TWI470349B - Photosensitive composition, cured film obtained from the composition, and display device having the cured film - Google Patents
Photosensitive composition, cured film obtained from the composition, and display device having the cured film Download PDFInfo
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- TWI470349B TWI470349B TW100126616A TW100126616A TWI470349B TW I470349 B TWI470349 B TW I470349B TW 100126616 A TW100126616 A TW 100126616A TW 100126616 A TW100126616 A TW 100126616A TW I470349 B TWI470349 B TW I470349B
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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Description
本發明是有關於一種用以製造液晶顯示元件或EL顯示元件等顯示元件之感光性組成物、由該組成物所製造之透明膜等硬化膜、以及具有該硬化膜之顯示元件。 The present invention relates to a photosensitive composition for producing a display element such as a liquid crystal display element or an EL display element, a cured film such as a transparent film produced from the composition, and a display element having the cured film.
圖案化之透明膜於間隔物、絕緣膜、保護膜等液晶顯示元件之眾多部分中使用,迄今為止,開始將各種感光性組成物用於液晶顯示元件或EL顯示元件等顯示元件中(例如參照日本專利特開2004-287232號公報)。圖案化之透明膜可藉由負型感光性材料或正型感光性材料而形成,所述負型感光性材料是將光硬化性聚合物組成物塗佈於基板上,介隔圖案對塗佈膜進行光照射,對光照射之膜進行清洗而將未進行光照射之未硬化之部分除去,由此而形成圖案化之膜;所述正型感光性材料是將進行了光照射之膜於鹼性顯影液中進行顯影而將由於光照射而可溶化之部分除去,由此而形成圖案化之膜。亦提出多種用以形成圖案化之透明膜的光硬化性聚合物組成物以及感光性組成物(例如參照日本專利特開2001-261761號公報)。 The patterned transparent film is used in a large number of liquid crystal display elements such as a spacer, an insulating film, and a protective film. Heretofore, various photosensitive compositions have been used for display elements such as liquid crystal display elements and EL display elements (for example, refer to Japanese Patent Laid-Open Publication No. 2004-287232). The patterned transparent film can be formed by a negative photosensitive material which is a photocurable polymer composition coated on a substrate, and a pattern pair coating The film is irradiated with light, and the film irradiated with the light is washed to remove the unhardened portion which is not irradiated with light, thereby forming a patterned film; the positive photosensitive material is a film which is irradiated with light. Development is carried out in an alkaline developing solution to remove a portion which is solubilized by light irradiation, thereby forming a patterned film. A photocurable polymer composition and a photosensitive composition for forming a patterned transparent film are also proposed (for example, refer to Japanese Laid-Open Patent Publication No. 2001-261761).
另一方面,於近年提出了利用噴墨方式之各種圖案化(例如參照日本專利特開平10-12377號公報)。而且,於利用噴墨方式之圖案化中,為了進行精密之噴墨圖案化,於進行利用噴墨方式之塗佈之前,形成畫素間之間壁(障壁材)。 On the other hand, various types of patterning by the inkjet method have been proposed in recent years (for example, refer to Japanese Laid-Open Patent Publication No. Hei 10-12377). Further, in the patterning by the inkjet method, in order to perform precise inkjet patterning, a wall (barrier material) between the pixels is formed before the application by the inkjet method.
該障壁材可藉由如上所述之使用光硬化性聚合物組成物以及感光性組成物的公知方法而形成為圖案化之膜。於此種障壁材中,要求不附著自噴墨裝置之噴嘴頭所噴出之液狀物質的特性、亦即撥墨性(例如參照日本專利特開平11-281815號公報以及日本專利特開2004-149699號公報)。另外,於半導體製造或LCD製造製程等中,進行UV臭氧灰化處理步驟以使應塗佈所述液狀物質之開口部的墨水塗佈性或濕潤性提高。此時,障壁材之表面亦被處理,因此需求障壁材之撥液性降低,但可耐此種處理,可抑制表面撥液性之降低的障壁材料。 The barrier material can be formed into a patterned film by a known method using the photocurable polymer composition and the photosensitive composition as described above. In the barrier material, the characteristics of the liquid substance which is not attached to the nozzle head of the ink jet apparatus, that is, the ink repellency, are required (for example, refer to Japanese Patent Laid-Open No. Hei 11-281815 and Japanese Patent Laid-Open No. 2004-- Bulletin No. 149699). Further, in a semiconductor manufacturing process or an LCD manufacturing process or the like, a UV ozone ashing treatment step is performed to improve the coating property or wettability of the ink to be applied to the opening of the liquid material. At this time, since the surface of the barrier material is also treated, it is required to reduce the liquid repellency of the barrier material, but it is resistant to such a treatment, and the barrier material which can reduce the surface repellency can be suppressed.
如上所述,光硬化性聚合物組成物以及感光性組成物之用途不僅僅是構成所述顯示元件中之層的材料,亦擴展至起到顯示元件之製造中的輔助性作用的膜,隨著此種用途之擴大,對光硬化性聚合物組成物以及感光性組成物要求較先前更多樣之性能。 As described above, the use of the photocurable polymer composition and the photosensitive composition is not only a material constituting a layer in the display element but also a film which functions as an auxiliary function in the production of the display element. With the expansion of such use, the photocurable polymer composition and the photosensitive composition are required to have more performance than before.
本發明之課題在於提供可形成撥液性以及耐UV臭氧灰化性優異之硬化膜的正型感光性組成物。而且,本發明之課題在於提供此種正型感光性組成物之硬化膜、以及具有此膜之顯示元件。 An object of the present invention is to provide a positive photosensitive composition which can form a cured film excellent in liquid repellency and UV ozone ashing resistance. Further, an object of the present invention is to provide a cured film of such a positive photosensitive composition and a display element having the film.
本發明者等人為了解決上述問題而進行了銳意研究,結果發現藉由於感光性組成物中使用含有多官能矽氧烷之單體共聚而成之聚合物,可獲得特別是撥液性以及耐UV臭氧灰化性優異之硬化膜,從而完成如下所示之本發明。 The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that, by using a polymer obtained by copolymerizing a monomer containing a polyfunctional siloxane in a photosensitive composition, it is possible to obtain liquid repellency and resistance. The cured film having excellent UV ozone ashing properties, thereby completing the present invention as shown below.
[1]一種感光性組成物,包括:包含矽氧烷結構之聚合物(A)以及1,2-醌二疊氮化合物(B),其中包含矽氧烷結構之聚合物(A)是包含如下化合物之單體的自由基聚合物:式(1)所表示之矽氧烷化合物、具有賦予聚合物(A)鹼可溶性之鹼溶性與自由基聚合性的鹼溶性自由基聚合性單體,
於式(1)中,R1~R4分別獨立地表示氫、或任意氫亦可經氟取代且並不連續之任意亞甲基亦可經氧取代之碳數1~30之烷基,A1以及A2分別表示自由基聚合性官能基,n表示1~1,000之整數。 In the formula (1), R 1 to R 4 each independently represent hydrogen, or any hydrogen which may be substituted by fluorine and which is not continuous, may be substituted with an oxygen group having an alkyl group having 1 to 30 carbon atoms. A 1 and A 2 each represent a radical polymerizable functional group, and n represents an integer of 1 to 1,000.
[2]如[1]所述之感光性組成物,其中,鹼溶性自由基聚合性單體包含選自由具有不飽和羧酸之自由基聚合性單體、具有不飽和羧酸酐之自由基聚合性單體、以及具有酚性羥基之自由基聚合性單體所構成之群組之一種以上。 [2] The photosensitive composition according to [1], wherein the alkali-soluble radically polymerizable monomer comprises a radical polymerization selected from a radically polymerizable monomer having an unsaturated carboxylic acid and having an unsaturated carboxylic anhydride. One or more of the group consisting of a monomer and a radical polymerizable monomer having a phenolic hydroxyl group.
[3]如[1]或[2]所述之感光性組成物,其中,鹼溶性自由基聚合性單體包含式(2)所表示之自由基聚合物單體,
於式(2)中,R5~R7分別表示氫、或任意之氫亦可經氟取代之碳數1~3之烷基,R8~R12分別表示氫,鹵素,-CN,-CF3,-OCF3,羥基,任意之亞甲基亦可經-COO-、-OCO-、-CO-取代且任意之氫亦可經鹵素取代之碳數1~5之烷基,或任意之氫亦可經鹵素取代之碳數1~5之烷氧基。其中,R8~R12中之至少1個為羥基。 In the formula (2), R 5 to R 7 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R 8 to R 12 respectively represent hydrogen, halogen, -CN, - CF 3 , -OCF 3 , a hydroxyl group, an arbitrary methylene group may be substituted by -COO-, -OCO-, -CO-, and any hydrogen may be substituted by halogen with a carbon number of 1 to 5, or any The hydrogen may also be substituted with a halogen to have an alkoxy group having 1 to 5 carbon atoms. Wherein at least one of R 8 to R 12 is a hydroxyl group.
[4]如[1]~[3]中任一項所述之感光性組成物,其中,包含矽氧烷結構之聚合物(A)是進一步包含式(1)所表示之矽氧烷化合物以及鹼溶性自由基聚合性單體以外之其他自由基聚合性單體的單體之自由基聚合物。 [4] The photosensitive composition according to any one of [1], wherein the polymer (A) comprising a siloxane structure further comprises a siloxane compound represented by the formula (1). And a radical polymer of a monomer other than the radically polymerizable monomer other than the alkali-soluble radical polymerizable monomer.
[5]如[4]所述之感光性組成物,其中,其他自由基聚合性單體包含式(3)所表示之矽氧烷化合物,
於式(3)中,R13~R17分別獨立地表示任意之氫亦可經氟取代且任意之亞甲基亦可經氧取代之碳數1~30之烷基、或矽數1~500之三(烷基/烷氧基)矽烷氧基,A3表示自由基聚合性官能基,n表示0~1,000之整數。 In the formula (3), R 13 to R 17 each independently represent an arbitrary alkyl group which may be substituted by fluorine, and any methylene group may be substituted with an oxygen group having an alkyl group having 1 to 30 carbon atoms or a number of turns 1~. 500 tris(alkyl/alkoxy)decyloxy, A 3 represents a radical polymerizable functional group, and n represents an integer of 0 to 1,000.
[6]如[5]所述之感光性組成物,其中,其他自由基聚合性單體是n為0之式(3)所表示之矽氧烷化合物。 [6] The photosensitive composition according to [5], wherein the other radical polymerizable monomer is a oxoxane compound represented by the formula (3) wherein n is 0.
[7]如[6]所述之感光性組成物,其中,式(3)之R13~R15分別如下述式(5)所示,
於式(5)中,R21~R23分別獨立地表示氫、碳數1~20之烷基、或碳數1~20之烷氧基(其中,末端之R21~R23之至少一個是所述烷基或所述烷氧基),m表示1~500之整數。 In the formula (5), R 21 to R 23 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms (wherein at least one of R 21 to R 23 at the terminal) Is the alkyl group or the alkoxy group), and m represents an integer of from 1 to 500.
[8]如[4]~[7]中任一項所述之感光性組成物,其中,其他自由基聚合性單體包含(甲基)丙烯酸衍生物。 [8] The photosensitive composition according to any one of [4], wherein the other radical polymerizable monomer contains a (meth)acrylic acid derivative.
[9]如[1]~[8]中任一項所述之感光性組成物,其進一步含有鹼可溶性聚合物(C),所述鹼可溶性聚合物(C)是式(1)所表示之矽氧烷化合物以外之單體的自由基聚合物,且具有鹼可溶性。 [9] The photosensitive composition according to any one of [1] to [8] further comprising an alkali-soluble polymer (C) represented by the formula (1) A radical polymer of a monomer other than a oxoxane compound, and having an alkali solubility.
[10]如[9]所述之感光性組成物,其中,鹼可溶性聚合物(C)是包含選自由具有不飽和羧酸之自由基聚合性單體、具有不飽和羧酸酐之自由基聚合性單體、以及具有酚性羥基之自由基聚合性單體所構成之群組之一種以上的單體之自由基聚合物。 [10] The photosensitive composition according to [9], wherein the alkali-soluble polymer (C) is a radical polymerization comprising a radically polymerizable monomer having an unsaturated carboxylic acid and having an unsaturated carboxylic anhydride. A radical polymer of one or more monomers of a group consisting of a monomer and a radical polymerizable monomer having a phenolic hydroxyl group.
