TW201344366A - Positive photosensitive resin composition, partition wall and optical element - Google Patents

Positive photosensitive resin composition, partition wall and optical element Download PDF

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Publication number
TW201344366A
TW201344366A TW102108258A TW102108258A TW201344366A TW 201344366 A TW201344366 A TW 201344366A TW 102108258 A TW102108258 A TW 102108258A TW 102108258 A TW102108258 A TW 102108258A TW 201344366 A TW201344366 A TW 201344366A
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resin composition
photosensitive resin
positive photosensitive
ink
group
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TW102108258A
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Chinese (zh)
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TWI575320B (en
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Masayuki Kawashima
Hideyuki Takahashi
Yutaka Furukawa
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Asahi Glass Co Ltd
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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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • 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
    • 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
    • G03F7/022—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
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Optical Filters (AREA)

Abstract

To provide: a positive photosensitive resin composition which has excellent ink repellency and still has the excellent ink repellency after an ultraviolet/ozone irradiation treatment, while being capable of providing a partition wall that has less residue in the dot, said positive photosensitive resin composition having sufficient storage stability; a partition wall which is formed using the resin composition; and an optical element. A positive photosensitive resin composition containing (A) an alkali-soluble resin, (B) a sensitizer and (C) an ink repellent agent, which is characterized in that the ink repellent agent (C) is composed of a partial hydrolysis-condensation product of a mixture that contains a fluorine-containing hydrolyzable silane compound and the ratio of the fluorine atom content in the hydrolyzable silane compound is 10-55% by mass; a partition wall which is formed using the resin composition; and an optical element.

Description

正型感光性樹脂組成物、隔壁及光學元件 Positive photosensitive resin composition, partition and optical component 發明領域 Field of invention

本發明係有關於一種正型感光性樹脂組成物、使用其而形成之隔壁及具有該隔壁之光學元件。 The present invention relates to a positive photosensitive resin composition, a partition wall formed using the same, and an optical element having the partition.

發明背景 Background of the invention

周知在光學元件之濾色器或有機EL(Electro-Luminescence)元件之像素部使用的隔壁係以將感光性樹脂組成物塗佈於基板並藉由光微影技術而形成之方法製造。 It is known that a partition used in a color filter of an optical element or a pixel portion of an organic EL (Electro-Luminescence) element is produced by a method in which a photosensitive resin composition is applied onto a substrate and formed by photolithography.

近年，作為濾色器或有機EL元件之像素部的製造方法，有提議一種利用噴墨法之低成本化處理製程。 In recent years, as a method of manufacturing a pixel portion of a color filter or an organic EL element, a low-cost processing process using an inkjet method has been proposed.

例如，在濾色器之製造中藉由光微影形成隔壁後，藉由噴墨法將R(紅)、G(綠)及B(藍)之印墨噴射至被隔壁包圍的開口部(點)，進行塗佈而形成像素。 For example, after forming a partition wall by photolithography in the manufacture of a color filter, inks of R (red), G (green), and B (blue) are ejected by an inkjet method to an opening surrounded by the partition wall ( Point), coating is performed to form a pixel.

在噴墨法中，必須防止在鄰接像素間之印墨混色。因此，針對隔壁會要求需有撥除噴墨吐出液包括水或有機溶劑印墨之性質，即所謂的撥墨性。另一方面，針對以噴墨法形成像素的印墨層則需要有優異的膜厚均勻性。所以，被隔壁包圍的點(dot)則要求需對吐出液具有良好的 濕潤性即所謂的親墨性。 In the ink jet method, it is necessary to prevent ink color mixing between adjacent pixels. Therefore, it is required for the partition wall to have the property of removing the inkjet discharge liquid including water or organic solvent ink, that is, so-called ink repellency. On the other hand, it is necessary to have excellent film thickness uniformity for an ink layer in which pixels are formed by an inkjet method. Therefore, the dot surrounded by the next wall requires a good need for the discharge liquid. Wetness is the so-called ink retention.

為了將隔壁表面製成撥墨性，研發出一種對使用於隔壁形成的感光性樹脂組成物添加撥墨劑之技術。 In order to make the surface of the partition wall ink-repellent, a technique of adding an ink-repellent to the photosensitive resin composition formed on the partition wall has been developed.

正型感光性樹脂在顯影後之殘渣(以下亦稱「顯影殘渣」)少之觀點上較負型感光性樹脂優異，有時適合作利用。例如專利文獻1中有記載一種使用含有表面自由能小之撥墨劑的正型感光性樹脂組成物對隔壁表面賦予撥墨性之技術。 The positive photosensitive resin is superior to the negative photosensitive resin in that the residue after development (hereinafter also referred to as "developing residue") is small, and may be suitably used. For example, Patent Document 1 discloses a technique of imparting ink repellency to a surface of a partition wall using a positive photosensitive resin composition containing a toner having a small surface free energy.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本特開2009-251327號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-251327

發明揭示 Invention

但，在專利文獻1中記載的正型感光性樹脂組成物有撥墨劑之表面移行性不夠充分且撥墨劑殘留於隔壁內部，使隔壁側面之親墨性變差之問題。亦有撥墨劑殘留於顯影後之點陣使印墨無法均勻地塗佈而產生印墨之白點的問題。在點洗淨上雖可使用紫外線/臭氧照射處理等，但以專利文獻1中記載之撥墨劑而言，亦有耐性不夠充分而使隔壁之撥墨性大幅降低之問題。 However, the positive-type photosensitive resin composition described in Patent Document 1 has a problem that the surface repellency of the ink-repellent agent is insufficient and the ink-repellent agent remains inside the partition wall, and the ink-repellency of the side wall of the partition wall is deteriorated. There is also a problem that the toner is left in the dot matrix after development so that the ink cannot be uniformly applied to cause white spots of the ink. In the case of the ink cleaning, the ink-repellent agent described in Patent Document 1 has insufficient resistance and the ink repellency of the partition wall is largely lowered.

本發明係有鑑於前述現況而進行者，其目的在於提供一種正型感光性樹脂組成物，其可形成撥墨性佳、即便經紫外線/臭氧照射處理撥墨性仍佳且於點少有殘留物 之隔壁，且貯藏穩定性亦佳。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a positive photosensitive resin composition which is excellent in ink repellency, and which is excellent in ink repellency even after ultraviolet/ozone irradiation treatment and has little residue at a point. Object It is next door and has good storage stability.

又，本發明目的在於提供一種光學元件，其具有撥墨性佳且即便經紫外線/臭氧照射處理撥墨性仍佳的隔壁。 Further, an object of the present invention is to provide an optical element which has a good ink repellency and is excellent in ink repellency even under ultraviolet/ozone irradiation treatment.

本發明提供一種具有以下[1]~[15]之構成的正型感光性樹脂組成物、隔壁及光學元件。 The present invention provides a positive photosensitive resin composition, a partition wall, and an optical element having the following configurations [1] to [15].

[1]一種正型感光性樹脂組成物，係含有鹼可溶性樹脂(A)、感光劑(B)及撥墨劑(C)者；前述撥墨劑(C)係由下述混合物的部分水解縮合物所構成：含有以下式(c-1)表示之水解性矽烷化合物及以下式(c-2)表示之水解性矽烷化合物之混合物；且前述撥墨劑(C)中之氟原子含有率為10~55質量%；[化1]Rf-Q1-SiX1 3…(c-1) RH1 p-SiX2 (4-p)…(c-2) [1] A positive photosensitive resin composition containing an alkali-soluble resin (A), a sensitizer (B), and an ink-repellent (C); the ink-repellent (C) is partially hydrolyzed by the following mixture; The condensate comprises a mixture of a hydrolyzable decane compound represented by the following formula (c-1) and a hydrolyzable decane compound represented by the following formula (c-2); and a fluorine atom content ratio in the above-mentioned ink-repellent (C) 10 to 55 mass%; [Chemical 1] R f -Q 1 -SiX 1 3 (c-1) R H1 p -SiX 2 (4-p) (c-2)

(式(c-1)及(c-2)中之記號如下：Rf：碳原子數1~6之全氟烷基、或以Rf1ORf2-表示之碳原子數2~40之1價基(Rf1係碳原子數1~6之全氟烷基，Rf2係在碳-碳原子間可具有醚性氧原子之全氟伸烷基)；Q1：碳原子數1~10且不含氟原子之2價有機基；RH1：碳原子數1~6之烴基；X1及X2：水解性基； p：0、1或2；惟，式(c-1)中之3個X1、式(c-2)中之(4-p)個X2及p個RH1可分別彼此相異亦可相同)。 (The symbols in the formulae (c-1) and (c-2) are as follows: R f : a perfluoroalkyl group having 1 to 6 carbon atoms or 1 to 40 carbon atoms represented by R f1 OR f2 - a valence group (R f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R f2 is a perfluoroalkyl group having an etheric oxygen atom between carbon-carbon atoms); Q 1 : a carbon number of 1 to 10 And a divalent organic group having no fluorine atom; R H1 : a hydrocarbon group having 1 to 6 carbon atoms; X 1 and X 2 : a hydrolyzable group; p: 0, 1 or 2; only, in the formula (c-1) The three X 1 and (4-p) X 2 and p R H1 in the formula (c-2) may be different from each other or the same).

[2]如上述[1]記載之正型感光性樹脂組成物，其中前述鹼可溶性樹脂(A)在正型感光性樹脂組成物之總固體成分中的含量為10~90質量%。 [2] The positive photosensitive resin composition according to the above [1], wherein the content of the alkali-soluble resin (A) in the total solid content of the positive photosensitive resin composition is from 10 to 90% by mass.

[3]如上述[1]或[2]記載之正型感光性樹脂組成物，其中前述感光劑(B)在正型感光性樹脂組成物之總固體成分中的含量為0.1~50質量%。 [3] The positive photosensitive resin composition according to the above [1], wherein the photosensitive agent (B) is contained in the total solid content of the positive photosensitive resin composition in an amount of 0.1 to 50% by mass. .

[4]如上述[1]~[3]中任一項記載之正型感光性樹脂組成物，其中前述撥墨劑(C)在正型感光性樹脂組成物之總固體成分中的含量為0.01~10質量%。 [4] The positive photosensitive resin composition according to any one of the above [1], wherein the content of the ink repellent (C) in the total solid content of the positive photosensitive resin composition is 0.01 to 10% by mass.

[5]如上述[1]~[4]中任一項記載之正型感光性樹脂組成物，其中前述撥墨劑(C)之數量平均分子量(Mn)在500以上且低於1,000,000。 [5] The positive photosensitive resin composition according to any one of the above [1], wherein the ink repellent (C) has a number average molecular weight (Mn) of 500 or more and less than 1,000,000.

[6]如上述[1]~[5]中任一項記載之正型感光性樹脂組成物，其中前述鹼可溶性樹脂(A)為酚醛清漆型苯酚樹脂。 [6] The positive photosensitive resin composition according to any one of the above [1], wherein the alkali-soluble resin (A) is a novolac type phenol resin.

[7]如上述[1]~[6]中任一項記載之正型感光性樹脂組成物，其中前述感光劑(B)係具有二疊氮醌基之化合物。 [7] The positive photosensitive resin composition according to any one of the above [1], wherein the photosensitive agent (B) is a compound having a diazide group.

[8]如上述[1]~[7]中任一項記載之正型感光性樹脂組成物，其中前述混合物更含有以下式(c-3)表示之水解性矽烷化合物：[化2] [8] The positive photosensitive resin composition according to any one of the above [1], wherein the mixture further contains a hydrolyzable decane compound represented by the following formula (c-3): [Chemical 2]

(式(c-3)中之記號如下：Y：氫原子亦可被鹵素原子、碳原子數1~3之烷基、碳原子數2~3之烯基或硝基取代之苯基；Q2：單鍵或2價有機基；RH2：碳原子數1~6之烴基；X3：水解性基；q：1或2；r：0或1且q+r成為1或2之數。惟，q個Y、Q2及Y-Q2以及(4-q-r)個X3可分別彼此相異亦可相同)。 (The symbol in the formula (c-3) is as follows: Y: a hydrogen atom may be substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms or a nitro group; Q 2 : a single bond or a divalent organic group; R H2 : a hydrocarbon group having 1 to 6 carbon atoms; X 3 : a hydrolyzable group; q: 1 or 2; r: 0 or 1 and q + r becomes 1 or 2 However, q Y, Q 2 and YQ 2 and (4-qr) X 3 may be different from each other or the same).

[9]如上述[1]~[8]中任一項記載之正型感光性樹脂組成物，其更含有溶媒(D)。 [9] The positive photosensitive resin composition according to any one of the above [1] to [8], further comprising a solvent (D).

[10]如上述[1]~[9]中任一項記載之正型感光性樹脂組成物，其更含有熱硬化劑(E)。 [10] The positive photosensitive resin composition according to any one of the above [1] to [9] further comprising a thermal curing agent (E).

[11]如上述[10]記載之正型感光性樹脂組成物，其更含有熱硬化促進劑(F)。 [11] The positive photosensitive resin composition according to [10] above, which further contains a thermosetting accelerator (F).

[12]如上述[1]~[11]中任一項記載之正型感光性樹脂組成物，其更含有著色劑(G)。 [12] The positive photosensitive resin composition according to any one of [1] to [11] further comprising a coloring agent (G).

[13]一種隔壁，係形成為將基板表面劃分成像素形成用之複數劃分區之形態者；其係由如上述[1]~[12]中任一項記載之正型感光性樹脂組成物之硬化膜所構成。 [13] A partition type is formed by dividing a surface of a substrate into a plurality of divided regions for forming a pixel, and the positive photosensitive resin composition according to any one of the above [1] to [12] The cured film is composed of.

[14]一種光學元件，係於基板表面具有複數像素及位在 鄰接像素間之隔壁者，前述隔壁係以如上述[13]記載之隔壁來形成。 [14] An optical component having a plurality of pixels on a surface of a substrate and In the case of the partition wall between the adjacent pixels, the partition wall is formed by the partition wall described in the above [13].

[15]如上述[14]記載之光學元件，其中前述光學元件係濾色器、TFT(Thin Film Transistor)陣列或有機EL元件。 [15] The optical element according to [14] above, wherein the optical element is a color filter, a TFT (Thin Film Transistor) array, or an organic EL element.

本發明之正型感光性樹脂組成物可形成撥墨性佳且即便經紫外線/臭氧照射處理撥墨性仍佳的隔壁，且貯藏穩定性亦佳。 The positive photosensitive resin composition of the present invention can form a partition wall which is excellent in ink repellency and which is excellent in ink repellency even by ultraviolet/ozone irradiation treatment, and has excellent storage stability.

本發明之光學元件具有撥墨性佳且即便經紫外線/臭氧照射處理撥墨性仍佳的隔壁，藉此可抑制白點現象等產生，外觀良好。 The optical element of the present invention has a good ink repellency and is excellent in ink repellency even after ultraviolet/ozone irradiation treatment, whereby white spots and the like can be suppressed, and the appearance is good.

1‧‧‧基板 1‧‧‧Substrate

2‧‧‧正型感光性樹脂組成物塗膜 2‧‧‧Positive type photosensitive resin composition coating film

3‧‧‧塗膜之未曝光部分 3‧‧‧Unexposed part of the film

4‧‧‧光罩 4‧‧‧Photomask

5‧‧‧光 5‧‧‧Light

6‧‧‧隔壁 6‧‧‧ next door

7‧‧‧點陣 7‧‧ ‧ dot matrix

10‧‧‧用於噴墨方式的光學元件 用基板 10‧‧‧Optical components for inkjet Substrate

圖1(I)~(III)係示意地顯示使用本發明之正型感光性樹脂組成物的光學元件用隔壁之製造例的截面圖。 (I) to (III) are cross-sectional views schematically showing a production example of a partition for an optical element using the positive photosensitive resin composition of the present invention.

用以實施發明之形態 Form for implementing the invention

在本說明書中，以式(c-1)表示之化合物稱為「化合物(c-1)」。其他化合物亦同。 In the present specification, the compound represented by the formula (c-1) is referred to as "compound (c-1)". Other compounds are also the same.

本說明書中之「總固體成分」係表示正型感光性樹脂組成物所含成分中，屬於隔壁形成成分而且是溶媒(D)等在隔壁形成過程中會因加熱等而揮發之揮發性成分以外的總成分。可視為在140℃下將正型感光性樹脂組成物加熱24小時而除去溶媒後之殘存物來測定。又，總固體成分亦可從各成分之饋入量計算。 The "total solid content" in the present specification means that the component contained in the positive photosensitive resin composition is a partition forming component and is a volatile component which is volatilized by heating or the like during the formation of the partition wall. The total composition. The measurement can be carried out by heating the positive photosensitive resin composition at 140 ° C for 24 hours to remove the solvent. Further, the total solid content can also be calculated from the feed amount of each component.

在本說明書中，已塗佈正型感光性樹脂組成物之膜稱為「塗膜」，使其呈乾燥狀態則稱為「膜」，另使其硬化而製得之膜則稱為「硬化膜」。 In the present specification, a film in which a positive photosensitive resin composition is applied is referred to as a "coating film", and a film which is dried in a dry state is referred to as a "film", and a film obtained by hardening is referred to as "hardening". membrane".

在本說明書中，隔壁之「表面」係作為僅表示隔壁上面之用語來使用。因此，隔壁之「表面」不含隔壁之側面。 In the present specification, the "surface" of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the "surface" of the partition wall does not include the side of the partition wall.

本說明書中之「印墨」係總稱在乾燥硬化後例如具有光學性、電性功能之液體者，不限於自習知即使用之著色材料。又，有關注入上述印墨而形成之「像素」亦同樣地係作為表示被隔壁劃分且具有光學性、電性功能之區分者來使用。 The "ink" in the present specification is generally referred to as a liquid having optical and electrical functions after drying and hardening, and is not limited to a coloring material which is used by self-learning. Further, the "pixel" formed by injecting the above-described ink is similarly used as a distinguisher that is partitioned by a partition wall and has an optical or electrical function.

本說明書中之「撥墨性」係指為了撥除上述印墨而適度具有撥水性及撥油性雙方之性質，例如可藉由後述方法進行評估。 The term "inking property" as used in the present specification means the property of having both water repellency and oil repellency in order to remove the ink, and can be evaluated, for example, by the method described later.

以下說明本發明之實施形態。而，本說明書中在未特別說明的情況下，符號%表示質量%。 Embodiments of the present invention will be described below. However, in the present specification, the symbol % indicates the mass % unless otherwise specified.

[鹼可溶性樹脂(A)] [alkali soluble resin (A)]

作為本發明之正型感光性樹脂組成物中之鹼可溶性樹脂(A)，可採用使用於正型感光性樹脂組成物的公知鹼可溶性樹脂。 As the alkali-soluble resin (A) in the positive photosensitive resin composition of the present invention, a known alkali-soluble resin used for the positive photosensitive resin composition can be used.

鹼可溶性樹脂(A)係藉由與後述之感光劑(B)一起使用而作為正型感光性樹脂組成物起作用。即，在正型感光性樹脂組成物中，在光微影等之曝光時，感光劑(B)會在曝光部活性化而使對顯影液之溶解性增大。該曝光部會在顯影 時溶解於顯影液(通常為鹼顯影液)而除去。未經光照射之部分(未曝光部分)即成為隔壁。而，鹼可溶性樹脂(A)中亦有在曝光前藉由與感光劑(B)組合而不溶化於顯影液之樹脂。 The alkali-soluble resin (A) functions as a positive photosensitive resin composition by being used together with the photosensitive agent (B) described later. In other words, in the positive photosensitive resin composition, when exposed to light lithography or the like, the photosensitive agent (B) is activated in the exposed portion to increase the solubility in the developer. The exposure portion will be in development It is dissolved in a developing solution (usually an alkali developing solution) and removed. The portion that is not irradiated with light (unexposed portion) becomes the partition wall. Further, the alkali-soluble resin (A) also has a resin which is not dissolved in the developer by a combination with the photosensitive agent (B) before exposure.

作為鹼可溶性樹脂(A)，可舉如苯酚類與醛類、此外有因應需求藉由添加各種改質劑進行聚縮合而製造之未改質或改質之酚醛清漆型苯酚樹脂、聚羥苯乙烯、聚鹵素化羥苯乙烯、N-(4-羥苯基)甲基丙烯醯胺之共聚物、及氫醌單甲基丙烯酸酯共聚物。又，亦可使用磺醯亞胺系聚合物、含羧基聚合物、含有苯酚性羥基之丙烯酸系樹脂、具磺醯胺基之丙烯酸系樹脂及胺甲酸乙酯系樹脂等各種鹼可溶性之高分子化合物。 Examples of the alkali-soluble resin (A) include phenols and aldehydes, and unmodified or modified novolak-type phenol resins and polyhydroxybenzenes which are produced by polycondensation by adding various modifiers as needed. A copolymer of ethylene, polyhalogenated hydroxystyrene, N-(4-hydroxyphenyl)methacrylamide, and a hydroquinone monomethacrylate copolymer. Further, various alkali-soluble polymers such as a sulfonimide-based polymer, a carboxyl group-containing polymer, an acrylic resin containing a phenolic hydroxyl group, an acrylic resin having a sulfonamide group, and an urethane resin may be used. Compound.

作為本發明之正型感光性樹脂組成物中之鹼可溶性樹脂(A)，以酚醛清漆型苯酚樹脂為佳。 The alkali-soluble resin (A) in the positive photosensitive resin composition of the present invention is preferably a novolac type phenol resin.

