy-6,12-bis(p-tolyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11- Di-oxy-6,12-bis(α-naphthyloxycarbonyloxy) fused tetraphenyl, and 2-ethyl-5,11-di-oxy-6,12-bis(β-naphthyloxy) Carbonyloxy) fused tetraphenyl and other aryloxycarbonyloxy substituted fused tetraphenyl compounds.
上述包含稠四苯環之化合物之中，較佳為5,11-二側氧基-6,12-雙(甲氧基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(乙氧基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(異丙氧基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(異丁氧基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(正丁基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(正戊基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(正庚醯氧基)稠四苯。 就與(B)光聚合性化合物之相溶性之方面而言，較佳為5,11-二側氧基-6,12-雙(異丙氧基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(異丁氧基羰氧基)稠四苯、5,11-二側氧基-6,12-雙(正丁醯氧基)稠四苯、5,11-二側氧基-6,12-雙(正戊醯氧基)稠四苯、5,11-二側氧基-6,12-雙(庚醯氧基)稠四苯。Among the above-mentioned compounds containing condensed tetraphenyl rings, preferred are 5,11-dioxy-6,12-bis(methoxycarbonyloxy) condensed tetraphenyl, 5,11-dioxy-6 ,12-bis(ethoxycarbonyloxy) fused tetraphenyl, 5,11-dioxy-6,12-bis(isopropoxycarbonyloxy) fused tetraphenyl, 5,11-dioxygen Base-6,12-bis(isobutoxycarbonyloxy) fused tetraphenyl, 5,11-dioxy-6,12-bis(n-butylcarbonyloxy) fused tetraphenyl, 5,11- Two-sided oxy-6,12-bis(n-pentylcarbonyloxy) condensed tetraphenyl, 5,11-di-oxy-6,12-bis(n-heptyloxy) condensed tetraphenyl. In terms of compatibility with the (B) photopolymerizable compound, 5,11-di-oxy-6,12-bis(isopropoxycarbonyloxy)condensed tetraphenyl, 5,11 - Two-sided oxy-6,12-bis(isobutoxycarbonyloxy) fused tetraphenyl, 5,11-two-sided oxy-6,12-bis(n-butyryloxy) fused tetraphenyl, 5 , 11-dioxy-6,12-bis(n-pentyloxy) fused tetraphenyl, 5,11-dioxy-6,12-bis(heptanoyloxy) fused tetraphenyl.
作為宜用作(C)增感劑之包含硫𠮿
作為(C)成分之增感劑之含量例如相對於感光性組合物中之(A)成分之合計100質量份為0.01質量份以上且2000質量份以下，較佳為0.01質量份以上且1000質量份以下，更佳為0.1質量份以上且150質量份以下，進而較佳為0.3質量份以上且100質量份以下。 再者，於設為相對於(B)成分之合計100質量份為0.01質量份以上且20質量份以下之情形時，可減輕因(C)成分之吸收而引起之著色，因此可獲得透明性或亮度良好之硬化物。The content of the sensitizer as the component (C) is, for example, 0.01 part by mass or more and 2000 parts by mass or less, preferably 0.01 part by mass or more and 1000 parts by mass with respect to 100 parts by mass of the total of the (A) component in the photosensitive composition. part or less, more preferably 0.1 part by mass or more and 150 parts by mass or less, and still more preferably 0.3 part by mass or more and 100 parts by mass or less. Moreover, when it is 0.01 mass part or more and 20 mass parts or less with respect to the total 100 mass parts of (B) component, the coloring by the absorption of (C) component can be reduced, so transparency can be obtained or hardened material with good brightness.
＜(D)著色劑＞ 感光性組合物可進而含有(D)著色劑。感光性組合物藉由含有作為(D)成分之著色劑，適宜用於例如液晶顯示器之彩色濾光片形成用途。又，第1態樣之感光性組合物藉由含有遮光劑作為著色劑，適宜用於例如顯示裝置之彩色濾光片中之黑矩陣形成用途。<(D) Colorant> The photosensitive composition may further contain (D) a colorant. By containing the coloring agent as (D)component, a photosensitive composition is suitably used for the color filter formation use of a liquid crystal display, for example. Moreover, since the photosensitive composition of the 1st aspect contains a light-shielding agent as a coloring agent, it is suitable for the black matrix formation application in the color filter of a display apparatus, for example.
作為感光性組合物所含有之(D)著色劑，並無特別限定，例如可使用於色料索引(C.I.；The Society of Dyers and Colourists公司發行)中歸為顏料(Pigment)類之化合物，具體而言，較佳為使用如下所述之標註有色料索引(C.I.)編號者。The (D) colorant contained in the photosensitive composition is not particularly limited, and for example, it can be used for compounds classified as pigments in the Color Index (C.I.; issued by The Society of Dyers and Colourists), specifically In particular, it is preferable to use the ones marked with the Color Index (C.I.) numbers as described below.
作為可較佳使用之黃色顏料之例，可列舉：C.I.顏料黃1(以下，「C.I.顏料黃」相同而僅記載編號)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、及185。Examples of yellow pigments that can be preferably used include: C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20 , 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110 , 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167 , 168, 175, 180, and 185.
作為可較佳使用之橙色顏料之例，可列舉：C.I.顏料橙1(以下，「C.I.顏料橙」相同而僅記載編號)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、及73。Examples of orange pigments that can be preferably used include: C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38 , 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.
作為可較佳使用之紫色顏料之例，可列舉：C.I.顏料紫1(以下，「C.I.顏料紫」相同而僅記載編號)、19、23、29、30、32、36、37、38、39、40、及50。Examples of violet pigments that can be preferably used include C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39 , 40, and 50.
作為可較佳使用之紅色顏料之例，可列舉：C.I.顏料紅1(以下，「C.I.顏料紅」相同而僅記載編號)2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、及265。Examples of red pigments that can be preferably used include: C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.
作為可較佳使用之藍色顏料之例，可列舉：C.I.顏料藍1(以下，「C.I.顏料藍」相同而僅記載編號)、2、15、15：3、15：4、15：6、16、22、60、64、及66。Examples of blue pigments that can be preferably used include: C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and only the number is described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.
作為可較佳使用之上述其他色相之顏料之例，可列舉：C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37等綠色顏料，C.I.顏料棕23、C.I.顏料棕25、C.I.顏料棕26、C.I.顏料棕28等棕色顏料，C.I.顏料黑1、C.I.顏料黑7等黑色顏料。Examples of pigments of the above-mentioned other hues that can be preferably used include green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, Brown pigments such as C.I. Pigment Brown 28, and black pigments such as C.I. Pigment Black 1 and C.I. Pigment Black 7.
又，於對感光性組合物賦予遮光性之情形時，感光性組合物較佳為包含黑色顏料作為(D)著色劑。包含黑色顏料之感光性組合物適於形成液晶顯示面板中之黑矩陣或黑間隔柱、或者有機EL元件中之發光層之劃分用之障壁。Moreover, when providing light-shielding property to the photosensitive composition, it is preferable that the photosensitive composition contains a black pigment as a (D) coloring agent. The photosensitive composition containing the black pigment is suitable for forming a black matrix or a black spacer in a liquid crystal display panel, or a barrier rib for dividing a light-emitting layer in an organic EL element.
作為黑色顏料之例，可列舉：碳黑、苝系顏料、內醯胺系顏料、鈦黑、銅、鐵、錳、鈷、鉻、鎳、鋅、鈣、銀等之金屬氧化物、複合氧化物、金屬硫化物、金屬硫酸鹽或金屬碳酸鹽等無論為有機物或無機物之各種顏料。該等黑色顏料之中，就易獲得性、或容易形成遮光性優異且電阻較高之硬化膜之方面而言，較佳為碳黑。 再者，黑色顏料之色相並不限定於色彩論上作為無彩色之黑色，亦可為帶有紫色之黑色、或帶有藍色之黑色、或帶有紅色之黑色。Examples of black pigments include metal oxides such as carbon black, perylene-based pigments, lactamide-based pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, and composite oxides. Various pigments, whether organic or inorganic, such as compounds, metal sulfides, metal sulfates or metal carbonates. Among these black pigments, carbon black is preferable from the viewpoint of easy availability and easy formation of a cured film having excellent light-shielding properties and high electrical resistance. Furthermore, the hue of the black pigment is not limited to black, which is achromatic in color theory, and may be black with violet, black with blue, or black with red.
作為碳黑，可使用煙囪黑、爐黑、熱碳黑、燈黑等公知碳黑，較佳為使用遮光性優異之煙囪黑。又，亦可使用樹脂被覆碳黑。As the carbon black, well-known carbon blacks such as chimney black, furnace black, thermal black, and lamp black can be used, and chimney black having excellent light-shielding properties is preferably used. In addition, resin-coated carbon black may also be used.
樹脂被覆碳黑由於與未經樹脂被覆之碳黑相比導電性較低，故而於作為如液晶顯示器之液晶顯示元件之黑矩陣使用之情形時，可製造漏電流較少、可靠性較高之低電耗顯示器。Resin-coated carbon black has lower electrical conductivity than non-resin-coated carbon black, so when used as a black matrix of a liquid crystal display element such as a liquid crystal display, it can produce less leakage current and higher reliability. Low power consumption display.
作為碳黑，亦較佳為實施有導入酸性基之處理之碳黑。對碳黑導入之酸性基係表現出基於布忍斯特(Bronsted)定義之酸性之官能基。作為酸性基之具體例，可列舉：羧基、磺酸基、磷酸基等。導入碳黑中之酸性基亦可形成鹽。與酸性基形成鹽之陽離子於無損本發明之目的之範圍內無特別限定。作為陽離子之例，可列舉：各種金屬離子、含氮化合物之陽離子、銨離子等，較佳為鈉離子、鉀離子、鋰離子等鹼金屬離子、或銨離子。As carbon black, the carbon black which performed the process to introduce|transduce an acidic group is also preferable. The acidic groups introduced to carbon black exhibit functional groups based on Bronsted's definition of acidity. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. Acid groups introduced into carbon black can also form salts. The cation that forms a salt with the acidic group is not particularly limited in the range that does not impair the object of the present invention. Examples of the cations include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, preferably alkali metal ions such as sodium ions, potassium ions, and lithium ions, or ammonium ions.
以上說明之實施有導入酸性基之處理之碳黑之中，就達成使用感光性組合物所形成之遮光性之硬化膜之高電阻之觀點而言，較佳為具有選自由羧酸基、羧酸鹽基、磺酸基、及磺酸鹽基所組成之群中之1種以上之官能基之碳黑。Among the carbon blacks to which the acid group-introducing treatment described above is performed, from the viewpoint of achieving high resistance of the light-shielding cured film formed using the photosensitive composition, it is preferable to have a carbon black selected from a carboxylic acid group, a carboxyl group, a Carbon black with one or more functional groups in the group consisting of an acid salt group, a sulfonic acid group, and a sulfonic acid salt group.
