TWI494687B - Photosensitive composition, partition, color filter and organic EL element (2) - Google Patents
Photosensitive composition, partition, color filter and organic EL element (2) Download PDFInfo
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- TWI494687B TWI494687B TW099146286A TW99146286A TWI494687B TW I494687 B TWI494687 B TW I494687B TW 099146286 A TW099146286 A TW 099146286A TW 99146286 A TW99146286 A TW 99146286A TW I494687 B TWI494687 B TW I494687B
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/122—Pixel-defining structures or layers, e.g. banks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/17—Passive-matrix OLED displays
- H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Description
本發明係有關於一種感光性組成物、使用其之隔壁、和具有該隔壁之彩色濾光片及有機EL元件。The present invention relates to a photosensitive composition, a partition wall using the same, and a color filter and an organic EL element having the partition wall.
近年來,感光性組成物係作為形成彩色濾光片的像素間之隔壁、有機EL(Electro-Luminescence;電致發光)顯示元件的像素間之隔壁、隔開有機TFT(Thin Film Transistor;薄膜電晶體)陣列的各TFT之隔壁、液晶顯示元件的ITO電極之隔壁、電路配線基板的隔壁等的永久膜之材料而受到注目。例如,在製造彩色濾光片時,係使用微影術而形成隔壁圖案(亦有達成黑色矩陣的效果)後,使用噴墨法在隔壁間的開口部塗布R(紅色)、G(綠色)及B(藍色)的油墨來形成像素。又,在製造有機EL元件時,係使用微影術而形成隔壁圖案後,使用噴墨法在隔壁間的開口部塗布電洞輸送材料、發光材料等的溶液來形成具有電洞輸送層、發光層等之像素。In recent years, the photosensitive composition is used as a partition between pixels forming a color filter, a partition between pixels of an organic EL (Electro-Luminescence) display element, and an organic TFT (Thin Film Transistor). The material of the permanent film of each of the TFTs of the crystal array, the partition walls of the ITO electrodes of the liquid crystal display element, and the partition walls of the circuit wiring board is attracting attention. For example, when a color filter is manufactured, a partition pattern is formed by lithography (the effect of achieving a black matrix is also obtained), and then R (red) and G (green) are applied to the opening between the partition walls by an inkjet method. And B (blue) ink to form a pixel. In the production of the organic EL device, a partition pattern is formed by using lithography, and a solution such as a hole transport material or a light-emitting material is applied to the opening between the partition walls by an inkjet method to form a hole transport layer and emit light. Pixels such as layers.
為了防止在此種彩色濾光片和有機EL元件之鄰接的像素間產生混色,在隔壁的上面係有必要具有不沾油墨的性質(亦即拒液性)。又,為了防止彩色濾光片和有機EL元件產生白點,隔壁間的開口部係有必要具有對油墨之濕潤性質(亦即親液性)。In order to prevent color mixture between adjacent pixels of such a color filter and an organic EL element, it is necessary to have ink-repellent properties (i.e., liquid repellency) on the upper surface of the partition wall. Further, in order to prevent white spots from occurring in the color filter and the organic EL element, it is necessary to have a wet property to the ink (that is, lyophilic property) in the opening between the partition walls.
為了得到此種隔壁所被要求的特性,有提案揭示一種含有在系內導入氟烷基鏈而成的共聚物之感光性樹脂組成物。In order to obtain the characteristics required for such a partition, it has been proposed to disclose a photosensitive resin composition containing a copolymer obtained by introducing a fluoroalkyl chain into a system.
在專利文獻1,係記載一種含有具有乙烯性不飽和雙鍵及氟烷基的乙烯基聚合物之隔壁用組成物(鹼性顯像型感光性光阻)。但是,得知依照隔壁用組成物之組成,會有因為表面的拒液性非常高,在顯像步驟所產生的氣泡吸附在表面而阻礙未曝光部的顯像,造成最後以顯像缺陷的形式殘留之情形。Patent Document 1 describes a composition for a partition wall (alkaline development type photosensitive photoresist) containing a vinyl polymer having an ethylenically unsaturated double bond and a fluoroalkyl group. However, it has been found that, depending on the composition of the partition wall composition, the liquid repellency of the surface is extremely high, and the bubbles generated in the developing step are adsorbed on the surface to hinder the development of the unexposed portion, resulting in the final development of the image defect. The form of residual form.
另一方面,為了提升與顯像液的易親和性,專利文獻2係記載一種負型感光性組成物,其係含有導入聚氧伸烷基鏈(polyoxyalkylene chain)來提升親水性而成之含氟聚合物。得知依照在此所例示的聚氧伸烷基鏈的長度,會有對顯像缺陷完全無效果之情形,另一方面因為其增加顯像液的易親合性,位於隔壁表面的拒液部分容易被削去,而產生拒液性低落之問題。On the other hand, in order to improve the affinity with the developing solution, Patent Document 2 describes a negative photosensitive composition containing a polyoxyalkylene chain to enhance hydrophilicity. Fluoropolymer. It is known that according to the length of the polyoxyalkylene chain exemplified herein, there is a case where the development defect is completely ineffective, and on the other hand, because it increases the affinity of the developing solution, the liquid repellency on the surface of the partition wall Some parts are easily cut off, resulting in a problem of low liquid repellency.
其次,在專利文獻3,記載一種含有乙烯基聚合物之隔壁用組成物(鹼性顯像型感光性光阻),該乙烯基聚合物係在聚氧伸烷基鏈的末端導入乙烯性不飽和雙鍵且具有氟烷基。但是因為在末端含有雙鍵部位之聚氧伸烷基鏈,由於曝光及硬化而容易被固定在隔壁的表面,致使側鏈的舉動受到限制,而未顯現充分的親水性效果。Next, Patent Document 3 describes a composition for a partition wall (alkaline developing type photosensitive resist) containing a vinyl polymer which is introduced into the terminal of the polyoxyalkylene chain. It has a saturated double bond and has a fluoroalkyl group. However, since the polyoxyalkylene chain having a double bond moiety at the terminal is easily fixed to the surface of the partition by exposure and hardening, the behavior of the side chain is restricted, and a sufficient hydrophilic effect is not exhibited.
專利文獻4係記載一種具有乙烯性不飽合雙鍵部位、氟烷基及氧伸烷基(oxyalkylene)之乙烯基聚合物。但是,該等物質係以在平版印刷領域提升油墨在印刷版的壓印性作為目的,所例示的化合物係對顯像缺陷無充分的效果之構成。Patent Document 4 describes a vinyl polymer having an ethylenic unsaturated double bond moiety, a fluoroalkyl group, and an oxyalkylene group. However, these materials are aimed at improving the embossability of the ink on the printing plate in the field of lithography, and the exemplified compounds have no sufficient effect on the development defects.
先前技術文獻Prior technical literature
專利文獻Patent literature
專利文獻1:國際公開第2007/69703號Patent Document 1: International Publication No. 2007/69703
專利文獻2:日本專利特開2009-168948號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-168948
專利文獻3:國際公開第2007/111356號Patent Document 3: International Publication No. 2007/111356
專利文獻4:日本專利特開2001-312053號公報Patent Document 4: Japanese Patent Laid-Open Publication No. 2001-312053
本發明係為了解決先前技術所具有的問題點而完成者,係以提供一種感光性組成物作為目的,該感光性組成物能夠形成一種無顯像缺陷,且即便經過顯像步驟亦具有拒液性良好的上面之隔壁,而且隔壁側面的親液性良好,能夠形成油墨容易濕潤擴展的開口部。又,本發明係以提供一種藉由將該感光性組成物硬化而形成之具有良好的性能的隔壁,和一種具有該隔壁之彩色濾光片及有機EL元件作為目的。The present invention has been made in order to solve the problems of the prior art, and aims to provide a photosensitive composition capable of forming a non-developing defect and having liquid repellent even after a developing step. The partition wall of the upper surface having good properties and the lyophilic property of the side surface of the partition wall are good, and an opening portion in which the ink is easily wetted and expanded can be formed. Moreover, the present invention has an object of providing a partition wall having good performance by curing the photosensitive composition, and a color filter and an organic EL element having the partition wall.
本發明係提供一種具有以下構成之感光性組成物、隔壁、彩色濾光片及有機EL元件。The present invention provides a photosensitive composition, a partition wall, a color filter, and an organic EL element having the following constitution.
[1] 一種感光性組成物,其特徵為含有聚合物(A)、光聚合起始劑(B)及具有酸性基及乙烯性雙鍵之感光性樹脂(C),該聚合物(A)係至少含有[1] A photosensitive composition comprising a polymer (A), a photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond, the polymer (A) At least
具有下述通式(1)所表示的基之側鏈,a side chain having a group represented by the following formula (1),
-CFXRf …(1)-CFXR f ...(1)
具有下述通式(2)所表示的基之側鏈,a side chain having a group represented by the following formula (2),
-(R11 -O)n -R12 ...(2)-(R 11 -O) n -R 12 ...(2)
及具有乙烯性雙鍵之側鏈,其中,式中的記號係表示以下的意思,X:氫原子、氟原子或三氟甲基,Rf :亦可具有醚性氧原子之碳數為1以上、20以下的氟烷基或氟原子,R11 :碳數1~5的伸烷基,R12 :碳數1~4的烷基,n:6~30的整數。And a side chain having an ethylenic double bond, wherein the symbol in the formula represents the following meaning, X: a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f : may also have an etheric oxygen atom having a carbon number of 1 The above is a fluoroalkyl group or a fluorine atom of 20 or less, R 11 is an alkylene group having 1 to 5 carbon atoms, R 12 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 6 to 30.
[2] 如[1]之感光性組成物,其中前述聚合物(A)的質量平均分子量為1.2×104 以上、15×104 以下。[2] The photosensitive composition according to [1], wherein the polymer (A) has a mass average molecular weight of 1.2 × 10 4 or more and 15 × 10 4 or less.
[3] 如[1]或[2]之感光性組成物,其中在前述聚合物(A)之氟原子的含量為5質量%以上、35質量%以下。[3] The photosensitive composition according to [1] or [2], wherein the content of the fluorine atom in the polymer (A) is 5% by mass or more and 35% by mass or less.
[4] 如[1]至[3]項中任一項之感光性組成物,其中在前述聚合物(A)之含有前述通式(2)所表示的基之聚合單元之比率為5質量%以上、50質量%以下。[4] The photosensitive composition according to any one of [1] to [3] wherein the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) is 5 mass. % or more and 50% by mass or less.
[5] 如[1]至[4]項中任一項之感光性組成物,其中在前述聚合物(A)係更含有具有酸性基之側鏈。[5] The photosensitive composition according to any one of [1] to [4] wherein the polymer (A) further contains a side chain having an acidic group.
[6] 如[1]至[5]項中任一項之感光性組成物,其更含有具有2個以上乙烯性雙鍵之交聯劑(D)[6] The photosensitive composition according to any one of [1] to [5], which further comprises a crosslinking agent having two or more ethylenic double bonds (D)
[7] 如[1]至[6]項中任一項之感光性組成物,其更含有著色劑(E)。[7] The photosensitive composition according to any one of [1] to [6] which further contains a coloring agent (E).
[8] 如[1]至[7]項中任一項之感光性組成物,其中相對於前述感光性組成物的總固體成分,聚合物(A)的含量為0.07質量%以上、1質量%以下。The photosensitive composition of any one of [1] to [7], wherein the content of the polymer (A) is 0.07% by mass or more and 1 mass with respect to the total solid content of the photosensitive composition. %the following.
[9] 一種隔壁,其被形成為將基板隔成複數個像素形成用間隔之狀態而被形成,其特徵為由如[1]至[8]項中任一項之感光性組成物的塗膜硬化物所構成。[9] A partition wall formed by separating a substrate into a plurality of pixel formation intervals, characterized by coating of the photosensitive composition according to any one of [1] to [8] It is composed of a cured film.
[10] 一種彩色濾光片,其係在基板上具有複素像素及位於鄰接像素間的隔壁之彩色濾光片,其特徵為前述隔壁係使用如[9]之隔壁所形成。[10] A color filter comprising a color filter on a substrate having a complex pixel and a partition wall between adjacent pixels, wherein the partition wall is formed using a partition wall of [9].
[11] 一種有機EL元件,係在基板上具有複素像素及位於相鄰接像素間的隔壁之有機EL元件,其特徵為前述隔壁係使用如[9]之隔壁所形成。[11] An organic EL device is an organic EL device having a complex pixel and a partition wall between adjacent pixels on a substrate, wherein the partition wall is formed using a partition wall of [9].
依照本發明的感光性組成物,能夠形成在顯像時無顯像缺陷,且具有拒液性良好的上面及親液性良好的側面之隔壁、以及油墨容易濕潤擴展的開口部。又,依照本發明,能夠提供一種藉由將該感光性組成物硬化來形成具有良好性能的隔壁、和具有該隔壁之彩色濾光片及有機EL元件。According to the photosensitive composition of the present invention, it is possible to form a partition wall having a side surface having good liquid repellency and a liquid repellency which is excellent in liquid repellency, and an opening portion in which the ink is easily wetted and spread. Moreover, according to the present invention, it is possible to provide a partition wall having excellent performance by curing the photosensitive composition, and a color filter and an organic EL element having the partition wall.
以下說明用以實施本發明之形態,但是本發明不被以下的實施形態限定。The mode for carrying out the invention will be described below, but the invention is not limited by the following embodiments.
又,在本說明書,只要未特別說明,%係表示質量%。又,(甲基)丙烯酸醯基係意味著使用作為丙烯醯基及甲基丙烯醯基的兩者之總稱。(甲基)丙烯酸酯係意味著使用作為丙烯酸酯及甲基丙烯酸酯的兩者之總稱。(甲基)丙烯酸係意味著使用作為丙烯酸及甲基丙烯酸的兩者之總稱。(甲基)丙烯醯胺係意味著使用作為丙烯醯胺及甲基丙烯醯胺的兩者之總稱。(甲基)烯丙基係意味著使用作為烯丙基及甲基烯丙基的兩者之總稱。將通式(1)所表示的基亦稱為基(1)。其他的基亦同樣。In addition, in this specification, unless otherwise indicated, % shows the mass %. Further, the fluorenyl (meth) acrylate group means a general term for both of an acryloyl group and a methacryl fluorenyl group. The (meth) acrylate means a general term for both acrylate and methacrylate. The (meth)acrylic acid means a general term for both of acrylic acid and methacrylic acid. The (meth) acrylamide system means a general term for both of acrylamide and methacrylamide. The (meth)allyl group means a general term for both of an allyl group and a methallyl group. The group represented by the formula (1) is also referred to as a group (1). The other bases are the same.
本發明的感光性組成物,其特徵為含有聚合物(A)、光聚合起始劑(B)及具有酸性基及乙烯性雙鍵之感光性樹脂(C),該聚合物(A)係至少含有具有下述通式(1)所表示的基之側鏈、具有下述通式(2)所表示的基之側鏈、及具有乙烯性雙鍵之側鏈,The photosensitive composition of the present invention is characterized by comprising a polymer (A), a photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond, the polymer (A) a side chain having a group represented by the following formula (1), a side chain having a group represented by the following formula (2), and a side chain having an ethylenic double bond,
-CFXRf …(1)-CFXR f ...(1)
(式(1)中,X為氫原子、氟原子或三氟甲基,Rf 為亦可具有醚性氧原子之碳數為1以上、20以下的氟烷基或氟原子)(In the formula (1), X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f is a fluoroalkyl group or a fluorine atom which may have an etheric oxygen atom of 1 or more and 20 or less)
下述通式(2)所表示的基之側鏈,a side chain of a group represented by the following formula (2),
-(R11 -O)n -R12 …(2)-(R 11 -O) n -R 12 ...(2)
(式(2)中,R11 係碳數1~5的伸烷基,R12 係碳數1~4的烷基,n係6~30的整數)(In the formula (2), R 11 is an alkylene group having 1 to 5 carbon atoms, R 12 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 6 to 30)
因為本發明的感光性組成物所含有的聚合物(A)係含有具有上述基(1)之側鏈,故在基板上藉由塗布本發明的感光性組成物而形成的塗膜於乾燥時,容易移動至塗膜的表面附近。又,因為聚合物(A)係含有具有乙烯性雙鍵之側鏈,曝光時硬化會進行,而容易被固定化在塗膜的表面附近。又,因為含有具有上述基(2)之側鏈,會抑制顯像時所產生之氣泡吸附在塗膜表面,能夠防止被認為起因於氣泡吸附之顯像缺陷。因而,藉由將曝光後的塗膜顯像所形成的隔壁,係無顯像缺陷且只有在隔壁上面顯現拒液性。因此,使用噴墨法在被隔壁包圍的開口部塗布油墨時,能夠抑制在鄰接的開口部間產生混色。又,因為藉此能夠確保隔壁側面及開口部之親液性良好,所以在開口部的油墨濕潤擴展性良好而亦能夠抑制產生白點。Since the polymer (A) contained in the photosensitive composition of the present invention contains the side chain having the above-mentioned group (1), the coating film formed by applying the photosensitive composition of the present invention on the substrate is dried. It is easy to move to the vicinity of the surface of the film. Further, since the polymer (A) contains a side chain having an ethylenic double bond, hardening proceeds during exposure, and is easily immobilized in the vicinity of the surface of the coating film. Further, since the side chain having the above-mentioned group (2) is contained, the bubbles generated during development are prevented from being adsorbed on the surface of the coating film, and the development defects considered to be caused by bubble adsorption can be prevented. Therefore, the partition wall formed by developing the exposed coating film has no development defects and only exhibits liquid repellency on the partition walls. Therefore, when the ink is applied to the opening surrounded by the partition wall by the inkjet method, color mixing can be suppressed between the adjacent openings. Moreover, since the lyophilic property of the side wall and the opening of the partition wall can be ensured, the ink wettability in the opening portion is good, and white spots can be suppressed.
在此,聚合物(A)之質量平均分子量(Mw)係以1.2×104 ~15×104 為佳,以3.0×104 ~12×104 為更佳,以5.5×104 ~11×104 為特佳。聚合物(A)之數量平均分子量(Mn)係以1.0×104 ~7.0×104 為佳,以2.5×104 ~6.0×104 為更佳。Here, the mass average molecular weight (Mw) of the polymer (A) is preferably 1.2 × 10 4 to 15 × 10 4 , more preferably 3.0 × 10 4 to 12 × 10 4 , and more preferably 5.5 × 10 4 to 11 ×10 4 is especially good. The number average molecular weight (Mn) of the polymer (A) is preferably 1.0 × 10 4 to 7.0 × 10 4 , more preferably 2.5 × 10 4 to 6.0 × 10 4 .
在此,於本說明書中之質量平均分子量(Mw)及數量平均分子量(Mn)係指使用凝膠滲透層析法,將聚苯乙烯設為標準物質而測定的值。Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification mean values measured by using gel permeation chromatography and using polystyrene as a standard substance.
聚合物(A)的質量平均分子量為小於1.2×104 時,隔壁間開口部的親液性有不充分的情形,使用噴墨法塗布油墨時,油墨有未充分地濕潤擴展之可能性。質量平均分子量為超過15×104 時,鹼溶解性、顯像性有不充分之可能性。又,聚合物(A)的數量平均分子量為小於1.0×104 時,隔壁間開口部的親液性有不充分的情形,使用噴墨法塗布油墨時,油墨有未充分地濕潤擴展之可能性。而且,質量平均分子量(Mw)為3.0×104 ~12×104 時,不管鹼的種類和濃度及噴淋條件如何,皆容易將拒液性保持較高,使得製造餘裕度擴大,乃是較佳。又,就聚合物(A)的製造容易性而言,亦是較佳。When the mass average molecular weight of the polymer (A) is less than 1.2×10 4 , the lyophilicity of the opening between the partition walls may be insufficient, and when the ink is applied by the inkjet method, the ink may not sufficiently wet and expand. When the mass average molecular weight is more than 15 × 10 4 , the alkali solubility and developability may be insufficient. Further, when the number average molecular weight of the polymer (A) is less than 1.0 × 10 4 , the lyophilicity of the opening between the partition walls may be insufficient, and when the ink is applied by the inkjet method, the ink may not sufficiently wet and expand. Sex. Further, when the mass average molecular weight (Mw) is from 3.0 × 10 4 to 12 × 10 4 , regardless of the type and concentration of the alkali and the spray conditions, it is easy to keep the liquid repellency high, and the manufacturing margin is expanded. Preferably. Further, it is also preferable in terms of ease of production of the polymer (A).