作為用以製造酚醛清漆型苯酚樹脂而使用的苯酚類，可舉例如苯酚、鄰甲酚、對甲酚、間甲酚等甲酚類；3,5-二甲苯酚、2,5-二甲苯酚、2,3-二甲苯酚、3,4-二甲苯酚等二甲苯酚類；2,3,4-三甲基苯酚、2,3,5-三甲基苯酚、2,4,5-三甲基苯酚、3,4,5-三甲基苯酚等三甲基苯酚類；2-三級丁基苯酚、3-三級丁基苯酚、4-三級丁基苯酚等三級丁基苯酚類；2-甲氧苯酚、3-甲氧苯酚、4-甲氧苯酚、2,3-二甲氧苯酚、2,5-二甲氧苯酚、3,5-二甲氧苯酚等甲氧苯酚類；2-乙基苯酚、3-乙基苯酚、4-乙基苯酚、2,3-二乙基苯酚、3,5-二乙基苯酚、2,3,5-三乙基苯酚、3,4,5-三乙基苯酚等乙基苯酚類；鄰氯苯酚、間氯苯酚、對氯苯酚、2,3-二氯苯酚等 氯苯酚類；間苯二酚、2-甲基間苯二酚、4-甲基間苯二酚、5-甲基間苯二酚等間苯二酚類；5-甲基兒茶酚等兒茶酚類；5-甲基五倍子酚等五倍子酚類；雙苯酚A、B、C、D、E、F等雙苯酚類；2,6-二羥甲基-對甲酚等羥甲基化甲酚類；及α-萘酚、β-萘酚等萘酚類等。該等可單獨使用1種亦可將2種以上併用。 Examples of the phenol used for producing the novolac type phenol resin include cresols such as phenol, o-cresol, p-cresol, and m-cresol; 3,5-xylenol and 2,5-dimethyl Dimethylphenols such as phenol, 2,3-xylenol, 3,4-xylenol; 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5 - trimethylphenol such as trimethylphenol or 3,4,5-trimethylphenol; three-stage butyl such as 2-tris-butylphenol, 3-tris-butylphenol and 4-tributylphenol Phenolics; 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, etc. Oxyphenols; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol , ethyl phenol such as 3,4,5-triethylphenol; o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, etc. Chlorophenols; resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol and other resorcinols; 5-methylcatechol Catechol; gallic phenol such as 5-methyl gallic phenol; bisphenol A, B, C, D, E, F and other bisphenols; 2,6-dimethylol-p-cresol and other methylol groups Resin phenols; and naphthols such as α-naphthol and β-naphthol. These may be used alone or in combination of two or more.

作為用以製造酚醛清漆型苯酚樹脂而使用之醛類，可舉如甲醛、三聚甲醛、三烷、乙醛、丙醛、聚縮醛、氯醛、糠醛、乙二醛、正丁醛、己醛、丙烯醛、安息香醛、巴豆醛、敗脂醛、四甲醛、苯基乙醛、鄰甲苯甲醛、柳醛等。該等可單獨使用1種亦可將2種以上併用。 Examples of the aldehyde used for producing the novolac type phenol resin include formaldehyde, trioxane, and trisole. Alkane, acetaldehyde, propionaldehyde, polyacetal, chloral, furfural, glyoxal, n-butyraldehyde, hexanal, acrolein, benzoin, crotonaldehyde, stearoaldehyde, tetraformaldehyde, phenylacetaldehyde, o Tolualdehyde, salicylaldehyde, and the like. These may be used alone or in combination of two or more.

上述酚醛清漆型苯酚樹脂中從易入手性、金屬雜質的稀少性等觀點看來，就苯酚類而言，以使用甲酚類、二甲苯酚類等之酚醛清漆型苯酚樹脂等為佳，且以使用甲酚類之酚醛清漆型苯酚樹脂(以下亦稱為「甲酚酚醛樹脂」)尤佳。 In the phenolic phenol resin, it is preferable to use a novolac type phenol resin such as cresol or xylenol, and the like, from the viewpoints of the ease of handling and the rarity of the metal impurities. It is especially preferable to use a phenolic novolac type phenol resin (hereinafter also referred to as "cresol novolac resin").

鹼可溶性樹脂(A)之質量平均分子量(Mw)以0.5×103~20×103為佳，且以2×103~15×103尤佳。質量平均分子量(Mw)若在上述範圍，曝光後之對顯影液之溶解性即佳。 The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 0.5 × 10 3 to 20 × 10 3 , and more preferably 2 × 10 3 to 15 × 10 3 . When the mass average molecular weight (Mw) is in the above range, the solubility in the developer after exposure is good.

而，在本說明書中，質量平均分子量(Mw)係表示藉由凝膠滲透層析術(GPC)以四氫呋喃為移動相進行測定並以標準聚苯乙烯為基準換算而測得的質量平均分子量。又，數量平均分子量(Mn)係表示以同樣的GPC所測得之數量平均分子量。 In the present specification, the mass average molecular weight (Mw) means a mass average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and converted based on standard polystyrene. Further, the number average molecular weight (Mn) means the number average molecular weight measured by the same GPC.

鹼可溶性樹脂(A)以對鹼顯影液之溶解性良好為宜。例如，作為正型感光性樹脂組成物之鹼顯影液，若以相對於一般的2.38質量%TMAH(氫氧化四甲銨)水溶液之溶解速度(埃/秒；以下僅稱「溶解速度」)為指標，以50~400埃/秒為佳，且以100~200埃/秒尤佳。溶解速度若在上述範圍，正型感光性樹脂組成物之顯影性即佳。 The alkali-soluble resin (A) is preferably soluble in an alkali developing solution. For example, the alkali developing solution which is a positive photosensitive resin composition has a dissolution rate (Eg/sec; hereinafter referred to as "dissolution rate") with respect to a general 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution. The index is preferably 50 to 400 angstroms/second, and is preferably 100 to 200 angstroms/second. When the dissolution rate is in the above range, the developability of the positive photosensitive resin composition is good.

鹼可溶性樹脂(A)亦可使用市售商品。就市售商品而言，可舉如皆為旭有機材工業公司製之商品名：EP4020G(Mw：9,000~14,000、溶解速度：160~250埃/秒)及EPR5010G(Mw：7,000~12,500、溶解速度：50~150埃/秒)(皆為甲酚酚醛樹脂)等。 A commercially available product can also be used for the alkali-soluble resin (A). As for the commercially available products, the products are manufactured by Asahi Organic Materials Co., Ltd.: EP4020G (Mw: 9,000 to 14,000, dissolution rate: 160 to 250 angstroms/second) and EPR5010G (Mw: 7,000 to 12,500, dissolved). Speed: 50~150 angstroms/second) (all are cresol novolac resin).

本發明之正型感光性樹脂組成物中之鹼可溶性樹脂(A)可單獨使用1種亦可將2種以上併用。 The alkali-soluble resin (A) in the positive-type photosensitive resin composition of the present invention may be used alone or in combination of two or more.

鹼可溶性樹脂(A)在正型感光性樹脂組成物之總固體成分中的含量以10~90質量%為佳，且以30~80質量%尤佳。含量若在上述範圍，正型感光性樹脂組成物之顯影性即佳。 The content of the alkali-soluble resin (A) in the total solid content of the positive photosensitive resin composition is preferably 10 to 90% by mass, and more preferably 30 to 80% by mass. When the content is in the above range, the developability of the positive photosensitive resin composition is good.

[感光劑(B)] [sensitizer (B)]

作為本發明之正型感光性樹脂組成物中之感光劑(B)，可採用使用於正型感光性樹脂組成物的公知感光劑。 As the photosensitive agent (B) in the positive photosensitive resin composition of the present invention, a known photosensitive agent used for the positive photosensitive resin composition can be used.

作為感光劑(B)，以具有二疊氮醌基之化合物為佳。作為具有二疊氮醌基之化合物，可使用與酚醛清漆型苯酚樹脂組合使用的公知之具有二疊氮醌基之化合物。 As the sensitizer (B), a compound having a diazonium group is preferred. As the compound having a diazide group, a known compound having a diazide group can be used in combination with a novolac type phenol resin.

作為感光劑(B)，可舉如可彼此縮合之後述具有 二疊氮醌基之化合物α與化合物β的完全縮合物或部分縮合物。 The photosensitive agent (B) may be condensed with each other and then A complete condensate or partial condensate of the compound a of the diazide group and the compound β.

化合物α具有可進行縮合反應的官能基。作為該可進行縮合反應的官能基，可舉如磺基、氯磺基等。作為化合物α，可舉如二疊氮苯醌磺酸、二疊氮萘醌磺酸、二疊氮蒽醌磺酸等磺酸及該等的磺醯氯。作為磺醯氯，具體上可舉如1,2-二疊氮萘醌-5-磺醯氯、1,2-二疊氮萘醌-4-磺醯氯、1,2-二疊氮苯醌-4-磺醯氯等。 The compound α has a functional group capable of undergoing a condensation reaction. The functional group capable of undergoing the condensation reaction may, for example, be a sulfo group or a chlorosulfo group. The compound α may, for example, be a sulfonic acid such as diazide benzoquinonesulfonic acid, diazonaphthoquinonesulfonic acid or diazidesulfonic acid or the like. Specific examples of the sulfonium chloride include 1,2-diazepinenaphthoquinone-5-sulfonyl chloride, 1,2-diazepinenaphthoquinone-4-sulfonium chloride, and 1,2-diazidobenzene.醌-4-sulfonyl chloride and the like.

化合物β具有可與化合物α進行縮合反應的官能基。作為該可進行縮合反應的官能基，可舉如羥基、胺基等，且以羥基為佳。 The compound β has a functional group which can undergo a condensation reaction with the compound α. The functional group capable of undergoing the condensation reaction may, for example, be a hydroxyl group or an amine group, and a hydroxyl group is preferred.

作為化合物β，在製得之隔壁具優異耐熱性之觀點下，以具有芳香環之化合物為佳。在耐熱性及可導入多數羥基之觀點下，該芳香族化合物中之芳香環數量以1~6個為佳，且以2~4個尤佳。 As the compound β, a compound having an aromatic ring is preferred from the viewpoint of excellent heat resistance of the obtained partition wall. From the viewpoint of heat resistance and introduction of a plurality of hydroxyl groups, the number of aromatic rings in the aromatic compound is preferably from 1 to 6, more preferably from 2 to 4.

作為化合物β，以鍵結於芳香環之氫原子之至少1個被羥基取代之芳香族化合物尤佳。1分子中之羥基數量以1~10個為佳，且以2~4個尤佳。 As the compound β, an aromatic compound in which at least one hydrogen atom bonded to the aromatic ring is substituted with a hydroxyl group is particularly preferable. The number of hydroxyl groups in one molecule is preferably from 1 to 10, and particularly preferably from 2 to 4.

就化合物β之具體例而言，可舉如：苯酚、4-甲基苯酚等苯酚類；2,3,4-三羥二苯基酮、2,3,4,4’-四羥二苯基酮等聚羥二苯基酮類；參(4-羥苯基)甲烷、1,1,1-參(4-羥苯基)乙烷、1,1-雙(4-羥苯基)-1-[α,α-二甲基-α-(4’-羥苯基)苯甲基]乙烷、雙(4- 羥基-3-甲基苯基)-2-羥苯基甲烷、雙(4-羥基-2,3,5-三甲基苯基)-2-羥苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-4-羥苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3-羥苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-2-羥苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-4-羥苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3-羥苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2-羥苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3,4-二羥苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3,4-二羥苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2,4-二羥苯基甲烷、雙(4-羥苯基)-3-甲氧基-4-羥苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-4-羥苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-3-羥苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-2-羥苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-3,4-二羥苯基甲烷、1,3,5-參(4-羥苯基二甲基苯甲基)苯等參苯酚型化合物；2,4-雙(3,5-二甲基-4-羥苯甲基)-5-羥苯酚、2,6-雙(2,5-二甲基-4-羥苯甲基)-4-甲基苯酚等線型3核苯酚化合物；1,1-雙[3-(2-羥基-5-甲基苯甲基)-4-羥基-5-環己基苯基]異丙烷、雙[2,5-二甲基-3-(4-羥基-5-甲基苯甲基)-4-羥苯基]甲烷、雙[2,5-二甲基-3-(4-羥苯甲基)-4-羥苯基]甲烷、雙[3-(3,5-二甲基-4-羥苯甲基)-4-羥基-5-甲基苯基]甲烷、雙[3-(3,5-二甲基-4-羥苯甲基)-4-羥基-5-乙基苯基]甲烷、雙[3-(3,5-二乙基-4-羥苯甲基)-4-羥基-5-甲基苯基]甲烷、雙[3-(3,5-二乙基-4-羥苯甲基)-4-羥基-5-乙基苯基]甲烷、雙[2-羥基-3-(3,5-二甲基-4-羥苯甲基)-5-甲基苯基]甲烷、雙[2- 羥基-3-(2-羥基-5-甲基苯甲基)-5-甲基苯基]甲烷、雙[4-羥基-3-(2-羥基-5-甲基苯甲基)-5-甲基苯基]甲烷、雙[2,5-二甲基-3-(2-羥基-5-甲基苯甲基)-4-羥苯基]甲烷等線型或環狀型4核苯酚化合物；2,4-雙[2-羥基-3-(4-羥苯甲基)-5-甲基苯甲基]-6-環己基苯酚、2,4-雙[4-羥基-3-(4-羥苯甲基)-5-甲基苯甲基]-6-環己基苯酚、2,6-雙[2,5-二甲基-3-(2-羥基-5-甲基苯甲基)-4-羥苯甲基]-4-甲基苯酚等線型或環狀型5核苯酚化合物等之線型或環狀型聚苯酚化合物；雙(2,3,4-三羥苯基)甲烷、雙(2,4-二羥苯基)甲烷、2,3,4-三羥苯基-4’-羥苯基甲烷、2-(2,3,4-三羥苯基)-2-(2’,3’,4’-三羥苯基)丙烷、2-(2,4-二羥苯基)-2-(2’,4’-二羥苯基)丙烷、2-(3,4-二羥苯基)-2-(3’,4’-二羥苯基)丙烷、2-(4-羥苯基)-2-(4’-羥苯基)丙烷、2-(3-氟-4-羥苯基)-2-(3’-氟-4’-羥苯基)丙烷、2-(2,4-二羥苯基)-2-(4’-羥苯基)丙烷、2-(2,3,4-三羥苯基)-2-(4’-羥苯基)丙烷、2-(2,3,4-三羥苯基)-2-(4’-羥基-3’,5’-二甲基苯基)丙烷等雙苯酚型化合物；1-[1,1-雙(4-羥苯基)乙基]-4-[1’,1’-雙(4’-羥苯基)乙基]苯、1-[1-(4-羥苯基)異丙基]-4-[1,1-雙(4-羥苯基)乙基]苯、1-[1-(3-甲基-4-羥苯基)異丙基]-4-[1,1-雙(3-甲基-4-羥苯基)乙基]苯等多核分支型化合物；1,1-雙(4-羥苯基)環己烷、2-雙[1,1-雙(4-羥苯基環己基)]-2-雙[1’,1’-雙(4’-羥苯基環己基)]丙烷等縮合型苯酚化合物；及 1,1’-螺二[1H-茚]-5,5’,6,6’-四醇、2,4,4-三甲基-2-(2,4-二羥苯基)-7-羥唍、五環[19,3,1,13,7,19,13,115,19]二十八-1,3,5,7,9,11,13,15,17,19,21,23-十二烯-4,6,10,12,16,18,22,24-八醇等。該等可單獨使用1種亦可將2種以上併用。 Specific examples of the compound β include phenols such as phenol and 4-methylphenol; 2,3,4-trihydroxydiphenyl ketone and 2,3,4,4'-tetrahydroxydiphenyl; Polyhydroxydiphenyl ketones such as ketones; ginseng (4-hydroxyphenyl)methane, 1,1,1-cis (4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl) -1-[α,α-dimethyl-α-(4'-hydroxyphenyl)benzyl]ethane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, Bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, Bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis ( 4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4- Hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, double (4 -hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane , bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyl Phenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2 -Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane, 1,3,5-paran (4-hydroxyphenyl dimethyl Phenylmethyl)benzene isoparametric phenolic compound; 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-di Linear 3-nuclear phenolic compound such as methyl-4-hydroxybenzyl)-4-methylphenol; 1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5 -cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-di Methyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5- Phenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-di Ethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5 -ethylphenyl]methane, bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3- (2-hydroxy-5-methyl Methyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5- Linear or cyclic 4-nuclear phenolic compound such as dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane; 2,4-bis[2-hydroxy-3- (4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzene Methyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4- a linear or cyclic polyphenol compound such as a linear or cyclic 5-nuclear phenol compound such as methylphenol; bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl) Methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyl Phenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(3,4-dihydroxyphenyl)-2-( 3',4'-Dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2 -(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4- Trishydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxybenzene a bisphenol type compound such as 2-(4'-hydroxy-3',5'-dimethylphenyl)propane; 1-[1,1-bis(4-hydroxyphenyl)ethyl]-4- [1',1'-bis(4'-hydroxyphenyl)ethyl]benzene, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyl) Phenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl) a multinuclear branched compound such as ethyl]benzene; 1,1-bis(4-hydroxyphenyl)cyclohexane, 2-bis[1,1-bis(4-hydroxyphenylcyclohexyl)]-2-double [ a condensation type phenol compound such as 1 ',1'-bis(4'-hydroxyphenylcyclohexyl)]propane; and 1,1'-spirobis[1H-茚]-5,5',6,6'-four Alcohol, 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxyl 唍, five rings [19,3,1,1 3,7 ,1 9,13 ,1 15,19 ] twenty eight-1,3,5,7,9,11,13,15,17,19, 21,23-dodecene-4,6,10,12,16,18,22,24-octaol and the like. These may be used alone or in combination of two or more.

作為感光劑(B)，以下述化合物α與化合物β的完全縮合物或部分縮合物較佳。 As the photosensitive agent (B), a complete condensate or a partial condensate of the following compound α and the compound β is preferred.

化合物α：1,2-二疊氮萘醌-5-磺醯氯、1,2-二疊氮萘醌-4-磺醯氯、1,2-二疊氮苯醌-4-磺醯氯等；化合物β：作為苯酚類，如苯酚、4-甲基苯酚；作為聚羥二苯基酮類，如2,3,4-三羥二苯基酮、2,3,4,4’-四羥二苯基酮；作為參苯酚型化合物，如參(4-羥苯基)甲烷、1,1,1-參(4-羥苯基)乙烷、1,1-雙(4-羥苯基)-1-[α,α-二甲基-α-(4’-羥苯基)苯甲基]乙烷、1,3,5-參(4-羥苯基二甲基苯甲基)苯；作為雙苯酚型化合物，如2,3,4-三羥苯基-4’-羥苯基甲烷、2-(3,4-二羥苯基)-2-(3’,4’-二羥苯基)丙烷、2-(2,4-二羥苯基)-2-(2’,4’-二羥苯基)丙烷、2-(2,3,4-三羥苯基)-2-(4’-羥苯基)丙烷；作為多核分支型化合物，如1-[1,1-雙(4-羥苯基)乙基]-4-[1’,1’-雙(4’-羥苯基)乙基]苯；作為縮合型苯酚化合物，如2-雙[1,1-雙(4-羥苯基環己基)]-2-雙[1’,1’-雙(4’-羥苯基環己基)]丙烷；及1,1’-螺二[1H-茚]-5,5’,6，6’-四醇、2,4,4-三甲基-2-(2,4-二羥苯基)-7-羥唍、五環[19,3,1,13,7,19,13,115,19]二十八 -1,3,5,7,9,11,13,15,17,19,21,23-十二烯-4,6,10,12,16,18,22,24-八醇。 Compound α: 1,2-diazepinenaphthoquinone-5-sulfonyl chloride, 1,2-diazepinenaphthoquinone-4-sulfonium chloride, 1,2-diazidobenzoquinone-4-sulfonium chloride Etc.; compound β: as a phenol such as phenol, 4-methylphenol; as a polyhydroxydiphenyl ketone such as 2,3,4-trihydroxydiphenyl ketone, 2,3,4,4'- Tetrahydroxydiphenyl ketone; as a phenol type compound such as ginseng (4-hydroxyphenyl)methane, 1,1,1-paraxyl (4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyl Phenyl)-1-[α,α-dimethyl-α-(4'-hydroxyphenyl)benzyl]ethane, 1,3,5-gin (4-hydroxyphenyldimethylbenzene) Benzo; as a bisphenol type compound, such as 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(3,4-dihydroxyphenyl)-2-(3',4 '-Dihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxybenzene 2-(4'-hydroxyphenyl)propane; as a multinuclear branched compound, such as 1-[1,1-bis(4-hydroxyphenyl)ethyl]-4-[1',1'- Bis(4'-hydroxyphenyl)ethyl]benzene; as a condensation type phenol compound, such as 2-bis[1,1-bis(4-hydroxyphenylcyclohexyl)]-2-bis[1',1' - bis(4'-hydroxyphenylcyclohexyl)propane; and 1,1'-spirobis[1H-indole]-5,5',6,6'-tetraol, 2,4,4-trimethyl Base-2-(2,4- Dihydroxyphenyl)-7-hydroxyl 唍, five rings [19,3,1,1 3,7 ,1 9,13 ,1 15,19 ] twenty eight-1,3,5,7,9,11,13,15,17,19, 21,23-dodecene-4,6,10,12,16,18,22,24-octaol.