對碳黑導入酸性基之方法並無特別限定。作為導入酸性基之方法，例如可列舉以下之方法。 1)藉由使用濃硫酸、發煙硫酸、氯磺酸等之直接置換法、或使用亞硫酸鹽、亞硫酸氫鹽等之間接置換法對碳黑導入磺酸基之方法。 2)使具有胺基及酸性基之有機化合物與碳黑進行二偶氮偶合之方法。 3)藉由威廉森(Williamson)之醚化法使具有鹵素原子及酸性基之有機化合物與具有羥基之碳黑進行反應之方法。 4)使具有鹵化羰基及經保護基保護之酸性基之有機化合物與具有羥基之碳黑進行反應之方法。 5)使用具有鹵化羰基及經保護基保護之酸性基之有機化合物，對碳黑進行夫里德耳-誇夫特(Friedel-Crafts)反應後進行脫保護之方法。The method of introducing an acidic group to carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example. 1) A method of introducing sulfonic acid groups to carbon black by direct displacement using concentrated sulfuric acid, oleum, chlorosulfonic acid, etc., or indirect displacement using sulfite, hydrogen sulfite, or the like. 2) A method of disazo coupling an organic compound having an amine group and an acidic group and carbon black. 3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by the etherification method of Williamson. 4) A method of reacting an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group. 5) A method of deprotecting carbon black after Friedel-Crafts reaction using an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group.
該等方法之中，就酸性基之導入處理容易且安全之方面而言，較佳為方法2)。作為方法2)中所使用之具有胺基與酸性基之有機化合物，較佳為於芳香族基上鍵結有胺基與酸性基之化合物。作為此種化合物之例，可列舉：磺胺酸之類之胺基苯磺酸、或4-胺基苯甲酸之類的胺基苯甲酸。Among these methods, the method 2) is preferable in that the introduction treatment of the acidic group is easy and safe. The organic compound having an amine group and an acidic group used in the method 2) is preferably a compound having an amine group and an acidic group bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acid such as sulfanilic acid, and aminobenzoic acid such as 4-aminobenzoic acid.
對碳黑導入之酸性基之莫耳數於無損本發明之目的之範圍內無特別限定。對碳黑導入之酸性基之莫耳數相對於碳黑100 g，較佳為1 mmol以上且200 mmol以下，更佳為5 mmol以上且100 mmol以下。The molar number of the acid group introduced into the carbon black is not particularly limited within a range that does not impair the object of the present invention. The molar number of the acid group introduced into carbon black is preferably 1 mmol or more and 200 mmol or less, more preferably 5 mmol or more and 100 mmol or less, relative to 100 g of carbon black.
亦可對導入有酸性基之碳黑實施藉由樹脂之被覆處理。 於使用包含經樹脂被覆之碳黑之感光性組合物之情形時，容易形成遮光性及絕緣性優異、且表面反射率較低之遮光性之硬化膜。再者，不會因樹脂被覆處理而對使用感光性組合物所形成之遮光性之硬化膜之介電常數產生特別之不良影響。作為可用於被覆碳黑之樹脂之例，可列舉：酚樹脂、三聚氰胺樹脂、二甲苯樹脂、鄰苯二甲酸二烯丙酯樹脂、甘酞樹脂、環氧樹脂、烷基苯樹脂等熱硬化性樹脂，或聚苯乙烯、聚碳酸酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、改性聚苯醚、聚碸、聚對伸苯基對苯二甲醯胺、聚醯胺醯亞胺、聚醯亞胺、聚胺基雙順丁烯二醯亞胺、聚醚碸、聚苯碸、聚芳酯、聚醚醚酮等熱塑性樹脂。關於樹脂對碳黑之被覆量，相對於碳黑質量與樹脂質量之合計，較佳為1質量%以上且30質量%以下。It is also possible to perform coating treatment with resin on the carbon black into which the acidic group is introduced. When the photosensitive composition containing resin-coated carbon black is used, it becomes easy to form a light-shielding cured film which is excellent in light-shielding property and insulating property, and has low surface reflectance. Furthermore, there is no particular adverse effect on the dielectric constant of the light-shielding cured film formed using the photosensitive composition due to the resin coating treatment. Examples of resins that can be used to coat carbon black include thermosetting properties such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glycerol resins, epoxy resins, and alkylbenzene resins. Resin, or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysiloxane, polyparaphenylene terephthalamide, Thermoplastic resins such as polyamide imide, polyimide, polyamine bismaleimide, polyether, polyphenylene, polyarylate, polyether ether ketone, etc. The coating amount of the carbon black with the resin is preferably 1 mass % or more and 30 mass % or less with respect to the total of the carbon black mass and the resin mass.
又，作為黑色顏料，亦可較佳地使用苝系顏料。作為苝系顏料之具體例，可列舉：下述式(d-1)所表示之苝系顏料、下述式(d-2)所表示之苝系顏料、及下述式(d-3)所表示之苝系顏料。於市售品中，BASF公司製造之製品名K0084及K0086、或顏料黑21、30、31、32、33及34等可較佳地作為苝系顏料使用。Moreover, as a black pigment, a perylene type pigment can also be used suitably. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d-1), a perylene-based pigment represented by the following formula (d-2), and the following formula (d-3) The indicated perylene pigments. Among the commercially available products, the product names K0084 and K0086 manufactured by BASF Company, or Pigment Black 21, 30, 31, 32, 33 and 34, etc. can be preferably used as perylene pigments.
[化16]
[化17]
[化18]
上述式(d-1)所表示之化合物、式(d-2)所表示之化合物、及式(d-3)所表示之化合物可採用例如日本專利特開昭62-1753號公報、日本專利特公昭63-26784號公報中記載之方法合成。即，以苝-3,5,9,10-四羧酸或其二酐與胺類作為原料，於水或有機溶劑中進行加熱反應。繼而，使所獲得之粗製物於硫酸中再沈澱、或者於水、有機溶劑或該等之混合溶劑中再結晶，藉此可獲得目標物。As the compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3), for example, Japanese Patent Laid-Open No. Sho 62-1753, Japanese Patent It was synthesized by the method described in Japanese Patent Publication No. 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the target product can be obtained by reprecipitating the obtained crude product in sulfuric acid, or recrystallizing in water, an organic solvent, or a mixed solvent of these.
為了使苝系顏料良好地分散於感光性組合物中，苝系顏料之平均粒徑較佳為10 nm以上且1000 nm以下。In order to disperse the perylene-based pigment well in the photosensitive composition, the average particle diameter of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less.
又，作為遮光劑，亦可包含內醯胺系顏料。作為內醯胺系顏料，例如可列舉下述式(d-4)所表示之化合物。Moreover, as a light-shielding agent, a lactamide-type pigment may be contained. As a lactamide type pigment, the compound represented by following formula (d-4) is mentioned, for example.
[化19]
式(d-4)中，Xd 表示雙鍵，作為幾何異構物，分別獨立為E體或Z體，Rd9 分別獨立表示氫原子、甲基、硝基、甲氧基、溴原子、氯原子、氟原子、羧基、或磺基，Rd10 分別獨立表示氫原子、甲基、或苯基，Rd11 分別獨立表示氫原子、甲基、或氯原子。 式(d-4)所表示之化合物可單獨使用或將2種以上組合使用。 就式(d-4)所表示之化合物易於製造之方面而言，Rd9 較佳為鍵結於二氫吲哚酮環之6位，Rd11 較佳為鍵結於二氫吲哚酮環之4位。就相同觀點而言，Rd9 、Rd10 及Rd11 較佳為氫原子。 式(d-4)所表示之化合物存在EE體、ZZ體、EZ體作為幾何異構物，可為該等任一者之單一化合物，亦可為該等幾何異構物之混合物。 式(d-4)所表示之化合物可藉由例如國際公開第2000/24736號及國際公開第2010/081624號中記載之方法製造。In formula (d-4), X d represents a double bond, and as geometric isomers, it is independently an E body or a Z body, and R d9 independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, A chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group, R d10 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R d11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom. The compound represented by formula (d-4) may be used alone or in combination of two or more. In terms of easy production of the compound represented by the formula (d-4), R d9 is preferably bonded to the 6-position of the indolinone ring, and R d11 is preferably bonded to the indolinone ring 4 digits. From the same viewpoint, R d9 , R d10 and R d11 are preferably hydrogen atoms. The compound represented by the formula (d-4) has EE, ZZ, and EZ as geometric isomers, and may be a single compound of any of these, or a mixture of these geometric isomers. The compound represented by the formula (d-4) can be produced by, for example, the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.
為了使內醯胺系顏料良好地分散於感光性組合物中，內醯胺系顏料之平均粒徑較佳為10 nm以上且1000 nm以下。In order to disperse the lactamide-based pigment well in the photosensitive composition, the average particle diameter of the lactamide-based pigment is preferably 10 nm or more and 1000 nm or less.
進而，以銀錫(AgSn)合金為主成分之微粒子(以下稱為「AgSn合金微粒子」)亦可較佳地用作黑色顏料。該AgSn合金微粒子只要AgSn合金為主成分即可，作為其他金屬成分，例如亦可包含Ni、Pd、Au等。 該AgSn合金微粒子之平均粒徑較佳為1 nm以上且300 nm以下。Furthermore, fine particles mainly composed of a silver-tin (AgSn) alloy (hereinafter referred to as "AgSn alloy fine particles") can also be preferably used as a black pigment. The AgSn alloy fine particles only need to have an AgSn alloy as the main component, and as other metal components, for example, Ni, Pd, Au and the like may be included. The average particle diameter of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.
於AgSn合金係以化學式AgxSn表示之情形時，可獲得化學上穩定之AgSn合金之x之範圍為1≦x≦10，可同時獲得化學穩定性與黑色度之x之範圍為3≦x≦4。 此處，若於上述x之範圍內求出AgSn合金中之Ag之質量比，則 於x＝1之情形時，Ag/AgSn＝0.4762 於x＝3之情形時，3・Ag/Ag3Sn＝0.7317 於x＝4之情形時，4・Ag/Ag4Sn＝0.7843 於x＝10之情形時，10・Ag/Ag10Sn＝0.9008。 因此，該AgSn合金於含有47.6質量%以上且90質量%以下之Ag之情形時，化學上穩定，於含有73.17質量%以上且78.43質量%以下之Ag之情形時，相對於Ag量，可有效獲得化學穩定性與黑色度。When the AgSn alloy is represented by the chemical formula AgxSn, the range of x that can obtain chemically stable AgSn alloy is 1≦x≦10, and the range of x that can simultaneously obtain chemical stability and blackness is 3≦x≦4 . Here, if the mass ratio of Ag in the AgSn alloy is obtained within the range of x above, when x=1, Ag/AgSn=0.4762, and when x=3, 3·Ag/Ag3Sn=0.7317 In the case of x=4, 4·Ag/Ag4Sn=0.7843 In the case of x=10, 10·Ag/Ag10Sn=0.9008. Therefore, the AgSn alloy is chemically stable when it contains 47.6 mass % or more and 90 mass % or less of Ag, and when it contains 73.17 mass % or more and 78.43 mass % or less of Ag, it is effective relative to the amount of Ag. Obtain chemical stability and blackness.
