TWI738634B - Positive photosensitive resin composition, hardened film and display element - Google Patents

Positive photosensitive resin composition, hardened film and display element Download PDF

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TWI738634B
TWI738634B TW104140780A TW104140780A TWI738634B TW I738634 B TWI738634 B TW I738634B TW 104140780 A TW104140780 A TW 104140780A TW 104140780 A TW104140780 A TW 104140780A TW I738634 B TWI738634 B TW I738634B
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竹田佳代
畑中真
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日商日產化學工業股份有限公司
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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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • 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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

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Abstract

本發明的課題為提供一種維持顯影時之密著性而可直接以高感度圖型形成，可形成圖型內殘渣少之硬化膜的正型感光性樹脂組成物。 The subject of the present invention is to provide a positive photosensitive resin composition that can directly form a high-sensitivity pattern while maintaining adhesion during development, and can form a cured film with less residue in the pattern.

本發明的解決手段為一種正型感光性樹脂組成物，其係含有下述(A)成分、(B)成分、(C)成分、及(D)溶劑。 The solution of the present invention is a positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, and (D) solvent.

(A)成分：使下述(A1)~(A4)進行共聚合所得之鹼可溶性丙烯酸共聚物 (A) Component: Alkali-soluble acrylic copolymer obtained by copolymerizing the following (A1) to (A4)

(A1)不飽和羧酸及/或不飽和羧酸酐、(A2)具有酚性羥基與聚合性不飽和基之單體、(A3)具有羥烷基與聚合性不飽和基之單體、(A4)N取代馬來醯亞胺化合物； (A1) Unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, ( A4) N-substituted maleimide compounds;

(B)成分：1,2-醌二疊氮(Quinonediazide)化合物、 (B) Component: 1,2-quinonediazide compound,

(C)成分：交聯劑 (C)Component: Crosslinking agent

(D)溶劑。 (D) Solvent.

Description

正型感光性樹脂組成物、硬化膜及顯示元件 Positive photosensitive resin composition, cured film and display element

本發明係關於正型感光性樹脂組成物及由該組成物所得之硬化膜。更詳細而言，本發明係關於在顯示器材料之用途中，適合之正型感光性樹脂組成物及其硬化膜、以及使用該硬化膜之各種材料。 The present invention relates to a positive photosensitive resin composition and a cured film obtained from the composition. In more detail, the present invention relates to a positive photosensitive resin composition suitable for use in a display material, a cured film thereof, and various materials using the cured film.

一般而言，在薄膜電晶體(TFT)型液晶顯示元件、有機EL(electroluminescent)元件等之顯示器元件，設置有經圖型形成之電極保護膜、平坦化膜、絕緣膜等。作為形成此等之膜的材料，感光性樹脂組成物當中，擁有所謂用以得到必要之圖型形狀之步驟數少，且具有充分平坦性的特徵的感光性樹脂組成物，較以往更被廣泛使用。 Generally speaking, display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements are provided with patterned electrode protection films, planarization films, insulating films, and the like. As a material for forming these films, among the photosensitive resin compositions, the number of steps required to obtain the necessary pattern shape is small, and the photosensitive resin composition has the characteristics of sufficient flatness, which is more widely used than before. use.

而且，上述此等之膜中，要求耐熱性、耐溶劑性、長時間燒成耐性、金屬濺鍍耐性等之製程耐性優異、與基底的密著性良好、具有可以配合使用目的之各式各樣製程條件形成圖型之廣泛操作界限(Process margin)， 此外，並要求高感度且高透明性以及顯影後之膜不均勻少等諸多特性。因此，從該要求特性的點來看，目前為止，作為上述之感光性樹脂組成物，一直通用包含萘醌二疊氮化合物之樹脂。 Moreover, among the above-mentioned films, it is required to have excellent process resistance such as heat resistance, solvent resistance, long-term firing resistance, metal sputtering resistance, etc., good adhesion to the substrate, and various types that can be used in conjunction with the purpose. The sample process conditions form the broad operating margin of the graph (Process margin), In addition, many characteristics such as high sensitivity, high transparency, and less unevenness of the film after development are required. Therefore, from the point of view of the required characteristics, a resin containing a naphthoquinonediazide compound has been commonly used as the above-mentioned photosensitive resin composition so far.

提案有此等之材料係藉由添加環氧交聯劑、或於丙烯酸樹脂中使含有羧基與環氧基，熱交聯經形成之圖型使其硬化(專利文獻1及2)。惟使用如此之樹脂的情況得不到充分的感度，與顯示器製造時之生產量(Throughput)降低有關聯。又藉由後烘烤時之烘烤溫度，圖型形狀易變化，故被要求精密溫度調控。 It has been proposed that these materials are cured by adding an epoxy crosslinking agent, or containing a carboxyl group and an epoxy group in an acrylic resin, and thermally crosslinking the formed pattern (Patent Documents 1 and 2). However, when such resin is used, sufficient sensitivity cannot be obtained, which is related to the decrease in throughput (Throughput) during display manufacturing. In addition, the shape of the pattern is easy to change due to the baking temperature during post-baking, so precise temperature control is required.

