TWI693473B - Photosensitive resin composition and photo-cured pattern prepared from the same - Google Patents
Photosensitive resin composition and photo-cured pattern prepared from the same Download PDFInfo
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- TWI693473B TWI693473B TW106112188A TW106112188A TWI693473B TW I693473 B TWI693473 B TW I693473B TW 106112188 A TW106112188 A TW 106112188A TW 106112188 A TW106112188 A TW 106112188A TW I693473 B TWI693473 B TW I693473B
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- 0 C*=C(C(*)=*OC*)C(C=CC[C@@]1C(*)=CC(*)=CC1)=*C=* Chemical compound C*=C(C(*)=*OC*)C(C=CC[C@@]1C(*)=CC(*)=CC1)=*C=* 0.000 description 8
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
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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
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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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13392—Gaskets; Spacers; Sealing of cells spacers dispersed on the cell substrate, e.g. spherical particles, microfibres
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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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
- G03F7/2055—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser for the production of printing plates; Exposure of liquid photohardening compositions
Abstract
本發明提供一種感光性樹脂組合物，其具有固化後優異的彈性回復率，同時能夠形成具有使外部壓力引起的變形較少的堅硬特性的光固化圖案，微細圖案的實現性優異，藉由調節光聚合引發劑的量，能夠調節圖案的大小。本發明涉及感光性樹脂組合物，更詳細言之，涉及感光性樹脂組合物，其包含鹼可溶性樹脂(A)、光聚合引發劑(B)、光聚合性化合物(C)、溶劑(D)，上述鹼可溶性樹脂(A)包含第一樹脂與第二樹脂，上述光聚合引發劑(B)包含特定結構的化合物。 The present invention provides a photosensitive resin composition which has an excellent elastic recovery rate after curing, and at the same time can form a photo-curable pattern having hard characteristics with less deformation due to external pressure, and the fine pattern can be realized by adjusting by adjusting The amount of the photopolymerization initiator can adjust the size of the pattern. The present invention relates to a photosensitive resin composition, and more specifically, to a photosensitive resin composition, which contains an alkali-soluble resin (A), a photopolymerization initiator (B), a photopolymerizable compound (C), and a solvent (D) The alkali-soluble resin (A) includes a first resin and a second resin, and the photopolymerization initiator (B) includes a compound with a specific structure.
Description
本發明涉及一種感光性樹脂組合物、一種用該組合物製造的光固化圖案及一種具有該光固化圖案的圖像顯示裝置。 The present invention relates to a photosensitive resin composition, a photocurable pattern manufactured using the composition, and an image display device having the photocurable pattern.
在一般的顯示裝置中，為了維持上下基板間的一定間隔，使用了具有一定的直徑的二氧化矽珠粒或塑膠珠粒等。但是，在這些珠粒在基板上無規則分散而位於畫素的內部的情況下，存在開口率降低、發生漏光現象的問題。為了解決該問題，開始使用在顯示裝置的內部藉由光刻形成的間隔物，現在幾乎全部顯示裝置中所使用的間隔物都藉由光刻形成。 In general display devices, in order to maintain a certain interval between the upper and lower substrates, silicon dioxide beads or plastic beads having a certain diameter are used. However, when these beads are randomly dispersed on the substrate and are located inside the pixels, there is a problem that the aperture ratio decreases and light leakage occurs. In order to solve this problem, spacers formed by photolithography inside the display device are used, and almost all spacers used in display devices are now formed by photolithography.
採用光刻的間隔物形成方法是在基板上塗布感光性樹脂組合物，經由遮罩被紫外線照射後，透過顯影過程，如遮罩中形成的圖案那樣，在基板上的所期望的位置形成間隔物。 The method of forming a spacer using photolithography is to apply a photosensitive resin composition on a substrate, irradiate ultraviolet rays through a mask, and then pass through a development process to form a gap at a desired position on the substrate like the pattern formed in the mask Thing.
最近，由於智慧手機與平板PC的普及，觸摸面板的需要在增加。因此，對於維持構成顯示裝置的濾色器基板與陣列基板之間的間隔的間隔物，不僅需要作為基本特性的彈性回復率，而且需要不存在由外部壓力引起的畫素變形的堅硬(hard)特 性。另外，隨著液晶顯示元件的高精細化而每一畫素的大小變小，對於間隔物，要求能夠形成比以往更微細的圖案。因此，在積極地進行有關感光性樹脂組合物的研究，但依然尚未滿足彈性回復率、微細圖案的實現等要求。 Recently, due to the popularity of smartphones and tablet PCs, the need for touch panels has increased. Therefore, a spacer that maintains the gap between the color filter substrate and the array substrate that constitute the display device requires not only an elastic recovery rate as a basic characteristic, but also hardness without pixel deformation caused by external pressure characteristic. In addition, as the liquid crystal display element becomes more precise, the size of each pixel becomes smaller, and it is required for the spacer to be able to form a finer pattern than in the past. Therefore, researches on photosensitive resin compositions are actively being conducted, but the requirements such as elastic recovery rate and realization of fine patterns have not yet been met.
作為一示例，韓國公開專利第2009-0056862號揭露一種感光性樹脂組合物，其包含作為不飽和羧酸及/或不飽和羧酸酐與脂肪族多環式環氧化合物的共聚物的黏結劑樹脂，但實際情況是依然尚未滿足微細圖案的實現及彈性回復率。 As an example, Korean Published Patent No. 2009-0056862 discloses a photosensitive resin composition including a binder resin as a copolymer of an unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and an aliphatic polycyclic epoxy compound However, the actual situation is that the realization of fine patterns and the elastic recovery rate have not yet been met.
專利文獻1：韓國公開專利第2009-0056862號 Patent Literature 1: Korean Patent Publication No. 2009-0056862
本發明的目的在於提供一種感光性樹脂組合物，其在固化後具有優異的彈性回復率，同時能夠形成具有使外部壓力引起的變形較少的堅硬特性的光固化圖案。 An object of the present invention is to provide a photosensitive resin composition which has an excellent elastic recovery rate after curing and can form a photo-curable pattern having hard characteristics with less deformation due to external pressure.
另外，本發明的目的在於提供一種感光性樹脂組合物，其固化時的微細圖案的實現性優異，藉由調節光聚合引發劑的量，能夠調節圖案的大小。 In addition, an object of the present invention is to provide a photosensitive resin composition which is excellent in realizing fine patterns at the time of curing, and the size of the patterns can be adjusted by adjusting the amount of the photopolymerization initiator.
進而，本發明的目的在於提供一種固化時具有優異的T/B比的值的感光性樹脂組合物。 Furthermore, an object of the present invention is to provide a photosensitive resin composition having an excellent value of T/B ratio during curing.
另外，本發明的目的在於提供一種用上述感光性樹 脂組合物製造的光固化圖案及一種具有該光固化圖案的圖像顯示裝置。 In addition, an object of the present invention is to provide a photocurable pattern produced using the photosensitive resin composition and an image display device having the photocurable pattern.
1．感光性樹脂組合物，其包含鹼可溶性樹脂(A)、光聚合引發劑(B)、光聚合性化合物(C)及溶劑(D)，上述鹼可溶性樹脂(A)包含含有選自下述化學式1與化學式2中的至少一種的化合物而聚合成的第一樹脂與含有具有脂環式環氧基的化合物而聚合成的第二樹脂，上述光聚合引發劑(B)包含由下述化學式3表示的化合物。 1. A photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerization initiator (B), a photopolymerizable compound (C), and a solvent (D), the alkali-soluble resin (A) containing A first resin polymerized with a compound of at least one of Chemical Formula 2 and a second resin polymerized with a compound containing an alicyclic epoxy group, the photopolymerization initiator (B) contains the following Chemical Formula 3 The indicated compound.
(上述化學式1中，R1為氫、(C1-C12)烷基、烯丙基、苯基、苄基、鹵素或(C1-C8)烷氧基。) (In the above Chemical Formula 1, R 1 is hydrogen, (C1-C12) alkyl, allyl, phenyl, benzyl, halogen, or (C1-C8) alkoxy.)
(上述化學式2中，R2為氫、(C1-C12)烷基、烯丙基、苯基、 苄基、鹵素或(C1-C8)烷氧基，n為1至10的整數。) (In the above Chemical Formula 2, R 2 is hydrogen, (C1-C12) alkyl, allyl, phenyl, benzyl, halogen, or (C1-C8) alkoxy, and n is an integer of 1 to 10.)
(上述化學式3中，R3與R4各自獨立地為氫或硝基，不過，R3與R4中的至少一個為硝基，R5與R6各自獨立地為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、羥基(C1-C20)烷基、羥基(C1-C20)烷氧基(C1-C20)烷基或(C3-C20)環烷基。) (In the above Chemical Formula 3, R 3 and R 4 are each independently hydrogen or nitro, but at least one of R 3 and R 4 is nitro, and R 5 and R 6 are each independently (C1-C20) alkane Group, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, hydroxy(C1-C20)alkyl, hydroxy(C1-C20)alkoxy(C1-C20)alkyl Or (C3-C20) cycloalkyl.)