該AgSn合金微粒子可採用通常之微粒子合成法製作。作為微粒子合成法，可列舉：氣相反應法、噴霧熱分解法、霧化法、液相反應法、冷凍乾燥法、水熱合成法等。The AgSn alloy microparticles can be produced by a conventional microparticle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray thermal decomposition method, an atomization method, a liquid phase reaction method, a freeze drying method, a hydrothermal synthesis method, and the like.
AgSn合金微粒子之絕緣性較高，但考慮到感光性組合物之用途，亦可利用絕緣膜被覆表面以進一步提高絕緣性。作為此種絕緣膜之材料，宜為金屬氧化物或有機高分子化合物。 作為金屬氧化物，宜使用具有絕緣性之金屬氧化物，例如氧化矽(silica)、氧化鋁(alumina)、氧化鋯(zirconia)、氧化釔(yttria)、氧化鈦(titania)等。 又，作為有機高分子化合物，宜使用具有絕緣性之樹脂，例如聚醯亞胺、聚醚、聚丙烯酸酯、聚胺化合物等。AgSn alloy fine particles have high insulating properties, but considering the application of the photosensitive composition, the insulating film can be used to coat the surface to further improve the insulating properties. As the material of the insulating film, a metal oxide or an organic polymer compound is suitable. As the metal oxide, an insulating metal oxide such as silicon oxide (silica), aluminum oxide (alumina), zirconia (zirconia), yttria (yttria), and titanium oxide (titania) is preferably used. Further, as the organic polymer compound, resins having insulating properties, such as polyimide, polyether, polyacrylate, polyamine compound, etc., are preferably used.
為了充分提高AgSn合金微粒子之表面之絕緣性，絕緣膜之膜厚較佳為1 nm以上且100 nm以下，更佳為5 nm以上且50 nm以下。 藉由表面改質技術或表面塗層技術可容易地形成絕緣膜。尤其若使用四乙氧基矽烷、三乙醇鋁等烷氧化物，可於相對低溫下形成膜厚均勻之絕緣膜，因此較佳。In order to sufficiently improve the insulating properties of the surface of the AgSn alloy fine particles, the thickness of the insulating film is preferably 1 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less. The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, if alkoxides such as tetraethoxysilane and aluminum triethoxide are used, an insulating film with a uniform thickness can be formed at a relatively low temperature, so it is preferable.
作為黑色顏料，上述苝系顏料、內醯胺系顏料、AgSn合金微粒子可單獨使用，亦可將該等組合使用。 另外，基於色調調整等目的，黑色顏料亦可包含紅、藍、綠、黃等色相之色素。黑色顏料中之其他色相之色素可自公知色素中適當選擇。例如，作為黑色顏料中之其他色相之色素，可使用上述各種顏料。黑色顏料中之其他色相之色素之使用量相對於黑色顏料之總質量，較佳為15質量%以下，更佳為10質量%以下。As the black pigment, the above-mentioned perylene-based pigments, lactamide-based pigments, and AgSn alloy fine particles may be used alone or in combination. In addition, the black pigment may also contain pigments of hues such as red, blue, green, and yellow for the purpose of adjusting the hue. Pigments of other hues in the black pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as pigments of other hues in black pigments. The use amount of the pigments of other hues in the black pigment is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the black pigment.
為了使上述著色劑均勻地分散於感光性組合物中，亦可進而使用分散劑。作為此種分散劑，較佳為使用聚伸乙基亞胺系、胺基甲酸酯樹脂系、丙烯酸樹脂系之高分子分散劑。尤其於使用碳黑作為(D)著色劑之情形時，較佳為使用丙烯酸樹脂系之分散劑作為分散劑。 再者，亦存在因分散劑導致硬化膜產生腐蝕性氣體之情況。因此，不使用分散劑而對顏料進行分散處理亦為較佳態樣之一例。In order to disperse the said coloring agent uniformly in a photosensitive composition, you may use a dispersing agent further. As such a dispersant, a polyethylenimine-based, urethane resin-based, or acrylic resin-based polymer dispersant is preferably used. In particular, when carbon black is used as the (D) colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant. Furthermore, there are cases in which corrosive gas is generated in the cured film due to the dispersant. Therefore, dispersing the pigment without using a dispersant is also an example of a preferable aspect.
再者，於感光性組合物中亦可組合使用顏料與染料。該染料自公知材料中適當選擇即可。 作為可應用於感光性組合物之染料，例如可列舉：偶氮染料、金屬錯鹽偶氮染料、蒽醌染料、三苯基甲烷染料、𠮿
感光性組合物中之(D)著色劑之使用量可於無損本發明之目的之範圍內適當選擇，典型而言，相對於感光性組合物之全體固形物成分之質量，較佳為2質量%以上且75質量%以下，更佳為3質量%以上且70質量%以下。The amount of the (D) colorant used in the photosensitive composition can be appropriately selected within a range that does not impair the object of the present invention, and typically, it is preferably 2 mass based on the mass of the entire solid content of the photosensitive composition % or more and 75 mass % or less, more preferably 3 mass % or more and 70 mass % or less.
尤其於使用感光性組合物形成黑矩陣之情形時，較佳為以黑矩陣之被膜每1 μm之OD值成為4以上之方式調整感光性組合物中之遮光劑之量。若黑矩陣之被膜每1 μm之OD值為4以上，則於用於液晶顯示器之黑矩陣之情形時，可獲得充分之顯示對比度。Especially when forming a black matrix using a photosensitive composition, it is preferable to adjust the quantity of the light-shielding agent in a photosensitive composition so that the OD value per 1 micrometer of the film of a black matrix may become 4 or more. If the OD value per 1 μm of the film of the black matrix is 4 or more, a sufficient display contrast can be obtained when it is used for the black matrix of a liquid crystal display.
於使用顏料作為(D)著色劑之情形時，較佳為使顏料於存在或不存在分散劑之條件下以適宜濃度分散而製成分散液後，添加於感光性組合物中。 再者，於本說明書中，關於上述顏料之使用量，可定義為亦包括該存在之分散劑在內之值。When a pigment is used as the (D) colorant, it is preferable to add the pigment to the photosensitive composition after dispersing the pigment at an appropriate concentration in the presence or absence of a dispersant to prepare a dispersion liquid. In addition, in this specification, the usage-amount of the said pigment can be defined as the value which also includes the dispersing agent which exists.
＜(E)鹼可溶性樹脂＞ 第1態樣之感光性組合物亦可含有作為(B)光聚合性化合物所使用之樹脂以外之其他樹脂。作為上述其他樹脂，可列舉：(E)鹼可溶性樹脂、藉由酸之作用而於顯影液中之溶解性變化之樹脂等，較佳為(E)鹼可溶性樹脂。藉由在感光性組合物中調配(E)鹼可溶性樹脂，可對感光性組合物賦予鹼性顯影性。<(E) Alkali-soluble resin> The photosensitive composition of 1st aspect may contain resin other than the resin used as (B) photopolymerizable compound. As said other resin, (E) alkali-soluble resin, the resin whose solubility in a developing solution changes by the action of an acid, etc. are mentioned, (E) alkali-soluble resin is preferable. Alkaline developability can be imparted to the photosensitive composition by mix|blending (E) alkali-soluble resin with a photosensitive composition.
於本說明書中，所謂鹼可溶性樹脂係指如下者：使用樹脂濃度20質量%之樹脂溶液(溶劑：丙二醇單甲醚乙酸酯)於基板上形成膜厚1 μm之樹脂膜，於濃度0.05質量%之KOH水溶液中浸漬1分鐘時，膜厚0.01 μm以上發生溶解。In this specification, the so-called alkali-soluble resin refers to a resin film having a thickness of 1 μm formed on a substrate using a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a resin film having a concentration of 0.05% by mass is used. When immersed in % KOH aqueous solution for 1 minute, the film thickness of 0.01 μm or more will dissolve.
(E)鹼可溶性樹脂之中，就製膜性優異之方面、或藉由選擇單體而容易調整樹脂特性等方面而言，較佳為具有乙烯性不飽和雙鍵之單體之聚合物。作為具有乙烯性不飽和雙鍵之單體，可列舉：(甲基)丙烯酸；(甲基)丙烯酸酯；(甲基)丙烯醯胺；丁烯酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸、該等二羧酸之酸酐；乙酸烯丙酯、己酸烯丙酯、辛酸烯丙酯、月桂酸烯丙酯、棕櫚酸烯丙酯、硬脂酸烯丙酯、苯甲酸烯丙酯、乙醯乙酸烯丙酯、乳酸烯丙酯、及烯丙氧基乙醇之類的烯丙基化合物；己基乙烯醚、辛基乙烯醚、癸基乙烯醚、乙基己基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙烯醚、氯乙基乙烯醚、1-甲基-2,2-二甲基丙基乙烯醚、2-乙基丁基乙烯醚、羥基乙基乙烯醚、二乙二醇乙烯醚、二甲胺基乙基乙烯醚、二乙胺基乙基乙烯醚、丁基胺基乙基乙烯醚、苄基乙烯醚、四氫糠基乙烯醚、乙烯基苯醚、乙烯基甲苯醚、乙烯基氯苯醚、乙烯基-2,4-二氯苯醚、乙烯基萘醚、及乙烯基蒽醚之類的乙烯醚；丁酸乙烯酯、異丁酸乙烯酯、乙酸乙烯基三甲酯、乙酸乙烯基二乙酯、特戊酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、甲氧基乙酸乙烯酯、丁氧基乙酸乙烯酯、乙酸乙烯基苯酯、乙醯乙酸乙烯酯、乳酸乙烯酯、丁酸乙烯基-β-苯酯、苯甲酸乙烯酯、水楊酸乙烯酯、氯苯甲酸乙烯酯、四氯苯甲酸乙烯酯、及萘甲酸乙烯酯之類的乙烯酯；苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基甲基苯乙烯、甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯、氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、及4-氟-3-三氟甲基苯乙烯之類的苯乙烯或苯乙烯衍生物；乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、及1-二十烯之類的烯烴。(E) Among the alkali-soluble resins, a polymer of a monomer having an ethylenically unsaturated double bond is preferable in terms of excellent film-forming properties, or the ease of adjustment of resin properties by selecting a monomer. As a monomer having an ethylenically unsaturated double bond, (meth)acrylic acid; (meth)acrylate; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids; allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, Allyl stearate, allyl benzoate, allyl acetylacetate, allyl lactate, and allyl compounds such as allyloxyethanol; hexyl vinyl ether, octyl vinyl ether, decyl Vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl toluene ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracene ether and the like Vinyl Ethers; Vinyl Butyrate, Vinyl Isobutyrate, Vinyl Trimethyl Acetate, Vinyl Diethyl Acetate, Vinyl Pivalate, Vinyl Caproate, Vinyl Chloroacetate, Vinyl Dichloroacetate, Vinyl Methoxyacetate, Vinyl Butoxy Vinyl Acetate, Vinyl Phenyl Acetate, Vinyl Acetyl Acetate, Vinyl Lactate, Vinyl-β-Phenyl Butyrate, Vinyl Benzoate, Vinyl Salicylate , vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl esters such as vinyl naphthoate; styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethyl styrene Oxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene , trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene , and styrene or styrene derivatives such as 4-fluoro-3-trifluoromethylstyrene; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1 -Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethylene 1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, Olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
作為具有乙烯性不飽和雙鍵之單體之聚合物的(E)鹼可溶性樹脂通常包含源自不飽和羧酸之單元。作為不飽和羧酸之例，可列舉：(甲基)丙烯酸；(甲基)丙烯醯胺；丁烯酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸、該等二羧酸之酸酐。關於用作鹼可溶性樹脂之具有乙烯性不飽和雙鍵之單體之聚合物中所含之源自不飽和羧酸之單元之量，只要使樹脂具有所需之鹼可溶性，則並無特別限定。用作鹼可溶性樹脂之樹脂中之源自不飽和羧酸之單元之量相對於樹脂之質量，較佳為5質量%以上且25質量%以下，更佳為8質量%以上且16質量%以下。The (E) alkali-soluble resin, which is a polymer of a monomer having an ethylenically unsaturated double bond, usually contains a unit derived from an unsaturated carboxylic acid. Examples of unsaturated carboxylic acids include: (meth)acrylic acid; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Aconic acid, anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility. . The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5% by mass or more and 25% by mass or less, more preferably 8% by mass or more and 16% by mass or less with respect to the mass of the resin. .
