TWI677524B - Colored photosensitive composition - Google Patents
Colored photosensitive composition Download PDFInfo
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- TWI677524B TWI677524B TW105121030A TW105121030A TWI677524B TW I677524 B TWI677524 B TW I677524B TW 105121030 A TW105121030 A TW 105121030A TW 105121030 A TW105121030 A TW 105121030A TW I677524 B TWI677524 B TW I677524B
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- 0 Cc1c(*I)cccc1 Chemical compound Cc1c(*I)cccc1 0.000 description 13
- GBYXBMVWUTWAHN-UHFFFAOYSA-N C=C(C(ONC1(CC(C2)C3)CC3CC2C1)=O)N Chemical compound C=C(C(ONC1(CC(C2)C3)CC3CC2C1)=O)N GBYXBMVWUTWAHN-UHFFFAOYSA-N 0.000 description 1
- FQJOMAYWNOVABJ-LLLYXHGFSA-N CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c(cc1)ccc1-c1ccccc1)=O)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O Chemical compound CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c(cc1)ccc1-c1ccccc1)=O)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O FQJOMAYWNOVABJ-LLLYXHGFSA-N 0.000 description 1
- CZRZCVZJAKTGSU-XVYOIFRPSA-N CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c(cc1)ccc1N1CC(c2cc([N+]([O-])=O)ccc2/C(/C(c(cc2)ccc2Sc(cc2)ccc2C(c2c(C)cccc2)=O)=O)=N/OC(C)=O)OCC1)=O)=O)/c(cc1)c(C)cc1[N+]([O-])=O)=O Chemical compound CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c(cc1)ccc1N1CC(c2cc([N+]([O-])=O)ccc2/C(/C(c(cc2)ccc2Sc(cc2)ccc2C(c2c(C)cccc2)=O)=O)=N/OC(C)=O)OCC1)=O)=O)/c(cc1)c(C)cc1[N+]([O-])=O)=O CZRZCVZJAKTGSU-XVYOIFRPSA-N 0.000 description 1
- VVDPCVVLMAZRAT-JCUPVDEDSA-N CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c1cc2ccccc2cc1)=O)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O Chemical compound CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c1cc2ccccc2cc1)=O)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O VVDPCVVLMAZRAT-JCUPVDEDSA-N 0.000 description 1
- FNLMLYBXRWLQFO-PNOGMODKSA-N CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c1ccccc1)=O)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O Chemical compound CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1C(c1ccccc1)=O)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O FNLMLYBXRWLQFO-PNOGMODKSA-N 0.000 description 1
- NVNZFGRFVDMAFQ-GYHWCHFESA-N CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1[N+]([O-])=O)=O)/c(cc1)c(C)cc1[N+]([O-])=O)=O Chemical compound CC(O/N=C(\C(c(cc1)ccc1Sc(cc1)ccc1[N+]([O-])=O)=O)/c(cc1)c(C)cc1[N+]([O-])=O)=O NVNZFGRFVDMAFQ-GYHWCHFESA-N 0.000 description 1
- ORPUSRKKPCICNB-GYHWCHFESA-N CC(O/N=C(\C(c(cc1)ccc1Sc1ccccc1)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O Chemical compound CC(O/N=C(\C(c(cc1)ccc1Sc1ccccc1)=O)/c(c(C)c1)ccc1[N+]([O-])=O)=O ORPUSRKKPCICNB-GYHWCHFESA-N 0.000 description 1
- LEQWYQASMALCDH-WCTVFOPTSA-N CCCC1(CCC)c2cc(C(/C(/CC3CCCCC3)=N\O)=O)ccc2-c2ccccc12 Chemical compound CCCC1(CCC)c2cc(C(/C(/CC3CCCCC3)=N\O)=O)ccc2-c2ccccc12 LEQWYQASMALCDH-WCTVFOPTSA-N 0.000 description 1
- SZJDGAGHSYBMKD-PBBVDAKRSA-N CCCC1(CCC)c2cc(C(/C(/c3c(C)cccc3)=N/O)=O)ccc2-c2ccccc12 Chemical compound CCCC1(CCC)c2cc(C(/C(/c3c(C)cccc3)=N/O)=O)ccc2-c2ccccc12 SZJDGAGHSYBMKD-PBBVDAKRSA-N 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N NC1CCCCC1 Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
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- 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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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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- C—CHEMISTRY; METALLURGY
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- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/56—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by doubly-bound oxygen atoms
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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- C07C2603/00—Systems containing at least three condensed rings
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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
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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Abstract
本發明提供一種能夠形成如下著色膜之著色感光性組合物，該著色膜為所需之色相且不含異物，難以自基板剝離；使用該著色感光性組合物形成之彩色濾光片；及具備該彩色濾光片之顯示裝置。 The present invention provides a colored photosensitive composition capable of forming a colored film having a desired hue and containing no foreign matter, which is difficult to peel from a substrate; a color filter formed using the colored photosensitive composition; and A display device for the color filter.
於包含(A)聚合性基材成分、(B)光聚合起始劑及(C)有彩色著色劑之著色感光性組合物中，使用下述式(1)之化合物作為(B)光聚合起始劑。式(1)中，Rb1為氫原子、硝基或1價有機基，Rb2及Rb3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，Rb2與Rb3亦可相互鍵結而形成環，Rb4為1價有機基，Rb5為氫原子、可具有取代基之碳原子數1~11之烷基或可具有取代基之芳基，w為0~4之整數，v為0或1。 In a colored photosensitive composition containing (A) a polymerizable substrate component, (B) a photopolymerization initiator, and (C) a colored colorant, a compound of the following formula (1) is used as (B) photopolymerization Initiator. In formula (1), R b1 is a hydrogen atom, a nitro group or a monovalent organic group, and R b2 and R b3 are a chain alkyl group which may have a substituent, a cyclic organic group or a hydrogen atom which may have a substituent, R b2 and R b3 may be bonded to each other to form a ring. R b4 is a monovalent organic group, R b5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. , W is an integer from 0 to 4, and v is 0 or 1.
Description
本發明係關於一種著色感光性組合物、使用該著色感光性組合物形成之彩色濾光片及具備彩色濾光片之顯示裝置。 The present invention relates to a colored photosensitive composition, a color filter formed using the colored photosensitive composition, and a display device provided with the color filter.
液晶顯示器等顯示裝置成為使液晶層夾持於相互對向並形成有成對電極之2片基板間之結構。並且，於一側之基板之內側形成有包含紅色(R)、綠色(G)、藍色(B)等各色之像素區域之彩色濾光片。於該彩色濾光片上，通常以區分紅色、綠色、藍色等各像素區域之方式形成有黑矩陣。 A display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates facing each other and a pair of electrodes is formed. In addition, a color filter including pixel regions of each color, such as red (R), green (G), and blue (B), is formed inside the substrate on one side. A black matrix is usually formed on the color filter to distinguish each pixel region such as red, green, and blue.
通常，彩色濾光片係藉由微影法而製造。即，首先於基板上塗佈黑色感光性樹脂組合物並使其乾燥後，進行曝光、顯影而形成黑矩陣。其次，對紅色、綠色、藍色等各色之感光性樹脂組合物反覆進行塗佈、乾燥、曝光及顯影，將各色之像素區域形成於特定位置而製造彩色濾光片。 Generally, a color filter is manufactured by a lithography method. That is, first, a black photosensitive resin composition is coated on a substrate and dried, and then exposed and developed to form a black matrix. Next, a photosensitive resin composition of each color, such as red, green, and blue, is repeatedly applied, dried, exposed, and developed, and pixel regions of each color are formed at specific positions to produce a color filter.
感光性樹脂組合物係以如下方式硬化：藉由作為其成分之一部分包含之光聚合起始劑之作用而使感光性樹脂組合物中所含的光聚合性化合物聚合。因此，已知感光性樹脂組合物之感度因其所含之光聚合起始劑之種類而受到影響。又，近年來，隨著液晶顯示器之生產台數增大而彩色濾光片之生產量亦增大，就進一步提昇生產性之觀點而言，需要能夠以低曝光量形成圖案之高感度之感光性樹脂組合物。於 此種狀況下，作為能夠使感光性樹脂組合物之感度良好之光聚合起始劑，於專利文獻1中，揭示有肟酯化合物等各種化合物。具體而言，於專利文獻1所記載之實施例中，揭示有下述結構式(a)~(d)所表示之化合物。 The photosensitive resin composition is cured in such a manner that a photopolymerizable compound contained in the photosensitive resin composition is polymerized by the action of a photopolymerization initiator contained as a part of the component. Therefore, it is known that the sensitivity of the photosensitive resin composition is affected by the type of the photopolymerization initiator contained therein. In addition, in recent years, as the number of liquid crystal displays has increased, the production volume of color filters has also increased. From the viewpoint of further improving productivity, a high-sensitivity photosensitivity capable of forming a pattern with a low exposure is required Sexual resin composition. to In such a situation, Patent Document 1 discloses various compounds such as an oxime ester compound as a photopolymerization initiator capable of improving the sensitivity of the photosensitive resin composition. Specifically, in Examples described in Patent Document 1, compounds represented by the following structural formulae (a) to (d) are disclosed.
[專利文獻1]日本專利特開2009-134289號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2009-134289
藉由包含有彩色著色劑與作為光聚合起始劑之上述結構式(a)~(d)所表示之化合物之組合物，而獲得能夠形成可用作彩色濾光片之著色膜的高感度之感光性樹脂組合物。 A composition containing a colorant and a compound represented by the above-mentioned structural formulae (a) to (d) as a photopolymerization initiator is used to obtain a high sensitivity capable of forming a coloring film that can be used as a color filter. A photosensitive resin composition.
但是，於使用包含有彩色著色劑及上述結構式(a)~(d)所表示之化合物之感光性樹脂組合物之情形時，存在著色膜之色相因形成著色 膜時的加熱而變更為所需之色相，或者容易於著色膜中產生微小之異物之問題。 However, when a photosensitive resin composition containing a coloring agent and a compound represented by the structural formulae (a) to (d) is used, the hue of the colored film may be colored due to the hue. When the film is heated, it changes to a desired hue, or it is easy to cause the problem of minute foreign matter in the colored film.
又，根據光聚合起始劑之種類，有時著色膜容易自基板剝離。 In addition, depending on the type of the photopolymerization initiator, the colored film may be easily peeled from the substrate.
本發明係鑒於以上之狀況而成者，其目的在於提供：一種能夠形成如下著色膜之著色感光性組合物，該著色膜為所需之色相且不含異物，難以自基板剝離；使用該著色感光性組合物形成之彩色濾光片；以及具備該彩色濾光片之顯示裝置。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a colored photosensitive composition capable of forming a colored film having a desired hue and containing no foreign matter, and which is difficult to peel off from a substrate; using the coloring A color filter formed of a photosensitive composition; and a display device including the color filter.
本發明者等人發現，藉由於包含(A)聚合性基材成分、(B)光聚合起始劑及(C)有彩色著色劑之著色感光性組合物中，使用特定結構之肟酯化合物作為(B)光聚合起始劑，能夠解決上述問題，從而達成本發明。具體而言，本發明提供以下者。 The present inventors have discovered that by using (A) a polymerizable substrate component, (B) a photopolymerization initiator, and (C) a colored coloring agent, a oxime ester compound having a specific structure is used. As the (B) photopolymerization initiator, the above-mentioned problems can be solved, and the present invention has been achieved. Specifically, the present invention provides the following.
本發明之第一態樣係一種著色感光性組合物，其包含(A)聚合性基材成分、(B)光聚合起始劑及(C)有彩色著色劑，(A)聚合性基材成分包含光聚合性化合物或光聚合性化合物與樹脂，(B)光聚合起始劑包含下式(1)：
(Rb1為氫原子、硝基或1價有機基，Rb2及Rb3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，Rb2與Rb3亦可相互鍵結而形成環，Rb4為1價有機基，Rb5為氫原子、可具有取代基之 碳原子數1~11之烷基或可具有取代基之芳基，w為0~4之整數，v為0或1) (R b1 is a hydrogen atom, a nitro group or a monovalent organic group, R b2 and R b3 are a chain alkyl group which may have a substituent, a cyclic organic group or a hydrogen atom which may have a substituent, R b2 and R b3 R b4 is a monovalent organic group, R b5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and w is 0 to An integer of 4 and v is 0 or 1)
所表示之化合物。 The indicated compound.
本發明之第二態樣係使用第一態樣之著色感光性組合物而形成之彩色濾光片。 A second aspect of the present invention is a color filter formed using the colored photosensitive composition of the first aspect.
本發明之第三態樣係具備第二態樣之彩色濾光片之顯示裝置。 A third aspect of the present invention is a display device having a second aspect of the color filter.
根據本發明，能夠提供：一種能夠形成如下著色膜之著色感光性組合物，該著色膜為所需之色相且不含異物，難以自基板剝離；使用該著色感光性組合物形成之彩色濾光片；及具備該彩色濾光片之顯示裝置。 According to the present invention, it is possible to provide a colored photosensitive composition capable of forming a colored film having a desired hue and containing no foreign matter, which is difficult to peel off from a substrate; and a color filter formed using the colored photosensitive composition. Sheet; and a display device having the color filter.
[著色感光性組合物] [Coloring photosensitive composition]
本發明之著色感光性組合物(以下，亦記作「感光性組合物」)至少含有(A)聚合性基材成分、(B)光聚合起始劑及(C)有彩色著色劑。以下，對本發明之感光性組合物中所含之各成分進行詳細地說明。 The colored photosensitive composition (hereinafter, also referred to as "photosensitive composition") of the present invention contains at least (A) a polymerizable substrate component, (B) a photopolymerization initiator, and (C) a colored colorant. Hereinafter, each component contained in the photosensitive composition of this invention is demonstrated in detail.
<(A)聚合性基材成分> <(A) polymerizable base material component>
(A)聚合性基材成分(以下，亦記作「(A)成分」)係對感光性組合物賦予光聚合性與膜形成能力之成分。若(A)聚合性基材成分為包含能夠藉由(B)光聚合起始劑而聚合之成分且能夠製備可形成膜之感光性組合物之成分，則並無特別限定。典型性而言，(A)聚合性基材成分包含光聚合性化合物或光聚合性化合物及樹脂。光聚合性化合物可為低分子化合物，亦可為如樹脂之高分子化合物。 The (A) polymerizable base material component (hereinafter, also referred to as "(A) component") is a component that imparts photopolymerization and film-forming ability to the photosensitive composition. The polymerizable substrate component (A) is not particularly limited as long as it contains a component that can be polymerized by the (B) photopolymerization initiator and can prepare a film-forming photosensitive composition. Typically, the (A) polymerizable substrate component includes a photopolymerizable compound or a photopolymerizable compound and a resin. The photopolymerizable compound may be a low-molecular compound or a high-molecular compound such as a resin.
就光聚合性之方面而言，(A)聚合性基材成分較佳為包含並非聚 合物之低分子量之光聚合性化合物(以下，亦記作「光聚合性單體」)及/或含乙烯性不飽和基之樹脂。 In terms of photopolymerization, (A) the polymerizable substrate component preferably contains A low molecular weight photopolymerizable compound (hereinafter, also referred to as "photopolymerizable monomer") and / or an ethylenically unsaturated group-containing resin.
又，於(A)聚合性基材成分包含樹脂之情形時，就鹼性顯影性之觀點而言，較佳為包含鹼可溶性樹脂。鹼可溶性樹脂亦可包含乙烯性不飽和基。包含乙烯性不飽和基(作為構成單元中之取代基，包含乙烯性不飽和基)之鹼可溶性樹脂就光聚合性與鹼性顯影性之兩者之觀點而言較佳。 Moreover, when (A) a polymerizable base material component contains a resin, it is preferable to contain an alkali soluble resin from a viewpoint of alkaline developability. The alkali-soluble resin may contain an ethylenically unsaturated group. An alkali-soluble resin containing an ethylenically unsaturated group (as a substituent in the constituent unit and containing an ethylenically unsaturated group) is preferred from the viewpoints of both photopolymerization and alkaline developability.
以下，依序對作為(A)成分中所含之較佳之成分的包含乙烯性不飽和基之樹脂、光聚合性單體及鹼可溶性樹脂進行說明。 Hereinafter, a resin containing an ethylenically unsaturated group, a photopolymerizable monomer, and an alkali-soluble resin, which are preferable components contained in the component (A), will be described in order.
[包含乙烯性不飽和基之樹脂] [Resin containing ethylenically unsaturated groups]
作為包含乙烯性不飽和基之樹脂，可列舉：(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；於使多元醇類與一元酸或多元酸縮合而獲得之聚酯預聚物中，使(甲基)丙烯酸反應而獲得之聚酯(甲基)丙烯酸酯；使多元醇與具有2個異氰酸酯基之化合物反應後，使(甲基)丙烯酸反應而獲得之聚胺基甲酸酯(甲基)丙烯酸酯；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)丙烯酸反應而獲得之環氧(甲基)丙烯酸酯樹脂等。進而，能夠較佳地使用使多元酸酐與環氧(甲基)丙烯酸酯樹脂反應而成之樹脂。再者，本說明書中，「(甲基)丙烯酸」係指「丙烯酸或甲基丙烯酸」。 Examples of the resin containing an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, fumaric acid monomethyl ester, fumaric acid monoethyl ester, ( 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide , Acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) Benzyl 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-hexanediol di (meth) acrylate Oligomers obtained by polymerizing esters, phenolphthalein-based epoxy diacrylates, etc .; in polyester prepolymers obtained by condensing polyhydric alcohols with mono- or polybasic acids, reacting (meth) acrylic acid to Polyester (meth) acrylate obtained; Polyurethane (meth) acrylate obtained by reacting a polyhydric alcohol with a compound having two isocyanate groups and reacting (meth) acrylic acid; Phenol A type epoxy resin, bisphenol F type Epoxy resin, bisphenol S epoxy resin, phenol or cresol novolac epoxy resin, soluble phenolic epoxy resin, triphenol methane epoxy resin, polycarboxylic acid polyglycidyl ester, polyhydric alcohol Glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene epoxy resin and other epoxy resin (meth) acrylic acid, etc. . Furthermore, a resin obtained by reacting a polybasic acid anhydride with an epoxy (meth) acrylate resin can be preferably used. In addition, in this specification, "(meth) acrylic acid" means "acrylic acid or methacrylic acid."
又，作為包含乙烯性不飽和基之樹脂，能夠較佳地使用：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的樹脂；藉由使包含來自不飽和羧酸之單位之聚合物中所含之羧基的至少一部分與具有脂環式環氧基之(甲基)丙烯酸酯及/或(甲基)丙烯酸環氧烷基酯反應而獲得之樹脂(以下，一併稱為「包含具有乙烯性不飽和基之構成單元之樹脂」)。 In addition, as the resin containing an ethylenically unsaturated group, a resin obtained by reacting an epoxy compound with a reactant of an unsaturated group-containing carboxylic acid compound and a polybasic acid anhydride can be preferably used; At least a part of the carboxyl group contained in the polymer derived from the unit of unsaturated carboxylic acid is obtained by reacting (meth) acrylate and / or (meth) acrylate alkylene oxide having an alicyclic epoxy group. Resin (hereinafter, collectively referred to as "resin containing a structural unit having an ethylenically unsaturated group").
作為具有乙烯性不飽和基之構成單元中之乙烯性不飽和基，較佳為(甲基)丙烯醯氧基。 As an ethylenically unsaturated group in the structural unit which has an ethylenically unsaturated group, a (meth) acryl fluorenyloxy group is preferable.
包含具有乙烯性不飽和基之構成單元之樹脂亦可包含下述其他單體(A1me)或聚合物(A3)中所列舉之單體(化合物)作為其他構成單元。 The resin containing a structural unit having an ethylenically unsaturated group may contain other monomers (compounds) listed in other monomers (A1me) or polymers (A3) described below as other structural units.
其中，較佳為包含具有乙烯性不飽和基之構成單元之樹脂或下述通式(a1)所表示之化合物。該通式(a1)所表示之化合物就其自身之光硬化性較高之方面而言較佳。 Among these, a resin containing a structural unit having an ethylenically unsaturated group or a compound represented by the following general formula (a1) is preferred. The compound represented by the general formula (a1) is preferable in terms of its high photocurability.
上述通式(a1)中，X表示下述通式(a2)所表示之基。 In the general formula (a1), X represents a group represented by the following general formula (a2).
上述通式(a2)中，R1a分別獨立地表示氫原子、碳數1~6之烴基或鹵素原子，R2a分別獨立地表示氫原子或甲基，W表示單鍵或下述結構式(a3)所表示之基。再者，通式(a2)及結構式(a3)中，「＊」係指2價基之鍵結鍵之末端。 In the general formula (a2), R 1a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R 2a each independently represents a hydrogen atom or a methyl group, and W represents a single bond or the following structural formula ( a3). In the general formula (a2) and the structural formula (a3), "*" means a terminal of a divalent bond.
上述通式(a1)中，Y表示自二羧酸酐中去除酸酐基(-CO-O-CO-)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、氯菌酸酐、甲基四氫鄰苯二甲酸酐、戊二酸酐等。 In the general formula (a1), Y represents a residue in which an acid anhydride group (-CO-O-CO-) is removed from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylidene. Tetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.
又，上述通式(a1)中，Z表示自四羧酸二酐中去除2個酸酐基之殘基。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、聯苯基四羧酸二酐、聯苯醚四羧酸二酐等。進而，上述通式(a1)中，a表示0~20之整數。 In the general formula (a1), Z represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride. Further, in the general formula (a1), a represents an integer of 0 to 20.
包含乙烯性不飽和基之樹脂之酸價以樹脂固形物成分計較佳為 10~150mgKOH/g，更佳為70~110mgKOH/g。藉由將酸價設為10mgKOH/g以上而獲得對於顯影液之充分之溶解性，因此較佳。又，藉由將酸價設為150mgKOH/g以下，能夠獲得充分之硬化性並能夠使表面性良好，因此較佳。 The acid value of the resin containing an ethylenically unsaturated group is preferably based on the solid content of the resin. 10 ~ 150mgKOH / g, more preferably 70 ~ 110mgKOH / g. By setting the acid value to 10 mgKOH / g or more, it is preferable to obtain sufficient solubility in a developing solution. In addition, when the acid value is 150 mgKOH / g or less, sufficient hardenability can be obtained and surface properties can be improved, which is preferable.
又，包含乙烯性不飽和基之樹脂之質量平均分子量較佳為1000~40000，更佳為2000~30000。藉由將質量平均分子量設為1000以上，能夠獲得良好之耐熱性、膜強度，因此較佳。又，藉由將質量平均分子量設為40000以下，能夠獲得良好之顯影性，因此較佳。 The mass average molecular weight of the resin containing an ethylenically unsaturated group is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. By setting the mass average molecular weight to 1,000 or more, it is preferable because good heat resistance and film strength can be obtained. Moreover, it is preferable to set a mass average molecular weight to 40,000 or less, since favorable developability can be obtained.
相對於感光性組合物之固形物成分之質量，感光性組合物中之包含乙烯性不飽和基的樹脂之含量較佳為40質量%以下，更佳為35~10質量%，尤佳為30~20質量%。又，(A)聚合性基材成分中之包含乙烯性不飽和基之樹脂之含量較佳為80質量%以下，更佳為75~20質量%，尤佳為70~40質量%。 The content of the resin containing an ethylenically unsaturated group in the photosensitive composition is preferably 40% by mass or less, more preferably 35 to 10% by mass, and even more preferably 30% with respect to the mass of the solid content component of the photosensitive composition. ~ 20% by mass. The content of the resin containing an ethylenically unsaturated group in the polymerizable substrate component (A) is preferably 80% by mass or less, more preferably 75 to 20% by mass, and even more preferably 70 to 40% by mass.
[光聚合性單體] [Photopolymerizable monomer]
於光聚合性單體中，存在單官能單體與多官能單體。以下，依序對單官能單體及多官能單體進行說明。 Among the photopolymerizable monomers, there are monofunctional monomers and polyfunctional monomers. Hereinafter, a monofunctional monomer and a polyfunctional monomer are demonstrated in order.
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、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基-2-羥基丙基苯 二甲酸酯、甘油單(甲基)丙烯酸酯、四氫呋喃甲基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、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，亦可組合使用2種以上。 Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl) Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, butyl Enoic acid, 2-acrylamido-2-methylpropanesulfonic acid, tertiary 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) acrylic acid 2 -Hydroxybutyl ester, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropylbenzene Diformate, glycerol mono (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, semi- (meth) acrylate of phthalic acid derivatives, etc. These monofunctional monomers may be used alone or in combination of two or more kinds.