聚合物(A)的分子量分布(質量平均分子量/數量平均分子量)係以8以下為佳,以4以下為更佳。在該範圍時,顯像性良好。分子量分布的下限係沒有特別限定,就容易合成及與顯像液的親和性之觀點,以1.5以上為佳。The molecular weight distribution (mass average molecular weight / number average molecular weight) of the polymer (A) is preferably 8 or less, more preferably 4 or less. In this range, the developability is good. The lower limit of the molecular weight distribution is not particularly limited, and from the viewpoint of easy synthesis and affinity with a developing solution, it is preferably 1.5 or more.
而且,關於聚合物(A)的分子量之調整,係在後述之聚合物(A)的製造方法進行說明。Further, the adjustment of the molecular weight of the polymer (A) will be described in the method for producing the polymer (A) to be described later.
聚合物(A)中的氟原子之含量係5~35質量%,而且以10~30質量%為更佳。氟原子之含量為小於5質量%時,隔壁的上面之拒液性有變為不充分的情形。超過35質量%時,隔壁與基板的密著性有低落的情形。又,聚合物(A)中的氟原子之含量係能夠藉由主要是以下說明的具有基(1)之側鏈在聚合物(A)的導入量來調整。The content of the fluorine atom in the polymer (A) is preferably 5 to 35% by mass, more preferably 10 to 30% by mass. When the content of the fluorine atom is less than 5% by mass, the liquid repellency of the upper surface of the partition wall may be insufficient. When it exceeds 35% by mass, the adhesion between the partition wall and the substrate may be lowered. Further, the content of the fluorine atom in the polymer (A) can be adjusted by the amount of introduction of the side chain having the group (1) mainly described below in the polymer (A).
在本發明所使用的聚合物(A),係在側鏈具有如上述通式(1)所表示之含有氟原子的基(1)。在基(1),Rf 係亦可具有醚性氧原子之碳數1~20的氟烷基時,Rf 係亦可具有氟原子以外之鹵素原子。作為此種鹵素原子,係以氯原子為佳。The polymer (A) used in the present invention has a fluorine atom-containing group (1) represented by the above formula (1) in a side chain. In the case where the group (1) and the Rf group may have a fluoroalkyl group having 1 to 20 carbon atoms of an etheric oxygen atom, the Rf group may have a halogen atom other than the fluorine atom. As such a halogen atom, a chlorine atom is preferred.
又,作為該氟烷基的構造,係沒有特別限定,可舉出直鏈構造、分枝構造、環構造、部分性具有環之構造等,以直鏈構造為佳。而且,Rf 係具有醚性氧原子之氟烷基時,醚性氧原子係可以存在於氟烷基的碳-碳鍵之間,亦可以存在於氟烷基的末端。In addition, the structure of the fluoroalkyl group is not particularly limited, and examples thereof include a linear structure, a branching structure, a ring structure, and a partial structure having a ring, and a linear structure is preferred. Further, when R f is a fluoroalkyl group having an etheric oxygen atom, the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or may be present at the terminal of the fluoroalkyl group.
作為基(1)之Rf ,係以上述亦可具有醚性氧原子之碳數1~20的氟烷基為佳。又,X係以氟原子為特佳。R f as the group (1) is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom. Further, X is particularly preferred as a fluorine atom.
上述基(1)中,Rf 係亦可具有醚性氧原子之碳數1~20的氟烷基時,作為Rf ,係只要具有該構成,沒有特別限定。作為Rf ,具體上可舉出-CF3 、-CF2 CF3 、-CF2 CHF2 、-(CF2 )2 CF3 、-(CF2 )3 CF3 、-(CF2 )4 CF3 、-(CF2 )5 CF3 、-(CF2 )6 CF3 、-(CF2 )7 CF3 、-(CF2 )8 CF3 、-(CF2 )9 CF3 、-(CF2 )11 CF3 、-(CF2 )15 CF3 、-CF(CF3 )O(CF2 )5 CF3 、-CF2 O(CF2 CF2 O)p CF3 (p係1~8的整數)、-CF(CF3 )O(CF2 CF(CF3 )O)q C6 F13 (q係1~4的整數)、-CF(CF3 )O(CF2 CF(CF3 )O)r C3 F7 (r係1~5的整數)等。In the above-mentioned group (1), when R f is a fluoroalkyl group having 1 to 20 carbon atoms of an etheric oxygen atom, R f is not particularly limited as long as it has such a configuration. Specific examples of R f include -CF 3 , -CF 2 CF 3 , -CF 2 CHF 2 , -(CF 2 ) 2 CF 3 , -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF. 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 6 CF 3 , -(CF 2 ) 7 CF 3 , -(CF 2 ) 8 CF 3 , -(CF 2 ) 9 CF 3 , -(CF 2 ) 11 CF 3 , -(CF 2 ) 15 CF 3 , -CF(CF 3 )O(CF 2 ) 5 CF 3 , -CF 2 O(CF 2 CF 2 O) p CF 3 (p system 1~8 Integer), -CF(CF 3 )O(CF 2 CF(CF 3 )O) q C 6 F 13 (q is an integer from 1 to 4), -CF(CF 3 )O(CF 2 CF(CF 3 ) )O) r C 3 F 7 (r is an integer of 1 to 5) and the like.
Rf 係亦可具有醚性氧原子之碳數1以上、20以下的氟烷基時,作為Rf ,係以不具有醚性氧原子之全氟烷基及具有醚性氧原子之全氟烷基為佳,以不具有醚性氧原子之全氟烷基為更佳。其碳數係以1~11為佳,以3~5為特佳。When R f is a fluoroalkyl group having an etheric oxygen atom having 1 or more carbon atoms and 20 or less carbon atoms, R f is a perfluoroalkyl group having no etheric oxygen atom and a perfluoro group having an etheric oxygen atom. An alkyl group is preferred, and a perfluoroalkyl group having no etheric oxygen atom is more preferred. The carbon number is preferably from 1 to 11, and particularly preferably from 3 to 5.
此種基(1)之中,在本發明係以全氟烷基或具有1個氫原子之多氟烷基為佳,以全氟烷基為特佳。而且,全氟烷基及多氟烷基係亦包含具有醚性氧原子者。又,作為上述具有1個氫原子之多氟烷基,係以X為氫原子之化合物為佳。藉此,使用本發明的感光性組成物所形成之隔壁,其上面的拒液性係變為良好。Among the above groups (1), in the present invention, a perfluoroalkyl group or a polyfluoroalkyl group having one hydrogen atom is preferred, and a perfluoroalkyl group is particularly preferred. Further, the perfluoroalkyl group and the polyfluoroalkyl group also include those having an etheric oxygen atom. Further, as the polyfluoroalkyl group having one hydrogen atom, a compound in which X is a hydrogen atom is preferred. As a result, the partition wall formed by using the photosensitive composition of the present invention has a good liquid repellency on the upper surface.
又,基(1)係以碳數4~6為佳。作為此種基(1),具體上可舉出-(CF2 )3 CF3 、-(CF2 )4 CF3 、-(CF2 )5 CF3 、-CF2 O(CF2 )2 OCF3 、-CF2 O(CF2 )2 O(CF2 )2 OCF3 等。將聚合物(A)在側鏈所具有的基(1)的碳數設為4~6時,能夠提升聚合物(A)與構成感光性組成物的其他成分之相溶性,因此能夠抑制藉由在塗布感光性組成物而形成的塗膜中之聚合物(A)的凝聚,其結果,能夠形成外觀良好的隔壁。Further, the base (1) is preferably a carbon number of 4 to 6. Specific examples of such a group (1) include -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 5 CF 3 , -CF 2 O(CF 2 ) 2 OCF. 3 , -CF 2 O(CF 2 ) 2 O(CF 2 ) 2 OCF 3 and the like. When the number of carbon atoms of the group (1) in the side chain of the polymer (A) is 4 to 6, the compatibility between the polymer (A) and other components constituting the photosensitive composition can be improved, so that it is possible to suppress borrowing. The aggregation of the polymer (A) in the coating film formed by applying the photosensitive composition can result in formation of a partition wall having a good appearance.
又,在聚合物(A)中,具有基(1)之側鏈之基(1)的導入數為1。在聚合物(A)之各個具有基(1)的側鏈中,基(1)可以相同亦可以不同。亦即,聚合物(A)在側鏈所具有的基(1)係可以是1種,亦可以是2種以上的組合。而且,在本發明所使用的聚合物(A),基(1)亦可以導入至全部之側鏈,但是較佳是以成為上述的氟原子含量之方式,來適當地調整被導入基(1)之側鏈相對於聚合物(A)整體之比率。具體上,係在藉由如後述的原料單體聚合來製造聚合物(A)時,調整相對於原料單體整體之具有基(1)的單體之調配量。又,具有基(1)之側鏈係可以藉由聚合反應來直接形成,亦可藉由聚合反應後的化學轉化來形成。Further, in the polymer (A), the number of introductions of the group (1) having the side chain of the group (1) was 1. In the side chain having the group (1) of each of the polymers (A), the groups (1) may be the same or different. In other words, the polymer (A) may have one type of the group (1) in the side chain, or a combination of two or more types. Further, in the polymer (A) used in the present invention, the group (1) may be introduced into all of the side chains, but it is preferred to appropriately adjust the introduced group so as to have the above fluorine atom content. The ratio of the side chain to the entirety of the polymer (A). Specifically, when the polymer (A) is produced by polymerization of a raw material monomer to be described later, the amount of the monomer having the group (1) with respect to the entire raw material monomer is adjusted. Further, the side chain having the group (1) may be directly formed by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction.
又,本發明所使用的聚合物(A)係在側鏈具有含有上述通式(2)所表示的聚氧伸烷基鏈之基(2)。所謂聚氧伸烷基鏈係指以-(R11 -O)n -所表示的部分。該聚氧伸烷基鏈係以具有親水性的鏈為佳,以n個存在的氧伸烷基之數目中有50~100%為氧伸乙基(oxyethylene group)為特佳。具有氧伸乙基之聚氧伸烷基鏈係能夠發揮良好的親水性。Further, the polymer (A) used in the present invention has a group (2) having a polyoxyalkylene chain represented by the above formula (2) in a side chain. The polyoxyalkylene chain means a moiety represented by -(R 11 -O) n -. The polyoxyalkylene chain is preferably a chain having hydrophilicity, and particularly preferably 50 to 100% of the number of n oxygen-extended alkyl groups present is an oxyethylene group. The polyoxyalkylene chain having an oxygen-extended ethyl group can exert good hydrophilicity.
又,在本發明所使用的聚合物(A)之含有上述通式(2)所表示的基之聚合單元的比率,係以5~50質量%為佳,以10~40質量%為更佳,以15~35質量%為特佳。在聚合物(A)之含有上述通式(2)所表示的基之聚合單元的比率為小於5質量%時,無法充分地抑制在顯像時所產生的氣泡吸附在塗膜表面,致使在最後所得到的隔壁和隔壁開口部有產生許多顯像缺陷之情形。又,上述聚合單元的比率為超過50質量%時,拒液性有低落之可能性。含有上述通式(2)所表示的基之聚合單元的比率為該範圍時,聚合物(A)周圍的基(2)(具有聚氧伸烷基之基)所存在的位置係均勻分布,且性能安定。In addition, the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) used in the present invention is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. It is particularly good at 15 to 35 mass%. When the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) is less than 5% by mass, the adsorption of bubbles generated during development cannot be sufficiently suppressed on the surface of the coating film, resulting in Finally, the partition wall and the partition opening portion which are obtained have a large number of development defects. Further, when the ratio of the polymerization unit is more than 50% by mass, the liquid repellency may be lowered. When the ratio of the polymerized unit containing the group represented by the above formula (2) is in this range, the position of the group (2) (the group having a polyoxyalkylene group) around the polymer (A) is uniformly distributed. And the performance is stable.
在上述基(2),R11 係碳數1~5的伸烷基(alkylene),且n個存在的R11 之數目中有50~100%係伸乙基(ethylene group)為佳。伸乙基以外的R11 係以碳數3~5之伸烷基為佳,以伸丙基為特佳。又,碳數3~5的伸烷基之構造係可以是直鏈構造,亦可以是分枝構造。n個R11 之中,伸乙基以外的伸烷基的數目之比率多時,作為親水基之效果減少,顯像時氣泡不容易吸附之效果低落,致使顯像缺陷增加。n個存在的R11 之數目中有80~100%係伸乙基為更佳,特別是實質上100%為伸乙基為特佳。亦即,聚氧伸烷基鏈係以聚氧伸乙基鏈為特佳。In the above group (2), R 11 is an alkylene having 1 to 5 carbon atoms, and preferably 50 to 100% of the number of n of R 11 present is an ethylene group. The R 11 group other than the ethyl group is preferably a C 3-5 alkylene group, particularly preferably a propyl group. Further, the structure of the alkyl group having 3 to 5 carbon atoms may be a linear structure or a branched structure. Among the n R 11 , when the ratio of the number of alkyl groups other than the ethyl group is large, the effect as a hydrophilic group is reduced, and the effect that the bubbles are not easily adsorbed at the time of development is lowered, resulting in an increase in development defects. Of the n number of R 11 present, 80 to 100% of the ethyl group is more preferably ethylidene, and particularly 100% of the ethyl group is particularly preferred. That is, the polyoxyalkylene chain is particularly preferred as a polyoxyalkylene chain.
-(R11 -O)n -係含有氧伸乙基及氧伸乙基以外的氧伸烷基時,基(2)係以氧伸乙基與其他氧伸烷基之嵌段共聚合鏈為佳。-(R 11 -O) n - is an oxygen-extended alkyl group other than an oxygen-extended ethyl group and an oxygen-extended ethyl group. The group (2) is a block copolymer chain of an oxygen-extended ethyl group and another oxygen-extended alkyl group. It is better.
又,在基(2),顯示-R11 -O-所表示的氧伸烷基的重複次數之n係6~30,以8~25為佳。n為6以上時,因為具有親水性的效果,能夠改善顯像液的濕潤性且能夠抑制氣泡吸附及安定化。n為30以下時,基(2)亦即聚氧伸烷基鏈在膜表面內的存在位置係均勻分布。Further, in the group (2), the number of repetitions of the oxygen-extended alkyl group represented by -R 11 -O- is 6 to 30, preferably 8 to 25. When n is 6 or more, since it has a hydrophilic effect, the wettability of the developing liquid can be improved, and bubble adsorption and stabilization can be suppressed. When n is 30 or less, the base (2), that is, the polyoxyalkylene chain is uniformly distributed in the surface of the film.
在此,在基(2)之n,係作為在聚合物(A)之含有基(2)的聚合單元間的平均值而使用之值。Here, n in the group (2) is a value used as an average value between the polymerization units containing the group (2) of the polymer (A).
又,在基(2),鍵結於聚氧伸烷基鏈:-(R11 -O)n -之末端基:R12 係碳數1~4的烷基,以甲基為佳。鍵結於聚氧伸烷基鏈之末端基係如羥基的反應性部位時,在將其他的反應性基改性之時會同時反應,造成導入聚氧伸烷基鏈的效果有減少之可能性。又,末端基:R12 的碳數為5以上時,因為疏水性增加,導入親水基的氧伸烷基鏈之效果降低。Further, in the group (2), a terminal group bonded to the polyoxyalkylene chain: -(R 11 -O) n -: R 12 is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. When it is bonded to a reactive group such as a hydroxyl group at the terminal group of the polyoxyalkylene chain, the other reactive groups are modified at the same time, and the effect of introducing the polyoxyalkylene chain is reduced. Sex. Further, when the carbon number of the terminal group: R 12 is 5 or more, since the hydrophobicity is increased, the effect of introducing an oxygen-extended alkyl chain of the hydrophilic group is lowered.
作為在本發明所使用的聚合物(A)在側鏈所具有的乙烯性雙鍵,係沒有特別限定,可舉出(甲基)丙烯醯基、烯丙基、乙烯基、乙烯氧基等的加成聚合性基。The ethylenic double bond which the polymer (A) used in the present invention has in the side chain is not particularly limited, and examples thereof include a (meth)acryl fluorenyl group, an allyl group, a vinyl group, a vinyloxy group, and the like. Addition polymerizable group.
聚合物(A)中的乙烯性雙鍵的含量,係以1.0~5.0mmol/g為佳,以1.2~2.5mmol/g為更佳。在該範圍時,聚合物(A)至隔壁的固定化及顯像性變為良好。The content of the ethylenic double bond in the polymer (A) is preferably 1.0 to 5.0 mmol/g, more preferably 1.2 to 2.5 mmol/g. In this range, the immobilization and development of the polymer (A) to the partition walls are good.
聚合物(A)係按照必要亦可以更含有具有酸性基之側鏈。藉此,曝光時未被硬化的聚合物(A)在顯像時容易從隔壁上面被除去。因此,能夠抑制未被硬化的聚合物(A)在後烘烤時流出至開口部,能夠使開口部的親液性提升。又,聚合物(A)在側鏈所具有的酸性基,可以是1種亦可以是2種以上。The polymer (A) may further contain a side chain having an acidic group as necessary. Thereby, the polymer (A) which is not hardened at the time of exposure is easily removed from the upper surface of the partition wall at the time of development. Therefore, it is possible to suppress the unhardened polymer (A) from flowing out to the opening portion during post-baking, and it is possible to improve the lyophilicity of the opening portion. Further, the acid group of the polymer (A) in the side chain may be one type or two or more types.
作為導入聚合物(A)之酸性基,係沒有特別限定,可舉出羧基、酚性羥基、磺酸基等。又,在本發明所使用的聚合物(A),係如後述,在藉由原料單體的聚合來製造聚合物(A)時,能夠藉由相對於原料單體整體,以所得到的聚合物(A)成為以下較佳酸值的方式適當地調整具有酸性基的單體之調配量來進行。The acidic group to be introduced into the polymer (A) is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. In the polymer (A) used in the present invention, when the polymer (A) is produced by polymerization of a raw material monomer, the obtained polymer can be obtained by polymerization with respect to the entire raw material monomer. The amount of the monomer (A) to be adjusted to the following preferable acid value is appropriately adjusted by adjusting the amount of the monomer having an acidic group.
聚合物(A)的酸值係以100mgKOH/g以下為佳,以10~50mgKOH/g為更佳。酸值在該範圍時,曝光時未被固定化的聚合物(A)在顯像時容易從隔壁上面被除去。在此,酸值係用以將試料1g中和所必要的氫氧化鉀之質量[mg],在本說明書,係將單位記載為mgKOH/g。The acid value of the polymer (A) is preferably 100 mgKOH/g or less, more preferably 10 to 50 mgKOH/g. When the acid value is in this range, the polymer (A) which is not immobilized at the time of exposure is easily removed from the upper surface of the partition wall during development. Here, the acid value is the mass [mg] of potassium hydroxide necessary for neutralizing 1 g of the sample, and in the present specification, the unit is described as mgKOH/g.
又,具有酸性基之側鏈係可以藉由聚合反應來直接形成,亦可藉由聚合反應後的化學轉化來形成。Further, the side chain system having an acidic group can be directly formed by a polymerization reaction or can be formed by chemical conversion after the polymerization reaction.
在本發明,聚合物(A)係能夠藉由將具有基(1)之單體、具有基(2)之單體、具有反應性基之單體、及按照必要與具有酸性基之單體及/或其他單體共聚合而得到共聚物(聚合物(A)的前驅物),並使該共聚物與具有能夠對該共聚物所具有的反應性基進行鍵結之官能基及乙烯性雙鍵之化合物反應來合成。In the present invention, the polymer (A) can be obtained by using a monomer having a group (1), a monomer having a group (2), a monomer having a reactive group, and a monomer having an acidic group as necessary. And/or other monomers are copolymerized to obtain a copolymer (precursor of the polymer (A)), and the copolymer has a functional group and an ethyl group having a reactive group capable of bonding to the copolymer. The compound of the double bond is reacted to synthesize.
作為製造聚合物(A)所使用之具有上述基(1)的單體,係以下述通式(3)所表示的化合物為佳。該等物質係可單獨使用1種,亦可併用2種以上。The monomer having the above-mentioned group (1) used for the production of the polymer (A) is preferably a compound represented by the following formula (3). These may be used alone or in combination of two or more.