作為感光劑(B)，以1,2-二疊氮萘醌-5-磺醯氯或1,2-二疊氮萘醌-4-磺醯氯與2,3,4,4’-四羥二苯基酮的縮合反應物，即以式(b-1)表示之化合物尤佳。 As the sensitizer (B), 1,2-diazepine naphthoquinone-5-sulfonyl chloride or 1,2-diazepinenaphthoquinone-4-sulfonium chloride and 2,3,4,4'-four The condensation reaction product of hydroxydiphenyl ketone, that is, the compound represented by the formula (b-1) is particularly preferable.

(式(b-1)中，D表示氫原子或以下式(b-2)表示之基。惟，D之至少1個係以式(b-2)表示之基。) (In the formula (b-1), D represents a hydrogen atom or a group represented by the following formula (b-2). However, at least one of D is a group represented by the formula (b-2).)

本發明之正型感光性樹脂組成物中之感光劑(B)亦可係1分子中之二疊氮醌基數不同的化合物之混合物，就感光劑(B)整體之平均值而言，以1分子中具有1~4個二疊氮醌基之化合物為佳，且以具有2.5~3個二疊氮醌基之化合物尤佳。 The photosensitive agent (B) in the positive photosensitive resin composition of the present invention may be a mixture of compounds having different numbers of diazide groups in one molecule, and the average value of the photosensitive agent (B) as a whole is 1 A compound having 1 to 4 diazide groups in the molecule is preferred, and a compound having 2.5 to 3 diazide groups is particularly preferred.

感光劑(B)在本發明之正型感光性樹脂組成物之總固體成分中的含量以0.1~50質量%為佳，且以1.0~30質量%尤佳。若在上述範圍，正型感光性樹脂組成物之顯影性即佳。一旦低於下限值，作為感光性樹組成物有時會無法獲得充分的感度；而一旦超過上限值，即有成分析出之虞。 The content of the photosensitive agent (B) in the total solid content of the positive photosensitive resin composition of the present invention is preferably from 0.1 to 50% by mass, particularly preferably from 1.0 to 30% by mass. In the above range, the developability of the positive photosensitive resin composition is good. Once it is below the lower limit, sufficient sensitivity may not be obtained as a photosensitive tree composition; and once it exceeds the upper limit, it may be analyzed.

[撥墨劑(C)] [Ink (C)]

本發明之正型感光性樹脂組成物中之撥墨劑(C)係由下述混合物(以下亦稱為「水解性矽烷化合物混合物」)的部分水解縮合物所構成：含有以下式(c-1)表示之水解性矽烷化合物(以下亦稱為化合物(c-1))及以下式(c-2)表示之水解性矽烷化合物(以下亦稱為化合物(c-2))之混合物；前述撥墨劑(C)中之氟原子含有率為10~55質量%。 The ink repellent (C) in the positive photosensitive resin composition of the present invention is composed of a partial hydrolysis condensate of the following mixture (hereinafter also referred to as "hydrolyzable decane compound mixture"): it contains the following formula (c- 1) a mixture of a hydrolyzable decane compound (hereinafter also referred to as compound (c-1)) and a hydrolyzable decane compound (hereinafter also referred to as compound (c-2)) represented by the following formula (c-2); The fluorine atom content in the ink-repellent (C) is 10 to 55 mass%.

[化5]Rf-Q1-SiX1 3…(c-1) RH1 p-SiX2 (4-p)…(c-2) R f -Q 1 -SiX 1 3 (c-1) R H1 p -SiX 2 (4-p) (c-2)

(式(c-1)及(c-2)中之記號如下：Rf：碳原子數1~6之全氟烷基、或以Rf1ORf2-表示之碳原子數2~40之1價基(Rf1係碳原子數1~6之全氟烷基，Rf2係在碳-碳原子間可具有醚性氧原子之全氟伸烷基)；Q1：碳原子數1~10且不含氟原子之2價有機基；RH1：碳原子數1~6之烴基；X1及X2：水解性基； p：0、1或2。 (The symbols in the formulae (c-1) and (c-2) are as follows: R f : a perfluoroalkyl group having 1 to 6 carbon atoms or 1 to 40 carbon atoms represented by R f1 OR f2 - a valence group (R f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R f2 is a perfluoroalkyl group having an etheric oxygen atom between carbon-carbon atoms); Q 1 : a carbon number of 1 to 10 And a divalent organic group having no fluorine atom; R H1 : a hydrocarbon group having 1 to 6 carbon atoms; X 1 and X 2 : a hydrolyzable group; p: 0, 1 or 2.

惟，X1、X2及RH1在式(c-1)或式(c-2)內存在複數個時，該等可彼此相異亦可相同。) However, when X 1 , X 2 and R H1 are present in a plurality of formulas (c-1) or (c-2), the ones may be different from each other or the same. )

撥墨劑(C)含有源自化合物(c-1)的全氟烷基，藉此可對使用正型感光性樹脂組成物形成之隔壁賦予優異的撥墨性。將正型感光性樹脂組成物塗佈至基板時，源自水解性矽烷化合物(c-1)的Rf容易滯留在與基板相反之側(即空氣側)。即，撥墨劑(C)容易滯留在與基板相反之側。又，由於化合物(c-1)具有Rf及矽原子，因此隔壁的撥墨性具優異的耐紫外線/臭氧性。 The ink-repellent (C) contains a perfluoroalkyl group derived from the compound (c-1), whereby excellent ink repellency can be imparted to the partition walls formed using the positive-type photosensitive resin composition. When the positive photosensitive resin composition is applied to the substrate, R f derived from the hydrolyzable decane compound (c-1) tends to stay on the side opposite to the substrate (that is, on the air side). That is, the ink-repellent (C) tends to stay on the side opposite to the substrate. Further, since the compound (c-1) has R f and a ruthenium atom, the ink repellency of the partition wall is excellent in ultraviolet ray resistance/ozone resistance.

撥墨劑(C)含有源自於化合物(c-2)的單元，藉此撥墨劑(C)對烴系溶媒之溶解性、造膜性佳。又可調整撥墨劑(C)之氟原子含有率。 The ink-repellent (C) contains a unit derived from the compound (c-2), whereby the ink-repellent (C) has good solubility in a hydrocarbon-based solvent and film-forming property. Further, the fluorine atom content of the ink-repellent (C) can be adjusted.

撥墨劑(C)之氟原子含有率為10~55質量%，以12~40質量%為佳，且以15~30質量%尤佳。氟原子含有率若在上述範圍，即可對使用正型感光性樹脂組物形成之隔壁賦予對紫外線或臭氧照射具耐性的撥墨性。 The fluorine atom content of the ink-repellent agent (C) is preferably 10 to 55 mass%, more preferably 12 to 40 mass%, and particularly preferably 15 to 30 mass%. When the fluorine atom content is in the above range, it is possible to impart ink repellency to ultraviolet rays or ozone irradiation to the partition walls formed using the positive photosensitive resin composition.

撥墨劑(C)宜具有矽醇基。就矽醇基之數量而言，以每1個矽原子有0.2~3.5個為佳，0.2~2個較佳，0.5~1.5個尤佳。若在上述範圍之下限值以上，使用正型感光性樹脂組成物來形成隔壁時，即可防止撥墨劑(C)從基板表面脫離。若在上述範圍之上限值以下，撥墨劑(C)在正型感光性樹脂組成物中與溶媒或其他成分的相溶性即佳。 The ink-repellent (C) preferably has a decyl group. In terms of the number of sterol groups, it is preferably from 0.2 to 3.5 per one argon atom, preferably from 0.2 to 2, and preferably from 0.5 to 1.5. When the partition wall is formed using a positive photosensitive resin composition at a lower limit or more in the above range, the ink repellent (C) can be prevented from being detached from the surface of the substrate. When it is below the upper limit of the above range, the ink-repellent (C) is preferably compatible with the solvent or other components in the positive-type photosensitive resin composition.

而，撥墨劑(C)中之矽醇基數係藉由以29Si-NMR測定之 具矽醇基之Si基與不具矽醇基之Si基的峰值面積之比而算出。 Further, the number of sterol groups in the ink-repellent (C) was calculated by the ratio of the peak area of the thiol group-containing Si group and the non-sterol group-containing Si group measured by 29 Si-NMR.

本發明之水解性矽烷化合物混合物含有化合物(c-1)及化合物(c-2)。此外，亦可含有1種或2種以上之化合物(c-1)及化合物(c-2)以外的水解性矽烷化合物。 The hydrolyzable decane compound mixture of the present invention contains the compound (c-1) and the compound (c-2). Further, one or two or more kinds of the compound (c-1) and the hydrolyzable decane compound other than the compound (c-2) may be contained.

作為前述化合物(c-1)及化合物(c-2)以外的水解性矽烷化合物，可舉如具有含苯基之有機基的水解性矽烷化合物(上述水解性矽烷化合物(c-1)及(c-2)除外)。例如，於矽原子鍵結有末端具有1或2個苯基之有機基、0或1個烴基、及1~3個水解性基之水解性矽烷化合物，且以後述化合物(c-3)為佳。 The hydrolyzable decane compound other than the compound (c-1) and the compound (c-2) may, for example, be a hydrolyzable decane compound having a phenyl group-containing organic group (the above hydrolyzable decane compound (c-1) and ( Except c-2). For example, a hydrolyzable decane compound having an organic group having 1 or 2 phenyl groups at the terminal, 0 or 1 hydrocarbon group, and 1 to 3 hydrolyzable groups is bonded to the ruthenium atom, and the compound (c-3) described later is good.

(水解性矽烷化合物(c-1)) (hydrolyzable decane compound (c-1))

水解性矽烷化合物(c-1)係上述以式(c-1)表示之矽烷化合物。 The hydrolyzable decane compound (c-1) is a decane compound represented by the above formula (c-1).

式(c-1)中，Rf以碳原子數1~6之全氟烷基或含醚性氧原子之碳原子數4~9之全氟烷基為佳，且以碳原子數6之全氟烷基尤佳。Rf若在上述範圍，使用正型感光性樹脂組成物形成之隔壁撥墨性即佳，尤其具有優異的具耐紫外線/臭氧性之撥墨性，此外對通用的溶媒之溶解性佳。 In the formula (c-1), R f is preferably a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 4 to 9 carbon atoms having an etheric oxygen atom, and having 6 carbon atoms. Perfluoroalkyl is especially preferred. When R f is in the above range, the ink repellency of the partition formed by using the positive photosensitive resin composition is excellent, and in particular, it has excellent ultraviolet ray/ozone-resistant ink repellency, and is excellent in solubility to a general-purpose solvent.

Rf之結構可舉如直鏈結構、支鏈結構、環結構或部分具環之結構，且以直鏈結構為佳。 The structure of R f may be, for example, a linear structure, a branched structure, a ring structure or a partially ring structure, and a linear structure is preferred.

作為Rf之具體例，可舉如以下之基。 Specific examples of R f include the following.

F(CF2)4-、F(CF2)6-。 F(CF 2 ) 4 -, F(CF 2 ) 6 -.

CF3CF2OCF2CF2OCF2-、CF3CF2OCF2CF2OCF2CF2-、 CF3CF2OCF2CF2OCF2CF2OCF2CF2OCF2-、CF3CF2OCF2CF2OCF2CF2OCF2CF2OCF2CF2-。 CF 3 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -.

CF3CF2CF2OCF2-、CF3CF2CF2OCF2CF2-、CF3CF2CF2OCF(CF3)-、CF3CF2CF2OCF(CF3)CF2-、CF3CF2CF2OCF(CF3)CF2OCF2CF2-、CF3CF2CF2OCF(CF3)CF2OCF(CF3)-、CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2-、CF3OCF(CF3)CF2OCF(CF3)-、CF3CF2OCF(CF3)CF2OCF(CF3)-。 CF 3 CF 2 CF 2 OCF 2 -, CF 3 CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 OCF(CF 3 )-, CF 3 CF 2 CF 2 OCF(CF 3 )CF 2 -, CF 3 CF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 OCF(CF 3 )CF 2 OCF(CF 3 )-, CF 3 CF 2 CF 2 OCF(CF 3 ) CF 2 OCF(CF 3 )CF 2 -, CF 3 OCF(CF 3 )CF 2 OCF(CF 3 )-, CF 3 CF 2 OCF(CF 3 )CF 2 OCF(CF 3 )-.

式(c-1)中，Q1係以分別於右側鍵鍵結Si且於左側鍵鍵結Rf表示時，具體而言以下述表示之基為佳：-(CH2)i1-(i1係1~5之整數)；-CH2O(CH2)i2-(i2係1~4之整數)；-SO2NR1-(CH2)i3-(R1係氫原子、甲基或乙基，i3係1以上且與R1之碳原子數的合計在4以下之整數)；及-(C=O)-NR1-(CH2)i4-(R1與前述相同，i4係1以上且與R1之碳原子數的合計在4以下之整數)。就Q1而言，以i1為2或3之-(CH2)i1-較佳，且以-(CH2)2-尤佳。 In the formula (c-1), when Q 1 is bonded to Si on the right side and R f is represented on the left side, specifically, the group represented by the following is preferable: -(CH 2 ) i1 -(i1 An integer of 1 to 5); -CH 2 O(CH 2 ) i2 - (i2 is an integer of 1 to 4); -SO 2 NR 1 -(CH 2 ) i3 - (R 1 is a hydrogen atom, a methyl group or Ethyl group, i3 is 1 or more and the total number of carbon atoms of R 1 is an integer of 4 or less; and -(C=O)-NR 1 -(CH 2 ) i4 - (R 1 is the same as the above, i4 is The total of 1 or more and the number of carbon atoms of R 1 is an integer of 4 or less). In the case of Q 1 , it is preferred that i1 is 2 or 3 -(CH 2 ) i1 - and is preferably -(CH 2 ) 2 -.

當Rf係碳原子數1~6之全氟烷基時，作為上述Q1，以-(CH2)i1-(i1與上述相同)表示之基為佳。i1以2~4之整數為佳，且以-(CH2)2-尤佳。 When R f is a perfluoroalkyl group having 1 to 6 carbon atoms, the group represented by -(CH 2 ) i1 - (i1 is the same as the above) is preferable as the above Q 1 . I1 is preferably an integer of 2 to 4, and is preferably -(CH 2 ) 2 -.

當Rf係含醚性氧原子之碳原子數4~9之全氟烷基時，作為上述Q1，以-(CH2)i1-、-CH2O(CH2)i2-、-SO2NR1-(CH2)i3-、及-(C=O)-NR1-(CH2)i4-表示之基(i1~i4及R1與上述相同)為佳。此時，仍以-(CH2)2-尤佳。 When R f is a perfluoroalkyl group having an etheric oxygen atom having 4 to 9 carbon atoms, as the above Q 1 , -(CH 2 ) i1 -, -CH 2 O(CH 2 ) i2 -, -SO 2 NR 1 -(CH 2 ) i3 -, and -(C=O)-NR 1 -(CH 2 ) i4 - represents a group (i1 to i4 and R 1 are the same as described above). At this time, it is still preferable to use -(CH 2 ) 2 -.

式(c-1)中，作為X1，可舉如烷氧基、鹵素原子、醯基、異氰酸酯基、胺基或胺基之氫原子已被烷基取代之 基。其中又以碳原子數1~4之烷氧基或鹵素原子為佳，且以甲氧基、乙氧基、氯原子尤佳。該等基藉由水解反應而成為羥基(矽醇基)，進而在分子間進行縮合反應可使形成Si-O-Si鍵結之反應圓滑地進行。 In the formula (c-1), examples of X 1 include a group in which a hydrogen atom of an alkoxy group, a halogen atom, a fluorenyl group, an isocyanate group, an amine group or an amine group has been substituted with an alkyl group. Among them, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred, and a methoxy group, an ethoxy group or a chlorine atom is particularly preferred. These groups are converted into a hydroxyl group (sterol group) by a hydrolysis reaction, and further, a condensation reaction between molecules can smoothly carry out a reaction for forming a Si-O-Si bond.

就化合物(c-1)之具體例而言，可舉如以下化合物。 Specific examples of the compound (c-1) include the following compounds.

F(CF2)4CH2CH2Si(OCH3)3、F(CF2)4CH2CH2Si(OCH2CH3)3、F(CF2)4CH2CH2SiCl3、F(CF2)6CH2CH2Si(OCH3)3、F(CF2)6CH2CH2Si(OCH2CH3)3、F(CF2)6CH2CH2SiCl3。 F(CF 2 ) 4 CH 2 CH 2 Si(OCH 3 ) 3 , F(CF 2 ) 4 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , F(CF 2 ) 4 CH 2 CH 2 SiCl 3 , F (CF 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 , F(CF 2 ) 6 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , F(CF 2 ) 6 CH 2 CH 2 SiCl 3 .

CF3OCF3CF2CF2CH2CH2Si(OCH3)3、F(CF2)2OCF2CF2OCF2CF2OCF2CF2OCF2CH2CH2Si(OCH2CH3)3、CF3OCF(CF3)CF2CH2CH2CH2Si(OCH3)3。 CF 3 OCF 3 CF 2 CF 2 CH 2 CH 2 Si(OCH 3 ) 3 , F(CF 2 ) 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , CF 3 OCF(CF 3 )CF 2 CH 2 CH 2 CH 2 Si(OCH 3 ) 3 .

F(CF2)2OCF2CF2OCF2CH2CH2CH2Si(OCH3)3、F(CF2)2O(CF2)2O(CF2)2CH2CH2Si(OCH3)3。 F(CF 2 ) 2 OCF 2 CF 2 OCF 2 CH 2 CH 2 CH 2 Si(OCH 3 ) 3 , F(CF 2 ) 2 O(CF 2 ) 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 .

F(CF2)3OCF2CF2CH2CH2SiCl3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3。 F(CF 2 ) 3 OCF 2 CF 2 CH 2 CH 2 SiCl 3 , F(CF 2 ) 3 OCF(CF 3 )CF 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 .

作為化合物(c-1)，其中又以F(CF2)6CH2CH2Si(OCH3)3、F(CF2)6CH2CH2Si(OCH2CH3)3、F(CF2)6CH2CH2SiCl3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3等尤佳。 As compound (c-1), in which F(CF 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 , F(CF 2 ) 6 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , F(CF 2 ) 6 CH 2 CH 2 SiCl 3 , F(CF 2 ) 3 OCF(CF 3 )CF 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 or the like is particularly preferable.

水解性矽烷化合物混合物中所含之化合物(c-1)可單獨使用1種亦可將2種以上併用。 The compound (c-1) contained in the hydrolyzable decane compound mixture may be used singly or in combination of two or more kinds.

(水解性矽烷化合物(c-2)) (hydrolyzable decane compound (c-2))

水解性矽烷化合物(c-2)係上述以式(c-2)表示之矽烷化 合物。 The hydrolyzable decane compound (c-2) is the above-described oximation represented by the formula (c-2) Compound.

式(c-2)中，RH1以碳原子數1~4之烷基為佳，以甲基或乙基較佳，且以甲基尤佳。 In the formula (c-2), R H1 is preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

X2係水解性基，同於上式(c-1)中之X1且包含理想態樣也相同。 The X 2 -based hydrolyzable group is the same as X 1 in the above formula (c-1) and contains the desired aspect.

p係0、1或2，當p為2時，2個RH1及(4-p)個X2可分別彼此相異亦可相同。 p is 0, 1, or 2. When p is 2, two R H1 and (4-p) X 2 may be different from each other or the same.

p以0或1為佳。 p is preferably 0 or 1.

在撥墨劑(C)中係藉由源自化合物(c-1)之Rf1及源自化合物(c-2)之RH1顯現撥水性，並主要藉由Rf顯現撥油性。又，撥墨劑(C)之硬化物為了顯現充分的撥油性，相對於撥墨劑(C)中Rf與RH1之合計，Rf宜佔高比率。p為0時，Rf在撥墨劑(C)中之比率會增高且撥油性提升，又造膜性佳。p為1或2時，藉由RH1有某程度的存在，可使撥墨劑(C)輕易地溶解於烴系溶媒，且在基板表面形成正型感光性樹脂組成物之塗膜時，可選擇較低價的溶媒。 In the ink-repellent (C), water repellency is exhibited by R f1 derived from the compound (c-1) and R H1 derived from the compound (c-2), and the oil repellency is mainly exhibited by R f . Further, the ink dial agent (C) of the cured product to show sufficient oil repellency, the ink relative to the total allocated agent (C) in the R H1 and R f, R f preferably contained in a high ratio. When p is 0, the ratio of R f in the ink repellent (C) is increased and the oil repellency is improved, and the film forming property is good. When p is 1 or 2, the ink repellent (C) can be easily dissolved in the hydrocarbon-based solvent by the presence of R H1 to some extent, and when a coating film of a positive photosensitive resin composition is formed on the surface of the substrate, A lower priced solvent can be selected.

作為化合物(c-2)，以下述化合物為佳。因應需求，亦可使用將其複數個預先進行部分水解縮合而得的部分水解縮合物。而，其他水解性矽烷化合物方面亦同。 As the compound (c-2), the following compounds are preferred. A partially hydrolyzed condensate obtained by partially hydrolyzing and condensing in advance may also be used depending on the demand. However, the same is true for other hydrolyzable decane compounds.