2．上述第1點的感光性樹脂組合物，其中，上述具有脂環式環氧基的化合物包含下述化學式4及化學式5中的至少一個。 2. In the photosensitive resin composition according to the first aspect, the compound having an alicyclic epoxy group contains at least one of the following Chemical Formula 4 and Chemical Formula 5.
(上述化學式4中，R7為氫或者被羥基取代或未取代的(C1-C4)烷基，X為單鍵或者含有雜原子或不含雜原子的(C1-C6)亞烷基。) (In the above Chemical Formula 4, R 7 is hydrogen or a (C1-C4) alkyl group substituted or unsubstituted by a hydroxyl group, and X is a single bond or a (C1-C6) alkylene group containing or not containing a hetero atom.)
(上述化學式5中，R8為氫或者被羥基取代或未取代的(C1-C4)烷基，X為單鍵或者含有雜原子或不含雜原子的(C1-C6)亞烷基。) (In the above Chemical Formula 5, R 8 is hydrogen or a (C1-C4) alkyl group substituted or unsubstituted by a hydroxyl group, and X is a single bond or a (C1-C6) alkylene group containing or not containing a hetero atom.)
3．上述第1點的感光性樹脂組合物，其中，上述R6為甲基、乙基、丙基、丁基、戊基、己基、苯基、萘基、聯苯基、三聯苯基、蒽基、茚基、菲基、苄基、羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基、羥基己基、羥基甲氧基甲基、羥基甲氧基乙基、羥基甲氧基丙基、羥基甲氧基丁基、羥基乙氧基甲基、羥基乙氧基乙基、羥基乙氧基丙基、羥基乙氧基丁基、羥基乙氧基戊基、羥基乙氧基己基、環丙基、環戊基或環己基。 3. The photosensitive resin composition according to the above-mentioned point 1, wherein R 6 is methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl , Indenyl, phenanthrenyl, benzyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxy Propyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxy Hexyl, cyclopropyl, cyclopentyl or cyclohexyl.
4．上述第1點的感光性樹脂組合物，其中，上述光聚合引發劑(B)還包含選自苯乙酮衍生物化合物及聯咪唑衍生物化合物中的至少一種。 4. The photosensitive resin composition according to the first aspect, wherein the photopolymerization initiator (B) further contains at least one selected from the group consisting of acetophenone derivative compounds and biimidazole derivative compounds.
5．上述第4點的感光性樹脂組合物，其中，相對於光聚合引發劑的總重量，上述光聚合引發劑(B)包含40至90重量%的上述化學式3的化合物。 5. The photosensitive resin composition of the above-mentioned point 4, wherein the photopolymerization initiator (B) contains 40 to 90% by weight of the compound of the chemical formula 3 relative to the total weight of the photopolymerization initiator.
6．上述第1點的感光性樹脂組合物，其中，以鹼可溶性樹脂的固體成分100重量份為基準，上述鹼可溶性樹脂(A) 包含第一樹脂10至95重量份與第二樹脂5至90重量份。 6. The photosensitive resin composition of the above-mentioned point 1, wherein the alkali-soluble resin (A) includes 10 to 95 parts by weight of the first resin and 5 to 90 parts by weight of the first resin based on 100 parts by weight of the solid content of the alkali-soluble resin. Copies.
7．上述第1點的感光性樹脂組合物，其中，以感光性樹脂組合物的固體成分為基準，包含5至90重量%的上述鹼可溶性樹脂(A)。 7. The photosensitive resin composition according to the above-mentioned point 1, wherein the alkali-soluble resin (A) is contained in an amount of 5 to 90% by weight based on the solid content of the photosensitive resin composition.
8．使用上述第1至7點的任一項所述的感光性樹脂組合物製造的光固化圖案。 8. The photocurable pattern produced using the photosensitive resin composition as described in any one of the above-mentioned points 1 to 7.
9．上述第8點的光固化圖案，其中，上述光固化圖案選自陣列平坦化膜圖案、保護膜圖案、絕緣膜圖案、光阻圖案、黑矩陣圖案及間隔物圖案。 9. The photocuring pattern of the eighth point, wherein the photocuring pattern is selected from the group consisting of array planarization film patterns, protective film patterns, insulating film patterns, photoresist patterns, black matrix patterns, and spacer patterns.
10．圖像顯示裝置，其具有上述第8點所述的光固化圖案。 10. An image display device having the photocurable pattern described in the above-mentioned point 8.
本發明的感光性樹脂組合物能夠形成具有優異的彈性回復率、同時具有使外部壓力引起的變形較少的堅硬特性的光固化圖案。 The photosensitive resin composition of the present invention can form a photocurable pattern having an excellent elastic recovery rate and having a hard characteristic that reduces deformation due to external pressure.
另外，本發明的感光性樹脂組合物的固化時的微細圖案的實現性優異，藉由調節光聚合引發劑的量，能夠調節圖案的大小。 In addition, the photosensitive resin composition of the present invention is excellent in realizing fine patterns at the time of curing, and the size of the patterns can be adjusted by adjusting the amount of the photopolymerization initiator.
進而，本發明的感光性樹脂組合物顯示優異的T/B比的值。 Furthermore, the photosensitive resin composition of this invention shows the value of the excellent T/B ratio.
因此，本發明的感光性樹脂組合物能夠有用地在光固化圖案中使用，較佳在間隔物圖案的形成及圖像顯示裝置的製 造中使用。 Therefore, the photosensitive resin composition of the present invention can be effectively used in a photocurable pattern, and is preferably used in the formation of a spacer pattern and the manufacture of an image display device.
第1圖為概略地表示T/B比的定義的圖。 FIG. 1 is a diagram schematically showing the definition of the T/B ratio.
本發明涉及感光性樹脂組合物、用該組合物製造的光固化圖案以及具有該光固化圖案的圖像顯示裝置，該感光性樹脂組合物包含鹼可溶性樹脂(A)、光聚合引發劑(B)、光聚合性化合物(C)及溶劑(D)。 The present invention relates to a photosensitive resin composition, a photocurable pattern produced using the composition, and an image display device having the photocurable pattern. The photosensitive resin composition includes an alkali-soluble resin (A) and a photopolymerization initiator (B ), photopolymerizable compound (C) and solvent (D).
以下對本發明詳細地說明。 The present invention will be described in detail below.
鹼可溶性樹脂通常具有光、熱的作用產生的反應性，並且具有鹼溶解性。 Alkali-soluble resins usually have reactivity due to the action of light and heat, and have alkali solubility.
本發明涉及的鹼可溶性樹脂(A)包含含有選自下述化學式1及化學式2中的至少一種的化合物(a11)而聚合成的第一樹脂。 The alkali-soluble resin (A) according to the present invention includes a first resin obtained by polymerizing a compound (a11) containing at least one selected from the following Chemical Formula 1 and Chemical Formula 2.
本發明涉及的鹼可溶性樹脂(A)藉由具有來自體積大(bulky)的選自上述化學式1與2中的至少一種化合物的重複單元，從而能夠形成下述的光固化圖案，該光固化圖案經由固化時的膜密度(film density)的上升而具有優異的彈性回復率，具有使由外部壓力產生的變形較少的堅硬特性，能夠形成高解析度的圖案。 The alkali-soluble resin (A) according to the present invention has a repeating unit derived from bulky at least one compound selected from the above chemical formulae 1 and 2 to form the following photocurable pattern, the photocurable pattern It has excellent elastic recovery rate through the increase in film density at the time of curing, and has the hard characteristics of less deformation due to external pressure, and can form a high-resolution pattern.
本發明涉及的鹼可溶性樹脂(A)的第一樹脂除了選自上述化學式1及化學式2中的至少一種化合物(a11)以外，為了顯示鹼可溶性，可進一步含有本領域中習知的具有不飽和鍵與羧基的化合物(a12)而聚合。 The first resin of the alkali-soluble resin (A) according to the present invention may contain, in addition to at least one compound (a11) selected from the above Chemical Formula 1 and Chemical Formula 2, in order to show alkali solubility, it may further contain unsaturated compounds known in the art. The compound (a12) having a bond with a carboxyl group is polymerized.