CH2 =CR4 -COO-Y-CFXRf …(3)CH 2 =CR 4 -COO-Y-CFXR f ...(3)
(式中,R4 係氫原子、氟原子、氯原子、溴原子、碘原子、甲基或三氟甲基,Y係單鍵或碳數1~6之不具有氟原子的2價有機基。-CFXRf 係相當於上述基(1)之基。亦即,X係氫原子、氟原子或三氟甲基。Rf 係亦可具有醚性氧原子之碳數1~20的氟烷基、或氟原子)(wherein R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a trifluoromethyl group, a Y-based single bond or a divalent organic group having a carbon number of 1 to 6 and having no fluorine atom; -CFXR f is a group corresponding to the above group (1), that is, an X-based hydrogen atom, a fluorine atom or a trifluoromethyl group, and the R f system may have an etheric oxygen atom and a carbon number of 1 to 20 fluorocarbon. Base or fluorine atom)
又,在上述化合物(3)之-CFXRf 的較佳態樣係與在上述關於基(1)的說明同樣。Further, the preferred aspect of the above-mentioned compound (3)-CFXR f is the same as that described above for the group (1).
在上述式(3),Y所表示的基之中,作為碳數1~6之不具有氟原子的2價有機基之Y,可舉出-R5 -、-R5 -NR6 -SO2 -、-R5 -NR6 -CO-、-CH2 CH(OH)-R7 -(R5 係碳數1~6的伸烷基,R6 係氫原子或甲基,R7 係單鍵或碳數1~4的伸烷基。但是,R6 為甲基時,鍵結在NR6 之R5 的碳數為1~5)等。Among the groups represented by the above formula (3) and Y, Y which is a divalent organic group having no fluorine atom and having 1 to 6 carbon atoms is -R 5 -, -R 5 -NR 6 -SO 2 -, -R 5 -NR 6 -CO-, -CH 2 CH(OH)-R 7 - (R 5 is an alkylene group having 1 to 6 carbon atoms, R 6 is a hydrogen atom or a methyl group, and R 7 is a A single bond or an alkylene group having 1 to 4 carbon atoms. However, when R 6 is a methyl group, the carbon number of R 5 bonded to NR 6 is 1 to 5).
作為R5 ,係具體上可舉出-CH2 -、-CH2 CH2 -、-CH(CH3 )-、-CH2 CH2 CH2 -、-C(CH3 )2 -、-CH(CH2 CH3 )-、-CH2 CH2 CH2 CH2 -、-CH(CH2 CH2 CH3 )-、-CH2 (CH2 )3 CH2 -、-CH(CH2 CH(CH3 )2 )-等。作為R7 ,係具體上可舉出-CH2 -、-CH2 CH2 -、-CH(CH3 )-、-CH2 CH2 CH2 -、-C(CH3 )2 -、-CH(CH2 CH3 )-、-CH2 CH2 CH2 CH2 -、-CH(CH2 CH2 CH3 )-等。Specific examples of R 5 include -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )-, -CH 2 CH 2 CH 2 -, -C(CH 3 ) 2 -, -CH. (CH 2 CH 3 )-, -CH 2 CH 2 CH 2 CH 2 -, -CH(CH 2 CH 2 CH 3 )-, -CH 2 (CH 2 ) 3 CH 2 -, -CH(CH 2 CH(( CH 3 ) 2 )-etc. Specific examples of R 7 include -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )-, -CH 2 CH 2 CH 2 -, -C(CH 3 ) 2 -, -CH. (CH 2 CH 3 )-, -CH 2 CH 2 CH 2 CH 2 -, -CH(CH 2 CH 2 CH 3 )-, and the like.
該等之中,作為在化合物(3)之Y,由容易取得之觀點,以碳數2~4的伸烷基為佳。Among these, as the Y of the compound (3), an alkylene group having 2 to 4 carbon atoms is preferred from the viewpoint of easy availability.
又,作為在化合物(3)之R4 ,以氫原子、氟原子、氯原子、甲基或三氟甲基為佳,以氫原子或甲基為特佳。亦即,化合物(3)係以(甲基)丙烯酸酯為特佳。Further, as R 4 of the compound (3), a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group is preferred, and a hydrogen atom or a methyl group is particularly preferred. That is, the compound (3) is particularly preferably a (meth) acrylate.
作為通式(3)所表示的化合物,係以-CFXRf 為碳數4~6的全氟烷基、且Y為碳數2~4的伸烷基之(甲基)丙烯酸酯為特佳。具體上可舉出(甲基)丙烯酸2-(全氟己基)乙酯、(甲基)丙烯酸2-(全氟丁基)乙酯等。The compound represented by the formula (3) is preferably a (meth) acrylate in which -CFXR f is a perfluoroalkyl group having 4 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms. . Specific examples thereof include 2-(perfluorohexyl)ethyl (meth)acrylate and 2-(perfluorobutyl)ethyl (meth)acrylate.
作為製造聚合物(A)所使用之具有上述基(2)的單體,以下述通式(4a)或(4b)所表示之化合物為佳。該等物質可單獨使用1種,亦可併用2種以上。As the monomer having the above-mentioned group (2) used for the production of the polymer (A), a compound represented by the following formula (4a) or (4b) is preferred. These may be used alone or in combination of two or more.
CH2 =CR10 -COO-(W-O)q -(R11 -O)n -R12 …(4a)CH 2 =CR 10 -COO-(WO) q -(R 11 -O) n -R 12 (4a)
CH2 =CR10 -O-(W-O)q -(R11 -O)n -R12 …(4b)CH 2 =CR 10 -O-(WO) q -(R 11 -O) n -R 12 (4b)
(式(4a)及(4b)中,R10 係氫原子、氯原子、溴原子、碘原子、氰基、碳數1~20的烷基、被碳數7~20的芳香基取代之烷基、碳數6~20的芳香基、或碳數3~20的環烷基。W係碳數1~10之不具有氟原子之2價的有機基。q係0或1。(R11 -O)n -R12 係相當於上述的基(2)之基。(In the formulae (4a) and (4b), R 10 is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group substituted with an aromatic group having 7 to 20 carbon atoms. a group, an aromatic group having 6 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. W is a divalent organic group having 1 to 10 carbon atoms and having no fluorine atom. q is 0 or 1. (R 11 -O) n - R 12 is a group corresponding to the above-mentioned group (2).
在上述化合物(4a)及(4b)之(R11 -O)n -R12 之較佳態樣係與在上述基(2)有關的說明同樣。The preferred aspects of (R 11 -O) n -R 12 in the above compounds (4a) and (4b) are the same as those described in the above group (2).
在化合物(4a)及(4b)之-(W-O)q -,q為0時係表示單鍵。q為1時,-(W-O)q -係在R11 側具有氧原子之有機基。q為1時,W係以碳數2~10的2價烴基為佳,以碳數2~6的伸烷基、碳數5或6的伸環烷基、在碳數5或6的伸環烷基的兩側或一側具有碳數1~2的伸烷基之合計碳數6~10之含伸環烷基的伸烷基為佳。但是,W係與R11 為同一伸烷基時,q係視為0。When -(WO) q -, q of the compounds (4a) and (4b) is 0, it means a single bond. When q is 1, -(WO) q - is an organic group having an oxygen atom on the R 11 side. When q is 1, W is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, an alkylene group having 2 to 6 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, and a stretching ratio of 5 or 6 carbon atoms. It is preferred that the alkyl group having a carbon number of 1 to 2 on both sides or one side of the cycloalkyl group has a total of from 6 to 10 carbon atoms of the cycloalkyl group. However, when the W system and R 11 are the same alkylene group, the q system is regarded as 0.
又,作為在化合物(4a)及(4b)之R10 ,係以氫原子、氟原子、氯原子、甲基或三氟甲基為佳,以氫原子或甲基為特佳。Further, R 10 of the compounds (4a) and (4b) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
而且,在製造聚合物(A)時,作為在側鏈導入基(2)之目的所使用的上述化合物(4a)及(4b),能夠使用市售品。作為此種市售品,可舉出例如BLEMMER-PME-400(商品名、日本油脂公司製、CH2 =C(CH3 )COO(CH2 CH2 O)n CH3 :式中的n係表示分子間的平均值,n為約9)、NK ESTER M-230G:(商品名、新中村化學工業公司製、CH2 =C(CH3 )COO(CH2 CH2 O)n CH3 :式中的n係表示分子間的平均值,n為約23)等。In the production of the polymer (A), a commercially available product can be used as the above-mentioned compounds (4a) and (4b) used for the purpose of introducing the group (2) into the side chain. As such a commercial item, for example, BLEMMER-PME-400 (trade name, manufactured by Nippon Oil & Fats Co., Ltd., CH 2 = C(CH 3 )COO(CH 2 CH 2 O) n CH 3 : n-type in the formula The average value between the molecules is shown, n is about 9), NK ESTER M-230G: (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH 2 = C(CH 3 )COO(CH 2 CH 2 O) n CH 3 : In the formula, n represents an average value between molecules, and n is about 23).
作為製造聚合物(A)所使用之具有反應性基之單體,係沒有特別限定,可舉出具有羥基之單體、具有乙烯性雙鍵之酸酐、具有羧基之單體、具有環氧基之單體等。該等物質可單獨使用1種,亦可併用2種以上。而且,具有反應性基之單體係以實質上不具有基(1)為佳。The monomer having a reactive group used for the production of the polymer (A) is not particularly limited, and examples thereof include a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, and an epoxy group. Monomers, etc. These may be used alone or in combination of two or more. Further, a single system having a reactive group is preferably substantially free of the group (1).
作為具有羥基之單體,可舉出(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3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸5-羥基戊酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基環己酯、新戊二醇一(甲基)丙烯酸酯、3-氯-2-羥丙基(甲基)丙烯酸酯、甘油一(甲基)丙烯酸酯、2-羥乙基乙烯醚、4-羥丁基乙烯醚、環己二醇一乙烯醚、2-羥乙基烯丙醚、N-羥甲基(甲基)丙烯醯胺、N,N-雙(羥甲基)(甲基)丙烯醯胺等。Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4- Hydroxybutyl ester, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-Chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2 - hydroxyethyl allyl ether, N-methylol (meth) acrylamide, N, N-bis(hydroxymethyl) (meth) acrylamide, and the like.
而且,具有羥基之單體亦可以具有末端為羥基之聚氧伸烷基鏈,可舉出CH2 =CHOCH2 C6 H10 CH2 O(CH2 CH2 O)k H、CH2 =CHOC4 H8 O(CH2 CH2 O)k H、CH2 =CHCOOCH2 CH2 O(CH2 CH2 O)k H、CH2 =C(CH3 )COOCH2 CH2 O(CH2 CH2 O)k H、CH2 =CHCOOCH2 CH2 O(CH2 CH2 O)m (C3 H6 O)j H、CH2 =C(CH3 )COOC2 H4 O(CH2 CH2 O)m (C3 H6 O)j H(k係1~100的整數,m係0~100的整數,j係1~100的整數,m+j係1~100)等。又,上述C6 H10 係伸環己基,C4 H8 係伸正丁基,C3 H6 係伸丙基。Further, the monomer having a hydroxyl group may have a polyoxyalkylene chain having a terminal hydroxyl group, and examples thereof include CH 2 =CHOCH 2 C 6 H 10 CH 2 O(CH 2 CH 2 O) k H, CH 2 =CHOC 4 H 8 O(CH 2 CH 2 O) k H, CH 2 =CHCOOCH 2 CH 2 O(CH 2 CH 2 O) k H,CH 2 =C(CH 3 )COOCH 2 CH 2 O(CH 2 CH 2 O) k H, CH 2 =CHCOOCH 2 CH 2 O(CH 2 CH 2 O) m (C 3 H 6 O) j H,CH 2 =C(CH 3 )COOC 2 H 4 O(CH 2 CH 2 O m (C 3 H 6 O) j H (k is an integer of 1 to 100, m is an integer of 0 to 100, j is an integer of 1 to 100, m + j is 1 to 100). Further, the above C 6 H 10 is a cyclohexyl group, the C 4 H 8 is an exobutyl group, and the C 3 H 6 is a propyl group.
k係以1~30的整數為佳,m係以0~30的整數為佳,j係以1~30的整數為佳,m+j係以1~30的整數為佳。k is preferably an integer of 1 to 30, m is preferably an integer of 0 to 30, j is preferably an integer of 1 to 30, and m+j is preferably an integer of 1 to 30.
作為具有乙烯性雙鍵之酸酐,可舉出順丁烯二酸酐、伊康酸酐、檸康酸酐、甲基-5-降烯-2,3-二羧酸酐、3,4,5,6-四氫酞酸酐、順式-1,2,3,6-四氫酞酸酐、2-丁烯-1-基-琥珀酸酐等。Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, and methyl-5-nor. Aceene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl-succinic anhydride Wait.
作為具有羧基之單體,可舉出丙烯酸、甲基丙烯酸、乙烯基乙酸、巴豆酸、伊康酸、順丁烯二酸、反丁烯二酸、桂皮酸及該等的鹽等。Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like.
作為具有環氧基之單體,可舉出(甲基)丙烯酸環氧丙酯、3,4-環氧環己基甲基丙烯酸甲酯等。Examples of the monomer having an epoxy group include glycidyl (meth)acrylate and methyl 3,4-epoxycyclohexylmethacrylate.
在製造聚合物(A),作為按照必要所使用之具有上述酸性基之單體,可舉出具有羧基之單體、具有酚性羥基之單體、具有磺酸基之單體等。該等物質係可單獨使用1種,亦可併用2種以上。而且,作為具有酸性基之單體,係使用具有羧基的單體,且作為具有反應性基的單體亦是使用具有羧基的單體時,最後未被導入乙烯性雙鍵而以羧基的形式殘留者被視作單體。In the production of the polymer (A), a monomer having a carboxyl group as required, a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, and the like can be given. These may be used alone or in combination of two or more. Further, as the monomer having an acidic group, a monomer having a carboxyl group is used, and when a monomer having a reactive group is used, a monomer having a carboxyl group is also used, and finally, an ethylenic double bond is not introduced and a carboxyl group is used. The residue is considered as a monomer.
作為具有酚性羥基之單體,可舉出鄰羥基苯乙烯、間羥基苯乙烯、對羥基苯乙烯;及該等物質的苯環之1個以上的氫原子被甲基、乙基、正丁基等的烷基、甲氧基、乙氧基、正丁氧基等的烷氧基、鹵素原子、具有1個以上的鹵素原子之鹵烷基、硝基、氰基、醯胺基取代而成之化合物等。Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene; and one or more hydrogen atoms of the benzene ring of the substance are methyl, ethyl, and n-butyl An alkoxy group such as an alkyl group, a methoxy group, an ethoxy group or a n-butoxy group, a halogen atom, a haloalkyl group having one or more halogen atoms, a nitro group, a cyano group or a decylamino group. Compounds and the like.
作為具有磺酸基之單體,可舉出乙烯基磺酸、苯乙烯磺酸、(甲基)烯丙基磺酸、2-羥基-3-(甲基)烯丙氧基丙烷磺酸、(甲基)丙烯酸2-磺酸基乙酯、(甲基)丙烯酸2-磺酸基丙酯、2-羥基-3-(甲基)丙烯醯氧基丙烷磺酸、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸等。Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, and 2-hydroxy-3-(methyl)allyloxypropanesulfonic acid. 2-sulfonic acid ethyl (meth)acrylate, 2-sulfonic acid propyl (meth)acrylate, 2-hydroxy-3-(meth)acryloxypropane sulfonic acid, 2-(methyl) Acrylamide-2-methylpropane sulfonic acid and the like.
作為在製造聚合物(A)中能夠任意地使用之上述以外的單體,可舉出烴系烯烴類、乙烯醚類、異丙烯醚類、烯丙醚類、乙烯酯類、烯丙酯類、(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、芳香族乙烯化合物、氯烯烴類、共軛二烯類、使用(甲基)丙烯醯基將一末端改性而成之線狀有機聚矽氧烷等,考慮隔壁的耐熱性時,以(甲基)丙烯酸酯類、或(甲基)丙烯醯胺類等為佳。又,該等化合物亦可具有羰基、烷氧基等的官能基。Examples of the monomer other than the above which can be arbitrarily used in the production of the polymer (A) include hydrocarbon olefins, vinyl ethers, isopropylene ethers, allyl ethers, vinyl esters, and allyl esters. , (meth) acrylates, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes, and wires modified with one end using a (meth) acrylonitrile group When considering the heat resistance of the partition wall, it is preferable to use a (meth) acrylate or a (meth) acrylamide. Further, these compounds may have a functional group such as a carbonyl group or an alkoxy group.
欲製造本發明所使用的聚合物(A),係能夠從上述說明的單體適當地選擇提供聚合之單體並以適當的比率使其共聚合。又,製造聚合物(A)時所使用之各種單體之較佳調配比率係如以下。To produce the polymer (A) used in the present invention, it is possible to appropriately select a monomer which provides polymerization from the monomer described above and copolymerize it at an appropriate ratio. Further, a preferred blending ratio of the various monomers used in the production of the polymer (A) is as follows.
相對於使其共聚合的單體之總質量,具有基(1)之單體的質量比率,係換算為在透過後述的反應性基而導入有乙烯性雙鍵的聚合物(A)之比率,以5~80質量%為佳,以25~60質量%為更佳。該比率太低時,聚合物(A)係變得難以移動至使用本發明的感光性組成物而形成的隔壁之上面附近,隔壁上面的拒液性有不充分之情形。該比率太高時,隔壁與基板的密著性有低落之情形。The ratio of the mass ratio of the monomer having the group (1) to the ratio of the polymer (A) into which the ethylenic double bond is introduced by the reactive group described later is converted to the total mass of the monomer to be copolymerized. It is preferably from 5 to 80% by mass, more preferably from 25 to 60% by mass. When the ratio is too low, the polymer (A) is difficult to move to the vicinity of the upper surface of the partition wall formed by using the photosensitive composition of the present invention, and the liquid repellency on the partition wall is insufficient. When the ratio is too high, the adhesion between the partition walls and the substrate is lowered.
相對於使其共聚合的單體之總質量,具有基(2)之單體的質量比率,係換算為在透過後述的反應性基而導入有乙烯性雙鍵的聚合物(A)之比率,以5~50質量%為佳,以10~40質量%為更佳,以15~35質量%為特佳。在該範圍時,能夠改善顯像液的濕潤性,且能夠抑制氣泡吸附及安定化。又,在膜表面內,基(2)(亦即聚氧伸烷基鏈)存在的位置係均勻分布。The ratio of the mass ratio of the monomer having the group (2) to the ratio of the polymer (A) into which the ethylenic double bond is introduced by the reactive group described later is converted to the total mass of the monomer to be copolymerized. It is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass. When it is in this range, the wettability of the developing liquid can be improved, and bubble adsorption and stabilization can be suppressed. Further, in the surface of the film, the position where the group (2) (i.e., the polyoxyalkylene chain) exists is uniformly distributed.
相對於使其共聚合的單體之總質量,具有反應性基之單體的質量比率,係換算為在透過後述的反應性基而導入有乙烯性雙鍵的聚合物(A)之比率,以5~50質量%為佳,以10~35質量%為更佳。在該範圍時,透過該反應性基並使用後述的方法導入之乙烯性雙鍵係會在聚合物(A)中存在有適當的量,具體上,係1.0~5.0mmol/g,又以1.2~2.5 mmol/g的量為更佳,聚合物(A)至隔壁的固定化及顯像性變為良好。The ratio of the mass ratio of the monomer having a reactive group to the ratio of the polymer (A) into which the ethylenic double bond is introduced by the reactive group described later is converted to the total mass of the monomer to be copolymerized. It is preferably 5 to 50% by mass, more preferably 10 to 35% by mass. In this range, the ethylenic double bond system introduced through the reactive group and introduced by the method described later may have an appropriate amount in the polymer (A), specifically, 1.0 to 5.0 mmol/g, and 1.2. The amount of ~2.5 mmol/g is more preferable, and the immobilization and development of the polymer (A) to the partition walls become good.