Si(OCH3)4、Si(OCH2CH3)4、CH3Si(OCH3)3、CH3Si(OCH2CH3)3、CH3CH2Si(OCH3)3、CH3CH2Si(OCH2CH3)3、(CH3)2Si(OCH3)2、(CH3)2Si(OCH2CH3)2、將Si(OCH3)4水解縮合之化合物(例如，COLCOAT公司 製之METHYLSILICATE 51(商品名))、及將Si(OCH2CH3)4水解縮合之化合物(例如，COLCOAT公司製之ETHYLSILICATE 40、ETHYLSILICATE 48(皆為商品名))。 Si(OCH 3 ) 4 , Si(OCH 2 CH 3 ) 4 , CH 3 Si(OCH 3 ) 3 , CH 3 Si(OCH 2 CH 3 ) 3 , CH 3 CH 2 Si(OCH 3 ) 3 , CH 3 CH 2 Si(OCH 2 CH 3 ) 3 , (CH 3 ) 2 Si(OCH 3 ) 2 , (CH 3 ) 2 Si(OCH 2 CH 3 ) 2 , a compound which hydrolyzes and condenses Si(OCH 3 ) 4 (for example, METHYLSILICATE 51 (trade name) manufactured by COLCOAT Co., Ltd., and a compound which hydrolyzes and condenses Si (OCH 2 CH 3 ) 4 (for example, ETHYLSILICATE 40 and ETHYLSILICATE 48 (all trade names) manufactured by COLCOAT Co., Ltd.).

本發明之水解性矽烷化合物混合物所含之化合物(c-2)可單獨使用1種亦可將2種以上併用。將2種以上併用時，亦可與4官能性化合物及/或3官能性化合物一起併用2官能性化合物。 The compound (c-2) contained in the hydrolyzable decane compound mixture of the present invention may be used alone or in combination of two or more. When two or more types are used together, a bifunctional compound may be used together with a tetrafunctional compound and/or a trifunctional compound.

水解性矽烷化合物混合物中之化合物(c-2)的含量係，相對於化合物(c-1)之1莫耳，化合物(c-2)在0.1~9莫耳為佳，且在0.5~9莫耳尤佳。 The content of the compound (c-2) in the hydrolyzable decane compound mixture is preferably 0.1 to 9 mol, and 0.5 to 9 based on 1 mol of the compound (c-1). Moer is better.

(水解性矽烷化合物(c-3)) (hydrolyzable decane compound (c-3))

水解性矽烷化合物(c-3)係以下式(c-3)表示之水解性矽烷化合物(以下亦稱為「化合物(c-3)」)。 The hydrolyzable decane compound (c-3) is a hydrolyzable decane compound represented by the following formula (c-3) (hereinafter also referred to as "compound (c-3)").

在式(c-3)中，表示水解性基之X3同於上述式(c-1)中之X1且包含理想態樣也相同。 In the formula (c-3), represents a hydrolyzable group of the same in X 3 (c-1) in the above formulas X 1 and includes over the same aspect.

又，RH2同於上述式(c-2)中之RH1且包含理想態樣也相同。 Further, R H2 is the same as R H1 in the above formula (c-2) and includes the ideal aspect.

式(c-3)中，Y表示氫原子亦可被鹵素原子、碳原子數1~3之烷基、碳原子數2~3之烯基或硝基取代之苯基。 In the formula (c-3), Y represents a phenyl group in which a hydrogen atom may be substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms or a nitro group.

Q2係將矽原子與苯基連結之基，為單鍵或2價有機基。 Q 2 is a group in which a halogen atom is bonded to a phenyl group, and is a single bond or a divalent organic group.

q係1或2，r係0或1，且q+r為1或2。 q is 1 or 2, r is 0 or 1, and q+r is 1 or 2.

而，式(c-3)中，q為2時，2個Q2可彼此相異亦可相同；q+r為1時，3個X3可彼此相異亦可相同；q+r為2時，2個X3可彼此相異亦可相同。 However, in the formula (c-3), when q is 2, two Q 2 may be different from each other or the same; when q + r is 1, three X 3 may be different from each other or the same; q + r is At 2 o'clock, the two X 3s may be different from each other or the same.

式(c-3)中，以q為1且r為1，或q為1且r為0為佳。 In the formula (c-3), it is preferable that q is 1 and r is 1, or q is 1 and r is 0.

式(c-3)中，作為Y，可舉如苯基、氟苯基、氯苯基、二氯苯基等，且以苯基尤佳。藉由使用上述化合物(c-3)，可製得高解析度且點部少有殘渣的隔壁。此推測是因為撥墨劑(C)移行至正型感光性樹脂組成物之膜表面後，源自於化合物(c-3)之苯基在顯影液中與感光劑(B)之二疊氮基進行偶氮耦合反應，藉此使撥墨劑(C)容易滯留於正型感光性樹脂組成物之膜表面所致。藉此，即便在經過顯影、後焙等之後，仍可使製得之隔壁表面保持撥墨性並使側面保持親墨性。 In the formula (c-3), examples of Y include a phenyl group, a fluorophenyl group, a chlorophenyl group, a dichlorophenyl group, and the like, and a phenyl group is particularly preferable. By using the above compound (c-3), a partition wall having high resolution and few residue at the point can be obtained. This is presumed because the phenyl group derived from the compound (c-3) in the developer and the sensitizer (B) is azide after the ink repellent (C) is transferred to the film surface of the positive photosensitive resin composition. The azo coupling reaction is carried out, whereby the ink-repellent (C) is easily retained on the film surface of the positive-type photosensitive resin composition. Thereby, even after development, post-baking, etc., the obtained partition wall surface can maintain the ink repellency and maintain the ink side on the side.

式(c-3)中Q2為2價有機基時，-(CH2)j-(j為1~6之整數)、-NH-、-NH-(CkH2k)-(k為1~6之整數)及-N(CgH2g+1)-(g為1~6之整數)係電子供應性基，且在易入手性之觀點上相當理想。作為Q2，以單鍵或-NH-尤佳。 When Q 2 in the formula (c-3) is a divalent organic group, -(CH 2 ) j - (j is an integer of 1 to 6), -NH-, -NH-(C k H 2k )-(k is An integer of 1 to 6 and -N(C g H 2g+1 )-(g is an integer of 1 to 6) are electron supply groups, and are preferable from the viewpoint of easy entry. As Q 2 , a single bond or -NH- is preferred.

就化合物(c-3)之具體例而言，可舉如以下化合物。 Specific examples of the compound (c-3) include the following compounds.

(C6H5)Si(OC2H5)3、(C6H5)NH(CH2)3Si(OCH3)3。 (C 6 H 5 )Si(OC 2 H 5 ) 3 , (C 6 H 5 )NH(CH 2 ) 3 Si(OCH 3 ) 3 .

本發明之水解性矽烷化合物混合物中所含之化合物 (c-3)可單獨使用1種亦可將2種以上併用。 a compound contained in a hydrolyzable decane compound mixture of the present invention (c-3) One type may be used alone or two or more types may be used in combination.

相對於水解性矽烷化合物(c-1)及(c-2)合計量之1莫耳，本發明之水解性矽烷化合物混合物中化合物(c-3)的摻混量在5莫耳以下為佳，且在4莫耳以下尤佳。 The blending amount of the compound (c-3) in the hydrolyzable decane compound mixture of the present invention is preferably 5 mol or less, relative to 1 mol of the total amount of the hydrolyzable decane compounds (c-1) and (c-2). And especially below 4 moules.

本發明之正型感光性樹脂組成物使用之撥墨劑(C)係上述原料之水解性矽烷化合物混合物的部分水解縮合物，通常係以聚合度等不同之複數縮合物構成之混合物。 The ink-repellent (C) used in the positive-type photosensitive resin composition of the present invention is a partially hydrolyzed condensate of the hydrolyzable decane compound mixture of the above-mentioned raw materials, and is usually a mixture of a plurality of condensates having different degrees of polymerization.

即，當撥墨劑(C)係使用水解性矽烷化合物(c-1)及化合物(c-2)作為必要成分且隨意使用化合物(c-3)而製造時，其會成為具有以下式(1)表示之平均組成式的結構者。惟，實際上為水解性基或矽醇基殘存之生成物(部分水解縮合物)，故難以化學式表示該生成物。 In other words, when the ink repellent (C) is produced by using the hydrolyzable decane compound (c-1) and the compound (c-2) as essential components and optionally using the compound (c-3), it has the following formula ( 1) The structure representing the average composition. However, since it is actually a product (partially hydrolyzed condensate) remaining in a hydrolyzable group or a sterol group, it is difficult to chemically represent the product.

在如上述所製造之部分水解縮合物中，以式(1)表示之平均組成式係水解性基或矽醇基全部完全水解、縮合形成矽氧烷鍵結時的化學式。 In the partially hydrolyzed condensate produced as described above, the chemical formula of the average composition formula hydrolyzable group or sterol group represented by the formula (1) is completely hydrolyzed and condensed to form a siloxane coupling.

式(1)中，Rf、RH1、RH2、Y、Q1、Q2、p、q及r的理想範圍與上述者相同。s、t及u係聚合度不同之複數含氟矽烷化合物混合物中各單元的平均存在莫耳數。 In the formula (1), the desirable ranges of R f , R H1 , R H2 , Y, Q 1 , Q 2 , p, q and r are the same as those described above. The average number of moles of each unit in the mixture of complex fluorine-containing decane compounds having different degrees of polymerization of s, t, and u.

在具有以式(1)表示之平均組成式結構的部分水解縮合物中，分別源自於化合物(c-1)、化合物(c-2)及化合 物(c-3)的單元推測係呈無規配列。 In the partially hydrolyzed condensate having the average composition formula represented by the formula (1), it is derived from the compound (c-1), the compound (c-2), and the compound, respectively. The unit of the substance (c-3) is estimated to be randomly arranged.

而，使用化合物(c-1)及化合物(c-2)時之下述平均組成式(2)中的s/t(莫耳比)，以撥墨劑(C)整體之平均值而言，以水解性矽烷化合物混合物中化合物(c-2)相對於化合物(c-1)之含量在上述範圍即10/1~90(莫耳比)為佳，且以10/5~90(莫耳比)尤佳。 On the other hand, in the case of using the compound (c-1) and the compound (c-2), the following average composition formula (2) is s/t (mole ratio), and the average value of the ink-repellent (C) as a whole is The content of the compound (c-2) relative to the compound (c-1) in the hydrolyzable decane compound mixture is preferably in the above range, i.e., 10/1 to 90 (mol ratio), and is 10/5 to 90 (Mo Ear ratio) is especially good.

式(2)中，Rf、RH1、Q1及p的理想範圍與上述者相同。s及t係聚合度不同之複數含氟矽烷化合物混合物中各單元的平均存在莫耳數。 In the formula (2), the desirable ranges of R f , R H1 , Q 1 and p are the same as those described above. The average number of moles of each unit in the mixture of complex fluorodecane compounds having different degrees of polymerization of s and t.

使用水解性矽烷化合物(c-1)、水解性矽烷化合物(c-2)及水解性矽烷化合物(c-3)來製造撥墨劑(C)時，會成為具有式(1)中源自於化合物(c-3)之單元進一步共縮合成式(2)之平均組成式的結構者。 When the ink-repellent (C) is produced by using the hydrolyzable decane compound (c-1), the hydrolyzable decane compound (c-2), and the hydrolyzable decane compound (c-3), it is derived from the formula (1). The unit of the compound (c-3) is further co-condensed to the structure of the average composition formula of the formula (2).

式(1)中，作為撥墨劑(C)整體之平均值，相對於(s+t)之1，u以上述範圍即在5以下(莫耳比)為佳，且在4以下(莫耳比)尤佳。 In the formula (1), as the average value of the entire ink-repellent agent (C), with respect to 1 of (s+t), u is preferably in the above range, that is, 5 or less (mole ratio), and is 4 or less (Mo) Ear ratio) is especially good.

本發明之正型感光性樹脂組成物中之撥墨劑(C)認為在曝光、硬化等過程中，所含之矽醇基進一步縮合，而可形成即便經紫外線/臭氧照射仍可顯示優異撥墨性的隔壁。 The ink repellent (C) in the positive photosensitive resin composition of the present invention is considered to have further condensed sterol groups during exposure, hardening, etc., and can be formed to exhibit excellent dialing even after ultraviolet/ozone irradiation. Ink next door.

本發明之正型感光性樹脂組成物中撥墨劑(C)之數量平均分子量(Mn)在500以上為佳，並以低於1,000,000為佳，且以低於10,000尤佳。數量平均分子量(Mn)若在上述範圍之下限值以上，使用正型感光性樹脂組成物來形成隔壁時，可防止從基板表面脫離。數量平均分子量(Mn)若低於上述範圍之上限值，對溶媒之溶解性即佳且作業性優異。撥墨劑(C)之數量平均分子量(Mn)可藉由選擇反應條件等而調節。 The ink repellent (C) of the positive photosensitive resin composition of the present invention preferably has a number average molecular weight (Mn) of 500 or more, more preferably less than 1,000,000, and particularly preferably less than 10,000. When the number average molecular weight (Mn) is at least the lower limit of the above range, when the partition wall is formed using the positive photosensitive resin composition, detachment from the surface of the substrate can be prevented. When the number average molecular weight (Mn) is less than the upper limit of the above range, the solubility in a solvent is good and workability is excellent. The number average molecular weight (Mn) of the ink-repellent (C) can be adjusted by selecting reaction conditions and the like.

(撥墨劑(C)之製造) (Manufacture of ink (C))

本發明之正型感光性樹脂組成物中的撥墨劑(C)可藉由使上述之水解性矽烷化合物混合物水解、部分縮合(以下亦稱為「反應步驟」)而製造。水解及部分縮合如上述係藉由水解性基之水解反應而生成矽醇基及藉由矽醇基彼此之脫水縮合反應而生成矽氧烷鍵結之反應。在反應步驟可無特別限制地適用使水解性矽烷化合物進行水解縮合反應一般常用的反應條件，例如可使用水、觸媒、有機溶媒等。 The ink repellent (C) in the positive photosensitive resin composition of the present invention can be produced by hydrolyzing and partially condensing the above hydrolyzable decane compound mixture (hereinafter also referred to as "reaction step"). Hydrolysis and partial condensation are the reactions in which a sterol group is formed by a hydrolysis reaction of a hydrolyzable group and a deuteration bond is formed by a dehydration condensation reaction of a sterol group with each other as described above. In the reaction step, a reaction condition which is generally used for the hydrolysis condensation reaction of the hydrolyzable decane compound can be applied without particular limitation. For example, water, a catalyst, an organic solvent or the like can be used.

在反應步驟中使用水時，相對於水解性矽烷化合物混合物之100質量份，其量以25~9,900質量份為佳，且以100~1,900質量份尤佳。令水量在上述範圍，較易於控制水解及縮合反應。 When water is used in the reaction step, the amount is preferably from 25 to 9,900 parts by mass, and more preferably from 100 to 1,900 parts by mass, per 100 parts by mass of the hydrolyzable decane compound mixture. When the amount of water is in the above range, it is easier to control the hydrolysis and condensation reaction.

作為反應步驟使用之觸媒，宜使用鹽酸、硫酸、硝酸、磷酸等無機酸及醋酸、草酸、馬來酸等有機酸。相對於水解性矽烷化合物混合物之100質量，使用之觸媒量以0.01~10質量份為佳，且以0.1~1質量份尤佳。 As the catalyst used in the reaction step, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as acetic acid, oxalic acid or maleic acid is preferably used. The amount of the catalyst to be used is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the hydrolyzable decane compound mixture.

在上述反應步驟亦可使用有機溶媒。作為該有機溶媒，可舉如使水解性矽烷化合物進行水解、縮合反應時一般常用的有機溶媒，具體上如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、異丁醇、2-甲基-2-丙醇、乙二醇、丙三醇、丙二醇等醇類；丙酮、甲基異丁基酮、環己酮等酮類；2-甲氧基乙醇、2-乙氧基乙醇等賽珞蘇類；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)乙醇等卡必醇類；乙酸甲酯、乙酸乙酯、丙二醇單甲基醚乙酸酯、4-丁內酯、乙酸丁酯、3-甲氧基乙酸丁酯等酯類；丙二醇單甲基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二丙二醇單甲基醚等二醇之單烷基醚類；及二乙二醇二甲基醚、二乙二醇乙基甲基醚、二丙二醇二甲基醚等二醇之二烷基醚類。其他可舉如苯甲醇、N,N-二甲基甲醯胺、二甲亞碸、二甲基乙醯胺及N-甲基吡咯啶酮等。有機溶媒可單獨使用1種亦可將2種以上併用。 An organic solvent can also be used in the above reaction step. The organic solvent is generally used as an organic solvent which is generally used for hydrolysis and condensation reaction of a hydrolyzable decane compound, and specifically, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butyl Alcohols, isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerol, propylene glycol and other alcohols; acetone, methyl isobutyl ketone, cyclohexanone and other ketones; 2-methoxy Ethyl acetate, 2-ethoxyethanol, etc.; bis(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxy) Carbitol such as ethoxy)ethanol; esters such as methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, 4-butyrolactone, butyl acetate, and butyl 3-methoxyacetate; a monoalkyl ether of a diol such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether or dipropylene glycol monomethyl ether; and diethylene glycol dimethyl ether; Dialkyl ethers of diols such as diethylene glycol ethyl methyl ether and dipropylene glycol dimethyl ether. Other examples include benzyl alcohol, N,N-dimethylformamide, dimethyl hydrazine, dimethylacetamide, and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more.

在反應步驟中，相對於水解性矽烷化合物混合物之100質量份，有機溶媒之量以25~9,900質量份為佳，且以100~1,900質量份尤佳。 In the reaction step, the amount of the organic solvent is preferably from 25 to 9,900 parts by mass, and particularly preferably from 100 to 1,900 parts by mass, based on 100 parts by mass of the hydrolyzable decane compound mixture.

製得之部分水解縮合物係與在反應步驟所用之溶媒一起摻混至正型感光性樹脂組成物。因此，作為反應步驟使用之溶媒，宜使用使撥墨劑(C)中之矽醇基穩定化之溶媒。作為使矽醇基穩定化之溶媒，可舉如具有羥基且在25℃下之介電率(ε)在5~20且理想在8~15範圍之化合物。 The partially hydrolyzed condensate obtained is blended with a solvent used in the reaction step to a positive photosensitive resin composition. Therefore, as the solvent to be used in the reaction step, a solvent which stabilizes the sterol group in the ink-repellent (C) is preferably used. The solvent for stabilizing the sterol group may, for example, be a compound having a hydroxyl group and having a dielectric constant (?) of from 5 to 20 and preferably from 8 to 15 at 25 °C.

具體上可舉如碳原子數2~8個之二醇系單烷基 醚乙酸酯溶媒、二醇系單烷基醚溶媒、甘二甲醚系溶媒及碳原子數2~4個之烴系醇等。 Specifically, a diol-based monoalkyl group having 2 to 8 carbon atoms is exemplified. An ether acetate solvent, a glycol monoalkyl ether solvent, a dimethyl ether solvent, and a hydrocarbon alcohol having 2 to 4 carbon atoms.

較具體而言，就二醇系單烷基醚乙酸酯溶媒可舉如丙二醇單甲基醚乙酸酯(ε：8.3)，就二醇系單烷基醚溶媒可舉如丙二醇單甲基醚(ε：12.3)，就烴系醇可舉如2-丙醇(ε：19.92)等。在矽醇基之穩定化效果高之觀點上，以丙二醇單甲基醚尤佳。 More specifically, the diol-based monoalkyl ether acetate solvent may be propylene glycol monomethyl ether acetate (ε: 8.3), and the diol monoalkyl ether solvent may be propylene glycol monomethyl. Ether (ε: 12.3), and the hydrocarbon-based alcohol may, for example, be 2-propanol (ε: 19.92). In view of the high stabilizing effect of the sterol group, propylene glycol monomethyl ether is particularly preferable.

反應步驟宜在室溫至溶媒沸點間之溫度下，在適當的攪拌條件下實施。 The reaction step is preferably carried out at a temperature between room temperature and the boiling point of the solvent under appropriate stirring conditions.

反應時間依使用之原料成分之量、反應溫度及攪拌條件等而定，舉例而言大概在0.5~24小時且理想為1~10小時。 The reaction time depends on the amount of the raw material component to be used, the reaction temperature, the stirring conditions, and the like, and is, for example, about 0.5 to 24 hours and preferably 1 to 10 hours.

反應結束後，亦可未除去有機溶媒便將製得之撥墨劑(C)添加至本發明之正型感光性樹脂組成物中。亦可藉由一般的方法先將有機溶媒除去使撥墨劑(C)單離後再添加至正型感光性樹脂組成物中。 After the completion of the reaction, the obtained ink-repellent (C) may be added to the positive-type photosensitive resin composition of the present invention without removing the organic solvent. The organic solvent may be removed by a general method to separate the ink-repellent (C) and then added to the positive-type photosensitive resin composition.