作為上述具有不飽和鍵與羧基的化合物(a12)，只要是具有可聚合的不飽和雙鍵的羧酸化合物，則能夠無限制地使用。作為上述具有不飽和鍵與羧基的化合物(a12)，例如可列舉出不飽和單羧酸，不飽和二羧酸或不飽和三羧酸這樣在分子中具有二個以上羧基的多元羧酸等。作為上述不飽和單羧酸，例如可 列舉出丙烯酸、甲基丙烯酸、巴豆酸等。作為上述不飽和多元羧酸，例如可列舉出馬來酸、富馬酸、檸康酸、中康酸、伊康酸等。上述多元羧酸可以為酸酐，作為上述不飽和多元羧酸酐，例如可列舉出馬來酸酐、伊康酸酐、檸康酸酐等。另外，上述不飽和多元羧酸可以是其的單(2-甲基丙烯醯氧基烷基)酯，例如可列舉出琥珀酸單(2-丙烯醯氧基乙基)酯、琥珀酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯等。上述不飽和多元羧酸可以為其兩末端二羧基聚合物的單(甲基)丙烯酸酯，例如可列舉出ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。另外，上述不飽和多元羧酸可以是在同一分子中含有羥基與羧基的不飽和丙烯酸酯，例如可列舉出α-(羥基甲基)丙烯酸等。這些中，丙烯酸、甲基丙烯酸、馬來酸酐等由於共聚反應性高而較佳被使用。 As the compound (a12) having an unsaturated bond and a carboxyl group, as long as it is a carboxylic acid compound having a polymerizable unsaturated double bond, it can be used without limitation. Examples of the compound (a12) having an unsaturated bond and a carboxyl group include polycarboxylic acids having two or more carboxyl groups in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or unsaturated tricarboxylic acid. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated polycarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. The polyvalent carboxylic acid may be an acid anhydride. Examples of the unsaturated polyvalent carboxylic acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polycarboxylic acid may be a mono(2-methacryloxyalkyl) ester thereof, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and succinic acid mono( 2-Methacryloyloxyethyl) ester, phthalic acid mono(2-propenyloxyethyl) ester, phthalic acid mono(2-methacryloyloxyethyl) ester, etc. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxyl polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate Ester etc. The unsaturated polycarboxylic acid may be an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, and examples thereof include α-(hydroxymeth)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of high copolymerization reactivity.
上述例示的(a12)能夠各自單獨地使用或者將二種以上組合使用。 The (a12) exemplified above can be used alone or in combination of two or more.
另外，本發明涉及的第一樹脂可進一步含有與上述(a11)及(a12)共聚並具有不飽和鍵的化合物(a13)而聚合成。 In addition, the first resin according to the present invention may further contain a compound (a13) copolymerized with the above-mentioned (a11) and (a12) and having an unsaturated bond to be polymerized.
與上述(a11)及(a12)共聚並具有不飽和鍵的化合物(a13)只要是具有可聚合的不飽和雙鍵的化合物，則並無特別限制。具體地，上述(a13)可列舉出(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-羥基 乙酯、2-羥基-鄰-苯基苯酚丙基丙烯酸酯、(甲基)丙烯酸氨基乙酯等不飽和羧酸的未取代或取代的烷基酯化合物、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸甲基環己酯、(甲基)丙烯酸環庚酯、(甲基)丙烯酸環辛酯、(甲基)丙烯酸薄荷酯、(甲基)丙烯酸環戊烯酯、(甲基)丙烯酸環己烯酯、(甲基)丙烯酸環庚烯酯、(甲基)丙烯酸環辛烯酯、(甲基)丙烯酸薄荷二烯酯、(甲基)丙烯酸異
以構成第一樹脂的(a11)、(a12)與(a13)的合計莫耳數為基準，上述第一樹脂可藉由將選自化學式1及化學式2中的至少一種化合物(a11)2至30莫耳%、具有不飽和鍵與羧基的化合物(a12)2至70莫耳%、以及與上述(a11)及(a12)共 聚並具有不飽和鍵的化合物(a13)2至95莫耳%共聚而得到，較佳地，可藉由將選自化學式1及化學式2中的至少一種化合物(a11)5至30莫耳%、具有不飽和鍵與羧基的化合物(a12)5至65莫耳%、以及與上述(a11)及(a12)共聚並具有不飽和鍵的化合物(a13)5至80莫耳%共聚而得到。如果在上述範圍內，可以製造顯影性、耐溶劑性、耐熱性及機械強度良好的感光性樹脂組合物。 Based on the total moles of (a11), (a12), and (a13) constituting the first resin, the first resin can be obtained by combining at least one compound (a11) 2 to 2 selected from Chemical Formula 1 and Chemical Formula 2 to 30 mol %, compound (a12) having unsaturated bond and carboxyl group 2 to 70 mol %, and compound (a13) copolymerized with (a11) and (a12) above and having unsaturated bond 2 to 95 mol% It is obtained by copolymerization. Preferably, it can be obtained by combining at least one compound (a11) selected from Chemical Formula 1 and Chemical Formula 2 from 5 to 30 mol% and a compound (a12) having an unsaturated bond and a carboxyl group from 5 to 65 mol. %, and the compound (a13) copolymerized with the above-mentioned (a11) and (a12) and having an unsaturated bond is copolymerized by 5 to 80 mole %. Within the above range, a photosensitive resin composition with good developability, solvent resistance, heat resistance, and mechanical strength can be produced.
另外，上述鹼可溶性樹脂(A)的第一樹脂可以進一步使具有不飽和鍵及環氧基的化合物(a14)與上述(a11)、(a12)及(a13)共聚而得到，也可以進一步含有其他單體化合物共聚而成。 In addition, the first resin of the alkali-soluble resin (A) may be obtained by copolymerizing the compound (a14) having an unsaturated bond and an epoxy group with the (a11), (a12), and (a13), or may further contain Copolymerized with other monomer compounds.
上述(a14)對鹼可溶性樹脂賦予光/熱固化性。上述(a14)具體地可列舉出(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己酯、(甲基)丙烯酸2,3-環氧環戊酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸甲基縮水甘油酯、(甲基)丙烯酸6,7-環氧庚酯、(甲基)丙烯酸甲基縮水甘油酯、(甲基)丙烯酸3.4-環氧三環[5.2.1.0 2,6]癸烷-9-基酯等。這些可以各自單獨地使用或者將二種以上組合使用。 The above (a14) imparts light/thermocurability to the alkali-soluble resin. The above (a14) specifically includes glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, and Group) 3,4-epoxycyclohexyl methyl acrylate, methyl glycidyl (meth)acrylate, 6,7-epoxyheptyl (meth) acrylate, methyl glycidyl (meth) acrylate, (Meth)acrylic acid 3.4-epoxy tricyclo[5.2.1.0 2,6]decane-9-yl ester, etc. These can be used individually or in combination of 2 or more types.
上述第一樹脂可藉由將以構成第一樹脂的(a11)、(a12)、(a13)及(a14)的合計莫耳數為基準的、選自化學式1及化學式2中的至少一種化合物(a11)2至30莫耳%、具有不飽和鍵及羧基的化合物(a12)2至70莫耳%、與上述(a11)及 (a12)共聚並具有不飽和鍵的化合物(a13)2至95莫耳%、以及以上述(a12)的莫耳數為基準的具有不飽和鍵及環氧基的化合物(a14)5至80莫耳%共聚而得到，較佳地，可藉由將選自化學式1及化學式2中的至少一種化合物(a11)5至30莫耳%、具有不飽和鍵及羧基的化合物(a12)5至65莫耳%、與上述(a11)及(a12)共聚並具有不飽和鍵的化合物(a13)5至80莫耳%、以及以上述(a12)的莫耳數為基準的具有不飽和鍵及環氧基的化合物(a14)10至80莫耳%共聚而得到。如果在上述範圍內，可以製造顯影性、耐溶劑性、耐熱性及機械強度良好的感光性樹脂組合物。 The first resin can be selected from at least one compound selected from Chemical Formula 1 and Chemical Formula 2 based on the total moles of (a11), (a12), (a13) and (a14) constituting the first resin (a11) 2 to 30 mol%, compound having unsaturated bond and carboxyl group (a12) 2 to 70 mol%, compound (a13) 2 to 70 which is copolymerized with the above (a11) and (a12) and has unsaturated bond 95 mol%, and the compound (a14) having an unsaturated bond and an epoxy group based on the mol number of (a12) above is obtained by copolymerizing 5 to 80 mol%, preferably, by selecting At least one compound (a11) from Chemical Formula 1 and Chemical Formula 2 is 5 to 30 mol%, and the compound (a12) having an unsaturated bond and a carboxyl group is 5 to 65 mol%, and is copolymerized with (a11) and (a12) above The compound (a13) having an unsaturated bond is 5 to 80 mol %, and the compound (a14) having an unsaturated bond and an epoxy group based on the mol number of (a12) above is copolymerized from 10 to 80 mol %. get. Within the above range, a photosensitive resin composition with good developability, solvent resistance, heat resistance, and mechanical strength can be produced.
本發明涉及的第一樹脂較佳為其聚苯乙烯換算的重量平均分子量在3,000至100,000的範圍內，更佳在5,000至50,000範圍內。如果含有不飽和基的第一樹脂的重量平均分子量在3,000至100,000的範圍內，則顯示出無畫素變形的硬(hard)特性。 The first resin involved in the present invention preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. If the weight-average molecular weight of the unsaturated group-containing first resin is in the range of 3,000 to 100,000, it exhibits hard characteristics without pixel deformation.