在共聚合時,按照必要使用具有酸性基之單體時,相對於使其共聚合單體之總質量,具有酸性基之單體質量比率為:令最後所得到的聚合物(A)的酸值為上述較佳範圍、具體上為100mgKOH/g以下、更佳是10~50mgKOH/g之比率為佳。如此的比率,雖然亦取決於具有酸性基之單體的種類,具體上係以2~20質量%為佳,以4~12質量%為更佳。在該範圍時,曝光時未被硬化的聚合物(A)係在顯像時容易被從隔壁沖洗掉。In the case of copolymerization, when a monomer having an acidic group is used as necessary, the mass ratio of the monomer having an acidic group is the acid of the finally obtained polymer (A) with respect to the total mass of the copolymerized monomer. The value is preferably in the above preferred range, specifically, in the range of 100 mgKOH/g or less, more preferably 10 to 50 mgKOH/g. Such a ratio depends on the type of the monomer having an acidic group, and is preferably 2 to 20% by mass, more preferably 4 to 12% by mass. In this range, the polymer (A) which is not hardened upon exposure is easily washed away from the partition wall during development.
在共聚合時,按照必要使用上述以外的其他單體時,相對於使其共聚合的單體之總質量,其他單體質量比率係換算為在透過後述的反應性基而導入有乙烯性雙鍵的聚合物(A)之比率,以50質量%以下為佳,以30質量%以下為更佳。該質量的比率超過50質量%時,鹼性顯像性有低落的情形。In the case of the copolymerization, if a monomer other than the above is used as necessary, the other monomer mass ratio is converted into an ethylene double in terms of the total amount of the monomer copolymerized. The ratio of the polymer (A) of the bond is preferably 50% by mass or less, more preferably 30% by mass or less. When the ratio of the mass exceeds 50% by mass, the basic developability may be lowered.
含有具有基(1)之側鏈、具有基(2)之側鏈、具有反應性基之側鏈,且按照必要含有具有酸性基之側鏈及/或其他側鏈之共聚物,係能夠藉由將具有基(1)之單體、具有基(2)之單體、具有反應性基之單體、按照必要之具有酸性基之單體及/或其他單體溶解在溶劑而加熱,並且添加聚合起始劑而使其共聚合來合成。又,使其共聚合時,係以按照必要添加鏈轉移劑為佳。又,亦可連續添加單體、聚合起始劑、溶劑及鏈轉移劑。a copolymer containing a side chain having a group (1), a side chain having a group (2), a side chain having a reactive group, and optionally containing a side chain having an acidic group and/or another side chain, can be borrowed Heating by dissolving a monomer having a group (1), a monomer having a group (2), a monomer having a reactive group, a monomer having an acidic group as necessary, and/or other monomer in a solvent, and The polymerization initiator is added and copolymerized to synthesize. Further, in the case of copolymerization, it is preferred to add a chain transfer agent as necessary. Further, a monomer, a polymerization initiator, a solvent, and a chain transfer agent may be continuously added.
作為上述共聚合所使用的溶劑,可舉出例如乙醇、1-丙醇、2-丙醇、1-丁醇、乙二醇等的醇類;丙酮、甲基異丁基酮、環己酮等的酮類;2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇等的賽路蘇類;2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、2-(2-丁氧基乙氧基)乙醇等的卡必醇類;乙酸甲酯、乙酸乙酯、乙酸正丁酯、丙醇酸乙酯、丙醇酸正丁酯、乙二醇一甲基醚乙酸酯、丙二醇一甲基醚乙酸酯、乙二醇二乙酸酯、甘油三乙酸酯等的酯類;二伸乙甘醇二甲基醚、二伸乙甘醇甲基乙基醚等。Examples of the solvent used in the copolymerization include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; acetone, methyl isobutyl ketone, and cyclohexanone. Ketones such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; 2-(2-methoxyethoxy)ethanol, 2-(2) - ethoxylated alcohols such as ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl propionate, Esters of n-butyl alkanolate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, triacetin, etc.; diethylene glycol Methyl ether, diethylene glycol ethyl methyl ether, and the like.
作為聚合起始劑,可舉出眾所周知的有機過氧化物、無機過氧化物、偶氮化合物等。有機過氧化物、無機過氧化物亦可與還原劑組合而使用作為氧化還原觸媒。該等聚合起始劑係可單獨使用1種,亦可併用2種以上。As a polymerization initiator, a well-known organic peroxide, an inorganic peroxide, an azo compound, etc. are mentioned. An organic peroxide or an inorganic peroxide may be used in combination with a reducing agent as a redox catalyst. These polymerization initiators may be used alone or in combination of two or more.
作為有機過氧化物,可舉出過氧化苯甲醯、過氧化月桂醯、過氧化異丁醯、第三丁基過氧化氫、過氧化第三丁基-α-異丙苯等。作為無機過氧化物,可舉出過硫酸銨、過硫酸鈉、過硫酸鉀、過氧化氫、過碳酸鹽等。作為偶氮化合物可舉出2,2’-偶氮雙異丁腈、1,1’-偶氮雙(環己烷-1-腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丁腈)、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙丁酸二甲酯、2,2’-偶氮雙(2-脒基丙烷)二鹽酸鹽等。Examples of the organic peroxide include benzammonium peroxide, laurel peroxide, isobutylammonium peroxide, t-butyl hydroperoxide, and tert-butyl-α-isopropylbenzene peroxide. Examples of the inorganic peroxide include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonate. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis (2,4-). Dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-dimethyl azobisbutyrate, 2,2'-azobis(2-amidinopropane) dihydrochloride, and the like.
作為鏈轉移劑,可舉出正丁基硫醇、正十二烷基硫醇、第三丁基硫醇、巰乙酸乙酯、巰乙酸2-乙基己酯、2-氫硫基乙醇等的硫醇類;氯仿、四氯化碳、四溴化碳等的鹵烷(alkyl halide)。Examples of the chain transfer agent include n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl acetate, 2-ethylhexyl acetate, 2-hydrogenthioethanol, and the like. Mercaptans; alkyl halides such as chloroform, carbon tetrachloride, and carbon tetrabromide.
聚合物(A)係能夠藉由使如此進行而得到之當作聚合物(A)的前驅物之共聚物、與具有能夠對該共聚物所具有的反應性基進行鍵結的官能基及乙烯性雙鍵之化合物進行反應來合成。The polymer (A) is a copolymer which can be obtained as a precursor of the polymer (A), a functional group having a reactive group capable of bonding to the copolymer, and ethylene. The compound of the double bond is reacted to synthesize.
針對上述共聚物所具有的反應性基,其與具有能夠對該反應性基進行鍵結的官能基與乙烯性雙鍵之化合物之組合,可舉出例如以下的組合。The combination of the reactive group of the above-mentioned copolymer and a compound having a functional group capable of bonding the reactive group to an ethylenic double bond may, for example, be the following combination.
(a)對羥基、具有乙烯性雙鍵之酸酐、(a) a hydroxyl group, an anhydride having an ethylenic double bond,
(b)對羥基、具有異氰酸酯基及乙烯性雙鍵之化合物、(b) a compound having a hydroxyl group, an isocyanate group, and an ethylenic double bond,
(c)對羥基、具有醯氯(acyl chloride)基及乙烯性雙鍵之化合物、(c) a compound having a hydroxyl group, an acyl chloride group and an ethylenic double bond,
(d)對酸酐、具有羥基及乙烯性雙鍵之化合物、(d) an acid anhydride, a compound having a hydroxyl group and an ethylenic double bond,
(e)對羧基、具有環氧基及乙烯性雙鍵之化合物、(e) a compound having a carboxyl group, an epoxy group, and an ethylenic double bond,
(f)對環氧基、具有羧基及乙烯性雙鍵之化合物。(f) a compound having an epoxy group, a carboxyl group, and an ethylenic double bond.
作為上述(a)組合中具有乙烯性雙鍵之酸酐,能夠使用在前述具有反應性基之單體所例示者。作為上述(b)組合中具有異氰酸酯基及乙烯性雙鍵之化合物,可舉出2-(甲基)丙烯醯氧基異氰酸乙酯、1,1-雙((甲基)丙烯醯氧基甲基)異氰酸乙酯等。作為上述(c)組合中具有醯氯基及乙烯性雙鍵之化合物,可舉出(甲基)丙烯醯氯等。As the acid anhydride having an ethylenic double bond in the above (a) combination, those exemplified as the above-mentioned monomer having a reactive group can be used. Examples of the compound having an isocyanate group and an ethylenic double bond in the above (b) combination include ethyl 2-(methyl) propylene oxy isocyanate and 1,1-bis ((meth) propylene oxyfluoride). Methyl) isocyanate ethyl ester or the like. Examples of the compound having a fluorenyl group and an ethylenic double bond in the above (c) combination include (meth) acrylonitrile and the like.
作為上述(d)組合中具有羥基及乙烯性雙鍵之化合物,能夠使用在前述具有羥基之單體所例示者。作為上述(e)組合中具有環氧基及乙烯性雙鍵之化合物,能夠使用在前述具有環氧基之單體所例示者。作為上述(f)組合中具有羧基及乙烯性雙鍵之化合物,能夠使用在前述具有羧基之單體所例示者。又,如上述(f)的反應等,利用反應後所產生的羥基等之反應性基,並且按照必要進而使用以酸酐等反應而成者亦可。As the compound having a hydroxyl group and an ethylenic double bond in the above (d) combination, those exemplified as the monomer having a hydroxyl group can be used. As the compound having an epoxy group and an ethylenic double bond in the above (e) combination, those exemplified as the above-mentioned monomer having an epoxy group can be used. As the compound having a carboxyl group and an ethylenic double bond in the above (f) combination, those exemplified as the monomer having a carboxyl group can be used. In addition, as the reaction of the above (f), a reactive group such as a hydroxyl group generated after the reaction may be used, and if necessary, an acid anhydride or the like may be used.
又,在使含有具有基(1)之側鏈、具有基(2)之側鏈、具有反應性基之側鏈、及按照必要之具有酸性基之側鏈之共聚物、與具有能夠對反應性基進行鍵結之官能基及乙烯性雙鍵之化合物反應時,相對於上述共聚物的反應性基,具有能夠對上述反應性基進行鍵結之官能基及乙烯性雙鍵之化合物之當量比係以0.5~2.0為佳,以0.8~1.5為更佳。該當量比係在該範圍時,將夠將在聚合物(A)之乙烯性雙鍵的含量設為上述較佳範圍、具體上係1.0~5.0mmol/g、更佳是1.2~2.5 mmol/g之量。該當量比小於0.5時,在聚合物(A)之乙烯性雙鍵的含量不能成為適當的量,聚合物(A)難以被固定化在隔壁的上面附近,被隔壁包圍之開口部的親液性有不充分的情形,超過2.0時,未反應的化合物變多,隔壁的外觀有低落的情形。Further, a copolymer containing a side chain having a group (1), a side chain having a group (2), a side chain having a reactive group, and a side chain having an acidic group as necessary, and a reaction capable of reacting When the compound having a functional group bonded to the ethylenic double bond is reacted with a compound having a functional group capable of bonding the reactive group and a compound having an ethylenic double bond with respect to the reactive group of the copolymer The ratio is preferably 0.5 to 2.0, more preferably 0.8 to 1.5. When the equivalent ratio is in this range, the content of the ethylenic double bond in the polymer (A) is sufficient to be the above preferred range, specifically 1.0 to 5.0 mmol/g, more preferably 1.2 to 2.5 mmol/ The amount of g. When the equivalent ratio is less than 0.5, the content of the ethylenic double bond in the polymer (A) cannot be an appropriate amount, and the polymer (A) is hardly immobilized in the vicinity of the upper surface of the partition wall, and the lyophilic portion of the opening surrounded by the partition wall is lyophilic. In the case where the properties are insufficient, when the amount exceeds 2.0, the amount of unreacted compounds increases, and the appearance of the partition wall is low.
聚合物(A)係能夠藉由使含有具有基(1)之側鏈、具有基(2)之側鏈、具有反應性基之側鏈、及按照必要之具有酸性基之側鏈之共聚物、及具有能夠對該共聚物所具有的反應性基進行鍵結之官能基及乙烯性雙鍵之化合物,溶解於按照上述(a)~(f)的組合之溶劑,並使用按照各組合之先前已知的條件使其反應來合成。The polymer (A) is a copolymer capable of containing a side chain having a side chain of the group (1), a side chain having a group (2), a side chain having a reactive group, and a side chain having an acidic group as necessary And a compound having a functional group capable of bonding the reactive group of the copolymer and an ethylenic double bond, dissolved in a solvent according to the combination of the above (a) to (f), and used in accordance with each combination The previously known conditions allow the reaction to be synthesized.
本發明的感光性組成物的總固體成分中之聚合物(A)的含量,係以0.07~1質量%的比率含有為佳,以0.1~0.5質量%的比率含有為更佳。聚合物(A)的含量係小於0.07質量%時,使用本發明的感光性組成物而形成的隔壁的上面之拒液性有不充分的情形,含量超過1質量%時,隔壁與基板的密著性有低落的情形。The content of the polymer (A) in the total solid content of the photosensitive composition of the present invention is preferably from 0.07 to 1% by mass, more preferably from 0.1 to 0.5% by mass. When the content of the polymer (A) is less than 0.07% by mass, the liquid repellency of the upper surface of the partition wall formed by using the photosensitive composition of the present invention may be insufficient. When the content exceeds 1% by mass, the partition wall and the substrate are dense. There is a low level of sexuality.
作為本發明的感光性組成物所含有的光聚合起始劑(B),係能夠沒有特別限制地使用在通常的自由基硬化型感光性組成物所使用的光聚合起始劑。The photopolymerization initiator (B) contained in the photosensitive composition of the present invention can be used without any particular limitation as a photopolymerization initiator used in a general radical-curable photosensitive composition.
作為光聚合起始劑(B)係只要是藉由照射光線來產生自由基之化合物,沒有特別限制,可舉出苯偶醯、聯乙醯、乙醛酸甲基苯酯、9,10-菲醌等的α-二酮類;苯偶姻等的醯偶姻(acyloin)類;苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚等的醯偶姻醚(acyloin ether)類;9-氧硫(thioxanthone)、2-氯9-氧硫、2-甲基9-氧硫、2,4-二甲基9-氧硫、異丙基9-氧硫、2,4-二乙基9-氧硫、2,4-二氯9-氧硫、2,4-二異丙基9-氧硫、9-氧硫-4-磺酸等的9-氧硫類;二苯基酮、4,4’-雙(二甲胺基)二苯基酮、4,4’-雙(二乙胺基)二苯基酮等的二苯基酮類;苯乙酮、2-(4-甲苯磺醯氧基)-2-苯基苯乙酮、對二甲胺基苯乙酮、2,2’-二甲氧基-2-苯基苯乙酮、對甲氧基苯乙酮、2-甲基-[4-(甲硫基)苯基]-2-啉-1-丙酮、2-苄基-2-二甲胺基-1-(4-啉苯基)-丁烷-1-酮等的苯乙酮類;蒽醌、2-乙基蒽醌、樟腦醌、1,4-萘醌等的醌類;2-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸(正丁氧基)乙酯、4-二甲胺基苯甲酸異戊酯、4-二甲胺基苯甲酸2-乙基己酯等的胺基苯甲酸類;苯甲醯甲基氯(phenacyl chloride)、三鹵甲基苯基碸等的鹵素化合物;醯基氧化膦類;過氧化二-第三丁基等的過氧化物;1-[4-(苯硫基)-1,2-辛二酮2-(0-苯甲醯肟)]、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑基-3-基]-乙酮-1-(O-乙醯肟),亦可併用2種以上。The photopolymerization initiator (B) is not particularly limited as long as it is a compound which generates a radical by irradiation with light, and examples thereof include benzoin, acetonide, methylphenyl glyoxylate, 9,10- A-diketones such as phenanthrene; acyloin of benzoin; acetoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (acyloin ether) class; 9-oxygen sulfur (thioxanthone), 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur 9-oxosulfuric acid such as 4-sulfonic acid Diphenyl ketones such as diphenyl ketone, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone; Ketone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, pair Methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2- Phenyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- Acetophenones such as phenylphenyl)-butan-1-one; anthraquinones such as hydrazine, 2-ethylhydrazine, camphorquinone, and 1,4-naphthoquinone; 2-dimethylaminobenzoic acid Ethyl ester, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzene Aminobenzoic acid such as 2-ethylhexyl formate; halogen compound such as phenacyl chloride or trihalomethylphenylhydrazine; fluorenylphosphine oxide; a peroxide such as butyl; 1-[4-(phenylthio)-1,2-octanedione 2-(0-benzamide)], 1-[9-ethyl-6-(2) -Methylbenzylidene)-9H-carbazolyl-3-yl]-ethanone-1-(O-acetamidine), or two or more types may be used in combination.
該等之中,作為本發明所使用的光聚合起始劑(B),係以下述通式(5)所表示的化合物為佳。Among these, the photopolymerization initiator (B) used in the present invention is preferably a compound represented by the following formula (5).
[化1][Chemical 1]
(式中,R21 係氫原子、碳數1~12的烷基、碳數3~8的環烷基、碳數2~5的烯基、被烷基取代或非取代之碳數6~20的苯基或是被烷基取代或非取代之碳數6~20的苯氧基,R22 係氫原子、碳數1~20的烷基、碳數3~8的環烷基、被烷基取代或取代之碳數6~20的苯基、碳數2~20的烷醯基、被烷基取代或非取代之碳數7~20的苯甲醯基、碳數2~12之烷氧基羰基或是被烷基取代或非取代之碳數7~20的苯氧基羰基,R23 係碳數1~12的烷基,R24 、R25 、R26 及R27 係各自獨立地為氫原子、碳數1~12的烷基、被烷基取代或非取代之碳數3~8的環己基、被烷基取代或非取代之碳數6~20的苯基、碳數2~20的烷醯基、被烷基取代或非取代之碳數7~20的苯甲醯基、被烷基取代或非取代之碳數7~20的苄基羰基、被烷基取代或非取代之碳數2~12的烷氧基羰基、被烷基取代或非取代之碳數7~20的苯氧基羰基、碳數1~20的醯胺基或硝基。)(wherein R 21 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group substituted or unsubstituted with 6 to 6 carbon atoms; A phenyl group of 20 is a phenoxy group having 6 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group, a hydrogen atom of R 22 , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a phenyl group. a phenyl group having 6 to 20 carbon atoms substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzamidine group having 7 to 20 carbon atoms substituted or unsubstituted, or a carbon number of 2 to 12 The alkoxycarbonyl group is an alkyl group substituted or unsubstituted phenyloxycarbonyl group having 7 to 20 carbon atoms, R 23 is an alkyl group having 1 to 12 carbon atoms, and R 24 , R 25 , R 26 and R 27 are each Independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group having 3 to 8 carbon atoms substituted or unsubstituted with an alkyl group, a phenyl group having 6 to 20 carbon atoms substituted or unsubstituted, or carbon 2 to 20 alkyl alkane groups, alkyl substituted or unsubstituted benzylidene groups having 7 to 20 carbon atoms, alkyl substituted or unsubstituted benzylcarbonyl groups having 7 to 20 carbon atoms, substituted by alkyl groups Or an unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, an alkyl group substituted or unsubstituted, and having 7 to 20 carbon atoms Phenoxycarbonyl group, acyl group or nitro group having a carbon number 1 to 20)
在通式(5)所表示之化合物,作為R21 ,係以碳數1~10的烷基或被烷基取代或非取代之碳數6~12的苯基為佳,可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、苯基等。該等之中,以碳數1~4的烷基為佳,以碳數1或2的烷基為更佳,以甲基為特佳。The compound represented by the formula (5), preferably R 21 , is an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms substituted or unsubstituted, and a methyl group is exemplified. , ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, phenyl, and the like. Among these, an alkyl group having 1 to 4 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is particularly preferred.
在通式(5)所表示的化合物,作為R22 ,係以碳數1~10的烷基或碳數2~5的烷氧基羰基為佳,例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、甲氧基羰基、乙氧基羰基、丙氧基羰基。其中,以碳數1~6的烷基為佳,以碳數1~3的烷基為更佳,以甲基為特佳。The compound represented by the formula (5), preferably R 22 , is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group or a butyl group. Base, pentyl, hexyl, heptyl, octyl, decyl, decyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl. Among them, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is particularly preferred.
在通式(5)所表示的化合物,作為R23 所表示之碳數1~12的烷基,可舉出例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基等。該等之中,以碳數1~8的烷基為佳,以碳數2~6的烷基為更佳,以乙基為特佳。The compound represented by the formula (5), and the alkyl group having 1 to 12 carbon atoms represented by R 23 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group. Octyl, decyl, decyl, undecyl, dodecyl and the like. Among these, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 2 to 6 carbon atoms is more preferred, and ethyl is particularly preferred.