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、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、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、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，甲苯二異氰酸酯、三甲基六亞甲基二異氰酸酯或六亞甲基二異氰酸酯等與(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，亦可組合使用2種以上。 Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (methyl). Acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (methyl) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (Meth) acryloxyoxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (methyl ) Acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether (Meth) acrylate, diglycidyl phthalate di (meth) acrylate, triglyceride, glycerol polyglycidyl ether poly (meth) acrylate, (meth) acrylic acid urethane Ester (that is, a reaction product of toluene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth) acrylate), methylene bis (meth) propylene Polyfunctional monomers such as fluorenamine, (meth) acrylamide methylene ether, polycondensates of polyhydric alcohols and N-methylol (meth) acrylamide, or tripropylene acetal formal. These polyfunctional monomers may be used alone or in combination of two or more kinds.
相對於感光性組合物之固形物成分之質量，感光性組合物中之光聚合性單體的含量較佳為40質量%以下，更佳為30~5質量%，尤佳為 25~10質量%。又，(A)聚合性基材成分中之光聚合性單體之含量較佳為80質量%以下，更佳為60~10質量%，尤佳為50~20質量%。 The content of the photopolymerizable monomer in the photosensitive composition is preferably 40% by mass or less, more preferably 30 to 5% by mass, and even more preferably, based on the mass of the solid content component of the photosensitive composition. 25 to 10% by mass. The content of the photopolymerizable monomer in the (A) polymerizable substrate component is preferably 80% by mass or less, more preferably 60 to 10% by mass, and even more preferably 50 to 20% by mass.
[鹼可溶性樹脂] [Alkali soluble resin]
鹼可溶性樹脂為顯示鹼可溶性之樹脂。本說明書中，所謂顯示鹼可溶性之樹脂，係指利用樹脂濃度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1μm之樹脂膜，在濃度0.05質量%之KOH水溶液中浸漬1分鐘時，溶解膜厚0.01μm以上者。 The alkali-soluble resin is a resin that exhibits alkali solubility. In this specification, a resin that exhibits alkali solubility refers to a resin film having a film thickness of 1 μm formed on a substrate by using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and a concentration of 0.05% by mass. When immersed in a KOH aqueous solution for 1 minute, the film thickness of 0.01 μm or more is dissolved.
鹼可溶性樹脂能夠自先前調配於各種感光性組合物中之樹脂適當選擇。作為較佳之鹼可溶性樹脂，可列舉：含有於主鏈上具有環結構之構成單元之聚合物、或作為包含如(甲基)丙烯酸之不飽和羧酸之單體之聚合物的具有不飽和鍵之單體之聚合物。再者，本說明書中，含有於主鏈上具有環結構之構成單元之聚合物係設為不包含具有不飽和鍵之單體之聚合物者。 The alkali-soluble resin can be appropriately selected from resins previously formulated in various photosensitive compositions. Examples of the preferable alkali-soluble resin include a polymer containing a structural unit having a ring structure on the main chain, or a polymer having an unsaturated bond as a polymer containing an unsaturated carboxylic acid such as (meth) acrylic acid. Polymer of monomer. In addition, in this specification, the polymer containing the structural unit which has a ring structure in the main chain is a polymer which does not contain the monomer which has an unsaturated bond.
以下，對含有於主鏈上具有環結構之構成單元之聚合物及具有不飽和鍵之單體之聚合物進行說明。 Hereinafter, a polymer containing a structural unit having a ring structure on the main chain and a polymer containing a monomer having an unsaturated bond will be described.
(含有於主鏈上具有環結構之構成單元之聚合物) (Polymer containing a constituent unit having a ring structure on the main chain)
若含有於主鏈上具有環結構之構成單元之聚合物為具有特定環結構並且具備特定鹼可溶性之樹脂，則並無特別限定。作為含有於主鏈上具有環結構之構成單元之聚合物的較佳之例，可列舉：含有來自順丁烯二醯亞胺之構成單元(以下，亦稱為「構成單元(A2a)」)之聚合物(以下，亦稱為「聚合物(A2)」)及含有下述式(A-1)所表示之構成單元(以下，亦稱為「構成單元(A1a)」)之聚合物(以下，亦稱為「聚合物(A1)」)。 The polymer containing a structural unit having a ring structure in the main chain is not particularly limited as long as it is a resin having a specific ring structure and having a specific alkali solubility. As a preferable example of a polymer containing a structural unit having a ring structure in the main chain, a polymer containing a structural unit derived from cis-butene difluorene imine (hereinafter, also referred to as a “structural unit (A2a)”) may be mentioned. A polymer (hereinafter, also referred to as "polymer (A2)") and a polymer (hereinafter, also referred to as "constituent unit (A1a)") containing a structural unit represented by the following formula (A-1) , Also known as "Polymer (A1)").
作為聚合物(A2)所具有之來自順丁烯二醯亞胺之構成單元(A2a)，只要為使具有順丁烯二醯亞胺骨架之單體聚合而獲得者，則並無特別限定。作為具有順丁烯二醯亞胺骨架之單體，例如可列舉： N-苄基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等。 The constituent unit (A2a) derived from maleimide diimide as a polymer (A2) is not particularly limited as long as it is obtained by polymerizing a monomer having a maleimide diimide skeleton. Examples of the monomer having a maleimide skeleton include: N-benzylcis-butenedifluoreneimine, N-phenylcis-butenedifluoreneimine, N-cyclohexylcis-butenedifluoreneimine and the like.
尤其是包含含有於主鏈上具有環結構之構成單元(A1a)之聚合物(A1)的感光性組合物對於顯影液之溶解性良好。 In particular, the photosensitive composition containing the polymer (A1) containing the structural unit (A1a) having a ring structure in the main chain has good solubility in a developing solution.
式(A-1)中，環A為具有1個氧原子作為環構成原子之碳數4~6之飽和脂肪族環式基。環A較佳為具有1個氧原子作為環構成原子之碳數4或5之飽和脂肪族環式基，更佳為四氫呋喃環或四氫吡喃環，進而較佳為下述式(A-3)所表示之構成單元(以下，亦稱為「構成單元(A1a1)」)中之四氫吡喃環或下述式(A-4)所表示之構成單元(以下，亦稱為「構成單元(A1a2)」)中之四氫呋喃環。 In the formula (A-1), the ring A is a saturated aliphatic cyclic group having 4 to 6 carbon atoms having one oxygen atom as a ring constituent atom. The ring A is preferably a saturated aliphatic cyclic group having 4 or 5 carbon atoms having one oxygen atom as a ring constituent atom, more preferably a tetrahydrofuran ring or a tetrahydropyran ring, and further preferably the following formula (A- 3) The tetrahydropyran ring in the structural unit (hereinafter, also referred to as "constituting unit (A1a1)") or the structural unit (hereinafter, also referred to as "constituting unit" Tetrahydrofuran ring in the unit (A1a2) ").
於主鏈上含有上述式(A-1)所表示之構成單元之聚合物(聚合物(A1))通常於主鏈上含有複數個上述式(A-1)所表示之構成單元(構成單元(A1a))。於複數個構成單元(A1a)中，各構成單元(A1a)中所含之環A於構成聚合物(A1)之一主鏈上可相同，亦可不同。具體而言，構成聚合物(A1)之一主鏈可為作為該主鏈中所含之上述式(A-1)所表示之構成單元而例如僅具有上述式(A-3)所表示之構成單元者，亦可為僅具 有上述式(A-4)所表示之構成單元者，亦可為併用上述式(A-3)所表示之構成單元與上述式(A-4)所表示之構成單元者。 A polymer (polymer (A1)) containing a constituent unit represented by the above formula (A-1) on the main chain usually contains a plurality of constituent units (constituent units) represented by the above formula (A-1) on the main chain. (A1a)). In the plurality of constitutional units (A1a), the ring A contained in each constitutional unit (A1a) may be the same on the main chain of the constitutional polymer (A1) or different. Specifically, one of the main chains constituting the polymer (A1) may be a constituent unit represented by the above-mentioned formula (A-1) contained in the main chain, and for example, may have only the unit represented by the above-mentioned formula (A-3). Constituent units may also have only Those who have the structural unit represented by the above formula (A-4) may also use the structural unit represented by the above formula (A-3) and the structural unit represented by the above formula (A-4).
上述式(A-1)、式(A-3)及式(A-4)中，R1及R2分別獨立為氫原子或-COOR，R分別獨立為氫原子或可具有取代基之碳數1~25之烴基。R1及R2較佳為-COOR。於構成含有上述式(A-1)所表示之構成單元之聚合物(聚合物(A1))的一主鏈含有複數個環A之情形時，鍵結於各環A上之-COOR分別獨立，亦可使相同或不同之基作為-COOR而鍵結於各環A上。 In the formulas (A-1), (A-3), and (A-4), R 1 and R 2 are each independently a hydrogen atom or -COOR, and R is each independently a hydrogen atom or a carbon that may have a substituent. A hydrocarbon group of 1 to 25. R 1 and R 2 are preferably -COOR. When a polymer (polymer (A1)) containing a constituent unit represented by the above formula (A-1) is constituted to include a plurality of rings A, -COOR bonded to each ring A is independent The same or different groups may be bonded to each ring A as -COOR.
作為R1及R2所表示之可具有取代基之碳數1~25之烴基，並無特別限定。作為烴基之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第三戊基、硬脂基、月桂基、2-乙基己基等直鏈狀或分支狀之烷基；苯基等芳基；環己基、第三丁基環己基、二環戊二烯基、三環癸基、異
於R1及R2為烴基之情形時，烴基之碳原子數較佳為8以下。作為碳原子數為8以下之烴基，就難以因酸或熱而脫離之方面而言，較佳為烴基所具有之單末端自由之鍵結鍵與一級碳原子或二級碳原子鍵結之烴基。作為此種烴基，較佳為碳原子數為1~8之直鏈狀或支鏈狀之烷基，較佳為碳原子數為1~5之直鏈狀或支鏈狀之烷基。 When R 1 and R 2 are hydrocarbon groups, the number of carbon atoms in the hydrocarbon group is preferably 8 or less. As the hydrocarbon group having a carbon number of 8 or less, in terms of being difficult to be detached by acid or heat, a hydrocarbon group having a single-end free bond and a primary carbon atom or a secondary carbon atom is preferred. . As such a hydrocarbon group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferred, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferred.
作為此種烴基之具體例，可列舉甲基、乙基、環己基、苄基等，較佳為甲基。 Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, and a methyl group is preferred.
於構成含有上述式(A-1)所表示之構成單元(構成單元(A1a))之聚合物(聚合物(A1))的一主鏈上含有複數個構成單元(A1a)之情形時，鍵結於各構成單元(A1a)上之R1及R2於各構成單元(A1a)間可相同，亦可不同。 When constituting a polymer (polymer (A1)) containing a structural unit (structural unit (A1a)) represented by the above-mentioned formula (A-1), a plurality of constituent units (A1a) are included in a main chain, and a bond R 1 and R 2 bonded to each constituent unit (A1a) may be the same or different among the constituent units (A1a).
於該各構成單元(A1a)間含有相同或不同之環A之情形時，R1及R2不依存於鍵結之各環A的種類而相互獨立。 When the same or different ring A is included between the constituent units (A1a), R 1 and R 2 are independent of each other without depending on the type of each ring A to be bonded.
具體而言，於構成聚合物(A1)之一主鏈上含有複數個上述式(A-3)所表示之構成單元(構成單元(A1a1))之情形時，各構成單元(A1a1)中之R1及R2於各構成單元(A1a1)間可相同，亦可不同。 Specifically, when a plurality of constituent units (constituent units (A1a1)) represented by the above formula (A-3) are contained in one main chain of the constituent polymer (A1), one of the constituent units (A1a1) R 1 and R 2 may be the same or different among the constituent units (A1a1).
於構成聚合物(A1)之一主鏈上含有複數個上述式(A-4)所表示之構成單元(構成單元(A1a2))之情形時，各構成單元(A1a2)中之R1及R2於各構成單元(A1a2)間可相同，亦可不同。 When one of the main chains of the constituent polymer (A1) contains a plurality of constituent units (constituent units (A1a2)) represented by the above formula (A-4), R 1 and R in each constituent unit (A1a2) 2 It may be the same or different between each constituent unit (A1a2).
進而，於構成聚合物(A1)之一主鏈上含有上述式(A-3)所表示之構成單元(構成單元(A1a1))與上述式(A-4)所表示之構成單元(構成單元(A1a2))之情形時，各構成單元(A1a1)中之R1及R2與各構成單元(A1a2)中之R1及R2可相同，亦可不同。 Furthermore, one of the main chains of the constituent polymer (A1) contains a constituent unit (structural unit (A1a1)) represented by the above formula (A-3) and a constituent unit (constituent unit) represented by the above formula (A-4) when (A 1 -a)) of the case, each of the constituent unit (A1a1 to) the R 1 and R 2 of each constituent unit (A 1 -a) in the R 1 and R 2 may be the same or different.
上述式(A-3)所表示之構成單元(構成單元(A1a1))可為下述式(A-5)所表示之重複單位(以下，亦稱為「重複單位(ar1)」)之一部分。上述式(A-4)所表示之構成單元(構成單元(A1a2))可為下述式(A-6)所表示之重複單位(以下，亦稱為「重複單位(ar2)」)之一部分。 The constituent unit (constituent unit (A1a1)) represented by the above formula (A-3) may be a part of the repeating unit (hereinafter, also referred to as "repeating unit (ar1)") represented by the following formula (A-5) . The constituent unit (constituent unit (A1a2)) represented by the above formula (A-4) may be a part of the repeating unit (hereinafter, also referred to as "repeating unit (ar2)") represented by the following formula (A-6) .
(式(A-5)及式(A-6)中，R1及R2分別獨立並與上述相同) (In formula (A-5) and formula (A-6), R 1 and R 2 are independent and the same as above)
作為給予上述式(A-5)及(A-6)所表示之各重複單位之單體，例如可列舉下述式所表示之1,6-二烯類。 As a monomer which gives each repeating unit represented by said formula (A-5) and (A-6), the 1,6-diene represented by a following formula is mentioned, for example.
(上述式中，R分別獨立並與上述相同) (In the above formula, R is independent and the same as above)
於給予在主鏈上含有上述式(A-1)所表示之構成單元(構成單元(A1a))之聚合物(聚合物(A1))的單體組合物中，相對於單體組合物中之單體之總量，給予含有構成單元(A1a)之重複單位(能夠包含上述構成單元(A1a1)及構成單元(A1a2))的單體(A1ma)之含有比率較佳為1質量%~60質量%，更佳為5質量%~50質量%，尤佳為10質量%~40質量%。 In a monomer composition given to a polymer (polymer (A1)) containing a constituent unit (constituent unit (A1a)) represented by the above formula (A-1) in the main chain, the monomer composition is The total amount of monomers is preferably 1% to 60% by weight based on the content of the monomer (A1ma) given to the repeating unit (which can include the above-mentioned constitutional unit (A1a1) and constitutional unit (A1a2)). Mass%, more preferably 5 mass% to 50 mass%, particularly preferably 10 mass% to 40 mass%.
聚合物(A1)較佳為含有於側鏈上具有氧基之重複單位(A1b)。若聚合物(A1)含有於側鏈上具有氧基之重複單位(A1b)，則能夠獲得鹼性顯影性優異之感光性組合物。作為構成於側鏈上具有氧基之重複單位(A1b)之單體(A1mb)，例如可列舉：(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基琥珀酸、伊康酸、ω-羧基-聚己內酯單丙烯酸酯等具有羧基之單體；順丁烯二酸酐、伊康酸酐等具有羧酸酐基之單體等。其中，較佳為(甲基)丙烯酸。 The polymer (A1) preferably contains a repeating unit (A1b) having an oxygen group on a side chain. When the polymer (A1) contains a repeating unit (A1b) having an oxygen group in a side chain, a photosensitive composition having excellent alkali developability can be obtained. Examples of the monomer (A1mb) constituting a repeating unit (A1b) having an oxygen group on a side chain include (meth) acrylic acid, 2- (meth) acryloxyethylethylsuccinic acid, and iconic acid. , Ω-carboxyl-polycaprolactone monoacrylate and other monomers having a carboxyl group; maleic anhydride, itaconic anhydride and other monomers having a carboxylic acid anhydride group, and the like. Among these, (meth) acrylic acid is preferred.
於給予聚合物(A1)之單體組合物中，相對於單體組合物中之單體之總量，構成於側鏈上具有氧基之重複單位(A1b)的單體(A1mb)之含有比率較佳為1質量%~50質量%，更佳為5質量%~40質量%，進而較佳為10質量%~35質量%。 The content of the monomer (A1mb) constituting the repeating unit (A1b) having an oxygen group on the side chain with respect to the total amount of the monomers in the monomer composition in the monomer composition for the polymer (A1) The ratio is preferably 1% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 10% to 35% by mass.
較佳為聚合物(A1)含有於側鏈上具有碳雙鍵之重複單位(A1c)。於側鏈上具有碳雙鍵之重複單位(A1c)能夠藉由如下方式獲得：以於 側鏈上具有氧基之重複單位(A1b)之氧基之一部分或全部(較佳為一部分)作為反應點而加成具有碳雙鍵之化合物。 The polymer (A1) preferably contains a repeating unit (A1c) having a carbon double bond in a side chain. The repeating unit (A1c) with a carbon double bond on the side chain can be obtained by: A part or all (preferably a part) of the oxy group of the repeating unit (A1b) having an oxy group on the side chain is added as a reaction point to a compound having a carbon double bond.
於側鏈上具有氧基之重複單位(A1b)之氧基為羧基之情形時，作為具有碳雙鍵之化合物，能夠使用具有環氧基及雙鍵之化合物、具有異氰酸酯基及雙鍵之化合物等。作為具有環氧基及雙鍵之化合物，例如可列舉：(甲基)丙烯酸縮水甘油酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、4-羥基丁基丙烯酸酯縮水甘油醚等。作為具有異氰酸酯基及雙鍵之化合物，可列舉2-異氰酸酯基乙基(甲基)丙烯酸酯等。於側鏈上具有氧基之重複單位(A1b)之氧基為羧酸酐基之情形時，作為具有碳雙鍵之化合物，能夠使用具有羥基及雙鍵之化合物。作為具有羥基及雙鍵之化合物，例如可列舉(甲基)丙烯酸2-羥基乙酯等。 When the oxy group of the repeating unit (A1b) having an oxy group on the side chain is a carboxyl group, as the compound having a carbon double bond, a compound having an epoxy group and a double bond, and a compound having an isocyanate group and a double bond can be used. Wait. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinyl benzyl glycidyl ether, M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and the like. Examples of the compound having an isocyanate group and a double bond include 2-isocyanate ethyl (meth) acrylate and the like. When the oxy group of the repeating unit (A1b) having an oxy group on the side chain is a carboxylic anhydride group, as the compound having a carbon double bond, a compound having a hydroxyl group and a double bond can be used. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.
聚合物(A1)可進而具有來自能夠與上述單體(A1ma)、單體(A1mb)及/或單體(A1mc)共聚合之其他單體(A1me)之其他重複單位(A1e)。 The polymer (A1) may further have other repeating units (A1e) derived from other monomers (A1me) that can be copolymerized with the monomer (A1ma), the monomer (A1mb), and / or the monomer (A1mc).
作為其他單體(A1me)，例如亦可為進而含有於側鏈上具有2以上之氧伸烷基之重複單位者。作為於側鏈上具有2以上之氧伸烷基之重複單位，例如可列舉下述式所表示之重複單位。 As another monomer (A1me), the repeating unit which has 2 or more oxyalkylene groups in a side chain may be contained, for example. As a repeating unit which has 2 or more oxyalkylene groups in a side chain, the repeating unit represented by a following formula is mentioned, for example.
上述式中，R7、R8及R9分別獨立為氫原子或甲基，較佳為氫原子。R10為碳數1~20之直鏈狀或分支狀之烷基、碳數2~20之直鏈狀 或分支狀之烯基或碳數6~20之芳香族烴基，較佳為氫原子、碳數1~20之直鏈狀烷基、碳數2~20之直鏈狀烯基或碳數6~20之芳香族烴基，更佳為碳數1~10之直鏈狀烷基或碳數6~12之芳香族烴基，進而較佳為碳數1~5之直鏈狀烷基、苯基或聯苯基，尤佳為甲基、苯基或聯苯基。再者，烷基、烯基及芳香族烴基可具有取代基。AO表示氧伸烷基。AO所表示之氧伸烷基之碳數為2~20，較佳為2~10，更佳為2~5，進而較佳為2。於側鏈上具有2以上之氧伸烷基之重複單位可包含1種或2種以上之氧伸烷基。x表示0~2之整數。y表示0或1。n表示氧伸烷基之平均加成莫耳數，為2以上，較佳為2~100，更佳為2~50，進而較佳為2~15。 In the above formula, R 7 , R 8 and R 9 are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R 10 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a hydrogen atom 1, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms or The aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferably a linear alkyl group, phenyl group, or biphenyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group, phenyl group, or biphenyl group. The alkyl group, alkenyl group, and aromatic hydrocarbon group may have a substituent. AO stands for oxyalkylene. The carbon number of the oxyalkylene group represented by AO is 2 to 20, preferably 2 to 10, more preferably 2 to 5, and even more preferably 2. The repeating unit having two or more oxyalkylene groups on the side chain may include one or two or more oxyalkylene groups. x represents an integer from 0 to 2. y means 0 or 1. n represents an average addition mole number of the oxyalkylene group, which is 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 15.
於側鏈上具有2以上之氧伸烷基之重複單位係藉由於側鏈上具有2以上之氧伸烷基之單體而構成。作為該單體，例如可列舉下述式所表示之單體。 The repeating unit having an oxyalkylene group of 2 or more on the side chain is constituted by a monomer having an oxyalkylene group of 2 or more on the side chain. Examples of the monomer include a monomer represented by the following formula.
(上述式中，R7、R8、R9、R10、AO、x、y及n係如上述所說明) (In the above formula, R 7 , R 8 , R 9 , R 10 , AO, x, y, and n are as described above)
作為上述於側鏈上具有2以上之氧伸烷基之單體，例如可列舉：乙氧基化鄰苯基苯酚(甲基)丙烯酸酯(EO2莫耳)、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯(EO4莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO9莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO13莫耳)、甲氧基三乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、丁氧基二乙二醇(甲基)丙烯酸酯、2-乙基己基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇 (甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯(EO4-17莫耳)、壬基苯氧基聚丙二醇(甲基)丙烯酸酯(PO5莫耳)、EO變性甲酚(甲基)丙烯酸酯(EO2莫耳)等。該等單體可單獨或組合2種以上使用。其中，較佳為乙氧基化鄰苯基苯酚(甲基)丙烯酸酯(EO2莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO9莫耳)、甲氧基聚乙二醇(甲基)丙烯酸酯(EO13莫耳)。進而較佳為乙氧基化鄰苯基苯酚丙烯酸酯(EO2莫耳)、甲氧基聚乙二醇丙烯酸酯(EO9莫耳)、甲氧基聚乙二醇丙烯酸酯(EO13莫耳)。再者，本說明書中，例如「EO2莫耳」、「PO5莫耳」等記法表示氧伸烷基之平均加成莫耳數。 Examples of the monomer having an oxyalkylene group of 2 or more in the side chain include ethoxylated o-phenylphenol (meth) acrylate (EO2 Mol), and phenoxydiethylene glycol ( (Meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO4 mole), methoxypolyethylene glycol (meth) acrylate (EO9 mole), methoxypolyethylene glycol Alcohol (meth) acrylate (EO13 mole), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (formaldehyde) Acrylate), 2-ethylhexyl diethylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy polypropylene glycol (Meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate (EO4-17 mole), nonylphenoxy polypropylene glycol (meth) acrylate (PO5 mole), EO Denatured cresol (meth) acrylate (EO2 mole) and the like. These monomers can be used individually or in combination of 2 or more types. Of these, ethoxylated o-phenylphenol (meth) acrylate (EO2 mole), methoxypolyethylene glycol (meth) acrylate (EO9 mole), and methoxypolyethylene glycol are preferred. Alcohol (meth) acrylate (EO13 mole). Further preferred are ethoxylated o-phenylphenol acrylate (EO2 mole), methoxy polyethylene glycol acrylate (EO9 mole), and methoxy polyethylene glycol acrylate (EO13 mole). In addition, in this specification, notation such as "EO2 Mohr" and "PO5 Mohr" means the average addition mole number of oxyalkylene.