[11]如[1]~[10]中任一項所述之感光性組成物,其進一步含有溶劑。 [11] The photosensitive composition according to any one of [1] to [10] further comprising a solvent.
[12]一種硬化膜,其是對如[1]~[11]中任一項所述之感光性組成物之膜進行煅燒而獲得。 [12] A cured film obtained by calcining a film of the photosensitive composition according to any one of [1] to [11].
[13]一種顯示元件,其具有如[12]所述之硬化膜。 [13] A display element having the cured film according to [12].
本發明之感光性組成物是包含式(1)所表示之矽氧烷化合物之單體的鹼可溶性自由基聚合物,因此可藉由適用於正型抗蝕劑劑中而形成在UV臭氧灰化處理之前後之任意情况中撥液性均優異之硬化膜。 The photosensitive composition of the present invention is an alkali-soluble radical polymer containing a monomer of a oxoxane compound represented by the formula (1), and thus can be formed in a UV ozone ash by being applied to a positive type resist. A cured film excellent in liquid repellency in any case after the treatment.
1.本發明之感光性組成物 1. The photosensitive composition of the present invention
本發明之感光性組成物包括:包含矽氧烷結構之聚合物(A)、1,2-醌二疊氮化合物(B)。包含矽氧烷結構之聚合物(A)可為一種亦可為兩種以上,且1,2-醌二疊氮化合物(B)可為一種亦可為兩種以上。感光性組成物可藉由將包含矽氧烷結構之聚合物(A)與1,2-醌二疊氮化合物(B)加以混合而獲得。 The photosensitive composition of the present invention comprises a polymer (A) comprising a decane structure and a 1,2-quinonediazide compound (B). The polymer (A) having a siloxane structure may be one type or two or more types, and the 1,2-quinonediazide compound (B) may be one type or two or more types. The photosensitive composition can be obtained by mixing a polymer (A) containing a decane structure and a 1,2-quinonediazide compound (B).
1-1.包含矽氧烷結構之聚合物(A) 1-1. Polymer containing a siloxane structure (A)
包含矽氧烷結構之聚合物(A)是包含如下化合物之單體的自由基聚合物:具有矽數2以上之直鏈矽氧烷結構與二個自由基聚合性官能基的式(1)所表示之矽氧烷化合物(以下亦稱為「自由基聚合性單體(a-1)」)、具有賦予聚合物(A)鹼可溶性之鹼溶性與自由基聚合性的鹼溶性自由基聚合性單體(以下亦稱為「自由基聚合性單體(a-2)」)。 The polymer (A) comprising a oxoxane structure is a radical polymer comprising a monomer of a compound having a linear oxime structure of 2 or more and two radically polymerizable functional groups (1) The alkoxysilane compound (hereinafter also referred to as "radical polymerizable monomer (a-1)"), and the alkali-soluble radical polymerization having alkali solubility and radical polymerizability imparting alkali solubility to the polymer (A) A monomer (hereinafter also referred to as "radical polymerizable monomer (a-2)").
包含矽氧烷結構之聚合物(A)具有由自由基聚合性單體(a-2)所賦予之鹼可溶性。包含矽氧烷結構之聚合物(A)所具有之鹼可溶性是指將藉由旋塗包含矽氧烷結構之聚合物(A)之溶液以及於100℃下加熱2分鐘而形成之厚度為0.01μm~100μm之膜,於例如25℃左右之2.38wt%之四甲基氫氧化銨水溶液中浸漬5分鐘後,藉由純水而洗濯時,並未殘留膜。 The polymer (A) having a siloxane structure has an alkali solubility imparted by the radical polymerizable monomer (a-2). The alkali solubility of the polymer (A) containing a oxoxane structure means a thickness of 0.01 by spin coating a solution of the polymer (A) containing a decane structure and heating at 100 ° C for 2 minutes. The film of μm to 100 μm was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at about 25 ° C for 5 minutes, and then washed with pure water, the film remained.
自由基聚合性單體(a-1)以及自由基聚合性單體(a-2)分別可為一種亦可為兩種以上。自表現出硬化膜之撥液性之觀點考慮,構成包含矽氧烷結構之聚合物(A)之所有單體中的自由基聚合性單體(a-1)之含量較佳的是0.1wt%~50wt%,更佳的是0.5wt%~30wt%,進一步更佳的是1wt%~20wt%。而且,自表現出硬化膜之製造中的充分之顯影性之觀點考慮,構成包含矽氧烷結構之聚合物(A)之所有單體中的自由基聚合性單體(a-2)之含量較佳的是0.1wt%~50wt%,更佳的是0.5wt%~30wt%,進一步更佳的是1wt%~20wt%。 The radically polymerizable monomer (a-1) and the radically polymerizable monomer (a-2) may be used alone or in combination of two or more. The content of the radical polymerizable monomer (a-1) in all the monomers constituting the polymer (A) containing a decane structure is preferably 0.1 wt% from the viewpoint of exhibiting the liquid repellency of the cured film. From 100% by weight to 50% by weight, more preferably from 0.5% by weight to 30% by weight, still more preferably from 1% by weight to 20% by weight. Further, the content of the radical polymerizable monomer (a-2) in all the monomers constituting the polymer (A) containing a siloxane chain structure is considered from the viewpoint of exhibiting sufficient developability in the production of the cured film. It is preferably from 0.1% by weight to 50% by weight, more preferably from 0.5% by weight to 30% by weight, still more preferably from 1% by weight to 20% by weight.
1-1-1.自由基聚合性單體(a-1) 1-1-1. Radical polymerizable monomer (a-1)
自由基聚合性單體(a-1)是具有矽數2以上之直鏈矽氧烷結構與二個自由基聚合性官能基之化合物,以式(1)而表示。 The radically polymerizable monomer (a-1) is a compound having a linear oxime structure having a number of turns of 2 or more and two radical polymerizable functional groups, and is represented by the formula (1).
於式(1)中,R1~R4分別獨立地表示氫、或任意氫亦可經氟取代且並不連續之任意亞甲基亦可經氧取代之碳數1~30之烷基。此種烷基例如包括氟化烷基或碳數1~20之烷氧基。 In the formula (1), R 1 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may be substituted by fluorine and which is not continuous, and which may be substituted with oxygen. Such an alkyl group includes, for example, a fluorinated alkyl group or an alkoxy group having 1 to 20 carbon atoms.
於式(1)中,A1以及A2分別表示自由基聚合性官能基。A1以及A2可相同亦可不同。自由基聚合性官能基可使用於自由基聚合性單體(a-1)中具有可自由基聚合之結構的基。此種自由基聚合性官能基可列舉公知之自由基聚合性官能基,例如可列舉乙烯基、1,2-伸乙烯基(vinylene)、1,1-亞乙烯基(vinylidene)、(甲基)丙烯醯基、以及苯乙烯基等。 In the formula (1), A 1 and A 2 each represent a radical polymerizable functional group. A 1 and A 2 may be the same or different. The radical polymerizable functional group can be used for a radical having a radically polymerizable structure in the radically polymerizable monomer (a-1). Examples of such a radical polymerizable functional group include a known radical polymerizable functional group, and examples thereof include a vinyl group, a 1,2-vinylene group, a vinylidene group, and a methyl group. An acrylonitrile group, a styryl group, and the like.
自由基聚合性官能基亦可於獲得自由基聚合性之範圍內進一步具有取代基。此種取代基例如可列舉碳數2~10之伸烷基;甲氧基、乙氧基等烷氧基;以及異丙基以及異 丁基等分支烷基。 The radical polymerizable functional group may further have a substituent within a range in which radical polymerizability is obtained. Examples of such a substituent include an alkylene group having 2 to 10 carbon atoms; an alkoxy group such as a methoxy group or an ethoxy group; and an isopropyl group and a different Branched alkyl such as butyl.
於式(1)中,n表示1~1,000之整數。自獲得良好之鹼顯影性之觀點考慮,n較佳的是2~500,更佳的是5~300,進一步更佳的是10~150。 In the formula (1), n represents an integer of 1 to 1,000. From the viewpoint of obtaining good alkali developability, n is preferably from 2 to 500, more preferably from 5 to 300, still more preferably from 10 to 150.
自由基聚合性單體(a-1)例如可列舉於式(1-1)所表示之兩末端具有甲基丙烯醯基之矽氧烷系單體。自初始之透明性高,且幾乎沒有於高溫下之煅燒所造成之透明性之劣化,另外顯影時對於鹼性水溶液之溶解性高(亦即顯影性高),容易地獲得圖案狀透明膜,且顯示出耐溶劑性、高耐水性、耐酸性、耐鹼性、耐熱性,另外與基底之密接性高的感光性組成物或硬化膜之觀點考慮,較佳的是於自由基聚合性單體(a-1)中使用矽氧烷系單體。另外,於式(1-1)中,n表示1~1,000之整數。 The radically polymerizable monomer (a-1) is, for example, a naphthenic monomer having a methacrylinyl group at both terminals represented by the formula (1-1). Since the initial transparency is high, and there is almost no deterioration in transparency due to calcination at a high temperature, and the solubility in an alkaline aqueous solution during development is high (that is, high developability), a pattern-like transparent film is easily obtained. Further, in view of solvent resistance, high water resistance, acid resistance, alkali resistance, and heat resistance, and a photosensitive composition having a high adhesion to a substrate or a cured film, it is preferably a radical polymerizable single. A siloxane-based monomer is used in the body (a-1). Further, in the formula (1-1), n represents an integer of 1 to 1,000.
自由基聚合性單體(a-1)亦存在有市售品。式(1-1)所表示之化合物例如可列舉Silaplane FM7711(商品名,CHISSO CORPORATION製造)。 Commercially available products are also available as the radical polymerizable monomer (a-1). The compound represented by the formula (1-1) is, for example, Silaplane FM7711 (trade name, manufactured by CHISSO CORPORATION).
1-1-2.自由基聚合性單體(a-2) 1-1-2. Radical polymerizable monomer (a-2)
自由基聚合性單體(a-2)具有賦予聚合物(A)鹼可溶性之鹼溶性與自由基聚合性。自由基聚合性單體(a-2) 所具有之鹼溶性是指即使於自由基聚合性單體(a-2)之自由基聚合後之形態下亦藉由鹼而形成水溶性之鹽。此種鹼溶性是藉由如下結構而賦予,所述結構具有與自由基聚合部位獨立而利用鹼形成水溶性鹽之部位,例如羧基或酚性羥基。而且,自由基聚合性單體(a-2)所具有之自由基聚合性是指與包括自由基聚合性單體(a-1)之其他單體進行自由基聚合之性質。此種自由基聚合性是藉由上述自由基聚合性官能基而賦予。因此,自由基聚合性單體(a-2)包括所述可溶解於鹼中之部位與自由基聚合性官能基。 The radical polymerizable monomer (a-2) has alkali solubility and radical polymerizability which impart alkali solubility to the polymer (A). Radical polymerizable monomer (a-2) The alkali solubility is a salt which forms a water-soluble salt by a base even in the form of radical polymerization of the radical polymerizable monomer (a-2). Such alkali solubility is imparted by a structure having a site which forms a water-soluble salt by a base independently of a radical polymerization site, such as a carboxyl group or a phenolic hydroxyl group. Further, the radical polymerizable property of the radical polymerizable monomer (a-2) means a property of radical polymerization with another monomer including the radical polymerizable monomer (a-1). Such radical polymerizability is imparted by the above-mentioned radical polymerizable functional group. Therefore, the radical polymerizable monomer (a-2) includes the moiety soluble in the base and the radical polymerizable functional group.
此種自由基聚合性單體(a-2)例如可列舉:含有不飽和羧酸之自由基聚合性單體、含有不飽和羧酸酐之自由基聚合性單體、以及含有酚性羥基之自由基聚合性單體。含有不飽和羧酸之自由基聚合性單體例如可列舉(甲基)丙烯酸,含有不飽和羧酸酐之自由基聚合性單體例如可列舉馬來酸酐,含有酚性羥基之自由基聚合性單體例如可列舉具有酚性羥基之乙烯基酮以及具有酚性羥基之苯乙烯衍生物。 Examples of the radically polymerizable monomer (a-2) include a radical polymerizable monomer containing an unsaturated carboxylic acid, a radical polymerizable monomer containing an unsaturated carboxylic acid anhydride, and a free phenolic hydroxyl group. Base polymerizable monomer. The radically polymerizable monomer containing an unsaturated carboxylic acid is, for example, (meth)acrylic acid, and the radically polymerizable monomer containing an unsaturated carboxylic acid anhydride is, for example, maleic anhydride, and a radical polymerizable single containing a phenolic hydroxyl group. Examples of the compound include a vinyl ketone having a phenolic hydroxyl group and a styrene derivative having a phenolic hydroxyl group.