上述第一樹脂的分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.5至6.0，更佳為1.8至4.0。如果分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]為1.5至6.0，則由於顯影性優異而較佳。 The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the above first resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. If the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.5 to 6.0, it is preferable because it is excellent in developability.
另外，本發明涉及的鹼可溶性樹脂(A)包含含有具有脂環式環氧基的化合物而聚合成的第二樹脂(a21)。本發明藉由包含第二樹脂，能夠顯示出優異的顯影性、耐溶劑性、耐熱性與機械強度。 In addition, the alkali-soluble resin (A) according to the present invention includes a second resin (a21) formed by polymerizing a compound containing an alicyclic epoxy group. By including the second resin, the present invention can exhibit excellent developability, solvent resistance, heat resistance, and mechanical strength.
較佳地，上述具有脂環式環氧基的化合物(a21)能夠包含下述化學式4及化學式5中的至少一個。 Preferably, the compound (a21) having an alicyclic epoxy group can contain at least one of the following Chemical Formula 4 and Chemical Formula 5.
為了顯示鹼可溶性，本發明涉及的第二樹脂可以在上述脂環式環氧化合物(a21)中進一步含有具有不飽和鍵與羧基的化合物(a22)而聚合成。 In order to show alkali solubility, the second resin according to the present invention may be polymerized by further containing a compound (a22) having an unsaturated bond and a carboxyl group in the alicyclic epoxy compound (a21).
作為上述具有不飽和鍵與羧基的化合物(a22)，能夠選擇上述的含有不飽和基的第一樹脂的(a12)中所說明的具有 不飽和鍵與羧基的化合物而使用。因此，關於其，省略詳細的說明。 As the compound (a22) having an unsaturated bond and a carboxyl group, the compound having an unsaturated bond and a carboxyl group described in (a12) of the above-mentioned unsaturated group-containing first resin can be selected and used. Therefore, detailed explanations are omitted.
上述化學式4的R7與化學式5的R8可以各自獨立地為氫；甲基、乙基、正丙基、異丙基、正丁基、二級丁基、三級丁基等烷基；羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基-正-丙基、2-羥基-正-丙基、3-羥基-正-丙基、1-羥基-異丙基、2-羥基-異丙基、1-羥基-正-丁基、2-羥基-正-丁基、3-羥基-正-丁基、4-羥基-正-丁基等含有羥基的烷基。其中，上述R7與R8較佳各自獨立地為氫、甲基、羥基甲基、1-羥基乙基或2-羥基乙基，進一步特別佳為氫或甲基。 R 4 in the chemical formula 7 and chemical formula 8, R 5 may each independently be hydrogen; methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tertiary-butyl groups; Hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl , 2-hydroxy-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, etc. . Among them, R 7 and R 8 are preferably independently hydrogen, methyl, hydroxymethyl, 1-hydroxyethyl or 2-hydroxyethyl, and more preferably hydrogen or methyl.
上述化學式4與5中的X，具體地，可以為單鍵；亞甲基、伸乙基、伸丙基等亞烷基；氧亞甲基、氧伸乙基、氧伸丙基、硫亞甲基、硫伸乙基、硫伸丙基、氨基亞甲基、氨基伸乙基、氨基伸丙基等含有雜原子的亞烷基。其中，X較佳為單鍵、亞甲基、伸乙基、氧亞甲基或氧伸乙基，進一步特別佳為單鍵或氧伸乙基。 The X in the above Chemical Formulas 4 and 5 may specifically be a single bond; alkylene groups such as methylene, ethylidene, and propylidene; oxymethylene, oxyethylidene, oxypropylene, and thionylene Hetero atom-containing alkylene groups such as methyl, thioethyl, thiopropyl, aminomethylene, aminoethyl, aminopropyl, etc. Among them, X is preferably a single bond, methylene, ethylidene, oxymethylene, or oxyethylidene, and further particularly preferably a single bond or oxyethylidene.
作為由上述化學式4表示的化合物，具體地，可列舉出下述化學式6至19的化合物。 As the compound represented by the above Chemical Formula 4, specifically, the compounds of the following Chemical Formulas 6 to 19 can be exemplified.
作為由上述化學式5表示的化合物，具體地，可列舉出下述化學式20至33的化合物。 As the compound represented by the above Chemical Formula 5, specifically, compounds of the following Chemical Formulas 20 to 33 can be exemplified.
作為由上述化學式4表示的化合物及由化學式5表示的化合物例示的化合物能夠各自單獨地使用或者將二種以上組合使用。 The compounds exemplified as the compound represented by the above Chemical Formula 4 and the compound represented by the Chemical Formula 5 can be used alone or in combination of two or more kinds.
另外，上述第二樹脂除了上述(a21)及(a22)以外，能夠用可與(a21)及(a22)聚合的具有不飽和鍵的化合物共聚。例如，第二樹脂可以與(a21)及(a22)一起將丙烯酸2-氨基乙酯、甲基丙烯酸2-氨基乙酯、丙烯酸2-二甲基氨基乙酯、甲基丙烯酸2-二甲基氨基乙酯、丙烯酸2-氨基丙酯、甲基丙烯酸2-氨基丙酯、丙烯酸2-二甲基氨基丙酯、甲基丙烯酸2-二甲基氨基丙酯、丙烯酸3-氨基丙酯、甲基丙烯酸3-氨基丙酯、丙烯酸3-二甲基氨基丙酯、甲基丙烯酸3-二甲基氨基丙酯等不飽和羧酸氨基烷基酯類；醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯類；乙烯基甲基醚、乙烯基乙基醚、烯丙基縮水甘油基醚等不飽和醚類；丙烯腈、甲基丙烯腈、α-氯丙烯腈、 偏二氰基乙烯等乙烯基氰化合物；丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基丙烯醯胺、N-2-羥基乙基甲基丙烯醯胺等不飽和醯胺類；馬來醯亞胺、苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等不飽和醯亞胺類；1,3-丁二烯、異戊二烯、氯丁二烯等脂肪族共軛二烯類；以及在聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯、聚矽氧烷的聚合物分子鏈的末端具有單丙烯醯基或單甲基丙烯醯基的大分子單體類等一起共聚。 In addition to the above (a21) and (a22), the second resin can be copolymerized with a compound having an unsaturated bond polymerizable with (a21) and (a22). For example, the second resin can be combined with (a21) and (a22) 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethyl methacrylate Aminoethyl, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, methylmethacrylate 3-aminopropyl acrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate and other unsaturated carboxylic acid amino alkyl esters; vinyl acetate, vinyl propionate, butyl Vinyl acid esters, vinyl benzoate and other carboxylic acid vinyl esters; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and other unsaturated ethers; acrylonitrile, methacrylonitrile, α- Vinyl cyanide compounds such as chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethyl Unsaturated amides such as methacrylamide; unsaturated amides such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide Amines; 1,3-butadiene, isoprene, chloroprene and other aliphatic conjugated dienes; and polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid Macromonomers such as butyl ester, poly-n-butyl methacrylate, and polysiloxane polymer chains having a mono-acrylic group or mono-methacryl group at the end of the polymer molecular chain are copolymerized together.
上述第二樹脂以構成第二樹脂的(a21)與(a22)的合計莫耳數為基準，可藉由將上述具有脂環式環氧基的化合物(a21)25至95莫耳%以及具有不飽和鍵與羧基的化合物(a22)5至75莫耳%共聚而得到，較佳地，可藉由將上述具有脂環式環氧基的化合物(a21)30至90莫耳%以及具有不飽和鍵與羧基的化合物(a22)10至70莫耳%共聚而得到。如果為上述範圍，則可以製造顯影性、耐溶劑性、耐熱性及機械強度良好的感光性樹脂組合物。 The above-mentioned second resin is based on the total mole number of (a21) and (a22) constituting the second resin, and the compound (a21) having an alicyclic epoxy group may be 25 to 95 mole% and has The unsaturated bond and the carboxyl compound (a22) are obtained by copolymerizing from 5 to 75 mol %, preferably, the above compound (a21) having an alicyclic epoxy group can be obtained by 30 to 90 mol% and having The compound (a22) having a saturated bond and a carboxyl group is obtained by copolymerizing from 10 to 70 mol %. Within the above range, a photosensitive resin composition with good developability, solvent resistance, heat resistance, and mechanical strength can be produced.
上述第二樹脂的較佳酸值為20至200(KOH毫克/公克(mg/g))的範圍。如果酸值在上述範圍內，則可以製造具有優異的彈性回復率的間隔物。 The preferred acid value of the above second resin is in the range of 20 to 200 (KOH milligrams per gram (mg/g)). If the acid value is within the above range, a spacer with excellent elastic recovery rate can be manufactured.