又，作為其他單體(A1me)，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸聯苯酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、丁氧基乙二醇(甲基)丙烯酸酯、2-乙基己基乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸聯苯氧基乙酯、(甲基)丙烯酸雙環戊酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸三環癸氧基乙酯、壬基苯氧基乙二醇(甲基)丙烯酸酯、壬基苯氧基丙二醇、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、乙氧基化鄰苯基苯酚(甲基)丙烯酸酯等(甲基)丙烯酸酯類；(甲基)丙烯醯基嗎啉(嗎啉基(甲基)丙烯酸酯)、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-異丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-第三辛基(甲基)丙烯醯胺、雙丙酮(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯 胺、N-環己基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-苄基(甲基)丙烯醯胺、N-三苯基甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺等(甲基)丙烯酸醯胺類；苯乙烯、乙烯基甲苯、α-甲基苯乙烯等芳香族乙烯基化合物；丁二烯、異戊二烯等丁二烯或經取代之丁二烯化合物；乙烯、丙烯、氯乙烯、丙烯腈等乙烯或經取代之乙烯化合物；乙酸乙烯酯等乙烯酯類等。該等單體可單獨或組合2種以上使用。 Examples of the other monomer (A1me) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (formaldehyde). N-butyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) ) Lauryl acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxy (meth) acrylate Ethyl ester, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxy (meth) acrylate Ethyl ester, biphenoxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentyloxy (meth) acrylate, (methyl ) Tricyclodecoxyethyl acrylate, nonylphenoxyethylene glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Ethoxylated o-phenyl (Meth) acrylates such as phenol (meth) acrylate; (meth) acrylamidomorpholine (morpholinyl (meth) acrylate), (meth) acrylamido, N-methyl ( (Meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-tert-butyl (Meth) acrylamide, N-third octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (Meth) acrylic acid Amine, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acryl (Meth) acrylic acid amines such as fluorene, N, N-dimethyl (meth) acrylamide; aromatic vinyl compounds such as styrene, vinyl toluene, and α-methylstyrene; butadiene , Butadiene, such as isoprene, or substituted butadiene compounds; ethylene, substituted ethylene compounds, such as ethylene, propylene, vinyl chloride, and acrylonitrile; vinyl esters such as vinyl acetate. These monomers can be used individually or in combination of 2 or more types.
於給予聚合物(A1)之單體組合物中，相對於單體組合物中之單體之總量，給予其他重複單位(A1e)之單體(A1me)之含有比率較佳為0質量%~55質量%，更佳為5質量%~50質量%，進而較佳為10質量%~45質量%。 In the monomer composition to which the polymer (A1) is administered, the content ratio of the monomer (A1me) to other repeating units (A1e) relative to the total amount of monomers in the monomer composition is preferably 0% by mass ~ 55 mass%, more preferably 5 mass% to 50 mass%, and still more preferably 10 mass% to 45 mass%.
聚合物(A1)可為無規共聚物，亦可為嵌段共聚物。作為聚合物(A1)，能夠單獨或組合2種以上使用。 The polymer (A1) may be a random copolymer or a block copolymer. The polymer (A1) can be used alone or in combination of two or more.
，聚合物(A1)之質量平均分子量以藉由利用四氫呋喃(THF)溶劑之凝膠滲透層析法(GPC)而測得之值計較佳為3,000~200,000，更佳為3,500~100,000，進而較佳為4,000~50,000。若為上述範圍，則能夠獲得確保耐熱性且具有適合於形成塗膜之黏度之感光性組合物。 The mass average molecular weight of the polymer (A1) is preferably 3,000 to 200,000, more preferably 3,500 to 100,000, and more preferably 3,500 to 100,000, as measured by a gel permeation chromatography (GPC) method using a tetrahydrofuran (THF) solvent. It is preferably 4,000 ~ 50,000. If it is the said range, the photosensitive composition which can ensure heat resistance and has viscosity suitable for forming a coating film can be obtained.
聚合物(A1)能夠利用任意之適當之方法使給予聚合物(A1)之單體組合物聚合而獲得。作為聚合方法，例如可列舉溶液聚合法。 The polymer (A1) can be obtained by polymerizing a monomer composition to be administered to the polymer (A1) by any appropriate method. Examples of the polymerization method include a solution polymerization method.
給予聚合物(A1)之單體組合物可包含任意之適當之溶劑。作為溶劑，例如可列舉：四氫呋喃、二
給予聚合物(A1)之單體組合物可包含任意之適當之聚合起始劑。作為聚合起始劑，例如可列舉：氫過氧化異丙苯、氫過氧化二異丙苯、過氧化二第三丁基、過氧化月桂醯、過氧化苯甲醯、過氧化異丙基碳酸第三丁酯、過氧化(2-乙基己酸)第三戊酯、過氧化(2-乙基己酸)第三丁酯等有機過氧化物；2,2'-偶氮雙(異丁腈)、1,1'-偶氮雙(環己腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、二甲基2,2'-偶氮雙(2-甲基丙酸酯)等偶氮化合物等。相對於單體組合物中之全部單體100質量份，聚合起始劑之含有比率較佳為0.1質量份~15質量份，更佳為0.5質量份~10質量份。 The monomer composition to be administered to the polymer (A1) may contain any appropriate polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, dicumyl hydroperoxide, di-tert-butyl peroxide, lauryl peroxide, benzamidine peroxide, and cumene peroxide. Organic peroxides such as tert-butyl ester, peroxy (2-ethylhexanoic acid) tert-amyl ester, peroxy (2-ethylhexanoic acid) tert-butyl ester, etc .; 2,2'-azobis (iso Butyronitrile), 1,1'-azobis (cyclohexanitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis ( 2-methylpropionate) and other azo compounds. The content ratio of the polymerization initiator is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, with respect to 100 parts by mass of the entire monomer in the monomer composition.
藉由溶液聚合法而使聚合物(A1)聚合時之聚合溫度較佳為40℃~150℃，更佳為60℃~130℃。 The polymerization temperature when the polymer (A1) is polymerized by the solution polymerization method is preferably 40 ° C to 150 ° C, and more preferably 60 ° C to 130 ° C.
於獲得含有在側鏈上具有碳雙鍵之重複單位(A1c)之聚合物(A1)之情形時，上述聚合後，將上述具有碳雙鍵之化合物加成於所獲得之聚合物上。作為加成具有碳雙鍵之化合物之方法，能夠採用任意之適當之方法。例如於聚合禁止劑及觸媒之存在下，使具有碳雙鍵之化合物反應並加成於在側鏈上具有氧基之重複單位(A1b)的氧基之一部分或全部(較佳為一部分)上，藉此能夠形成於側鏈上具有碳雙鍵之重複單位(A1c)。 In the case of obtaining a polymer (A1) containing a repeating unit (A1c) having a carbon double bond on a side chain, the above-mentioned compound having a carbon double bond is added to the obtained polymer after the above polymerization. As a method for adding a compound having a carbon double bond, any appropriate method can be adopted. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond is reacted and added to a part or all (preferably a part) of an oxygen group of a repeating unit (A1b) having an oxygen group on a side chain. As a result, a repeating unit (A1c) having a carbon double bond on a side chain can be formed.
相對於上述聚合後之聚合物(即，加成具有碳雙鍵之化合物前之聚合物)100質量份，上述具有碳雙鍵之化合物之加成量較佳為5質量份以上，更佳為10質量份以上，進而較佳為15質量份以上，尤佳為20質量份以上。若為上述範圍，則能夠獲得曝光感度優異之感光性組合物。若使用此種感光性組合物，則有容易形成緻密之硬化塗膜並獲得基板密接性亦優異之圖案之傾向。又，若具有碳雙鍵之化合物之加成 量為上述範圍，則藉由具有碳雙鍵之化合物之加成而充分地生成羥基，能夠獲得對於鹼性顯影液之溶解性優異之感光性組合物。相對於上述聚合後之聚合物(即，加成具有碳雙鍵之化合物前之聚合物)100質量份，上述具有碳雙鍵之化合物之加成量之上限較佳為170質量份以下，更佳為150質量份以下，進而較佳為140質量份以下。若具有碳雙鍵之化合物之加成量於上述範圍內，則能夠維持感光性組合物之保存穩定性及溶解性。 The addition amount of the compound having a carbon double bond is preferably 5 parts by mass or more relative to 100 parts by mass of the polymer after the polymerization (that is, a polymer before adding a compound having a carbon double bond). 10 parts by mass or more, more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more. If it is the said range, the photosensitive composition excellent in exposure sensitivity can be obtained. When such a photosensitive composition is used, it tends to be easy to form a dense hardened coating film and to obtain a pattern which is also excellent in the adhesiveness of a board | substrate. In addition, if a compound having a carbon double bond is added, When the amount is in the above range, a hydroxyl group is sufficiently formed by addition of a compound having a carbon double bond, and a photosensitive composition having excellent solubility in an alkaline developer can be obtained. The upper limit of the addition amount of the compound having a carbon double bond is preferably 170 parts by mass or less with respect to 100 parts by mass of the polymer after the polymerization (that is, a polymer before adding a compound having a carbon double bond). It is preferably 150 parts by mass or less, and more preferably 140 parts by mass or less. When the addition amount of the compound having a carbon double bond is within the above range, the storage stability and solubility of the photosensitive composition can be maintained.
作為聚合禁止劑，例如可列舉6-第三丁基-2,4-二甲苯酚等烷酚化合物。作為觸媒，例如可列舉二甲基苄基胺、三乙基胺等三級胺。 Examples of the polymerization inhibitor include alkylphenol compounds such as 6-third butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.
(具有不飽和鍵之單體之聚合物) (Polymer with unsaturated bond monomer)
於使用具有不飽和鍵之單體之聚合物(以下，亦稱為「聚合物(A3)」)作為鹼可溶性樹脂之情形時，該鹼可溶性樹脂能夠自先前調配於各種感光性組合物中的具有不飽和鍵之單體之聚合物適當選擇。聚合物(A3)可為單獨聚合物，亦可為共聚物。 When a polymer (hereinafter, also referred to as "polymer (A3)") having a monomer having an unsaturated bond is used as the alkali-soluble resin, the alkali-soluble resin can be previously formulated in various photosensitive compositions. The polymer of the monomer having an unsaturated bond is appropriately selected. The polymer (A3) may be a single polymer or a copolymer.
作為聚合物(A3)，亦可使用(a1)不飽和羧酸與除不飽和羧酸以外之其他共聚合成分之共聚物。作為較佳之共聚合成分，就容易獲得給予破壞強度或與基板之密接性優異之著色膜的感光性組合物之方面而言，可列舉(a2)含環氧基之不飽和化合物。 As the polymer (A3), a copolymer of (a1) an unsaturated carboxylic acid and a copolymerization component other than the unsaturated carboxylic acid may be used. As a preferable copolymerization component, the point which is easy to obtain the photosensitive composition which gives a coloring film with a breaking strength or excellent adhesiveness with a board | substrate is mentioned (a2) an epoxy compound containing unsaturated compound.
作為(a1)不飽和羧酸，可列舉：(甲基)丙烯酸、丁烯酸等單羧酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸等二羧酸；該等二羧酸之無水物；等。該等之中，就共聚合反應性、所獲得之樹脂之鹼溶解性、獲得之容易性等方面而言，較佳為(甲基)丙烯酸及順丁烯二酸酐。該等(a1)不飽和羧酸能夠單獨或組合2種以上使用。 Examples of (a1) unsaturated carboxylic acids include: monocarboxylic acids such as (meth) acrylic acid and butenoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Dicarboxylic acids; the anhydrous form of these dicarboxylic acids; etc. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the obtained resin, and ease of obtaining. These (a1) unsaturated carboxylic acids can be used individually or in combination of 2 or more types.
作為(a2)含環氧基之不飽和化合物，可列舉(a2-I)具有脂環式環 氧基之不飽和化合物及(a2-II)不具有脂環式環氧基之不飽和化合物，較佳為(a2-I)具有脂環式環氧基之不飽和化合物。 Examples of (a2) an epoxy-containing unsaturated compound include (a2-I) which has an alicyclic ring The unsaturated compound having an oxy group and the (a2-II) unsaturated compound having no alicyclic epoxy group, the unsaturated compound having an alicyclic epoxy group (a2-I) is preferred.
於(a2-I)具有脂環式環氧基之不飽和化合物中，構成脂環式環氧基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
具體而言，作為(a2-I)含脂環式環氧基之不飽和化合物，例如可列舉下述式(a2-1)~(a2-16)所表示之化合物。該等之中，為了使顯影性為適度者，較佳為下述式(a2-1)~(a2-6)所表示之化合物，更佳為下述式(a2-1)~(a2-4)所表示之化合物。 Specifically, examples of the (a2-I) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulae (a2-1) to (a2-16). Among these, in order to make the developability moderate, the compounds represented by the following formulae (a2-1) to (a2-6) are preferable, and the following formulae (a2-1) to (a2- 4) The compound represented.
再者，於下述式(a2-1)~(a2-16)所表示之化合物中，存在異構物之情形時，下述式表示任一異構物，並不限定於特定之異構物。尤其是於(a2-2)(a2-3)中，可為任一異構物，均較佳。 When an isomer exists in the compounds represented by the following formulae (a2-1) to (a2-16), the following formula represents any isomer and is not limited to a specific isomer. Thing. Especially in (a2-2) (a2-3), any of the isomers is preferable.
上述式中，R11表示氫原子或甲基，R12表示碳數1~6之2價脂肪族飽和烴基，R13表示碳數1~10之2價烴基，n表示0~10之整數。作 為R12，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、伸戊基、六亞甲基。作為R13，例如較佳為亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、伸戊基、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 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R 13 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R 12 is preferably a linear or branched alkylene group, such as methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentylyl, and hexamethylene . As R 13 , for example, methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentyl, hexamethylene, phenylene, cyclohexyl, -CH 2 are preferred. -Ph-CH 2- (Ph stands for phenylene).
作為(a2-II)不具有脂環式基之含環氧基之不飽和化合物，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)丙烯酸環氧烷基酯類；α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、α-乙基丙烯酸6,7-環氧庚酯等α-烷基丙烯酸環氧烷基酯類；等。該等之中，就共聚合反應性、硬化後之樹脂之強度等方面而言，較佳為(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯及(甲基)丙烯酸6,7-環氧庚酯。該等(a2-II)不具有脂環式基之含環氧基之不飽和化合物能夠單獨或組合2種以上使用。 Examples of the (a2-II) epoxy-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, (methyl ) Alkyl (meth) acrylates such as 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth) acrylate; glycidyl α-ethylacrylate, α-n-propyl Α-alkyl acrylate alkylene oxides such as glycidyl acrylate, α-n-butyl acrylate glycidyl ester, α-ethyl acrylate 6,7-epoxyheptyl acrylate; etc. Among these, in terms of copolymerization reactivity, strength of the cured resin, and the like, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and (meth) ) Acrylic acid 6,7-epoxyheptyl. These (a2-II) epoxy group-containing unsaturated compounds which do not have an alicyclic group can be used individually or in combination of 2 or more types.
作為相對於(a1)不飽和羧酸之共聚合成分，亦較佳為(a3)不具有環氧基之含脂環式基之不飽和化合物。 As a copolymerization component with respect to (a1) an unsaturated carboxylic acid, (a3) an alicyclic group-containing unsaturated compound which does not have an epoxy group is also preferable.
作為(a3)含脂環式基之不飽和化合物，若為具有脂環式基之不飽和化合物，則並無特別限定。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：金剛烷基、降
具體而言，作為(a3)含脂環式基之不飽和化合物，例如可列舉下述式(a3-1)~(a3-7)所表示之化合物。該等之中，就容易獲得顯影性良好之感光性組合物之方面而言，較佳為下述式(a3-3)~(a3-8)所表示之化合物，更佳為下述式(a3-3)、(a3-4)所表示之化合物。 Specifically, examples of the (a3) alicyclic group-containing unsaturated compound include compounds represented by the following formulae (a3-1) to (a3-7). Among these, a compound represented by the following formulae (a3-3) to (a3-8) is preferable, and a formula ( a3-3) and (a3-4).
上述式中，R21表示氫原子或甲基，R22表示單鍵或碳數1~6之2價脂肪族飽和烴基，R23表示氫原子或碳數1~5之烷基。作為R22，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、伸戊基、六亞甲基。作為R23，例如較佳為甲基、乙基。 In the above formula, R 21 represents a hydrogen atom or a methyl group, R 22 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R 23 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 22 is preferably a single bond, linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentyl, hexamethylene Methylene. R 23 is preferably methyl or ethyl, for example.
作為除(a2)含環氧基之不飽和化合物及(a3)不具有環氧基之含脂環式基之不飽和化合物以外的共聚合成分，可列舉：(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、烯丙基化合物、乙烯醚類、乙烯酯類、苯乙烯類等。該等化合物能夠單獨或組合2種以上使用。 Examples of copolymerization components other than (a2) an epoxy-containing unsaturated compound and (a3) an alicyclic group-containing unsaturated compound having no epoxy group include (meth) acrylates, ( (Meth) acrylamidines, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used individually or in combination of 2 or more types.
作為(甲基)丙烯酸酯類，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；氯(甲基)丙烯酸乙酯、(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；等。 Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and (meth) acrylic acid. Linear or branched alkyl (meth) acrylates such as trioctyl ester; ethyl chloro (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, (methyl) 2-hydroxyethyl acrylate, tris Methylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; etc.
作為(甲基)丙烯醯胺類，可列舉：(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N-芳基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺、N，N-芳基(甲基)丙烯醯胺、N-甲基-N-苯基(甲基)丙烯醯胺、N-羥乙基-N-甲基(甲基)丙烯醯胺等。 Examples of (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-diamine Alkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-formyl (Meth) acrylamide and the like.
作為烯丙基化合物，可列舉：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、乳酸烯丙酯等烯丙基酯類；烯丙氧基乙醇；等。 Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, Allyl acetate, such as allyl acetate, allyl lactate; allyloxyethanol; etc.
作為乙烯醚類，可列舉：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、羥乙基乙烯醚、二乙二醇乙烯醚、二甲基胺基乙基乙烯醚、二乙基胺基乙基乙烯醚、丁基胺基乙基乙烯醚、苄基乙烯醚、四氫呋喃甲基乙烯醚等烷基乙烯醚；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、乙烯基鄰胺苯甲醚等乙烯基芳醚；等。 Examples of vinyl ethers include 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, dimethylamino ethyl vinyl ether, di Alkyl vinyl ethers such as ethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, and tetrahydrofuran methyl vinyl ether; vinyl phenyl ether, vinyl toluene ether, vinyl chlorophenyl ether, Vinyl aromatic ethers such as vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl o-anisole; etc.
作為乙烯酯類，可列舉：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、戊酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、乙酸乙烯基甲氧基酯、乙酸乙烯基丁氧基酯、乙酸乙烯基苯基酯、乙酸乙烯基乙醯基酯、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、萘甲酸乙烯酯等。 Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, and dichloride. Vinyl acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl ethyl acetate, vinyl lactate, vinyl butyrate-beta-phenyl ester, benzene Vinyl formate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate and the like.
作為苯乙烯類，可列舉：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等烷基苯乙烯；甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯等烷氧基苯乙烯；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、4-氟-3-三氟甲基苯乙烯等鹵代苯乙烯；等。 Examples of the styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, Hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, Alkyl styrenes such as chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, and ethoxymethylstyrene; methoxystyrene, 4-methoxy-3-methyl Alkoxystyrene such as styrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, Halostyrene such as iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene; etc.
來自上述(a1)不飽和羧酸之構成單元於聚合物(A3)中所占之比率較佳為1~50質量%，更佳為5~40質量%。 The proportion of the constituent units derived from the (a1) unsaturated carboxylic acid in the polymer (A3) is preferably 1 to 50% by mass, and more preferably 5 to 40% by mass.
聚合物(A3)之質量平均分子量(Mw：藉由凝膠滲透層析法(GPC)之經聚苯乙烯換算之測定值。本說明書中，相同)較佳為2000~200000，更佳為5000~30000。藉由設為上述範圍，有容易取得感光性組合物之膜形成能力、曝光後之顯影性的平衡之傾向。 The mass average molecular weight of the polymer (A3) (Mw: measured value by polystyrene conversion by gel permeation chromatography (GPC). In this specification, the same) is preferably 2000 to 200000, and more preferably 5000 ~ 30000. By setting it as the said range, there exists a tendency for the balance of the film-forming ability of the photosensitive composition, and the developability after exposure to become easy easily.
聚合物(A3)能夠藉由公知之自由基聚合法而製造。即，能夠藉由如下方法製造：將各化合物及公知之自由基聚合起始劑溶解於聚合溶劑中後，進行加熱攪拌。 The polymer (A3) can be produced by a known radical polymerization method. That is, it can manufacture by dissolving each compound and a well-known radical polymerization initiator in a polymerization solvent, and heating and stirring.
又，作為聚合物(A3)，亦能夠較佳地使用如下樹脂，該樹脂包含：至少含有來自上述(a1)不飽和羧酸之構成單元、及具有能夠與下述(B)光聚合性單體聚合之部位之構成單元的共聚物(A4)；或至少含有來自上述(a1)不飽和羧酸之構成單元、來自上述(a2)含環氧基之不飽和化合物之構成單元、及具有能夠與下述光聚合性單體(B)聚合之部位之構成單元的共聚物(A5)。 Further, as the polymer (A3), it is also possible to preferably use a resin containing a structural unit derived from at least the unsaturated carboxylic acid (a1) and having a photopolymerizable monomer capable of reacting with the following (B) Copolymer (A4) of the structural unit of the polymerized portion; or at least a structural unit derived from the (a1) unsaturated carboxylic acid, a structural unit derived from the (a2) epoxy-containing unsaturated compound, and The copolymer (A5) of the structural unit of the site | part polymerized with the following photopolymerizable monomer (B).
共聚物(A4)及共聚物(A5)屬於包含乙烯性不飽和基之鹼可溶性樹脂。 The copolymer (A4) and the copolymer (A5) belong to an alkali-soluble resin containing an ethylenically unsaturated group.
於聚合物(A3)包含共聚物(A4)或共聚物(A5)之情形時，有感光性組合物對於基板之密接性、感光性組合物之硬化後的破壞強度較高之傾向。 When the polymer (A3) includes the copolymer (A4) or the copolymer (A5), there is a tendency that the adhesion of the photosensitive composition to the substrate and the breaking strength of the photosensitive composition after curing are high.
共聚物(A4)及共聚物(A5)亦可為使針對於共聚合成分而作為其他化合物所記載之(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、烯丙基化合物、乙烯醚類、乙烯酯類、苯乙烯類等進而共聚合者。 The copolymer (A4) and the copolymer (A5) may be (meth) acrylates, (meth) acrylamides, allyl compounds, ethylene, etc., which are described as other compounds for the copolymerization component. Ethers, vinyl esters, styrenes, etc. are further copolymerized.
具有能夠與(B)光聚合性單體聚合之部位之構成單元較佳為具有乙烯性不飽和基作為能夠與(B)光聚合性單體聚合之部位者。共聚物(A4)能夠藉由使上述(a1)不飽和羧酸之單獨聚合物中所含之羧基的至少一部分與上述(a2)含環氧基之不飽和化合物反應而製備。又，共聚物(A5)能夠藉由使具有來自上述(a1)不飽和羧酸之構成單元及來自上述(a2)含環氧基之不飽和化合物之構成單元的共聚物中之環氧基之至少一部分與(a1)不飽和羧酸反應而製備。 The constituent unit having a site capable of polymerizing with (B) a photopolymerizable monomer is preferably one having an ethylenically unsaturated group as a site capable of polymerizing with (B) a photopolymerizable monomer. The copolymer (A4) can be prepared by reacting at least a part of the carboxyl group contained in the separate polymer of the unsaturated carboxylic acid (a1) with the unsaturated compound containing the epoxy group in the (a2). In addition, the copolymer (A5) can be obtained by making the epoxy group in the copolymer having a structural unit derived from the (a1) unsaturated carboxylic acid and a structural unit derived from the (a2) epoxy-containing unsaturated compound. It is prepared by reacting at least a part with (a1) an unsaturated carboxylic acid.