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2000-103937號公報 [Patent Document 1] JP 2000-103937 A

[專利文獻2]日本特開平4-352101號公報 [Patent Document 2] Japanese Patent Application Laid-Open No. 4-352101

本發明係鑑於上述事情而完成者，可提供一種維持顯影時之密著性而可直接以高感度圖型形成，可形成圖型內殘渣少之硬化膜的正型感光性樹脂組成物。 The present invention has been accomplished in view of the foregoing, and can provide a positive photosensitive resin composition that maintains adhesion during development, can be directly formed with a high-sensitivity pattern, and can form a cured film with less residue in the pattern.

本發明者為了解決上述之課題進行努力研究 的結果，而終至發現本發明。亦即，本發明係關於下述。 The inventors have made diligent research to solve the above-mentioned problems As a result, the invention was finally discovered. That is, the present invention relates to the following.

1.一種正型感光性樹脂組成物，其係含有下述(A)成分、(B)成分、(C)成分、及(D)溶劑，(A)成分：使下述(A1)~(A4)進行共聚合所得之鹼可溶性丙烯酸共聚物(A1)不飽和羧酸及/或不飽和羧酸酐、(A2)具有酚性羥基與聚合性不飽和基之單體、(A3)具有羥烷基與聚合性不飽和基之單體、(A4)N取代馬來醯亞胺化合物；(B)成分：1,2-醌二疊氮化合物、(C)成分：交聯劑(D)溶劑。 1. A positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, and (D) solvent, and (A) component: the following (A1)~( A4) Alkali-soluble acrylic copolymer obtained by copolymerization (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) monomers with phenolic hydroxyl groups and polymerizable unsaturated groups, (A3) with hydroxyalkanes Monomers with polymerizable unsaturated groups, (A4) N-substituted maleimide compound; (B) component: 1,2-quinonediazide compound, (C) component: crosslinking agent (D) solvent .

2.如上述1之正型感光性樹脂組成物，其中，(A2)具有酚性羥基與聚合性不飽和基之單體為p-羥基苯基(甲基)丙烯酸酯。 2. The positive photosensitive resin composition of 1 above, wherein (A2) the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth)acrylate.

3.如上述1或2之正型感光性樹脂組成物，其中，(A)成分之鹼可溶性丙烯酸聚合物的數平均分子量以聚苯乙烯換算為2,000~30,000。 3. The positive photosensitive resin composition of 1 or 2 above, wherein the number average molecular weight of the alkali-soluble acrylic polymer of the component (A) is 2,000 to 30,000 in terms of polystyrene.

4.如上述1~3之正型感光性樹脂組成物，其中，相對於(A)成分之100質量份，(B)成分為5~100質量份。 4. The positive photosensitive resin composition of 1 to 3 above, wherein the (B) component is 5 to 100 parts by mass relative to 100 parts by mass of the (A) component.

5.如上述1~4中任一項之正型感光性樹脂組成物，其中，相對於(A)成分之100質量份，(C)成分為5~50質量份。 5. The positive photosensitive resin composition according to any one of 1 to 4 above, wherein the (C) component is 5 to 50 parts by mass relative to 100 parts by mass of the (A) component.

6.上述1~5中任一項之正型感光性樹脂組成物，其中，作為(E)成分，相對於(A)成分之100質量份，係將界 面活性劑進一步含有0.01~1.0質量份。 6. The positive photosensitive resin composition of any one of the above 1 to 5, wherein, as the component (E), relative to 100 parts by mass of the component (A), it is The surfactant further contains 0.01 to 1.0 parts by mass.

7.上述1~6中任一項之正型感光性樹脂組成物，其中，作為(F)成分，相對於(A)成分之100質量份，係將密著促進劑進一步含有0.1~20質量份。 7. The positive photosensitive resin composition of any one of 1 to 6 above, wherein, as the component (F), the adhesion promoter further contains 0.1-20 mass parts relative to 100 parts by mass of the component (A) share.

8.一種硬化膜，其係硬化如上述1~7中任一項之正型感光性樹脂組成物而成。 8. A cured film formed by curing the positive photosensitive resin composition of any one of 1 to 7 above.

9.一種顯示元件，其係具有如上述8之硬化膜。 9. A display device having the cured film as in 8 above.

10.一種顯示元件，其係具有如上述8之硬化膜作為顯示器用陣列平坦化膜。 10. A display element having the cured film of 8 as the array flattening film for displays.

11.一種顯示元件，其係具有如上述8之硬化膜作為層間絕緣膜。 11. A display element having the cured film of 8 as an interlayer insulating film.

本發明之正型感光性樹脂組成物係維持顯影時之密著性而可直接以高感度圖型形成，可形成圖型內殘渣少之硬化膜。 The positive photosensitive resin composition of the present invention maintains the adhesion during development and can be directly formed with a high-sensitivity pattern, and can form a cured film with few residues in the pattern.