於作為選自以上例示單體中之1種以上之單體之聚合物的具有乙烯性不飽和雙鍵之單體之聚合物之中，較佳為選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物。以下，對選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物進行說明。Among the polymers of monomers having an ethylenically unsaturated double bond, which are polymers of one or more monomers selected from the above-exemplified monomers, preferably selected from (meth)acrylic acid and (methyl) ) A polymer of one or more monomers in acrylate. Hereinafter, a polymer of one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylate will be described.
用於製備選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物的(甲基)丙烯酸酯於無損本發明之目的之範圍內無特別限定，自公知之(甲基)丙烯酸酯中適當選擇。The (meth)acrylate used to prepare a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate is not particularly limited within the range that does not impair the purpose of the present invention, and is known from the public. (meth)acrylate is appropriately selected.
作為(甲基)丙烯酸酯之適宜例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸第三辛酯等直鏈狀或支鏈狀之(甲基)丙烯酸烷基酯；(甲基)丙烯酸氯乙酯、(甲基)丙烯酸2,2-二甲基羥基丙酯、(甲基)丙烯酸2-羥基乙酯、三羥甲基丙烷單(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸糠酯；含有具有環氧基之基之(甲基)丙烯酸酯；含有具有脂環式骨架之基之(甲基)丙烯酸酯。於下文記述有關含有具有環氧基之基之(甲基)丙烯酸酯及含有具有脂環式骨架之基之(甲基)丙烯酸酯的詳細內容。Preferable examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Linear or branched alkyl (meth)acrylates such as tert-octyl acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, (meth)acrylate base) 2-hydroxyethyl acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; (methyl) containing a group having an epoxy group Acrylate; (meth)acrylate containing a group having an alicyclic skeleton. Details about the (meth)acrylate containing a group having an epoxy group and the (meth)acrylate containing a group having an alicyclic skeleton are described below.
於選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物之中，就使用感光性組合物所形成之透明絕緣膜對基材之密接性或機械強度優異之方面而言，較佳為包含源自含有具有環氧基之基之(甲基)丙烯酸酯之單元的樹脂。In a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester, the adhesiveness or mechanical strength of the transparent insulating film formed using the photosensitive composition to the substrate It is preferable that it is a resin containing the unit derived from the (meth)acrylate containing the group which has an epoxy group from an excellent point.
含有具有環氧基之基之(甲基)丙烯酸酯可為含有具有鏈狀脂肪族環氧基之基之(甲基)丙烯酸酯，亦可為如後所述之含有具有脂環式環氧基之基之(甲基)丙烯酸酯。The (meth)acrylate containing a group having an epoxy group may be a (meth)acrylate containing a group having a chain aliphatic epoxy group, or may be a (meth)acrylate containing a group having an alicyclic epoxy group as described later. The (meth)acrylate of the base.
含有具有環氧基之基之(甲基)丙烯酸酯亦可含有芳香族基。作為構成芳香族基之芳香環之例，可列舉：苯環、萘環。作為含有芳香族基、且含有具有環氧基之基之(甲基)丙烯酸酯之例，可列舉：(甲基)丙烯酸4-縮水甘油氧基苯酯、(甲基)丙烯酸3-縮水甘油氧基苯酯、(甲基)丙烯酸2-縮水甘油氧基苯酯、(甲基)丙烯酸4-縮水甘油氧基苯基甲酯、(甲基)丙烯酸3-縮水甘油氧基苯基甲酯、及(甲基)丙烯酸2-縮水甘油氧基苯基甲酯等。The (meth)acrylate containing the group which has an epoxy group may contain an aromatic group. As an example of the aromatic ring which comprises an aromatic group, a benzene ring and a naphthalene ring are mentioned. Examples of the (meth)acrylate containing an aromatic group and containing a group having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate and 3-glycidyl (meth)acrylate. Oxyphenyl ester, 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate , and 2-glycidyloxyphenylmethyl (meth)acrylate, etc.
於要求使用感光性組合物所形成之膜具有透明性之情形時，含有具有環氧基之基之(甲基)丙烯酸較佳為不含芳香族基者。When the film formed using the photosensitive composition is required to have transparency, the (meth)acrylic acid containing a group having an epoxy group preferably does not contain an aromatic group.
作為含有具有鏈狀脂肪族環氧基之基之(甲基)丙烯酸酯之例，可列舉(甲基)丙烯酸環氧烷基酯、及(甲基)丙烯酸環氧烷氧基烷基酯等之類的於酯基(-O-CO-)中之氧基(-O-)上鍵結有鏈狀脂肪族環氧基之(甲基)丙烯酸酯。此種(甲基)丙烯酸酯所具有之鏈狀脂肪族環氧基於鏈中可包含1個或複數個氧基(-O-)。鏈狀脂肪族環氧基之碳原子數並無特別限定，較佳為3以上且20以下，更佳為3以上且15以下，尤佳為3以上且10以下。Examples of the (meth)acrylate containing a group having a chain aliphatic epoxy group include epoxyalkyl (meth)acrylate, epoxyalkyloxyalkyl (meth)acrylate, and the like. Such a (meth)acrylate in which a chain aliphatic epoxy group is bonded to an oxy group (-O-) in an ester group (-O-CO-). The chain-like aliphatic epoxy group which such a (meth)acrylate has may contain one or a plurality of oxygen groups (-O-) in a chain. The number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less.
作為含有具有鏈狀脂肪族環氧基之基之(甲基)丙烯酸酯之具體例，可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸6,7-環氧庚酯等(甲基)丙烯酸環氧烷基酯；(甲基)丙烯酸2-縮水甘油氧基乙酯、(甲基)丙烯酸3-縮水甘油氧基正丙酯、(甲基)丙烯酸4-縮水甘油氧基正丁酯、(甲基)丙烯酸5-縮水甘油氧基正己酯、(甲基)丙烯酸6-縮水甘油氧基正己酯等(甲基)丙烯酸環氧烷氧基烷基酯。Specific examples of the (meth)acrylate containing a group having a chain-like aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, (meth)acrylate base) 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth)acrylate and other epoxyalkyl (meth)acrylates; 2-glycidyloxyethyl (meth)acrylate , 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, (meth)acrylic acid 6-Glycidoxyn-hexyl (meth)acrylic acid alkylene oxide.
於包含源自含有具有環氧基之基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物中，源自含有具有環氧基之基之(甲基)丙烯酸酯之單元之含量相對於樹脂之重量，較佳為1質量%以上且95質量%以下，更佳為40質量%以上且80質量%以下。In a polymer containing at least one monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid ester containing a unit derived from a (meth)acrylate having a group having an epoxy group, derived from 1 mass % or more and 95 mass % or less are preferable with respect to the resin weight, and, as for content of the unit containing the (meth)acrylate which has a group which has an epoxy group, 40 mass % or more and 80 mass % or less are more preferable.
又，於選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物之中，就使用感光性組合物容易形成透明性優異之透明絕緣膜之方面而言，亦較佳為包含源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的樹脂。In addition, in the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester, it is easy to form a transparent insulating film with excellent transparency using the photosensitive composition , and preferably a resin containing a unit derived from a (meth)acrylate containing a group having an alicyclic skeleton.
含有具有脂環式骨架之基之(甲基)丙烯酸酯中，具有脂環式骨架之基可為具有脂環式烴基之基，亦可為具有脂環式環氧基之基。構成脂環式骨架之脂環式基可為單環亦可為多環。作為單環之脂環式基，可列舉：環戊基、環己基等。又，作為多環之脂環式基，可列舉：降𦯉基、異𦯉基、三環壬基、三環癸基、四環十二烷基等。In the (meth)acrylate containing a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Moreover, as a polycyclic alicyclic group, a nordicyl group, an isosacyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned.
含有具有脂環式骨架之基之(甲基)丙烯酸酯之中，作為含有具有脂環式烴基之基之(甲基)丙烯酸酯，例如可列舉下述式(d1-1)～(d1-8)所表示之化合物。該等之中，較佳為下述式(d1-3)～(d1-8)所表示之化合物，更佳為下述式(d1-3)或(d1-4)所表示之化合物。Among the (meth)acrylates containing a group having an alicyclic skeleton, examples of the (meth)acrylates containing a group having an alicyclic hydrocarbon group include the following formulae (d1-1) to (d1- 8) The compound represented. Among these, the compounds represented by the following formulae (d1-3) to (d1-8) are preferable, and the compounds represented by the following formula (d1-3) or (d1-4) are more preferable.
[化20]
上述式中，Rd1 表示氫原子或甲基，Rd2 表示單鍵或碳原子數1以上且6以下之2價脂肪族飽和烴基，Rd3 表示氫原子或碳原子數1以上且5以下之烷基。作為Rd2 ，較佳為單鍵、直鏈狀或支鏈狀之伸烷基，例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基。作為Rd3 ，較佳為甲基、乙基。In the above formula, R d1 represents a hydrogen atom or a methyl group, R d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group with 1 or more and 6 or less carbon atoms, and R d3 represents a hydrogen atom or one with 1 or more and 5 or less carbon atoms alkyl. As R d2 , it is preferably a single bond, linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylidene, pentamethylene, hexamethylene. As R d3 , a methyl group or an ethyl group is preferable.