再者，關於如共聚物(A4)及共聚物(A5)之包含具有能夠與(B)光聚合性單體聚合之部位的構成單元之樹脂，其單獨能夠較佳地用作(A)聚合性基材成分。 In addition, as for the resin including the copolymer (A4) and the copolymer (A5), which contains a structural unit having a site capable of polymerizing with the (B) photopolymerizable monomer, the resin alone can be preferably used as the (A) polymerization. Base material composition.
共聚物(A4)及共聚物(A5)之質量平均分子量較佳為2000~50000，更佳為5000~30000。藉由設為上述範圍，有容易取得感光性組合物之膜形成能力、曝光後之顯影性的平衡之傾向。 The mass average molecular weight of the copolymer (A4) and the copolymer (A5) is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By setting it as the said range, there exists a tendency for the balance of the film-forming ability of the photosensitive composition, and the developability after exposure to become easy easily.
以上所說明之鹼可溶性樹脂亦可組合並包含含有於主鏈上具有環結構之構成單元之聚合物與具有不飽和鍵的單體之聚合物。又，鹼可溶性樹脂亦可與含有於主鏈上具有環結構之構成單元之聚合物及具有不飽和鍵的單體之聚合物一起包含除該等樹脂以外之樹脂。 The alkali-soluble resin described above may also be combined and include a polymer containing a constituent unit having a ring structure on the main chain and a polymer containing a monomer having an unsaturated bond. The alkali-soluble resin may contain a resin other than these resins together with a polymer containing a constituent unit having a ring structure on the main chain and a polymer having a monomer having an unsaturated bond.
於鹼可溶性樹脂組合並包含含有於主鏈上具有環結構之構成單元之聚合物與具有不飽和鍵的單體之聚合物之情形時，兩者之混合比並無特別限定。含有於主鏈上具有環結構之構成單元之聚合物之質量相對於含有在主鏈上具有環結構之構成單元的聚合物之質量與具有不飽和鍵之單體之聚合物之質量的合計之比率較佳為1~99質量%，更佳為10~90質量%，尤佳為30~70質量%。 When the alkali-soluble resin is combined and contains a polymer containing a constituent unit having a ring structure on the main chain and a polymer containing a monomer having an unsaturated bond, the mixing ratio of the two is not particularly limited. The mass of the polymer containing a constituent unit having a ring structure on the main chain is relative to the total of the mass of the polymer containing a constituent unit having a ring structure on the main chain and the mass of the polymer having a monomer having an unsaturated bond. The ratio is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and even more preferably 30 to 70% by mass.
相對於感光性組合物之固形物成分之質量，感光性組合物中之鹼可溶性樹脂之含量較佳為40質量%以下，更佳為30~10質量%，尤佳為25~15質量%。又，(A)聚合性基材成分中之鹼可溶性樹脂之含量較佳為80質量%以下，更佳為60~20質量%，尤佳為50~30質量%。 The content of the alkali-soluble resin in the photosensitive composition is preferably 40% by mass or less, more preferably 30 to 10% by mass, and even more preferably 25 to 15% by mass, relative to the mass of the solid components of the photosensitive composition. The content of the alkali-soluble resin in the (A) polymerizable substrate component is preferably 80% by mass or less, more preferably 60 to 20% by mass, and even more preferably 50 to 30% by mass.
於作為感光性組合物中之鹼可溶性樹脂，含有包含乙烯性不飽和基(作為構成單元中之取代基而包含乙烯性不飽和基)的鹼可溶性樹脂之情形時，相對於感光性組合物之固形物成分之質量，較佳為60質量%以下，更佳為45~10質量%，尤佳為50~15質量%。又，(A)聚合性基材成分中之鹼可溶性樹脂之含量亦可為100質量%，較佳為100~30質量%。 When the alkali-soluble resin in the photosensitive composition contains an alkali-soluble resin containing an ethylenically unsaturated group (the ethylenically unsaturated group is contained as a substituent in the constituent unit), the content of the alkali-soluble resin is larger than that of the photosensitive composition. The mass of the solid component is preferably 60% by mass or less, more preferably 45 to 10% by mass, and even more preferably 50 to 15% by mass. The content of the alkali-soluble resin in the (A) polymerizable substrate component may be 100% by mass, and preferably 100 to 30% by mass.
<(B)光聚合起始劑> <(B) Photopolymerization initiator>
感光性組合物含有包含下述式(1)所表示之化合物(B1)(以下，亦記作化合物(B1))之(B)光聚合起始劑(以下，亦記作「(B)成分」)。本發明之感光性組合物包含化合物(B1)作為(B)光聚合起始劑，故而感度非常優異。因此，藉由使用本發明之感光性組合物，能夠以低曝光量形成所需形狀之圖案。 The photosensitive composition contains (B) a photopolymerization initiator (hereinafter, also referred to as "(B) component") containing the compound (B1) (hereinafter, also referred to as compound (B1)) represented by the following formula (1) "). Since the photosensitive composition of the present invention contains the compound (B1) as a (B) photopolymerization initiator, the sensitivity is very excellent. Therefore, by using the photosensitive composition of the present invention, a pattern in a desired shape can be formed with a low exposure.
又，感光性組合物包含化合物(B1)作為(B)光聚合起始劑，藉此能夠形成對於基板之密接性良好，幾乎不含異物，為所需色相之著色膜。 In addition, the photosensitive composition contains the compound (B1) as a (B) photopolymerization initiator, whereby a colored film having good adhesion to the substrate, almost no foreign matter, and a desired hue can be formed.
(Rb1為氫原子、硝基或1價有機基，Rb2及Rb3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，Rb2與Rb3亦可相互鍵結而形成環，Rb4為1價有機基，Rb5為氫原子、可具有取代基之碳原子數1~11之烷基或可具有取代基之芳基，w為0~4之整數，v為0或1) (R b1 is a hydrogen atom, a nitro group or a monovalent organic group, R b2 and R b3 are a chain alkyl group which may have a substituent, a cyclic organic group or a hydrogen atom which may have a substituent, R b2 and R b3 R b4 is a monovalent organic group, R b5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and w is 0 to An integer of 4 and v is 0 or 1)
式(1)中，Rb1為氫原子、硝基或1價有機基。Rb1係於式(1)中之茀環上，鍵結於與鍵結於-(CO)v-所表示之基上之6員芳香環不同的6員芳香環上。式(1)中，Rb1相對於茀環之鍵結位置並無特別限定。於化合物(B1)具有1以上之Rb1之情形時，就化合物(B1)之合成較容易之方面等而言，較佳為1以上之Rb1中之1個鍵結於茀環中之2位上。於Rb1為複數之情形時，複數之Rb1可相同，亦可不同。 In the formula (1), R b1 is a hydrogen atom, a nitro group, or a monovalent organic group. R b1 is attached to the fluorene ring in formula (1) and is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the base represented by-(CO) v- . In formula (1), the bonding position of R b1 with respect to the fluorene ring is not particularly limited. In the case where the compound (B1) has R b1 of 1 or more, in terms of easier synthesis of the compound (B1), one of R b1 of 1 or more is preferably bonded to 2 of the fluorene ring Bit on. When R b1 is plural, the plural R b1 may be the same or different.
於Rb1為有機基之情形時，Rb1於不損害本發明之目的之範圍內，並無特別限定，自各種有機基適當選擇。作為Rb1為有機基之情形時之較佳之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、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或2之有機基取代之胺基、嗎啉-1-基及哌
於Rb1為烷基之情形時，烷基之碳原子數較佳為1~20，更佳為1~6。又，於Rb1為烷基之情形時，可為直鏈，亦可為支鏈。作為Rb1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Rb1為烷基之情 形時，烷基亦可於碳鏈中包含醚鍵(-O-)。作為於碳鏈上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 b1 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 6. When R b1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R b1 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third 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- Decyl and isodecyl. When R b1 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 on the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl and methoxypropyl.
於Rb1為烷氧基之情形時，烷氧基之碳原子數較佳為1~20，更佳為1~6。又，於Rb1為烷氧基之情形時，可為直鏈，亦可為支鏈。作為Rb1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Rb1為烷氧基之情形時，烷氧基亦可於碳鏈中包含醚鍵(-O-)。作為於碳鏈上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 b1 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 20, and more preferably 1 to 6. When R b1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R b1 is an alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and second butoxy , Third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. When R b1 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond on the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy Groups, propoxyethoxyethoxy and methoxypropoxy.
於Rb1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3~10，更佳為3~6。作為Rb1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Rb1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 b1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples when R b1 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R b1 is a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
於Rb1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2~21，更佳為2~7。作為Rb1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Rb1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 b1 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyl group, the number of carbon atoms of the saturated aliphatic fluorenyl group or the saturated aliphatic fluorenyl group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R b1 is a saturated aliphatic fluorenyl group include ethyl fluorenyl, propionyl, n-butylfluorenyl, 2-methylpropylfluorenyl, n-pentylfluorenyl, and 2,2-dimethyl Propyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridyl, n-thyl Carbofluorenyl, n-pentadecafluorenyl and n-hexadecanocarbyl. Specific examples in the case where R b1 is a saturated aliphatic fluorenyloxy group include ethoxyl, propionyloxy, n-butyridyloxy, 2-methylpropionyloxy, and n-pentamyloxy , 2,2-dimethylpropoxyl, n-hexamethyleneoxy, n-heptylfluorenyloxy, n-octylfluorenyloxy, n-nonylfluorenyloxy, n-decylfluorenyloxy, n-undecylfluorenyloxy, N-dodecylfluorenyloxy, n-tridecylfluorenyloxy, n-tetradecylfluorenyloxy, n-pentadecafluorenyloxy, n-hexadecylfluorenyloxy, etc.
於Rb1為烷氧羰基之情形時，烷氧羰基之碳原子數較佳為2~20，更佳為2~7。作為Rb1為烷氧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 b1 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 20, and more preferably 2 to 7. Specific examples when R b1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and isobutoxycarbonyl , Second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy Carbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonoxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxy Carbonyl, etc.
於Rb1為苯基烷基之情形時，苯基烷基之碳原子數較佳為7~20，更佳為7~10。又，於Rb1為萘基烷基之情形時，萘基烷基之碳原子數較佳為11~20，更佳為11~14。作為Rb1為苯基烷基之情形時之具體例，可列舉：苄基、2-苯乙基、3-苯基丙基及4-苯基丁基。作為Rb1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Rb1為苯基烷基或萘基烷基之情形時，Rb1亦可於苯基或萘基上進而具有取代基。 When R b1 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. When R b1 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, and more preferably 11 to 14. Specific examples when R b1 is a phenylalkyl group include benzyl, 2-phenethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R b1 is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) ) Ethyl. When R b1 is phenylalkyl or naphthylalkyl, R b1 may further have a substituent on phenyl or naphthyl.
於Rb1為雜環基之情形時，雜環基為包含1以上之N、S、O之5員或6員之單環，或者為該單環彼此或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，設為至環數3為止者。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、
於Rb1為雜環基羰基之情形時，雜環基羰基中所含之雜環基與Rb1為雜環基之情形相同。 When R b1 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when R b1 is a heterocyclic group.
於Rb1為經1或2之有機基取代之胺基之情形時，作為有機基之較佳之例，可列舉：碳原子數1~20之烷基、碳原子數3~10之環烷基、碳原子數2~21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7~20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11~20之萘基烷基及雜環基等。該等較佳之有機基之具體例與Rb1相同。作為經1或2之有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、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 b1 is an amine group substituted with an organic group of 1 or 2, as a preferable example of the organic group, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms can be cited. Saturated aliphatic fluorenyl group having 2 to 21 carbon atoms, phenyl group which may have a substituent, benzamidine group which may have a substituent, phenylalkyl group which may have a substituent of 7 to 20 carbon atoms, may A naphthyl group having a substituent, a naphthylmethyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a carbon atom having 11 to 20, a heterocyclic group, and the like. Specific examples of these preferable organic groups are the same as those of R b1 . Specific examples of the amino group substituted with an organic group of 1 or 2 include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, and isopropyl Amino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamine Group, phenylamino group, naphthylamino group, ethylamino group, propionylamino group, n-butylmethylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, Octylamino, n-decanoylamino, benzamidineamino, α-naphthylamino and β-naphthylamino, and the like.
作為Rb1中所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基，可列舉：碳原子數1~6之烷基、碳原子數1~6之烷氧基、碳原子數2~7之飽和脂肪族醯基、碳原子數2~7之烷氧羰基、碳原子數2~7之飽和脂肪族醯氧基、具有碳原子數1~6之烷基之單烷基胺基、具有碳原子數1~6之烷基之二烷基胺基、嗎啉-1-基、哌
以上所說明之基中，作為Rb1，若為硝基或Rb6-CO-所表示之基，則有感度提昇之傾向，因此較佳。Rb6於不損害本發明之目的之範圍內，並無特別限定，能夠自各種有機基中選擇。作為適合作為Rb6之基之例，可列舉：碳原子數1~20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Rb6，該等基中，尤佳為2-甲基苯基、噻吩-2-基及α-萘基。 Among the bases described above, as R b1 , if it is a base represented by a nitro group or R b6 -CO-, the sensitivity tends to increase, so it is preferable. R b6 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of a suitable group for R b6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As R b6 , among these groups, 2-methylphenyl, thien-2-yl, and α-naphthyl are particularly preferred.
又，若Rb1為氫原子，則有透明性變得良好之傾向，因此較佳。再者，若Rb1為氫原子且Rb4為下述式(R4-2)所表示之基，則有透明性變得更良好之傾向。 In addition, if R b1 is a hydrogen atom, the transparency tends to be good, so it is preferable. When R b1 is a hydrogen atom and R b4 is a group represented by the following formula (R4-2), the transparency tends to be better.
式(1)中，Rb2及Rb3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。Rb2與Rb3亦可相互鍵結而形成環。該等基中，作為Rb2及Rb3，較佳為可具有取代基之鏈狀烷基。於Rb2及Rb3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 b2 and R b3 are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R b2 and R b3 may be bonded to each other to form a ring. Among these groups, R b2 and R b3 are preferably a linear alkyl group which may have a substituent. When R b2 and R b3 are a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.
於Rb2及Rb3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1~20，更佳為1~10，尤佳為1~6。作為Rb2及Rb3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Rb2及Rb3為烷基之情形時，烷基亦可於碳鏈上包含醚鍵(-O-)。作為於碳鏈上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 b2 and R b3 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6. Specific examples when R b2 and R b3 are linear alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third 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. When R b2 and R b3 are alkyl groups, the alkyl group may include an ether bond (-O-) on the carbon chain. Examples of the alkyl group having an ether bond on the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl and methoxypropyl.
於Rb2及Rb3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1~20，更佳為1~10，尤佳為1~6。於該情形時，取代基 之碳原子數不包含於鏈狀烷基之碳原子數中。具有取代基之鏈狀烷基較佳為直鏈狀。 When R b2 and R b3 are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The linear alkyl group having a substituent is preferably linear.
烷基可具有之取代基於不損害本發明之目的之範圍內，並無特別限定。作為取代基之較佳之例，可列舉氰基、鹵素原子、環狀有機基及烷氧羰基。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Rb1為環烷基之情形時之較佳之例相同。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Rb1為雜環基之情形時之較佳之例相同。於Rb1為烷氧羰基之情形時，烷氧羰基中所含之烷氧基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。烷氧羰基中所含之烷氧基之碳原子數較佳為1~10，更佳為1~6。 The substitution which an alkyl group may have is not specifically limited within the range which does not impair the objective of this invention. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. A specific example of the cycloalkyl group is the same as a preferable example when R b1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. Specific examples of the heterocyclic group are the same as the preferable examples when R b1 is a heterocyclic group. When R b1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.
於鏈狀烷基具有取代基之情形時，取代基之數並無特別限定。較佳之取代基之數根據鏈狀烷基之碳原子數而變化。典型性而言，取代基之數為1~20，較佳為1~10，更佳為1~6。 When a linear alkyl group has a substituent, the number of substituents is not specifically limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. Typically, the number of substituents is 1 to 20, preferably 1 to 10, and more preferably 1 to 6.
於Rb2及Rb3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Rb2及Rb3為環狀有機基之情形時，環狀有機基可具有之取代基與Rb2及Rb3為鏈狀烷基之情形相同。 When R b2 and R b3 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. When R b2 and R b3 are cyclic organic groups, the substituents which the cyclic organic group may have are the same as when R b2 and R b3 are chain alkyl groups.
於Rb2及Rb3為芳香族烴基之情形時，芳香族烴基較佳為苯基，或者為複數之苯環經由碳-碳鍵而鍵結所形成之基，或者為複數之苯環縮合而形成之基。於芳香族烴基為苯基，或者為複數之苯環鍵結或縮合而形成之基之情形時，芳香族烴基中所含的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 b2 and R b3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by a plurality of benzene rings bonded via a carbon-carbon bond, or a plurality of benzene rings condensed and Formation of 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 rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, but it is preferably 3 or less, more preferably It is preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.
於Rb2及Rb3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並無特別限定，較佳為3~20，更佳為3~10。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
於Rb2及Rb3為雜環基之情形時，雜環基為包含1以上之N、S、O的5員或6員之單環，或者該單環彼此或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，設為至環數3為止者。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、
Rb2與Rb3亦可相互鍵結而形成環。包含Rb2與Rb3所形成之環之基較佳為環亞烷基。於Rb2與Rb3鍵結而形成環亞烷基之情形時，構成環亞烷基之環較佳為5員環~6員環，更佳為5員環。 R b2 and R b3 may be bonded to each other to form a ring. The group containing a ring formed by R b2 and R b3 is preferably a cycloalkylene group. In the case where R b2 and R b3 are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.
於Rb2與Rb3鍵結而形成之基為環亞烷基之情形時，環亞烷基亦可與1以上之其他環縮合。作為可與環亞烷基縮合之環之例，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
作為以上所說明之Rb2及Rb3中較佳之基之例，可列舉式-A1-A2所表示之基。式中，A1為直鏈伸烷基，A2為烷氧基、氰基、鹵素原子、鹵素化烷基、環狀有機基或烷氧羰基。 As examples of preferred bases among R b2 and R b3 described above, the bases represented by the formulas -A 1 -A 2 may be mentioned. In the formula, A 1 is a linear alkylene group, and A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
A1之直鏈伸烷基之碳原子數較佳為1~10，更佳為1~6。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1~10，更佳為1~6。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為鹵素化烷基之情形時，鹵素化烷基中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。鹵素化烷基可為直鏈狀，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Rb2及Rb3作為取代基而具有之環狀有機基相同。於A2為烷氧羰基之情形時，烷氧羰基之例與Rb2及Rb33作為取代基而具有之烷氧羰基相同。 The number of carbon atoms of the linear alkylene group of A 1 is preferably 1 to 10, and more preferably 1 to 6. When A 2 is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. When A 2 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. In the case where 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, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or 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 group which R b2 and R b3 have as a substituent. In the case where A 2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group having R b2 and R b33 as substituents.
作為Rb2及Rb3之較佳之具體例，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-正辛基等氰烷基；2-苯乙基、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-正戊基等鹵素化烷基。 Preferred specific examples of R b2 and R b3 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-methyl Oxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy -Alkoxyalkyl groups such as n-hexyl, 7-ethoxy-n-heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano- Cyanoalkyl groups such as n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl and 8-cyano-n-octyl; 2-phenethyl, 3 -Phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl Groups such as phenylalkyl; 2-cyclohexylethyl; 3-cyclohexyl-n-propyl; 4-cyclohexyl-n-butyl; 5-cyclohexyl-n-pentyl; 6-cyclohexyl-n-hexyl; -Cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl Cycloalkylalkyl groups such as n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-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-ethoxy Alkane such as carbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl 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-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo- Halogenated alkyl groups such as n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.
作為Rb2及Rb3，上述中較佳之基為乙基、正丙基、正丁基、正戊基、2-甲氧基乙基、2-氰乙基、2-苯乙基、2-環己基乙基、2-甲氧基羰乙基、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。 As R b2 and R b3 , preferred groups among the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenethyl, 2- Cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5 -Heptafluoro-n-pentyl.
作為Rb4之較佳之有機基之例，與Rb1相同，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、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或2之有機基取代之胺基、嗎啉-1-基及哌
於有機基中，作為Rb4，較佳為烷基、環烷基、可具有取代基之苯基或環烷基烷基、可於芳香環上具有取代基之苯基硫烷基。作為烷基，較佳為碳原子數1~20之烷基，更佳為碳原子數1~8之烷基，尤佳為碳原子數1~4之烷基，最佳為甲基。於可具有取代基之苯基中，較佳為甲基苯基，更佳為2-甲基苯基。環烷基烷基中所含之環烷基之 碳原子數較佳為5~10，更佳為5~8，尤佳為5或6。環烷基烷基中所含之伸烷基之碳原子數較佳為1~8，更佳為1~4，尤佳為2。環烷基烷基之中，較佳為環戊基乙基。可於芳香環上具有取代基之苯基硫烷基中所含之伸烷基之碳原子數較佳為1~8，更佳為1~4，尤佳為2。可於芳香環上具有取代基之苯基硫烷基中，較佳為2-(4-氯苯基硫)乙基。 Among the organic groups, R b4 is preferably an alkyl group, a cycloalkyl group, a phenyl group or a cycloalkylalkyl group which may have a substituent, and a phenylsulfanyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. 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 of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and even more preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and even more preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylsulfanyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and even more preferably 2. Among the phenylsulfanyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylsulfanyl) ethyl is preferred.
又，作為Rb4，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 b4 , a group represented by -A 3 -CO-OA 4 is also preferable. A 3 is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. A 4 is a monovalent organic group, and is 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1~10，更佳為1~6，尤佳為1~4。 When A 3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. In the case where A 3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
作為A4之較佳之例，可列舉：碳原子數1~10之烷基、碳原子數7~20之芳烷基及碳原子數6~20之芳香族烴基。作為A4之較佳之具體例，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。 Preferred examples of A 4 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. Preferred specific examples of A 4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, and n-hexyl. , Phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl and β-naphthylmethyl.
作為-A3-CO-O-A4所表示之基之較佳之具體例，可列舉：2-甲氧基羰乙基、2-乙氧基羰乙基、2-正丙氧基羰乙基、2-正丁氧基羰乙基、2-正戊氧基羰乙基、2-正己氧基羰乙基、2-苄氧基羰乙基、2-苯氧基羰乙基、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。 Preferred 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Rb4進行了說明，作為Rb4，較佳為下述式(R4-1)或(R4-2)所表示之基。 As described above, R b4 has been described, and R b4 is preferably a base represented by the following formula (R4-1) or (R4-2).
(式(R4-1)及(R4-2)中，Rb7及Rb8分別為有機基，p為0~4之整數，於Rb7及Rb8存在於苯環上之鄰接之位置之情形時，Rb7與Rb8亦可相互鍵結而形成環，q為1~8之整數，r為1~5之整數，s為0~(r+3)之整數，Rb9為有機基) (In the formulae (R4-1) and (R4-2), R b7 and R b8 are organic groups respectively, and p is an integer of 0 to 4, in the case where R b7 and R b8 are adjacent to each other on the benzene ring. When R b7 and R b8 are bonded to each other to form a ring, q is an integer from 1 to 8, r is an integer from 1 to 5, s is an integer from 0 to (r + 3), and R b9 is an organic group)
關於式(R4-1)中之Rb7及Rb8之有機基之例與Rb1相同。作為Rb7，較佳為烷基或苯基。於Rb7為烷基之情形時，其碳原子數較佳為1~10，更佳為1~5，尤佳為1~3，最佳為1。即，Rb7最佳為甲基。於Rb7與Rb8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。作為式(R4-1)所表示之基、即Rb7與Rb8形成環之基的較佳之例，可列舉萘-1-基或1,2,3,4-四氫化萘-5-基等。上述式(R4-1)中，p為0~4之整數，較佳為0或1，更佳為0。 Examples of the organic groups of R b7 and R b8 in the formula (R4-1) are the same as those of R b1 . R b7 is preferably an alkyl group or a phenyl group. When R b7 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R b7 is preferably a methyl group. When R b7 and R b8 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. As a preferable example of the group represented by formula (R4-1), that is, the group in which R b7 and R b8 form a ring, naphthalen-1-yl or 1,2,3,4-tetrahydronaphthalen-5-yl Wait. In the above formula (R4-1), p is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
上述式(R4-2)中，Rb9為有機基。作為有機基，可列舉：與針對於Rb1所說明之有機基相同之基。於有機基中，較佳為烷基。烷基可為直鏈狀，亦可為支鏈狀。烷基之碳原子數較佳為1~10，更佳為1~5，尤佳為1~3。作為Rb9，可較佳地例示甲基、乙基、丙基、異丙基、丁基等，該等之中，更佳為甲基。 In the formula (R4-2), R b9 is an organic group. Examples of the organic group include the same groups as those described for R b1 . Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3. Examples of R b9 include methyl, ethyl, propyl, isopropyl, and butyl. Among these, methyl is more preferred.