具有酚性羥基之乙烯基酮例如可列舉式(2)所表示之化合物。 The vinyl ketone having a phenolic hydroxyl group may, for example, be a compound represented by the formula (2).
於式(2)中,R5~R7分別表示氫、或任意之氫亦可經氟取代之碳數1~3之烷基,R8~R12分別表示氫,鹵素,-CN,-CF3,-OCF3,羥基,任意之亞甲基亦可經-COO-、-OCO-、-CO-取代且任意之氫亦可經鹵素取代之碳數1~5之烷基,或任意之氫亦可經鹵素取代之碳數1~5之烷氧基。其中,R8~R12中之至少1個為羥基。 In the formula (2), R 5 to R 7 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R 8 to R 12 respectively represent hydrogen, halogen, -CN, - CF 3 , -OCF 3 , a hydroxyl group, an arbitrary methylene group may be substituted by -COO-, -OCO-, -CO-, and any hydrogen may be substituted by halogen with a carbon number of 1 to 5, or any The hydrogen may also be substituted with a halogen to have an alkoxy group having 1 to 5 carbon atoms. Wherein at least one of R 8 to R 12 is a hydroxyl group.
自提高鹼可溶性之觀點考慮,較佳的是R5~R7以及除羥基以外之R8~R12為氫。式(2)所表示之化合物例如可列舉4-羥基苯基乙烯基酮。 From the viewpoint of improving alkali solubility, it is preferred that R 5 to R 7 and R 8 to R 12 other than the hydroxyl group are hydrogen. The compound represented by the formula (2) is, for example, 4-hydroxyphenyl vinyl ketone.
具有酚性羥基之乙烯基酮可藉由公知之方法合成而獲得,或者可以市售品之形式獲得。例如,4-羥基苯基乙烯基酮可如日本專利特開2004-189715號公報中所記載般藉由如下方式而獲得:於2-氯乙基-4-甲氧基苯基酮之二氯甲烷溶液中添加氯化鋁,使所得之混合物回流、冷卻,以乙酸乙酯而萃取有機相,以NaOH水溶液萃取所獲得之有機相,藉由鹽酸使其為酸性後,再次藉由乙酸乙酯進行萃取。 The vinyl ketone having a phenolic hydroxyl group can be obtained by a known method, or can be obtained in the form of a commercially available product. For example, 4-hydroxyphenyl vinyl ketone can be obtained by the following method as described in Japanese Patent Laid-Open Publication No. 2004-189715: dichlorochloride of 2-chloroethyl-4-methoxyphenyl ketone Aluminium chloride is added to the methane solution, and the resulting mixture is refluxed and cooled. The organic phase is extracted with ethyl acetate. The organic phase is extracted with aqueous NaOH, acidified with hydrochloric acid, and then ethyl acetate. Perform extraction.
具有酚性羥基之苯乙烯衍生物除了酚性羥基以外,具有苯乙烯所具有之聚合性雙鍵。具有酚性羥基之苯乙烯衍生物例如可列舉鄰羥基苯乙烯、間羥基苯乙烯、以及對羥基苯乙烯。 The styrene derivative having a phenolic hydroxyl group has a polymerizable double bond of styrene in addition to a phenolic hydroxyl group. Examples of the styrene derivative having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.
1-1-3.其他之自由基聚合性單體(a-3) 1-1-3. Other radical polymerizable monomers (a-3)
自使包含矽氧烷結構之聚合物(A)所具有之特性提高或增加之觀點考慮,較佳的是包含矽氧烷結構之聚合物(A)是進一步包含自由基聚合性單體(a-1)以及自由基 聚合性單體(a-2)以外之其他自由基聚合性單體(以下亦稱為「自由基聚合性單體(a-3)」)的單體之自由基聚合物。自由基聚合性單體(a-3)可為一種亦可為兩種以上。自提高包含矽氧烷結構之聚合物(A)所具有之特性或者賦予包含矽氧烷結構之聚合物(A)之進一步之特性的觀點考慮,構成包含矽氧烷結構之聚合物(A)之所有單體中的自由基聚合性單體(a-3)之含量較佳的是50.0wt%~99.9wt%,更佳的是70.0wt%~99.5wt%,進一步更佳的是80.0wt%~99.0wt%。 From the viewpoint of increasing or increasing the properties of the polymer (A) containing a decane structure, it is preferred that the polymer (A) comprising a siloxane structure further contains a radical polymerizable monomer (a). -1) and free radicals A radical polymer of a monomer other than the polymerizable monomer (a-2) (hereinafter also referred to as "radical polymerizable monomer (a-3)"). The radically polymerizable monomer (a-3) may be one type or two or more types. A polymer comprising a siloxane structure (A) is considered from the viewpoint of improving the properties of the polymer (A) containing a siloxane structure or imparting further properties to the polymer (A) containing a siloxane structure. The content of the radical polymerizable monomer (a-3) in all the monomers is preferably from 50.0% by weight to 99.9% by weight, more preferably from 70.0% by weight to 99.5% by weight, still more preferably 80.0% by weight. %~99.0wt%.
自由基聚合性單體(a-3)例如可列舉式(3)所表示之矽氧烷化合物、含有環氧基之自由基聚合性單體、(甲基)丙烯酸衍生物、N取代馬來醯亞胺、以及包含二環戊基之自由基聚合性單體。 Examples of the radically polymerizable monomer (a-3) include a decyl alkane compound represented by the formula (3), a radical polymerizable monomer containing an epoxy group, a (meth)acrylic acid derivative, and an N-substituted Malay. A quinone imine and a radical polymerizable monomer containing a dicyclopentyl group.
於式(3)中,R13~R17分別獨立地表示任意之氫亦可經氟取代且任意之亞甲基亦可經氧取代之碳數1~30之烷基、或烷基之碳數1~20的矽數1~500之三(烷基/烷氧基)矽烷氧基,A3表示自由基聚合性官能基,n表示0~1,000之整數。其中,較佳的是於n為0時,R13~R15分別為式 (5)所示之基。另外,自由基聚合性官能基A3與上述式(1)中之自由基聚合性官能基同義。而且,「三(烷基/烷氧基)」是表示包含烷基以及烷氧基之一者或兩者的三個基。 In the formula (3), R 13 to R 17 each independently represent an alkyl group in which any hydrogen may be substituted by fluorine and an arbitrary methylene group may be substituted by oxygen, an alkyl group having 1 to 30 carbon atoms, or an alkyl group. The number 1 to 20 is 1 to 500 tris (alkyl/alkoxy) nonyloxy group, A 3 is a radical polymerizable functional group, and n is an integer of 0 to 1,000. Among them, it is preferred that when n is 0, R 13 to R 15 are each a group represented by the formula (5). Further, the radical polymerizable functional group A 3 has the same meaning as the radical polymerizable functional group in the above formula (1). Further, "tris(alkyl/alkoxy)" means three groups including one or both of an alkyl group and an alkoxy group.
於式(5)中,R21~R23分別獨立地表示氫、碳數1~20之烷基或碳數1~20之烷氧基(其中,末端之R21~R23之至少一個是所述烷基或所述烷氧基)。m表示1~500之整數。 In the formula (5), R 21 to R 23 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms (wherein at least one of R 21 to R 23 at the terminal is The alkyl group or the alkoxy group). m represents an integer from 1 to 500.
式(3)所表示之矽氧烷化合物例如可列舉式(3-1)所表示之α-丁基-ω-(3-甲基丙烯醯氧基丙基)聚二甲基矽氧烷(商品名:FM0711、CHISSO CORPORATION製造)。其自由於所含有之矽而使表面撥液性提高之觀點考慮較佳。 The alkane compound represented by the formula (3) is, for example, α-butyl-ω-(3-methylpropenyloxypropyl)polydimethyloxane represented by the formula (3-1). Product name: FM0711, manufactured by CHISSO CORPORATION). It is preferable from the viewpoint that it is free from the enthalpy contained therein to improve the surface liquid repellency.
而且,以式(3)而表示且n為0之矽氧烷化合物例如 可列舉3-甲基丙烯醯氧基丙基三甲氧基矽烷(商品名:S710、CHISSO CORPORATION製造)、3-甲基丙烯醯氧基丙基三(三甲基矽烷氧基)矽烷(商品名:TM0701T、CHISSO CORPORATION製造)、以及3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷(商品名:KBM-502、信越化學工業股份有限公司製造)。其中,自提高對於鹼性顯影液之溶解性之觀點考慮,較佳的是3-甲基丙烯醯氧基丙基三甲氧基矽烷。 Further, a oxoxane compound represented by the formula (3) and having n is 0, for example 3-methylacryloxypropyltrimethoxydecane (trade name: S710, manufactured by CHISSO CORPORATION), 3-methacryloxypropyltris(trimethyldecyloxy)decane (trade name) : TM0701T, manufactured by CHISSO CORPORATION), and 3-methacryloxypropylmethyldimethoxydecane (trade name: KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, 3-methylpropenyloxypropyltrimethoxydecane is preferred from the viewpoint of improving the solubility in an alkaline developer.
含有環氧基之自由基聚合性單體例如可列舉(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、(甲基)丙烯酸-3,4-環氧環己基甲酯、以及3-乙基-3-(甲基)丙烯醯氧基甲基環氧丙烷。該些化合物自容易獲得,以及提高所得之圖案狀透明膜之耐溶劑性、耐水性、耐酸性、耐鹼性、耐熱性、透明性之觀點考慮較佳。 Examples of the epoxy group-containing radical polymerizable monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. And 3-ethyl-3-(meth)acryloxymethyl propylene oxide. These compounds are preferable from the viewpoint of easy availability and improvement in solvent resistance, water resistance, acid resistance, alkali resistance, heat resistance and transparency of the resulting patterned transparent film.
(甲基)丙烯酸衍生物若為具有(甲基)丙烯酸所具有之聚合性雙鍵的衍生物即可。(甲基)丙烯酸衍生物例如可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸己酯、甲基丙烯酸乙基己酯等甲基丙烯酸烷基酯;甲基丙烯酸苄酯、甲基丙烯酸苯氧基乙酯等具有芳香環之甲基丙烯酸烷基酯;甲基丙烯酸羥基甲酯、甲基丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基丙酯、甲基丙烯酸-4-羥基丁酯、甲基丙烯酸羥基戊酯、甲基丙烯酸羥基己酯等具有羥基之甲基丙烯酸烷酯;甲基丙烯酸二甲胺基乙酯等甲基丙烯酸二烷基胺基烷基 酯;以及甲基丙烯酸苯酯等甲基丙烯酸芳基酯。 The (meth)acrylic acid derivative may be a derivative having a polymerizable double bond of (meth)acrylic acid. Examples of the (meth)acrylic acid derivative include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. An alkyl methacrylate such as butyl methacrylate, hexyl methacrylate or ethylhexyl methacrylate; a methyl group having an aromatic ring such as benzyl methacrylate or phenoxyethyl methacrylate; Alkyl acrylate; hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxyamyl methacrylate, A An alkyl methacrylate having a hydroxyl group such as hydroxyhexyl acrylate; a dialkylaminoalkyl methacrylate such as dimethylaminoethyl methacrylate An ester; and an aryl methacrylate such as phenyl methacrylate.
N取代馬來醯亞胺例如可列舉N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丁基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-(4-乙醯基苯基)馬來醯亞胺、N-(2,6-二乙基苯基)馬來醯亞胺、N-(4-二甲胺基-3,5-二硝基苯基)馬來醯亞胺、N-(1-苯胺基萘基-4)馬來醯亞胺、N-[4-(2-苯并噁唑基)苯基]馬來醯亞胺、以及N-(9-吖啶基)馬來醯亞胺。 Examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(4-ethylmercaptophenyl)maleimide, N-(2,6-diethylphenyl) Maleic imine, N-(4-dimethylamino-3,5-dinitrophenyl)maleimide, N-(1-anilinophthyl-4)maleimide, N-[4-(2-benzoxazolyl)phenyl]maleimide, and N-(9-acridinyl)maleimide.
包含二環戊基之自由基聚合性單體例如可列舉丙烯酸二環戊基酯以及甲基丙烯酸二環戊基酯。 Examples of the radical polymerizable monomer containing a dicyclopentyl group include dicyclopentyl acrylate and dicyclopentyl methacrylate.