含有具有脂環式骨架之基之(甲基)丙烯酸酯之中，作為含有具有脂環式環氧基之基之(甲基)丙烯酸酯之具體例，例如可列舉下述式(d2-1)～(d2-16)所表示之化合物。該等之中，為了使感光性組合物具有適度之顯影性，較佳為下述式(d2-1)～(d2-6)所表示之化合物，更佳為下述式(d2-1)～(d2-4)所表示之化合物。Among the (meth)acrylates containing a group having an alicyclic skeleton, as a specific example of the (meth)acrylate containing a group having an alicyclic epoxy group, the following formula (d2-1) may be mentioned, for example. ) to the compounds represented by (d2-16). Among these, the compounds represented by the following formulae (d2-1) to (d2-6) are preferred, and the following formula (d2-1) is more preferred in order for the photosensitive composition to have moderate developability. The compound represented by ~(d2-4).
[化21]
上述式中，Rd4 表示氫原子或甲基，Rd5 表示碳數1以上且6以下之2價脂肪族飽和烴基，Rd6 表示碳數1以上且10以下之2價烴基，n表示0以上且10以下之整數。作為Rd5 ，較佳為直鏈狀或支鏈狀之伸烷基，例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基。作為Rd6 ，較佳為例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基、伸苯基、伸環己基、-CH2 -Ph-CH2 -(Ph表示伸苯基)。In the above formula, R d4 represents a hydrogen atom or a methyl group, R d5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R d6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 or more and an integer less than 10. As R d5 , preferably straight-chain or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene, pentamethylene, hexamethylene base. As R d6 , for example, methylene, ethylidene, propylidene, tetramethylene, ethylethylidene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH are preferable. 2 -Ph-CH 2 - (Ph represents a phenylene group).
於選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物為包含源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的樹脂之情形時，樹脂中之源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元之量較佳為5質量%以上且95質量%以下，更佳為10質量%以上且90質量%以下，進而較佳為30質量%以上且70質量%以下。A polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylate is a resin containing a unit derived from a (meth)acrylate containing a group having an alicyclic skeleton. In this case, the amount of the unit derived from the (meth)acrylate containing a group having an alicyclic skeleton in the resin is preferably 5 mass % or more and 95 mass % or less, more preferably 10 mass % or more and 90 mass % % or less, more preferably 30 mass % or more and 70 mass % or less.
又，包含源自含有具有脂環式骨架之基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物之中，較佳為包含源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂。使用包含此種(E)鹼可溶性樹脂之感光性組合物所形成之膜對基材之密接性優異。又，於使用此種樹脂之情形時，可使樹脂所含之羧基與脂環式環氧基進行自反應。因此，若使用包含此種樹脂之感光性組合物，則採用將膜加熱之方法等而使羧基與脂環式環氧基進行自反應，藉此可提高所形成之膜之諸如硬度之機械物性。Moreover, in the polymer which contains one or more types of monomers selected from (meth)acrylic acid and (meth)acrylic acid ester which is derived from the unit which contains the (meth)acrylic acid ester of the group which has an alicyclic skeleton , Preferably it is a resin containing the unit derived from (meth)acrylic acid and the unit derived from the (meth)acrylate containing the group which has an alicyclic epoxy group. The film formed using the photosensitive composition containing such an alkali-soluble resin (E) is excellent in adhesiveness to a base material. Moreover, in the case of using such a resin, the carboxyl group and the alicyclic epoxy group contained in the resin can be self-reacted. Therefore, when a photosensitive composition containing such a resin is used, the carboxyl group and the alicyclic epoxy group are self-reacted by a method of heating the film, etc., whereby the mechanical properties such as hardness of the formed film can be improved .
包含源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自(甲基)丙烯酸之單元之量較佳為1質量%以上且95質量%以下，更佳為10質量%以上且50質量%以下。包含源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元之量較佳為1質量%以上且95質量%以下，更佳為30質量%以上且70質量%以下。The amount of the unit derived from (meth)acrylic acid in the resin containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylate containing a group having an alicyclic epoxy group Preferably it is 1 mass % or more and 95 mass % or less, More preferably, it is 10 mass % or more and 50 mass % or less. In a resin containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylate containing a group having an alicyclic epoxy group, the 1 mass % or more and 95 mass % or less are preferable, and, as for the quantity of the unit of the (meth)acrylate of a group, 30 mass % or more and 70 mass % or less are more preferable.
包含源自(甲基)丙烯酸之單元與源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的選自(甲基)丙烯酸及(甲基)丙烯酸酯中之1種以上之單體之聚合物之中，較佳為包含源自(甲基)丙烯酸之單元、源自含有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂。1 selected from the group consisting of (meth)acrylic acid and (meth)acrylate containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylate containing a group having an alicyclic epoxy group Among the polymers of one or more monomers, those containing units derived from (meth)acrylic acid, units derived from (meth)acrylates containing an alicyclic hydrocarbon group, and those derived from units containing an alicyclic hydrocarbon group Resin of epoxy group-based (meth)acrylate unit.
包含源自(甲基)丙烯酸之單元、源自含有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自(甲基)丙烯酸之單元之量較佳為1質量%以上且95質量%以下，更佳為10質量%以上且50質量%以下。包含源自(甲基)丙烯酸之單元、源自含有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自含有脂環式烴基之(甲基)丙烯酸酯之單元之量較佳為1質量%以上且95質量%以下，更佳為10質量%以上且70質量%以下。包含源自(甲基)丙烯酸之單元、源自含有脂環式烴基之(甲基)丙烯酸酯之單元、及源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元的樹脂中，樹脂中之源自含有具有脂環式環氧基之基之(甲基)丙烯酸酯之單元之量較佳為1質量%以上且95質量%以下，更佳為30質量%以上且80質量%以下。Contains a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylate containing an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylate containing a group containing an alicyclic epoxy group In the resin of , the amount of the unit derived from (meth)acrylic acid in the resin is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. Contains a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylate containing an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylate containing a group containing an alicyclic epoxy group In the resin, the amount of the unit derived from the alicyclic hydrocarbon group-containing (meth)acrylate in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 70% by mass or less . Contains a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylate containing an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylate containing a group containing an alicyclic epoxy group In the resin of , the amount of the unit derived from the (meth)acrylate containing a group having an alicyclic epoxy group in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 80% by mass or less.
(E)鹼可溶性樹脂之質量平均分子量(Mw：基於凝膠滲透層析法(GPC)之聚苯乙烯換算所獲得之測定值。於本說明書中相同)較佳為2000以上且200000以下，更佳為2000以上且18000以下。藉由設為上述範圍，存在容易實現感光性組合物於成膜能力、曝光後之顯影性之間之均衡性之傾向。(E) The mass-average molecular weight of the alkali-soluble resin (Mw: a measured value obtained in terms of polystyrene by gel permeation chromatography (GPC). The same applies in this specification) is preferably 2,000 or more and 200,000 or less, and more Preferably it is 2000 or more and 18000 or less. By setting it as the said range, there exists a tendency for the balance between the film-forming ability and the developability after exposure of the photosensitive composition to be easily achieved.
於感光性組合物包含(E)鹼可溶性樹脂等樹脂之情形時，感光性組合物中之(E)鹼可溶性樹脂等樹脂之含量相對於感光性組合物中之溶劑以外之成分之質量之合計，較佳為15質量%以上且95質量%以下，更佳為35質量%以上且85質量%以下，尤佳為50質量%以上且70質量%以下。When the photosensitive composition contains resins such as (E) alkali-soluble resin, the total content of resins such as (E) alkali-soluble resin in the photosensitive composition relative to the mass of components other than the solvent in the photosensitive composition , preferably 15 mass % or more and 95 mass % or less, more preferably 35 mass % or more and 85 mass % or less, and particularly preferably 50 mass % or more and 70 mass % or less.
＜其他成分＞ 第1態樣之感光性組合物視需要亦可含有各種添加劑。具體而言，可例示：溶劑、增感劑、硬化促進劑、光交聯劑、分散助劑、填充劑、填料、密接促進劑、矽烷偶合劑、抗靜電劑、抗氧化劑、紫外線吸收劑、抗凝集劑、熱聚合抑制劑、塑化劑、阻燃劑、消泡劑、調平劑、填料、增黏劑、觸變性賦予劑、界面活性劑等。<Other components> The photosensitive composition of the 1st aspect may contain various additives as needed. Specifically, a solvent, a sensitizer, a hardening accelerator, a photocrosslinking agent, a dispersing aid, a filler, a filler, an adhesion accelerator, a silane coupling agent, an antistatic agent, an antioxidant, an ultraviolet absorber, Anti-agglomeration agent, thermal polymerization inhibitor, plasticizer, flame retardant, defoamer, leveling agent, filler, tackifier, thixotropy imparting agent, surfactant, etc.
第1態樣之感光性組合物可使各成分分散・溶解於溶劑中而製備，但若上述(B)成分為液狀，則亦可不使用溶劑。於包含溶劑之情形時，作為感光性組合物中使用之溶劑，例如可列舉：乙二醇單甲醚、乙二醇單***、乙二醇正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單***等(聚)伸烷基二醇單烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等(聚)伸烷基二醇單烷基醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲基***、二乙二醇二***、四氫呋喃等其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等乳酸烷基酯類；2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3-甲基-3-甲氧基丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類等。該等溶劑可單獨使用，亦可將2種以上組合使用。The photosensitive composition of the first aspect can be prepared by dispersing and dissolving each component in a solvent, but if the component (B) is in a liquid state, a solvent may not be used. When a solvent is included, the solvent used in the photosensitive composition includes, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, and diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol Methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionate methyl ester, 2- Alkyl lactate such as ethyl hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxy propionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methyl butyrate, 3-methyl-3-methoxy acetate Butyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isobutyl acetate Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetone Methyl acetate, ethyl acetate, ethyl 2-oxybutyrate and other esters; Aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide Amines such as amines, N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more.
上述溶劑之中，丙二醇單甲醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單***乙酸酯、二乙二醇二甲醚、二乙二醇甲基***(MEDG)、環己酮、乙酸3-甲氧基丁酯(MBA)對上述(A)成分及(B)成分顯示出優異之溶解性、且可使上述(D)成分之分散性變得良好，因此較佳，尤佳為使用丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯。溶劑根據感光性組合物之用途而適當決定即可，作為一例，可列舉：相對於感光性組合物中之溶劑以外之成分之質量之合計100質量份為50質量份以上且900質量份以下左右。Among the above-mentioned solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether (MEDG), cyclohexanone, and 3-methoxybutyl acetate (MBA) show excellent solubility for the above-mentioned (A) components and (B) components, and can disperse the above-mentioned (D) components Since the property becomes favorable, it is preferable, and it is especially preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. The solvent may be appropriately determined according to the application of the photosensitive composition. As an example, it is about 50 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the total mass of the components other than the solvent in the photosensitive composition. .