撥墨劑(C)在本發明之正型感光性樹脂組成物總固體成分中的含量以0.01~10質量%為佳，以0.1~6質量%較佳，且以0.2~3質量%尤佳。撥墨劑(C)含量若在上述範圍，正型感光性樹脂組成物之貯藏穩定性即佳，又使用該正型感光性樹脂組成物形成的光學元件之隔壁撥墨性佳且具平滑的表面。 The content of the ink-repellent (C) in the total solid content of the positive-type photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 6% by mass, and particularly preferably 0.2 to 3% by mass. . When the content of the ink repellent (C) is in the above range, the storage stability of the positive photosensitive resin composition is excellent, and the optical element formed using the positive photosensitive resin composition has good ink repellency and smoothness. surface.

[溶媒(D)] [Solvent (D)]

本發明之正型感光性樹脂組成物亦可含有溶媒(D)。 The positive photosensitive resin composition of the present invention may further contain a solvent (D).

藉由含有溶媒(D)，可使該組成物對基板之塗敷性及與基板表面之密著性較佳。又，藉由含有溶媒(D)，可使撥墨劑(C)穩定地存在於該組成物中。 By containing the solvent (D), the coating property of the composition on the substrate and the adhesion to the substrate surface can be improved. Further, by containing the solvent (D), the ink-repellent (C) can be stably present in the composition.

溶媒(D)只要是可使正型感光性樹脂組成物作為必要成分而含有之鹼可溶性樹脂(A)、感光劑(B)、撥墨劑(C)以及作為隨意成分而含有之熱硬化劑(E)、熱硬化促進劑(F)及其他添加劑均勻地溶解或分散，且與正型感光性樹脂組成物所含之各成分不具反應性者，即無特別限制。 The solvent (D) is an alkali-soluble resin (A), a sensitizer (B), an ink-repellent (C), and a heat-hardener which are contained as an optional component, which can be used as an essential component of a positive photosensitive resin composition. (E), the thermosetting accelerator (F) and other additives are uniformly dissolved or dispersed, and are not particularly limited as long as they are not reactive with the components contained in the positive photosensitive resin composition.

就溶媒(D)之具體例而言，可舉如乙醇、1-丙醇、2-丙醇、1-丁醇、乙二醇等醇類；丙酮、甲基異丁基酮、環己酮等酮類；2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇等賽珞蘇類；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)乙醇等卡必醇類；乙酸甲酯、乙酸乙酯、乙酸正丁酯、乳酸乙酯、乳酸正丁酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、丙二醇單甲基醚乙酸酯、乙二醇二乙酸酯、丙二醇二乙酸酯、乙基-3-乙氧基丙酸酯、環己醇乙酸酯、乳酸丁酯、γ-丁內酯、3-甲基-3-甲氧基乙酸丁酯、丙三醇三乙酸酯等酯類；及二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、三乙二醇二甲基醚、四乙二醇二甲基醚、丙二醇二甲基醚、二丁基醚、二乙二醇甲基乙基醚等。其他可舉如正丁烷、正己烷等鏈式烴；環己烷等環式飽和烴；及甲苯、二甲苯、苯甲醇等芳 香族烴等。該等可單獨使用1種亦可將2種以上併用。 Specific examples of the solvent (D) include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; acetone, methyl isobutyl ketone, and cyclohexanone. Ketones; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; bismuth; 2-(2-methoxyethoxy)ethanol, 2-(2-B Carbitol such as oxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, B Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ethyl acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropyl Ester, cyclohexanol acetate, butyl lactate, γ-butyrolactone, 3-methyl-3-methoxyacetic acid butyl ester, glycerol triacetate, etc.; and diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether Glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether. Other examples include chain hydrocarbons such as n-butane and n-hexane; cyclic saturated hydrocarbons such as cyclohexane; and toluene, xylene, benzyl alcohol and the like. Aromatic hydrocarbons, etc. These may be used alone or in combination of two or more.

相對於正型感光性樹脂組成物之總固體成分100質量%，本發明之正型感光性樹脂組成物的溶媒(D)含量以5~2,000質量%為佳，且以100~500質量%較佳。 The solvent (D) content of the positive photosensitive resin composition of the present invention is preferably 5 to 2,000% by mass, and 100 to 500% by mass, based on 100% by mass of the total solid content of the positive photosensitive resin composition. good.

[熱硬化劑(E)] [thermosetting agent (E)]

本發明之正型感光性樹脂組成物亦可含有熱硬化劑(E)作為促進熱硬化之隨意成分。 The positive photosensitive resin composition of the present invention may further contain a thermosetting agent (E) as an optional component for promoting thermal curing.

作為熱硬化劑(E)，以選自於由胺基樹脂、環氧化合物、唑啉化合物、聚異氰酸酯化合物及聚碳二醯亞胺化合物所構成群組中之至少1種為佳。 As the thermosetting agent (E), selected from the group consisting of an amine based resin, an epoxy compound, At least one of the group consisting of an oxazoline compound, a polyisocyanate compound, and a polycarbodiimide compound is preferred.

作為胺基樹脂，可舉如三聚氰胺系化合物、胍胺系化合物、脲系化合物等之胺基一部分或全部經羥甲基化之化合物，或以甲醇、乙醇、正丁醇、2-甲基-1-丙醇等將該經羥甲基化之化合物的羥基一部分或全部醚化之化合物，例如六甲氧基甲基三聚氰胺等。 The amine-based resin may be a compound in which a part or all of an amine group such as a melamine-based compound, a guanamine-based compound or a urea-based compound is methylolated, or methanol, ethanol, n-butanol or 2-methyl- A compound such as 1-propanol which partially or completely etherifies a hydroxyl group of the methylolated compound, for example, hexamethoxymethylmelamine or the like.

作為環氧化合物，可舉如雙苯酚A型環氧樹脂、雙苯酚F型環氧樹脂、苯酚‧酚醛型環氧樹脂、甲酚‧酚醛型環氧樹脂、參苯酚甲烷型環氧樹脂、溴化環氧樹脂等縮水甘油醚類；3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、雙(2,3-環氧環戊基)醚等脂環式環氧樹脂；六氫苯二甲酸二縮水甘油酯、四氫苯二甲酸二縮水甘油酯、苯二甲酸二縮水甘油酯等縮水甘油酯類；四縮水甘油二胺基二苯基甲烷、三縮水甘油對胺基苯酚等縮水甘油胺類；及三縮水甘油異三聚氰酸酯等雜環式環氧樹脂等。 Examples of the epoxy compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol ‧ phenol type epoxy resin, a cresol ‧ phenol type epoxy resin, a phenol phenol methane type epoxy resin, and bromine a glycidyl ether such as an epoxy resin; an alicyclic ring such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or bis(2,3-epoxycyclopentyl) ether Epoxy resin; diglycidyl hexahydrocarbonate, diglycidyl phthalate, diglycidyl phthalate and other glycidyl esters; tetraglycidyl diaminodiphenylmethane, three A glycidylamine such as glycidol to aminophenol; and a heterocyclic epoxy resin such as triglycidyl isocyanurate.

作為唑啉化合物，可舉如2-乙烯基-2-唑啉、2-乙烯基-4-甲基-2-唑啉、2-乙烯基-5-甲基-2-唑啉、2-異丙烯基-2-唑啉及2-異丙烯基-4-甲基-2-唑啉等聚合性單體之共聚物等。 As An oxazoline compound, such as 2-vinyl-2- Oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2- Oxazoline, 2-isopropenyl-2- Oxazoline and 2-isopropenyl-4-methyl-2- A copolymer of a polymerizable monomer such as oxazoline or the like.

該等化合物可單獨使用1種亦可將2種以上併用。 These compounds may be used alone or in combination of two or more.

作為熱硬化劑(E)，尤以1分子中具有2個以上環氧基之化合物為佳。正型感光性樹脂組成物含有熱硬化劑(E)，藉此可形成在曝光時正型感光性樹脂組成物之硬化性較佳且熱硬化後之形狀穩定化的隔壁。 The thermosetting agent (E) is preferably a compound having two or more epoxy groups in one molecule. The positive photosensitive resin composition contains a thermosetting agent (E), whereby a partition wall in which the positive photosensitive resin composition is preferably cured and the shape after heat curing is stabilized can be formed.

熱硬化劑(E)在本發明之正型感光性樹脂組成物總固體成分中的含量以5~20質量%為佳，且以10~15質量%尤佳。若在上述範圍，使用正型感光性樹脂組成物來形成具有隔壁之硬化膜時，隔壁表面以外(點)的印墨濕潤性即較為優異。 The content of the thermal curing agent (E) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 5 to 20% by mass, and more preferably 10 to 15% by mass. When the cured film having a partition wall is formed using the positive photosensitive resin composition in the above range, the ink wettability other than the surface of the partition wall (dot) is excellent.

[熱硬化促進劑(F)] [thermosetting accelerator (F)]

本發明之正型感光性樹脂組成物亦可含有熱硬化促進劑(F)作為促進熱硬化之隨意成分。 The positive photosensitive resin composition of the present invention may further contain a thermosetting accelerator (F) as an optional component for promoting thermal curing.

熱硬化促進劑(F)係具有藉由加熱而於正型感光性樹脂組成物中形成交聯結構之作用的化合物。 The thermosetting accelerator (F) has a function of forming a crosslinked structure in a positive photosensitive resin composition by heating.

作為熱硬化促進劑(F)，可舉例如其本身與熱硬化劑(E)起反應進行交聯而形成交聯結構之化合物，或其本身不進行交聯而對熱硬化劑(E)具有觸媒作用之化合物。 The thermosetting accelerator (F) may, for example, be a compound which reacts with the thermosetting agent (E) to form a crosslinked structure, or which does not crosslink itself and has a contact with the thermosetting agent (E). The compound of the media.

作為熱硬化劑(E)使用環氧化合物時，作為形成交聯結構之熱硬化促進劑(F)舉如有多胺類、聚硫醇類及聚羧酸 酐。較具體而言，作為多胺類可舉如乙二胺、三乙二胺、三伸乙四胺、四伸乙五胺、六亞甲二胺、聚氧伸烷基多胺、異佛爾酮二胺、烯二胺及3,9-雙(3-胺基丙基)-2,4,8,10-四氧雜螺(5,5)十一烷。作為聚硫醇類可舉如聚醚聚硫醇；而作為聚羧酸酐可舉如琥珀酸酐、甲基四氫酞酐、六氫酞酐及4-甲基六氫酞酐等。 When an epoxy compound is used as the thermosetting agent (E), examples of the thermosetting accelerator (F) forming a crosslinked structure include polyamines, polythiols, and polycarboxylic anhydrides. More specifically, as the polyamines, there may be mentioned ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylene polyamine, and isophor. Ketodiamine, Alkylenediamine and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane. Examples of the polythiol type include a polyether polythiol; and examples of the polycarboxylic acid anhydride include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.

就具有觸媒作用者而言，可舉如3級胺類、咪唑類、路易士酸類、鎓鹽類、二氰二胺類、有機酸二醯肼類及膦類等之硬化觸媒。較具體而言，可舉如2-甲咪唑、2-乙基-4-甲咪唑、參(二甲基胺基甲基)苯酚、三氟化硼-胺錯合物、二氰二胺、六氟磷酸二苯基錪鎓及六氟磷酸三苯基鋶鎓等。 The catalyst having a catalytic action may, for example, be a hardening catalyst such as a tertiary amine, an imidazole, a Lewis acid, a phosphonium salt, a dicyandiamide, an organic acid dioxane or a phosphine. More specifically, it may, for example, be 2-metimidazole, 2-ethyl-4-methylimidazole, ginxyl (dimethylaminomethyl)phenol, boron trifluoride-amine complex, dicyandiamide, Diphenylphosphonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate.

熱硬化促進劑(F)可將該等單獨使用1種亦可將2種以上併用。 One type of the heat-hardening accelerator (F) may be used alone or two or more types may be used in combination.

當熱硬化劑(E)係1分子中具有2個以上環氧基之化合物時，作為熱硬化促進劑(F)以2-甲咪唑及4-甲基-2-苯基咪唑尤佳。 When the thermosetting agent (E) is a compound having two or more epoxy groups in one molecule, it is particularly preferable to use 2-methylimidazole and 4-methyl-2-phenylimidazole as the thermosetting accelerator (F).

熱硬化促進劑(F)在本發明之感光性樹脂組成物總固體成分中的含量以0.1~10質量%為佳，且以0.5~3質量%尤佳。 The content of the thermosetting accelerator (F) in the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass, and more preferably 0.5 to 3% by mass.

[著色劑(G)] [Colorant (G)]

將本發明之正型感光性樹脂組成物用以使用於黑色矩陣形成時，宜含有著色劑(G)。前述黑色矩陣係包圍液晶顯示元件之濾色器R、G及B三色像素之格狀的黑色部分。 When the positive photosensitive resin composition of the present invention is used for the formation of a black matrix, it is preferred to contain a coloring agent (G). The black matrix surrounds a lattice-shaped black portion of the three color pixels of the color filters R, G, and B of the liquid crystal display element.

著色劑(G)可舉例如碳黑、苯胺黑、蒽醌系黑色顏料及 苝系黑色顏料，具體上如C.I.顏料黑1、6、7、12、20、31等。作為著色劑(G)，亦可使用紅色顏料、藍色顏料、綠色顏料等有機顏料或無機顏料之混合物。 The coloring agent (G) may, for example, be carbon black, aniline black or an anthraquinone black pigment. The lanthanide black pigment is specifically as C.I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. As the colorant (G), an organic pigment such as a red pigment, a blue pigment, or a green pigment, or a mixture of inorganic pigments can also be used.

使本發明之正型感光性樹脂組成物含有著色劑(G)並使用於黑色矩陣形成等時，著色劑(G)在該正型感光性樹脂組成物之總固體成分中的含量以15~65質量%為佳，且以20~50質量%尤佳。若在上述範圍，正型感光性樹脂組成物之感度即佳，又形成之隔壁遮光性佳。 When the positive photosensitive resin composition of the present invention contains a coloring agent (G) and is used for formation of a black matrix or the like, the content of the coloring agent (G) in the total solid content of the positive photosensitive resin composition is 15~ 65% by mass is preferred, and preferably 20 to 50% by mass. In the above range, the sensitivity of the positive photosensitive resin composition is good, and the barrier properties of the partition walls formed are good.

本發明之正型感光性樹脂組成物含有上述著色劑(G)等之分散性材料時，為了使其分散性提升，亦可進一步含有高分子分散劑、分散助劑等。該等可在不損及本發明效果之範圍含量下含於正型感光性樹脂組成物中。 When the positive photosensitive resin composition of the present invention contains a dispersing material such as the coloring agent (G), a polymer dispersing agent, a dispersing aid, or the like may be further contained in order to improve the dispersibility. These may be contained in the positive photosensitive resin composition at a content which does not impair the effects of the present invention.

[矽烷耦合劑(H)] [Chane coupling agent (H)]

本發明之正型感光性樹脂組成物亦可因應需求含有矽烷耦合劑(H)。藉由含有矽烷耦合劑(H)，可使形成之硬化膜的基板密著性較為優異。 The positive photosensitive resin composition of the present invention may contain a decane coupling agent (H) as needed. By containing a decane coupling agent (H), the formed cured film can be excellent in substrate adhesion.

作為矽烷耦合劑(H)，可舉如四乙氧基矽烷、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-甲基丙烯醯基氧基丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、十七氟辛基乙基三甲氧基矽烷、含聚氧伸烷基鏈之三乙氧基矽烷等。該等可單獨使用1種亦可將2種以上併用。 The decane coupling agent (H) may, for example, be tetraethoxydecane, 3-glycidoxypropyltrimethoxydecane, methyltrimethoxydecane, vinyltrimethoxydecane or 3-methylpropene. Mercaptooxypropyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, heptadecafluorooctylethyl Trimethoxy decane, triethoxy decane containing a polyoxyalkylene chain, and the like. These may be used alone or in combination of two or more.

矽烷耦合劑(H)在本發明之正型感光性樹脂組成 物總固體成分中的含量以0.1~20質量%為佳，且以1~10質量%尤佳。若在上述範圍之下限值以上，由正型感光性樹脂組成物形成之硬化膜的基板密著性即較為優異，且若在上述範圍之上限值以下，硬化膜之撥墨性即佳。 The decane coupling agent (H) is composed of the positive photosensitive resin of the present invention. The content in the total solid content is preferably from 0.1 to 20% by mass, and more preferably from 1 to 10% by mass. When it is more than the lower limit of the above range, the cured film formed of the positive photosensitive resin composition is excellent in substrate adhesion, and if it is at most the above upper limit of the above range, the ink repellency of the cured film is preferably .

[微粒子(I)] [Microparticle (I)]

本發明之正型感光性樹脂組成物亦可因應需求含有微粒子(I)。藉由含有微粒子(I)，可防止使用正型感光性樹脂組成物而形成之隔壁的熱塌。 The positive photosensitive resin composition of the present invention may contain fine particles (I) as needed. By containing the fine particles (I), it is possible to prevent thermal collapse of the partition walls formed by using the positive photosensitive resin composition.

作為微粒子(I)並無特別限定，可舉如二氧化矽、二氧化鋯、氟化鎂、錫摻雜氧化銦(ITO)、銻摻雜氧化錫(ATO)等無機系微粒子；及聚乙烯、聚甲基丙烯酸甲酯(PMMA)等有機系微粒子等。從耐熱性觀點看來，以無機系微粒子為佳；從易入手性及分散穩定性之觀點看來，以二氧化矽或二氧化鋯尤佳。 The fine particles (I) are not particularly limited, and examples thereof include inorganic fine particles such as cerium oxide, zirconium dioxide, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO); and polyethylene. Or organic fine particles such as polymethyl methacrylate (PMMA). From the viewpoint of heat resistance, inorganic fine particles are preferred; from the viewpoint of ease of handling and dispersion stability, it is particularly preferable to use ceria or zirconia.

又，當正型感光性樹脂組成物含有著色劑(G)及高分子分散劑時，若慮及該高分子分散劑之吸附能，微粒子(I)宜帶有負電。 Further, when the positive photosensitive resin composition contains the colorant (G) and the polymer dispersant, the fine particles (I) are preferably negatively charged in consideration of the adsorption energy of the polymer dispersant.

此外，若慮及正型感光性樹脂組成物之曝光感度，微粒子(I)以不吸收曝光時所照射之光為佳，且以不吸收超高壓水銀燈之主發光波長i線(365nm)、h線(405nm)及g線(436nm)尤佳。 Further, in consideration of the exposure sensitivity of the positive photosensitive resin composition, the fine particles (I) preferably absorb light irradiated at the time of exposure, and do not absorb the main light-emitting wavelength i line (365 nm) of the ultrahigh pressure mercury lamp, h Line (405 nm) and g line (436 nm) are particularly preferred.

微粒子(I)之平均粒徑從隔壁之表面平滑性變佳之觀點看來，以平均粒徑在1μm以下為佳，且在200nm以下尤佳。其中，就平均粒徑而言又以5~100nm最為理想。 The average particle diameter of the fine particles (I) is preferably 1 μm or less, and more preferably 200 nm or less, from the viewpoint of improving the surface smoothness of the partition walls. Among them, the average particle diameter is preferably from 5 to 100 nm.

微粒子(I)在本發明之正型感光性樹脂組成物總固體成分中的含量以5~35質量%為佳，且以10~30質量%尤佳。含量若在上述範圍之下限值以上，即有撥墨性之降低抑制效果，且若在上述範圍之上限值以下，正型感光性樹脂組成物之貯藏穩定性即佳。 The content of the fine particles (I) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 5 to 35% by mass, and more preferably 10 to 30% by mass. When the content is at least the lower limit of the above range, the effect of suppressing the decrease in the ink repellent property is obtained, and if it is at most the upper limit of the above range, the storage stability of the positive photosensitive resin composition is excellent.

[其他添加劑] [Other additives]

本發明之正型感光性樹脂組成物中，作為其他添加劑亦可因應需求在不損及本發明效果之範圍下摻混選自於由增黏劑、可塑劑、消泡劑、調平劑、抗縮孔劑及紫外線吸收劑所構成群組中之1種以上。 The positive photosensitive resin composition of the present invention may be blended, as a further additive, from a tackifier, a plasticizer, an antifoaming agent, a leveling agent, or the like as a further additive, without departing from the effects of the present invention. One or more of the group consisting of an anti-cratering agent and an ultraviolet absorber.

[正型感光性樹脂組成物之製造方法] [Manufacturing Method of Positive Photosensitive Resin Composition]

作為製造正型感光性樹脂組成物之方法，以將鹼可溶性樹脂(A)、感光劑(B)、撥墨劑(C)以及因應需求與溶媒(D)、熱硬化劑(E)、熱硬化促進劑(F)、著色劑(G)、矽烷耦合劑(H)、微粒子(I)及其他添加劑混合之方法為佳。 As a method of producing a positive photosensitive resin composition, an alkali-soluble resin (A), a sensitizer (B), an ink-repellent (C), and a solvent (D), a heat hardener (E), and heat are required. A method of mixing a hardening accelerator (F), a coloring agent (G), a decane coupling agent (H), fine particles (I), and other additives is preferred.

混合係使用攪拌機在溫度20℃~25℃及時間3hr~6hr下進行，並將製得之組成物直接作使用。 The mixing was carried out using a stirrer at a temperature of 20 ° C to 25 ° C and a time of 3 hr to 6 hr, and the obtained composition was used as it was.