上述式(R4-2)中，r為1~5之整數，較佳為1~3之整數，更佳為1或2。上述式(R4-2)中，s為0~(r+3)，較佳為0~3之整數，更佳為0~2之整數，尤佳為0。上述式(R4-2)中，q為1~8之整數，較佳為1~5之整數，更佳為1~3之整數，尤佳為1或2。 In the formula (R4-2), r is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (R4-2), s is 0 to (r + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0. In the above formula (R4-2), q is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
式(1)中，Rb5為氫原子、可具有取代基之碳原子數1~11之烷基 或可具有取代基之芳基。作為Rb5為烷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Rb1為芳基之情形時可具有之取代基，可較佳地例示碳原子數1~5之烷基、烷氧基、鹵素原子等。 In the formula (1), R b5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Examples of the substituent which R b5 may have when it is an alkyl group include a phenyl group and a naphthyl group. In addition, examples of the substituent which may be possessed when R b1 is an aryl group include alkyl groups having 1 to 5 carbon atoms, alkoxy groups, and halogen atoms.
式(1)中，作為Rb5，可較佳地例示氫原子、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，更佳為甲基或苯基。 In formula (1), as R b5 , a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl, etc. can be preferably exemplified. Among these, methyl or phenyl is more preferable.
相對於感光性組合物之固形物成分之合計100質量份，作為(B)成分之光聚合起始劑之含量較佳為0.001~30質量份，更佳為0.1~20質量份，進而較佳為0.5~10質量份。 The content of the photopolymerization initiator as the component (B) is preferably 0.001 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 100 parts by mass of the total solid components of the photosensitive composition. It is 0.5 to 10 parts by mass.
又，相對於(A)成分與(B)成分之總和，作為(B)成分之光聚合起始劑之含量較佳為0.1~50質量%，更佳為0.5~30質量%，進而較佳為1~20質量%。 The content of the photopolymerization initiator as the component (B) is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, and even more preferably relative to the total of the components (A) and (B). It is 1 to 20% by mass.
化合物(B1)之含量只要相對於例如(B)成分整體而為1~100質量%之範圍，則較佳為50質量%以上，更佳為70~100質量%。 The content of the compound (B1) is, for example, in the range of 1 to 100% by mass based on the entire (B) component, preferably 50% by mass or more, and more preferably 70 to 100% by mass.
(B)成分中之化合物(B1)可單獨使用，亦可使用2種以上，於使用2種以上之情形時，較佳為以下之(i)~(iii)。 The compound (B1) in the component (B) may be used singly, or two or more kinds may be used. When two or more kinds are used, the following (i) to (iii) are preferred.
(i)Rb1為氫原子之化合物與Rb1為硝基之化合物之組合 (i) Combination of a compound in which R b1 is a hydrogen atom and a compound in which R b1 is a nitro group
(ii)Rb4為式(R4-1)之化合物與Rb4為式(R4-2)之化合物之組合 (ii) the combination of R b4 is a compound of formula (R4-1) and R b4 is a compound of formula (R4-2)
(iii)Rb4為式(R4-1)或式(R4-2)之化合物與Rb4為碳原子數1~4之烷基之化合物 compound (III) R b4 is of formula (R4-1) or Formula (R4-2) and R b4 is a number of carbon atoms of an alkyl group of 1 to 4
其中，就感度及硬化物之透過率等特性提昇之方面而言，較佳為上述(i)之組合，更佳為滿足上述(i)與(ii)或(iii)之組合。 Among these, in terms of improvement in characteristics such as sensitivity and transmittance of the hardened material, the combination of the above (i) is preferable, and the combination of the above (i) and (ii) or (iii) is more preferable.
上述(i)~(iii)之組合之各化合物之調配比(質量比)只要根據目標感度等特性而適當調整即可，例如較佳為1：99~99：1，更佳為10：90~90：10，進而較佳為30：70~70：30。 The compounding ratio (mass ratio) of each compound in the combination of the above (i) to (iii) may be appropriately adjusted according to characteristics such as target sensitivity, for example, 1:99 to 99: 1 is preferred, and 10:90 is more preferred. ~ 90: 10, more preferably 30: 70 ~ 70: 30.
化合物(B1)之製造方法並無特別限定。化合物(B1)較佳為藉由包 括將下式(2)所表示之化合物中所含之肟基(=N-OH)轉換成=N-O-CORb5所表示之肟酯基的步驟之方法而製造。Rb5與式(1)中之Rb5相同。 The manufacturing method of a compound (B1) is not specifically limited. The compound (B1) is preferably a method comprising a step of converting an oxime group (= N-OH) contained in the compound represented by the following formula (2) into an oxime ester group represented by = NO-COR b5 Manufacturing. Same as R (1) and b5 R b5 in the formula.
(Rb1、Rb2、Rb3、Rb4、v及w與式(1)相同。w為0~4之整數，v為0或1) (R b1 , R b2 , R b3 , R b4 , v, and w are the same as in formula (1). W is an integer from 0 to 4, and v is 0 or 1)
因此，上述式(2)所表示之化合物作為化合物(B1)之合成用中間物而較為有用。 Therefore, the compound represented by the formula (2) is useful as an intermediate for the synthesis of the compound (B1).
將肟基(=N-OH)轉換成=N-O-CORb5所表示之肟酯基之方法並無特別限定。典型性而言，可列舉：使給予-CORb5所表示之醯基之醯基化劑與肟基中之羥基反應之方法。作為醯基化劑，可列舉：(Rb5CO)2O所表示之酸酐或Rb5COHal(Hal為鹵素原子)所表示之醯鹵化物。 The method for converting an oxime group (= N-OH) into an oxime ester group represented by = NO-COR b5 is not particularly limited. Typical methods include a method of reacting a sulfonating agent which imparts a fluorenyl group represented by -COR b5 with a hydroxyl group in an oxime group. Examples of the fluorenating agent include an acid anhydride represented by (R b5 CO) 2 O or a fluorene halide represented by R b5 COHal (Hal is a halogen atom).
關於化合物(B1)，於v為0之情形時，例如能夠根據下述流程1而合成。於流程1中，使用下述式(1-1)所表示之茀衍生物作為原料。於Rb1為硝基或1價有機基之情形時，式(1-1)所表示之茀衍生物能夠利用周知之方法於以Rb2及Rb3取代9位之茀衍生物中導入取代基Rb1而獲得。關於以Rb2及Rb3取代9位之茀衍生物，例如於Rb2及Rb3為烷基之情形時，能夠如日本專利特開平06-234668號公報中所記載般，於鹼性金屬氫氧化物之存在下使茀與烷基化劑於非質子性極性有機溶劑中反應而獲得。又，於茀之有機溶劑溶液中添加如鹵素化烷基之烷基化劑、鹼性金屬氫氧化物之水溶液及如碘化四丁基銨或鉀第三丁氧化物 之相間轉移觸媒而進行烷基化反應，藉此能夠獲得9,9-烷基取代茀。 About compound (B1), when v is 0, it can synthesize | combine according to the following scheme 1, for example. In Scheme 1, a fluorene derivative represented by the following formula (1-1) was used as a raw material. When R b1 is a nitro group or a monovalent organic group, a fluorene derivative represented by the formula (1-1) can be introduced into a fluorene derivative substituted with R b2 and R b3 at the 9-position by a known method. R b1 . Regarding the fluorene derivative in which the 9-position is substituted with R b2 and R b3 , for example, when R b2 and R b3 are alkyl groups, they can be used in basic metal hydrogen as described in Japanese Patent Laid-Open No. 06-234668. Obtained by reacting amidine with an alkylating agent in an aprotic polar organic solvent in the presence of an oxide. In addition, to the organic solvent solution of rhenium, an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and an interphase transfer catalyst such as tetrabutylammonium iodide or potassium third butoxide are added, and By performing an alkylation reaction, 9,9-alkyl substituted fluorene can be obtained.
利用夫里得-誇夫特醯基化反應於式(1-1)所表示之茀衍生物中導入-CO-Rb4所表示之醯基而獲得式(1-3)所表示之茀衍生物。用於導入-CO-Rb4所表示之醯基之醯基化劑可為鹵羰基化合物，亦可為酸酐。作為醯基化劑，較佳為式(1-2)所表示之鹵羰基化合物。式(1-2)中，Hal為鹵素原子。於茀環上導入有醯基之位置能夠藉由適當變更夫里得-誇夫特反應之條件、或者於除醯基化之位置以外之其他位置實施保護及脫保護的方法而進行選擇。 The hydrazone derivative represented by formula (1-3) is obtained by introducing a fluorenyl group represented by -CO-R b4 into a fluorene derivative represented by formula (1-1) by using a Fridt-quarf hydration reaction. Thing. The halogenating agent for introducing the fluorenyl group represented by -CO-R b4 may be a halocarbonyl compound or an acid anhydride. The halogenating agent is preferably a halocarbonyl compound represented by the formula (1-2). In the formula (1-2), Hal is a halogen atom. The position at which the fluorene group is introduced into the fluorene ring can be selected by appropriately changing the conditions of the Fridt-Quarft reaction or by performing protection and deprotection at positions other than the position of the fluorene group.
其次，將所獲得之式(1-3)所表示之茀衍生物中之-CO-Rb4所表示之基轉換成-C(=N-OH)-Rb4所表示之基而獲得式(1-4)所表示之肟化合物。將-CO-Rb4所表示之基轉換成-C(=N-OH)-Rb4所表示之基的方法並無特別限定，較佳為藉由羥胺之肟化。能夠使式(1-4)之肟化合物與下式(1-5)所表示之酸酐((Rb5CO)2O)或下述通式(1-6)所表示之醯鹵化物(Rb5COHal、Hal為鹵素原子)反應而獲得下述式(1-7)所表示之化合物。 Next, the base represented by -CO-R b4 in the obtained europium derivative represented by formula (1-3) is converted into a base represented by -C (= N-OH) -R b4 to obtain a formula ( The oxime compound represented by 1-4). The method for converting the group represented by -CO-R b4 to the group represented by -C (= N-OH) -R b4 is not particularly limited, and it is preferably oximation by hydroxylamine. The oxime compound of the formula (1-4) and the acid anhydride ((R b5 CO) 2 O) represented by the following formula (1-5) or the phosphonium halide (R represented by the following general formula (1-6)) b5 COHal and Hal are halogen atoms) to obtain a compound represented by the following formula (1-7).
再者，式(1-1)、(1-2)、(1-3)、(1-4)、(1-5)、(1-6)及(1-7)中，Rb1、Rb2、Rb3、Rb4及Rb5與式(1)相同。 Furthermore, in the formulae (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), R b1 , R b2 , R b3 , R b4 and R b5 are the same as those in formula (1).
又，流程1中，式(1-2)、式(1-3)及式(1-4)分別含有之Rb4可相同，亦可不同。即，式(1-2)、式(1-3)及式(1-4)中之Rb4亦可於流程1所示之合成過程中受到化學修飾。作為化學修飾之例，可列舉：酯化、醚化、醯基化、醯胺化、鹵素化、藉由胺基中之氫原子之有機基之取代等。Rb4可受到之化學修飾並不限定於該等。 In Scheme 1, R b4 contained in formula (1-2), formula (1-3), and formula (1-4) may be the same or different. That is, R b4 in Formula (1-2), Formula (1-3), and Formula (1-4) may also be chemically modified during the synthesis process shown in Scheme 1. Examples of the chemical modification include esterification, etherification, amidation, amidation, halogenation, substitution of an organic group with a hydrogen atom in an amine group, and the like. The chemical modifications that R b4 can undergo are not limited to these.
<流程1> <Process 1>
於v為1之情形時，化合物(B1)例如能夠依據下述流程2而合成。於流程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依據與流程1相同之方法，利用夫里得-誇夫特反應將-CO-CH2-Rb4所表示之醯基導入至式(1-1)所表示之化合物中而獲得。作為醯基化劑，較佳為式(1-8)：Hal-CO-CH2-Rb4所表示之羧醯鹵化物。其次，使存在於式(2-1)所表示之化合物中之Rb4與羰基之間的亞甲基肟化而獲得下式(2-3)所表示之酮肟化合物。使亞甲基肟化之方法並無特別限定，較佳為於鹽酸之存在下使下述通式(2-2)所表示之亞硝酸酯(RONO、R為碳數1~6之烷基)反應的方法。其次，能夠使下述式(2-3)所表示之酮肟化合物與下述式(2-4)所表示之酸酐((Rb5CO)2O)或下述通式(2-5)所表示之醯鹵化物(Rb5COHal、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，Rb1、Rb2、Rb3、Rb4及Rb5與通式(1)相同。 When v is 1, the compound (B1) can be synthesized according to the following scheme 2, for example. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by formula (2-1) is based on the same method as in Scheme 1, and the fluorenyl group represented by -CO-CH 2 -R b4 is introduced into the formula (1- 1). The fluorenating agent is preferably a carboxylic phosphonium halide represented by the formula (1-8): Hal-CO-CH 2 -R b4 . Next, the methylene oxime between R b4 and the carbonyl group in the compound represented by the formula (2-1) is oxidized to obtain a ketoxime compound represented by the following formula (2-3). The method for oximizing methylene is not particularly limited, and it is preferred that a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (2-2) in the presence of hydrochloric acid ) Method of reaction. Next, the ketoxime compound represented by the following formula (2-3) and the acid anhydride ((R b5 CO) 2 O) represented by the following formula (2-4) or the following general formula (2-5) The fluorene halide represented (R b5 COHal, Hal is a halogen atom) is reacted to obtain a compound represented by the following formula (2-6). In addition, in the following formulae (2-1), (2-3), (2-4), (2-5), and (2-6), R b1 , R b2 , R b3 , R b4, and R b5 is the same as the general formula (1).
於v為1之情形時，有能夠進一步降低使用含有化合物(B1)之感光性組合物形成之圖案中的異物之產生之傾向。 When v is 1, there is a tendency that the generation of foreign matter in a pattern formed using the photosensitive composition containing the compound (B1) can be further reduced.
又，流程2中，式(1-8)、式(2-1)及式(2-3)分別含有之Rb4可相同，亦可不同。即，式(1-8)、式(2-1)及式(2-3)中之Rb4亦可於流程2所示之合成過程中受到化學修飾。作為化學修飾之例，可列舉：酯化、醚化、醯基化、醯胺化、鹵素化、藉由胺基中之氫原子之有機基之取代等。Rb4所受到之化學修飾並不限定於該等。 In Scheme 2, R b4 contained in Formula (1-8), Formula (2-1), and Formula (2-3) may be the same or different. That is, R b4 in Formula (1-8), Formula (2-1), and Formula (2-3) may also be chemically modified during the synthesis process shown in Scheme 2. Examples of the chemical modification include esterification, etherification, amidation, amidation, halogenation, substitution of an organic group with a hydrogen atom in an amine group, and the like. The chemical modification of R b4 is not limited to these.
<流程2> <Process 2>
作為化合物(B1)之較佳之具體例，可列舉以下之化合物1~化合物41。 Specific preferable examples of the compound (B1) include the following compounds 1 to 41.
感光性組合物視需要亦可包含除式(1)所表示之化合物以外之光聚合起始劑(B2)(以下，亦記作起始劑(B2))。作為其他光聚合起始劑之具體例，可列舉：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-(甲基硫)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟、2,4,6-三甲基苯甲醯基二苯基氧化膦、4-苯甲醯基-4'-甲基二甲基硫化物、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-2-乙基己基苯甲酸、4-二甲基胺基-2-異戊基苯甲酸、苄基-β-甲氧基乙基縮醛、苄基二甲基縮酮、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、鄰苯甲醯基苯甲酸甲酯、2,4-二乙基9-氧硫
作為起始劑(B2)，可列舉下述式(B-1)所表示之化合物。 Examples of the initiator (B2) include compounds represented by the following formula (B-1).
上述式(B-1)中，Rb10表示碳數1~10之烷基、可具有取代基之苯基或可具有取代基之咔唑基。a為0或1。Rb11表示可具有取代基之碳數1~10之烷基或可具有取代基之苯基。Rb12表示氫原子、碳數1~6之烷基或可具有取代基之苯基。 In the formula (B-1), R b10 represents an alkyl group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. a is 0 or 1. R b11 represents a C1-C10 alkyl group which may have a substituent or a phenyl group which may have a substituent. R b12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.
於Rb11為碳數1~10之烷基之情形時，烷基可為直鏈，亦可為支鏈。於該情形時，烷基之碳數較佳為1~8，更佳為1~5。 When R b11 is an alkyl group having 1 to 10 carbon atoms, the alkyl group may be a straight chain or a branched chain. In this case, the carbon number of the alkyl group is preferably 1 to 8, more preferably 1 to 5.
於Rb11為可具有取代基之苯基之情形時，取代基之種類於不損害本發明之目的之範圍內，並無特別限定。作為苯基可具有之取代基之較佳之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、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、胺基、經1或2之有機基取代之胺基、嗎啉-1-基及哌
於苯基所具有之取代基為烷基之情形時，其碳數較佳為1~20，更佳為1~10，進而較佳為1~6，尤佳為1~3，最佳為1。又，烷基可為直鏈，亦可為支鏈。作為苯基所具有之取代基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，烷基亦可於碳鏈上包含醚鍵(-O-)。於該情形時，作為苯基所具有之取代基，例如可列舉烷氧基烷基、烷氧基烷氧基烷基。於苯基所具有之取代基為烷氧基烷基之情形時，較佳為-Rb13-O-Rb14所表示之基。Rb13係可為碳數1~10之直鏈，亦可為支鏈之伸烷基。Rb14係可為碳數1~10之直鏈，亦可為支鏈之烷基。Rb13之碳數較佳為1~8，更佳為1~5，尤佳為1~3。Rb14之碳數較佳為1~ 8，更佳為1~5，尤佳為1~3，最佳為1。作為於碳鏈上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 the substituent of the phenyl group is an alkyl group, its carbon number is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 6, particularly preferably from 1 to 3, and most preferably 1. The alkyl group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third 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. The alkyl group may include an ether bond (-O-) on the carbon chain. In this case, examples of the substituent included in the phenyl group include an alkoxyalkyl group and an alkoxyalkoxyalkyl group. When the phenyl group has an alkoxyalkyl group, the group represented by -R b13 -OR b14 is preferred. R b13 can be a straight chain with 1 to 10 carbon atoms, or a branched alkylene. R b14 can be a straight chain with 1 to 10 carbon atoms, or a branched alkyl group. The carbon number of R b13 is preferably from 1 to 8, more preferably from 1 to 5, and even more preferably from 1 to 3. The carbon number of R b14 is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Examples of the alkyl group having an ether bond on the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl and methoxypropyl.
於苯基所具有之取代基為烷氧基之情形時，其碳數較佳為1~20，更佳為1~6。又，烷氧基可為直鏈，亦可為支鏈。作為苯基所具有之取代基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，烷氧基亦可於碳鏈上包含醚鍵(-O-)。作為於碳鏈上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、2-甲氧基-1-甲基乙氧基、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 the substituent of the phenyl group is an alkoxy group, its carbon number is preferably from 1 to 20, more preferably from 1 to 6. The alkoxy group may be linear or branched. Specific examples when the phenyl group has an alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, Second butoxy, third butoxy, n-pentyloxy, isopentyloxy, second pentoxy, third pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyl Oxygen, second octyloxy, third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. The alkoxy group may include an ether bond (-O-) on the carbon chain. Examples of the alkoxy group having an ether bond on the carbon chain include methoxyethoxy, ethoxyethoxy, 2-methoxy-1-methylethoxy, and methoxyethyl Ethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, methoxypropoxy and the like.
於苯基所具有之取代基為環烷基或環烷氧基之情形時，其碳數較佳為3~10，更佳為3~6。作為苯基所具有之取代基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。作為苯基所具有之取代基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 the substituent of the phenyl group is a cycloalkyl group or a cycloalkoxy group, its carbon number is preferably 3 to 10, and more preferably 3 to 6. Specific examples in the case where the substituent included in the phenyl group is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when the phenyl group has a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyl Oxygen, etc.
於苯基所具有之取代基為飽和脂肪族醯基或飽和脂肪族醯氧基之情形時，其碳數較佳為2~20，更佳為2~7。作為苯基所具有之取代基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。作為苯基所具有之取代基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 the substituent of the phenyl group is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms thereof is preferably 2 to 20, and more preferably 2 to 7. Specific examples when the substituent of the phenyl group is a saturated aliphatic fluorenyl group include ethyl fluorenyl, propionyl, n-butylfluorenyl, 2-methylpropanyl, n-pentyl, 2, 2-dimethylpropanyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecylfluorenyl, n-dodecylfluorenyl, n-tridecylfluorenyl Base, n-tetradecylfluorenyl, n-pentadecafluorenyl and n-hexadecylfluorenyl. When the phenyl group is a saturated aliphatic fluorenyl group Specific examples include ethoxyl, propionyloxy, n-butylpyroxy, 2-methylpropylpyroxy, n-pentylpyroxy, 2,2-dimethylpropylpyroxy, N-hexylfluorenyloxy, n-heptylfluorenyloxy, n-octylfluorenyloxy, n-nonanthoxyl, n-decylfluorenyloxy, n-undecylfluorenyloxy, n-dodecylfluorenyloxy, n-tridecylfluorenyl Oxy, n-tetradecanofluorenyloxy, n-pentadecafluorenyloxy, n-hexadecanofluorenyloxy and the like.
於苯基所具有之取代基為烷氧羰基之情形時，其碳數較佳為2~20，更佳為2~7。作為苯基所具有之取代基為烷氧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 the substituent of the phenyl group is an alkoxycarbonyl group, its carbon number is preferably from 2 to 20, more preferably from 2 to 7. Specific examples when the substituent of the phenyl group is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, Isobutoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl , N-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonoxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl And isodecoxycarbonyl.
於苯基所具有之取代基為苯基烷基之情形時，其碳數較佳為7~20，更佳為7~10。又，於苯基所具有之取代基為萘基烷基之情形時，其碳數較佳為11~20，更佳為11~14。作為苯基所具有之取代基為苯基烷基之情形時之具體例，可列舉苄基、2-苯乙基、3-苯基丙基及4-苯基丁基。作為苯基所具有之取代基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。於苯基所具有之取代基為苯基烷基或萘基烷基之情形時，取代基亦可於苯基或萘基上進而具有取代基。 In the case where the substituent of the phenyl group is a phenylalkyl group, the carbon number thereof is preferably 7 to 20, and more preferably 7 to 10. When the substituent of the phenyl group is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14. Specific examples in the case where the substituent of the phenyl group is a phenylalkyl group include benzyl, 2-phenethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when the substituent of the phenyl group is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) ethyl. When the phenyl group has a phenylalkyl or naphthylalkyl substituent, the substituent may have a substituent on the phenyl or naphthyl group.
於苯基所具有之取代基為雜環基之情形時，雜環基為包含1以上之N、S、O之5員或6員之單環，或者為該單環彼此或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，設為至環數3為止者。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、
於苯基所具有之取代基為經1或2之有機基取代之胺基之情形時，作為有機基之較佳之例，可列舉：碳數1~20之烷基、碳數3~10之環烷基、碳數2~20之飽和脂肪族醯基、碳數2~20之飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之碳數7~20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、可具有取代基之碳數11~20之萘基烷基及雜環基等。作為該等較佳之有機基之具體例，可列舉：與針對於苯基所具有之取代基所述者相同者。作為經1或2之有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、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、β-萘甲醯基胺基及N-乙醯基-N-乙醯氧基胺基等。 When a phenyl group has an amine group substituted with an organic group of 1 or 2, as a preferable example of the organic group, an alkyl group having 1 to 20 carbon atoms and an alkyl group having 3 to 10 carbon atoms can be listed. A cycloalkyl group, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamidine group which may have a substituent, and a substitution 7 to 20 carbon atoms of phenyl group, naphthyl group which may have substituents, naphthylmethyl group which may have substituents, naphthyl alkyl group which may have substituents, and heterocyclic group Wait. Specific examples of such preferable organic groups include the same as those described for the substituents included in the phenyl group. Specific examples of the amino group substituted with an organic group of 1 or 2 include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, and isopropyl Amino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamine Group, phenylamino group, naphthylamino group, ethylamino group, propionylamino group, n-butylmethylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, Octylamino, n-decanoylamino, benzamidoamino, α-naphthylmethylamino, β-naphthylmethylamino, and N-ethynyl-N-ethoxymethylamino Wait.