作為第1態樣之感光性組合物中使用之熱聚合抑制劑，例如可列舉：對苯二酚、對苯二酚單***等。又，作為消泡劑，可例示：聚矽氧系、氟系等之化合物，作為界面活性劑，可例示：陰離子系、陽離子系、非離子系等之化合物。As a thermal polymerization inhibitor used for the photosensitive composition of the 1st aspect, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. Moreover, as a defoaming agent, the compound, such as a polysiloxane type, a fluorine type, can be illustrated, and as a surfactant, an anionic type, a cation type, a nonionic type compound, etc. can be illustrated.
[感光性組合物之製備方法] 第1態樣之感光性組合物可藉由將上述各成分均勻攪拌、混合，使之均勻溶解、分散後，視需要利用0.2 μm以下之膜濾器、0.5 μm以上且1 μm以下之膜濾器等過濾器進行過濾而製備。[Preparation method of photosensitive composition] The photosensitive composition of the first aspect can be uniformly dissolved and dispersed by uniformly stirring and mixing the above-mentioned components, and then using a membrane filter of 0.2 μm or less, 0.5 μm or less, if necessary. It is prepared by filtration with a filter such as a membrane filter of 1 μm or more.
≪硬化物形成方法、及硬化物≫ 硬化物形成方法除使用上述感光性組合物以外，與先前使用感光性組合物形成硬化物之硬化物形成方法相同。≪Cured product formation method, and hardened product≫ The hardened product formation method is the same as the hardened product formation method which used the photosensitive composition to form the hardened product previously except using the said photosensitive composition.
使用上述感光性組合物形成硬化物之方法並無特別限制，可自先前採用之方法中適當選擇。硬化物藉由感光性組合物塗佈時之塗膜形狀之控制、或位置選擇性曝光與顯影之組合，作為所需形狀之成形體而形成。作為適宜之硬化物形成方法，可列舉包括使用上述感光性組合物形成塗膜之塗膜形成步驟與對上述塗膜進行曝光之曝光步驟之方法。於位置選擇性地進行曝光之情形時，利用顯影液將經曝光之塗膜進行顯影，而可獲得經圖案化之硬化物。The method of forming a hardened|cured material using the said photosensitive composition is not specifically limited, It can select suitably from the method previously used. The cured product is formed as a molded body of a desired shape by controlling the shape of the coating film at the time of coating the photosensitive composition, or by combining the position-selective exposure and development. As a suitable hardened|cured material formation method, the method including the coating-film formation process of forming a coating film using the said photosensitive composition, and the exposure process of exposing the said coating film can be mentioned. In the case of position-selective exposure, the exposed coating film is developed with a developer to obtain a patterned cured product.
首先，於塗膜形成步驟中，例如使用輥式塗佈機、反向塗佈機、棒式塗佈機等接觸轉印型塗佈裝置或旋轉器(旋轉式塗佈裝置)、分注器、噴墨機、噴霧器、網版印刷機、淋幕式平面塗裝機等非接觸型塗佈裝置，於應形成硬化物之基板上塗佈本發明之感光性組合物，視需要藉由乾燥(預烘烤)去除溶劑而形成塗膜。 再者，為方便起見，亦將遍佈於基板上之液滴、或嵌入至具有凹凸之基板之凹部內之感光性組合物、或填充至模具之凹部內之感光性組合物等稱為「塗膜」。First, in the coating film forming step, for example, a contact transfer type coating apparatus such as a roll coater, a reverse coater, and a bar coater, a spinner (rotary coater), a dispenser, etc. are used. , inkjet machine, sprayer, screen printing machine, curtain-type flat coating machine and other non-contact coating devices, coat the photosensitive composition of the present invention on the substrate that should form the hardened product, and dry it as needed (Pre-baking) The solvent is removed to form a coating film. Furthermore, for the sake of convenience, the droplets spread on the substrate, or the photosensitive composition embedded in the concave portion of the substrate with unevenness, or the photosensitive composition filled in the concave portion of the mold, etc. are also referred to as "" coating".
繼而，將所形成之塗膜供於曝光步驟。於曝光步驟中，光源並無特別限定，例如可列舉：高壓水銀燈、超高壓水銀燈、氙氣燈、碳弧燈、LED等。使用此種光源，對塗膜照射ArF準分子雷射、KrF準分子雷射、F2 準分子雷射、極紫外線(EUV)、真空紫外線(VUV)、電子束、X射線、軟X射線、g射線、i射線、h射線、j射線、k射線等放射線或電磁波而將塗膜進行曝光。對塗膜之曝光可經由負型光罩而位置選擇性地進行。曝光量根據感光性組合物之組成而異，例如較佳為10 mJ/cm2 以上且2000 mJ/cm2 以下，更佳為100 mJ/cm2 以上且1500 mJ/cm2 以下，進而較佳為500 mJ/cm2 以上且1200 mJ/cm2 以下。 就節約能源或減輕環境負荷之觀點而言，作為光源，較佳為LED。作為利用LED之曝光中採用之波長，例如可列舉365～405 nm、更具體而言385 nm、395 nm、405 nm等UV區域者。一般而言，利用LED所照射之能量線量容易變少。然而，以上說明之感光性組合物於一併含有上述(A)光聚合起始劑與(C)增感劑之情形時感度優異，因此即便使用LED作為光源進行曝光，亦會充分硬化，可有效獲得具有良好特性之硬化物。Next, the formed coating film is subjected to an exposure step. In the exposure step, the light source is not particularly limited, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an LED. Using this light source, the coating film is irradiated with ArF excimer laser, KrF excimer laser, F 2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, The coating film is exposed to radiation or electromagnetic waves such as g-rays, i-rays, h-rays, j-rays, and k-rays. Exposure to the coating film can be performed positionally via a negative mask. The exposure amount varies depending on the composition of the photosensitive composition, but for example, it is preferably 10 mJ/cm 2 or more and 2000 mJ/cm 2 or less, more preferably 100 mJ/cm 2 or more and 1500 mJ/cm 2 or less, and more preferably It is 500 mJ/cm 2 or more and 1200 mJ/cm 2 or less. From the viewpoint of saving energy or reducing environmental load, LEDs are preferable as the light source. As a wavelength used for exposure by LED, for example, 365-405 nm, More specifically, those in the UV region, such as 385 nm, 395 nm, and 405 nm, are mentioned. Generally speaking, the amount of energy rays irradiated by LEDs tends to decrease. However, since the photosensitive composition described above is excellent in sensitivity when it contains the above-mentioned (A) photopolymerization initiator and (C) sensitizer together, even if an LED is used as a light source for exposure, it is sufficiently cured, and it is possible to Effectively obtain a hardened product with good properties.
視需要將經曝光之塗膜進行顯影。 上述感光性組合物於曝光後在鹼性顯影液中不易過度溶解。因此，藉由使用上述感光性組合物，容易形成具有以曝光部作為凸部、以未曝光部作為凹部之良好形狀之經圖案化之硬化物。The exposed coating film is developed if necessary. The said photosensitive composition is hard to melt|dissolve excessively in an alkaline developing solution after exposure. Therefore, by using the said photosensitive composition, it becomes easy to form the patterned hardened|cured material which has the favorable shape which has an exposed part as a convex part, and has an unexposed part as a recessed part.
於顯影步驟中，利用顯影液將經曝光之塗膜進行顯影，藉此形成具有所需形狀圖案之硬化物。顯影方法並無特別限定，可採用浸漬法、噴霧法等。作為顯影液之具體例，可列舉：單乙醇胺、二乙醇胺、三乙醇胺等有機系者、或氫氧化鈉、氫氧化鉀、碳酸鈉、氨、四級銨鹽等之水溶液。In the developing step, the exposed coating film is developed with a developing solution, thereby forming a cured product having a desired shape pattern. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developer include organic-based ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
進而，視需要可對曝光後之硬化物、或顯影後之經圖案化之硬化物實施後烘烤而進一步推進加熱硬化。後烘烤之溫度較佳為150℃以上且270℃以下。Furthermore, if necessary, post-baking can be performed on the cured product after exposure or the patterned cured product after development to further advance heat curing. The post-baking temperature is preferably 150°C or higher and 270°C or lower.
硬化物係使用上述感光性組合物所形成。上述硬化物較佳為絕緣膜、或積層於光阻劑膜上之保護膜。於感光性組合物不含著色劑(D)而透明之情形時，上述硬化物於製成厚度3.5 μm(光程長度3.5 μm)之試樣時對波長400 nm以上且650 nm以下之範圍內之光線之透過率之平均值通常為90%以上，較佳為93%以上，更佳為95%以上。如此，上述硬化物之透過率優異，因此適宜作為內嵌式觸控面板方式之液晶顯示裝置、UHA(Ultra High Aperture，超高開口率)面板等需要透明性優異之絕緣膜之顯示裝置用絕緣膜使用。The cured product is formed using the above-mentioned photosensitive composition. The above-mentioned cured product is preferably an insulating film or a protective film laminated on the photoresist film. In the case where the photosensitive composition does not contain the colorant (D) and is transparent, when the cured product is prepared as a sample with a thickness of 3.5 μm (optical path length of 3.5 μm), the wavelength is 400 nm or more and 650 nm or less. The average light transmittance is usually above 90%, preferably above 93%, more preferably above 95%. In this way, the above-mentioned cured product has excellent transmittance, so it is suitable as an insulation for display devices that require an insulating film with excellent transparency, such as a liquid crystal display device of an in-cell touch panel method and a UHA (Ultra High Aperture) panel. membrane use.
又，於使用上述感光性組合物經由半色調光罩進行曝光而形成經圖案化之硬化膜之情形時，於所形成之經圖案化之硬化物中，不僅可使全色調曝光部與半色調曝光部之間存在充分之高度差，且可確保半色調曝光部具有充分之高度。因此，使用上述感光性組合物所形成之硬化膜適宜用作液晶顯示面板等顯示面板中所使用之間隔件、尤其是黑間隔柱。Moreover, when a patterned cured film is formed by exposing the above-mentioned photosensitive composition through a halftone mask, in the formed patterned cured product, not only the full-tone exposed part and the halftone can be made There is a sufficient height difference between the exposure portions, and a sufficient height of the halftone exposure portion can be ensured. Therefore, the cured film formed using the said photosensitive composition is suitable as a spacer used for display panels, such as a liquid crystal display panel, especially a black spacer.