在通式(5)所表示的化合物,作為R24 、R26 及R27 ,係以氫原子為佳。In the compound represented by the formula (5), as R 24 , R 26 and R 27 , a hydrogen atom is preferred.
在通式(5)所表示的化合物,作為R25 ,係以被烷基取代或非取代之碳數7~20的苯甲醯基或是被烷基取代或非取代之碳數7~20的苄基羰基為佳,以2-甲基苯甲醯基、苄基羰基、或1,3,5-三甲基苄基羰基為特佳。The compound represented by the formula (5), as R 25 , is an alkyl substituted or unsubstituted benzylidene group having 7 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 7 to 20 carbon atoms. The benzylcarbonyl group is preferably a 2-methylbenzhydryl group, a benzylcarbonyl group or a 1,3,5-trimethylbenzylcarbonyl group.
作為在通式(5)所表示的化合物(O-醯肟系化合物)係沒有特別限定,在通式(5),可舉出R21 為苯基、R22 為辛基、R23 為乙基、R24 、R26 及R27 為氫原子、R25 為苯甲醯基之化合物;R21 為甲基、R22 為丁基、庚基或辛基、R23 為乙基、R24 、R26 及R27 為氫原子、R25 為苯甲醯基之化合物;R21 為苯基、R22 為辛基、R23 為乙基、R24 、R26 及R27 為氫原子、R25 為2-甲基苯甲醯基之化合物;R21 為甲基、R22 為甲基或辛基、R23 為乙基、R24 、R26 及R27 為氫原子、R25 為2-甲基苯甲醯基之化合物;R21 及R22 為甲基、R23 為乙基、R24 、R26 及R27 為氫原子、R25 為2-甲基-5-四氫呋喃基甲氧基苯甲醯基、2-甲基-4-四氫呋喃基甲氧基苯甲醯基或2-甲基-5-四氫呋喃基甲氧基苯甲醯基之化合物等。The compound (O-anthracene compound) represented by the formula (5) is not particularly limited, and in the formula (5), R 21 is a phenyl group, R 22 is an octyl group, and R 23 is an alkyl group. a compound wherein R 24 , R 26 and R 27 are a hydrogen atom and R 25 is a benzamidine group; R 21 is a methyl group; R 22 is a butyl group, a heptyl group or an octyl group, and R 23 is an ethyl group; R 24 R 26 and R 27 are a hydrogen atom, and R 25 is a benzamidine group; R 21 is a phenyl group; R 22 is an octyl group; R 23 is an ethyl group; and R 24 , R 26 and R 27 are a hydrogen atom; R 25 is a 2-methylbenzhydryl group; R 21 is a methyl group; R 22 is a methyl group or an octyl group; R 23 is an ethyl group; R 24 , R 26 and R 27 are a hydrogen atom, and R 25 is a compound of 2-methylbenzhydryl; R 21 and R 22 are methyl, R 23 is ethyl, R 24 , R 26 and R 27 are a hydrogen atom, and R 25 is a 2-methyl-5-tetrahydrofuranyl group. A compound of methoxybenzimidyl, 2-methyl-4-tetrahydrofurylmethoxybenzylidene or 2-methyl-5-tetrahydrofuranylmethoxybenzylidene.
作為光聚合起始劑(B),能夠使用市售品。作為市售品,可舉出例如OXE02(商品名、CIBA SPECIALTY CHEMICALS公司製、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑基-3-基]-乙酮-1-(O-乙醯肟):在上述通式(5),R21 及R22 為甲基、R23 為乙基、R24 、R26 及R27 為氫原子、R25 為2-甲基苯甲醯基之化合物)。A commercially available product can be used as the photopolymerization initiator (B). As a commercial item, for example, OXE02 (trade name, manufactured by CIBA SPECIALTY CHEMICALS, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazolyl-3-yl) -Ethyl ketone-1-(O-acetamidine): in the above formula (5), R 21 and R 22 are a methyl group, R 23 is an ethyl group, and R 24 , R 26 and R 27 are a hydrogen atom. R 25 is a compound of 2-methylbenzhydryl group).
在本發明的感光性組成物的總固體成分中之光聚合起始劑(B)的含量,係以1~10質量%為佳,以2~5質量%為更佳。在該範圍時,硬化性良好且藉由曝光、顯像能夠形成接近光罩圖案之圖案和線寬。The content of the photopolymerization initiator (B) in the total solid content of the photosensitive composition of the present invention is preferably from 1 to 10% by mass, more preferably from 2 to 5% by mass. In this range, the hardenability is good, and the pattern and line width close to the mask pattern can be formed by exposure and development.
又,與光聚合起始劑(B)同時使用2-氫硫基苯并咪唑、2-氫硫基苯并唑、2-氫硫基苯并噻唑、1,4-丁醇雙(3-氫硫基丁酸酯)、參(2-甲基氫硫基丙醯氧基乙基)異三聚氰酸酯、新戊四醇肆(3-氫硫基丁酸酯)等的硫醇化合物時,有顯現敏化之效果。Further, 2-hydroxythiobenzimidazole and 2-hydrothiobenzoate are simultaneously used together with the photopolymerization initiator (B). Azole, 2-hydrothiobenzothiazole, 1,4-butanol bis(3-hydrothiobutyrate), ginseng (2-methylhydrothiopropenyloxyethyl)isocyanuric acid When a thiol compound such as an ester or neopentyl sterol (3-hydrogenthiobutyrate) exhibits sensitization effect.
本發明的感光性組成物所含有的感光性樹脂(C),係具有酸性基及乙烯性雙鍵之感光性樹脂,且係藉由上述光聚合起始劑(B)所產生的自由基來聚合、硬化而形成塗膜硬化物,而該塗膜硬化物係能夠鹼性顯像。The photosensitive resin (C) contained in the photosensitive composition of the present invention is a photosensitive resin having an acidic group and an ethylenic double bond, and is a radical generated by the photopolymerization initiator (B). The film is cured and hardened to form a cured film, and the cured film is capable of alkaline development.
因為感光性樹脂(C)係在1分子內具有酸性基及乙烯性雙鍵,能夠使用鹼性顯像液來選擇性地除去未被硬化的感光性組成物之未曝光部,其結果,能夠形成隔壁。又,感光性樹脂(C)係聚合物(A)以外的化合物,以實質上不具有基(1)為佳。Since the photosensitive resin (C) has an acidic group and an ethylenic double bond in one molecule, it is possible to selectively remove the unexposed portion of the photosensitive composition which is not cured by using an alkaline developing solution. Form the next door. Further, the compound other than the photosensitive resin (C)-based polymer (A) preferably contains no group (1).
作為具有感光性樹脂(C)之酸性基,係沒有特別限定,可舉出羧基、酚性羥基、磺酸基、磷酸基等,亦可併用2種以上。The acidic group having the photosensitive resin (C) is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group, and two or more kinds thereof may be used in combination.
作為感光性樹脂(C)所具有的乙烯性雙鍵,係沒有特別限定,可舉出(甲基)丙烯醯基、烯丙基、乙烯基、乙烯氧基等的加成聚合性基所具有的雙鍵,亦可併用2種以上。而且,該等加成聚合性基所具有之氫原子的一部分或全部亦可被烴基、較佳是甲基取代。The ethylenic double bond of the photosensitive resin (C) is not particularly limited, and examples thereof include an addition polymerizable group such as a (meth)acryl fluorenyl group, an allyl group, a vinyl group, or a vinyloxy group. Two or more types of double bonds can be used in combination. Further, part or all of the hydrogen atoms of the addition polymerizable group may be substituted with a hydrocarbon group, preferably a methyl group.
作為感光性樹脂(C)係沒有特別限定,具體上可舉出含有具有酸性基之側鏈及具有乙烯性雙鍵之側鏈之樹脂(C-1)、在環氧樹脂導入乙烯性雙鍵及酸性基而成之樹脂(C-2)等。該等物質可單獨使用1種,亦可併用2種以上。The photosensitive resin (C) is not particularly limited, and specific examples thereof include a resin (C-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an ethylenic double bond introduced into the epoxy resin. And an acid-based resin (C-2). These may be used alone or in combination of two or more.
樹脂(C-1)係除了不使用具有具有基(1)的單體的單體以外,能夠與聚合物(A)同樣地進行來合成。又,作為具有磷酸基之單體,係沒有特別限定,可舉出2-(甲基)丙烯醯氧基乙烷磷酸等。The resin (C-1) can be synthesized in the same manner as the polymer (A) except that the monomer having the monomer having the group (1) is not used. In addition, the monomer having a phosphate group is not particularly limited, and examples thereof include 2-(meth)acryloxymethoxyethane phosphate.
樹脂(C-2)係例如能夠藉由使環氧基與具有羧基及乙烯性雙鍵之化合物反應後,使其與多元性羧酸或其酐反應來合成。具體上能夠藉由使環氧樹脂與具有羧基及乙烯性雙鍵之化合物反應,羧基與環氧樹脂的環氧基反應而導入乙烯性雙鍵。隨後,能夠藉由使導入乙烯性雙鍵後之樹脂的羥基與多元性羧酸或其酐反應來導入羧基。The resin (C-2) can be synthesized, for example, by reacting an epoxy group with a compound having a carboxyl group and an ethylenic double bond, and then reacting it with a polyvalent carboxylic acid or an anhydride thereof. Specifically, an epoxy resin can be reacted with a compound having a carboxyl group and an ethylenic double bond, and a carboxyl group can be reacted with an epoxy group of the epoxy resin to introduce an ethylenic double bond. Subsequently, the carboxyl group can be introduced by reacting a hydroxyl group of the resin into which the ethylenic double bond is introduced with a polyvalent carboxylic acid or an anhydride thereof.
作為環氧樹脂係沒有特別限定,可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、參酚甲烷型環氧樹脂、具有萘骨架之環氧樹脂、下述通式(6)所表示之具有聯苯骨架之環氧樹脂、下述通式(7)所表示之環氧樹脂、下述通式(8)所表示之環氧樹脂等。The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, and phenolic methane ring. An epoxy resin, an epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (6), an epoxy resin represented by the following formula (7), and the following formula (8) ) The epoxy resin represented by the like.
[化2][Chemical 2]
(式中,s係1~50,以2~10為佳)(In the formula, s is 1 to 50, preferably 2 to 10)
[化3][Chemical 3]
(式中,R31 、R32 、R33 及R34 係各自獨立地為氫原子、氯原子或碳數1~5的烷基,t係0~10)(wherein R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and t is 0 to 10)
[化4][Chemical 4]
(式(8)中,苯環的氫原子係各自獨立地亦可被碳數1~12的烷基、鹵素原子、或亦可具有取代基之苯基取代。u係0~10)(In the formula (8), the hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent. The system is 0 to 10)
而且,通式(6)、通式(7)或通式(8)所表示之環氧樹脂、與具有羧基及乙烯性雙鍵之化合物反應後,使其與多元性羧酸酐反應時,作為多元性羧酸酐,係以使用二羧酸酐及四羧酸二酐的混合物為佳。此時,藉由使二羧酸酐與四羧酸二酐的比率變化,能夠控制分子量。Further, when an epoxy resin represented by the formula (6), the formula (7) or the formula (8) is reacted with a compound having a carboxyl group and an ethylenic double bond, and then reacted with a polyvalent carboxylic anhydride, The polyvalent carboxylic anhydride is preferably a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride. At this time, the molecular weight can be controlled by changing the ratio of the dicarboxylic anhydride to the tetracarboxylic dianhydride.
作為在環氧樹脂導入酸性基及乙烯性雙鍵而成之樹脂(C-2)的市售品,可舉出KAYARAD PCR-1069、K-48C、CCR-1105、CCR-1115、CCR-1163H、CCR-1166H、CCR-1159H、TCR-1025、TCR-1064H、TCR-1286H、ZAR-1535H、ZFR-1122H、ZFR-1124H、ZFR-1185H、ZFR-1492H、ZCR-1571H、ZCR-1569H、ZCR-1580H、ZCR-1581H、ZCR-1588H、ZCR-1629H(以上、日本化藥公司製)等。Commercial products of a resin (C-2) obtained by introducing an acidic group and an ethylenic double bond into an epoxy resin include KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, and CCR-1163H. , CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR -1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H (above, manufactured by Nippon Kayaku Co., Ltd.).
在本發明所使用的上述感光性樹脂(C),係質量平均分子量以1.5×103 ~20×103 為佳,以2.0×103 ~15×103 為更佳。該質量平均分子量小於1.5×103 時,曝光時的硬化係不充分,超過20×103 時,顯像性有低落的情形。The photosensitive resin (C) used in the present invention preferably has a mass average molecular weight of from 1.5 × 10 3 to 20 × 10 3 and more preferably from 2.0 × 10 3 to 15 × 10 3 . When the mass average molecular weight is less than 1.5 × 10 3 , the curing at the time of exposure is insufficient, and when it exceeds 20 × 10 3 , the development property may be lowered.
感光性樹脂(C)所具有的乙烯性雙鍵之數目係在平均1分子內以3個以上為佳,以6個以上為更佳。該乙烯性雙鍵的數目為3個以上時,容易增加曝光部分與未曝光部分之鹼溶解度差異,能夠以較少的曝光量來形成微細的圖案。The number of the ethylenic double bonds of the photosensitive resin (C) is preferably 3 or more in an average of 1 molecule, and more preferably 6 or more. When the number of the ethylenic double bonds is three or more, the difference in alkali solubility between the exposed portion and the unexposed portion is easily increased, and a fine pattern can be formed with a small amount of exposure.
感光性樹脂(C)係酸值以10~300mgKOH/g為佳,以30~150mgKOH/g為更佳。酸值在該範圍時,感光性組成物的顯像性良好。The photosensitive resin (C) preferably has an acid value of 10 to 300 mgKOH/g, more preferably 30 to 150 mgKOH/g. When the acid value is in this range, the developability of the photosensitive composition is good.
在本發明的感光性組成物的總固體成分中之感光性樹脂(C)的含量,係以5~80質量%為佳,以10~60質量%為更佳。感光性樹脂(C)的含量在該範圍時,感光性組成物的顯像性良好。The content of the photosensitive resin (C) in the total solid content of the photosensitive composition of the present invention is preferably from 5 to 80% by mass, more preferably from 10 to 60% by mass. When the content of the photosensitive resin (C) is within this range, the developability of the photosensitive composition is good.
在本發明的感光性組成物,係將上述聚合物(A)、光聚合起始劑(B)、及具有酸性基及乙烯性雙鍵的感光性樹脂(C)設為必要成分而含有,但是在不損害本發明效果的範圍,能夠將提升各種功能設為目的而含有以下說明的任意成分。In the photosensitive composition of the present invention, the polymer (A), the photopolymerization initiator (B), and the photosensitive resin (C) having an acidic group and an ethylenic double bond are contained as essential components. However, it is possible to include any component described below for the purpose of improving various functions without impairing the effects of the present invention.
在本發明之感光性組成物,亦可按照必要而含有具有2個以上的乙烯性雙鍵之交聯劑(D)。藉此,感光性樹脂的硬化性提升,能夠減少形成隔壁時之曝光量。The photosensitive composition of the present invention may contain a crosslinking agent (D) having two or more ethylenic double bonds as necessary. Thereby, the curability of the photosensitive resin is improved, and the amount of exposure when the partition walls are formed can be reduced.
作為交聯劑(D),係沒有特別限定,以具有2~10個(甲基)丙烯醯氧基之化合物為佳。具體上可舉出二伸乙甘醇二(甲基)丙烯酸酯、四伸乙甘醇二(甲基)丙烯酸酯、三伸丙甘醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(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、雙三羥甲基丙烷四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、乙氧基化異三聚氰酸三丙烯酸酯、胺甲酸酯丙烯酸酯等,亦可併用2種以上。The crosslinking agent (D) is not particularly limited, and a compound having 2 to 10 (meth) acryloxy groups is preferred. Specific examples thereof include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and neopentyl glycol di( Methyl) acrylate, 1,9-nonanediol di(meth) acrylate, trimethylolpropane di(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol Tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated iso-cyanuric acid triacrylate, amine A Two or more kinds of ester acrylates and the like may be used in combination.
作為上述交聯劑(D)之市售品,可舉出KAYARAD DPHA(商品名、日本化藥公司製、二新戊四醇五丙烯酸酯與二新戊四醇六丙烯酸酯之混合物)、NK酯A-9300(商品名、新中村化學工業公司製、乙氧基化異三聚氰酸三丙烯酸酯)、NK酯A-9300-1CL(商品名、新中村化學工業公司製、ε-己內酯改性異三聚氰酸參(2-丙烯醯氧基乙基)酯)、BANI-M(商品名、丸善石油化學公司製、雙[4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺)苯基]甲烷)、BANI-X(商品名、丸善石油化學公司製、N,N’-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺))等。The commercially available product of the above-mentioned crosslinking agent (D) includes KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK. Ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ε-己Lactone modified isocyanuric acid (2-propenyloxyethyl) ester, BANI-M (trade name, Maruzen Petrochemical Co., Ltd., bis [4-(allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxylimenine)phenyl]methane), BANI-X (trade name, Maruzen Petrochemical Co., Ltd., N,N'-m-xylylene-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine)) and the like.
又,作為胺甲酸酯丙烯酸酯,可舉出日本化藥公司製KAYARADUX系列,作為具體上的商品名,可舉出UX-3204、UX-6101、UX-0937、DPHA-40H、UXE-3501、UX-5000、UX-5002D-P20等。Further, the urethane acrylate may be a KAYARADUX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, and UXE-3501. , UX-5000, UX-5002D-P20 and so on.
在本發明的感光性組成物的總固體成分中之交聯劑(D)的含量,係以5~50質量%為佳,以10~30質量%為更佳。交聯劑(D)的含量在此範圍時,感光性組成物的圖案形狀變為良好。The content of the crosslinking agent (D) in the total solid content of the photosensitive composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the crosslinking agent (D) is in this range, the pattern shape of the photosensitive composition becomes good.
在本發明之感光性組成物,亦可具有而添加著色劑(E)。例如,本發明的感光性組成物之硬化物係被使用於如黑色矩陣被要求遮光性之用途時,能夠按照被要求之隔壁的光學濃度而使用黑色著色劑(E)。作為黑色著色劑(E),係沒有特別限定,可舉出碳黑、苯胺黑、蒽醌系黑色顏料、苝(perylene)系黑色顏料等。具體上可舉出C.I.顏料黑1、6、7、12、20、31等。又,黑色著色劑(E)亦可以是紅色顏料、藍色顏料、綠色顏料等有機顏料和無機顏料之混合物。該等之中,考慮遮光性大小時,以碳黑為佳。又,碳黑亦可以使用樹脂等表面處理。又,為了調整黑色著色劑(E)的色調,能夠將碳黑與藍色顏料和紫色顏料併用。The photosensitive composition of the present invention may have a coloring agent (E) added thereto. For example, when the cured product of the photosensitive composition of the present invention is used for applications in which a black matrix is required to have light shielding properties, a black coloring agent (E) can be used in accordance with the optical density of a desired partition wall. The black coloring agent (E) is not particularly limited, and examples thereof include carbon black, aniline black, an anthraquinone black pigment, and a perylene black pigment. Specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31 and the like can be mentioned. Further, the black colorant (E) may be a mixture of an organic pigment such as a red pigment, a blue pigment, or a green pigment, and an inorganic pigment. Among these, carbon black is preferred in consideration of the light-shielding property. Further, carbon black may be treated with a surface treatment such as a resin. Further, in order to adjust the color tone of the black colorant (E), carbon black can be used in combination with a blue pigment and a violet pigment.
又,作為著色劑(E)所使用的碳黑,係藉由BET法之比表面積以50~200m2 /g為佳。該比表面積太小時,有造成隔壁的形狀劣化之情形,比表面積太大時,後述的分散助劑會過度地吸附在黑色著色劑(E),而產生必須添加大量的分散助劑之情形。Further, the carbon black used as the colorant (E) is preferably 50 to 200 m 2 /g by the specific surface area of the BET method. When the specific surface area is too small, the shape of the partition wall is deteriorated. When the specific surface area is too large, the dispersing aid described later is excessively adsorbed on the black coloring agent (E), and a large amount of dispersing aid must be added.
而且,考慮感光性組成物之曝光敏感度時,作為著色劑(E)所使用的碳黑,其酞酸二丁酯的吸油量係以120cc/100g以下為佳,以較小者為更佳。Further, in consideration of the exposure sensitivity of the photosensitive composition, the carbon black used as the colorant (E) preferably has an oil absorption of dibutyl phthalate of 120 cc/100 g or less, more preferably a smaller one. .