本發明之正型感光性樹脂組成物與一般的正型感光性樹脂組成物同樣地可作為光微影等之材料使用，且製得之硬化膜可作為一般的正型感光性樹脂組成物之硬化膜所適用之光學元件的構件使用。 The positive photosensitive resin composition of the present invention can be used as a material such as photolithography as in the case of a general positive photosensitive resin composition, and the obtained cured film can be used as a general positive photosensitive resin composition. The member of the optical element to which the cured film is applied is used.

[隔壁及其製造方法] [Partition and its manufacturing method]

本發明之隔壁係用以在基板上設置劃分區而形成之隔壁，由將上述本發明之正型感光性樹脂組成物塗佈、乾燥 並使其硬化而成之硬化膜所構成。 The partition wall of the present invention is a partition wall formed by providing a partitioning region on a substrate, and the positive photosensitive resin composition of the present invention is coated and dried. And it is composed of a hardened film which is hardened.

本發明之隔壁適合使用於光學元件用途，當上述正型感光性樹脂組成物含有著色劑(G)時，製得之隔壁可適用作為黑色矩陣。 The partition wall of the present invention is suitably used for an optical element. When the positive photosensitive resin composition contains a coloring agent (G), the obtained partition wall can be suitably used as a black matrix.

本發明之隔壁可適用於例如在基板上具有複數像素及位在鄰接像素間之隔壁的光學元件用隔壁。 The partition wall of the present invention can be applied to, for example, a partition wall for an optical element having a plurality of pixels on a substrate and a partition wall positioned between adjacent pixels.

作為使用本發明之正型感光性樹脂組成物來製造光學元件用隔壁之方法，可舉例如以下方法。 As a method of producing a partition wall for an optical element using the positive photosensitive resin composition of the present invention, for example, the following method can be mentioned.

將本發明之正型感光性樹脂組成物塗佈於基板上形成塗膜(塗膜形成步驟)；接下來使該塗膜乾燥製成膜(預焙步驟)；再來僅使該膜中不會成為隔壁的部分曝光(曝光步驟)；其後除去上述經曝光之部分的塗膜而形成由上述塗膜之未曝光部分所構成之隔壁(顯影步驟)。接下來，因應需求使上述形成之隔壁等進一步熱硬化(後焙步驟)，藉此可製造本發明之光學元件用隔壁。 The positive photosensitive resin composition of the present invention is applied onto a substrate to form a coating film (coating film forming step); the coating film is subsequently dried to form a film (prebaking step); and only the film is not A partial exposure of the partition wall is formed (exposure step); thereafter, the coating film of the exposed portion is removed to form a partition wall composed of the unexposed portion of the coating film (developing step). Next, the partition walls and the like formed as described above are further thermally cured (post-baking step) in accordance with the demand, whereby the partition wall for an optical element of the present invention can be produced.

基板材質並無特別限定，可使用各種玻璃板；聚酯(聚對苯二甲酸乙二酯等)、聚烯烴(聚乙烯、聚丙烯等)、聚碳酸酯、聚甲基丙烯酸甲酯、聚碸、聚亞醯胺、聚甲基丙烯酸樹脂、丙烯酸樹脂等熱可塑性塑膠片；環氧樹脂、不飽和聚酯等熱硬化性樹脂之硬化片等。尤其從耐熱性之觀點看來，以玻璃板、聚亞醯胺等耐熱性塑膠為佳。又，以透明基板為佳。 The material of the substrate is not particularly limited, and various glass plates can be used; polyester (polyethylene terephthalate or the like), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, and poly Thermoplastic plastic sheets such as enamel, polyamidoamine, polymethacrylic resin, and acrylic resin; hardened sheets of thermosetting resins such as epoxy resin and unsaturated polyester. Particularly, from the viewpoint of heat resistance, a heat-resistant plastic such as a glass plate or a polyimide may be preferred. Further, a transparent substrate is preferred.

就基板形狀或形成隔壁之表面並無特別限制，可依照用途作適當選擇。基板為板狀時，可為平板，亦可整 面或一部分具有曲率。基板厚度可依隔壁之用途適當選擇，一般以0.5~10mm為佳。 The shape of the substrate or the surface on which the partition walls are formed is not particularly limited and may be appropriately selected depending on the application. When the substrate is in the form of a plate, it may be a flat plate or an entire plate. The face or part has a curvature. The thickness of the substrate can be appropriately selected according to the use of the partition wall, and is generally preferably 0.5 to 10 mm.

本發明使用之基板宜預先以醇洗淨、紫外線/臭氧洗淨等將欲塗佈正型感光性樹脂組成物之面洗淨。 The substrate to be used in the present invention is preferably washed with an alcohol washing, ultraviolet/ozone cleaning or the like in advance to coat the surface of the positive photosensitive resin composition.

圖1係示意地顯示使用本發明之正型感光性樹脂組成物的光學元件用隔壁之製造例的截面圖。 Fig. 1 is a cross-sectional view schematically showing a production example of a partition for an optical element using the positive photosensitive resin composition of the present invention.

圖1(I)係顯示已於基板1上形成由本發明之正型感光性樹脂組成物所構成之塗膜2之狀態之截面之圖。 Fig. 1(I) is a view showing a cross section of a state in which the coating film 2 composed of the positive photosensitive resin composition of the present invention is formed on the substrate 1.

圖1(II)係示意地顯示曝光步驟之圖。 Fig. 1 (II) is a view schematically showing an exposure step.

圖1(III)係顯示顯影步驟後之基板1與已形成於基板上之隔壁6之截面圖。 Fig. 1 (III) is a cross-sectional view showing the substrate 1 after the development step and the partition wall 6 which has been formed on the substrate.

以下，使用圖1具體說明使用本發明之正型感光性樹脂組成物的光學元件用隔壁之製造方法。 Hereinafter, a method of producing a partition for an optical element using the positive photosensitive resin composition of the present invention will be specifically described with reference to Fig. 1 .

(塗膜形成步驟) (coating film forming step)

如圖1(I)截面顯示，在基板1上塗佈上述本發明之正型感光性樹脂組成物，來形成由正型感光性樹脂組成物所構成之塗膜2。 As shown in the cross section of Fig. 1(I), the positive photosensitive resin composition of the present invention is applied onto the substrate 1 to form a coating film 2 composed of a positive photosensitive resin composition.

就正型感光性樹脂組成物之塗佈方法而言，只要是可形成膜厚均勻的塗膜之方法即無特別限制，可使用一般用於塗膜形成之方法如旋塗法、噴塗法、狹縫塗佈法、輥塗法、旋轉塗佈法及棒塗法等。 The method of applying the positive-type photosensitive resin composition is not particularly limited as long as it can form a coating film having a uniform film thickness, and a method generally used for forming a coating film such as a spin coating method or a spray coating method can be used. Slot coating method, roll coating method, spin coating method, bar coating method, and the like.

塗膜2之膜厚係考慮最終製得之隔壁高度而決定。塗膜2之膜厚以最終製得之隔壁高度之100~200%為佳，且以100~130%尤佳。塗膜2之膜厚以0.3~325μm為佳，且以1.3 ~65μm尤佳。 The film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably 100 to 200% of the height of the partition wall finally obtained, and is preferably 100 to 130%. The film thickness of the coating film 2 is preferably 0.3 to 325 μm, and is 1.3. ~65μm is especially good.

(預焙步驟) (prebaking step)

將上述塗膜形成步驟中形成於基板1上之塗膜2加熱而製得膜2。藉由加熱，可將構成塗膜之正型感光性樹脂組成物中所含之包含溶媒的揮發成分揮發、除去，且製得無黏著性之膜。又，撥墨劑(C)會移行至膜表面附近。 The coating film 2 formed on the substrate 1 in the above coating film forming step is heated to obtain the film 2. By heating, the volatile component containing the solvent contained in the positive photosensitive resin composition constituting the coating film can be volatilized and removed, and a film having no adhesiveness can be obtained. Also, the ink-repellent (C) migrates to the vicinity of the film surface.

就加熱方法而言，可舉如藉由熱板、烘箱等加熱裝置將塗膜2與基板1一起在50~120℃且理想為70~110℃下進行加熱處理10~2,000秒鐘且理想為30~180秒鐘左右的方法。 In the heating method, the coating film 2 and the substrate 1 are heat-treated at 50 to 120 ° C and preferably 70 to 110 ° C for 10 to 2,000 seconds, preferably by a heating means such as a hot plate or an oven. 30 to 180 seconds or so.

為了除去溶媒等之揮發成分，亦可在預焙步驟前另外設置加熱(乾燥)以外之真空乾燥等乾燥步驟。又，為了不使塗膜外觀產生不均並有效率地乾燥，以併用兼具上述預焙步驟之乾燥的加熱及真空乾燥較佳。真空乾燥之條件雖依各成分之種類及摻混比率等而異，但可在500~10Pa且10~300秒鐘左右的寬鬆範圍下進行。 In order to remove volatile components such as a solvent, a drying step such as vacuum drying other than heating (drying) may be separately provided before the pre-baking step. Further, in order to prevent the appearance of the coating film from being uneven and to efficiently dry, it is preferred to use both the heating and vacuum drying in which the drying in the prebaking step is used in combination. The conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but can be carried out in a loose range of about 500 to 10 Pa and about 10 to 300 seconds.

(曝光步驟) (exposure step)

如圖1(II)顯示，隔著預定圖案之光罩4對膜2照射光5。光5僅會穿透被切割於上述光罩4上之預定圖案部分而到達基板1上之膜2。由於僅曝光部為鹼可溶化，故將上述預定圖案設定為適合隔壁形狀之形態。後焙步驟後，隔壁的寬度平均在100μm以下為佳，且在20μm以下尤佳。又，鄰接隔壁間之距離平均在300μm以下為佳，且在100μm以下尤佳。作為光罩4，宜使用已將圖案形成為在該範圍內者。 As shown in Fig. 1 (II), the film 2 is irradiated with light 5 through a mask 4 of a predetermined pattern. The light 5 only penetrates the predetermined pattern portion cut on the reticle 4 to reach the film 2 on the substrate 1. Since only the exposed portion is alkali-soluble, the predetermined pattern is set to a shape suitable for the partition wall shape. After the post-baking step, the width of the partition walls is preferably 100 μm or less on average, and particularly preferably 20 μm or less. Further, the distance between adjacent partition walls is preferably 300 μm or less on average, and preferably 100 μm or less. As the photomask 4, it is preferable to use a pattern in which the pattern is formed within the range.

在圖1(II)中，已被光照射之膜的曝光部分會成為正型感光性樹脂組成物之可溶化部分，另一方面，未曝光部分3係維持正型感光性樹脂組成物之膜2的原本狀態。 In Fig. 1 (II), the exposed portion of the film which has been irradiated with light becomes a solubilized portion of the positive photosensitive resin composition, and on the other hand, the unexposed portion 3 is a film which maintains the positive photosensitive resin composition. The original state of 2.

作為照射之光5，可舉如可見光；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準分子雷射等準分子雷射；X射線；及電子射線等。又，作為照射光5，以波長100~600nm之電磁波為佳，以具有分布在300~500nm範圍之光線較佳，且以i線(365nm)、h線(405nm)及g線(436nm)尤佳。 As the illuminating light 5, there may be mentioned visible light; ultraviolet ray; far ultraviolet ray; KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 Excimer lasers such as excimer lasers; X-rays; and electron beams. Further, as the irradiation light 5, electromagnetic waves having a wavelength of 100 to 600 nm are preferable, and light having a distribution in the range of 300 to 500 nm is preferable, and i lines (365 nm), h lines (405 nm), and g lines (436 nm) are particularly preferable. good.

作為照射裝置(未圖示)，可使用公知之超高壓水銀燈或深(Deep)UV燈等。曝光量以5~1,000mJ/cm2為佳，且以50~400mJ/cm2尤佳。曝光量若在上述範圍之下限值以上，正型感光性樹脂組成物之可溶化部分對顯影液之溶解性即充分，且不會有顯影殘渣。若在上述範圍之上限值以下，即可獲得高解析度。 As the irradiation device (not shown), a known ultrahigh pressure mercury lamp or a deep UV lamp or the like can be used. The exposure amount is preferably 5 to 1,000 mJ/cm 2 , and more preferably 50 to 400 mJ/cm 2 . When the exposure amount is at least the lower limit of the above range, the solubility of the solubilized portion of the positive photosensitive resin composition to the developer is sufficient, and there is no development residue. If it is below the upper limit of the above range, high resolution can be obtained.

就曝光時間而言，雖依曝光量、感光組成物之組成及塗膜厚度等而定，但以1~60秒鐘為佳，且以5~20秒鐘尤佳。 The exposure time is preferably 1 to 60 seconds, and preferably 5 to 20 seconds, depending on the amount of exposure, the composition of the photosensitive composition, and the thickness of the coating film.

(顯影步驟) (development step)

使用顯影液進行顯影來除去圖1(II)所示之基板1上的曝光部分。藉此，可製得如圖1(III)截面圖顯示的構成，即基板1與藉由正型感光性樹脂組成物之膜而形成於上述基板上之隔壁6的構成。又，被隔壁6與基板1包圍之部分係藉 由印墨注入等形成像素之稱為點7的部分。製得之基板10經過後述之後焙步驟，可使用於利用噴墨方式之光學元件。 Development was carried out using a developing solution to remove the exposed portion on the substrate 1 shown in Fig. 1 (II). Thereby, the configuration shown in the cross-sectional view of Fig. 1 (III), that is, the configuration of the substrate 1 and the partition wall 6 formed on the substrate by the film of the positive photosensitive resin composition can be obtained. Moreover, the portion surrounded by the partition wall 6 and the substrate 1 is borrowed A portion called a dot 7 which is formed by ink injection or the like. The obtained substrate 10 can be used for an optical element using an inkjet method by a post-baking step which will be described later.

作為顯影液，可使用含有無機鹼類、胺類、醇胺類、第4級銨鹽等鹼類之鹼水溶液，且理想可使用含有氫氧化四甲銨等鹼類之鹼水溶液。 As the developer, an aqueous alkali solution containing an alkali such as an inorganic base, an amine, an alcohol amine or a fourth-order ammonium salt can be used, and an aqueous alkali solution containing a base such as tetramethylammonium hydroxide can be preferably used.

又，為了溶解性之提升及殘渣除去，可於顯影液添加界面活性劑或醇等有機溶媒。 Further, in order to improve the solubility and remove the residue, an organic solvent such as a surfactant or an alcohol may be added to the developer.

顯影時間(接觸於顯影液之時間)以5~180秒鐘為佳，且以10~60秒鐘較佳。 The development time (time to contact with the developer) is preferably from 5 to 180 seconds, and preferably from 10 to 60 seconds.

顯影方法舉如有覆液法、浸漬法及淋浴法等。顯影後，進行高壓水洗或流水洗淨並以壓縮空氣或壓縮氮使其風乾，藉此可除去基板1及隔壁6上之水分。 The development method includes a liquid coating method, a dipping method, a shower method, and the like. After the development, high-pressure water washing or running water washing is performed and air-dried by compressed air or compressed nitrogen, whereby moisture on the substrate 1 and the partition wall 6 can be removed.

(後焙步驟) (post-baking step)

作為後焙步驟，將基板1上之隔壁6加熱。就加熱方法而言，可舉如藉由熱板、烘箱等加熱裝置將隔壁6與基板1一起在150~250℃下進行加熱處理5~90分鐘之方法。 As a post-baking step, the partition wall 6 on the substrate 1 is heated. The heating method may be a method in which the partition wall 6 and the substrate 1 are heat-treated at 150 to 250 ° C for 5 to 90 minutes by a heating device such as a hot plate or an oven.

藉由加熱，使基板1上由正型感光性樹脂組成物之硬化膜所構成之隔壁6進一步硬化，且被隔壁6與基板1包圍之點7之形狀亦可更加固定化。而，上述加熱溫度在180℃以上尤佳。加熱溫度一旦過低，隔壁6之硬化便會不夠充分而無法獲得充分的耐藥性。在後述之印墨注入步驟中將印墨注入至點7時，依該印墨所含之溶媒，恐有隔壁6膨潤或印墨模糊之虞。另一方面，加熱溫度一旦過高，恐有產生隔壁6之熱分解之虞。 By heating, the partition wall 6 composed of the cured film of the positive photosensitive resin composition on the substrate 1 is further cured, and the shape of the point 7 surrounded by the partition wall 6 and the substrate 1 can be further fixed. Further, the above heating temperature is preferably 180 ° C or more. When the heating temperature is too low, the hardening of the partition wall 6 is insufficient and sufficient chemical resistance cannot be obtained. When the ink is injected into the dot 7 in the ink injecting step described later, depending on the solvent contained in the ink, the partition wall 6 may be swollen or the ink may be blurred. On the other hand, if the heating temperature is too high, there is a fear that thermal decomposition of the partition wall 6 occurs.

形成之隔壁的寬度平均在100μm以下為佳，且在20μm以下尤佳。其中又以5~20μm最為理想。 The width of the partition walls to be formed is preferably 100 μm or less on average, and more preferably 20 μm or less. Among them, 5~20μm is most ideal.

又，鄰接隔壁間之距離(點寬度)平均在300μm以下為佳，且在100μm以下尤佳。其中又以30~80μm最為理想。 Further, the distance (dot width) between adjacent partition walls is preferably 300 μm or less on average, and more preferably 100 μm or less. Among them, 30~80μm is most ideal.

又，隔壁的高度平均以0.05~50μm為佳，且以0.2~10μm尤佳。 Further, the height of the partition walls is preferably 0.05 to 50 μm on average, and particularly preferably 0.2 to 10 μm.

[光學元件之製造方法] [Method of Manufacturing Optical Element]

本發明之光學元件在藉由上述製造方法於基板上形成隔壁後，可藉由例如下述方法製得：於被上述基板與上述隔壁包圍之區域內已露出之基板表面進行親墨化處理(親墨化處理步驟)，接下來藉由噴墨法於上述區域注入印墨而形成上述像素(印墨注入步驟)。 After forming the partition wall on the substrate by the above-described manufacturing method, the optical element of the present invention can be obtained by, for example, performing ink retouching treatment on the surface of the substrate exposed in the region surrounded by the substrate and the partition wall ( In the ink repelling treatment step), the above-described pixels are formed by injecting ink in the above region by an inkjet method (ink injection step).

(親墨化處理步驟) (inktion processing step)

作為親墨化處理之方法，可舉如利用鹼水溶液之洗淨處理、紫外線洗淨處理、紫外線/臭氧洗淨處理、準分子洗淨處理、電暈放電處理及氧電漿處理等之方法。 Examples of the method of the ink receptive treatment include a washing treatment using an aqueous alkali solution, an ultraviolet cleaning treatment, an ultraviolet/ozone cleaning treatment, an excimer washing treatment, a corona discharge treatment, and an oxygen plasma treatment.

利用鹼水溶液之洗淨處理係使用鹼水溶液(氫氧化鉀、氫氧化四甲銨水溶液等)來洗淨基板表面之濕式處理。 The washing treatment using an aqueous alkali solution is a wet treatment in which the surface of the substrate is washed with an aqueous alkali solution (potassium hydroxide, aqueous tetramethylammonium hydroxide or the like).

紫外線洗淨處理係使用紫外線來洗淨基板表面之乾式處理。 The ultraviolet cleaning treatment uses ultraviolet rays to clean the surface of the substrate.

紫外線/臭氧洗淨處理係使用發出185nm與254nm之光的低壓水銀燈來洗淨基板表面之乾式處理。 The ultraviolet/ozone cleaning treatment uses a low-pressure mercury lamp emitting light of 185 nm and 254 nm to dry the surface of the substrate.

準分子洗淨處理係使用發出172nm之光的氙準分子燈來洗淨基板表面之乾式處理。 The excimer cleaning treatment uses a xenon excimer lamp that emits light of 172 nm to clean the surface of the substrate.

電暈放電處理係利用高頻高電壓使空氣中產生電暈放電來洗淨基板表面之乾式處理。 The corona discharge treatment is a dry treatment in which a high-frequency high voltage is used to generate a corona discharge in the air to wash the surface of the substrate.

氧電漿處理主要係使用在真空中將高頻電源等作為觸發器使氧激發而形成反應性高之「電漿狀態」來洗淨基板表面之乾式處理。 The oxygen plasma treatment is mainly a dry treatment in which a high-frequency power source or the like is used as a trigger to excite oxygen to form a highly reactive "plasma state" to clean the surface of the substrate.

作為親墨化處理之方法，在簡便觀點上，以紫外線/臭氧洗淨處理等乾式處理法為佳。紫外線/臭氧可使用市售裝置來產生。 As a method of the ink receptive treatment, a dry treatment method such as an ultraviolet/ozone cleaning treatment is preferred from the viewpoint of convenience. UV/ozone can be produced using commercially available equipment.

藉由於紫外線/臭氧裝置內部設置已形成隔壁之基板，並在空氣中及室溫下，在不損及隔壁之撥油性的範圍內進行處理1~10分左右，可進行親墨化處理。而，有關處理時間，配合各紫外線/臭氧裝置，以不損及隔壁之撥墨性之範圍的方式進行調整即可。 The substrate is formed by the inside of the ultraviolet/ozone device, and the ink is treated in the air and at room temperature in a range that does not damage the oil repellency of the partition wall for about 1 to 10 minutes. Further, the processing time may be adjusted so as not to impair the range of the ink repellency of the partition wall in accordance with each of the ultraviolet/ozone devices.