≪感光性接著劑、及接著方法≫ 上述感光性組合物可較佳地用作感光性接著劑。於使用感光性組合物作為感光性接著劑之情形時，基於賦予視認性或賦予遮光性之目的，感光性組合物可包含亦可不含著色劑(D)。 如上所述，作為感光性接著劑使用之感光性組合物之硬化性(尤其是表面硬化性)優異。因此，於使用上述感光性組合物作為感光性接著劑之情形時，藉由曝光，接著劑快速硬化。 尤其於形成膜厚1 μm以上且500 μm以下(較佳為膜厚3 μm以上且200 μm以下，更佳為膜厚5 μm以上且100 μm以下，進而較佳為膜厚8 μm以上且50 μm以下)之接著劑層進行接著之情形時，適宜使用上述感光性接著劑。≪Photosensitive Adhesive and Adhesion Method≫ The above-mentioned photosensitive composition can be preferably used as a photosensitive adhesive. When a photosensitive composition is used as a photosensitive adhesive, the photosensitive composition may contain or may not contain a colorant (D) for the purpose of imparting visibility or imparting light-shielding properties. As described above, the photosensitive composition used as a photosensitive adhesive is excellent in curability (especially, surface curability). Therefore, when using the said photosensitive composition as a photosensitive adhesive agent, by exposure, an adhesive agent hardens rapidly. In particular, it is formed with a film thickness of 1 μm or more and 500 μm or less (preferably a film thickness of 3 μm or more and 200 μm or less, more preferably a film thickness of 5 μm or more and 100 μm or less, and still more preferably a film thickness of 8 μm or more and 50 μm or less. In the case where the adhesive layer of (μm or less) is bonded, the above-mentioned photosensitive adhesive is preferably used.
尤其若將有機EL或液晶顯示元件等之面板用密封材料、製造汽車、機車、自行車、軌道車輛、飛機、船舶、各種建築用構件等時或利用產業用機器人製造各種製品時之焊接、螺固、釘固等接合作業更替為使用上述感光性接著劑之接著，則具有助益於所接合之最終製品之輕量化、或避免於藉由螺固或釘固進行接合時因金屬疲勞等引起之螺絲或螺釘之斷裂、或避免於接合異種金屬之情形時因電池硬化引起之腐蝕等各種優點。In particular, when sealing materials for panels such as organic EL or liquid crystal display elements, when manufacturing automobiles, locomotives, bicycles, rail vehicles, airplanes, ships, various building components, etc., or when using industrial robots to manufacture various products, welding and screwing , nailing and other joining operations are replaced by the use of the above-mentioned photosensitive adhesive, which is beneficial to the weight reduction of the final product to be joined, or avoids metal fatigue when joining by screwing or nailing. Various advantages such as breakage of screws or screws, or avoidance of corrosion due to battery hardening in the case of joining dissimilar metals.
使用上述感光性接著劑之接著方法並無特別限定。於接著各種物品中之被接著面之方法中，可使用上述感光性接著劑。 作為典型之接著方法，可列舉如下方法，其包括： 於對向之被接著面之一者或兩者形成包含感光性接著劑之接著劑層；及藉由曝光使接著劑層硬化。The bonding method using the above-mentioned photosensitive adhesive is not particularly limited. The above-mentioned photosensitive adhesive can be used in the method of bonding the surface to be bonded in various articles. As a typical bonding method, a method including: forming an adhesive layer containing a photosensitive adhesive on one or both of the opposing surfaces to be bonded; and hardening the adhesive layer by exposure.
包含感光性接著劑之接著劑層之形成方法並無特別限定。典型而言，於對向之被接著面之一者或兩者塗佈感光性接著劑而形成接著劑層。 又，亦可於被接著面之間形成有所需寬度之間隙之狀態下，向間隙內注入感光性接著劑。The formation method of the adhesive layer containing a photosensitive adhesive is not specifically limited. Typically, an adhesive layer is formed by applying a photosensitive adhesive to one or both of the opposing surfaces to be bonded. In addition, the photosensitive adhesive may be injected into the gap in a state in which a gap of a desired width is formed between the surfaces to be bonded.
接著對象之物品之數量可為1個，亦可為2個以上之複數個。於接著對象之物品之材質具有可撓性、柔軟性之情形時，存在接著對象之物品之數量為1個之情況。作為接著對象之物品之數量為1個之情形，例如可列舉將1片矩形之塑膠板捲曲成圓筒狀，對塑膠板之接縫部分進行接著之情況。The number of the object to be followed may be one, or a plurality of two or more. When the material of the object to be attached has flexibility and softness, there is a case where the number of objects to be attached is one. When the number of articles to be bonded is one, for example, a rectangular plastic sheet is rolled into a cylindrical shape, and the joint portion of the plastic sheet is bonded.
曝光係藉由與上述形成硬化膜之情形相同之方式進行。於接著對象之物品透明之情形時，對接著劑層照射曝光之光之方法並無特別限制。於該情形時，可透過接著對象之物品對接著劑層照射曝光之光，亦可以使曝光之光自接著劑層之端面射入之方式照射曝光之光。 於接著對象之物品包含金屬之類的不透明材質之情形時，以使曝光之光自接著劑層之端面射入之方式進行曝光。Exposure is performed by the same method as the case of forming a cured film mentioned above. When the article to be bonded is transparent, the method of irradiating the adhesive layer with exposure light is not particularly limited. In this case, the exposure light may be irradiated to the adhesive layer through the article to be bonded, or the exposure light may be irradiated by allowing the exposure light to enter from the end face of the adhesive layer. When the object to be bonded contains opaque materials such as metal, exposure is performed in such a way that the exposure light is injected from the end face of the adhesive layer.
≪其他用途≫ 上述感光性組合物可用於半導體加工或玻璃加工等中之形成蝕刻遮罩等先前使用感光性組合物之各種用途。 又，上述感光性組合物亦可應用於包括形成感光性組合物層之步驟之利用所謂3D印刷的立體造形法中之感光性組合物層之形成。 3D印刷中之藉由曝光硬化之層之積層係有關使用感光性組合物所形成之硬化物之層之所謂自接著。因此，使用包含上述感光性組合物之感光性接著劑之利用3D印刷之立體造形法亦作為一態樣包含於使用感光性接著劑之上述接著方法中。 由於上述感光性組合物之硬化性(尤其是表面硬化性)優異，故而即便增大感光性組合物層之膜厚，感光性組合物層亦可於短時間內藉由曝光而良好地硬化。因此，若將上述感光性組合物應用於利用3D印刷之立體造形，則藉由增大感光性組合物層之膜厚，可減少感光性組合物層之積層次數與曝光次數，可於短時間內製作所需形狀之立體造形物。 [實施例]≪Other Applications≫ The above-mentioned photosensitive composition can be used in various applications for which the photosensitive composition was previously used, such as formation of an etching mask in semiconductor processing and glass processing. In addition, the above-mentioned photosensitive composition can also be applied to the formation of the photosensitive composition layer in the three-dimensional modeling method by so-called 3D printing including the step of forming the photosensitive composition layer. The lamination of a layer cured by exposure in 3D printing is a so-called self-adhesion of a layer of a cured product formed using a photosensitive composition. Therefore, the three-dimensional modeling method by 3D printing using the photosensitive adhesive containing the above-mentioned photosensitive composition is also included in the above-mentioned bonding method using the photosensitive adhesive as one aspect. Since the said photosensitive composition is excellent in hardenability (especially surface hardenability), even if it increases the film thickness of the photosensitive composition layer, the photosensitive composition layer can be hardened favorably by exposure in a short time. Therefore, if the above-mentioned photosensitive composition is applied to three-dimensional modeling by 3D printing, by increasing the film thickness of the photosensitive composition layer, the number of laminations and exposure times of the photosensitive composition layer can be reduced, and the number of times of lamination and exposure of the photosensitive composition layer can be reduced. Three-dimensional objects of the desired shape are made inside. [Example]
以下，例示實施例而更具體地說明本發明，但本發明之範圍並不限定於該等實施例。Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited to these examples.
[合成例1] 合成下述式所表示之化合物1。 [化22]
(9,9-二正丙基茀之合成) 使茀6.64 g(40 mmol)溶解於27 mL之THF(tetrahydrofuran，四氫呋喃)。於氮氣氛圍下於所獲得之溶液中緩慢地添加第三丁醇鉀0.12 g(1.1 mmol)、1-溴丙烷12.30 g(100 mmol)、及濃度50質量%之氫氧化鈉水溶液27 mL。將所獲得之混合物於80℃下攪拌3小時而進行反應。於反應後之混合物中添加乙酸乙酯33 g及水33 g後，分液為有機相與水相。利用無水硫酸鈉將所獲得之有機相進行脫水後，使用旋轉蒸發器自有機相中去除溶劑，而獲得9,9-二正丙基茀8.32 g(產率83%)。(Synthesis of 9,9-di-n-propyl fluoride) 6.64 g (40 mmol) of fluoride was dissolved in 27 mL of THF (tetrahydrofuran). Under a nitrogen atmosphere, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of an aqueous sodium hydroxide solution having a concentration of 50 mass % were slowly added to the obtained solution. The obtained mixture was stirred at 80°C for 3 hours to react. After adding 33 g of ethyl acetate and 33 g of water to the mixture after the reaction, the organic phase and the aqueous phase were separated. After the obtained organic phase was dehydrated with anhydrous sodium sulfate, the solvent was removed from the organic phase using a rotary evaporator to obtain 8.32 g of 9,9-di-n-propyl fluoride (yield 83%).
(2-(2-氟苯甲醯基)-9,9-二正丙基茀之合成) 使9,9-二正丙基茀10.02 g(40 mmol)及氯化鋁5.87 g(44 mmol)溶解於二氯甲烷40 mL。一面將二氯甲烷溶液於冰浴中冷卻，一面將2-氟苯甲醯氯6.98 g(44 mmol)以5℃以下之溫度滴加至二氯甲烷溶液中。滴加後，一面攪拌反應液，一面歷時1小時將反應液之溫度升至室溫，繼而，於室溫下繼續反應3小時。(Synthesis of 2-(2-fluorobenzyl)-9,9-di-n-propyl fluoride) 10.02 g (40 mmol) of 9,9-di-n-propyl fluoride and 5.87 g (44 mmol) of aluminum chloride were prepared ) was dissolved in 40 mL of dichloromethane. While cooling the dichloromethane solution in an ice bath, 6.98 g (44 mmol) of 2-fluorobenzyl chloride was added dropwise to the dichloromethane solution at a temperature below 5°C. After the dropwise addition, while stirring the reaction solution, the temperature of the reaction solution was raised to room temperature over 1 hour, and then the reaction was continued at room temperature for 3 hours.
將所獲得之反應液滴加至裝有冰水300 mL之燒杯中。將燒杯中之混合物移至分液漏斗後，於分液漏斗中添加乙酸乙酯200 mL，將生成物萃取至有機相中。分離有機相後，進而利用乙酸乙酯100 mL萃取水相中之生成物。將經2次萃取所獲得之有機相利用10%碳酸鈉水溶液300 mL清洗後，再利用水300 mL清洗。將清洗後之有機相利用無水硫酸鎂加以乾燥後，使用旋轉蒸發器自有機相中蒸餾去除溶劑，而獲得油狀物質。藉由矽膠管柱層析法(展開溶劑，乙酸乙酯：正己烷＝1：1(質量比))精製油狀物質，而獲得淡黃色固體(2-(2-氟苯甲醯基)-9,9-二正丙基茀)14.20 g(產率95%)。The obtained reaction was added dropwise to a beaker containing 300 mL of ice water. After the mixture in the beaker was transferred to a separatory funnel, 200 mL of ethyl acetate was added to the separatory funnel, and the resultant was extracted into the organic phase. After separating the organic phase, the product in the aqueous phase was extracted with 100 mL of ethyl acetate. The organic phase obtained by twice extraction was washed with 300 mL of 10% sodium carbonate aqueous solution, and then washed with 300 mL of water. After drying the organic phase after washing with anhydrous magnesium sulfate, the solvent was distilled off from the organic phase using a rotary evaporator to obtain an oily substance. The oily substance was purified by silica gel column chromatography (developing solvent, ethyl acetate:n-hexane=1:1 (mass ratio)) to obtain a pale yellow solid (2-(2-fluorobenzyl)- 9,9-di-n-propyl fluoride) 14.20 g (yield 95%).