作為苯基所具有之取代基中所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基，可列舉：碳數1~6之烷基、碳數1~6之烷氧基、碳數2~7之飽和脂肪族醯基、碳數2~7之烷氧羰基、碳數2~7之飽和脂肪族醯氧基、具有碳數1~6之烷基之單烷基胺基、具有碳數1~6之烷基之二烷基胺基、嗎啉-1-基、哌
以上，對Rb11為可具有取代基之苯基之情形時之取代基進行說明，該等取代基中，較佳為烷基或烷氧基烷基。 The substituents in the case where R b11 is a phenyl group which may have a substituent have been described above. Among these substituents, an alkyl group or an alkoxyalkyl group is preferred.
於Rb11為可具有取代基之苯基之情形時，取代基之數與取代基之鍵結位置於不損害本發明之目的之範圍內，並無特別限定。於Rb11為可具有取代基之苯基之情形時，就鹼之產生效率優異之方面而言，可具有取代基之苯基較佳為可具有取代基之鄰甲苯基。 When R b11 is a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituent are within a range that does not impair the object of the present invention, and are not particularly limited. When R b11 is a phenyl group which may have a substituent, the phenyl group which may have a substituent is preferably an o-tolyl group which may have a substituent in terms of excellent base production efficiency.
Rb10為碳數1~10之烷基、可具有取代基之苯基或可具有取代基之咔唑基。於Rb10為可具有取代基之咔唑基之情形時，咔唑基上之氮原子亦可經碳數1~6之烷基取代。 R b10 is an alkyl group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. When R b10 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.
Rb10中，苯基或咔唑基所具有之取代基於不損害本發明之目的之範圍內，並無特別限定。作為苯基或咔唑基可於碳原子上具有之較佳之取代基之例，可列舉：碳數1~20之烷基、碳數1~20之烷氧基、碳數3~10之環烷基、碳數3~10之環烷氧基、碳數2~20之飽和脂肪族醯基、碳數2~20之烷氧羰基、碳數2~20之飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯硫基、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、可具有取代基之碳數7~20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、可具有取代基之碳數11~20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、胺基、經1或2之有機基取代之胺基、嗎啉-1-基及哌
於Rb10為咔唑基之情形時，作為咔唑基可於氮原子上具有之較佳 之取代基之例，可列舉：碳數1~20之烷基、碳數3~10之環烷基、碳數2~20之飽和脂肪族醯基、碳數2~20之烷氧羰基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之碳數7~20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、可具有取代基之萘氧基羰基、可具有取代基之碳數11~20之萘基烷基、可具有取代基之雜環基及可具有取代基之雜環基碳基等。於該等取代基中，較佳為碳數1~20之烷基，更佳為碳數1~6之烷基，尤佳為乙基。 In the case where R b10 is a carbazolyl group, examples of the preferable substituent that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have a substituent, benzamidine group which may have a substituent, and phenoxycarbonyl group which may have a substituent , 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, A naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclic carbon group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.
關於咔唑基可具有之取代基之具體例，就烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、飽和脂肪族醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基烷基、可具有取代基之雜環基及經1或2之有機基取代之胺基而言，與Rb11為可具有取代基之苯基之情形時的苯基所具有之取代基之例相同。 Specific examples of the substituent which the carbazolyl group may have include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic fluorenyl, alkoxycarbonyl, saturated aliphatic fluorenyl, and optionally substituted Phenylalkyl, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, and amine group substituted with an organic group of 1 or 2, and R b11 is a benzene which may have a substituent In the case of a radical, the examples of the substituent which the phenyl group has are the same.
Rb10中，作為咔唑基所具有之取代基中所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基之例，可列舉：碳數1~6之烷基；碳數1~6之烷氧基；碳數2~7之飽和脂肪族醯基；碳數2~7之烷氧羰基；碳數2~7之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳數1~6之烷基、嗎啉-1-基、哌
於Rb10為可具有取代基之碳數1~10之烷基之情形時，烷基可為直鏈，亦可為支鏈。於該情形時，烷基之碳數較佳為1~8，更佳為1 ~5。 When R b10 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, the alkyl group may be a straight chain or a branched chain. In this case, the carbon number of the alkyl group is preferably 1 to 8, more preferably 1 to 5.
Rb10中，烷基或苯基所具有之取代基於不損害本發明之目的之範圍內，並無特別限定。 In R b10 , the substitution of the alkyl group or the phenyl group is not particularly limited as long as the purpose of the present invention is not impaired.
作為烷基可於碳原子上具有之較佳之取代基之例，可列舉：碳數1~20之烷氧基、碳數3~10之環烷基、碳數3~10之環烷氧基、碳數2~20之飽和脂肪族醯基、碳數2~20之烷氧羰基、碳數2~20之飽和脂肪族醯氧基、可具有取代基之苯基、可具有取代基之苯氧基、可具有取代基之苯硫基、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、可具有取代基之碳數7~20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、可具有取代基之碳數11~20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、胺基、經1或2之有機基取代之胺基、嗎啉-1-基及哌
作為苯基可於碳原子上具有之較佳之取代基之例，除作為烷基可於碳原子上具有之較佳之取代基而於上述中所例示的基以外，亦可列舉碳數1~20之烷基。 As an example of a preferable substituent which a phenyl group may have on a carbon atom, in addition to the groups exemplified above as a preferable substituent which an alkyl group may have on a carbon atom, a carbon number of 1-20 Of alkyl.
關於烷基或苯基可具有之取代基之具體例，就烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、飽和脂肪族醯氧基、可具有取代基之苯基烷基、可具有取代基之萘基烷基、可具有取代基之雜環基及經1或2之有機基取代之胺基而言，與Rb11為可具有取代基之苯基之情形時的苯基所具有之取代基之例相同。 Specific examples of the substituent which the alkyl group or the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyl group, and In the case of a phenylalkyl group having a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with an organic group of 1 or 2, R b11 may have a substituent In the case of a phenyl group, examples of the substituent which the phenyl group has are the same.
Rb10中，作為烷基或苯基所具有之取代基中所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基之例，可列舉：碳數1~6之烷基；碳數1~6之烷氧基；碳數2~7之飽和脂肪族醯基；碳數2~7之烷氧羰基；碳數2~7之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；
萘甲醯基；經選自由碳數1~6之烷基、嗎啉-1-基、哌
就式(B-1)所表示之化合物之鹼產生效率之方面而言，作為Rb10，較佳為下述式(B-2)：
所表示之基或下述式(B-3)：
所表示之基。 The indicated base.
式(B-2)中，Rb15為1價有機基，Rb16為1價有機基或硝基(其中，b=0之情形)，b為0或1。式(B-3)中，Rb17為選自由1價有機基、胺基、鹵素、硝基及氰基所構成之群中之基，A為S或O，c為0~4之整數。 In the formula (B-2), R b15 is a monovalent organic group, R b16 is a monovalent organic group or a nitro group (where b = 0), and b is 0 or 1. In the formula (B-3), R b17 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, A is S or O, and c is an integer of 0 to 4.
式(B-2)中之Rb15能夠於不損害本發明之目的之範圍內自各種有機基中選擇。作為Rb15之較佳之例，可列舉：碳數1~20之烷基、碳數3 ~10之環烷基、碳數2~20之飽和脂肪族醯基、碳數2~20之烷氧羰基、可具有取代基之苯基、可具有取代基之苯甲醯基、可具有取代基之苯氧基羰基、可具有取代基之碳數7~20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、可具有取代基之萘氧基羰基、可具有取代基之碳數11~20之萘基烷基、可具有取代基之雜環基及可具有取代基之雜環基羰基等。 R b15 in the formula (B-2) can be selected from various organic groups within a range that does not impair the object of the present invention. Preferable examples of R b15 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and an alkoxy group having 2 to 20 carbon atoms. Carbonyl, phenyl which may have a substituent, benzamidine which may have a substituent, phenoxycarbonyl which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, may have a substituent Naphthyl, naphthylmethyl which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthylalkyl having 11 to 20 carbon atoms which may have a substituent, heterocyclic group which may have a substituent, and A heterocyclic carbonyl group having a substituent and the like.
於Rb15中，較佳為碳數1~20之烷基，更佳為碳數1~6之烷基，尤佳為乙基。 In R b15 , an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.
式(B-2)中之Rb16於不損害本發明之目的之範圍內，並無特別限定，能夠自各種有機基中選擇。作為適合作為Rb16之基之具體例，可列舉：碳數1~20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Rb16，於b=1之情形時，該等基中，更佳為可具有取代基之苯基、可具有取代基之萘基、可具有取代基之噻吩基及可具有取代基之呋喃基，尤佳為2-甲基苯基、萘基、噻吩基及呋喃基。於b=0之情形時，較佳為硝基。 R b16 in formula (B-2) is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of a suitable group for R b16 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As R b16 , when b = 1, among these groups, phenyl which may have a substituent, naphthyl which may have a substituent, thienyl which may have a substituent, and furan which may have a substituent are more preferred. Is particularly preferably 2-methylphenyl, naphthyl, thienyl and furyl. In the case of b = 0, a nitro group is preferred.
作為Rb15或Rb16中所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基，可列舉：碳數1~6之烷基、碳數1~6之烷氧基、碳數2~7之飽和脂肪族醯基、碳數2~7之烷氧羰基、碳數2~7之飽和脂肪族醯氧基、具有碳數1~6之烷基之單烷基胺基、具有碳數1~6之烷基之二烷基胺基、嗎啉-1-基、哌
於式(B-3)中之Rb17為有機基之情形時，Rb17能夠於不損害本發明之目的之範圍內自各種有機基中選擇。作為式(B-3)中，Rb17為有
機基之情形時之較佳之例，可列舉：碳數1~6之烷基；碳數1~6之烷氧基；碳數2~7之飽和脂肪族醯基；碳數2~7之烷氧羰基；碳數2~7之飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；經選自由碳數1~6之烷基、嗎啉-1-基、哌
於Rb17中，較佳為苯甲醯基；萘甲醯基；經選自由碳數1~6之烷基、嗎啉-1-基、哌
又，式(B-3)中，c較佳為0~3之整數，更佳為0~2之整數，尤佳為0或1。於c為1之情形時，Rb17所鍵結之位置較佳為相對於Rb17所鍵結之苯基與-A-鍵結之鍵結鍵而為對位。 In formula (B-3), c is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1. In the case when c is 1, the R b17 are bonded with respect to the preferred position of R b17 are bonded bonded bonded bond of -A- and a phenyl group and for the bit.
Rb12為氫原子、碳數1~6之烷基或可具有取代基之苯基。於為可具有取代基之苯基之情形時，苯基可具有之取代基與Rb10為可具有取代基之苯基之情形相同。作為Rb12，較佳為甲基、乙基或苯基，更佳為甲基或苯基。 R b12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. When it is a phenyl group which may have a substituent, the substituent which a phenyl group may have is the same as that when R b10 is a phenyl group which may have a substituent. R b12 is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.
於a為0之情形時，上述式(B-1)所表示之肟酯化合物例如能夠藉由以下所說明之方法而合成。首先，利用使羥胺Rb10-CO-Rb11所表示之酮化合物肟化而獲得Rb10-(C=N-OH)-Rb11所表示之肟化合物。其次，利用Rb12-CO-Hal(Hal表示鹵素)所表示之酸鹵素化物或(Rb12CO)2O所表示之酸酐使所獲得之肟化合物醯基化而獲得a為0的上述式(B-1)所表示之肟酯化合物。 When a is 0, the oxime ester compound represented by the said Formula (B-1) can be synthesize | combined by the method demonstrated below, for example. First, an oxime compound represented by R b10- (C = N-OH) -R b11 is obtained by oximatizing a ketone compound represented by hydroxylamine R b10 -CO-R b11 . Next, the obtained oxime compound is amidated with an acid halide represented by R b12 -CO-Hal (Hal represents halogen) or an acid anhydride represented by (R b12 CO) 2 O to obtain the above-mentioned formula where a is 0 ( The oxime ester compound represented by B-1).
又，於a為1之情形時，上述式(B-1)所表示之肟酯化合物例如能 夠藉由以下所說明之方法而合成。首先，使Rb10-CO-CH2-Rb11所表示之酮化合物於鹽酸之存在下與亞硝酸酯反應而獲得Rb10-CO-(C=N-OH)-Rb11所表示之肟化合物。其次，利用Rb12-CO-Hal(Hal表示鹵素)所表示之酸鹵素化物或(Rb12CO)2O所表示之酸酐使所獲得之肟化合物醯基化而獲得a為1的上述式(B-1)所表示之肟酯化合物。 When a is 1, the oxime ester compound represented by the formula (B-1) can be synthesized, for example, by a method described below. First, a ketone compound represented by R b10 -CO-CH 2 -R b11 is reacted with a nitrite in the presence of hydrochloric acid to obtain an oxime compound represented by R b10 -CO- (C = N-OH) -R b11 . Next, the obtained oxime compound is amidated with an acid halide represented by R b12 -CO-Hal (Hal represents halogen) or an acid anhydride represented by (R b12 CO) 2 O to obtain the above formula (a) (1 The oxime ester compound represented by B-1).
作為上述式(B-1)所表示之化合物，可列舉下述式(B-4)所表示之化合物。 Examples of the compound represented by the formula (B-1) include compounds represented by the following formula (B-4).
上述式(B-4)中，a及Rb10如上所述。Rb18為選自由1價有機基、胺基、鹵素、硝基及氰基所構成之群中之基，d為0~4之整數，Rb19為氫原子或碳數1~6之烷基。 In the formula (B-4), a and R b10 are as described above. R b18 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, d is an integer of 0 to 4, R b19 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms .
上述式(B-4)中，Rb18於不損害本發明之目的之範圍內，並無特別限定，於為有機基之情形時，自各種有機基適當選擇。作為Rb18之較佳之例，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、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、胺基、經1或2之有機基取代之胺基、嗎啉-1-基、哌
於Rb18為烷基之情形時，較佳為碳數1~20，更佳為碳數1~6。又，於Rb18為烷基之情形時，可為直鏈，亦可為支鏈。作為Rb18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Rb18為烷基之情形時，烷基亦可於碳鏈上包含醚鍵(-O-)。作為於碳鏈上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 b18 is an alkyl group, it is preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. When R b18 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R b18 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third 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- Decyl and isodecyl. When R b18 is an alkyl group, the alkyl group may include an ether bond (-O-) on the carbon chain. Examples of the alkyl group having an ether bond on the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl and methoxypropyl.
於Rb18為烷氧基之情形時，較佳為碳數1~20，更佳為碳數1~6。又，於Rb18為烷氧基之情形時，可為直鏈，亦可為支鏈。作為Rb18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Rb18為烷氧基之情形時，烷氧基亦可於碳鏈上包含醚鍵(-O-)。作為於碳鏈上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 b18 is an alkoxy group, it is preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. When R b18 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R b18 is an alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and second butoxy , Third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. When R b18 is an alkoxy group, the alkoxy group may include an ether bond (-O-) on the carbon chain. Examples of the alkoxy group having an ether bond on the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy Groups, propoxyethoxyethoxy and methoxypropoxy.
於Rb18為環烷基或環烷氧基之情形時，較佳為碳數3~10，更佳為碳數3~6。作為Rb18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Rb18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 b18 is a cycloalkyl group or a cycloalkoxy group, a carbon number of 3 to 10 is preferred, and a carbon number of 3 to 6 is more preferred. Specific examples when R b18 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R b18 is a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy and the like.
於Rb18為飽和脂肪族醯基或飽和脂肪族醯氧基之情形時，較佳為碳數2~20，更佳為碳數2~7。作為Rb18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Rb18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 b18 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyl group, the number of carbon atoms is preferably 2 to 20, and the number of carbon atoms is more preferably 2 to 7. Specific examples when R b18 is a saturated aliphatic fluorenyl group include ethyl fluorenyl, propionyl, n-butylfluorenyl, 2-methylpropylfluorenyl, n-pentylfluorenyl, and 2,2-dimethyl Propyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridyl, n-thyl Carbofluorenyl, n-pentadecafluorenyl and n-hexadecanocarbyl. Specific examples when R b18 is a saturated aliphatic fluorenyloxy group include ethoxyl, propionyloxy, n-butylfluorenyloxy, 2-methylpropanyloxy, n-pentamyloxy , 2,2-dimethylpropoxyl, n-hexamethyleneoxy, n-heptylfluorenyloxy, n-octylfluorenyloxy, n-nonylfluorenyloxy, n-decylfluorenyloxy, n-undecylfluorenyloxy, N-dodecylfluorenyloxy, n-tridecylfluorenyloxy, n-tetradecylfluorenyloxy, n-pentadecafluorenyloxy, n-hexadecylfluorenyloxy, etc.
於Rb18為烷氧羰基之情形時，較佳為碳數2~20，更佳為碳數2~7。作為Rb18為烷氧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 b18 is an alkoxycarbonyl group, it is preferably 2 to 20 carbon atoms, and more preferably 2 to 7 carbon atoms. Specific examples when R b18 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and isobutoxycarbonyl , Second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy Carbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonoxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxy Carbonyl, etc.
於Rb18為苯基烷基之情形時，較佳為碳數7~20，更佳為碳數7~10。又，於Rb18為萘基烷基之情形時，較佳為碳數11~20，更佳為碳數11~14。作為Rb18為苯基烷基之情形時之具體例，可列舉：苄基、2-苯乙基、3-苯基丙基及4-苯基丁基。作為Rb18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Rb18為苯基烷基或萘基烷基之情形時，Rb18亦可於苯 基或萘基上進而具有取代基。 When R b18 is a phenylalkyl group, a carbon number of 7 to 20 is preferable, and a carbon number of 7 to 10 is more preferable. When R b18 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and the number of carbon atoms is more preferably 11 to 14. Specific examples when R b18 is a phenylalkyl group include benzyl, 2-phenethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R b18 is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) ) Ethyl. When R b18 is phenylalkyl or naphthylalkyl, R b18 may further have a substituent on phenyl or naphthyl.
於Rb18為雜環基之情形時，雜環基為包含1以上之N、S、O之5員或6員之單環，或者為該單環彼此或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，設為至環數3為止者。作為構成該雜環基之雜環，可列舉：呋喃、噻吩、吡咯、
於Rb18為經1或2之有機基取代之胺基之情形時，作為有機基之較佳之例，可列舉：碳數1~20之烷基、碳數3~10之環烷基、碳數2~20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、可具有取代基之碳數7~20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、可具有取代基之碳數11~20之萘基烷基及雜環基等。該等較佳之有機基之具體例與Rb18相同。作為經1或2之有機基取代之胺基之具體例，可列舉：甲基胺基、乙基胺基、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、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 b18 is an amine group substituted with an organic group of 1 or 2, as a preferable example of the organic group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, carbon 2 to 20 saturated aliphatic fluorenyl groups, phenyl groups which may have substituents, benzamidine groups which may have substituents, phenyl alkyl groups which may have 7 to 20 carbon atoms, and A naphthyl group, a naphthylmethyl group which may have a substituent, a naphthyl alkyl group which may have a substituent and a heterocyclic group having 11 to 20 carbon atoms, and the like. Specific examples of these preferable organic groups are the same as those of R b18 . Specific examples of the amino group substituted with an organic group of 1 or 2 include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, and isopropyl Amino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamine Group, phenylamino group, naphthylamino group, ethylamino group, propionylamino group, n-butylmethylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, Octylamino, n-decanoylamino, benzamidineamino, α-naphthylamino and β-naphthylamino, and the like.
作為Rb18中所含之苯基、萘基及雜環基進而具有取代基之情形時之取代基，可列舉：碳數1~6之烷基、碳數1~6之烷氧基、碳數2~7之飽和脂肪族醯基、碳數2~7之烷氧羰基、碳數2~7之飽和脂肪族醯
氧基、具有碳數1~6之烷基之單烷基胺基、具有碳數1~6之烷基之二烷基胺基、嗎啉-1-基、哌
Rb18之中，就化學性穩定之方面、立體阻礙較少而肟酯化合物之合成較容易之方面等而言，較佳為選自由碳數1~6之烷基、碳數1~6之烷氧基及碳數2~7之飽和脂肪族醯基所構成之群中之基，更佳為碳數1~6之烷基，尤佳為甲基。 Among R b18 , in terms of chemical stability, less steric hindrance, and easier synthesis of the oxime ester compound, it is preferably selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. The group in the group consisting of an alkoxy group and a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.
關於Rb18鍵結於苯基上之位置，於針對於Rb18所鍵結之苯基，將苯基與肟酯化合物之主骨架的鍵結鍵之位置設為1位，將甲基之位置設為2位之情形時，較佳為4位或5位，更佳為5位。又，d較佳為0~3之整數，更佳為0~2之整數，尤佳為0或1。 About R b18 bonded to the phenyl position, in respect to the R b18 are bonded a phenyl group, bonding position of the bond of the main skeleton with a phenyl group of the oxime ester compound is set to 1, the position of methyl In the case of two digits, four or five digits are preferred, and five digits are more preferred. In addition, d is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.
上述式(B-4)中之Rb19為氫原子或碳數1~6之烷基。作為Rb19，較佳為甲基或乙基，更佳為甲基。 R b19 in the above formula (B-4) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R b19 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
將適合作為式(B-1)所表示之化合物的化合物之具體例示於以下。 Specific examples of compounds suitable as the compound represented by the formula (B-1) are shown below.
作為與化合物(B1)組合使用之肟系光聚合起始劑，例如亦能夠較佳地使用上述專利文獻1中所記載之下述結構式(a)~(d)所表示之化合物。 As the oxime-based photopolymerization initiator used in combination with the compound (B1), for example, compounds represented by the following structural formulae (a) to (d) described in the above-mentioned Patent Document 1 can also be preferably used.
於(B)光聚合起始劑組合並包含化合物(B1)與起始劑(B2)之情形時，(B)光聚合起始劑中之化合物(B1)之含量較佳為0.1質量%以上，更佳為1質量%以上，尤佳為10質量%以上。 In the case where (B) the photopolymerization initiator is combined and includes the compound (B1) and the initiator (B2), the content of the compound (B1) in the (B) photopolymerization initiator is preferably 0.1% by mass or more It is more preferably 1% by mass or more, and even more preferably 10% by mass or more.
於(B)光聚合起始劑包含化合物(B1)及起始劑(B2)之情形時，質量比((B1)：(B2))較佳為0.1：99.9~99.9：0.1，更佳為1：99~99：1，尤佳為10：90~90：10。 In the case where (B) the photopolymerization initiator contains the compound (B1) and the initiator (B2), the mass ratio ((B1): (B2)) is preferably from 0.1: 99.9 to 99.9: 0.1, more preferably 1: 99 ~ 99: 1, particularly preferably 10: 90 ~ 90: 10.
相對於感光性組合物之固形物成分之質量，作為(B)成分之光聚合起始劑之含量較佳為0.1~50質量%，更佳為1~45質量%。藉由設為上述範圍內，能夠獲得充分之耐熱性、耐化學品性，並且提昇膜形成能力，抑制光硬化不良。 The content of the photopolymerization initiator as the component (B) is preferably 0.1 to 50% by mass, and more preferably 1 to 45% by mass based on the mass of the solid component of the photosensitive composition. By setting it as the said range, sufficient heat resistance and chemical resistance can be obtained, and a film-forming ability can be improved and a photo-hardening defect can be suppressed.
<(C)著色劑> <(C) Colorant>
感光性組合物包含(C)有彩色著色劑(以下，亦記作「(C)成分」)。組合選自有彩色中之不同之數種色相而構成彩色濾光片，藉 此能夠獲得可顯示彩色圖像之顯示元件。 The photosensitive composition includes (C) a colored colorant (hereinafter, also referred to as "(C) component"). Combining several different hues selected from the colored to form a color filter, This makes it possible to obtain a display element capable of displaying a color image.
感光性組合物組合並包含上述(B)光聚合起始劑與(C)有彩色著色劑，藉此能夠抑制膜形成時之著色膜之變色，形成所需色相之著色膜。 The photosensitive composition contains the above-mentioned (B) photopolymerization initiator and (C) chromatic colorant in combination, whereby the discoloration of the colored film during film formation can be suppressed, and a colored film having a desired hue can be formed.