藉由親墨化處理，於上述隔壁形成後充分地進行殘留在點之顯影殘渣之除去等，藉此可充分地圖謀點之親墨化，並可防止使用所製得之光學元件的彩色顯示裝置等之白點現象。又，只要採用使用本發明之正型感光性樹脂組成物而形成的隔壁，在上述紫外線洗淨處理等中，可不使隔壁之撥墨性降低又可進行親墨化。 By the ink repellent treatment, after the formation of the partition walls, the development residue remaining at the dots is sufficiently removed, whereby the ink stick can be sufficiently captured, and the color display using the obtained optical element can be prevented. A white point phenomenon such as a device. In addition, in the ultraviolet cleaning treatment or the like, the partition wall formed by using the positive photosensitive resin composition of the present invention can be ink-retained without lowering the ink repellency of the partition walls.

在此，由正型感光性樹脂組成物形成之硬化膜的撥墨性(撥水撥油性)可以水及PGMEA(丙二醇單甲基醚乙酸酯：經常使用作為印墨之溶媒的有機溶媒)之接觸角進行估算。 Here, the ink repellency (water repellency) of the cured film formed of the positive photosensitive resin composition may be water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent which is often used as a solvent for the ink) The contact angle is estimated.

利用具有使用本發明之正型感光性樹脂組成物所形成 之隔壁的基板來製造光學元件時，會要求隔壁在上述親墨化處理後仍具有充分的撥墨性。隔壁之水接觸角在90度以上為佳，且在95度以上尤佳。又，隔壁之PGMEA接觸角在30度以上為佳，且在35度以上尤佳。 Formed by using a positive photosensitive resin composition using the present invention When the optical element is manufactured by the substrate of the partition, the partition wall is required to have sufficient ink repellent property after the ink repellent treatment. The water contact angle of the partition wall is preferably 90 degrees or more, and more preferably 95 degrees or more. Further, the PGMEA contact angle of the partition wall is preferably 30 degrees or more, and more preferably 35 degrees or more.

另一方面，利用具有使用本發明之正型感光性樹脂組成物所形成之隔壁的基板來製造光學元件時，就點會要求親墨性，且其水接觸角在20度以下為佳，在10度以下尤佳。 On the other hand, when an optical element is manufactured using a substrate having a partition wall formed using the positive photosensitive resin composition of the present invention, ink affinity is required, and the water contact angle is preferably 20 degrees or less. 10 degrees or less is especially good.

(印墨注入步驟) (Ink injection step)

藉由噴墨法於親墨化處理步驟後之點注入印墨而形成像素之步驟。 The step of forming a pixel by injecting ink at a point after the ink retouching step by an inkjet method.

該步驟可使用在噴墨法中一般使用的噴墨裝置，並以與一般的方法同樣的方式進行。就上述像素形成使用之噴墨裝置並無特別限定，可使用利用下述各種方法之噴墨裝置：連續地噴射帶電之印墨並藉由磁場進行控制之方法；使用壓電元件間歇地噴射印墨之方法；及將印墨加熱並利用其發泡，間歇地進行噴射之方法等。 This step can be carried out in the same manner as the general method using an ink jet apparatus generally used in an ink jet method. The ink jet device used for forming the above-described pixels is not particularly limited, and an ink jet device using various methods described below may be used: a method of continuously jetting a charged ink and controlling by a magnetic field; and intermittently jetting using a piezoelectric element The method of ink; and a method of heating the ink and using the foaming thereof, intermittently spraying, and the like.

作為使用本發明之正型感光性樹脂組成物而製造之光學元件，可舉如濾色器、有機EL元件及有機TFT陣列等。 Examples of the optical element produced by using the positive photosensitive resin composition of the present invention include a color filter, an organic EL device, and an organic TFT array.

[濾色器之製造] [Manufacture of color filters]

隔壁之形成、點之親墨化處理及利用噴墨法之印墨注入如上述。 The formation of the partition walls, the inking treatment of the dots, and the ink injection by the ink jet method are as described above.

在濾色器中，形成之像素形狀亦可設為條紋型、鑲嵌狀型、三角型及4像素配置型等公知的任一種配列。 In the color filter, the pixel shape to be formed may be any well-known arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.

像素形成使用的印墨主要含有著色成分、黏合劑樹脂成分及溶媒。 The ink used for pixel formation mainly contains a coloring component, a binder resin component, and a solvent.

作為著色成分，宜使用耐熱性、耐光性等優異的顏料及染料。 As the coloring component, pigments and dyes excellent in heat resistance, light resistance, and the like are preferably used.

作為黏合劑樹脂成分，以透明且耐熱性良好的樹脂為佳，可舉如丙烯酸樹脂、三聚氰胺樹脂及胺甲酸乙酯樹脂等。 As the binder resin component, a resin which is transparent and has good heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.

水性印墨含有水及因應需求的水溶性有機溶媒作為溶媒，並含有水溶性樹脂或水分散性樹脂作為黏合劑樹脂成分，且因應需求含有各種助劑。 The water-based ink contains water and a water-soluble organic solvent as a solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as required.

又，油性印墨含有有機溶媒作為溶媒，並含有可溶於有機溶媒之樹脂作為黏合劑樹脂成分，且因應需求含有各種助劑。 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, and contains various auxiliary agents as required.

藉由噴墨法注入印墨後，因應需求宜進行乾燥、加熱硬化及/或紫外線硬化。 After the ink is injected by the inkjet method, drying, heat curing, and/or ultraviolet curing are required depending on the demand.

像素形成後，因應需求使用保護膜用塗佈液來形成保護膜層。 After the formation of the pixel, the protective film layer is formed by using the coating liquid for a protective film as needed.

在提升表面平坦性之目的及遮斷來自隔壁或像素部之印墨的溶出物到達液晶層之目的下，宜形成保護膜層。 The protective film layer is preferably formed for the purpose of improving the flatness of the surface and blocking the discharge of the ink from the partition or the pixel portion to reach the liquid crystal layer.

形成保護膜層時，宜事先除去隔壁之撥墨性。在未除去撥墨性的情況下會將保護膜用塗佈液撥除而無法獲得均勻的膜厚，故非理想。 When the protective film layer is formed, it is preferable to remove the ink repellency of the partition walls in advance. When the ink repellency is not removed, the protective film coating liquid is removed and a uniform film thickness cannot be obtained, which is not preferable.

作為除去隔壁之撥墨性的方法，可舉如電漿灰化(Plasma Ashing)處理及光灰化處理等。 As a method of removing the ink repellency of the partition walls, a plasma ashing treatment and a light ashing treatment may be mentioned.

此外，因應需求，為了使用濾色器而製造之液晶面板的高品級化，宜在以隔壁構成之黑色矩陣上形成光間隔物。 Further, in order to increase the grade of the liquid crystal panel manufactured by using a color filter, it is preferable to form a photo spacer on a black matrix formed of partition walls.

[有機EL元件之製造] [Manufacture of Organic EL Elements]

使用本發明之正型感光性樹脂組成物來形成隔壁之前，藉由濺鍍法等將錫摻雜氧化銦(ITO)等透明電極製膜於玻璃等透明基板，並因應需求將透明電極蝕刻成所期望的圖案。接下來，使用本發明之正型感光性樹脂組成物來形成隔壁，並進行點之親墨化處理後，使用噴墨法依序將電洞輸送材料及發光材料之溶液塗佈於點並使其乾燥而形成電洞輸送層及發光層。其後藉由蒸鍍法等形成鋁等之電極而製得有機EL元件之像素。 Before the partition wall is formed by using the positive photosensitive resin composition of the present invention, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and the transparent electrode is etched into a required surface. The desired pattern. Next, using the positive photosensitive resin composition of the present invention to form a partition wall, and performing a point-removing treatment, a solution of a hole transporting material and a light-emitting material is sequentially applied to a dot by an inkjet method. It is dried to form a hole transport layer and a light-emitting layer. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like to obtain a pixel of the organic EL element.

[有機TFT陣列之製造] [Manufacture of Organic TFT Array]

經由以下(1)~(3)之步驟可製造有機TFT陣列。 The organic TFT array can be manufactured through the following steps (1) to (3).

(1)於玻璃等透明基板使用本發明之正型感光性樹脂組成物形成隔壁。接下來，在進行點之親墨化處理後，使用噴墨法於點塗佈閘極電極材料之溶液而形成閘極電極。 (1) A partition wall is formed using a positive photosensitive resin composition of the present invention on a transparent substrate such as glass. Next, after performing the inking treatment of the dots, a gate electrode is formed by dot-coating a solution of the gate electrode material by an inkjet method.

(2)使閘極電極形成後，於其上形成閘極絕緣膜。接下來，在閘極絕緣膜上使用本發明之正型感光性樹脂組成物形成隔壁，並在進行點之親墨化處理後使用噴墨法於點塗佈源極‧汲極電極材料之溶液而形成源極‧汲極電極。 (2) After the gate electrode is formed, a gate insulating film is formed thereon. Next, a positive-type photosensitive resin composition of the present invention is used to form a partition wall on the gate insulating film, and a solution of the source ‧ 汲 electrode material is applied by spot method using an inkjet method after performing a point-removing treatment The source ‧ the pole electrode is formed.

(3)使源極‧汲極電極形成後，以包圍包含一對源極‧汲極電極之區域的方式使用本發明之正型感光性樹脂組成物來形成隔壁。接下來，在進行點之親墨化處理後，使用噴墨法於點塗佈有機半導體之溶液，使有機半導體層形成 於源極‧汲極電極間。 (3) After the source ‧th pole electrode is formed, the positive-type photosensitive resin composition of the present invention is used to form a partition wall so as to surround a region including a pair of source ‧ 汲 electrodes. Next, after the ink-removing treatment of the dots, the solution of the organic semiconductor is applied to the dots by an inkjet method to form an organic semiconductor layer. Between the source and the 汲 pole electrode.

而，步驟(1)~(3)可僅在其等之1步驟中形成、利用使用本發明之正型感光性樹脂組成物的隔壁，亦可在2個以上之步驟中形成、利用使用本發明之正型感光性樹脂組成物的隔壁。 Further, in the steps (1) to (3), the partition wall using the positive photosensitive resin composition of the present invention may be formed only in one step, or may be formed in two or more steps and used. A partition wall of the positive photosensitive resin composition of the invention.

實施例 Example

以下使用實施例進一步詳細說明本發明，惟本發明並不受該等實施例限定解釋。 The invention is further illustrated in the following examples, but the invention is not to be construed as limited.

例1~4係實施例，例5係比較例。 Examples 1 to 4 are examples, and examples 5 are comparative examples.

各測定係以下述方法進行。 Each measurement system was carried out in the following manner.

[數量平均分子量(Mn)] [Quantum average molecular weight (Mn)]

使用市售之GPC測定裝置(東曹公司製、裝置名：HLC-8320GPC)來測定作為分子量測定用標準試料之市售聚合度相異的數種單分散聚苯乙烯聚合物之凝膠滲透層析(GPC)，並以聚苯乙烯之分子量與保持時間(滯留時間)之關係為依據製作出檢測線。 A commercially available GPC measuring device (manufactured by Tosoh Corporation, device name: HLC-8320GPC) was used to measure a gel permeation layer of several monodisperse polystyrene polymers having different commercial polymerization degrees as standard samples for molecular weight measurement. (GPC), and the detection line was prepared based on the relationship between the molecular weight of polystyrene and the retention time (residence time).

以四氫呋喃將試料稀釋成1.0質量%並使其通過0.5μm之濾器後，使用前述GPC測定裝置測定出有關該試料之GPC。 The sample was diluted to 1.0% by mass with tetrahydrofuran and passed through a 0.5 μm filter, and then the GPC of the sample was measured using the GPC measuring apparatus.

使用前述檢測線將試料之GPC譜進行電腦解析，藉此求算出該試料之數量平均分子量(Mn)。 The number average molecular weight (Mn) of the sample was calculated by computer analysis of the GPC spectrum of the sample using the aforementioned detection line.

[水接觸角] [water contact angle]

藉由不濡液滴法，依據JIS R3257「基板玻璃表面的濕潤性試驗方法」，於基板上之測定表面3處載置水滴並就各 水滴進行測定。液滴為2μL/滴且測定在20℃下進行。接觸角係以3測定值之平均值(n=3)表示。 According to JIS R3257 "Test method for wettability of substrate glass surface", water droplets are placed on the measurement surface 3 on the substrate by the non-drop method. Water droplets were measured. The droplets were 2 μL/drop and the measurement was carried out at 20 °C. The contact angle is expressed as the average of 3 measured values (n=3).

[PGMEA接觸角] [PGMEA contact angle]

藉由不濡液滴法，依據JIS R3257「基板玻璃表面之濕潤性試驗方法」，於基板上之測定表面3處載置PGMEA滴並就各PGMEA滴進行測定。液滴為2μL/滴且測定在20℃下進行。接觸角係以3測定值之平均值(n=3)表示。 According to JIS R3257 "Test method for wettability of substrate glass surface", PGMEA droplets were placed on the measurement surface 3 on the substrate by the liquid droplet method, and each PGMEA droplet was measured. The droplets were 2 μL/drop and the measurement was carried out at 20 °C. The contact angle is expressed as the average of 3 measured values (n=3).

合成例1~5及例1~5中所用之化合物之縮語如下。 The abbreviations of the compounds used in Synthesis Examples 1 to 5 and Examples 1 to 5 are as follows.

(鹼可溶性樹脂(A)) (alkali soluble resin (A))

EP4020G(商品名；EP4020G、旭有機材工業公司製、甲酚酚醛樹脂(質量平均分子量(Mw)：11,600、溶解速度：164(埃/秒))。 EP4020G (trade name; EP4020G, manufactured by Asahi Organic Materials Co., Ltd., cresol novolac resin (mass average molecular weight (Mw): 11,600, dissolution rate: 164 (angstroms/second)).

(感光劑(B)) (sensitizer (B))

4NT-250(商品名；4NT-250、東洋合成公司製(2,3,4,4’-四羥二苯基酮與6-重氮-5,6-二氫-5-氧-萘-1-磺酸之(單~四)酯))。 4NT-250 (trade name; 4NT-250, manufactured by Toyo Synthetic Co., Ltd. (2,3,4,4'-tetrahydroxydiphenyl ketone and 6-diazo-5,6-dihydro-5-oxo-naphthalene- 1-sulfonic acid (mono-tetra) ester)).

(作為撥墨劑(C)原料的水解性矽烷化合物) (hydrolyzable decane compound as a raw material for the ink (C))

相當於水解性矽烷化合物(c-1)之化合物(c-11)：CF3(CF2)5CH2CH2Si(OCH3)3(旭硝子公司製)。 The compound (c-11) corresponding to the hydrolyzable decane compound (c-1): CF 3 (CF 2 ) 5 CH 2 CH 2 Si(OCH 3 ) 3 (manufactured by Asahi Glass Co., Ltd.).

相當於水解性矽烷化合物(c-2)之化合物(c-21)：Si(OC2H5)4(COLCOAT公司製)。 Compound (c-21) corresponding to hydrolyzable decane compound (c-2): Si(OC 2 H 5 ) 4 (manufactured by COLCOAT).

相當於水解性矽烷化合物(c-3)之化合物(c-31)：C6H5Si(OC2H5)3(信越化學工業公司製)。 The compound (c-31) corresponding to the hydrolyzable decane compound (c-3): C 6 H 5 Si(OC 2 H 5 ) 3 (manufactured by Shin-Etsu Chemical Co., Ltd.).

相當於水解性矽烷化合物(c-3)之化合物(c-32)：C6H5NH(CH2)3Si(OCH3)3(信越化學工業公司製)。 The compound (c-32) corresponding to the hydrolyzable decane compound (c-3): C 6 H 5 NH(CH 2 ) 3 Si(OCH 3 ) 3 (manufactured by Shin-Etsu Chemical Co., Ltd.).

C6FMA：CH2=C(CH3)COOCH2CH2(CF2)6F。 C6FMA: CH 2 =C(CH 3 )COOCH 2 CH 2 (CF 2 ) 6 F.

MEK：甲基乙基酮。 MEK: methyl ethyl ketone.

MAA：甲基丙烯酸。 MAA: methacrylic acid.

GMA：甲基丙烯酸縮水甘油酯。 GMA: glycidyl methacrylate.

MMA：甲基丙烯酸甲酯。 MMA: methyl methacrylate.

V-65：(商品名；和光化學工業公司製(2,2’-偶氮雙(2.4二甲基戊腈)(聚合引發劑))。 V-65: (trade name; manufactured by Photochemical Industries, Ltd. (2,2'-azobis(2.4-dimethylvaleronitrile) (polymerization initiator)).

(溶媒(D)) (Solvent (D))

PGMEA：丙二醇單甲基醚乙酸酯。 PGMEA: propylene glycol monomethyl ether acetate.

PGME：丙二醇單甲基醚(東邦化學公司製)。 PGME: propylene glycol monomethyl ether (manufactured by Toho Chemical Co., Ltd.).

(熱硬化劑(E)) (thermosetting agent (E))

TEP-G(商品名；TEP-G、旭有機材工業公司製、環氧樹脂)。 TEP-G (trade name; TEP-G, manufactured by Asahi Organic Materials Co., Ltd., epoxy resin).

(熱硬化促進劑(F)) (thermosetting accelerator (F))

2-MI(商品名；東京化成工業公司製(2-甲咪唑))。 2-MI (trade name; manufactured by Tokyo Chemical Industry Co., Ltd. (2-methylimidazole)).

[合成例1~3：撥墨劑(CA1)~(CA3)之合成及(CA1-1)~(CA3-1)液之調製] [Synthesis Examples 1 to 3: Synthesis of ink-repellent (CA1) to (CA3) and preparation of (CA1-1) to (CA3-1) liquid]

於備有攪拌機之50cm3三口燒瓶放入上述化合物(c-11)0.57g、上述化合物(c-21)1.27g及上述化合物(c-31)0.74g而製得撥墨劑(C1)之原料混合物。接下來，於該原料混合物放入9.85g之PGME而製成溶液(原料溶液)。 Into a 50 cm 3 three-necked flask equipped with a stirrer, 0.57 g of the above compound (c-11), 1.27 g of the above compound (c-21) and 0.74 g of the above compound (c-31) were placed to prepare an ink repellent (C1). Raw material mixture. Next, 9.85 g of PGME was placed in the raw material mixture to prepare a solution (raw material solution).

於所得之原料溶液在室溫下一邊攪拌一邊滴下作為觸 媒之1.33g的1.0質量%磷酸水溶液。滴下結束後進一步攪拌5小時，進行水解及部分縮合反應，而製得含有10質量%之撥墨劑(CA1)的PGME溶液之(CA1-1)液。 The resulting raw material solution is dripped as a touch while stirring at room temperature 1.33 g of a 1.0% by mass aqueous phosphoric acid solution. After the completion of the dropwise addition, the mixture was further stirred for 5 hours to carry out hydrolysis and partial condensation reaction, thereby preparing a (CA1-1) solution of a PGME solution containing 10% by mass of an ink-repellent (CA1).

作為觸媒而使用1.33g之表1顯示者來取代1.0質量%磷酸水溶液以外，以與合成例1同樣的方式實施，而製得含有10質量%之撥墨劑(CA2)~(CA3)的PGME溶液之(CA2-1)~(CA3-1)液。 In the same manner as in Synthesis Example 1, except that 1.03 g of the phosphoric acid aqueous solution was used as the catalyst, the same as in the synthesis example 1 was used, and 10% by mass of the ink-repellent (CA2) to (CA3) was obtained. (CA2-1)~(CA3-1) solution of PGME solution.

[合成例4：撥墨劑(CA4)之合成及(CA4-1)液之調製] [Synthesis Example 4: Synthesis of ink-repellent (CA4) and preparation of (CA4-1) liquid]

使用上述化合物(c-32)來取代上述化合物(c-31)以外，以與合成例1同樣的方式實施，而調製出撥墨劑(CA4)之原料溶液。 A raw material solution of an ink-repellent (CA4) was prepared in the same manner as in Synthesis Example 1 except that the above compound (c-32) was used instead of the above compound (c-31).

於所得之原料溶液在室溫下一邊攪拌一邊滴下0.93g之1.0質量%硝酸水溶液。滴下結束後進一步攪拌5小時，進行水解及部分縮合反應，而製得含有10質量%之撥墨劑(CA4)的PGME溶液之(CA4-1)液。 To the obtained raw material solution, 0.93 g of a 1.0% by mass aqueous solution of nitric acid was added dropwise while stirring at room temperature. After the completion of the dropwise addition, the mixture was further stirred for 5 hours to carry out hydrolysis and partial condensation reaction, thereby preparing a (CA4-1) solution of a PGME solution containing 10% by mass of an ink-repellent (CA4).

[合成例5：撥墨劑(CA5)及(CA5-1)液之調製] [Synthesis Example 5: Preparation of liquid ink (CA5) and (CA5-1) liquid]

於備有攪拌機之內容積1000cm3的高壓釜饋入420.0g之MEK、86.4g之C6FMA、18.0g之MAA、21.6g之GMA、54.0g之MMA及0.8g之V-65，一邊在氮氣體環境下進行攪拌一邊在50℃下使其聚合反應24小時而合成粗共聚物。於所得之粗共聚物溶液加入己烷進行再沉積、純化後，進行真空乾燥。於所得之固體物加入14,643g之PGMEA進行攪拌，而製得含有10質量%之撥墨劑(CA5)的PGMEA溶液之(CA5-1) 液。 The autoclave with a volume of 1000 cm 3 equipped with a stirrer was fed with 420.0 g of MEK, 86.4 g of C6FMA, 18.0 g of MAA, 21.6 g of GMA, 54.0 g of MMA and 0.8 g of V-65, while nitrogen gas was used. The crude copolymer was synthesized by polymerization at 50 ° C for 24 hours while stirring. After the obtained crude copolymer solution was added to hexane for redeposition and purification, it was vacuum dried. To the obtained solid, 14,643 g of PGMEA was added and stirred to prepare a (CA5-1) solution of a PGMEA solution containing 10% by mass of an ink-repellent (CA5).