上述第二樹脂的聚苯乙烯換算的重量平均分子量為3,000至100,000，較佳為5,000至50,000。如果上述第二樹脂的重量平均分子量在上述範圍內，則防止顯影時膜的減少，圖案部 分的脫落性變得良好，因此較佳。 The weight average molecular weight in terms of polystyrene of the second resin is 3,000 to 100,000, preferably 5,000 to 50,000. If the weight average molecular weight of the second resin is within the above range, the reduction of the film during development is prevented, and the peelability of the pattern portion becomes good, which is preferable.
上述第二樹脂的分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.5至6.0，更佳為1.8至4.0。如果上述分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]包含在上述範圍內，則顯影性優異，因此較佳。 The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the second resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. If the above molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is included in the above range, the developability is excellent, which is preferable.
作為上述鹼可溶性樹脂(A)，將上述的第一樹脂與第二樹脂混合使用的情況下，用以鹼可溶性樹脂(A)的固體成分為基準的重量分率表示，上述鹼可溶性樹脂(A)較佳由第一樹脂10至95重量%與第二樹脂5至90重量%組成。 As the alkali-soluble resin (A), when the above-mentioned first resin and second resin are used in combination, the weight fraction based on the solid content of the alkali-soluble resin (A) is expressed. ) Is preferably composed of 10 to 95% by weight of the first resin and 5 to 90% by weight of the second resin.
在上述第一樹脂與第二樹脂的含量包含在上述範圍內的情況下，可以製造具有優異的彈性回復率、同時具有使外部壓力引起的變形較少的堅硬特性的光固化圖案。 When the contents of the first resin and the second resin are included in the above range, a photo-curable pattern having excellent elastic recovery rate and having hard characteristics with less deformation due to external pressure can be produced.
相對於感光性樹脂組合物中的全部固體成分，上述鹼可溶性樹脂(A)的含量通常在5至90重量%，較佳在10至70重量%的範圍。如果鹼可溶性樹脂(A)的含量按上述的基準計，為5至90重量%，則在顯影液中的溶解性充分，顯影性優異，可以製造具有優異的彈性回復率、並且具有使外部壓力引起的變形較少的堅硬特性的間隔物。 The content of the alkali-soluble resin (A) is usually 5 to 90% by weight, preferably 10 to 70% by weight with respect to the entire solid content in the photosensitive resin composition. If the content of the alkali-soluble resin (A) is 5 to 90% by weight based on the above-mentioned standard, the solubility in the developing solution is sufficient, the developability is excellent, it is possible to produce an excellent elastic recovery rate, and have an external pressure A spacer with hard characteristics that causes less deformation.
本發明中的固體成分意味著將溶劑除去後的成分的合計。 The solid content in the present invention means the total of components after removing the solvent.
本發明包含由下述化學式3表示的化合物作為本發 明的光聚合引發劑。 The present invention includes a compound represented by the following Chemical Formula 3 as the photopolymerization initiator of the present invention.
含有包含由下述化學式3表示的化合物的光聚合引發劑(B)的感光性樹脂組合物能夠使上述的鹼可溶性樹脂(A)的期待效果最大化，微細圖案的實現性優異。另外，具有藉由調節光聚合引發劑中所含的由化學式3表示的化合物的量從而能夠調節圖案的大小的優點。 The photosensitive resin composition containing the photopolymerization initiator (B) containing the compound represented by the following Chemical Formula 3 can maximize the expected effect of the alkali-soluble resin (A) described above, and is excellent in realization of fine patterns. In addition, there is an advantage that the size of the pattern can be adjusted by adjusting the amount of the compound represented by Chemical Formula 3 contained in the photopolymerization initiator.
上述的「烷基」、「烷氧基」及其他的包含「烷基」部分的取代體全部包含直鏈狀或分支狀，「環烷基」不僅包含單環系、也包含多環系的烴。本說明書中記載的「芳基」為藉由至少一個氫原子的除去而由芳香族烴衍生的原子團，包含在各環中適當地含有4至7個、較佳5或6個環原子的單一或稠合環系，甚至包含多個芳基透過單鍵連接而成的形態。「羥基烷基」意味 著羥基與上述定義的烷基結合的OH-烷基。「羥基烷氧基烷基」意味著烷氧基與上述羥基烷基結合的羥基烷基-O-烷基。 The above-mentioned "alkyl", "alkoxy" and other substituents containing "alkyl" moieties all include linear or branched forms, and "cycloalkyl" includes not only monocyclic systems but also polycyclic systems. hydrocarbon. The "aryl group" described in this specification is an atomic group derived from an aromatic hydrocarbon by the removal of at least one hydrogen atom, and contains a single unit containing 4 to 7, preferably 5 or 6 ring atoms in each ring. Or condensed ring system, even containing multiple aryl groups connected by a single bond. "Hydroxyalkyl" means an OH-alkyl group in which a hydroxy group is bonded to the above-defined alkyl group. "Hydroxyalkoxyalkyl" means a hydroxyalkyl-O-alkyl group in which an alkoxy group is bonded to the hydroxyalkyl group.
另外，上述的「(C1-C20)烷基」較佳為(C1-C10)烷基，更佳為(C1-C6)烷基。「(C6-C20)芳基」較佳為(C6-C18)芳基。「(C1-C20)烷氧基」較佳為(C1-C10)烷氧基，更佳為(C1-C4)烷氧基。「(C6-C20)芳基(C1-C20)烷基」較佳為(C6-C18)芳基(C1-C10)烷基，更佳為(C6-C18)芳基(C1-C6)烷基。「羥基(C1-C20)烷基」較佳為羥基(C1-C10)烷基，更佳為羥基(C1-C6)烷基。「羥基(C1-C20)烷氧基(C1-C20)烷基」較佳為羥基(C1-C10)烷氧基(C1-C10)烷基，更佳為羥基(C1-C4)烷氧基(C1-C6)烷基。「(C3-C20)環烷基」較佳為(C3-C10)環烷基。 In addition, the above-mentioned "(C1-C20)alkyl" is preferably (C1-C10)alkyl, more preferably (C1-C6)alkyl. "(C6-C20)aryl" is preferably (C6-C18)aryl. "(C1-C20)alkoxy" is preferably (C1-C10)alkoxy, and more preferably (C1-C4)alkoxy. "(C6-C20)aryl(C1-C20)alkyl" is preferably (C6-C18)aryl(C1-C10)alkyl, more preferably (C6-C18)aryl(C1-C6)alkyl base. The "hydroxy(C1-C20)alkyl" is preferably a hydroxy(C1-C10)alkyl, more preferably a hydroxy(C1-C6)alkyl. "Hydroxy(C1-C20)alkoxy(C1-C20)alkyl" is preferably hydroxy(C1-C10)alkoxy(C1-C10)alkyl, more preferably hydroxy(C1-C4)alkoxy (C1-C6) alkyl. "(C3-C20)cycloalkyl" is preferably (C3-C10)cycloalkyl.
具體地，上述R3為氫，R4為硝基，或者上述R3為硝基，R4為氫，或者上述R3與R4全部為硝基。 Specifically, R 3 is hydrogen, R 4 is nitro, or R 3 is nitro, R 4 is hydrogen, or all of R 3 and R 4 are nitro.
具體地，上述R5與R6各自獨立地為甲基、乙基、丙基、丁基、戊基、己基、苯基、萘基、聯苯基、三聯苯基、蒽基、茚基、菲基、甲氧基、乙氧基、丙氧基、丁氧基、苄基、羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基、羥基己基、羥基甲氧基甲基、羥基甲氧基乙基、羥基甲氧基丙基、羥基甲氧基丁基、羥基乙氧基甲基、羥基乙氧基乙基、羥基乙氧基丙基、羥基乙氧基丁基、羥基乙氧基戊基、羥基乙氧基己基、環丙基、環戊基、環己基、乙醯基或苯甲醯基。 Specifically, R 5 and R 6 are each independently methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, Phenanthrene, methoxy, ethoxy, propoxy, butoxy, benzyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxymethoxymethoxy Group, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl , Hydroxyethoxypentyl, hydroxyethoxyhexyl, cyclopropyl, cyclopentyl, cyclohexyl, acetyl or benzoyl.
更佳地，上述R5為甲基、乙基、戊基、環戊基、環己基或苯基，R6為甲基。在R5與R6為上述的取代基的情況下，微細圖案的實現性更為優異。 More preferably, R 5 is methyl, ethyl, pentyl, cyclopentyl, cyclohexyl or phenyl, and R 6 is methyl. When R 5 and R 6 are the aforementioned substituents, the realization of the fine pattern is more excellent.
上述光聚合引發劑(B)能夠在由上述化學式3表示的化合物中進一步包含苯乙酮衍生物化合物與聯咪唑衍生物化合物中的至少一種。藉由進一步將苯乙酮衍生物化合物與聯咪唑衍生物化合物併用，除了上述的優異的微細圖案的實現的效果以外，能夠進一步提高圖案的T/B比的值。 The photopolymerization initiator (B) can further contain at least one of an acetophenone derivative compound and a biimidazole derivative compound in the compound represented by the above Chemical Formula 3. By further using the acetophenone derivative compound and the biimidazole derivative compound together, in addition to the effect achieved by the above-mentioned excellent fine pattern, the value of the T/B ratio of the pattern can be further increased.