自提高由感光性組成物所形成之硬化膜之耐熱性之觀點考慮,較佳的是自由基聚合性單體(a-3)包含N取代馬來醯亞胺以及包含二環戊基之自由基聚合性單體之一者或兩者。 From the viewpoint of improving the heat resistance of the cured film formed of the photosensitive composition, it is preferred that the radical polymerizable monomer (a-3) contains an N-substituted maleimide and a free radical containing a dicyclopentyl group. One or both of the base polymerizable monomers.
關於包含矽氧烷結構之聚合物(A)之單體,自提高包含矽氧烷結構之聚合物(A)之鹼可溶性之觀點考慮,較佳的是選自由(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸衍生物、以及具有酚性羥基之苯乙烯衍生物所構成之群組之一種以上包含於所述單體中。 The monomer of the polymer (A) having a siloxane structure is preferably selected from the group consisting of hydroxyethyl (meth) acrylate from the viewpoint of improving the alkali solubility of the polymer (A) containing a decane structure. One or more groups of the (meth)acrylic acid derivative and the styrene derivative having a phenolic hydroxyl group are contained in the monomer.
包含矽氧烷結構之聚合物(A)可藉由如下方式而獲得:添加自由基聚合性單體(a-1)以及自由基聚合性單體(a-2),而且視需要進一步添加自由基聚合性單體(a-3),使該些化合物自由基聚合。該自由基聚合可藉由公知之方法而進行。 The polymer (A) containing a decane structure can be obtained by adding a radical polymerizable monomer (a-1) and a radical polymerizable monomer (a-2), and further adding as needed The base polymerizable monomer (a-3) is subjected to radical polymerization of the compounds. The radical polymerization can be carried out by a known method.
包含矽氧烷結構之聚合物(A)之聚合方法雖無特別限制,但較佳的是於使用溶劑之溶液中的自由基聚合。聚合溫度若為由所使用之聚合起始劑而充分產生自由基之溫度,則並無特別限定,通常為50℃~150℃之範圍。聚合時間亦無特別限定,通常為1小時~24小時之範圍。而且,該聚合可於加壓、減壓或大氣壓之任意壓力下進行。 The polymerization method of the polymer (A) containing a decane structure is not particularly limited, but is preferably a radical polymerization in a solution using a solvent. The polymerization temperature is not particularly limited as long as it is a radical which sufficiently generates a radical by the polymerization initiator to be used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is also not particularly limited and is usually in the range of 1 hour to 24 hours. Moreover, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.
自由基聚合中所使用之溶劑較佳的是可溶解所使用之自由基聚合性單體以及生成物的溶劑。溶劑可為一種亦可為兩種以上。溶劑例如可列舉甲醇、乙醇、1-丙醇、2-丙醇、丙酮、2-丁酮、乙酸乙酯、乙酸丙酯、四氫呋喃、乙腈、二噁烷、甲苯、二甲苯、環己酮、乙二醇單乙醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、以及N,N-二甲基甲醯胺。 The solvent used in the radical polymerization is preferably a solvent which can dissolve the radical polymerizable monomer and the product to be used. The solvent may be one type or two or more types. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, and cyclohexanone. Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, 3-ethyl Ethyl oxypropionate and N,N-dimethylformamide.
自由基聚合中所使用之聚合起始劑例如可列舉藉由熱而產生自由基之化合物、偶氮雙異丁腈等偶氮系起始劑、以及過氧化苯甲醯等過氧化物系起始劑。聚合起始劑之使用量相對於成為原料之單體總量100重量份而言較佳的是1重量份~30重量份,更佳的是5重量份~25重量份。 Examples of the polymerization initiator to be used in the radical polymerization include a compound which generates a radical by heat, an azo initiator such as azobisisobutyronitrile, and a peroxide such as benzamidine peroxide. Starting agent. The amount of the polymerization initiator to be used is preferably from 1 part by weight to 30 parts by weight, more preferably from 5 parts by weight to 25 parts by weight, per 100 parts by weight of the total amount of the monomers to be used as the raw material.
而且,於自由基聚合中,為了調節分子量,亦可添加巰基乙酸等鏈轉移劑。鏈轉移劑之添加量相對於成為原料之單體總量100重量份而言較佳的是0.001重量份~0.05重量份,更佳的是0.005重量份~0.03重量份。 Further, in the radical polymerization, a chain transfer agent such as thioglycolic acid may be added in order to adjust the molecular weight. The amount of the chain transfer agent to be added is preferably 0.001 part by weight to 0.05 part by weight, more preferably 0.005 part by weight to 0.03 part by weight, per 100 parts by weight of the total amount of the monomer to be used as the raw material.
自曝光部分於鹼性顯影液中直至溶解之顯影時間適 當,且於顯影時膜之表面難以變粗糙之觀點考慮,較佳的是包含矽氧烷結構之聚合物(A)之重量平均分子量為1,000~100,000。進一步自顯影殘渣變得極其少之觀點考慮,重量平均分子量更佳的是1,500~50,000,進一步更佳的是2,000~20,000。 Suitable for the development time from the exposure portion to the alkaline developer until the dissolution When the surface of the film is hard to be roughened at the time of development, it is preferred that the polymer (A) having a siloxane structure has a weight average molecular weight of 1,000 to 100,000. Further, the weight average molecular weight is more preferably from 1,500 to 50,000, and still more preferably from 2,000 to 20,000, from the viewpoint that the amount of the self-developing residue becomes extremely small.
重量平均分子量可藉由以聚苯乙烯為標準之GPC分析而求出,例如可使用分子量為500~150,000之聚苯乙烯(例如Polymer Laboratories製造之PL2010-0102(S-M2-10)standard),所述測定時之管柱可使用Shodex PLgel MIXED-D(Polymer Laboratories製造),所述測定時之流動相可使用THF。可於此種條件下測定所述重量平均分子量。 The weight average molecular weight can be determined by GPC analysis using polystyrene as a standard, and for example, polystyrene having a molecular weight of 500 to 150,000 (for example, PL2010-0102 (S-M2-10) standard manufactured by Polymer Laboratories) can be used. As the column for the measurement, Shodex PLgel MIXED-D (manufactured by Polymer Laboratories) can be used, and the mobile phase at the time of the measurement can be THF. The weight average molecular weight can be determined under such conditions.
另外,包含矽氧烷結構之聚合物(A)之單體可藉由可確認包含矽氧烷結構之聚合物(A)中之包含矽原子之特定結構與源自自由基聚合性官能基之結構的公知之分析方法而確認,例如可藉由利用檢測出1H-NMR之Si-CH3之峰值與檢測出伸乙基(ethylene)或伸丙基(propylene)之峰值而確認。 Further, the monomer of the polymer (A) containing a decane structure can be confirmed by a specific structure containing a ruthenium atom in the polymer (A) containing a siloxane structure and a radical polymerizable functional group. It is confirmed by a known analysis method of the structure, for example, by detecting the peak of Si-CH 3 which detects 1 H-NMR and detecting the peak of ethylene or propylene.
1-2.1,2-醌二疊氮化合物(B) 1-2.1,2-醌diazide compound (B)
1,2-醌二疊氮化合物(B)例如可使用於抗蝕劑領域中作為光敏劑而使用之化合物。1,2-醌二疊氮化合物(B)例如可列舉:羥基二苯甲酮化合物與1,2-苯醌二疊氮-4-磺酸或1,2-苯醌二疊氮-5-磺酸之酯、羥基二苯甲酮化合物與1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸之酯、酚 化合物與1,2-苯醌二疊氮-4-磺酸或1,2-苯醌二疊氮-5-磺酸之酯、酚化合物與1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸之酯、酚化合物之羥基被取代為胺基之化合物與1,2-苯醌二疊氮-4-磺酸或1,2-苯醌二疊氮-5-磺酸之磺醯胺、酚化合物之羥基被取代為胺基之化合物與1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸之磺醯胺。 The 1,2-quinonediazide compound (B) can be used, for example, as a compound used as a photosensitizer in the field of resists. Examples of the 1,2-quinonediazide compound (B) include a hydroxybenzophenone compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-. Ester of sulfonic acid, hydroxybenzophenone compound and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid ester, phenol An ester of a compound with 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, a phenolic compound and 1,2-naphthoquinonediazide-4-sulfonate An acid or an ester of 1,2-naphthoquinonediazide-5-sulfonic acid, a compound in which a hydroxyl group of a phenol compound is substituted with an amine group, and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2- a sulfonamide of phenylhydrazine diazide-5-sulfonic acid, a compound in which a hydroxyl group of a phenol compound is substituted with an amine group, and a 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinone Sulfonamide of nitrogen-5-sulfonic acid.
羥基二苯甲酮化合物例如可列舉2,3,4-三羥基二苯甲酮、2,4,6-三羥基二苯甲酮、2,2',4,4'-四羥基二苯甲酮、2,3,3',4-四羥基二苯甲酮、以及2,3,4,4'-四羥基二苯甲酮。 Examples of the hydroxybenzophenone compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. Ketone, 2,3,3',4-tetrahydroxybenzophenone, and 2,3,4,4'-tetrahydroxybenzophenone.
酚化合物例如可列舉雙(2,4-二羥基苯基)甲烷、雙(對羥基苯基)甲烷、三(對羥基苯基)甲烷、1,1,1-三(對羥基苯基)乙烷、雙(2,3,4-三羥基苯基)甲烷、2,2-雙(2,3,4-三羥基苯基)丙烷、1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚、雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷、3,3,3',3'-四甲基-1,1'-螺二茚-5,6,7,5',6',7'-己醇、以及2,2,4-三甲基-7,2',4'-三羥基黃酮。 Examples of the phenol compound include bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)B. Alkane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl 4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene Bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobifluorene -5,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavone.
自提高感光性組成物之透明性之觀點考慮,較佳的是1,2-醌二疊氮化合物(B)為選自由2,3,4-三羥基二苯甲酮與1,2-萘醌二疊氮-4-磺酸之酯、2,3,4-三羥基二苯甲酮與1,2-萘醌二疊氮-5-磺酸之酯、2,3,4,4'-四羥基二苯甲酮與1,2-萘醌二疊氮-4-磺酸之酯、2,3,4,4'-四羥基二苯甲酮與1,2-萘醌二疊氮-5-磺酸之酯、4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚與1,2-萘醌二疊氮-4-磺酸之 酯、以及4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚與1,2-萘醌二疊氮-5-磺酸之酯所構成之群組之一種以上。 From the viewpoint of improving the transparency of the photosensitive composition, it is preferred that the 1,2-quinonediazide compound (B) is selected from the group consisting of 2,3,4-trihydroxybenzophenone and 1,2-naphthalene. An ester of quinonezide-4-sulfonic acid, an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid, 2,3,4,4' - ester of tetrahydroxybenzophenone with 1,2-naphthoquinonediazide-4-sulfonic acid, 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide -5-sulfonic acid ester, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2 -naphthoquinone diazide-4-sulfonic acid Ester, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone One or more groups consisting of esters of nitrogen-5-sulfonic acid.
1-3.其他成分 1-3. Other ingredients
感光性組成物可於充分獲得本發明之效果之範圍內進一步含有上述包含矽氧烷結構之聚合物(A)以及1,2-醌二疊氮化合物(B)以外之其他成分。此種其他成分例如可列舉鹼可溶性聚合物(C)、溶劑、添加物、以及多元羧酸酐。 The photosensitive composition may further contain other components other than the above-described polymer (A) having a oxoxane structure and the 1,2-quinonediazide compound (B) within a range in which the effects of the present invention are sufficiently obtained. Examples of such other components include an alkali-soluble polymer (C), a solvent, an additive, and a polycarboxylic acid anhydride.