又,作為著色劑(E)所使用的碳黑,其平均一次粒徑係以20~50nm為佳。該平均一次粒徑太小時,在高濃度變為難以使其分散,而有難以得到經時安定性良好的感光性組成物的情形,平均一次粒徑太大時,有造成隔壁的形狀劣化之情形。又,該碳黑係平均二次粒徑以80~200nm為佳。在此,碳黑的粒徑能夠使用透射型電子顯微鏡來測定。Further, the carbon black used as the colorant (E) preferably has an average primary particle diameter of 20 to 50 nm. When the average primary particle diameter is too small, it is difficult to disperse it at a high concentration, and it is difficult to obtain a photosensitive composition having good stability over time. When the average primary particle diameter is too large, the shape of the partition wall is deteriorated. situation. Further, the carbon black-based average secondary particle diameter is preferably from 80 to 200 nm. Here, the particle diameter of carbon black can be measured using a transmission electron microscope.
在本發明的感光性組成物的總固體成分中之著色劑(E)的含量,係在不損害本發明效果的範圍能夠依照著色劑(E)被要求的功能而適當地選擇。例如由本發明之感光性組成物所形成的塗膜硬化物中,調配用以對該塗膜硬化物賦予如黑色矩陣的遮光性之黑色的著色劑(E)時,著色劑(E)的含量係亦取決於被要求的遮光性、光學濃度,相對於組成物的總固體成分,以15~60質量%為佳,以20~50質量%為更佳,以25~40質量%為特佳。此時,黑色的著色劑(E)的含量太少時,隔壁的光學濃度有不足的情形,含量太多時,有感光性組成物的硬化性低落、隔壁的外觀低落、拒液性低落之情形。The content of the coloring agent (E) in the total solid content of the photosensitive composition of the present invention can be appropriately selected in accordance with the function required for the coloring agent (E) insofar as the effects of the present invention are not impaired. For example, when the coloring agent (E) for imparting a black color-blocking black coloring agent (E) to the cured film of the coating film is prepared by the photosensitive film formed of the photosensitive composition of the present invention, the content of the coloring agent (E) It is also preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 40% by mass, based on the required light-shielding property and optical density. . In this case, when the content of the black coloring agent (E) is too small, the optical density of the partition wall may be insufficient. When the content is too large, the curing property of the photosensitive composition is lowered, the appearance of the partition wall is lowered, and the liquid repellency is lowered. situation.
在本發明之感光性組成物,係以含有用以提升上述黑色著色劑(E)的分散性之高分子分散劑為佳。作為高分子分散劑係沒有特別限定,可舉出胺甲酸酯系、聚醯亞胺系、醇酸系、環氧系、聚酯系、三聚氰胺系、酚系、丙烯酸系、聚醚系、氯乙烯系、氯乙烯乙酸乙烯酯系共聚物系、聚醯胺系、聚碳酸酯系等,其中,以胺甲酸酯系、或聚酯系為佳。又,高分子分散劑亦可具有氧伸乙基及氧伸丙基。The photosensitive composition of the present invention preferably contains a polymer dispersant for enhancing the dispersibility of the black colorant (E). The polymer dispersant is not particularly limited, and examples thereof include an urethane type, a polyimide type, an alkyd type, an epoxy type, a polyester type, a melamine type, a phenol type, an acrylic type, and a polyether type. Examples of the vinyl chloride-based, vinyl chloride-vinyl acetate-based copolymer, polyamine-based, and polycarbonate-based compounds are preferably urethane-based or polyester-based. Further, the polymer dispersant may have an oxygen-extended ethyl group and an oxygen-extended propyl group.
考慮對上述黑色著色劑等的著色劑(E)之親和性時,高分子分散劑係以具有鹼性基為佳。作為鹼性基,係沒有特別限定,可舉出1級、2級或3級的胺基。In consideration of the affinity for the coloring agent (E) such as the above black coloring agent, the polymer dispersing agent preferably has a basic group. The basic group is not particularly limited, and examples thereof include amine groups of the first, second or third stage.
作為高分子分散劑的市售品,可舉出例如DISPARLON DA-7301(楠本化成公司製)、BYK161、BYK162、BYK163、BYK182(以上、BYK-Chemie公司製)、SOLSPERSE 5000、SOLSPERSE 17000(以上、ZENECA公司製)等。As a commercial product of a polymer dispersing agent, for example, DISPARLON DA-7301 (manufactured by Nanben Chemical Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (above, BYK-Chemie), SOLSPERSE 5000, SOLSPERSE 17000 (above, ZENECA company) and so on.
相對於上述黑色著色劑等的著色劑(E),高分子分散劑的添加量係以5~30質量%為佳,以10~25質量%為更佳。該添加量太少時,提高分散性之效果有變為不充分之情形,添加量太多時,顯像性有低落之情形。The amount of the polymer dispersant to be added is preferably from 5 to 30% by mass, more preferably from 10 to 25% by mass, based on the coloring agent (E) of the black colorant or the like. When the amount of addition is too small, the effect of improving the dispersibility may be insufficient, and when the amount of addition is too large, the development property may be lowered.
又,本發明之感光性組成物,亦可含有酞菁系顏料衍生物和金屬酞菁磺醯胺化合物作為分散助劑。認為分散助劑係吸附在上述黑色著色劑等的著色劑(E)及高分子分散劑而具有使其提升分散安定性之功能。Further, the photosensitive composition of the present invention may further contain a phthalocyanine-based pigment derivative and a metal phthalocyanine sulfonamide compound as a dispersing aid. It is considered that the dispersing agent is adsorbed to the coloring agent (E) such as the black coloring agent and the polymer dispersing agent, and has a function of improving dispersion stability.
本發明之感光性組成物,係按照必要亦可含有微粒子。藉此,在後述之後烘烤時能夠抑制隔壁的形狀變化。The photosensitive composition of the present invention may contain fine particles as necessary. Thereby, it is possible to suppress the shape change of the partition wall at the time of post-baking described later.
作為微粒子,係沒有特別限定,可舉出二氧化矽、氧化鋯、氟化鎂、ITO(錫摻雜氧化銦)、ATO(銻摻雜氧化錫)等的無機系微粒子;聚乙烯、PMMA(聚甲基丙烯酸甲酯)等的有機系微粒子。作為微粒子,考慮耐熱性時,以無機系微粒子為佳,考慮取得容易性和分散安定性時,以二氧化矽、或氧化鋯為佳。又,感光性組成物係含有上述黑色著色劑等的著色劑(E)及用以使其分散性提升之高分子分散劑時,考慮該高分子分散劑的吸附能力時,微粒子係以帶負電為佳。而且,考慮感光性組成物的曝光敏感度時,微粒子係以不吸收曝光時所照射的光線為佳,以不吸收超高壓水銀燈的主發光波長,亦即i射線(365nm)、h射線(405nm)、g射線(436nm)為特佳。The fine particles are not particularly limited, and examples thereof include inorganic fine particles such as cerium oxide, zirconium oxide, magnesium fluoride, ITO (tin-doped indium oxide), and ATO (yttrium-doped tin oxide); polyethylene and PMMA ( Organic fine particles such as polymethyl methacrylate. When the heat resistance is considered as the fine particles, inorganic fine particles are preferable, and in view of ease of availability and dispersion stability, cerium oxide or zirconium oxide is preferred. Further, when the photosensitive composition contains the coloring agent (E) such as the above black coloring agent and the polymer dispersing agent for improving the dispersibility, the fine particles are negatively charged in consideration of the adsorption ability of the polymer dispersing agent. It is better. Further, in consideration of the exposure sensitivity of the photosensitive composition, the fine particles are preferably not absorbed by the light irradiated during exposure, so as not to absorb the main emission wavelength of the ultrahigh pressure mercury lamp, that is, i-ray (365 nm), h-ray (405 nm). ), g-ray (436 nm) is particularly good.
就隔壁的表面平滑性變為良好而言,微粒子的平均粒徑係以1μm以下為佳,以200nm以下為更佳。The surface smoothness of the partition walls is good, and the average particle diameter of the fine particles is preferably 1 μm or less, more preferably 200 nm or less.
在本發明的感光性組成物的總固體成分中之微粒子的含量,係以3~20質量%為佳,以5~15質量%為更佳。該含量太少時,在後烘烤時隔壁的形狀有變化之情形,含量太多時,感光性組成物的分散安定性有低落的情形。The content of the fine particles in the total solid content of the photosensitive composition of the present invention is preferably from 3 to 20% by mass, more preferably from 5 to 15% by mass. When the content is too small, the shape of the partition wall may change during post-baking, and when the content is too large, the dispersion stability of the photosensitive composition may be lowered.
本發明之感光性組成物,係按照必要亦可含有矽烷偶合劑。藉此,能夠使隔壁與基板的密著性提升。The photosensitive composition of the present invention may contain a decane coupling agent as necessary. Thereby, the adhesion between the partition wall and the substrate can be improved.
作為矽烷偶合劑,係沒有特別限定。具體上可舉出四乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、甲基三甲氧基矽烷、乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷、十七氟辛基乙基三甲氧基矽烷、N-苯基-3-胺丙基三甲氧基矽烷、具有三乙氧基矽烷基之聚氧乙烯、咪唑矽烷等,亦可併用2種以上。The decane coupling agent is not particularly limited. Specific examples thereof include tetraethoxydecane, 3-glycidoxypropyltrimethoxydecane, methyltrimethoxydecane, vinyltrimethoxydecane, and 3-methylpropenyloxypropyltrimethyl. Oxydecane, 3-chloropropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, heptadecafluorooctyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxy Further, two or more kinds may be used in combination with a decyl alkane, a polyoxyethylene having a triethoxyalkylene group, an imidazolium or the like.
本發明的感光性組成物係按照必要亦可含有磷酸化合物。藉此,能夠提升隔壁與基板的密著性。The photosensitive composition of the present invention may contain a phosphoric acid compound as necessary. Thereby, the adhesion between the partition wall and the substrate can be improved.
作為磷酸化合物,可舉出一(甲基)丙烯醯氧基磷酸乙酯、二(甲基)丙烯醯氧基磷酸乙酯、三(甲基)丙烯醯氧基磷酸乙酯等。Examples of the phosphoric acid compound include mono(meth)acryloxyethyl phosphate, di(meth)acryloxyethyl phosphate, and tris(meth)acryloxyethyl phosphate.
在本發明之感光性組成物,係按照必要亦可含有熱硬化劑。藉此,能夠提升隔壁的耐熱性、耐透水性。The photosensitive composition of the present invention may contain a thermosetting agent as necessary. Thereby, the heat resistance and water permeability of the partition walls can be improved.
作為熱硬化劑,係沒有特別限定,可舉出胺基樹脂、具有2個以上的環氧基之化合物、具有2個以上的肼基之化合物、聚碳化二亞胺化合物、具有2個以上的唑啉基之化合物、具有2個以上的吖環丙烷之化合物、多價金屬類、具有2個以上的氫硫基之化合物、聚異氰酸酯化合物等,亦可併用2種以上。其中,考慮隔壁的耐藥品性時,以胺基樹脂、具有2個以上的環氧基之化合物或具有2個以上的唑啉之化合物為佳。The thermosetting agent is not particularly limited, and examples thereof include an amine-based resin, a compound having two or more epoxy groups, a compound having two or more mercapto groups, a polycarbodiimide compound, and two or more. A compound having an oxazoline group, a compound having two or more indole cyclopropanes, a polyvalent metal, a compound having two or more hydrogenthio groups, a polyisocyanate compound, or the like may be used in combination of two or more kinds. In the case of considering the chemical resistance of the partition wall, an amine-based resin, a compound having two or more epoxy groups, or two or more compounds may be used. The compound of oxazoline is preferred.
又,在本發明之感光性組成物,係除了上述各種成分以外,亦可按照必要含有硬化促進劑、增黏劑、可塑劑、消泡劑、調平劑、防收縮斑劑、紫外線吸收劑等。Further, in the photosensitive composition of the present invention, in addition to the above various components, a curing accelerator, a tackifier, a plasticizer, an antifoaming agent, a leveling agent, an anti-shrinking agent, and an ultraviolet absorber may be contained as necessary. Wait.
在本發明之感光性組成物,能夠藉由將上述說明的各種必要成分及按照必要之任意成分,依照上述調配量使用通常的方法均勻地混合來調製。The photosensitive composition of the present invention can be prepared by uniformly mixing the various essential components described above and any necessary components in accordance with the above-described blending amount by a usual method.
使用本發明的感光性組成物來形成隔壁時,在使用以溶劑稀釋感光性組成物而成的稀釋液形成塗膜(濕潤膜)後,以將溶劑揮發除去來形成感光性組成物的塗膜為佳。When a partition film is formed by using the photosensitive composition of the present invention, a coating film (wet film) is formed by using a diluent obtained by diluting the photosensitive composition with a solvent, and then the solvent is volatilized and removed to form a coating film of the photosensitive composition. It is better.
作為稀釋感光性組成物之溶劑係沒有特別限定。具體上可舉出乙醇、1-丙醇、2-丙醇、1-丁醇、乙二醇等的醇類;丙酮、甲基異丁基酮、環己酮等的酮類;2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇等的賽路蘇類;2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、2-(2-丁氧基乙氧基)乙醇等的卡必醇類;乙酸甲酯、乙酸乙酯、乙酸正丁酯、丙醇酸乙酯、丙醇酸正丁酯、乙二醇一甲基醚乙酸酯、乙二醇一乙基醚乙酸酯、乙二醇一丁基醚乙酸酯、二伸乙甘醇一甲基醚乙酸酯、二伸乙甘醇一乙基醚乙酸酯、二伸乙甘醇一丁基醚乙酸酯、丙二醇一甲基醚乙酸酯、乙二醇二乙酸酯、丙二醇二乙酸酯、3-乙氧基丙酸乙酯、環己醇乙酸酯、乳酸乙酯、乳酸正丁酯、γ-丁內酯、3-甲氧基乙酸丁酯、3-甲基-3-甲氧基乙酸丁酯、甘油三乙酸酯等的酯類;二伸乙甘醇二甲基醚、二伸乙甘醇二乙基醚、二伸乙甘醇二丁基醚、三伸乙甘醇二甲基醚、四伸乙甘醇二甲基醚、丙二醇二甲基醚、二伸丙甘醇二甲基醚、二丁基醚、二伸乙甘醇甲基乙基醚等的醚類,亦可併用2種以上。The solvent system for diluting the photosensitive composition is not particularly limited. Specific examples thereof include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; and ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Cypresses such as oxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy) Carbitol such as ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl propionate, n-butyl propionate, ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Ethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, 3-ethoxypropionic acid Ethyl ester, cyclohexanol acetate, ethyl lactate, n-butyl lactate, γ-butyrolactone, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, glycerol Esters such as acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, three Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, etc. The ethers may be used in combination of two or more.
又,以溶劑稀釋感光性組成物而成的稀釋液,係以感光性組成物濃度亦即固體成分濃度成為5~40質量%的方式調製為佳,以成為10~25質量%的方式調製為更佳。In addition, it is preferable to prepare a dilution liquid in which the photosensitive composition is diluted with a solvent, and the concentration of the photosensitive component is 5 to 40% by mass, and is adjusted to 10 to 25% by mass. Better.
本發明的隔壁係使用上述本發明之感光性組成物的塗膜硬化物,且係被形成為將基板分隔成複數個像素形成用間隔之狀態者,能夠應用在彩色濾光片和有機EL元件的黑色矩陣等。In the partition wall of the present invention, the cured film of the photosensitive composition of the present invention is used, and the substrate is formed into a plurality of pixel formation intervals, and can be applied to a color filter and an organic EL element. Black matrix and so on.
以下,作為製造本發明的隔壁的方法之一個例子,係說明有關使用本發明的感光性組成物藉由微影術步驟來製造隔壁之方法。Hereinafter, as an example of a method of producing the partition wall of the present invention, a method of producing a partition wall by a lithography step using the photosensitive composition of the present invention will be described.
首先,將本發明的感光性組成物的稀釋液塗布在基板。作為基板,係沒有特別限定,可舉出各種玻璃板;SiC基板、矽等的無機基板;ITO等的無機氧化物基板;聚酯(聚對酞酸乙二酯等)、聚烯烴(聚乙烯、聚丙烯等)、聚碳酸酯、聚甲基丙烯酸甲酯、聚碸、聚醯亞胺、聚(甲基)丙烯酸樹脂等的熱塑性樹脂片;環氧樹脂、不飽和聚酯等的熱硬化性樹脂之硬化片等。考慮耐熱性時,作為基板,係以玻璃板及聚醯亞胺等的耐熱性樹脂為佳。又,因為能夠從基板之未形成有隔壁之側的面曝光之觀點,基板係以透明為佳。而且,基板亦可以是在玻璃基板等的透明基板上,形成有機膜或TFT、ITO、SiO2 等的無機氧化物膜而成之基板或經圖案化之基板,亦可為將該等基板積層之積層基板。First, a diluent of the photosensitive composition of the present invention is applied onto a substrate. The substrate is not particularly limited, and examples thereof include various glass plates, inorganic substrates such as SiC substrates and tantalum, inorganic oxide substrates such as ITO, polyester (polyethylene terephthalate or the like), and polyolefin (polyethylene). , polypropylene, etc.), thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, polyfluorene, polyimine, poly(meth)acrylic resin, etc.; thermosetting of epoxy resin, unsaturated polyester, etc. Hardened sheet of resin, etc. When heat resistance is considered, it is preferable to use a heat resistant resin such as a glass plate or a polyimide. Further, since the surface of the substrate on which the partition wall is not formed can be exposed, the substrate is preferably transparent. Further, the substrate may be a substrate obtained by forming an organic film, an inorganic oxide film such as TFT, ITO or SiO 2 on a transparent substrate such as a glass substrate, or a patterned substrate, or may be laminated on the substrate. The laminated substrate.
作為塗布方法,係沒有特別限定,可舉出旋轉塗布法、噴霧法、狹縫塗布法、輥塗布法、轉動塗布法、棒塗布法等。The coating method is not particularly limited, and examples thereof include a spin coating method, a spray method, a slit coating method, a roll coating method, a spin coating method, and a bar coating method.
隨後,將在基板所形成的塗膜乾燥。藉此,因為將溶劑揮發,能夠得到無黏著性的感光性組成物之塗膜。作為乾燥方法,係沒有特別限定,可舉出真空乾燥、加熱乾燥。為了不產生塗膜外觀不均且能夠效率良好地使其乾燥,以併用真空乾燥及加熱乾燥為佳。乾燥條件係依照在感光性組成物所含有的成分之種類、組成等而異,真空乾燥係以10~500Pa(絕對壓力)進行10~300秒為佳,加熱乾燥係以50~120℃進行10~2000秒為佳。Subsequently, the coating film formed on the substrate is dried. Thereby, since the solvent is volatilized, a coating film of the non-adhesive photosensitive composition can be obtained. The drying method is not particularly limited, and examples thereof include vacuum drying and heat drying. In order to prevent the appearance of the coating film from being uneven and to dry it efficiently, it is preferred to use vacuum drying and heat drying in combination. The drying conditions vary depending on the type and composition of the components contained in the photosensitive composition, and vacuum drying is preferably carried out at 10 to 500 Pa (absolute pressure) for 10 to 300 seconds, and heat drying is carried out at 50 to 120 ° C. ~ 2000 seconds is better.
隨後,透過預定圖案的光罩而將塗膜曝光。作為曝光時所照射的光線係沒有特別限定,可舉出可見光、紫外線、遠紫外線、KrF準分子雷射、ArF準分子雷射、F2 準分子雷射、Kr2 準分子雷射、KrAr準分子雷射、Ar2 準分子雷射等的準分子雷射、X射線、電子射線等。波長係以100~600nm的光線為佳,波長係以300~500nm的光線為更佳,以i射線(365nm)、h射線(405nm)、g射線(436nm)為特佳。而且,作為光源,能夠使用眾所周知的超高壓水銀燈等。Subsequently, the coating film is exposed through a mask of a predetermined pattern. The light to be irradiated is not particularly limited, and examples thereof include visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, and KrAr Excimer lasers such as molecular lasers, Ar 2 excimer lasers, X-rays, electron beams, and the like. The wavelength is preferably 100 to 600 nm, and the wavelength is preferably 300 to 500 nm, and particularly preferably i rays (365 nm), h rays (405 nm), and g rays (436 nm). Further, as the light source, a well-known ultrahigh pressure mercury lamp or the like can be used.