自先前以來，作為廣泛使用之彩色濾光片之例，可列舉：RGB(紅、綠、藍)之原色系過濾器或CMYG(氰色、深紅色、黃色、綠色)系之補色系過濾器。 Examples of color filters that have been widely used include the primary color filters of RGB (red, green, and blue) and the complementary color filters of CMYG (cyan, magenta, yellow, and green). .
作為(C)成分，就使用著色膜作為彩色濾光片之情形時之彩色濾光片的耐光性及耐候性之方面而言，較佳為有機顏料。有機顏料並無特別限定，例如較佳為使用色指數(C.I.；The Society of Dyer sand Colourists公司發行)中分類為顏料(Pigment)之化合物，具體而言，附有如下所述之色指數(C.I.)編號者。 As the (C) component, an organic pigment is preferable in terms of light resistance and weather resistance of the color filter when a colored film is used as the color filter. The organic pigment is not particularly limited. For example, it is preferable to use a compound classified as a pigment in the color index (issued by The Society of Dyer sand Colourists). Specifically, a color index (CI ) Numbered by.
再者，(C)成分亦可為了調整色相而包含少量黑、白等無彩色著色劑。 Furthermore, the component (C) may contain a small amount of achromatic colorants such as black and white in order to adjust the hue.
C.I.顏料黃1(以下，「C.I.顏料黃」相同，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、185；C.I.顏料橙1(以下，「C.I.顏料橙」相同，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、73；C.I.顏料紫1(以下，「C.I.顏料紫」相同，僅記載編號)、19、23、29、30、32、36、37、38、39、40、50；C.I.顏料紅1(以下，「C.I.顏料紅」相同，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、265；C.I.顏料藍1(以下，「C.I.顏料藍」相同，僅記載編號)、2、15、15：3、15：4、15：6、16、22、60、64、66；C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37、顏料綠58、顏料綠59、顏料綠60；C.I.顏料棕23、C.I.顏料棕25、C.I，顏料棕26、C.I.顏料棕28；C.I.顏料黑1、C.I.顏料黑7。 CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, 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, 185; CI Pigment Orange 1 ( Hereinafter, "CI Pigment Orange" is the same, and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same, only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, only the number is described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 15, 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, 265; CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, only the number is described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66; CI Pigment Green 7. CI Pigment Green 36, CI Pigment Green 37, Pigment Green 58, Pigment Green 59, Pigment Green 60; CI Pigment Brown 23, CI Pigment Brown 25, CI, Pigment Brown 26, CI Pigment Brown 28; CI Pigment Black 1, CI Pigment Black 7.
(C)成分亦可使用染料。於使用染料之情形時，能夠單獨使用，更佳為與顏料組合。作為能夠使用之染料，例如可列舉亮綠、茜素綠、甲基綠、速綠、亮藍、亮甲酚藍、專利藍、苯酚藍、四溴苯酚藍、溴苯酚藍、亞甲基藍、溶劑藍35，但並不限定於此。 (C) A dye can also be used for a component. When a dye is used, it can be used alone, and more preferably in combination with a pigment. Examples of usable dyes include bright green, alizarin green, methyl green, fast green, bright blue, bright cresol blue, patent blue, phenol blue, tetrabromophenol blue, bromophenol blue, methylene blue, and solvent blue. 35, but not limited to this.
(C)成分亦可藉由再結晶法、再沈澱法、溶劑洗淨法、昇華法、真空過熱法或該等之組合而進行純化。 The component (C) can also be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum superheating method, or a combination thereof.
關於感光性組合物中之(C)成分之含量，就形成透明性及色純度優異的像素之方面而言，相對於感光性組合物之除(C)成分以外之固形物成分，較佳為10~200質量%，更佳為50~150質量%。 The content of the component (C) in the photosensitive composition is preferably a solid component other than the component (C) in the photosensitive composition in terms of forming a pixel having excellent transparency and color purity. 10 to 200 mass%, more preferably 50 to 150 mass%.
再者，作為(C)成分之著色劑較佳為於使用分散劑製成以適當之 濃度分散之分散液後，添加於感光性組合物中。作為公知之分散劑，較佳為聚合物分散劑，例如可列舉：丙烯酸系共聚物分散劑、聚胺基甲酸酯系分散劑、聚酯系分散劑、聚伸乙亞胺系分散劑、聚烯丙基胺系分散劑等。其中，較佳為聚胺基甲酸酯系分散劑。若使用該等聚合物分散劑，則能夠改善(C)成分之分散性及分散穩定性，提昇色相、對比率、耐熱性。 Furthermore, the coloring agent as the component (C) is preferably prepared by using a dispersant in a suitable manner. After the dispersion liquid is dispersed in the concentration, it is added to the photosensitive composition. The known dispersant is preferably a polymer dispersant, and examples thereof include an acrylic copolymer dispersant, a polyurethane dispersant, a polyester dispersant, a polyethyleneimine dispersant, Polyallylamine-based dispersants and the like. Among them, a polyurethane-based dispersant is preferred. When these polymer dispersants are used, the dispersibility and dispersion stability of the component (C) can be improved, and the hue, contrast ratio, and heat resistance can be improved.
關於本發明之感光性組合物之(C)成分，於RGB之紅色中，較佳為包含C.I.顏料紅254等吡咯并吡咯二酮系顏料之2種以上。吡咯并吡咯二酮系顏料較佳為設為(C)成分整體之40質量%以上，更佳為60~99質量%，進而較佳為70~90質量%。組合於吡咯并吡咯二酮系顏料中之其他(C)成分可為顏料或染料。作為其他(C)成分，較佳為C.I.顏料黃139等異吲哚啉系黃色顏料等。 Regarding the (C) component of the photosensitive composition of this invention, it is preferable to contain 2 or more types of pyrrolopyrrole dione pigments, such as C.I. pigment red 254, among RGB red. The pyrrolopyrrole dione pigment is preferably 40% by mass or more of the entire (C) component, more preferably 60 to 99% by mass, and even more preferably 70 to 90% by mass. The other (C) component combined with a pyrrolopyrrole dione pigment may be a pigment or a dye. As the other (C) component, an isoindoline-based yellow pigment such as C.I. Pigment Yellow 139 is preferable.
於RGB之藍及綠中，較佳為包含C.I.顏料綠36、58或C.I.顏料藍15：3、15：4、15：6等酞菁系顏料。酞菁系顏料較佳為(C)成分整體之10質量%以上，更佳為30質量%以上，進而較佳為40質量%以上，亦可為100質量%。於組合2種以上之情形時，酞菁系顏料更佳為(C)成分整體之30~99質量%，進而較佳為40~97質量%。 Among blue and green of RGB, phthalocyanine-based pigments such as C.I. Pigment Green 36, 58 or C.I. Pigment Blue 15: 3, 15: 4, 15: 6 are preferred. The phthalocyanine pigment is preferably 10% by mass or more of the entire (C) component, more preferably 30% by mass or more, still more preferably 40% by mass or more, and may also be 100% by mass. When two or more types are combined, the phthalocyanine-based pigment is more preferably 30 to 99% by mass of the entire (C) component, and more preferably 40 to 97% by mass.
組合於酞菁系顏料系顏料中之其他(C)成分可為顏料或染料。 The other (C) component combined with a phthalocyanine pigment-based pigment may be a pigment or a dye.
於為藍色之情形時，作為其他(C)成分，可較佳地列舉C.I.顏料紫23等二
於為綠色之情形時，作為組合於綠色系之酞菁系顏料系顏料中之其他(C)成分，可較佳地列舉C.I.顏料黃150等鎳錯合物系黃色顏料、上述藍色系之酞菁系顏料或染料(染料較佳為亮綠等綠色系之三 芳基甲烷系染料)等。其他(C)成分可使用複數種。該組合之其他(C)成分之比率例如為1~70質量%，較佳為1~50質量%。 In the case of a green color, as the other (C) component combined with the green phthalocyanine pigment type pigment, a nickel complex yellow pigment such as CI Pigment Yellow 150 and the blue type Phthalocyanine pigment or dye Aryl methane dyes) and the like. A plurality of other (C) components can be used. The ratio of the other (C) component of the combination is, for example, 1 to 70% by mass, and preferably 1 to 50% by mass.
<其他成分> <Other ingredients>
於本發明之感光性組合物中，視需要亦可添加各種添加劑。具體而言，可例示：溶劑、增感劑、硬化促進劑、光交聯劑、光增感劑、分散助劑、填充劑、密接促進劑、抗氧化劑、紫外線吸收劑、抗凝集劑、熱聚合禁止劑、消泡劑、界面活性劑等。 Various additives may be added to the photosensitive composition of the present invention as necessary. Specific examples include solvents, sensitizers, hardening accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants, Thermal polymerization inhibitors, defoamers, surfactants, etc.
作為本發明之感光性組合物中所使用之溶劑，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-甲基部碳酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、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、酪酸乙酯、酪酸正丙酯、酪酸異丙酯、酪酸正丁酯、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，亦可組合使用2種以上。 Examples of the solvent used in the photosensitive composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethyl ether. Diethylene 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 mono Methyl 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 (Poly) alkylene glycol monoalkyl ethers such as monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether ethyl (Poly) alkylene glycol monoalkyl ether acetates such as esters, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether Ethers, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate , Isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, 2- Other esters such as ethyl oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide And so on amines and so on. These solvents may be used alone or in combination of two or more.
於上述溶劑中，丙二醇單甲醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、二乙二醇二甲醚、二乙二醇甲基***、環己酮、3-甲氧基丁基乙酸酯能夠對上述(A)成分及(B)成分顯示優異之溶解性，並且使上述(C)成分之分散性良好，故而較佳，尤佳為使用丙二醇單甲醚乙酸酯、3-甲氧基丁基乙酸酯。溶劑只要根據感光性組合物之用途而適當決定即可，作為一例，相對於感光性組合物之固形物成分之合計100質量份，可列舉50~900質量份左右。 In the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol methyl ether , Cyclohexanone, and 3-methoxybutyl acetate are preferable because they can exhibit excellent solubility in the components (A) and (B), and also have good dispersibility in the component (C). Preferably, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are used. The solvent may be appropriately determined according to the use of the photosensitive composition. As an example, the solvent may be about 50 to 900 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive composition.
作為本發明之感光性組合物中所使用之熱聚合禁止劑，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、非離子等之化合物。 Examples of the thermal polymerization inhibitor used in the photosensitive composition of the present invention include hydroquinone and hydroquinone monoethyl ether. Examples of the antifoaming agent include compounds of the polysiloxane type and fluorine type, and examples of the surfactant include compounds of the anionic type, cationic type, and nonionic type.
[感光性組合物之製備方法] [Preparation method of photosensitive composition]
本發明之感光性組合物係藉由利用攪拌機將上述各成分全部混合而製備。再者，亦可以所製備之感光性組合物變得均勻之方式使用過濾器進行過濾。 The photosensitive composition of the present invention is prepared by mixing all the above components with a stirrer. Furthermore, the prepared photosensitive composition may be filtered using a filter in such a manner that the prepared photosensitive composition becomes uniform.
將各成分混合之順序並無特別限定。例如於光聚合性單體與(C)光聚合起始劑之混合物調配其他成分而製備感光性組合物。又，亦可於樹脂與(C)光聚合起始劑之混合物中調配其他成分而製備感光性組合物。 The order in which the components are mixed is not particularly limited. For example, a photosensitive composition is prepared by blending other components in a mixture of a photopolymerizable monomer and a (C) photopolymerization initiator. Further, a photosensitive composition may be prepared by blending other components in a mixture of the resin and the (C) photopolymerization initiator.
[圖案形成方法] [Pattern forming method]
於使用本發明之感光性組合物形成圖案時，首先使用輥式塗佈機、反向塗佈機、棒式塗佈機等接觸轉印型塗佈裝置或旋轉塗佈機(旋轉式塗佈裝置)、淋幕式平面塗裝機等非接觸型塗佈裝置於基板上 塗佈感光性組合物。 When forming a pattern using the photosensitive composition of the present invention, first, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater or a spin coater (spin coat) is used. Device), non-contact coating device such as curtain-type flat coating machine on substrate Applying a photosensitive composition.
其次，使塗佈之感光性組合物乾燥而形成塗膜。乾燥方法並無特別限定，例如可列舉：(1)利用加熱板於80~120℃、較佳為90~100℃之溫度下乾燥60~120秒之方法、(2)於室溫下放置數小時~數日之方法、(3)加入至熱風加熱器或紅外線加熱器中數分鐘~數小時而去除溶劑之方法等。 Next, the applied photosensitive composition is dried to form a coating film. The drying method is not particularly limited, and examples include: (1) a method of drying at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds using a hot plate, and (2) standing at room temperature Methods of hours to days, (3) Methods of adding solvents to hot air heaters or infrared heaters for minutes to hours to remove solvents, etc.
其次，對於該塗膜，經由負型遮罩照射紫外線、準分子雷射光等活性能量線而進行局部曝光。照射之能量線量根據感光性組合物之組成而不同，例如較佳為30~2000mJ/cm2左右。若如已說明般使用本發明之感光性組合物，則感度優異，能夠提昇液晶顯示面板之生產性。 Next, the coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of energy rays to be irradiated varies depending on the composition of the photosensitive composition, and is preferably about 30 to 2000 mJ / cm 2 , for example. If the photosensitive composition of the present invention is used as described, the sensitivity is excellent, and the productivity of the liquid crystal display panel can be improved.
其次，藉由利用顯影液使曝光後之膜顯影而以所需之形狀圖案化。顯影方法並無特別限定，例如能夠使用浸漬法、噴霧法等。作為顯影液，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。 Secondly, the exposed film is patterned in a desired shape by developing a developing solution. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic solvents such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
其次，較佳為於200~250℃左右下對顯影後之圖案進行後烘烤。 Secondly, it is preferable to post-bake the developed pattern at about 200-250 ° C.
以此種方式形成之圖案例如能夠較佳地用作如液晶顯示器等之顯示裝置中之彩色濾光片。此種彩色濾光片或具備該彩色濾光片之顯示裝置亦為本發明之一。 The pattern formed in this manner can be preferably used, for example, as a color filter in a display device such as a liquid crystal display. Such a color filter or a display device having the same is also one aspect of the present invention.
以下，藉由實施例而對本發明進行更具體地說明，但本發明之範圍並不限定於該等實施例。 Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these examples.
[實施例] [Example]
以下，於實施例及比較例中，使用下述化合物6、化合物7、化合物9~11及化合物20與下述比較化合物1及比較化合物2作為光聚合起始劑。 Hereinafter, in Examples and Comparative Examples, the following Compound 6, Compound 7, Compounds 9-11, and 20 and the following Comparative Compound 1 and Comparative Compound 2 were used as photopolymerization initiators.
化合物6、化合物7、化合物9~11及化合物20係使用根據以下之合成例1~合成例7而獲得者。 Compound 6, Compound 7, Compounds 9-11, and Compound 20 were obtained by using Synthesis Examples 1 to 7 below.
[合成例1] [Synthesis example 1]
(9,9-二正丙基茀之合成) (Synthesis of 9,9-di-n-propylphosphonium)
使茀6.64g(40mmol)溶解於27mL之THF中。於所獲得之溶液中，在氮氣環境下緩緩添加鉀第三丁氧化物0.12g(1.1mmol)、1-溴丙烷12.30g(100mmol)及濃度50質量%之氫氧化鈉水溶液27mL。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33g及水33g後，分液為有機層與水層。使用無水硫酸鈉使所獲得之有機層脫水後，使用旋轉蒸發器自有機層中去除溶劑而獲得9,9-二正丙基茀8.32g(產率83%)。 茀 6.64 g (40 mmol) was dissolved in 27 mL of THF. To the obtained solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of a 50% by mass sodium hydroxide aqueous solution were slowly added under a nitrogen environment. The obtained mixture was stirred at 80 ° C for 3 hours to perform a reaction. After adding 33 g of ethyl acetate and 33 g of water to the reaction mixture, the mixture was separated into an organic layer and an aqueous layer. After the obtained organic layer was dehydrated using anhydrous sodium sulfate, the solvent was removed from the organic layer using a rotary evaporator to obtain 9,9-di-n-propylphosphonium 8.32 g (yield 83%).
[合成例2] [Synthesis example 2]
(化合物6之合成) (Synthesis of Compound 6)
於氯化鋁2.62g之存在下，在二氯甲烷溶劑50ml中並於冰浴冷卻下使9,9-二正丙基茀4.10g(16.37mmol)與(2-甲基苯基)乙酸氯化物3.04g(18.00mmol)反應1小時。將反應混合物倒入冰水中，對有機層進行分液。使用無水硫酸鎂將回收之有機層乾燥後，進行蒸發。使用乙酸乙酯/己烷=1/2之溶離液使殘渣矽膠管柱純化而獲得2-(2-甲基苯基)乙醯基-9,9-二正丙基茀5.95g(15.55mmol)。於亞硝酸異丁酯2.42g(23.33mmol)之存在下，在二甲基甲醯胺溶劑25ml中並於冰浴冷卻下使2-(2-甲基苯基)乙醯基-9,9-二正丙基茀5.95g(15.55mmol)與濃鹽酸1.60g(15.55mmol)反應3小時。使反應液蒸發並於殘渣中添加乙酸乙酯，用飽和食鹽水洗淨併用無水硫酸鎂乾燥後，進行蒸發而獲得下述結構之2-[2-甲基苯基(羥基亞胺基)乙醯基]-9,9-二正丙基茀4.80g(11.67mmol)。 In the presence of 2.62 g of aluminum chloride, 4.10 g (16.37 mmol) of 9,9-di-n-propylfluorene and (2-methylphenyl) acetic acid chloride were dissolved in 50 ml of a dichloromethane solvent under cooling in an ice bath. 3.04 g (18.00 mmol) of the compound was reacted for 1 hour. The reaction mixture was poured into ice water, and the organic layer was separated. The recovered organic layer was dried using anhydrous magnesium sulfate, and then evaporated. The residue was purified by a silica gel column using an eluent of ethyl acetate / hexane = 1/2 to obtain 2- (2-methylphenyl) ethylfluorenyl-9,9-di-n-propylfluorene 5.95 g (15.55 mmol ). In the presence of 2.42 g (23.33 mmol) of isobutyl nitrite, in 25 ml of dimethylformamide solvent and cooling in an ice bath, 2- (2-methylphenyl) acetamidin-9,9 -5.95 g (15.55 mmol) of di-n-propylpyrene are reacted with 1.60 g (15.55 mmol) of concentrated hydrochloric acid for 3 hours. The reaction solution was evaporated, and ethyl acetate was added to the residue. The residue was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to obtain 2- [2-methylphenyl (hydroxyimino) ethyl having the following structure. Fluorenyl] -9,9-di-n-propylfluorene 4.80 g (11.67 mmol).
2-[2-甲基苯基(羥基亞胺基)乙醯基]-9,9-二正丙基茀之1H-NMR之測定結果如下所示。 The 1 H-NMR measurement results of 2- [2-methylphenyl (hydroxyimino) ethylfluorenyl] -9,9-di-n-propylphosphonium are shown below.
1H-NMR(600MHz,CDCl3,ppm)：8.60(bs,1H),8.15(d,1H),8.14(s,1H),7.76-8.00(m,2H),7.26-7.53(m,7H),2.35(s,3H),1.98-2.01(m,4H),0.63-0.67(m,10H) 1 H-NMR (600 MHz, CDCl 3 , ppm): 8.60 (bs, 1H), 8.15 (d, 1H), 8.14 (s, 1H), 7.76-8.00 (m, 2H), 7.26-7.53 (m, 7H ), 2.35 (s, 3H), 1.98-2.01 (m, 4H), 0.63-0.67 (m, 10H)
將2-[2-甲基苯基(羥基亞胺基)乙醯基]-9,9-二正丙基茀4.80g(11.67mmol)、乙酸酐1.43g(13.42mmol)、三乙基胺1.36g(13.42 mmol)與二甲基甲醯胺溶劑45.00ml混合並於35℃下攪拌3小時。冷卻至室溫後，於反應液中添加乙酸乙酯，用水洗淨併用無水硫酸鎂乾燥後，進行蒸發。使用乙酸乙酯/己烷=2/1之溶離液使殘渣矽膠管柱純化而獲得化合物6 4.76g(10.50mmol、產率72%)。化合物6之1H-NMR之測定結果如下所示。 Add 2- [2-methylphenyl (hydroxyimino) ethenyl] -9,9-di-n-propylsulfonium 4.80 g (11.67 mmol), acetic anhydride 1.43 g (13.42 mmol), and triethylamine 1.36 g (13.42 mmol) was mixed with 45.00 ml of a dimethylformamide solvent and stirred at 35 ° C for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate, and evaporated. The residue in a silica gel column was purified using an eluent of ethyl acetate / hexane = 2/1 to obtain 4.76 g (10.50 mmol, yield 72%) of Compound 6. The measurement results of 1 H-NMR of Compound 6 are shown below.
1H-NMR(600MHz,CDCl3,ppm)：8.25(d,1H),8.22(s,1H),7.83(d,1H),7.81(dd,1H),7.33-7.40(m,3H),7.26-7.33(m,4H),2.35(s,3H),2.14(s,3H),1.95-2.07(m,4H),0.63-0.66(m,10H). 1 H-NMR (600MHz, CDCl 3 , ppm): 8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7.33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (m, 4H), 0.63-0.66 (m, 10H).
[合成例3] [Synthesis example 3]
(化合物7之合成) (Synthesis of Compound 7)
將(2-甲基苯基)乙酸氯化物3.04g(18.00mmol)變更為3-環己基丙酸氯化物3.14g(18.00mmol)，除此以外，以與合成例2相同之方式獲得作為中間物之下述結構之2-[環己基甲基(羥基亞胺基)乙醯基]-9,9-二正丙基茀及化合物7 4.96g(10.80mmol、產率75%)。 Except changing 3.04 g (18.00 mmol) of (2-methylphenyl) acetic acid chloride to 3.14 g (18.00 mmol) of 3-cyclohexylpropanoic acid chloride, an intermediate was obtained in the same manner as in Synthesis Example 2 except that The following structure of 2- [cyclohexylmethyl (hydroxyimino) ethylfluorenyl] -9,9-di-n-propylfluorene and compound 7 4.96 g (10.80 mmol, yield 75%).
2-[環己基甲基(羥基亞胺基)乙醯基]-9,9-二正丙基茀之1H-NMR之測定結果如下所示。 The measurement results of 1- H-NMR of 2- [cyclohexylmethyl (hydroxyimino) ethylfluorenyl] -9,9-di-n-propylphosphonium are shown below.
1H-NMR(600MHz,CDCl3,ppm)：8.80(bs,1H),7.90-7.98(m,2H),7.70-7.80(m,2H),7.30-7.40(m,3H),2.72(d,2H),1.88-2.02(m,4H),1.54-1.80(m,6H),0.95-1.28(m,5H),0.67-0.77(m,10H) 1 H-NMR (600MHz, CDCl 3 , ppm): 8.80 (bs, 1H), 7.90-7.98 (m, 2H), 7.70-7.80 (m, 2H), 7.30-7.40 (m, 3H), 2.72 (d , 2H), 1.88-2.02 (m, 4H), 1.54-1.80 (m, 6H), 0.95-1.28 (m, 5H), 0.67-0.77 (m, 10H)
化合物7之1H-NMR之測定結果如下所示。 The measurement results of 1 H-NMR of Compound 7 are shown below.
1H-NMR(600MHz,CDCl3,ppm)：8.08-8.14(m,2H),7.70- 7.79(m,2H),7.32-7.40(m,3H),2.78(d,2H),2.28(s,3H),1.88-2.10(m,4H),1.53-1.78(m,6H),1.00-1.30(m,5H),0.60-0.77(m,10H). 1 H-NMR (600MHz, CDCl 3 , ppm): 8.08-8.14 (m, 2H), 7.70-7.79 (m, 2H), 7.32-7.40 (m, 3H), 2.78 (d, 2H), 2.28 (s , 3H), 1.88-2.10 (m, 4H), 1.53-1.78 (m, 6H), 1.00-1.30 (m, 5H), 0.60-0.77 (m, 10H).