1-3-1.鹼可溶性聚合物(C) 1-3-1. Alkali soluble polymer (C)
自進一步提高感光性組成物之鹼可溶性而容易地獲得圖案狀透明膜之觀點,以及提高耐溶劑性、高耐水性、高耐酸性、高耐鹼性、以及高耐熱性等所得之硬化膜之特性的觀點考慮,較佳的是感光性組成物進一步含有鹼可溶性聚合物(C)。鹼可溶性聚合物(C)可為一種亦可為兩種以上。而且,鹼可溶性聚合物(C)中之「鹼可溶性」是指將藉由旋塗鹼可溶性聚合物(C)之溶液以及於100℃下加熱2分鐘而形成之厚度為0.01μm~100μm之膜,於例如25℃左右之2.38wt%之四甲基氫氧化銨水溶液中浸漬5分鐘後,藉由純水而清洗時,並未殘留膜。 A cured film obtained by further improving the alkali solubility of the photosensitive composition to easily obtain a patterned transparent film, and improving solvent resistance, high water resistance, high acid resistance, high alkali resistance, and high heat resistance From the viewpoint of characteristics, it is preferred that the photosensitive composition further contains an alkali-soluble polymer (C). The alkali-soluble polymer (C) may be one type or two or more types. Further, the "alkali-soluble" in the alkali-soluble polymer (C) means a film having a thickness of 0.01 μm to 100 μm formed by spin-coating a solution of the alkali-soluble polymer (C) and heating at 100 ° C for 2 minutes. After immersing in an aqueous solution of 2.38 wt% of tetramethylammonium hydroxide at about 25 ° C for 5 minutes, for example, after washing with pure water, no film remains.
於鹼可溶性聚合物(C)中可使用自由基聚合物,所述自由基聚合物是以所獲得之聚合物具有鹼可溶性之方式,使自由基聚合性單體(a-2)、或自由基聚合性單體(a-2)以及自由基聚合性單體(a-3)中所含之兩種以上自由基聚 合性單體進行自由基聚合而成。此種自由基聚合性單體可考慮於本發明之感光性組成物中具有矽氧烷結構之聚合物(A)之使用量,以獲得所期望之功能之量而用於鹼可溶性聚合物(C)中。 A radical polymer which is a radically polymerizable monomer (a-2), or a free radical in a manner that the obtained polymer has alkali solubility can be used in the alkali-soluble polymer (C) Two or more kinds of radicals contained in the base polymerizable monomer (a-2) and the radical polymerizable monomer (a-3) The conjugated monomer is formed by radical polymerization. Such a radical polymerizable monomer can be used for an alkali-soluble polymer in consideration of the amount of the polymer (A) having a decane structure in the photosensitive composition of the present invention to obtain a desired function. C).
於鹼可溶性聚合物(C)之單體中,可使用自由基聚合性單體(a-2)作為具有酚性羥基之自由基聚合性單體。自提高感光性組成物之鹼可溶性之觀點考慮,較佳的是鹼可溶性聚合物(C)之單體包含選自由(甲基)丙烯酸、馬來酸酐、羥基苯乙烯、以及4-羥基苯基乙烯基酮所構成之群組之一種以上。 Among the monomers of the alkali-soluble polymer (C), a radical polymerizable monomer (a-2) can be used as the radical polymerizable monomer having a phenolic hydroxyl group. From the viewpoint of improving the alkali solubility of the photosensitive composition, it is preferred that the monomer of the alkali-soluble polymer (C) comprises a solvent selected from the group consisting of (meth)acrylic acid, maleic anhydride, hydroxystyrene, and 4-hydroxyphenyl group. One or more groups of vinyl ketones.
自曝光部分於鹼性顯影液中直至溶解之顯影時間適當,且於顯影時膜之表面難以變粗糙之觀點考慮,較佳的是鹼可溶性聚合物(C)之重量平均分子量與包含矽氧烷結構之聚合物(A)同樣地為1,000~100,000;進一步自顯影殘渣變得極其少之觀點考慮,更佳的是1,500~50,000,進一步更佳的是2,000~20,000。鹼可溶性聚合物(C)之重量平均分子量例如可藉由與包含矽氧烷結構之聚合物(A)相同之條件的GPC分析而求出。 It is preferred that the weight-average molecular weight of the alkali-soluble polymer (C) and the oxymethane are contained from the viewpoint that the exposure portion is in the alkaline developing solution until the development time of the dissolution is appropriate, and the surface of the film is hard to be roughened at the time of development. The polymer (A) of the structure is similarly 1,000 to 100,000; further, from the viewpoint that the amount of the self-developing residue becomes extremely small, it is more preferably 1,500 to 50,000, still more preferably 2,000 to 20,000. The weight average molecular weight of the alkali-soluble polymer (C) can be determined, for example, by GPC analysis under the same conditions as the polymer (A) containing a decane structure.
鹼可溶性聚合物(C)例如可藉由與包含矽氧烷結構之聚合物(A)同樣之聚合方法而獲得。而且,鹼可溶性聚合物(C)之單體例如可藉由如下方式而推定:於使鹼可溶性聚合物(C)熱分解時,藉由GC-MS而測定由於熱分解所產生之氣體。 The alkali-soluble polymer (C) can be obtained, for example, by the same polymerization method as the polymer (A) containing a decane structure. Further, the monomer of the alkali-soluble polymer (C) can be estimated, for example, by measuring the gas generated by thermal decomposition by GC-MS when the alkali-soluble polymer (C) is thermally decomposed.
1-3-2.溶劑 1-3-2. Solvent
感光性組成物較佳為進一步含有溶劑。溶劑較佳的是可溶解感光性組成物中所調配之包含矽氧烷結構之聚合物(A)、1,2-醌二疊氮化合物(B)、以及鹼可溶性聚合物(C)之溶劑。而且,溶劑較佳的是沸點為100℃~300℃之溶劑。溶劑可為一種亦可為兩種以上。 The photosensitive composition preferably further contains a solvent. The solvent is preferably a solvent which can dissolve the polymer (A), the 1,2-quinonediazide compound (B), and the alkali-soluble polymer (C) which are formulated in the photosensitive composition. . Further, the solvent is preferably a solvent having a boiling point of from 100 ° C to 300 ° C. The solvent may be one type or two or more types.
沸點為100℃~300℃之溶劑例如可列舉乙酸丁酯、丙酸丁酯、乳酸乙酯、氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-氧基丙酸甲酯、3-氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸甲酯、2-側氧丁酸乙酯、二噁烷、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、乙二醇單異丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、環己酮、環戊酮、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二 乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、甲苯、二甲苯、γ-丁內酯、以及N,N-二甲基乙醯胺。 Examples of the solvent having a boiling point of 100 ° C to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, and the like. Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropane Ethyl acetate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl ester, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropanoate, 2-methoxy-2-methyl Methyl propyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2- Methyl acetobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4- Glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol single Butyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, two Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N,N-dimethylacetamide.
自提高形成感光性組成物之膜時的塗佈均一性之觀點考慮,較佳的是溶劑是選自由丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、乳酸乙酯以及乙酸丁酯所構成之群組之一種以上。另外,自對人體之安全性之觀點考慮,更佳的是溶劑是選自由丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、二乙二醇甲基乙基醚、乳酸乙酯、以及乙酸丁酯所構成之群組之一種以上。 From the viewpoint of improving coating uniformity when forming a film of the photosensitive composition, it is preferred that the solvent be selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methyl Methyl oxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol One or more groups of methyl ethyl ether, ethyl lactate, and butyl acetate. Further, from the viewpoint of safety of the human body, it is more preferred that the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and diethyl ether. One or more groups of diol methyl ethyl ether, ethyl lactate, and butyl acetate.
溶劑亦可為含有20wt%以上之沸點為100℃~300℃之溶劑的混合溶劑。混合溶劑中之沸點為100℃~300℃之溶劑以外的溶劑可使用公知之溶劑之一種或兩種以上。 The solvent may also be a mixed solvent containing 20% by weight or more of a solvent having a boiling point of 100 ° C to 300 ° C. A solvent other than the solvent having a boiling point of from 100 ° C to 300 ° C in the mixed solvent may be one or two or more kinds of known solvents.
1-3-3.添加劑 1-3-3. Additives
自使解析度、塗佈均一性、顯影性、以及接著性等感光性組成物以及所形成之硬化膜之特性進一步提高之觀點考慮,較佳的是感光性組成物進一步含有添加劑。添加劑可使用於抗蝕劑劑領域中,於感光性組成物或硬化膜之特性之提高中所利用的各種添加劑。添加劑可為一種亦可為兩種以上。此種添加劑例如可列舉丙烯酸系、苯乙烯系、聚乙烯亞胺系或聚胺酯系高分子分散劑,陰離子系、陽離子系、非離子系或氟系之界面活性劑,矽氧樹脂系塗佈性 改善劑,矽烷偶合劑等密接性改善劑,烷氧基二苯甲酮類等紫外線吸收劑,聚丙烯酸鈉等凝聚抑制劑,環氧化合物、三聚氰胺化合物或雙疊氮化物等熱交聯劑,以及有機羧酸等鹼溶性促進劑。 From the viewpoint of further improving the characteristics of the photosensitive composition such as the resolution, the coating uniformity, the developability, and the adhesion, and the cured film formed, it is preferred that the photosensitive composition further contains an additive. The additive can be used in various additives used in the field of resists for improving the characteristics of a photosensitive composition or a cured film. The additive may be one type or two or more types. Examples of such an additive include acrylic acid, styrene-based, polyethyleneimine-based or polyurethane-based polymer dispersing agents, anionic, cationic, nonionic or fluorine-based surfactants, and epoxy resin-based coating properties. A curing agent, an adhesion improving agent such as a decane coupling agent, an ultraviolet absorber such as an alkoxybenzophenone, a coacervation inhibitor such as sodium polyacrylate, or a thermal crosslinking agent such as an epoxy compound, a melamine compound or a double azide. And an alkali soluble accelerator such as an organic carboxylic acid.
更具體而言,添加劑例如可列舉Polyflow No.45、Polyflow KL-245、Polyflow No.75、Polyflow No.90、Polyflow No.95(以上均為商品名、共榮社化學股份有限公司製造)、Disperbyk 161、Disperbyk 162、Disperbyk 163、Disperbyk 164、Disperbyk 166、Disperbyk 170、Disperbyk 180、Disperbyk 181、Disperbyk 182、BYK300、BYK306、BYK310、BYK320、BYK330、BYK344、BYK346(以上均為商品名、BYK-CHEMIE JAPAN K.K.製造)、KP-341、KP-358、KP-368、KF-96-50CS、KF-50-100CS(以上均為商品名、信越化學工業股份有限公司製造)、Surflon SC-101、Surflon KH-40(以上均為商品名、AGC SEIMI CHEMICAL Co.,Ltd.製造)、Ftergent 222F、Ftergent 251、FTX-218(以上均為商品名、Neos股份有限公司製造)、EFTOP EF-351、EFTOP EF-352、EFTOP EF-601、EFTOP EF-801、EFTOP EF-802(以上均為商品名、Mitsubishi Material Co.,Ltd.製造)、Megafac F-171、Megafac F-177、Megafac F-475、Megafac R-08、Megafac R-30(以上均為商品名、DIC股份有限公司製造)、氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基碘化銨、氟烷基甜菜鹼、氟烷磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷 基三甲銨鹽、氟烷基胺基磺酸鹽、聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯烷基醚、聚氧乙烯月桂醚、聚氧乙烯油基醚、聚氧乙烯十三烷基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、聚氧乙烯月桂基胺、山梨糖醇酐月桂酸酯、山梨醇酐棕櫚酸酯、山梨醇酐硬脂酸酯、山梨醇酐油酸酯、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐月桂酸酯、聚氧乙烯山梨醇酐棕櫚酸酯、聚氧乙烯山梨醇酐硬脂酸酯、聚氧乙烯山梨醇酐油酸酯、聚氧乙烯萘基醚、烷基苯磺酸鹽、以及烷基二苯醚二磺酸鹽。較佳的是添加劑為選自該些化合物之一種以上。 More specifically, examples of the additive include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all of which are trade names, manufactured by Kyoeisha Chemical Co., Ltd.). Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all of the above are trade names, BYK-CHEMIE JAPAN KK), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of which are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all of which are trade names, manufactured by AGC SEIMI CHEMICAL Co., Ltd.), Ftergent 222F, Ftergent 251, FTX-218 (all of which are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are trade names, manufactured by Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-475, Megafac R-08, Megafac R-30 (all of the above are trade names, DIC Manufactured by the company, fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, halothane sulfonate, diglycerin Tetrakis(fluoroalkyl polyoxyethylene ether), halothane Trimethylammonium salt, fluoroalkylamine sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oil base Ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, poly Oxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitol Anhydride laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, And an alkyl diphenyl ether disulfonate. Preferably, the additive is one or more selected from the group consisting of these compounds.