曝光量係通常以i射線基準為5~1000mJ/cm2 ,以10~400mJ/cm2 為佳,以20~200mJ/cm2 為更佳,以50~100mJ/cm2 為特佳。曝光量為小於5mJ/cm2 時,塗膜的硬化變為不充分,顯像性有低落之情形,超過1000mJ/cm2 時,有無法得到高解像度之情形。The exposure amount is usually 5 to 1000 mJ/cm 2 on an i-ray basis, preferably 10 to 400 mJ/cm 2 , more preferably 20 to 200 mJ/cm 2 , and particularly preferably 50 to 100 mJ/cm 2 . When the amount of exposure is less than 5 mJ/cm 2 , the curing of the coating film is insufficient, and the development property is lowered. When the amount is more than 1000 mJ/cm 2 , a high resolution cannot be obtained.
隨後,使用顯像液而除去塗膜的未曝光部來顯像。作為顯像液係沒有特別限定,可舉出無機鹼類、胺類、烷醇胺類、第4級銨鹽等鹼的水溶液。顯像時間亦即使其接觸顯像液之時間係以5~180秒為佳。作為顯像方法,係沒有特別限定,可舉出液體盛裝法、浸漬法、噴淋法等。Subsequently, the unexposed portion of the coating film was removed using a developing solution to develop. The developing liquid system is not particularly limited, and examples thereof include an aqueous solution of an alkali such as an inorganic base, an amine, an alkanolamine or a fourth-order ammonium salt. The development time is preferably 5 to 180 seconds even if it is in contact with the developing solution. The development method is not particularly limited, and examples thereof include a liquid holding method, a dipping method, and a shower method.
又,在顯像後,進行流水洗淨,並藉由使用壓縮空氣和壓縮氮氣使其風乾,能夠除去基板上的水分。Further, after development, the running water was washed, and air was dried by using compressed air and compressed nitrogen gas to remove moisture on the substrate.
隨後,亦可對被顯像後的隔壁進行後曝光。此時,可從形成有隔壁之側及未形成有隔壁之側的面的任一者進行曝光,亦可從兩面進行曝光。曝光時所照射的光線係以紫外線為佳。Subsequently, post-exposure of the partition wall after development can also be performed. At this time, exposure may be performed from any of the side on which the partition wall is formed and the side on which the partition wall is not formed, and exposure may be performed from both surfaces. The light that is irradiated during exposure is preferably ultraviolet light.
作為光源,能夠使用眾所周知的超高壓水銀燈、高壓水銀燈等。該等光源係發射有助於隔壁硬化之波長600nm以下的光線,且成為隔壁氧化分解的原因之波長為200nm以下的光線係發射較少者。而且,在光源所使用的石英管玻璃係以具有阻隔200nm以下的光線之功能為佳。As the light source, a well-known ultrahigh pressure mercury lamp, a high pressure mercury lamp, or the like can be used. These light sources emit light having a wavelength of 600 nm or less which contributes to the hardening of the partition walls, and the light having a wavelength of 200 nm or less which causes oxidative decomposition of the partition walls is less likely to emit light. Further, it is preferable that the quartz tube glass used in the light source has a function of blocking light of 200 nm or less.
曝光量係通常為50mJ/cm2 以上,以200mJ/cm2 以上為佳,以1000mJ/cm2 以上為佳,以2000mJ/cm2 以上為特佳。The exposure amount is usually 50 mJ/cm 2 or more, preferably 200 mJ/cm 2 or more, more preferably 1000 mJ/cm 2 or more, and particularly preferably 2,000 mJ/cm 2 or more.
又,作為光源,亦可使用低壓水銀燈,因為低壓水銀燈係發射較多波長為200nm以下的光線,曝光量以500mJ/cm2 以下為佳,以300mJ/cm2 以下為更佳。Further, as the light source, a low-pressure mercury lamp can be used. Since the low-pressure mercury lamp emits a large amount of light having a wavelength of 200 nm or less, the exposure amount is preferably 500 mJ/cm 2 or less, and more preferably 300 mJ/cm 2 or less.
在顯像後(進行後曝光時,係後曝光後),以將隔壁加熱為佳。加熱條件係以在150~250℃、5~90分鐘為佳,加熱溫度係以180℃以上為更佳。加熱溫度太低時,有耐藥品性不充分之情形,且在隔壁塗布油墨時,有隔壁膨脹、或油墨滲透之情形。另一方面,加熱溫度太高時,有隔壁產生熱分解之情形。After the development (after the post-exposure, after the post-exposure), it is preferred to heat the partition walls. The heating conditions are preferably 150 to 250 ° C for 5 to 90 minutes, and the heating temperature is preferably 180 ° C or higher. When the heating temperature is too low, there is a case where the chemical resistance is insufficient, and when the ink is applied to the partition wall, the partition wall is swollen or the ink is infiltrated. On the other hand, when the heating temperature is too high, there is a case where the partition wall is thermally decomposed.
作為加熱裝置,能夠使用加熱板、烘箱等。As the heating device, a hot plate, an oven, or the like can be used.
藉由經過如以上的微影術步驟而使本發明的感光性組成物硬化,能夠形成本發明的隔壁。在本發明的隔壁,按照必要而藉由在其製造所使用的感光性組成物調配黑色著色劑(E),能夠構成呈黑色之黑色矩陣。此時,藉由使用感光性組成物而形成隔壁,來形成黑色矩陣。The partition wall of the present invention can be formed by curing the photosensitive composition of the present invention by the lithography step as described above. In the partition wall of the present invention, a black colorant (E) can be formed by a photosensitive composition used for the production as necessary, thereby forming a black matrix in black. At this time, a black matrix is formed by forming a partition wall using a photosensitive composition.
本發明的隔壁,其寬度(平均值)係以100μm以下為佳,以20μm以下為更佳。又,相鄰接的隔壁之間的距離、亦即開口部的寬度(平均值)係以300μm以下為佳,以100μm以下為更佳。而且,隔壁的高度(平均值)係以0.05~50μm為佳,以0.2~10μm為更佳。The partition wall of the present invention preferably has a width (average value) of 100 μm or less and more preferably 20 μm or less. Further, the distance between the adjacent partition walls, that is, the width (average value) of the opening portion is preferably 300 μm or less, more preferably 100 μm or less. Further, the height (average value) of the partition walls is preferably 0.05 to 50 μm, more preferably 0.2 to 10 μm.
通常,作為由感光性組成物的塗膜硬化物所構成之隔壁的拒液性(拒油墨性),可舉出拒水性及拒油性,各自能夠藉由水及PGMEA(丙二醇一甲基醚乙酸酯:多半被使用作油墨的溶劑之有機溶劑)的接觸角來評價。本發明的隔壁之上面,其水接觸角係以90°~150°為佳,以95°~120°為更佳。又,隔壁之上面,其PGMEA接觸角係以35°~55°為佳,以40°~50°為更佳。In general, the liquid repellency (ink repellency) of the partition wall composed of the cured film of the photosensitive composition is water repellency and oil repellency, and each of them can be water and PGMEA (propylene glycol monomethyl ether B). The contact angle of the acid ester: mostly used as an organic solvent of a solvent for the ink was evaluated. The water contact angle of the upper surface of the partition wall of the present invention is preferably 90 to 150, and more preferably 95 to 120. Further, the PGMEA contact angle of the upper surface of the partition wall is preferably 35 to 55, and more preferably 40 to 50.
本發明的彩色濾光片,係在基板上具有複數像素、及位於相鄰接像素之間之隔壁,其特徵為前述隔壁係使用上述本發明的隔壁所形成。又,在本發明的彩色濾光片,隔壁係以光學濃度為2~7左右的黑色矩陣為佳。The color filter of the present invention has a plurality of pixels on a substrate and a partition wall between adjacent pixels, and the partition wall is formed by using the partition wall of the present invention. Further, in the color filter of the present invention, the partition wall is preferably a black matrix having an optical density of about 2 to 7.
本發明的彩色濾光片係如前述,能夠藉由在基板上形成隔壁、例如黑色矩陣後,例如使用噴墨法在隔壁的開口部塗布油墨而形成像素來製造。As described above, the color filter of the present invention can be produced by forming a partition wall, for example, a black matrix on a substrate, and then forming an ink by applying ink to the opening of the partition wall by, for example, an inkjet method.
作為噴墨法,係沒有特別限定,可舉出藉由連續地噴射帶電的油墨並以磁場控制之方法;使用壓電元件而間歇地噴射油墨之方法;及將油墨加熱並利用其發泡而間歇地噴射之方法等。The inkjet method is not particularly limited, and examples thereof include a method of continuously ejecting charged ink and controlling by a magnetic field, a method of intermittently ejecting ink using a piezoelectric element, and heating and foaming the ink. A method of intermittently spraying, and the like.
作為像素的配列,係沒有特別限定,可舉出條紋型、馬賽克型、三角型、4像素配置型等眾所周知的配列。The arrangement of the pixels is not particularly limited, and examples thereof include well-known arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.
油墨係主要含有著色成分、黏合劑樹脂成分及溶劑,且水性油墨及油性油墨之任一者均可。作為著色成分,以耐熱性、耐光性等優良的顏料及/或染料為佳。作為黏合劑樹脂成分,以透明且耐熱性優良的樹脂為佳,可舉出丙烯酸樹脂、三聚氰胺樹脂、胺甲酸酯樹脂等。水性油墨係以水作為溶劑且按照必要含有水溶性有機溶劑,且含有水溶性樹脂及/或水分散性樹脂作為黏合劑樹脂成分。又,油性油墨係含有有機溶劑作為溶劑,且含有對有機溶劑可溶的樹脂作為黏合劑樹脂成分。The ink system mainly contains a coloring component, a binder resin component, and a solvent, and may be any of an aqueous ink and an oil ink. As the coloring component, a pigment and/or a dye excellent in heat resistance and light resistance are preferred. The resin component which is excellent in transparency and heat resistance is preferable as the binder resin component, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The aqueous ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin and/or a water-dispersible resin as a binder resin component. Further, the oil-based ink contains an organic solvent as a solvent and contains a resin soluble in an organic solvent as a binder resin component.
又,使用噴墨法在隔壁、例如黑色矩陣的開口部塗布油墨後,能夠按照必要而進行乾燥、加熱硬化、紫外線硬化等來形成像素。Further, after the ink is applied to the partition walls, for example, the openings of the black matrix by the inkjet method, the pixels can be formed by drying, heat curing, ultraviolet curing, or the like as necessary.
而且,在隔壁(黑色矩陣)的開口部形成像素之後,能夠按照必要而形成保護膜。藉此,在使彩色濾光片的表面平滑性提升之同時,能夠隔離來自隔壁(黑色矩陣)和像素的溶出物到達鄰接的液晶層。Further, after the pixels are formed in the openings of the partition walls (black matrix), the protective film can be formed as necessary. Thereby, while the surface smoothness of the color filter is improved, it is possible to isolate the eluted substances from the partition walls (black matrix) and the pixels from reaching the adjacent liquid crystal layer.
此時,在形成保護膜之前,以除去隔壁(黑色矩陣)上面的拒液性為佳。藉此,能夠抑制隔壁(黑色矩陣)的上面沾不上保護膜用的塗布液之情形。作為除去隔壁(黑色矩陣)的上面之拒液性之方法,沒有特別限定,可舉出電漿灰化處理、光灰化處理等。At this time, it is preferable to remove the liquid repellency on the partition wall (black matrix) before forming the protective film. Thereby, it is possible to suppress the case where the coating liquid for the protective film is not stained on the upper surface of the partition wall (black matrix). The method for removing the liquid repellency of the upper surface of the partition wall (black matrix) is not particularly limited, and examples thereof include a plasma ashing treatment and a light ashing treatment.
而且,為了將使用本發明的彩色濾光片而製造的液晶面板高品質化,亦可按照必要而在隔壁、例如黑色矩陣上形成光間隙子。Further, in order to improve the quality of the liquid crystal panel manufactured by using the color filter of the present invention, a light spacer may be formed on a partition wall such as a black matrix as necessary.
本發明的有機EL元件,係在基板上具有複數像素、及位於相鄰接像素之間之隔壁,其特徵為前述隔壁係使用上述本發明的隔壁所形成,且前述像素係使用噴墨法形成者。The organic EL device of the present invention has a plurality of pixels on a substrate and a partition wall between adjacent pixels, wherein the partition wall is formed using the partition wall of the present invention, and the pixel is formed by an inkjet method. By.
本發明的有機EL元件係能夠如以下進行來製造。首先,使用濺鍍法等在玻璃基板等的透明基板形成ITO等的透明電極,並且按照必要將透明電極蝕刻成所需要的圖案。隨後,與彩色濾光片時同樣地進行,在基板上形成隔壁、例如黑色矩陣後,例如使用噴墨法在隔壁(黑色矩陣)的開口部依照順序塗布作為油墨之電洞輸送材料的溶液及發光材料的溶液並乾燥,來形成電洞輸送層及發光層。而且,藉由使用蒸鍍法等形成鋁等的電極且形成像素,能夠得到有機EL元件。The organic EL device of the present invention can be produced as follows. First, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate by a sputtering method or the like, and the transparent electrode is etched into a desired pattern as necessary. Subsequently, in the same manner as in the case of the color filter, after forming a partition wall, for example, a black matrix on the substrate, for example, a solution of the hole transporting material as an ink is applied in order to the opening of the partition (black matrix) by an inkjet method. The solution of the luminescent material is dried to form a hole transport layer and a luminescent layer. Further, an organic EL device can be obtained by forming an electrode such as aluminum by a vapor deposition method or the like and forming a pixel.
以下,基於實施例而說明本發明,但是本發明不被該等限定。又,份係意味著質量份。Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Also, the parts mean parts by mass.
在以下的各例所使用的化合物之略號如以下所表示。The abbreviations of the compounds used in the following examples are shown below.
C6FMA:CH2 =C(CH3 )COOCH2 CH2 (CF2 )6 FC6FMA: CH 2 =C(CH 3 )COOCH 2 CH 2 (CF 2 ) 6 F
MAA:甲基丙烯酸MAA: Methacrylic acid
MMA:甲基丙烯酸甲酯MMA: Methyl methacrylate
2-HEMA:甲基丙烯酸2-羥基乙酯2-HEMA: 2-hydroxyethyl methacrylate
PME-200:BLEMMER-PME-200(日本油脂公司製:α-甲基-ω-甲基丙烯醯聚(氧伸乙基):CH2 =C(CH3 )COO(CH2 CH2 O)k CH3 :式中的k係表示分子間的平均值,k的值為4)PME-200: BLEMMER-PME-200 (manufactured by Nippon Oil Co., Ltd.: α-methyl-ω-methacryl oxime (oxygen extension ethyl): CH 2 = C(CH 3 )COO(CH 2 CH 2 O) k CH 3 : The k series in the formula represents the average value between molecules, and the value of k is 4)
PME-400:BLEMMER-PME-400(日本油脂公司製:α-甲基-ω-甲基丙烯醯聚(氧伸乙基):CH2 =C(CH3 )COO(CH2 CH2 O)k CH3 :式中的k係表示分子間的平均值,k的值為9)PME-400: BLEMMER-PME-400 (manufactured by Nippon Oil Co., Ltd.: α-methyl-ω-methacryl oxime (oxygen extension ethyl): CH 2 = C(CH 3 )COO(CH 2 CH 2 O) k CH 3 : The k series in the formula represents the average value between molecules, and the value of k is 9)
PME-4000:BLEMMER-PME-4000(日本油脂公司製:α-甲基-ω-甲基丙烯醯聚(氧伸乙基):CH2 =C(CH3 )COO(CH2 CH2 O)k CH3 :式中的k係表示分子間的平均值,k的值為90)PME-4000: BLEMMER-PME-4000 (manufactured by Nippon Oil Co., Ltd.: α-methyl-ω-methacryl oxime (oxygen extension ethyl): CH 2 = C(CH 3 )COO(CH 2 CH 2 O) k CH 3 : The k series in the formula represents the average value between molecules, and the value of k is 90)
PE-350:BLEMMER-PME-350(日本油脂公司製:α-氫-ω-甲基丙烯醯聚(氧伸乙基):CH2 =C(CH3 )COO(CH2 CH2 O)k H:式中的k係表示分子間的平均值,k的值為8)PE-350: BLEMMER-PME-350 (manufactured by Nippon Oil & Fats Co., Ltd.: α-hydrogen-ω-methacryl oxime (oxygen extension ethyl): CH 2 =C(CH 3 )COO(CH 2 CH 2 O) k The k series in the formula H represents the average value between molecules, and the value of k is 8)
V-65:(和光純藥公司製、2,2’-偶氮雙(2,4-二甲基戊腈))V-65: (2,2'-azobis(2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd.)
AOI:KARENZ AOI(昭和電工公司製、2-(甲基)丙烯醯氧基異氰酸乙酯)AOI: KARENZ AOI (manufactured by Showa Denko, 2-(methyl) propylene oxime ethoxylate)
DBTDL:二月桂酸二丁基錫DBTDL: Dibutyltin dilaurate
TBQ:第三丁基-對苯醌TBQ: tert-butyl-p-benzoquinone
MEK:2-丁酮MEK: 2-butanone
OXEO2:OXEO2(CIBA SPECIALTY CHEMICALS公司製、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑基-3-基]-乙酮-1-(O-乙醯肟)(在通式(5),R21 及R22 係甲基、R23 係乙基、R24 、R26 及R27 係氫原子、R25 係2-甲基苯甲醯基之化合物)OXEO2: OXEO2 (manufactured by CIBA SPECIALTY CHEMICALS, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazolyl-3-yl]-ethanone-1-(O-) Ethylene (in the formula (5), R 21 and R 22 are methyl, R 23 is ethyl, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is 2-methylbenzhydryl Compound)
ZCR1569H:ZCR-1569H(日本化藥公司製、在通式(6)所表示之具有聯苯基骨架之環氧樹脂導入乙烯性雙鍵及酸性基而成之樹脂的溶液、固體成分為70質量%、質量平均分子量為4710)ZCR1569H: ZCR-1569H (a solution of a resin obtained by introducing a vinyl double bond and an acidic group into an epoxy resin having a biphenyl skeleton represented by the formula (6), manufactured by Nippon Kayaku Co., Ltd., and having a solid content of 70% by mass %, mass average molecular weight is 4710)
DPHA:KAYARAD DPHA(日本化藥公司製、二新戊四醇五丙烯酸酯與二新戊四醇六丙烯酸酯之混合物)DPHA: KAYARAD DPHA (manufactured by Nippon Kagaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
PGMEA:丙二醇一甲基醚乙酸酯PGMEA: propylene glycol monomethyl ether acetate
CB:碳黑分散液(平均二次粒徑120nm、分散介質:PGMEA、碳黑20質量%、胺值為18mgKOH/g的聚胺甲酸酯系高分子分散劑5質量%)CB: carbon black dispersion (average secondary particle diameter: 120 nm, dispersion medium: PGMEA, carbon black: 20% by mass, and polyurethane-based polymer dispersant having an amine value of 18 mgKOH/g: 5% by mass)
二氧化矽:二氧化矽分散液(平均粒徑20nm、分散介質PGMEA、固體成分30質量%)Ceria: cerium oxide dispersion (average particle size 20 nm, dispersion medium PGMEA, solid content 30% by mass)
在具備攪拌機之內容積1L的高壓釜,添加420.0g MEK、81.0g C6FMA、36.0g 2-HEMA、54.0g PME-400、9.0g MMA及1.1g聚合起始劑V-65,並邊在氮氣環境下攪拌邊使其在50℃聚合24小時,來得到共聚物1的溶液。共聚物1係數量平均分子量為34,200、質量平均分子量為63,900。In an autoclave having a 1 L internal volume of a stirrer, 420.0 g of MEK, 81.0 g of C6FMA, 36.0 g of 2-HEMA, 54.0 g of PME-400, 9.0 g of MMA, and 1.1 g of a polymerization initiator V-65 were added, and nitrogen gas was added thereto. The mixture was polymerized at 50 ° C for 24 hours while stirring to obtain a solution of the copolymer 1. The copolymer 1 coefficient had an average molecular weight of 34,200 and a mass average molecular weight of 63,900.