(2-氟苯基(9,9-二正丙基茀-2-基)酮肟酯之合成) 使所獲得之淡黃色固體7.45 g(20 mmol)與鹽酸羥胺1.5 g(21 mmol)溶解於乙醇100 mL後，使乙醇溶液進行2小時回流。自回流後之反應液中蒸餾去除乙醇後，對殘渣進行水洗。使洗淨之殘渣溶解於乙酸乙酯後，將乙酸乙酯溶液利用硫酸鎂加以乾燥。使用旋轉蒸發器，自乾燥後之乙酸乙酯溶液中去除乙酸乙酯，而獲得作為殘渣之肟體(2-氟苯基(9,9-二正丙基茀-2-基)酮肟)。使所獲得之肟體溶解於THF 60 mL後，於THF中添加乙醯氯(3.45 g，44 mmol)，於攪拌下進行反應。反應後，於室溫下於反應液中滴加三乙基胺(4.7 g，46 mmol)。於滴加之同時確認到鹽之沈澱。將添加有三乙基胺之反應液攪拌2小時後，於反應液中添加水40 ml。繼而，利用乙酸乙酯40 mL萃取反應液中之生成物。將有機相利用水40 mL清洗2次，繼而利用飽和碳酸鉀水溶液40 mL清洗2次。將清洗後之有機相利用硫酸鎂加以乾燥後，使用旋轉蒸發器自有機相中去除溶劑而獲得殘渣。藉由矽膠管柱層析法(展開溶劑，乙酸乙酯：正己烷＝1：1(質量比))精製殘渣，而獲得淡黃色固體(2-氟苯基(9,9-二正丙基茀-2-基)酮肟酯)6.79 g(15.80 mmol，產率79%)。(Synthesis of 2-fluorophenyl(9,9-di-n-propylpyridin-2-yl)ketoxime ester) 7.45 g (20 mmol) of the obtained pale yellow solid were dissolved in 1.5 g (21 mmol) of hydroxylamine hydrochloride After adding 100 mL of ethanol, the ethanol solution was refluxed for 2 hours. After ethanol was distilled off from the reaction liquid after reflux, the residue was washed with water. The washed residue was dissolved in ethyl acetate, and the ethyl acetate solution was dried over magnesium sulfate. Using a rotary evaporator, ethyl acetate was removed from the dried ethyl acetate solution to obtain an oxime (2-fluorophenyl(9,9-di-n-propylpyridin-2-yl)ketoxime) as a residue. . After dissolving the obtained oxime in 60 mL of THF, acetyl chloride (3.45 g, 44 mmol) was added to THF, and the reaction was carried out with stirring. After the reaction, triethylamine (4.7 g, 46 mmol) was added dropwise to the reaction solution at room temperature. Precipitation of salt was confirmed at the same time as the dropwise addition. After stirring the reaction liquid to which triethylamine was added for 2 hours, 40 ml of water was added to the reaction liquid. Then, the product in the reaction solution was extracted with 40 mL of ethyl acetate. The organic phase was washed twice with 40 mL of water, and then twice with 40 mL of saturated aqueous potassium carbonate solution. After drying the organic phase after washing with magnesium sulfate, the solvent was removed from the organic phase using a rotary evaporator to obtain a residue. The residue was purified by silica gel column chromatography (developing solvent, ethyl acetate:n-hexane=1:1 (mass ratio)) to obtain a pale yellow solid (2-fluorophenyl(9,9-di-n-propyl) Plen-2-yl)ketoxime ester) 6.79 g (15.80 mmol, 79% yield).
(化合物1之合成) 將所獲得之淡黃色固體6.44 g(15.0 mmol)添加至二甲基亞碸(DMSO)(85 mL)中，對所獲得者添加K2 CO3 6.23 g(45.0 mmol)及2,2,3,3-四氟-1-丙醇2.05 g(15.5 mmol)。將上述反應混合物加熱至40℃，攪拌一晩。冷卻至室溫後，將所獲得之反應液滴加至裝有冰水150 mL之燒杯中。將燒杯中之混合物移至分液漏斗後，於分液漏斗中添加乙酸乙酯100 mL，將生成物萃取至有機相中。分離有機相後，進而利用乙酸乙酯50 mL萃取水相中之生成物。將經2次萃取所獲得之有機相利用10質量%碳酸鈉水溶液150 mL清洗後，再利用水150 mL清洗。將清洗後之有機相利用無水硫酸鎂加以乾燥後，使用旋轉蒸發器自有機相中蒸餾去除溶劑，而獲得淡黃色固體之化合物1 6.07 g(11.2 mmol，產率75%)。(Synthesis of Compound 1) 6.44 g (15.0 mmol) of the obtained pale yellow solid was added to dimethylsulfoxide (DMSO) (85 mL), and 6.23 g (45.0 mmol) of K 2 CO 3 was added to the obtained and 2,2,3,3-tetrafluoro-1-propanol 2.05 g (15.5 mmol). The above reaction mixture was heated to 40°C and stirred overnight. After cooling to room temperature, the obtained reaction was added dropwise to a beaker containing 150 mL of ice water. After the mixture in the beaker was transferred to a separatory funnel, 100 mL of ethyl acetate was added to the separatory funnel, and the resultant was extracted into the organic phase. After separating the organic phase, the product in the aqueous phase was extracted with 50 mL of ethyl acetate. The organic phase obtained by the two extractions was washed with 150 mL of a 10% by mass sodium carbonate aqueous solution, and then washed with 150 mL of water. The washed organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off from the organic phase using a rotary evaporator to obtain 6.07 g (11.2 mmol, 75% yield) of compound 1 as a pale yellow solid.
化合物1之1 H-NMR之測定結果如下所示。1 H-NMR (600 MHz, CDCl3 , ppm) : 7.65-7.73 (m, 2H), 7.63 (m, 1H), 7.42-7.53 (m, 1H), 7.15-7.38 (m, 6H), 7.00 (d, 1H), 5.60 (t, 1H), 4.30 (bs, 1H), 2.07 (s, 3H), 1.88 (m, 4H), 0.71 (m, 10H).The measurement results of 1 H-NMR of Compound 1 are shown below. 1 H-NMR (600 MHz, CDCl 3 , ppm) : 7.65-7.73 (m, 2H), 7.63 (m, 1H), 7.42-7.53 (m, 1H), 7.15-7.38 (m, 6H), 7.00 ( d, 1H), 5.60 (t, 1H), 4.30 (bs, 1H), 2.07 (s, 3H), 1.88 (m, 4H), 0.71 (m, 10H).
[合成例2] (化合物2之合成) [化23]
[合成例3] (化合物3之合成) [化24]
[實施例1～3及比較例1～3] 分別將下述表1中記載之種類及量之(A)成分、(B)成分及(C)成分均勻地混合，而獲得各實施例及比較例之感光性組合物。 於實施例1～3中，作為(A)光聚合起始劑，分別使用上述合成例中所獲得之化合物1～3。[Examples 1 to 3 and Comparative Examples 1 to 3] The types and amounts of component (A), component (B) and component (C) described in Table 1 below were uniformly mixed to obtain each of the examples and the The photosensitive composition of the comparative example. In Examples 1 to 3, the compounds 1 to 3 obtained in the above synthesis examples were used as the (A) photopolymerization initiator, respectively.
另一方面，於比較例1～3中，分別使用下述式所表示之比較化合物1～3。 [化25]
又，於各實施例及比較例中，作為上述式(1)所表示之化合物以外之其他光聚合起始劑(A')，使用下述式所表示之醯基氧化膦系光聚合起始劑化合物(A'-1)。 [化26]
於各實施例及比較例中，作為(B)光聚合性化合物，使用環氧丙烷改性新戊二醇二丙烯酸酯(商品名EBECRYL145；Daicel Allnex公司製造)。 作為(C)增感劑，使用2-異丙基-9H-硫𠮿
＜LED曝光(波長405 nm)及寬波段(broad-band)曝光下之黏性評價＞ 利用點滴器於基板上滴下1滴所獲得之感光性組合物後， 使用(1)市售之LED燈(波長405 nm)照射120秒，或 使用(2)曝光機(商品名TME-150RTO；TOPCON公司製造，光源：超高壓水銀燈)，以1000 mJ/cm2 對感光性組合物之液滴(膜厚10～20 μm)照射寬波段光。 針對曝光後之液滴，基於下述1～5之評價基準而評價黏性(發黏)。 1：未硬化。 2：存在固形物，但使用擦拭布可輕易擦除。 3：經擦拭布擦拭後仍有一部分附著於玻璃上。 4：雖有黏性，但液滴內部硬化。 5：幾乎無黏性。 將評價結果示於表1。<Viscosity evaluation under LED exposure (wavelength 405 nm) and broad-band exposure> After dropping 1 drop of the obtained photosensitive composition on the substrate with a dropper, (1) a commercially available LED lamp was used (wavelength 405 nm) for 120 seconds, or (2) exposure machine (trade name TME-150RTO; manufactured by TOPCON Corporation, light source: ultra-high pressure mercury lamp), at 1000 mJ/cm 2 to the droplet (film) of the photosensitive composition 10-20 μm thick) to irradiate broadband light. The droplet after exposure was evaluated for viscosity (tackiness) based on the following evaluation criteria of 1 to 5. 1: Not hardened. 2: There is solid matter, but it can be easily wiped off with a wiping cloth. 3: After being wiped with a wiping cloth, a part still adheres to the glass. 4: Although there is viscosity, the inside of the droplet is hardened. 5: Almost no stickiness. The evaluation results are shown in Table 1.
[表1]
根據表1所示之結果可知，於405 nm之LED曝光下，比較例1～3之硬化不充分，另一方面，實施例1～3雖有黏性，但硬化進行。 又，於寬波段曝光下，比較例1～3雖硬化進行，但仍有黏性，相對於此，實施例1～3中硬化充分進行而幾乎無黏性。From the results shown in Table 1, it can be seen that under the LED exposure of 405 nm, the curing of Comparative Examples 1 to 3 was insufficient. On the other hand, although the Examples 1 to 3 were sticky, the curing progressed. In addition, although the comparative examples 1-3 were hardened under broadband exposure, they were still sticky, whereas in Examples 1-3, hardening progressed sufficiently, and there was almost no stickiness.
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