於表1顯示在上述合成例1~5中調製而得之含有10質量%之撥墨劑的溶液(CA1-1)~(CA5-1)之溶媒除外的組成物即撥墨劑(CA1)~(CA5)之含氟含有率(氟原子之質量%)及數量平均分子量(Mn)。 Table 1 shows the ink-repellent (CA1) which is a composition excluding the solvent of the solution (CA1-1) to (CA5-1) containing 10% by mass of the ink-repellent prepared in the above Synthesis Examples 1 to 5. The fluorine content (% by mass of fluorine atom) and the number average molecular weight (Mn) of ~(CA5).

又，撥墨劑(CA1)~(CA5)之饋入量組成(莫耳%)亦顯示於表1。 Further, the composition of the amount of the ink-repellent (CA1) to (CA5) (% by mole) is also shown in Table 1.

[表1] [Table 1]

[例1] [example 1]

(正型感光性樹脂組成物1之製造) (Manufacture of positive photosensitive resin composition 1)

將(CA1-1)液1g(固體成分為0.1g、剩餘為PGME(溶媒))、15.6g之EP4020G、5.4g之4NT-250、3.1g之TEP-G、0.8g之2-MI及74.1g之PGMEA放入500cm3的攪拌用容器，攪拌30分鐘而調製出正型感光性樹脂組成物1。 1 g of (CA1-1) solution (solid content: 0.1 g, remaining PGME (solvent)), 15.6 g of EP4020G, 5.4 g of 4NT-250, 3.1 g of TEP-G, 0.8 g of 2-MI and 74.1 The PGMEA of g was placed in a 500 cm 3 stirring vessel and stirred for 30 minutes to prepare a positive photosensitive resin composition 1.

(硬化膜之製造) (Manufacture of cured film)

將10cm正方形玻璃基板以乙醇超音波洗淨30秒鐘，接下來進行5分鐘之紫外線/臭氧洗淨。在紫外線/臭氧洗淨作為紫外線/臭氧產生裝置係使用PL7-200(SENENGINEERING公司製)。而，有關以下全部的紫外線/臭氧處理亦是使用本裝置作為紫外線/臭氧產生裝置。 The 10 cm square glass substrate was ultrasonically washed with ethanol for 30 seconds, followed by ultraviolet/ozone cleaning for 5 minutes. In the ultraviolet/ozone cleaning, PL7-200 (manufactured by SENENGINEERING Co., Ltd.) was used as the ultraviolet/ozone generating device. However, all of the following ultraviolet/ozone treatments are also using the device as an ultraviolet/ozone generating device.

於上述洗淨後之玻璃基板表面使用旋轉器塗佈正型感光性樹脂組成物1後，在100℃下在熱板上使其乾燥2分鐘而形成膜厚1.3μm之膜。於所得之膜表面，從膜側隔著具有開孔圖案(2.5cm×5cm)之光罩(可對該圖案部區域進行光照射之光罩)隔開50μm之間隙，並在25mW/cm2下照射高壓水銀燈之紫外線10秒鐘。 The positive photosensitive resin composition 1 was applied onto the surface of the glass substrate after the above-mentioned cleaning using a spinner, and then dried on a hot plate at 100 ° C for 2 minutes to form a film having a film thickness of 1.3 μm. On the surface of the obtained film, a reticle having an opening pattern (2.5 cm × 5 cm) (a reticle capable of illuminating the pattern portion) was separated from the film side by a gap of 50 μm and at 25 mW/cm 2 . The ultraviolet light of the high pressure mercury lamp was irradiated for 10 seconds.

接下來將業經曝光處理之玻璃基板浸漬於2.38質量%氫氧化四甲銨水溶液40秒鐘進行顯影，並以水將曝光部分之膜沖洗後，使其乾燥。接下來，使之在熱板上以230℃加熱20分鐘，藉此製得於上述開孔圖案部除外之區域形成有正型感光性樹脂組成物1之硬化膜的玻璃基板1。 Next, the exposed glass substrate was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 40 seconds for development, and the exposed portion of the film was rinsed with water and then dried. Then, it was heated at 230 ° C for 20 minutes on a hot plate to obtain a glass substrate 1 in which a cured film of the positive photosensitive resin composition 1 was formed in a region excluding the above-described opening pattern portion.

(評估) (assessment)

就上述所得之正型感光性樹脂組成物1及形成有硬化膜(隔壁)之玻璃基板1進行以下評估。 The positive photosensitive resin composition 1 obtained above and the glass substrate 1 on which the cured film (partition wall) was formed were evaluated as follows.

<撥墨性(隔壁)、親墨性(點陣)及顯影殘渣> <Ink-repellent (partition), ink-receptive (lattice) and development residue>

測定所得之玻璃基板1的硬化膜即隔壁表面(未曝光部分)相對於PGMEA之接觸角、及藉由顯影而除去膜之部分即點部分(玻璃基板表面)相對於水之接觸角。此時，藉由點部分相對於水之接觸角來進行有關顯影殘渣之評估。評估係如以下進行。 The contact angle of the surface of the partition wall (unexposed portion) of the obtained glass substrate 1 with respect to the PGMEA, and the contact portion of the portion (the surface of the glass substrate) of the portion where the film was removed by development was measured with respect to water. At this time, the evaluation of the development residue is performed by the contact angle of the dot portion with respect to water. The evaluation is performed as follows.

○(良好)：水接觸角低於30度。 ○ (good): The water contact angle is less than 30 degrees.

×(不良)：水接觸角在30度以上。 × (bad): The water contact angle is 30 degrees or more.

其後，於玻璃基板1已形成硬化膜之側的表面整體進行1分鐘的紫外線/臭氧照射。測出照射1分鐘後之硬化膜表面相對於PGMEA之接觸角及玻璃基板表面相對於水之接觸角。測定方法如上述。評估結果顯示於表2。 Thereafter, the entire surface on the side where the cured film was formed on the glass substrate 1 was subjected to ultraviolet/ozone irradiation for 1 minute. The contact angle of the surface of the cured film with respect to PGMEA after 1 minute of irradiation and the contact angle of the surface of the glass substrate with respect to water were measured. The measurement method is as described above. The evaluation results are shown in Table 2.

<貯藏穩定性> <Storage stability>

將正型用感光性組成物以玻璃製螺旋瓶在23℃(室溫)下保存一個月。保存一個月後，在以與例1同樣的方法加以洗淨之10cm×10cm的玻璃基板表面使用旋轉器塗佈正型用感光性組成物並形成塗膜。接下來，在100℃下在熱板上使其乾燥2分鐘而形成膜厚1μm之膜。以目測觀察膜之外觀，並如以下進行評估。 The positive photosensitive composition was stored in a glass spiral bottle at 23 ° C (room temperature) for one month. After the storage for one month, the photosensitive composition of the positive type was applied to the surface of the glass substrate of 10 cm × 10 cm which was washed in the same manner as in Example 1 using a spinner to form a coating film. Next, it was dried on a hot plate at 100 ° C for 2 minutes to form a film having a film thickness of 1 μm. The appearance of the film was visually observed and evaluated as follows.

○(良好)：膜上之異物在5個以下。 ○ (good): The number of foreign substances on the film is 5 or less.

×(不良)：膜上之異物在6個以上且有觀察到自玻璃基板中心部呈放射狀之筋痕模樣。 × (defect): The foreign matter on the film was six or more, and a rib-like pattern which was radially from the center of the glass substrate was observed.

[例2~5] [Example 2~5]

除使用表中顯示之(CA2-1)~(CA5-1)液來取代(CA1-1)液以外，以與例1同樣的方式製作正型感光性樹脂組成物2~5及形成有正型感光性樹脂組成物2~5之硬化膜的玻璃基板2~5，並就其等以與例1同樣的方式進行評估。 The positive photosensitive resin compositions 2 to 5 were formed in the same manner as in Example 1 except that the (CA2-1) to (CA5-1) liquid was used instead of the (CA1-1) liquid. The glass substrates 2 to 5 of the cured film of the photosensitive resin compositions 2 to 5 were evaluated in the same manner as in Example 1.

結果彙整顯示於表2。又，例1~5中所得之組成物之組成亦合併顯示於表2。 The resulting summary is shown in Table 2. Further, the compositions of the compositions obtained in Examples 1 to 5 are also shown in Table 2.

[表2] [Table 2]

如從表2可知，例1~4中所得之正型感光性樹脂組成物貯藏穩定性優異。藉由使用該組成物，可製得無顯影殘渣的隔壁。可知，由於例1~4中所得之硬化膜使用了本發明之撥墨劑，因此撥墨性佳，即便紫外線/臭氧照射後撥墨性仍佳，且點(玻璃基板表面)具有良好的親墨性。另一方面，使用未依據本發明之撥墨劑的例5中所得之硬化膜，紫外線/臭氧照射後的撥墨性則不夠充分。 As is clear from Table 2, the positive photosensitive resin compositions obtained in Examples 1 to 4 were excellent in storage stability. By using this composition, a partition wall free from development residue can be obtained. It can be seen that since the cured film obtained in Examples 1 to 4 uses the ink-repellent of the present invention, the ink repellency is good, and the ink repellency is good even after ultraviolet/ozone irradiation, and the dots (glass substrate surface) have good pros. Ink. On the other hand, using the cured film obtained in Example 5 which was not in accordance with the ink-repellent of the present invention, the ink repellency after ultraviolet/ozone irradiation was insufficient.

產業上之可利用性 Industrial availability

本發明之正型感光性樹脂組成物可製得撥墨性優異、即便經紫外線/臭氧照射撥墨性仍佳且點少有殘留物的隔壁，可適當使用於利用噴墨記錄技術法的濾色器之製造、有機EL元件之製造及有機TFT陣列之製造中的隔壁形成，尤其適合使用於大面積基板的隔壁形成。 The positive photosensitive resin composition of the present invention can be used as a partition wall which is excellent in ink repellent property and which is excellent in ink repellency by ultraviolet/ozone irradiation and has little residue, and can be suitably used for filtration by an ink jet recording technique. The manufacture of a color former, the manufacture of an organic EL element, and the formation of a partition in the manufacture of an organic TFT array are especially suitable for formation of the partition of a large-area board|substrate.

而，在此係引用已於2012年3月9日提出申請之日本專利申請案2012-053448號說明書、申請專利範圍、圖式及摘要之全部內容，並將之納入作為本發明說明書之揭示。 The entire disclosure of Japanese Patent Application No. 2012-053448, filed on-

1‧‧‧基板 1‧‧‧Substrate

2‧‧‧正型感光性樹脂組成物塗膜 2‧‧‧Positive type photosensitive resin composition coating film

3‧‧‧塗膜之未曝光部分 3‧‧‧Unexposed part of the film

4‧‧‧光罩 4‧‧‧Photomask

5‧‧‧光 5‧‧‧Light

6‧‧‧隔壁 6‧‧‧ next door

7‧‧‧點 7 o'clock

10‧‧‧用於噴墨方式的光學元件用基板 10‧‧‧Substrate for optical components for inkjet systems

Claims (15)

一種正型感光性樹脂組成物，係含有鹼可溶性樹脂(A)、感光劑(B)及撥墨劑(C)者；其特徵在於：前述撥墨劑(C)係由下述混合物的部分水解縮合物所構成：含有以下式(c-1)表示之水解性矽烷化合物及以下式(c-2)表示之水解性矽烷化合物之混合物；且前述撥墨劑(C)中之氟原子含有率為10~55質量%；[化1]Rf-Q1-SiX1 3…(c-1) RH1 p-SiX2 (4-p)…(c-2)(式(c-1)及(c-2)中之記號如下：Rf：碳原子數1~6之全氟烷基、或以Rf1ORf2-表示之碳原子數2~40之1價基(而，Rf1係碳原子數1~6之全氟烷基，Rf2係在碳-碳原子間可具有醚性氧原子之全氟伸烷基)；Q1：碳原子數1~10且不含氟原子之2價有機基；RH1：碳原子數1~6之1價烴基；X1及X2：水解性基；p：0、1或2；惟，式(c-1)中之3個X1、式(c-2)中之(4-p)個X2及p個RH1可分別彼此相異亦可相同)。 A positive photosensitive resin composition containing an alkali-soluble resin (A), a sensitizer (B), and an ink-repellent (C); characterized in that the ink-repellent (C) is a part of the following mixture The hydrolyzed condensate comprises a mixture of a hydrolyzable decane compound represented by the following formula (c-1) and a hydrolyzable decane compound represented by the following formula (c-2); and the fluorine atom in the above-mentioned ink repellent (C) contains The ratio is 10 to 55% by mass; [Chemical 1] R f -Q 1 -SiX 1 3 (c-1) R H1 p -SiX 2 (4-p) (c-2) (Formula (c-1) And the symbols in (c-2) are as follows: R f : a perfluoroalkyl group having 1 to 6 carbon atoms or a valent group having 2 to 40 carbon atoms represented by R f1 OR f2 - (R, R F1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R f2 is a perfluoroalkyl group having an etheric oxygen atom between carbon-carbon atoms; Q 1 : a carbon number of 1 to 10 and no fluorine a divalent organic group of an atom; R H1 : a monovalent hydrocarbon group having 1 to 6 carbon atoms; X 1 and X 2 : a hydrolyzable group; p: 0, 1 or 2; only, 3 in the formula (c-1) The X 1 and (4-p) X 2 and p R H1 in the formula (c-2) may be different from each other or the same). 如申請專利範圍第1項之正型感光性樹脂組成物，其中 前述鹼可溶性樹脂(A)在正型感光性樹脂組成物之總固體成分中的含量為10~90質量%。 For example, a positive photosensitive resin composition of claim 1 of the patent scope, wherein The content of the alkali-soluble resin (A) in the total solid content of the positive photosensitive resin composition is from 10 to 90% by mass. 如申請專利範圍第1或2項之正型感光性樹脂組成物，其中前述感光劑(B)在正型感光性樹脂組成物之總固體成分中的含量為0.1~50質量%。 The positive photosensitive resin composition of the first or second aspect of the invention, wherein the photosensitive agent (B) is contained in an amount of from 0.1 to 50% by mass based on the total solid content of the positive photosensitive resin composition. 如申請專利範圍第1至3項中任一項之正型感光性樹脂組成物，其中前述撥墨劑(C)在正型感光性樹脂組成物之總固體成分中的含量為0.01~10質量%。 The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the ink-repellent (C) in the total solid content of the positive-type photosensitive resin composition is 0.01 to 10 mass %. 如申請專利範圍第1至4項中任一項之正型感光性樹脂組成物，其中前述撥墨劑(C)之數量平均分子量(Mn)在500以上且低於1,000,000。 The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the ink repellent (C) has a number average molecular weight (Mn) of 500 or more and less than 1,000,000. 如申請專利範圍第1至5項中任一項之正型感光性樹脂組成物，其中前述鹼可溶性樹脂(A)為酚醛清漆型苯酚樹脂。 The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) is a novolac type phenol resin. 如申請專利範圍第1至6項中任一項之正型感光性樹脂組成物，其中前述感光劑(B)係具有二疊氮醌基之化合物。 The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the sensitizer (B) is a compound having a diazide fluorenyl group. 如申請專利範圍第1至7項中任一項之正型感光性樹脂組成物，其中前述混合物更含有以下式(c-3)表示之水解性矽烷化合物： (式(c-3)中之記號如下：Y：氫原子亦可被鹵素原子、碳原子數1~3之烷基、碳原子數2~3之烯基或硝基取代之苯基；Q2：單鍵或2價有機基；RH2：碳原子數1~6之1價烴基；X3：水解性基；q：1或2；r：0或1且q+r成為1或2之數；惟，q個Y、Q2及Y-Q2以及(4-q-r)個X3可分別彼此相異亦可相同)。 The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the mixture further contains a hydrolyzable decane compound represented by the following formula (c-3): (The symbol in the formula (c-3) is as follows: Y: a hydrogen atom may be substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms or a nitro group; Q 2 : a single bond or a divalent organic group; R H2 : a monovalent hydrocarbon group having 1 to 6 carbon atoms; X 3 : a hydrolyzable group; q: 1 or 2; r: 0 or 1 and q + r becomes 1 or 2 The number; however, q Y, Q 2 and YQ 2 and (4-qr) X 3 may be different from each other or the same). 如申請專利範圍第1至8項中任一項之正型感光性樹脂組成物，其更含有溶媒(D)。 The positive photosensitive resin composition according to any one of claims 1 to 8, which further contains a solvent (D). 如申請專利範圍第1至9項中任一項之正型感光性樹脂組成物，其更含有熱硬化劑(E)。 The positive photosensitive resin composition according to any one of claims 1 to 9, which further contains a thermosetting agent (E). 如申請專利範圍第10項之正型感光性樹脂組成物，其更含有熱硬化促進劑(F)。 The positive photosensitive resin composition of claim 10, which further contains a thermosetting accelerator (F). 如申請專利範圍第1至11項中任一項之正型感光性樹脂組成物，其更含有著色劑(G)。 The positive photosensitive resin composition according to any one of claims 1 to 11, which further contains a coloring agent (G). 一種隔壁，係形成為將基板表面劃分成像素形成用之複數個劃分區之形態者；其係由如申請專利範圍第1至12項中任一項之正型感光性樹脂組成物之硬化膜所構成。 A partition wall formed by dividing a surface of a substrate into a plurality of divided regions for forming a pixel, which is a cured film of a positive photosensitive resin composition according to any one of claims 1 to 12. Composition. 一種光學元件，係於基板表面具有複數像素及位在鄰接像素間之隔壁者，前述隔壁係以如申請專利範圍第13項 之隔壁來形成。 An optical component having a plurality of pixels on a surface of a substrate and a spacer between adjacent pixels, wherein the partition wall is as in claim 13 It is formed next door. 如申請專利範圍第14項之光學元件，其中前述光學元件係濾色器、TFT陣列或有機EL元件。 The optical element according to claim 14, wherein the optical element is a color filter, a TFT array or an organic EL element.
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KR20170053442A (en) * 2015-11-06 2017-05-16 롬엔드하스전자재료코리아유한회사 Photosensitive resin composition and cured film prepared therefrom
KR102310794B1 (en) * 2016-05-19 2021-10-12 롬엔드하스전자재료코리아유한회사 Photosensitive resin composition and cured film prepared therefrom
KR20230165863A (en) * 2017-04-21 2023-12-05 닛산 가가쿠 가부시키가이샤 Photosensitive resin composition
US11800738B2 (en) * 2018-01-18 2023-10-24 Sharp Kabushiki Kaisha Display device, method of manufacturing display device, apparatus for manufacturing a display device
KR20210073517A (en) 2018-10-12 2021-06-18 도레이 카부시키가이샤 A photosensitive resin composition, a cured film, and the display device using this cured film
JPWO2021177252A1 (en) * 2020-03-04 2021-09-10
JPWO2021177251A1 (en) 2020-03-04 2021-09-10
KR20230142489A (en) * 2021-02-03 2023-10-11 닛산 가가쿠 가부시키가이샤 Positive photosensitive resin composition
JPWO2022181351A1 (en) * 2021-02-24 2022-09-01
WO2024038814A1 (en) * 2022-08-19 2024-02-22 Ａｇｃ株式会社 Positive-type photosensitive resin composition, partition wall, and optical element

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4283582B2 (en) * 2002-04-15 2009-06-24 シャープ株式会社 Radiation-sensitive resin composition, method for forming patterned insulating film, active matrix substrate, flat display device including the same, and method for manufacturing flat display device
TWI411884B (en) * 2006-05-16 2013-10-11 Nissan Chemical Ind Ltd Positive type photosensitive resin composition containing siloxane compound
KR20090010044A (en) * 2006-05-16 2009-01-28 닛산 가가쿠 고교 가부시키 가이샤 Positive photosensitive resin composition and porous film obtained therefrom
JP5173543B2 (en) 2008-04-08 2013-04-03 東京応化工業株式会社 Positive photosensitive resin composition
WO2010013816A1 (en) * 2008-08-01 2010-02-04 旭硝子株式会社 Negative working photosensitive composition, partition wall for optical element using the nagative working photosensitive composition, and optical element comprising the partition wall
JP5338258B2 (en) * 2008-10-30 2013-11-13 Ｊｎｃ株式会社 Positive photosensitive composition, cured film obtained from the composition, and display element having the cured film
JP5397152B2 (en) * 2009-10-22 2014-01-22 Ｊｓｒ株式会社 Positive radiation-sensitive composition, interlayer insulating film and method for forming the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI667542B (en) * 2014-08-12 2019-08-01 日商東京應化工業股份有限公司 Positive photosensitive resin composition and cured film
TWI698421B (en) * 2015-08-18 2020-07-11 日商迪愛生股份有限公司 Novolac type phenolic hydroxyl group-containing resin and resist film

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