自提高感光性組成物之塗佈均一性之觀點考慮,更佳的是添加劑為氟系界面活性劑以及矽氧樹脂系塗佈性改善劑之一者或兩者。更具體而言,自提高感光性組成物之塗佈均一性之觀點考慮,更佳的是添加物為選自由氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基碘化銨、氟烷基甜菜鹼、氟烷磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲銨鹽、氟烷基胺基磺酸鹽、BYK306、BYK344、BYK346、KP-341、KP-358、以及KP-368所構成之群組之一種以上。 From the viewpoint of improving the coating uniformity of the photosensitive composition, it is more preferable that the additive is one or both of a fluorine-based surfactant and a silicone resin-based coating property improving agent. More specifically, from the viewpoint of improving coating uniformity of the photosensitive composition, it is more preferred that the additive is selected from the group consisting of fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, and fluoroalkylpolyoxyethylene. Ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkanesulfonate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, One or more of the groups consisting of BYK306, BYK344, BYK346, KP-341, KP-358, and KP-368.
1-3-4.多元羧酸酐 1-3-4. Polycarboxylic anhydride
自提高由具有環氧基之感光性組成物所形成之硬化膜之耐熱性以及耐化學品性的觀點,以及防止由於保存時1,2-醌二疊氮化合物(B)之分解所造成的感光性組成物著 色之觀點考慮,較佳的是感光性組成物進一步含有多元羧酸酐。多元羧酸酐可藉由加熱而與具有環氧基之感光性組成物中之環氧基反應。多元羧酸酐可為一種亦可為兩種以上。多元羧酸酐例如可列舉偏苯三甲酸酐、鄰苯二甲酸酐、以及4-甲基環己烷-1,2-二甲酸酐。多元羧酸酐中較佳的是偏苯三甲酸酐。 From the viewpoint of improving the heat resistance and chemical resistance of the cured film formed of the photosensitive composition having an epoxy group, and preventing decomposition of the 1,2-quinonediazide compound (B) by storage. Photosensitive composition From the viewpoint of color, it is preferred that the photosensitive composition further contains a polycarboxylic acid anhydride. The polycarboxylic acid anhydride can be reacted with an epoxy group in the photosensitive composition having an epoxy group by heating. The polycarboxylic acid anhydride may be one type or two or more types. Examples of the polyvalent carboxylic anhydride include trimellitic anhydride, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride. Preferred among the polycarboxylic acid anhydrides is trimellitic anhydride.
1-4.感光性組成物中之各成分之含量 1-4. Content of each component in the photosensitive composition
自表現出硬化膜之撥液性之觀點考慮,感光性組成物中之包含矽氧烷結構之聚合物(A)之含量較佳的是20wt%~80wt%,更佳的是30wt%~70wt%,進一步更佳的是40wt%~60wt%。 The content of the polymer (A) containing a oxoxane structure in the photosensitive composition is preferably from 20% by weight to 80% by weight, more preferably from 30% by weight to 70% by weight from the viewpoint of exhibiting the liquid repellency of the cured film. %, further preferably 40% by weight to 60% by weight.
自於硬化膜中形成精細之圖案之觀點考慮,感光性組成物中之1,2-醌二疊氮化合物(B)之含量相對於包含矽氧烷結構之聚合物(A)以及鹼可溶性聚合物(C)之合計量100重量份而言較佳的是5重量份~50重量份,更佳的是10重量份~40重量份,進一步更佳的是15重量份~30重量份。 From the viewpoint of forming a fine pattern in the cured film, the content of the 1,2-quinonediazide compound (B) in the photosensitive composition is relative to the polymer (A) containing a siloxane structure and alkali-soluble polymerization. The total amount of the component (C) is preferably from 5 parts by weight to 50 parts by weight, more preferably from 10 parts by weight to 40 parts by weight, still more preferably from 15 parts by weight to 30 parts by weight.
於感光性組成物中,自充分表現鹼可溶性之提高效果之觀點考慮,於將包含矽氧烷結構之聚合物(A)之含量設為100重量份時,鹼可溶性聚合物(C)之含量較佳的是20重量份~150重量份,更佳的是50重量份~120重量份,進一步更佳的是70重量份~100重量份。 In the photosensitive composition, the content of the alkali-soluble polymer (C) when the content of the polymer (A) containing a siloxane structure is 100 parts by weight from the viewpoint of sufficiently exhibiting an effect of improving alkali solubility It is preferably 20 parts by weight to 150 parts by weight, more preferably 50 parts by weight to 120 parts by weight, still more preferably 70 parts by weight to 100 parts by weight.
自提高感光性組成物之塗佈均一性之觀點考慮,以及自對人體之安全性之觀點考慮,較佳的是感光性組成物中 之溶劑之含量是感光性組成物中之所有固體成分之含量成為5wt%~50wt%之量,更佳的是成為10wt%~45wt%之量,進一步更佳的是成為15wt%~40wt%之量。 From the viewpoint of improving the uniformity of coating of the photosensitive composition, and from the viewpoint of safety of the human body, it is preferred to be in the photosensitive composition. The content of the solvent is such that the content of all the solid components in the photosensitive composition is from 5 wt% to 50 wt%, more preferably from 10 wt% to 45 wt%, still more preferably from 15 wt% to 40 wt%. the amount.
自賦予以及提高感光性組成物以及硬化膜之特性的觀點考慮,感光性組成物中之添加劑之含量相對於包含矽氧烷結構之聚合物(A)以及鹼可溶性聚合物(C)之合計量100重量份而言較佳的是0.01重量份~1重量份,更佳的是0.03重量份~0.7重量份,進一步更佳的是0.05重量份~0.5重量份。 From the viewpoint of imparting and improving the characteristics of the photosensitive composition and the cured film, the content of the additive in the photosensitive composition is based on the total amount of the polymer (A) containing the siloxane structure and the alkali-soluble polymer (C). It is preferably 0.01 parts by weight to 1 part by weight, more preferably 0.03 parts by weight to 0.7 parts by weight, still more preferably 0.05 parts by weight to 0.5 parts by weight, per 100 parts by weight.
自提高上述硬化膜之特性以及防止感光性組成物著色之觀點考慮,感光性組成物中之多元羧酸酐之含量相對於包含矽氧烷結構之聚合物(A)以及鹼可溶性聚合物(C)之合計量100重量份而言較佳的是1重量份~30重量份,更佳的是2重量份~20重量份,進一步更佳的是3重量份~15重量份。 The content of the polycarboxylic acid anhydride in the photosensitive composition is relative to the polymer (A) containing a siloxane structure and the alkali-soluble polymer (C) from the viewpoint of improving the characteristics of the cured film and preventing coloring of the photosensitive composition. The total amount of 100 parts by weight is preferably from 1 part by weight to 30 parts by weight, more preferably from 2 parts by weight to 20 parts by weight, still more preferably from 3 parts by weight to 15 parts by weight.
1-5.感光性組成物之保存 1-5. Preservation of photosensitive components
自穩定地保存感光性組成物之觀點考慮,較佳的是感光性組成物於-30℃~25℃下遮光保存,自防止產生析出物之觀點考慮,更佳的是保存溫度為-20℃~10℃。 From the viewpoint of stably storing the photosensitive composition, it is preferred that the photosensitive composition is stored in a light-shielding manner at -30 ° C to 25 ° C, and it is more preferable that the storage temperature is -20 ° C from the viewpoint of preventing the occurrence of precipitates. ~10 °C.
2.本發明之硬化膜 2. The cured film of the present invention
本發明之硬化膜可藉由對上述本發明之感光性組成物之膜進行煅燒而獲得。感光性組成物適於形成透明之硬化膜,且圖案化時之解析度比較高,因此適於形成開有10μm以下之小孔的絕緣膜。此處,所謂絕緣膜例如是指用以使 配置為層狀之配線間絕緣而設置之膜(層間絕緣膜)等。 The cured film of the present invention can be obtained by calcining a film of the photosensitive composition of the present invention described above. The photosensitive composition is suitable for forming a transparent cured film, and has a relatively high resolution when patterned, and thus is suitable for forming an insulating film having a small hole of 10 μm or less. Here, the insulating film is used, for example, to make A film (interlayer insulating film) or the like which is provided as a layered wiring between the wirings.
透明膜以及絕緣膜等之硬化膜可藉由於抗蝕劑領域中形成硬化膜之通常方法而形成,例如可以下述方式而形成。 A cured film such as a transparent film or an insulating film can be formed by a usual method of forming a cured film in the field of a resist, and can be formed, for example, in the following manner.
首先,形成感光性組成物之膜。感光性組成物之膜可藉由旋塗、輥塗、狹縫塗佈等公知之方法而將感光性組成物塗佈於玻璃等基板上而形成。較佳之塗佈方法例如可列舉旋塗、輥塗、狹縫塗佈。基板例如可列舉白板玻璃、青板玻璃、二氧化矽塗層青板玻璃等透明玻璃基板,聚碳酸酯、聚醚碸、聚酯、丙烯酸樹脂、氯乙烯樹脂、芳香族聚醯胺樹脂、聚醯胺醯亞胺、聚醯亞胺等合成樹脂製薄板、薄膜或基板,鋁板、銅板、鎳板、不鏽鋼板等金屬基板,其他陶瓷板,具有光電轉換元件之半導體基板等。於該些基板上,可視需要而進行矽烷偶合劑等之化學處理、電漿處理、離子電鍍、濺鍍、氣相反應法、真空蒸鍍等預處理。 First, a film of a photosensitive composition is formed. The film of the photosensitive composition can be formed by applying a photosensitive composition to a substrate such as glass by a known method such as spin coating, roll coating, or slit coating. Preferred coating methods include spin coating, roll coating, and slit coating. Examples of the substrate include transparent glass substrates such as white glass, blue glass, and ceria coated green glass, and polycarbonate, polyether oxime, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, and poly A synthetic resin sheet such as amidoxime or a polyimide, a film or a substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate or a stainless steel plate, and another ceramic plate having a semiconductor substrate of a photoelectric conversion element. Pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum evaporation, etc. of a decane coupling agent may be performed on the substrates as needed.
其次,對感光性組成物之膜進行乾燥。感光性組成物之膜例如可藉由加熱板或烘箱對具有感光性組成物之膜的基板進行加熱而使其乾燥。通常於60℃~120℃下進行1分鐘~5分鐘之乾燥。 Next, the film of the photosensitive composition is dried. The film of the photosensitive composition can be dried, for example, by heating a substrate having a film of a photosensitive composition by a hot plate or an oven. Drying is usually carried out at 60 ° C to 120 ° C for 1 minute to 5 minutes.
其次,介隔所期望之圖案形狀之遮罩而對乾燥之感光性組成物之膜照射放射線。對感光性組成物之膜的放射線之照射,例如可藉由介隔遮罩而對基板上之乾燥之感光性組成物之膜照射紫外線而進行。照射條件根據感光性組成物中之光敏劑之種類而定,例如感光性組成物含有1,2-醌二疊氮化合物(B),因此i線適當的是5mJ/cm2~1,000 mJ/cm2。另外,於形成不具有圖案之硬化膜之情形時,無須該放射線之照射步驟。 Next, the film of the dried photosensitive composition is irradiated with radiation through a mask of a desired pattern shape. Irradiation of the radiation of the film of the photosensitive composition can be performed, for example, by irradiating the film of the dried photosensitive composition on the substrate with ultraviolet rays by means of a mask. The irradiation condition depends on the kind of the photosensitizer in the photosensitive composition. For example, the photosensitive composition contains the 1,2-quinonediazide compound (B), so the i line is suitably 5 mJ/cm 2 to 1,000 mJ/cm. 2 . Further, in the case of forming a cured film having no pattern, the irradiation step of the radiation is not required.
其次,藉由顯影液洗滌照射了放射線之感光性組成物之膜而進行顯影。照射了放射線之感光性組成物之膜中的1,2-醌二疊氮化合物(B)迅速成為茚羧酸而成為溶解於顯影液中之狀態。藉由該顯影,膜中之被放射線照射之部分迅速溶解於顯影液中。顯影方法並無特別限定,可使用浸漬顯影、浸置式顯影、噴淋顯影等公知之方法之任意種。另外,於形成未具有圖案之硬化膜之情形時,亦無須該顯影步驟。 Next, development is carried out by washing a film of the photosensitive composition irradiated with radiation by a developing solution. The 1,2-quinonediazide compound (B) in the film of the photosensitive composition irradiated with radiation rapidly becomes a hydrazine carboxylic acid and is dissolved in the developing solution. By this development, the portion irradiated with radiation in the film is quickly dissolved in the developer. The development method is not particularly limited, and any of various known methods such as immersion development, dip development, and shower development can be used. Further, in the case of forming a cured film having no pattern, the development step is not required.