在具備攪拌機之內容積1L的高壓釜,添加500g上述共聚物1的溶液、32.6g AOI、0.13g DBTDL、1.6g TBQ及17.1g MEK,邊攪拌邊在40℃使其反應24小時,來合成粗聚合物。在所得到的粗聚合物的溶液添加己烷而再沈澱精製後,真空乾燥而得到165.0g相當於聚合物(A)之聚合物(A-1)。聚合物(A-1)係數量平均分子量為34,900、質量平均分子量為69,300、F原子含量為21.1質量%、乙烯性雙鍵的含量為1.26×10-3 mol/g、酸值為26.8mg KOH/g。Into an autoclave having a 1 L internal volume of a stirrer, 500 g of the solution of the above copolymer 1, 32.6 g of AOI, 0.13 g of DBTDL, 1.6 g of TBQ, and 17.1 g of MEK were added, and the mixture was reacted at 40 ° C for 24 hours while stirring to synthesize it. Crude polymer. After adding hexane to the solution of the obtained crude polymer and reprecipitating and purifying, it was dried under vacuum to obtain 165.0 g of the polymer (A-1) corresponding to the polymer (A). The polymer (A-1) has a coefficient average molecular weight of 34,900, a mass average molecular weight of 69,300, an F atom content of 21.1% by mass, an ethylenic double bond content of 1.26 × 10 -3 mol/g, and an acid value of 26.8 mg KOH. /g.
在聚合物(A-1)的合成,除了如表1變更原料的調配以外,係藉由同樣的反應,來合成共聚物2~5。使用所得到的共聚物2~5並依照表2的原料調配,與上述同樣地進行而得到的相當於聚合物(A)之聚合物(A-2)~(A-5)。In the synthesis of the polymer (A-1), in addition to the modification of the raw materials as shown in Table 1, the copolymers 2 to 5 were synthesized by the same reaction. The polymer (A-2) to (A-5) corresponding to the polymer (A) obtained in the same manner as above was prepared by using the obtained copolymers 2 to 5 in the same manner as described above.
在聚合物(A-1)的合成,除了如表1變更原料的調配以外,係藉由同樣的反應,來合成共聚物6、8~10。使用所得到的共聚物6、8~10並依照表2的原料調配,與上述同樣地進行而得到不符合本發明的聚合物(A)之比較例聚合物(R-1)、(R-3)~(R-5)。In the synthesis of the polymer (A-1), in addition to the modification of the raw materials as shown in Table 1, the copolymers 6, 8 to 10 were synthesized by the same reaction. Using the obtained copolymers 6, 8 to 10, and mixing the raw materials according to Table 2, the comparative polymer (R-1) and (R-) which did not satisfy the polymer (A) of the present invention were obtained in the same manner as above. 3) ~ (R-5).
在具備攪拌機之內容積1L的高壓釜,添加420.0g MEK、99.0g C6FMA、18.0g 2-HEMA、27.0g PME-400、18.0g MAA、18.0g MMA及1.1g聚合起始劑V-65,並邊在氮氣環境下攪拌邊使其在50℃聚合24小時,來得到共聚物7的溶液。In an autoclave having a 1 L internal volume of a stirrer, 420.0 g of MEK, 99.0 g of C6FMA, 18.0 g of 2-HEMA, 27.0 g of PME-400, 18.0 g of MAA, 18.0 g of MMA, and 1.1 g of a polymerization initiator V-65 were added. Further, the mixture was polymerized at 50 ° C for 24 hours while stirring under a nitrogen atmosphere to obtain a solution of the copolymer 7.
在所得到的溶液添加己烷而再沈澱精製後,真空乾燥而得到170.0g不符合本發明聚合物(A)之聚合物(R-2)。聚合物(R-2)係數量平均分子量為26,600、質量平均分子量為57,600、F原子含量為31.4質量%、酸值為65.2mg KOH/g。After adding hexane to the obtained solution and reprecipitating and purifying, it was dried under vacuum to obtain 170.0 g of a polymer (R-2) which did not correspond to the polymer (A) of the present invention. The polymer (R-2) coefficient had an average molecular weight of 26,600, a mass average molecular weight of 57,600, an F atom content of 31.4% by mass, and an acid value of 65.2 mg KOH/g.
上述所得到的各聚合物(A)及比較例聚合物(R)的產量、聚合物中具有基(2)的聚合單元之比率、及使用以下的方法測定的數量平均分子量(Mn)、質量平均分子量(Mw)、分子量分布(Mw/Mn)、氟原子(F)的含量、乙烯性雙鍵(C=C)的含量、酸值係顯示在表2。The yield of each of the polymer (A) and the comparative polymer (R) obtained above, the ratio of the polymer unit having the group (2) in the polymer, and the number average molecular weight (Mn) and mass measured by the following method The average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the content of the fluorine atom (F), the content of the ethylenic double bond (C=C), and the acid value are shown in Table 2.
數量平均分子量(Mn)及質量平均分子量(Mw)係使用凝膠滲透層儀析法,並將聚苯乙烯設為標準物質來測定。作為凝膠滲透層析儀,係使用HPLC-8220GPC(TOSOH公司製)。作為管柱,係使用將3支shodex LF-604連接而成者。作為檢測器,係使用RI檢測器。作為標準物質,係使用EasiCal PS1(Polymer Laboratories公司製)。而且,測定數量平均分子量及質量平均分子量時,係將管柱保持在37℃且使用四氫呋喃作為洗提液,並將流速設為0.2mL/分鐘,來注入40μL之測定試樣的0.5%四氫呋喃溶液。The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography, and polystyrene was used as a standard substance. As a gel permeation chromatograph, HPLC-8220GPC (manufactured by TOSOH Co., Ltd.) was used. As the column, three shodex LF-604 were used. As the detector, an RI detector is used. As a standard substance, EasiCal PS1 (manufactured by Polymer Laboratories Co., Ltd.) was used. Further, when the number average molecular weight and the mass average molecular weight were measured, the column was kept at 37 ° C and tetrahydrofuran was used as the eluent, and the flow rate was set to 0.2 mL/min to inject 40 μL of the 0.5% tetrahydrofuran solution of the measurement sample. .
聚合物中的氟原子含量,係藉由將1,4-雙三氟甲基苯設為標準物質而進行19 F NMR測定來算出。The fluorine atom content in the polymer was calculated by performing 19 F NMR measurement using 1,4-bistrifluoromethylbenzene as a standard material.
聚合物中的乙烯性雙鍵含量,係藉由將1,4-雙三氟甲基苯設為標準物質而進行1 H NMR測定來算出。The content of the ethylenic double bond in the polymer was calculated by 1 H NMR measurement using 1,4-bistrifluoromethylbenzene as a standard material.
酸值係從原料亦即單體的調配比率所算出之理論值。The acid value is a theoretical value calculated from the ratio of the raw materials, that is, the monomer.
將0.06份聚合物(A-1)、1.3份作為光聚合起始劑(B)之OXE02、12.9份作為感光性樹脂(C)的分散液之ZCR1569H、3.9份作為交聯劑(D)之DPHA、38.6份作為黑色著色劑(E)的分散液之CB、15.0份作為二氧化矽分散液之二氧化矽及28.24份作為溶劑之PGMEA混合而得到感光性組成物的稀釋液。感光性組成物的稀釋液之總固體成分中的聚合物(A-1)之含量為0.20質量%。0.06 parts of the polymer (A-1), 1.3 parts of OXE02 as a photopolymerization initiator (B), 12.9 parts of ZCR1569H as a dispersion of the photosensitive resin (C), and 3.9 parts as a crosslinking agent (D) DPHA, 38.6 parts of CB as a dispersion of black colorant (E), 15.0 parts of cerium oxide as a cerium oxide dispersion, and 28.24 parts of PGMEA as a solvent were mixed to obtain a diluted solution of a photosensitive composition. The content of the polymer (A-1) in the total solid content of the diluted solution of the photosensitive composition was 0.20% by mass.
使用旋轉塗布器,將感光性組成物的稀釋液塗布在玻璃基板上之後,在熱板上、於100℃使其乾燥2分鐘,來形成膜厚度為2.0μm的感光性組成物之塗膜。隨後,使用超高壓水銀燈將曝光量以i射線(365nm)基準為100mJ/cm2 的光線,通過光罩而照射塗膜來進行曝光。又,光罩係遮光部為150μm×400μm、光線透射部為20μm的格子狀圖案,所形成的開口部之容積為40pL,又,圖案的面積為10cm2 。隨後,使用顯像機進行顯像。此時,顯像液係使用無機鹼型顯像液SEMICLEAN DL-A4(商品名、橫濱油脂工業公司製)的10倍稀釋水溶液,而且噴嘴係使用將對基板的角度收縮至8度以下者,並且藉由施加0.15MPa的壓力而吐出至基板而使其產生氣泡來進行旋轉顯像。隨後,使用水沖洗未曝光部並使其乾燥,來得到形成有隔壁之實施例1的玻璃基板試樣(1)。The diluted solution of the photosensitive composition was applied onto a glass substrate using a spin coater, and then dried on a hot plate at 100 ° C for 2 minutes to form a coating film of a photosensitive composition having a film thickness of 2.0 μm. Subsequently, light having an exposure amount of 100 mJ/cm 2 on the basis of i-ray (365 nm) was irradiated with an ultra-high pressure mercury lamp, and the coating film was irradiated through a photomask to perform exposure. Further, the mask-shielding portion was a lattice pattern of 150 μm × 400 μm and the light-transmitting portion was 20 μm, and the volume of the opening formed was 40 pL, and the area of the pattern was 10 cm 2 . Subsequently, the development is performed using a video camera. In this case, a 10-fold diluted aqueous solution of an inorganic alkali-based developing solution SEMICLEAN DL-A4 (trade name, manufactured by Yokohama Oil & Fats Co., Ltd.) is used as the developing solution, and the nozzle is used to shrink the angle of the substrate to 8 degrees or less. Further, rotation development was performed by applying a pressure of 0.15 MPa to discharge the substrate to generate bubbles. Subsequently, the unexposed portion was washed with water and dried to obtain a glass substrate sample (1) of Example 1 in which the partition walls were formed.
又,除了不使用光罩而進行曝光以外,與上述同樣地進行至曝光,隨後,將玻璃基板浸漬於無機鹼型顯像液SEMICLEAN DL-A4的10倍稀釋水溶液而進行顯像且使其乾燥。得到形成有顯像後的感光性組成物的塗膜之硬化物之實施例1的玻璃基板試樣(2)。In addition, exposure was performed in the same manner as described above except that exposure was carried out without using a photomask, and then the glass substrate was immersed in a 10-fold diluted aqueous solution of an inorganic alkali-type developing liquid SEMICLEAN DL-A4, and developed and dried. . The glass substrate sample (2) of Example 1 in which the cured film of the photosensitive film of the photosensitive composition after image formation was formed was obtained.
又,與上述玻璃基板試樣(2)同樣地製造,進而在熱板上於220℃加熱玻璃板30分鐘,來得到實施例1的玻璃基板試樣(3)。Further, the glass substrate sample (2) was produced in the same manner as in the above-described glass substrate sample (2), and the glass plate sample (3) of Example 1 was obtained by heating the glass plate at 220 ° C for 30 minutes on a hot plate.
除了將各成分的調配如表3所表示變更以外,與實施例1同樣地進行而得到形成有隔壁之實施例2~5、比較例1~5的玻璃基板試樣(1)、和形成有顯像後的感光性組成物的塗膜之硬化物之玻璃基板試樣(2),以及與上述玻璃基板試樣(2)進行同樣的步驟且最後進行熱處理之形成有感光性組成物的塗膜之硬化物之玻璃基板試樣(3),該隔壁係由分別含有在上記合成例所得到的聚合物(A-2)~(A-5)、比較例聚合物(R-1)~(R-5)之感光性組成物的塗膜硬化物所構成者。The glass substrate sample (1) of Examples 2 to 5 and Comparative Examples 1 to 5 in which the partition walls were formed was obtained in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 3. The glass substrate sample (2) of the cured product of the photosensitive film of the photosensitive composition after development, and the same procedure as the glass substrate sample (2), and finally heat-treated to form a photosensitive composition The glass substrate sample (3) of the cured film of the film contains the polymers (A-2) to (A-5) and the comparative polymer (R-1) obtained in the above-mentioned synthesis examples. The composition of the cured film of the photosensitive composition of (R-5).
使用實施例1~5及比較例1~5的玻璃基板試樣(1)、(2)及(3),並藉由以下方法來評價顯像性、拒水拒油性、開口部內的油墨濕潤擴展性。將評價結果與在感光性組成物的總固體成分之各成分的含有質量%同時顯示在表4。The glass substrate samples (1), (2), and (3) of Examples 1 to 5 and Comparative Examples 1 to 5 were used, and the development property, water and oil repellency, and ink wetness in the opening portion were evaluated by the following methods. Scalability. The evaluation results are shown in Table 4 together with the content % of each component of the total solid content of the photosensitive composition.
表中,◎係表示最佳、○係良、△係可、×係不好。本發明係以全部的評價為◎或○者為良好。In the table, ◎ indicates that it is the best, ○ is good, △ is OK, and × is not good. In the present invention, all of the evaluations are ◎ or ○, which is good.
在玻璃基板(1),將每面積的顯像缺陷數為小於30個者判定為○、顯像缺陷數為30個以上、小於50個者判定為△,顯像缺陷數50個以上者判定為×。又,該評價方法係故意使氣泡大量地產生之方法,在該評價小於30個時,係意味著在實際的製造生產線,係幾乎無顯像缺陷。In the glass substrate (1), if the number of development defects per area is less than 30, it is judged as ○, the number of development defects is 30 or more, less than 50 is judged as Δ, and the number of development defects is determined to be 50 or more. For ×. Further, this evaluation method is a method for intentionally causing a large amount of bubbles to be generated. When the evaluation is less than 30, it means that there is almost no development defect in the actual production line.
藉由測定玻璃基板(2)的塗膜硬化物的表面之水的接觸角,來評價拒水性。所謂接觸角係在固體與液體接觸點之對液體表面的切線與固體表面所構成的角,且以包含液體之側的角度來定義之。因此,接觸角越大係表示塗膜硬化物的拒水性越優良。The water repellency was evaluated by measuring the contact angle of water on the surface of the cured film of the glass substrate (2). The contact angle is the angle formed by the tangent to the liquid surface at the point of contact of the solid with the liquid and the solid surface, and is defined by the angle of the side containing the liquid. Therefore, the larger the contact angle is, the more excellent the water repellency of the cured film of the coating film is.
又,將水的接觸角為95°以上者判定為○,90°以上、小於95°者為△,小於90°者判定為×。In addition, when the contact angle of water is 95° or more, it is judged as ○, and when it is 90° or more and less than 95°, it is Δ, and when it is less than 90°, it is judged as ×.
藉由測定玻璃基板(3)的塗膜硬化物的表面之PGMEA的接觸角,來評價拒油性。接觸角的定義係與拒水性同樣,接觸角越大係表示塗膜硬化物的拒油性越優良。The oil repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate (3). The contact angle is defined as the water repellency, and the larger the contact angle is, the more excellent the oil repellency of the cured film is.
又,將PGMEA的接觸角為40°以上、50°以下者判定為○,35°以上、小於40°者為△,小於35°者判定為×。In addition, when the contact angle of PGMEA is 40° or more and 50° or less, it is judged as ○, and when it is 35° or more and less than 40°, it is Δ, and when it is less than 35°, it is judged as ×.
將6.25g液狀EPOXY ME-562(日本PELNOX公司製)、6.25g硬化劑HV-562(日本PELNOX公司製)、12.5g己二酸二乙酯及25.0g丙二酸二乙酯,使用攪拌器攪拌混合1小時來調製油墨。6.25 g of liquid EPOXY ME-562 (manufactured by PELNOX Co., Ltd.), 6.25 g of hardener HV-562 (manufactured by PELNOX Co., Ltd., Japan), 12.5 g of diethyl adipate, and 25.0 g of diethyl malonate were stirred. The mixture was stirred and mixed for 1 hour to prepare an ink.
將約10pL或約20pL上述所調製的油墨藉由使用噴墨法來塗布在玻璃基板(1)的開口部,並藉由觀察使用超深度形狀測定顯微鏡VK-8500(KEYENCE公司製)所拍攝的照片,來評價開口部內的油墨之濕潤擴展性。About 10 pL or about 20 pL of the ink prepared above was applied to the opening of the glass substrate (1) by an inkjet method, and was observed by using an ultra-depth shape measuring microscope VK-8500 (manufactured by KEYENCE). Photograph to evaluate the wet spreadability of the ink in the opening.
關於在上述所得到的照片之10個隔壁間開口部位置,油墨不沾的部分為0個位置者,判定為◎,1~2個位置者為○,3~5個位置者為△,5~10個位置者為×。Regarding the position of the opening portion between the ten partitions in the photograph obtained as described above, the portion where the ink does not adhere to the zero position is determined to be ◎, the position of 1 to 2 positions is ○, and the position of 3 to 5 positions is Δ, 5 The number of ~10 locations is ×.
如表4所表示,使用實施例1~5的感光性樹脂組成物時,係顯示顯像缺陷少,而且亦充分顯示拒水性、拒油性、液體對隔壁的濕潤擴展的特性。另一方面,關於未導入基(2)亦即聚氧伸烷基鏈之比較例1,在拒水性、拒油性、濕潤擴展性方面係顯示非常良好的結果。但是產生許多顯像缺陷。又,關於在聚合物(A)未導入乙烯性雙鍵之側鏈之比較例2,雖然顯像缺陷係良化,但是顯像後的拒水性及拒油性係大幅度地降低。關於聚氧伸烷基鏈較短之比較例3,係產生許多顯像缺陷而無效果。另一方面,相較於實施例1~5所使用的範圍的長度之聚氧伸烷基的情況,聚氧伸烷基鏈較長之比較例4係顯像缺陷增加。關於比較例5,雖然拒液性良好,但是因為在聚氧伸烷基鏈的末端具有雙鍵,由於光硬化而被固定,對顯像缺陷無效果。As shown in Table 4, when the photosensitive resin compositions of Examples 1 to 5 were used, it was found that the development defects were small, and the water repellency, the oil repellency, and the wet spreading of the liquid to the partition walls were sufficiently exhibited. On the other hand, Comparative Example 1 in which the polyoxyalkylene chain was not introduced into the group (2) showed very good results in terms of water repellency, oil repellency, and wettability. However, many imaging defects occur. Further, in Comparative Example 2 in which the side chain of the ethylenic double bond was not introduced into the polymer (A), the development defect was improved, but the water repellency and oil repellency after development were greatly lowered. In Comparative Example 3 in which the polyoxyalkylene chain was short, many development defects were produced without effect. On the other hand, in the case of the polyoxyalkylene group of the length of the range used in Examples 1 to 5, Comparative Example 4 in which the polyoxyalkylene alkyl chain was long was increased in developmental defects. In Comparative Example 5, although the liquid repellency was good, since it had a double bond at the terminal of the polyoxyalkylene chain, it was fixed by photocuring, and it had no effect on development defects.
因為本發明的感光性組成物係儘管具有充分的拒液性,但是無顯像缺陷,即便經過顯像步驟亦能夠形成具有拒液性良好的上面、親液性良好的側面之隔壁,而且能夠形成油墨容易濕潤擴展的開口部。此種本發明的感光性組成物係適合形成隔壁,例如作為利用了噴墨記錄技術法之彩色濾光片製造用、有機EL顯示元件製造用者。而且,適合使用作為形成隔開有機TFT(Thin Film Transistor;薄膜電晶體)陣列的各TFT之隔壁、液晶顯示元件的ITO電極之隔壁、電路配線基板的隔壁等的永久膜之材料。The photosensitive composition of the present invention has sufficient liquid repellency, but has no development defects, and can form a partition wall having a good liquid repellency and a side surface having good lyophilicity even after a development step. An opening portion in which the ink is easily wetted and expanded is formed. The photosensitive composition of the present invention is suitable for forming a partition wall, and is, for example, a manufacturer of an organic EL display element for producing a color filter using an ink jet recording technique. Further, it is suitable to use a material which is a permanent film which forms a partition wall of each TFT which separates an organic TFT (Thin Film Transistor) array, a partition wall of an ITO electrode of a liquid crystal display element, and a partition of a circuit wiring board.
又,將2009年12月28日申請之日本特許出願2009-298960號的說明書、申請專利範圍、圖式及摘要的全部內容引用於此,且併入作為本發明的說明書的揭示。In addition, the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2009-298960, filed on Dec.
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