T/B比為用間隔物圖案中的上部的直徑除以下部的直徑所得的值，T/B比的值越大越佳。本發明中，圖案的上部定義為相對於圖案的全體高度、從底面開始全體高度的95%的部位的水平面。另外，圖案的下部定義為相對於圖案的全體高度、從底面開始全體高度的5%的部位的水平面。 The T/B ratio is a value obtained by dividing the diameter of the upper portion in the spacer pattern by the diameter of the lower portion, and the larger the value of the T/B ratio, the better. In the present invention, the upper part of the pattern is defined as the horizontal plane of a portion of 95% of the total height from the bottom with respect to the entire height of the pattern. In addition, the lower part of the pattern is defined as the horizontal plane of a portion of 5% of the total height from the bottom surface relative to the total height of the pattern.
作為上述苯乙酮衍生物化合物，例如可列舉出二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯偶醯二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲硫基苯基)-2-
作為上述聯咪唑化合物，例如可列舉出2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'- 四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑、4,4',5,5'位的苯基被烷氧羰基取代的咪唑化合物等。這些中，較佳使用2,2'雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2',4-三(2-氯苯基)-5-(3,4-二甲氧基苯基)-4',5'-二苯基-1,1'-聯咪唑。 Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkane Oxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 4,4',5 , 5'position phenyl is substituted by alkoxycarbonyl imidazole compounds and so on. Among these, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) are preferably used )-4,4',5,5'-tetraphenylbiimidazole, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4 ',5'-diphenyl-1,1'-biimidazole.
在上述光聚合引發劑(B)與其他引發劑化合物並用的情況下，相對於光聚合引發劑的總重量，較佳包含40至90重量%的上述化學式3所示的化合物，更佳包含40至70重量%。如果在上述範圍內，則能夠獲得更為優異的T/B比的值。 In the case where the above-mentioned photopolymerization initiator (B) is used in combination with other initiator compounds, it is preferably 40 to 90% by weight of the compound represented by the above Chemical Formula 3 relative to the total weight of the photopolymerization initiator, more preferably 40 Up to 70% by weight. Within the above range, a more excellent T/B ratio can be obtained.
對苯乙酮衍生物及聯咪唑衍生物的含量比並無特別限制，例如可以為1：9至9：1。 The content ratio of the acetophenone derivative and the biimidazole derivative is not particularly limited, and may be 1:9 to 9:1, for example.
另外，只要是不損害本發明的效果的程度，可進一步將在該領域中通常使用的其他光聚合引發劑等並用。作為其他光聚合引發劑，例如可列舉出苯偶姻系化合物、二苯甲酮系化合物、9-氧硫
在上述光聚合引發劑(B)中也能夠將光聚合引發助劑組合使用。如果在上述光聚合引發劑(B)中將光聚合引發助劑並用，則含有它們的感光性樹脂組合物進一步成為高感度，能夠實現間隔物形成時的生產率的提高，因此較佳。 The photopolymerization initiator (B) can also be used in combination with a photopolymerization initiator. When the photopolymerization initiator (B) is used in combination with the photopolymerization initiation aid, the photosensitive resin composition containing them further has a high sensitivity and can improve productivity when forming a spacer, which is preferable.
作為上述光聚合引發助劑，較佳使用胺化合物、羧 酸化合物。 As the above-mentioned photopolymerization initiator, amine compounds and carboxylic acid compounds are preferably used.
相對於鹼可溶性樹脂(A)及光聚合性化合物(C)的合計100重量份，光聚合引發劑(B)的使用量可以為0.1至40重量份，較佳為1至30重量份。如果上述光聚合引發劑(B)的使用量在上述範圍內，則感光性樹脂組合物高感度化，使用該組合物形成的間隔物的強度、平滑性變得良好，因此較佳。 The use amount of the photopolymerization initiator (B) may be 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight with respect to the total of 100 parts by weight of the alkali-soluble resin (A) and the photopolymerizable compound (C). If the amount of the photopolymerization initiator (B) used is within the above range, the photosensitive resin composition is increased in sensitivity, and the strength and smoothness of the spacer formed using the composition become good, which is preferable.
本發明的感光性樹脂組合物中所含有的光聚合性化合物(C)是在上述光聚合引發劑(B)的作用下能夠聚合的化合物，可列舉出單官能單體、二官能單體、其他多官能單體等。 The photopolymerizable compound (C) contained in the photosensitive resin composition of the present invention is a compound that can be polymerized by the action of the photopolymerization initiator (B), and examples thereof include monofunctional monomers, difunctional monomers, Other multifunctional monomers, etc.
就本發明中使用的光聚合性化合物(C)而言，為了改善間隔物形成用樹脂組合物的顯影性、感度、密合性、表面的問題等，能夠將官能團的結構、官能團的數量不同的二個或其以上的光聚合性化合物混合而使用，對其範圍沒有限制。 For the photopolymerizable compound (C) used in the present invention, in order to improve the developability, sensitivity, adhesion, surface problems of the resin composition for forming a spacer, the structure of the functional group and the number of functional groups can be different Two or more photopolymerizable compounds are mixed and used, and the range is not limited.
作為單官能單體的具體例，可列舉出壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯烷酮等。 Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy acrylate Ethyl ester, N-vinylpyrrolidone, etc.
作為二官能單體的具體例，可列舉出1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、雙酚A的雙(丙烯醯氧基乙基)醚、3-甲基戊二醇二(甲基)丙烯酸酯等。 Specific examples of the difunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.
作為其他多官能單體的具體例，可列舉出三羥甲基 丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、乙氧基化二新戊四醇六(甲基)丙烯酸酯、丙氧基化二新戊四醇六(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯等。其中，較佳使用二官能以上的多官能單體。 Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylol. Propane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxy Dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trineopentaerythritol (Meth) acrylate, etc. Among them, it is preferable to use a polyfunctional monomer having more than two functions.
以間隔物形成用感光性組合物的固體成分為基準，相對於上述鹼可溶性樹脂(A)及光聚合性化合物(C)的合計100重量份，上述光聚合性化合物(C)能夠在1至90重量份的範圍內使用，較佳在10至80重量份的範圍內使用。如果光聚合性化合物(C)為上述的基準的範圍，則間隔物圖案的強度、平滑性變得良好，因此較佳。 Based on the solid content of the photosensitive composition for spacer formation, the photopolymerizable compound (C) can be in the range of 1 to 100 parts by weight relative to the total amount of the alkali soluble resin (A) and the photopolymerizable compound (C). It is used in the range of 90 parts by weight, preferably in the range of 10 to 80 parts by weight. If the photopolymerizable compound (C) is within the above-mentioned standard range, the strength and smoothness of the spacer pattern become good, which is preferable.
溶劑(D)只要是該領域中通常使用的溶劑，則能夠無任何限制地使用。 The solvent (D) can be used without any limitation as long as it is a solvent generally used in this field.
作為上述溶劑的具體例，可列舉出乙二醇單烷基醚類；二甘醇二烷基醚類；乙二醇烷基醚乙酸酯類；亞烷基二醇烷基醚乙酸酯類；丙二醇單烷基醚類；丙二醇二烷基醚類；丙二醇烷基醚丙酸酯類；丁二醇單烷基醚類；丁二醇單烷基醚乙酸酯類；丁二醇單烷基醚丙酸酯類；二丙二醇二烷基醚類；芳香族烴類；酮類；醇類；酯類；環狀酯類等。在此列舉的溶劑可以各自單獨 地使用或者將二種以上混合使用。 Specific examples of the above solvents include ethylene glycol monoalkyl ethers; diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetates; alkylene glycol alkyl ether acetates; Propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; propylene glycol alkyl ether propionates; butylene glycol monoalkyl ethers; butylene glycol monoalkyl ether acetates; butylene glycol monoalkyl ethers Propionates; dipropylene glycol dialkyl ethers; aromatic hydrocarbons; ketones; alcohols; esters; cyclic esters, etc. The solvents listed here can be used alone or in combination of two or more.
作為上述溶劑，如果考慮塗布性及乾燥性，能夠較佳使用亞烷基二醇烷基醚乙酸酯類、酮類、丁二醇烷基醚乙酸酯類、丁二醇單烷基醚類、酯類。更佳地，能夠使用二甘醇乙基甲基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、環己酮、乙酸甲氧基丁酯、甲氧基丁醇、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯等。 As the above solvent, in consideration of coating properties and drying properties, alkylene glycol alkyl ether acetates, ketones, butylene glycol alkyl ether acetates, butylene glycol monoalkyl ethers, Esters. More preferably, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, 3-Ethoxypropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, etc.