顯影液較佳的是鹼溶液。顯影液可適宜使用鹼之水溶液。鹼溶液中所含有之鹼例如可列舉四甲基氫氧化銨、四乙基氫氧化銨、2-羥乙基三甲基氫氧化銨、碳酸鈉、碳酸氫鈉、碳酸鉀、碳酸氫鉀、氫氧化鈉、以及氫氧化鉀。較佳之顯影液更具體而言可列舉:四甲基氫氧化銨、四乙基氫氧化銨、以及2-羥乙基三甲基氫氧化銨等有機鹼類等之水溶液,以及碳酸鈉、氫氧化鈉、或氫氧化鉀等無機鹼類之水溶液。 The developer is preferably an alkali solution. As the developer, an aqueous solution of a base can be suitably used. Examples of the base contained in the alkali solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate. Sodium hydroxide, and potassium hydroxide. More preferably, the developing solution is preferably an aqueous solution of an organic base such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or 2-hydroxyethyltrimethylammonium hydroxide, or sodium carbonate or hydrogen. An aqueous solution of an inorganic base such as sodium oxide or potassium hydroxide.
為了減低顯影殘渣或實現圖案形狀之適當化,亦可於顯影液中添加甲醇、乙醇或界面活性劑。界面活性劑例如可使用選自陰離子系、陽離子系、以及非離子系之界面活性劑。於該些中,特別是若添加非離子系之聚氧乙烯烷基醚,則自提高解析度之觀點而言較佳。 In order to reduce the development residue or to optimize the shape of the pattern, methanol, ethanol or a surfactant may be added to the developer. As the surfactant, for example, an anionic, cationic, or nonionic surfactant can be used. Among these, in particular, when a nonionic polyoxyethylene alkyl ether is added, it is preferable from the viewpoint of improving the resolution.
其次,對顯影之膜進行清洗。膜之清洗例如可藉由純 水而對膜與基板一同進行充分洗濯而進行。 Next, the developed film is cleaned. Membrane cleaning can be done, for example, by pure Water is applied to the film and the substrate together with sufficient washing.
其次,對所清洗之膜之前面照射放射線。藉由該放射線之照射而使殘餘之1,2-醌二疊氮化合物(B)去活化。作為該放射線之照射,例如於放射線為紫外線之情形時,藉由以100mJ/cm2~1,000mJ/cm2之曝光量對膜照射紫外線而進行。 Next, the front surface of the film to be cleaned is irradiated with radiation. The residual 1,2-quinonediazide compound (B) is deactivated by irradiation of the radiation. When the radiation is irradiated with ultraviolet rays, for example, when the radiation is ultraviolet rays, the film is irradiated with ultraviolet rays at an exposure amount of 100 mJ/cm 2 to 1,000 mJ/cm 2 .
其次,對照射了放射線之膜進行煅燒而獲得硬化膜。該膜之煅燒例如可藉由如下之方式而進行:將具有膜之基板於180℃~250℃下加熱10分鐘~120分鐘。藉由此種步驟,獲得硬化膜而作為所期望之圖案化之透明膜。 Next, the film irradiated with radiation is calcined to obtain a cured film. The calcination of the film can be carried out, for example, by heating the substrate having the film at 180 ° C to 250 ° C for 10 minutes to 120 minutes. By this step, a cured film is obtained as a desired patterned transparent film.
如此而所獲得之圖案狀透明膜亦可用作圖案狀絕緣膜。於絕緣膜上所形成之孔之形狀,於自正上方查看之情形時,較佳的是正方形、長方形、圓形或橢圓形。另外,亦可於該絕緣膜上形成透明電極,藉由蝕刻而進行圖案化後,形成進行配向處理之膜。該絕緣膜之耐濺鍍性高,因此即使形成透明電極亦不於絕緣膜上產生皺折,可保持高的透明性。 The pattern-like transparent film thus obtained can also be used as a pattern-like insulating film. The shape of the hole formed in the insulating film is preferably square, rectangular, circular or elliptical when viewed from above. Further, a transparent electrode may be formed on the insulating film, and after patterning by etching, a film subjected to alignment treatment may be formed. Since the insulating film has high sputtering resistance, wrinkles are not formed on the insulating film even when a transparent electrode is formed, and high transparency can be maintained.
3.本發明之顯示元件 3. Display element of the present invention
本發明之顯示元件具有上述之本發明之硬化膜。顯示元件中之硬化膜之用途例如可列舉透明膜、絕緣膜、以及用以防止液體附著於圖案之周圍的障壁膜。 The display element of the present invention has the above-described cured film of the present invention. Examples of the use of the cured film in the display element include a transparent film, an insulating film, and a barrier film for preventing liquid from adhering to the periphery of the pattern.
顯示元件除了於所述用途中使用本發明之硬化膜以外,具有與公知之顯示元件同樣之構成,可與公知之顯示元件同樣地製造。顯示元件例如可使如上所述那樣於基板 上具有圖案化之硬化膜的元件基板、作為對向基板之彩色濾光片基板對準預先於各基板上所附之標記之位置而進行壓接,其後進行熱處理而將基板以外之其他部件組合,於對向之基板間注入液晶,將注入口密封,藉此而製作為液晶顯示元件。 The display element has the same configuration as the known display element except that the cured film of the present invention is used for the above-described use, and can be produced in the same manner as the known display element. The display element can be, for example, as described above on the substrate The element substrate having the patterned cured film and the color filter substrate as the opposite substrate are bonded to each other at positions marked with marks attached to the respective substrates, and then heat-treated to separate the other members from the substrate. In combination, liquid crystal is injected between the opposing substrates, and the injection port is sealed to form a liquid crystal display element.
於液晶顯示元件之製造中,液晶之封入亦可藉由如下方式而進行:於元件基板上散布液晶後,使元件基板與彩色濾光片基板重合,以液晶不漏出之方式加以密封。顯示元件亦可為如此而製作之液晶顯示元件。 In the manufacture of the liquid crystal display device, the sealing of the liquid crystal may be performed by dispersing the liquid crystal on the element substrate, superimposing the element substrate on the color filter substrate, and sealing the liquid crystal so as not to leak. The display element can also be a liquid crystal display element fabricated as such.
液晶、亦即液晶化合物以及含有其之組成物並無特別限定,可使用任意之液晶化合物以及液晶組成物。 The liquid crystal, that is, the liquid crystal compound and the composition containing the same are not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.
本發明之感光性組成物例如可形成具有對於圖案化透明膜以及絕緣膜所通常要求之高耐溶劑性、高耐水性、高耐酸性、高耐鹼性、高耐熱性、高透明性、與基底之密接性等各種特性,且撥液性優異之硬化膜。 The photosensitive composition of the present invention can be formed, for example, to have high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, and the like, which are generally required for a patterned transparent film and an insulating film. A cured film having various properties such as adhesion to a substrate and excellent liquid repellency.
而且,本發明之感光性組成物除了上述之高撥液性、耐UV臭氧灰化性以外,關於顯影性、耐化學品性、以及密接性等作為抗蝕劑劑材料所要求之通常特性,亦具有作為抗蝕劑劑材料而言至少充分之性能。因此,本發明之感光性組成物可形成除撥液性以外,圖案形成性亦優異之硬化膜。而且,該膜可用作透明膜、絕緣膜或保護膜,因此可作為顯示元件而使用。 Further, in addition to the above-described high liquid repellency and UV ozone ashing resistance, the photosensitive composition of the present invention has normal characteristics required as a resist material in terms of developability, chemical resistance, and adhesion. It also has at least sufficient performance as a resist material. Therefore, the photosensitive composition of the present invention can form a cured film excellent in pattern formability in addition to liquid repellency. Moreover, the film can be used as a transparent film, an insulating film or a protective film, and thus can be used as a display element.
本發明之硬化膜由本發明之感光性組成物而形成,因此即使於溶劑、酸、鹼溶液等中受到浸漬、接觸、熱處理 等處理亦難以產生表面粗糙。因此,本發明之顯示元件的硬化膜中之光透射率高,可獲得高的顯示品質。 Since the cured film of the present invention is formed from the photosensitive composition of the present invention, it is subjected to immersion, contact, and heat treatment even in a solvent, an acid, an alkali solution or the like. It is also difficult to produce surface roughness by equal treatment. Therefore, the light transmittance in the cured film of the display element of the present invention is high, and high display quality can be obtained.
而且,本發明之硬化膜由感光性組成物而形成,因此撥液性優異,於顯示元件之製造過程中,防止供給至硬化膜之圖案(開口部)的液狀材料附著於圖案以外之部分,而且該附著之所期望之液體容易向開口部移動。因此,可效率良好地獲得所期望之性能的顯示元件,期待顯示元件之生產性之進一步提高。 Further, since the cured film of the present invention is formed of a photosensitive composition, it is excellent in liquid repellency, and the liquid material supplied to the pattern (opening) of the cured film is prevented from adhering to portions other than the pattern during the production of the display element. And the desired desired liquid is easily moved to the opening. Therefore, the display element of the desired performance can be efficiently obtained, and further improvement in the productivity of the display element is expected.
[實例] [Example]
以下,藉由實例對本發明進一步加以說明,但本發明並不限定於該些實例。 Hereinafter, the present invention will be further illustrated by way of examples, but the invention is not limited to the examples.
[合成例1]包含矽氧烷結構之聚合物(A1)之合成 [Synthesis Example 1] Synthesis of polymer (A1) containing a siloxane structure
於附有攪拌機之4口燒瓶中裝入作為溶劑之16g之二乙二醇甲基乙基醚,另一方面,於11g之二乙二醇甲基乙基醚中以下述之重量而混合作為自由基聚合性單體(a-1)之式(1-1)所表示之α,ω-雙(3-甲基丙烯醯氧基丙基)聚二甲基矽氧烷(CHISSO CORPORATION製造之FM7711、數量平均分子量:1,000)、作為自由基聚合性單體(a-2)之4-羥基苯基乙烯基酮、作為自由基聚合性單體(a-3)之甲基丙烯酸縮水甘油酯、3-甲基丙烯醯氧基丙基三甲氧基矽烷、作為聚合起始劑之2,2'-偶氮雙(2-甲基丙酸酯)二甲酯,將所得之混合溶液以1小時滴加至維持為110℃之4口燒瓶中的溶劑中,於滴加後,於110℃下進一步加熱2小時。 Into a four-necked flask equipped with a stirrer, 16 g of diethylene glycol methyl ethyl ether as a solvent was placed, and on the other hand, 11 g of diethylene glycol methyl ethyl ether was mixed as the following weight. α,ω-bis(3-methylpropenyloxypropyl)polydimethyloxane represented by the formula (1-1) of the radical polymerizable monomer (a-1) (manufactured by CHISSO CORPORATION) FM7711, number average molecular weight: 1,000), 4-hydroxyphenyl vinyl ketone as a radical polymerizable monomer (a-2), glycidyl methacrylate as a radical polymerizable monomer (a-3) , 3-methacryloxypropyltrimethoxydecane, 2,2'-azobis(2-methylpropionate) dimethyl ester as a polymerization initiator, and the obtained mixed solution is 1 The mixture was added dropwise to the solvent in a 4-neck flask maintained at 110 ° C, and further heated at 110 ° C for 2 hours after the dropwise addition.
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之包含矽氧烷結構之聚合物(A1)的33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)而測定重量平均分子量。其結果,包含矽氧烷結構之聚合物(A1)之重量平均分子量為4,000。 The obtained reaction liquid was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (A1) containing no oxoxane structure containing no dimethyl 2,2'-azobis(2-methylpropionate) dimethyl ester. . A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A1) containing a siloxane structure was 4,000.
[合成例2]包含矽氧烷結構之聚合物(A2)之合成 [Synthesis Example 2] Synthesis of polymer (A2) containing a siloxane structure
以下述重量使用下述成分而調製所述混合溶液,與合成例1同樣地進行聚合。 The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之包含矽氧烷結構之聚合物(A2)的33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)而測定重量平均分子量。其結果,包含矽氧烷結構之聚合物(A2)之重量平均分子量為3,100。 The obtained reaction liquid was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (A2) containing no oxoxane structure containing no dimethyl 2,2'-azobis(2-methylpropionate) dimethyl ester. . A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A2) containing a siloxane structure was 3,100.