[合成例4] [Synthesis example 4]
(化合物9之合成) (Synthesis of Compound 9)
將(2-甲基苯基)乙酸氯化物3.04g(18.00mmol)變更為3-環戊基丙酸氯化物2.89g(18.00mmol)，除此以外，以與合成例2相同之方式獲得化合物9 4.46g(10.02mmol、產率72%)。化合物9之1H-NMR之測定結果如下所示。 A compound was obtained in the same manner as in Synthesis Example 2 except that 3.04 g (18.00 mmol) of (2-methylphenyl) acetic acid chloride was changed to 2.89 g (18.00 mmol) of 3-cyclopentylpropionic acid chloride. 9 4.46 g (10.02 mmol, 72% yield). The measurement results of 1 H-NMR of Compound 9 are shown below.
1H-NMR(600MHz,CDCl3,ppm)：8.06-8.12(m,2H),7.71-7.78(m,2H),7.31-7.40(m,3H),2.52(d,2H),2.27(s,3H),1.89-2.19(m,5H),1.48-1.80(m,6H),1.19-1.26(m,2H),0.61-0.77(m,10H). 1 H-NMR (600MHz, CDCl 3 , ppm): 8.06-8.12 (m, 2H), 7.71-7.78 (m, 2H), 7.31-7.40 (m, 3H), 2.52 (d, 2H), 2.27 (s , 3H), 1.89-2.19 (m, 5H), 1.48-1.80 (m, 6H), 1.19-1.26 (m, 2H), 0.61-0.77 (m, 10H).
[合成例5] [Synthesis example 5]
(化合物10之合成) (Synthesis of Compound 10)
將(2-甲基苯基)乙酸氯化物3.04g(18.00mmol)變更為(α-萘基)乙酸氯化物3.68g(18.00mmol)，除此以外，以與合成例2相同之方式獲得化合物10 5.29g(10.80mmol、產率78%)。化合物10之1H-NMR之測定結果如下。 A compound was obtained in the same manner as in Synthesis Example 2 except that 3.04 g (18.00 mmol) of (2-methylphenyl) acetic acid chloride was changed to 3.68 g (18.00 mmol) of (α-naphthyl) acetic acid chloride. 10 5.29 g (10.80 mmol, 78% yield). The measurement results of 1 H-NMR of Compound 10 are as follows.
1H-NMR(600MHz,CDCl3,ppm)：8.26(d,1H),8.24(s,1H),7.82(d,1H),7.82(dd,1H),7.30-7.70(m,10H),2.14(s,3H),1.94-2.05(m,4H),0.62-0.66(m,10H). 1 H-NMR (600MHz, CDCl 3 , ppm): 8.26 (d, 1H), 8.24 (s, 1H), 7.82 (d, 1H), 7.82 (dd, 1H), 7.30-7.70 (m, 10H), 2.14 (s, 3H), 1.94-2.05 (m, 4H), 0.62-0.66 (m, 10H).
[合成例6] [Synthesis example 6]
(化合物11之合成) (Synthesis of Compound 11)
將(2-甲基苯基)乙酸氯化物3.04g(18.00mmol)變更為1,1'-聯苯基-2-乙酸氯化物4.15g(18.00mmol)，除此以外，以與合成例2相同之方式獲得化合物11 5.36g(10.40mmol、產率73%)。化合物11之1H-NMR之測定結果如下。 Except that 3.04 g (18.00 mmol) of (2-methylphenyl) acetic acid chloride was changed to 4.15 g (18.00 mmol) of 1,1'-biphenyl-2-acetic acid chloride, the same procedure was used as in Synthesis Example 2 In the same manner, 5.36 g (10.40 mmol, yield 73%) of Compound 11 was obtained. The measurement results of 1 H-NMR of Compound 11 are as follows.
1H-NMR(600MHz,CDCl3,ppm)：8.22(d,1H),8.19(s,1H),7.84(d,1H),7.83(dd,1H),7.20-7.45(m,12H),2.15(s,3H),1.94-2.07(m,4H),0.63-0.66(m,10H). 1 H-NMR (600MHz, CDCl 3 , ppm): 8.22 (d, 1H), 8.19 (s, 1H), 7.84 (d, 1H), 7.83 (dd, 1H), 7.20-7.45 (m, 12H), 2.15 (s, 3H), 1.94-2.07 (m, 4H), 0.63-0.66 (m, 10H).
[合成例7] [Synthesis example 7]
(化合物20之合成) (Synthesis of Compound 20)
於氯化鋁2.62g之存在下，在二氯甲烷溶劑50ml中並於冰浴冷卻下使9,9-二正丙基茀4.10g(16.37mmol)與苯基乙酸氯化物2.78g(18.00mmol)反應1小時。將反應混合物倒入冰水中，對有機層進行分液。使用無水硫酸鎂將回收之有機層乾燥後，進行蒸發。使用乙酸乙酯/己烷=1/2之溶離液使殘渣矽膠管柱純化而獲得2-苯基乙醯基-9,9-二正丙基茀。於亞硝酸異丁酯2.42g(23.33mmol)之存在下，在二甲基甲醯胺溶劑25ml中並於冰浴冷卻下使2-苯基乙醯基-9,9-二正丙基茀5.73g(15.55mmol)與濃鹽酸1.60g(15.55mmol)反應3小時。使反應液蒸發並於殘渣中添加乙酸乙酯，使用飽和食鹽水洗淨並使用無水硫酸鎂乾燥後，進行蒸發而獲得下述結構之2-[苯基(羥基亞胺基)乙醯基]-9,9-二正丙基茀。 In the presence of 2.62 g of aluminum chloride, 4.10 g (16.37 mmol) of 9,9-di-n-propylpyrene and 2.78 g (18.00 mmol of phenylacetic acid chloride) in 50 ml of dichloromethane solvent and cooling in an ice bath. ) Reaction for 1 hour. The reaction mixture was poured into ice water, and the organic layer was separated. The recovered organic layer was dried using anhydrous magnesium sulfate, and then evaporated. The residue in a silica gel column was purified using an eluent of ethyl acetate / hexane = 1/2 to obtain 2-phenylethylfluorenyl-9,9-di-n-propylphosphonium. In the presence of 2.42 g (23.33 mmol) of isobutyl nitrite, 2-phenylethylfluorenyl-9,9-di-n-propylfluorene was dissolved in 25 ml of dimethylformamide solvent and cooled in an ice bath. 5.73 g (15.55 mmol) was reacted with 1.60 g (15.55 mmol) of concentrated hydrochloric acid for 3 hours. The reaction solution was evaporated, and ethyl acetate was added to the residue. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then evaporated to obtain 2- [phenyl (hydroxyimino) acetamidine] having the following structure. -9,9-di-n-propylhydrazone.
2-[苯基(羥基亞胺基)乙醯基]-9,9-二正丙基茀之1H-NMR之測定結果如下。 The 1 H-NMR measurement results of 2- [phenyl (hydroxyimino) ethylfluorenyl] -9,9-di-n-propylphosphonium are as follows.
1H-NMR(600MHz,CDCl3,ppm)：8.05(s,1H),7.76-7.92(m,2H),7.75(m,2H),7.61(m,2H),7.30-7.41(m,5H),1.92-2.05(m,4H),0.58-0.70(m,10H). 1 H-NMR (600MHz, CDCl 3 , ppm): 8.05 (s, 1H), 7.76-7.92 (m, 2H), 7.75 (m, 2H), 7.61 (m, 2H), 7.30-7.41 (m, 5H ), 1.92-2.05 (m, 4H), 0.58-0.70 (m, 10H).
將2-[苯基(羥基亞胺基)乙醯基]-9,9-二正丙基茀4.64g(11.67 mmol)、乙酸酐1.43g(13.42mmol)、三乙基胺1.36g(13.42mmol)與二甲基甲醯胺溶劑45.00ml混合，於35℃下攪拌3小時。冷卻至室溫後，於反應液中添加乙酸乙酯，用水洗淨併用無水硫酸鎂乾燥後，進行蒸發。使用乙酸乙酯/己烷=2/1之溶離液使殘渣矽膠管柱純化而獲得化合物20 4.44g(10.10mmol、產率69%)。化合物20之1H-NMR之測定結果如下。 Add 2- [phenyl (hydroxyimino) ethenyl] -9,9-di-n-propylphosphonium 4.64 g (11.67 mmol), acetic anhydride 1.43 g (13.42 mmol), and triethylamine 1.36 g (13.42 mmol) was mixed with 45.00 ml of dimethylformamide solvent, and stirred at 35 ° C. for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate, and evaporated. The residue in a silica gel column was purified using an eluent of ethyl acetate / hexane = 2/1 to obtain 4.44 g (10.10 mmol, 69% yield) of Compound 20. The measurement results of 1 H-NMR of Compound 20 are as follows.
1H-NMR(600MHz,CDCl3,ppm)：7.97(s,1H),7.87(dd,1H),7.74-7.79(m,4H),7.72-7.80(m,1H),7.35-7.52(m,5H),1.95-2.03(m,4H),1.94(s,3H),0.58-0.65(m,10H). 1 H-NMR (600 MHz, CDCl 3 , ppm): 7.97 (s, 1H), 7.87 (dd, 1H), 7.74-7.79 (m, 4H), 7.72-7.80 (m, 1H), 7.35-7.52 (m , 5H), 1.95-2.03 (m, 4H), 1.94 (s, 3H), 0.58-0.65 (m, 10H).
於實施例及比較例中，作為(A)聚合性基材成分，使用以下之A1~A4。 In Examples and Comparative Examples, the following A1 to A4 were used as the (A) polymerizable substrate component.
A1：下式之包含乙烯性不飽和基之鹼可溶性樹脂。 A1: An alkali-soluble resin containing an ethylenically unsaturated group of the following formula.
A2：下述合成例8中所獲得之含有於主鏈上具有環結構之構成單元之聚合物。 A2: A polymer containing a structural unit having a ring structure on the main chain obtained in the following Synthesis Example 8.
A3：下述合成例9中所獲得之含有於主鏈上具有環結構之構成單元之聚合物。 A3: A polymer containing a constituent unit having a ring structure on the main chain obtained in the following Synthesis Example 9.
A4：上述式(a2-2)中，R11為甲基之單體/甲基丙烯酸/甲基丙烯酸三環癸基酯=72/18/10(質量比)、質量平均分子量14000之鹼可溶性樹脂(其中，上述式(a2-2)中，R11為甲基之單體包含甲基丙烯酸3,4-環氧三環-[5.2.1.02,6]癸烷-8(或9）-基之異構物混合物)。 A4: In the above formula (a2-2), R 11 is a monomer of methyl group / methacrylic acid / tricyclodecyl methacrylate = 72/18/10 (mass ratio) and alkali solubility of a mass average molecular weight of 14000 Resin (wherein, in the above formula (a2-2), the monomer in which R 11 is a methyl group includes methacrylic 3,4-epoxytricyclo- [5.2.1.0 2,6 ] decane-8 (or 9) -Radical isomer mixture).
A5：二季戊四醇六丙烯酸酯(光聚合性單體)。 A5: dipentaerythritol hexaacrylate (photopolymerizable monomer).
[合成例8] [Synthesis example 8]
作為反應槽，使用附有冷卻管之可分離式燒瓶。於反應槽中加入丙二醇單甲醚乙酸酯(PGMEA)，進行氮氣置換後，一面攪拌一面利用油浴進行加熱而使反應槽之溫度提昇至90℃。 As a reaction tank, a separable flask with a cooling tube was used. Propylene glycol monomethyl ether acetate (PGMEA) was added to the reaction tank, and after nitrogen substitution, the temperature of the reaction tank was raised to 90 ° C. while heating with an oil bath while stirring.
另一方面，於單體槽中，將二甲基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯(MD)40質量份、甲基丙烯酸(MAA)32質量份、甲基丙烯酸甲酯(MMA)68質量份、甲基丙烯酸環己酯(CHMA)60質量份、過氧化(2-乙基己酸)第三丁酯(PBO)2.6質量份、PGMEA 40質量份混合。 On the other hand, in the monomer tank, 40 parts by mass of dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate (MD) and 32 methacrylic acid (MAA) were added. Parts by mass, 68 parts by mass of methyl methacrylate (MMA), 60 parts by mass of cyclohexyl methacrylate (CHMA), 2.6 parts by mass of third (2-ethylhexanoate) third butyl ester (PBO), PGMEA 40 parts by mass are mixed.
又，於鏈轉移劑槽中，將正十二烷硫醇5.2質量份、PGMEA 27質量份混合。 In a chain transfer agent tank, 5.2 parts by mass of n-dodecanethiol and 27 parts by mass of PGMEA were mixed.
反應槽之溫度穩定於90℃後，開始自單體槽及鏈轉移劑槽向反應槽之滴加而開始聚合。一面將溫度保持於90℃，一面自單體槽及鏈轉移劑槽分別進行135分鐘滴加。滴加結束60分鐘後開始升溫而將反應槽之內溫提昇至110℃。於110℃下維持3小時後，將反應槽之內容物冷卻至室溫而獲得A2之溶液。 After the temperature of the reaction tank was stabilized at 90 ° C, dripping was started from the monomer tank and the chain transfer agent tank to the reaction tank to start polymerization. While maintaining the temperature at 90 ° C, dripping was performed from the monomer tank and the chain transfer agent tank for 135 minutes, respectively. 60 minutes after the end of the dropwise addition, the temperature was started to raise the internal temperature of the reaction tank to 110 ° C. After maintaining at 110 ° C for 3 hours, the contents of the reaction tank were cooled to room temperature to obtain a solution of A2.
[合成例9] [Synthesis example 9]
將二甲基-2,2'-[氧基雙(亞甲基)]雙-2-丙烯酸酯(MD)40質量份變更為N-苄基順丁烯二醯亞胺40質量份，除此以外，以與合成例8相同 之方式獲得A3之溶液。 40 parts by mass of dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate (MD) was changed to 40 parts by mass of N-benzyl cis butene difluorene imide, except Otherwise, it is the same as in Synthesis Example 8. In this way, a solution of A3 was obtained.
於實施例及比較例中，作為(C)有彩色著色劑，以表1中所記載之質量比使用以下之C1~C9。(C)有彩色著色劑係用作固形物成分濃度20質量%之分散液。著色劑之分散液包含相對於分散液之質量而為2質量%之丙烯酸樹脂系高分子分散劑(商品名：DisperBYK2001、BYK-Chemie公司製造)。進而，分散液中所含之溶劑為3-甲氧基丁基乙酸酯與丙二醇單甲基乙酸酯之混合溶劑(質量比6：4)。 In Examples and Comparative Examples, as (C) a colored colorant, the following C1 to C9 were used at the mass ratios described in Table 1. (C) A colored colorant is used as a dispersion liquid having a solid content concentration of 20% by mass. The dispersion liquid of the colorant contains an acrylic resin-based polymer dispersant (trade name: DisperBYK2001, manufactured by BYK-Chemie) at 2% by mass based on the mass of the dispersion liquid. Furthermore, the solvent contained in the dispersion liquid was a mixed solvent of 3-methoxybutyl acetate and propylene glycol monomethyl acetate (mass ratio 6: 4).
C1：C.I.顏料紅254 C1: C.I. Pigment Red 254
C2：C.I.顏料黃139 C2: C.I. Pigment Yellow 139
C3：C.I.顏料藍15：6 C3: C.I. Pigment Blue 15: 6
C4：C.I.顏料紫23 C4: C.I. Pigment Violet 23
C5：C.I.顏料綠36 C5: C.I. Pigment Green 36
C6：C.I.顏料黃150 C6: C.I. Pigment Yellow 150
C7：玫瑰紅B(染料、東京化成工業製造) C7: Rose Red B (dye, manufactured by Tokyo Chemical Industry)
C8：鹼性藍7(染料、東京化成工業製造) C8: Basic Blue 7 (dye, manufactured by Tokyo Chemical Industry)
C9：亮綠(染料、和光純藥工業製造) C9: Bright green (dye, Wako Pure Chemical Industries)
於實施例及比較例中，作為溶劑，使用3-甲氧基丁基乙酸酯、環己酮與丙二醇單甲基乙酸酯之混合溶劑。考慮上述(C)有彩色著色劑所含之溶劑之質量後，將組合物中之整體之溶劑組成比調整至3-甲氧基丁基乙酸酯：環己酮：丙二醇單甲基乙酸酯=3：3：4。 In Examples and Comparative Examples, as the solvent, a mixed solvent of 3-methoxybutyl acetate, cyclohexanone, and propylene glycol monomethyl acetate was used. After considering the mass of the solvent contained in the (C) colored colorant, the overall solvent composition ratio in the composition was adjusted to 3-methoxybutyl acetate: cyclohexanone: propylene glycol monomethylacetic acid Ester = 3: 3: 4.
[實施例1~36及比較例1~9] [Examples 1 to 36 and Comparative Examples 1 to 9]
以固形物成分濃度成為15質量%之方式使表1中所記載之種類及量之(A)聚合性基材成分、表1中所記載之種類之(B)光聚合起始劑5質量份、與為表1中所記載之種類及質量比且總量50質量份之(C)有彩色著色劑於溶劑中均勻地分散、溶解，獲得各實施例及比較例之感光性組合物。 5 parts by mass of (A) a polymerizable substrate component of the type and amount described in Table 1 and (B) a photopolymerization initiator of the type described in Table 1 so that the solid component concentration becomes 15% by mass (C) The colored coloring agent of the type and mass ratio shown in Table 1 and 50 parts by mass in total was uniformly dispersed and dissolved in a solvent to obtain the photosensitive compositions of the respective examples and comparative examples.
再者，於實施例25及26中，作為光聚合起始劑，組合使用1質量份之化合物6及4質量份之比較化合物2。 In Examples 25 and 26, 1 part by mass of compound 6 and 4 parts by mass of comparative compound 2 were used as a photopolymerization initiator in combination.
對於各實施例及比較例之感光性組合物，依據以下之方法而進行圖案剝離之有無、由後烘烤所引起之著色之評價、異物量之評價。將各感光性組合物之評價結果記載於表2中。 For the photosensitive compositions of each of the examples and comparative examples, the presence or absence of pattern peeling, the evaluation of coloring caused by post-baking, and the evaluation of the amount of foreign matter were performed according to the following methods. Table 2 shows the evaluation results of each photosensitive composition.
[圖案剝離評價] [Pattern peeling evaluation]
對於實施例1~36及比較例1~9之感光性組合物，分別按照以下之工序進行圖案剝離之評價。 The photosensitive compositions of Examples 1 to 36 and Comparative Examples 1 to 9 were evaluated for pattern peeling according to the following steps.
首先，將感光性組合物旋轉塗佈於玻璃基板(10cm×10cm)上，於90℃下加熱120秒，藉此於玻璃基板之表面形成膜厚2.0μm之塗佈膜。其後，以曝光量50或200mJ/cm2對塗佈膜進行曝光。使用26℃之0.04質量%KOH水溶液對曝光後之膜進行30~50秒顯影後，獲得具備30μm尺寸、矩陣形狀之圖案之著色膜。 First, a photosensitive composition was spin-coated on a glass substrate (10 cm × 10 cm) and heated at 90 ° C. for 120 seconds to form a coating film having a thickness of 2.0 μm on the surface of the glass substrate. Thereafter, the coating film was exposed at an exposure amount of 50 or 200 mJ / cm 2 . After the exposed film was developed using a 0.04 mass% KOH aqueous solution at 26 ° C for 30 to 50 seconds, a colored film having a pattern with a size of 30 μm and a matrix shape was obtained.
對於所獲得之圖案，使用顯微鏡觀察剝離之有無。將圖案之剝離之有無記載於表2中。 For the obtained pattern, the presence or absence of peeling was observed using a microscope. The presence or absence of pattern peeling is shown in Table 2.
[著色評價] [Coloring evaluation]
對於實施例1~36及比較例1~9之感光性組合物，分別按照以下之工序進行著色評價。 The photosensitive compositions of Examples 1 to 36 and Comparative Examples 1 to 9 were subjected to coloring evaluation according to the following procedures, respectively.
首先，將感光性組合物旋轉塗佈於玻璃基板(10cm×10cm)上，於90℃下加熱120秒，藉此於玻璃基板之表面形成1.0μm之塗佈膜。其後，以曝光量200mJ/cm2對塗佈膜進行曝光。使用26℃之0.04質量%KOH水溶液對曝光後之膜進行30~50秒顯影後，以230℃-30分鐘進行後烘烤。使用瞬間多測光系統(MCPD-3000：大塚電子股份有限公司製造)對後烘烤前後之塗佈膜之380nm~780nm波長區域的透過率差之絕對值△Y進行測定。基於△Y之值並按照以下之基準而對著色進行評價。將著色評價之結果記載於表2中。 First, a photosensitive composition was spin-coated on a glass substrate (10 cm × 10 cm) and heated at 90 ° C. for 120 seconds to form a 1.0 μm coating film on the surface of the glass substrate. Thereafter, the coating film was exposed at an exposure amount of 200 mJ / cm 2 . After the exposed film was developed using a 0.04% by mass KOH aqueous solution at 26 ° C. for 30 to 50 seconds, post-baking was performed at 230 ° C. for 30 minutes. The instantaneous multiple photometry system (MCPD-3000: manufactured by Otsuka Electronics Co., Ltd.) was used to measure the absolute value ΔY of the transmittance difference in the wavelength range of 380 nm to 780 nm of the coating film before and after post-baking. The coloring was evaluated based on the value of ΔY and the following criteria. The results of the coloring evaluation are shown in Table 2.
○：△Y之值為0.5以下 ○: The value of △ Y is 0.5 or less
△：△Y之值超過0.5且為0.7以下 △: The value of △ Y exceeds 0.5 and is 0.7 or less
×：△Y之值超過0.7 ×: The value of △ Y exceeds 0.7
[異物評價] [Foreign body evaluation]
對於實施例1~36及比較例1~9之感光性組合物，分別按照以下之工序進行異物評價。 For the photosensitive compositions of Examples 1 to 36 and Comparative Examples 1 to 9, foreign matter evaluation was performed according to the following procedures.
首先，將感光性組合物旋轉塗佈於玻璃基板(680mm×880mm)上，於90℃下加熱120秒，藉此於玻璃基板之表面形成膜厚2.0μm之塗佈膜。其後，以曝光量90mJ/cm2對塗佈膜進行曝光。使用26℃之0.04質量%KOH水溶液對曝光後之膜進行30~50秒顯影而獲得具備6μm矩陣圖案之著色膜。 First, a photosensitive composition was spin-coated on a glass substrate (680 mm × 880 mm) and heated at 90 ° C. for 120 seconds to form a coating film having a thickness of 2.0 μm on the surface of the glass substrate. Thereafter, the coating film was exposed at an exposure amount of 90 mJ / cm 2 . A 0.04 mass% KOH aqueous solution at 26 ° C. was used to develop the exposed film for 30 to 50 seconds to obtain a colored film having a 6 μm matrix pattern.
對於所獲得之著色膜，使用TAKANO公司製造之外觀檢測裝置測定100μm烴以上之異物之個數。基於異物之個數並按照以下之基準而進行評價。將異物之評價結果記載於表2中。 With respect to the obtained colored film, the number of foreign matter of 100 μm or more hydrocarbon was measured using an appearance inspection device manufactured by TAKANO. The evaluation was performed based on the number of foreign objects in accordance with the following criteria. Table 2 shows the evaluation results of the foreign matter.
◎：異物數0 ◎: Number of foreign objects 0
○：異物數1或2 ○: Number of foreign objects 1 or 2
△：異物數3~5 △: Number of foreign objects 3 to 5
×：異物數6以上 ×: Number of foreign objects 6 or more
根據表1及表2，可知若使用包含通式(1)所表示之肟酯化合物作為光聚合起始劑且包含有彩色著色劑之實施例之感光性組合物，則能夠形成難以自基板剝離，具有變色較少之所需色相，異物較少之著色膜。 From Tables 1 and 2, it can be seen that when the photosensitive composition of the example containing the oxime ester compound represented by the general formula (1) as a photopolymerization initiator and containing a coloring agent can be formed, it is possible to form a substrate that is difficult to peel off It has a tint with less discoloration and less foreign matter.
另一方面，根據比較例，可知於包含有彩色著色劑之感光性組合物中調配除式(1)以外之結構之光聚合起始劑之情形時，著色膜容易因膜形成時之加熱而變色，著色膜中之異物量較多，容易產生著色膜自基板之剝離。 On the other hand, according to the comparative example, it can be seen that when a photopolymerization initiator having a structure other than the formula (1) is blended in a photosensitive composition containing a coloring agent, the colored film is likely to be caused by heating during film formation. Discoloration, the amount of foreign matter in the colored film is large, and peeling of the colored film from the substrate is likely to occur.
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