相對於感光性樹脂組合物的合計100重量份，上述溶劑(D)的含量可以為40至95重量份，較佳為45至85重量份。如果滿足上述範圍，則採用旋轉塗布器、狹縫旋轉塗布器、狹縫塗布器(也有時稱為「模壓塗布器」、「簾式流動塗布器」)、噴墨裝置等塗布裝置塗布時塗布性變得良好，因此較佳。 The content of the aforementioned solvent (D) may be 40 to 95 parts by weight, preferably 45 to 85 parts by weight with respect to a total of 100 parts by weight of the photosensitive resin composition. If the above range is satisfied, coating is carried out by a coating device such as a spin coater, a slit spin coater, a slit coater (sometimes referred to as a "mold coater" or a "curtain flow coater"), an inkjet device, etc. Sex becomes good, so it is better.
本發明涉及的感光性樹脂組合物根據需要可進一步包含填充劑、其他高分子化合物、固化劑、流平劑、密合促進劑、抗氧化劑、紫外線吸收劑、防凝聚劑、鏈轉移劑等添加劑。 The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, chain transfer agents, etc. as needed. .
本發明的目的在於提供用上述感光性樹脂組合物製造的光固化圖案以及具有該光固化圖案的圖像顯示裝置。 An object of the present invention is to provide a photocurable pattern produced using the above-mentioned photosensitive resin composition and an image display device having the photocurable pattern.
用上述感光性樹脂組合物製造的光固化圖案的彈性回復率、密合性、殘膜率等係優異的。由此能夠用於圖像顯示裝置中的各種圖案，例如黏接劑層、陣列平坦化膜、保護膜、絕緣 膜圖案等，也能夠用於光阻、黑矩陣、柱狀間隔物圖案、黑色柱狀間隔物圖案等。但是，並不限定於這些，特別適合作為間隔物圖案。 The photocurable pattern produced using the above-mentioned photosensitive resin composition is excellent in elastic recovery rate, adhesion, residual film rate, and the like. This can be used for various patterns in image display devices, such as adhesive layers, array planarization films, protective films, insulating film patterns, etc., as well as photoresist, black matrix, column spacer patterns, black Column spacer pattern, etc. However, it is not limited to these, and is particularly suitable as a spacer pattern.
作為具有這樣的光固化圖案或者在製造過程中使用上述圖案的圖像顯示裝置，可列舉出液晶顯示裝置、OLED、可撓性顯示器等。但是，並不限定於這些，可列舉出可應用的該領域中的習知的全部圖像顯示裝置。 Examples of the image display device having such a photocurable pattern or using the above pattern in the manufacturing process include liquid crystal display devices, OLEDs, and flexible displays. However, it is not limited to these, and all known image display devices in this field that can be applied can be cited.
光固化圖案能夠藉由將上述的本發明的感光性樹脂組合物在基材上塗布、(根據需要經過了顯影製程後)形成光固化圖案而製造。 The photocurable pattern can be produced by applying the above-mentioned photosensitive resin composition of the present invention on a substrate and forming a photocurable pattern (after a development process as necessary).
以下藉由製造例、實施例、比較例及實驗例對本發明進一步詳細地說明。但是，下述的製造例、實施例、比較例及實驗例是為了對本發明進行例示，本發明並不限定於下述的製造例、實施例、比較例及實驗例，而能夠進行多種修正與改變。 Hereinafter, the present invention will be described in further detail through production examples, examples, comparative examples, and experimental examples. However, the following manufacturing examples, examples, comparative examples, and experimental examples are for exemplifying the present invention, and the present invention is not limited to the following manufacturing examples, examples, comparative examples, and experimental examples, and various modifications and change.
製造例1及2中，重量平均分子量(Mw)及數量平均分子量(Mn)的測定係使用GPC法在以下的條件下進行。再者，將重量平均分子量與數量平均分子量之比作為分子量分佈(Mw/Mn)。 In Production Examples 1 and 2, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions using the GPC method. In addition, the ratio of the weight average molecular weight to the number average molecular weight is defined as the molecular weight distribution (Mw/Mn).
裝置：HLC-8120GPC(Tosoh(東曹)公司製造) Device: HLC-8120GPC (manufactured by Tosoh)
柱：TSK-GELG4000HXL+TSK-GELG2000HXL(串聯連接) Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)
柱溫度：40℃ Column temperature: 40℃
移動相溶劑：四氫呋喃 Mobile phase solvent: tetrahydrofuran
流速：1.0毫升/分鐘 Flow rate: 1.0 ml/min
注入量：50微升(μl) Injection volume: 50 microliters (μl)
檢測器：RI Detector: RI
測定試樣濃度：0.6重量%(溶劑=四氫呋喃) Determination of sample concentration: 0.6% by weight (solvent = tetrahydrofuran)
校正用標準物質：TSK STANDARD POLYSTYRENE F-40、F-4、F-1、A-2500、A-500(Tosoh公司製造) Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh)
在具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮導入管的燒瓶中投入丙二醇單甲基醚乙酸酯182公克，使燒瓶內的氣氛從空氣變為氮後，升溫到100℃。然後，將在包含乙烯基甲苯35.4公克(0.30莫耳)、丙烯酸36.0公克(0.50莫耳)、2-羥基-鄰-苯基苯酚丙基丙烯酸酯59.6公克(0.2莫耳)及丙二醇單甲基醚乙酸酯136公克的混合物中添加了偶氮二異丁腈3.6公克的溶液，從滴液漏斗歷時2小時滴入燒瓶中，在100℃下持續攪拌5小時。接下來，使燒瓶內的氣氛從氮變為空氣，將甲基丙烯酸縮水甘油酯22.5公克[0.15莫耳、(相對於本反應中使用的丙烯酸，為50莫耳%)]、三(二甲基氨基甲基)苯酚0.9公克與氫醌0.145公克投入燒瓶內，在110℃下繼續反應6小時。由此得到了固體成分酸值為121.1毫克KOH/公克的含有不飽和基的第一樹脂A-1。藉由GPC測定的聚苯乙烯換算的重量平均分子量為31,000， 分子量分佈(Mw/Mn)為2.2。 A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube was charged with 182 g of propylene glycol monomethyl ether acetate, the atmosphere in the flask was changed from air to nitrogen, and the temperature was raised to 100°C. Then, it contains 35.4 g (0.30 mol) of vinyl toluene, 36.0 g (0.50 mol) of acrylic acid, 59.6 g (0.2 mol) of 2-hydroxy-o-phenylphenol propyl acrylate and monomethyl of propylene glycol A solution of 3.6 g of azobisisobutyronitrile was added to the 136 g of ether acetate mixture, which was dropped into the flask from the dropping funnel over 2 hours, and stirring was continued at 100° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% relative to the acrylic acid used in this reaction)], tri(dimethyl 0.9 g of aminoaminomethyl)phenol and 0.145 g of hydroquinone were put into the flask, and the reaction was continued at 110° C. for 6 hours. Thus, the unsaturated group-containing first resin A-1 having a solid component acid value of 121.1 mg KOH/g was obtained. The weight-average molecular weight in terms of polystyrene measured by GPC was 31,000, and the molecular weight distribution (Mw/Mn) was 2.2.
在具備回流冷凝器、滴液漏斗及攪拌器的1公升的燒瓶內，以0.02公升/分鐘使氮流入而成為氮氣氛，放入二甘醇乙基甲基醚150公克，邊攪拌邊加熱到70℃。接下來，將上述化學式6及化學式20的混合物(莫耳比為50：50)198.2公克(0.90莫耳)及甲基丙烯酸8.6公克(0.10莫耳)溶解於二甘醇乙基甲基醚150公克中而製備溶液。 In a 1 liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced at 0.02 liters/minute to form a nitrogen atmosphere. 150 g of diethylene glycol ethyl methyl ether was placed and heated while stirring to 70℃. Next, 198.2 g (0.90 mol) and 8.6 g (0.10 mol) of methacrylic acid and 198.2 g (0.90 mol) of the mixture of the above chemical formula 6 and chemical formula 20 were dissolved in diethylene glycol ethyl methyl ether 150 The solution is prepared in grams.
使用滴液漏斗將製備的溶解液滴入燒瓶內後，使用另外的滴液漏斗、歷時4小時將聚合引發劑2,2'-偶氮二(2,4-二甲基戊腈)27.9公克(0.11莫耳)溶解於二甘醇乙基甲基醚200公克中的溶液滴入燒瓶內。聚合引發劑的溶液的滴加結束後，維持於70℃歷時4小時，然後冷卻到室溫。由此得到了固體成分41.6質量%、酸值59毫克-KOH/公克(固體成分換算)的共聚物(樹脂A-2)的溶液。得到的樹脂A-2的重量平均分子量Mw為7790，分子量分佈為1.9。 After dropping the prepared dissolution liquid into the flask using a dropping funnel, the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was 27.9 g using a separate dropping funnel for 4 hours (0.11 mol) A solution dissolved in 200 g of diethylene glycol ethyl methyl ether was dropped into the flask. After the dropping of the solution of the polymerization initiator was completed, the temperature was maintained at 70°C for 4 hours, and then cooled to room temperature. Thus, a solution of a copolymer (Resin A-2) having a solid content of 41.6% by mass and an acid value of 59 mg-KOH/g (solid content conversion) was obtained. The weight average molecular weight Mw of the obtained resin A-2 was 7790, and the molecular weight distribution was 1.9.