[合成例3]鹼可溶性聚合物(C1)之合成 [Synthesis Example 3] Synthesis of alkali-soluble polymer (C1)
使用式(3-1)所表示之α-丁基-ω-(3-甲基丙烯醯氧基丙基)聚二甲基矽氧烷(CHISSO CORPORATION製造之FM0711、數量平均分子量:1,000)而代替α,ω-雙(3-甲基丙烯醯氧基丙基)聚二甲基矽氧烷,以下述重量使用下述成分而調製所述混合溶液,與合成例1同樣地進行聚合。 Α-butyl-ω-(3-methacryloxypropyl)polydimethyloxane represented by the formula (3-1) (FM0711 manufactured by CHISSO CORPORATION, number average molecular weight: 1,000) was used. The mixed solution was prepared by using the following components in the following weight instead of α,ω-bis(3-methylpropenyloxypropyl)polydimethyloxane, and polymerization was carried out in the same manner as in Synthesis Example 1.
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之鹼可溶性聚合物(C1)之33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)而測定重量平均分子量。其結果,鹼可溶性聚合物(C1)之重量平均分子量為2,800。 The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C1) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C1) was 2,800.
[合成例4]鹼可溶性聚合物(C2)之合成 [Synthesis Example 4] Synthesis of alkali-soluble polymer (C2)
以下述重量使用下述成分而調製所述混合溶液,與合成例1同樣地進行聚合。 The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之鹼可溶性聚合物(C2)之33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,鹼可溶性聚合物(C2)之重量平均分子量為3,500。 The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C2) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C2) was 3,500.
[合成例5]鹼可溶性聚合物(C3)之合成 [Synthesis Example 5] Synthesis of alkali-soluble polymer (C3)
以下述重量使用下述成分而調製所述混合溶液,與合成例1同樣地進行聚合。 The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.
二乙二醇甲基乙基醚 11.0g
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之鹼可溶性聚合物(C3)之33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)而測定重量平均分子量。其結果,鹼可溶性聚合物(C3)之重量平均分子量為2,800。 The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C3) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C3) was 2,800.
[合成例6]鹼可溶性聚合物(C4)之合成 [Synthesis Example 6] Synthesis of alkali-soluble polymer (C4)
以下述重量使用下述成分而調製所述混合溶液,與合成例1同樣地進行聚合。 The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之鹼可溶性聚合物(C4)之33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,鹼可溶性聚合物(C4)之重量平均分子量為2,800。 The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C4) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C4) was 2,800.
[比較合成例1]包含矽氧烷結構之聚合物(D1)之合成 [Comparative Synthesis Example 1] Synthesis of polymer (D1) containing a siloxane structure
以下述重量使用下述成分而調製所述混合溶液,將混合溶液之滴下時以及其後之反應中的4口燒瓶中之溶劑的溫度設為90℃,除此以外與合成例1同樣地進行聚合。 The mixed solution was prepared by using the following components in the following manner, and the same procedure as in Synthesis Example 1 was carried out except that the mixed solution was prepared in the same manner as in Synthesis Example 1 except that the temperature of the solvent in the four-necked flask in the reaction of the mixed solution and the subsequent reaction was 90° C. polymerization.
將所得之反應液冷卻至室溫,獲得不含2,2'-偶氮雙(2-甲基丙酸酯)二甲酯之包含矽氧烷結構之聚合物(D1)之33.3wt%溶液。對反應液之一部分進行取樣,藉由GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,包含矽氧烷結構之聚合物(D1)之重量平均分子量為2,700。 The obtained reaction liquid was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (D1) containing no oxoxane structure containing no dimethyl 2,2'-azobis(2-methylpropionate) dimethyl ester. . A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (D1) containing a decane structure was 2,700.
[實例1] [Example 1]
[正型感光性組成物之製造] [Manufacture of positive photosensitive composition]
將合成例1中所得之共聚物(A1)、合成例6中所得之共聚物(C4)、作為1,2-醌二疊氮化合物之4,4'-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚與1,2-萘醌二疊氮-5-磺醯氯之縮合物(平均酯化率為58%、以下稱為「PAD」)、作為添加劑之矽系界面活性劑BYK344(商品名:BYK-CHEMIE JAPAN K.K.、以下簡稱為「BYK344」)、作為溶劑之二乙二醇甲基乙基醚以下述 重量進行混合溶解,獲得固形物濃度為35wt%之正型感光性組成物1。 The copolymer (A1) obtained in Synthesis Example 1, the copolymer (C4) obtained in Synthesis Example 6, and 4,4'-[1-[4-[1- as a 1,2-quinonediazide compound. a condensate of [4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinonediazide-5-sulfonyl chloride (average esterification rate is 58 %, hereinafter referred to as "PAD"), 矽-based surfactant BYK344 (product name: BYK-CHEMIE JAPAN KK, hereinafter abbreviated as "BYK344"), and diethylene glycol methyl ethyl ether as solvent Description The weight was mixed and dissolved to obtain a positive photosensitive composition 1 having a solid concentration of 35 wt%.
[正型感光性組成物之評價方法] [Evaluation method of positive photosensitive composition]
1)圖案狀透明膜之形成方法 1) Method for forming patterned transparent film
將感光性組成物1以600rpm而旋塗於玻璃基板上10秒,以100℃之加熱板進行2分鐘之乾燥。將該基板於空氣中介隔孔圖案形成用光罩而使用TOPCON股份有限公司製造之近接式曝光機TME-150PRC,介隔波長截止濾光器截止350nm以下之光而出射g、h、i線,以曝光間隙100μm而進行曝光。曝光量設為150mJ/cm2。曝光量是藉由Ushio Inc.製造之累計光量計UIT-102以及光接收器UVD-365PD而進行測定。將曝光後之玻璃基板於0.4wt%之四甲基氫氧化銨水溶液中浸漬顯影60秒,除去曝光部之樹脂組成物。將顯影後之基板於純水中洗滌60秒後,以100℃之加熱板乾燥2分鐘。將該基板於曝光機中,並不介隔光罩而以300mJ/cm2進行整個面曝光後,於烘箱中、230℃下進行30分鐘之後烘烤,形成膜厚為3μm之圖案狀透明膜。 The photosensitive composition 1 was spin-coated on a glass substrate at 600 rpm for 10 seconds, and dried on a hot plate at 100 ° C for 2 minutes. The substrate was used in a mask for forming an air-intervening pattern, and a proximity exposure machine TME-150PRC manufactured by TOPCON Co., Ltd. was used to emit light, g, h, and i lines through a wavelength cut-off filter that cuts off light of 350 nm or less. Exposure was performed with an exposure gap of 100 μm. The exposure amount was set to 150 mJ/cm 2 . The exposure amount was measured by an integrated light meter UIT-102 manufactured by Ushio Inc. and a light receiver UVD-365PD. The exposed glass substrate was immersed and developed in a 0.4 wt% aqueous solution of tetramethylammonium hydroxide for 60 seconds to remove the resin composition of the exposed portion. The developed substrate was washed in pure water for 60 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. The substrate was exposed to the entire surface at 300 mJ/cm 2 without interposing a mask in an exposure machine, and then baked in an oven at 230 ° C for 30 minutes to form a pattern-like transparent film having a film thickness of 3 μm. .
2)顯影後殘膜率 2) Residual film rate after development
於顯影之前後測定膜厚,根據下式而進行計算。 The film thickness was measured before and after development, and was calculated according to the following formula.
(顯影後之膜厚/顯影前之膜厚)×100(%) (film thickness after development / film thickness before development) × 100 (%)
膜厚是使用KLA-Tencor Japan股份有限公司製造之觸針式膜厚計P-15,測定3處,取其平均值。 The film thickness was measured by using a stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd., and the average value was taken.
3)解析度 3) Resolution
藉由光學顯微鏡於400倍下觀察上述1)中所得之圖案狀透明膜之基板,確認於孔圖案之底露出玻璃之遮罩尺寸。將未形成孔圖案之情形記為不良(NG)。 The substrate of the patterned transparent film obtained in the above 1) was observed under an optical microscope at 400 times, and it was confirmed that the mask size of the glass was exposed at the bottom of the hole pattern. The case where the hole pattern was not formed was described as defective (NG).
4)密接性 4) Adhesion
藉由柵格剝離試驗(交叉切割試驗)而評價上述1)中所得之圖案狀透明膜之基板。評價是於藉由切入而形成有100個1mm見方之柵格的圖案狀透明膜上貼附黏著帶(住友3M股份有限公司製造之「聚酯膠帶No.56:黏著力;5.5N/cm」),以膠帶剝離後之殘存柵格數表示。 The substrate of the pattern-like transparent film obtained in the above 1) was evaluated by a grid peeling test (cross-cut test). The evaluation was carried out by attaching an adhesive tape to a patterned transparent film having 100 grids of 1 mm square formed by cutting ("PET tape No. 56: adhesive force; 5.5 N/cm" manufactured by Sumitomo 3M Co., Ltd. ), expressed as the number of remaining grids after tape peeling.
5)UV/O3灰化處理 5) UV/O 3 ashing treatment
除了未形成圖案以外,亦即除了並不進行介隔光罩之曝光以外,與上述1)同樣地形成透明膜,藉由以下之裝置,於以下之條件下對所得之透明膜進行處理。 A transparent film was formed in the same manner as in the above 1) except that the film was not formed, and the obtained transparent film was treated under the following conditions by the following apparatus.
裝置:PL2003N-12(SEN LIGHTS Co.,Ltd.製造之PHOTO SURFACE PROCESSOR) Device: PL2003N-12 (PHOTO SURFACE PROCESSOR manufactured by SEN LIGHTS Co., Ltd.)
諸設定值:紫外線波長(254nm)、曝光量(525mJ/cm2) Setting values: ultraviolet wavelength (254 nm), exposure (525 mJ/cm 2 )
另外,使用CUSTOM股份有限公司製造之UVC-254而測定254nm之曝光量。 Further, the exposure amount at 254 nm was measured using UVC-254 manufactured by CUSTOM Co., Ltd.
6)接觸角 6) Contact angle
藉由協和界面化學股份有限公司製造之Drop Master500而於25℃環境下測定上述5)之UV/O3灰化處理前後之所述透明膜的純水之接觸角。將純水附著1秒後之值作為接觸角值。 The contact angle of the pure water of the transparent film before and after the UV/O 3 ashing treatment of the above 5) was measured at 25 ° C by a Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd. The value after attaching pure water for 1 second was taken as the contact angle value.
將感光性組成物1之組成以及藉由上述之評價方法而所得之結果示於表1。 The composition of the photosensitive composition 1 and the results obtained by the above evaluation methods are shown in Table 1.
[實例2~實例5以及比較例1~比較例4] [Example 2 to Example 5 and Comparative Example 1 to Comparative Example 4]
藉由表1中所示之組合以及量而與實例1同樣地調製作為聚合物溶液之感光性組成物2~感光性組成物5以及比較用可溶性組成物1~比較用可溶性組成物4,進行評價。將該些感光性組成物之組成以及評價結果示於表1中。 In the same manner as in Example 1, the photosensitive composition 2 to the photosensitive composition 5 and the comparative soluble composition 1 to the comparative soluble composition 4 were prepared in the same manner as in Example 1 in the same manner as in Example 1. Evaluation. The composition and evaluation results of the photosensitive compositions are shown in Table 1.
由表1可知,於實例1~實例5中,與比較例1~比較 例4相比而言,即使於UV/O3灰化處理後亦可獲得高的接觸角。 As is clear from Table 1, in Examples 1 to 5, a high contact angle was obtained even after the UV/O 3 ashing treatment as compared with Comparative Examples 1 to 4.
[產業上之可利用性] [Industrial availability]
如以上所說明那樣,本發明之感光性組成物可藉由已知之微影法而進行處理,所得之硬化膜具有作為障壁材料之充分之撥液性。而且,於電路基板製造製程等中,可抑制為了提高濕潤性而進行UV/O3灰化處理所造成之障壁材料表面之撥液性之降低,且於處理後亦維持充分之撥液性。 As described above, the photosensitive composition of the present invention can be treated by a known lithography method, and the obtained cured film has sufficient liquid repellency as a barrier material. Further, in the circuit board manufacturing process or the like, it is possible to suppress a decrease in the liquid repellency of the surface of the barrier material due to the UV/O 3 ashing treatment for improving the wettability, and to maintain sufficient liquid repellency after the treatment.
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JP2012037595A (en) | 2012-02-23 |
JP5482553B2 (en) | 2014-05-07 |
KR20120023540A (en) | 2012-03-13 |
TW201207561A (en) | 2012-02-16 |
KR101814587B1 (en) | 2018-01-04 |
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