按照下述表1的組成及含量(單位：重量份)，製 備了實施例1至10及比較例1至5的感光性樹脂組合物。 The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared according to the composition and content (unit: parts by weight) of Table 1 below.
將2英寸見方的玻璃基板(EAGLE2000、Corning(康寧)公司製造)用中性洗滌劑、水及醇依次清洗後，乾燥。在該玻璃基板上分別旋塗上述實施例及比較例中製備的感光性樹脂組合物後，在潔淨烘箱中在90℃下進行了3分鐘預烘焙。將進行了上述預烘焙的基板冷卻到常溫後，使與石英玻璃製造的光遮罩的間隔成為150微米，使用曝光機(TME-150RSK、TOPCON(拓普康)公司製造)以60毫焦耳/平方公分(mJ/cm2)的曝光量(405奈米基準)進行了光照射。就此時對聚合性樹脂組合物的照射而言，使來自超高壓汞燈的放射光藉由光學濾波器(LU0400、朝日分光股份有限公司製造)，將400奈米以下的光截斷而使用。此時，作為光遮罩，使用了將以下的圖案在同一平面上形成的光遮罩(具有直徑20微米的圓形的透光部(圖案)，該圖案的間隔為100微米)。 A 2-inch square glass substrate (EAGLE2000, manufactured by Corning) was washed with neutral detergent, water, and alcohol in this order, and then dried. After the photosensitive resin compositions prepared in the above examples and comparative examples were spin-coated on this glass substrate, respectively, pre-baking was carried out in a clean oven at 90° C. for 3 minutes. After cooling the pre-baked substrate to room temperature, the distance from the photomask made of quartz glass was 150 microns, and the exposure machine (TME-150RSK, manufactured by TOPCON) was used at 60 mJ/ The exposure amount (square nanometer standard) of square centimeters (mJ/cm 2 ) was irradiated with light. For the irradiation of the polymerizable resin composition at this time, the light emitted from the ultra-high pressure mercury lamp was used by intercepting light of 400 nm or less through an optical filter (LU0400, manufactured by Asahi Spectroscopy Co., Ltd.). At this time, as the light mask, a light mask (a circular light-transmitting portion (pattern) having a diameter of 20 μm and an interval of 100 μm between the patterns) formed on the same plane was used.
照射後，在25℃下將上述塗膜在含有非離子系表面活性劑0.12%及氫氧化鉀0.04%的水系顯影液中浸漬100秒而顯影，進行了水洗。然後，在烘箱中、220℃下進行了20分鐘後烘焙。得到的膜的厚度為3微米。膜厚使用膜厚測定裝置(DEKTAK6M、Veeco公司製造)測定。對於這樣得到的圖案， 進行了下述的物性評價。將其結果示於下述表2中。 After the irradiation, the above coating film was immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 100 seconds for development and washed with water. Then, it baked at 220 degreeC for 20 minutes in an oven. The thickness of the resulting film was 3 microns. The film thickness was measured using a film thickness measuring device (DEKTAK6M, manufactured by Veeco). For the pattern thus obtained, the following physical property evaluation was performed. The results are shown in Table 2 below.
(1)底部CD的測定 (1) Measurement of the bottom CD
對於上述得到的固化膜，使用三維形狀測定裝置(SIS-2000 Systems、SNU PRECISION(史那精密)公司製造)，在光遮罩大小及此時的塗膜厚度的基準分別為20微米、3.0微米時，對於塗膜的厚度維持2.85微米的最小的尺寸的圖案，測定圖案的高度及底部CD。 For the cured film obtained above, a three-dimensional shape measuring device (SIS-2000 Systems, SNU PRECISION) was used. The standards of the size of the light mask and the thickness of the coating film at this time were 20 μm and 3.0 μm, respectively. At that time, the height of the pattern and the bottom CD were measured for the pattern with the minimum size of 2.85 μm for the thickness of the coating film.
如第1圖所示，將高度的5%的部位的線寬定義為底部CD的值。底部CD越小，感度越好，因此優異。 As shown in Fig. 1, the line width of the 5% height portion is defined as the value of the bottom CD. The smaller the bottom CD, the better the sensitivity, and therefore excellent.
(2)圖案的上下寬度比的測定(T/B比) (2) Measurement of the vertical width ratio of the pattern (T/B ratio)
對於上述(1)中得到的點圖案，使用三維形狀測定裝置(SIS-2000 Systems、SNU PRECISION公司製造)，將與圖案的底面相距全體高度的5%的部位定義為底部CD(a)，將與底面相距全體高度的95%的部位定義為頂部CD(b)，將用(b)的長度除以(a)的長度後乘以100所得的值(=b/a×100)定義為T/B比。 For the dot pattern obtained in (1) above, using a three-dimensional shape measuring device (SIS-2000 Systems, manufactured by SNU PRECISION), a portion 5% of the overall height from the bottom surface of the pattern is defined as the bottom CD (a), and 95% of the total height from the bottom surface is defined as the top CD (b), and the value obtained by dividing the length of (b) by the length of (a) and multiplying by 100 (=b/a×100) is defined as T /B ratio.
(3)顯影密合力 (3) Development adhesion
就顯影密合性而言，採用顯微鏡對採用分別具有1000個圓形圖案的光遮罩將膜厚形成為3微米的圖案進行評價，計數脫落的圖案的數量，如下述數學式1那樣算出顯影密合力(%)。將其結果記載於下述表2中。 Regarding the development adhesiveness, a microscope was used to evaluate patterns with a thickness of 3 micrometers using photomasks each having 1000 circular patterns, and the number of patterns dropped was counted, and the development was calculated as in the following mathematical formula 1. Cohesion (%). The results are described in Table 2 below.
[數學式1]顯影密合力(%)=[1000-(脫落的圖案的數量)]/1000×100 [Mathematical Formula 1] Development adhesion (%)=[1000-(number of patterns dropped)]/1000×100
(4)機械特性(回復率) (4) Mechanical characteristics (recovery rate)
對於上述得到的固化膜，使用動態超微小硬度計(DUH-W201、Shimadzu Corporation(島津公司)製造)，採用以下的測定條件測定了其總位移量(微米)及彈性位移量(微米)。使用測定的數值，如下述數學式2那樣算出了回復率(%)。如果回復率大，則判斷為硬。 For the cured film obtained as described above, using a dynamic ultra-fine hardness tester (DUH-W201, manufactured by Shimadzu Corporation (Shimadzu Corporation)), the total displacement amount (micrometer) and the elastic displacement amount (micrometer) were measured under the following measurement conditions. Using the measured values, the recovery rate (%) was calculated as in the following mathematical formula 2. If the response rate is large, it is judged as hard.
[數學式2]回復率(%)=[彈性位移量(微米)]/[總位移量(微米)]×100 [Mathematical formula 2] Recovery rate (%)=[elastic displacement (micron)]/[total displacement (micron)]×100
試驗模式：載荷-卸載試驗 Test mode: load-unload test
試驗力：5公克力(gf)[SI單位換算值49.0毫牛頓(mN)] Test force: 5 gram force (gf) [SI unit conversion value 49.0 milliNewton (mN)]
載荷速度：0.45公克力/秒[SI單位換算值4.41毫牛頓/秒] Load speed: 0.45 gf/s [SI unit conversion value 4.41 mN/s]
保持時間：5秒 Hold time: 5 seconds
壓頭：圓錐台的壓頭(直徑50微米) Indenter: Indenter of truncated cone (diameter 50 microns)
參照上述表2，對應於本發明範圍且使用了包含由上述化學式3表示的化合物的光聚合引發劑的實施例的感光性樹脂組合物在底部CD、T/B比及彈性回復率上顯示出優異的結果，顯影密合力顯示出與以往的感光性樹脂組合物同等以上的水準。而比較例的感光性樹脂組合物則不是這樣。特別是在比較例5的情況下，沒有形成圖案，未能測定底部CD、T/B比、顯影密合力及彈性回復率。 Referring to the above Table 2, the photosensitive resin composition of an example corresponding to the scope of the present invention and using a photopolymerization initiator including the compound represented by the above Chemical Formula 3 shows the bottom CD, T/B ratio, and elastic recovery rate As a result of excellent results, the development adhesion showed a level equal to or higher than that of the conventional photosensitive resin composition. This is not the case with the photosensitive resin composition of the comparative example. In particular, in the case of Comparative Example 5, no pattern was formed, and the bottom CD, T/B ratio, development adhesion, and elastic recovery rate could not be measured.
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