本發明之感光性樹脂組成物係含有下述(A)成分、(B)成分、(C)成分、及(D)溶劑之正型感光性樹脂組成物，(A)成分：使下述(A1)~(A4)進行共聚合所得之鹼可溶性丙烯酸共聚物(A1)不飽和羧酸及/或不飽和羧酸酐、(A2)具有酚性羥 基與聚合性不飽和基之單體、(A3)具有羥烷基與聚合性不飽和基之單體、(A4)N取代馬來醯亞胺化合物；(B)成分：1,2-醌二疊氮化合物、(C)成分：交聯劑(D)溶劑。 The photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, and (D) solvent, and (A) component: A1)~(A4) Alkali-soluble acrylic copolymer obtained by copolymerization (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) having phenolic hydroxyl Monomers with polymerizable unsaturated groups, (A3) monomers having hydroxyalkyl and polymerizable unsaturated groups, (A4) N-substituted maleimide compound; (B) component: 1,2-quinone Diazide compound, (C) component: crosslinking agent (D) solvent.

以下，說明各成分之細節。 Hereinafter, the details of each component will be explained.

<(A)成分> <(A) Ingredient>

(A)成分係共聚合(A1)不飽和羧酸及/或不飽和羧酸酐、(A2)具有酚性羥基與聚合性不飽和基之單體、(A3)具有羥烷基與聚合性不飽和基之單體、(A4)N取代馬來醯亞胺化合物所得之鹼可溶性丙烯酸聚合物。 (A) Component system copolymerization (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) monomers having phenolic hydroxyl groups and polymerizable unsaturated groups, (A3) having hydroxyalkyl groups and polymerizable unsaturated groups Saturated monomer, (A4) N-substituted maleimide compound is an alkali-soluble acrylic polymer.

本發明中，所謂丙烯酸聚合物，係指丙烯酸酯、甲基丙烯酸酯、苯乙烯、馬來醯亞胺等之聚合性不飽和基，亦即使用具有於構造中包含C=C雙鍵之聚合性基的單體所得之聚合物。 In the present invention, the so-called acrylic polymer refers to polymerizable unsaturated groups such as acrylate, methacrylate, styrene, maleimide, etc., that is, the polymer having a C=C double bond in the structure is used. The polymer derived from the monomer of the sex group.

(A)成分之鹼可溶性丙烯酸聚合物若為鹼可溶性丙烯酸聚合物即可，對於構成丙烯酸聚合物之高分子主鏈之骨架及側鏈的種類等並未特別限定。 (A) The alkali-soluble acrylic polymer of the component may be an alkali-soluble acrylic polymer, and the types of the backbone and side chains of the polymer main chain constituting the acrylic polymer are not particularly limited.

(A)成分之鹼可溶性丙烯酸聚合物若為數平均分子量超過30,000成為過大者時，降低對於段差之平坦化性能，另外，數平均分子量未滿2,000成為過小者時，有熱硬化時變硬化不足而降低溶劑耐性的情況。據此，數平均分子量為2,000~30,000的範圍內者。 If the number average molecular weight of the alkali-soluble acrylic polymer of component (A) exceeds 30,000 and becomes too large, the flattening performance against the step will be reduced. In addition, if the number average molecular weight is less than 2,000 and become too small, it may become insufficiently hardened during thermal curing. Conditions that reduce solvent resistance. Accordingly, the number average molecular weight is within the range of 2,000 to 30,000.

如上述，(A)成分之鹼可溶丙烯酸聚合物之合成方法係共聚合(A1)具有羧基及/或酸酐基之單體、(A2)具有酚性羥基與聚合性不飽和基之單體、(A3)具有羥烷基與聚合性不飽和基之單體、及(A4)包含N取代馬來醯亞胺之單體混合物的方法，係為簡便。 As mentioned above, the method for synthesizing the alkali-soluble acrylic polymer of component (A) is to copolymerize (A1) monomers having carboxyl groups and/or acid anhydride groups, and (A2) monomers having phenolic hydroxyl groups and polymerizable unsaturated groups. , The method of (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A4) a monomer mixture containing an N-substituted maleimide is simple.

以下，雖列舉(A)成分之構成單體的具體例，但並被限定於此等者。 Although specific examples of the constituent monomers of the component (A) are listed below, they are not limited to these.

作為(A1)成分之具有不飽和羧酸之單體，例如可列舉丙烯酸、甲基丙烯酸、巴豆酸、單-(2-(丙烯醯氧基)乙基)苯二甲酸酯、單-(2-(甲基丙烯醯氧基)乙基)苯二甲酸酯、N-(羧基苯基)馬來醯亞胺、N-(羧基苯基)甲基丙烯醯胺、N-(羧基苯基)丙烯醯胺等，又作為具有不飽和羧酸酐之單體，可列舉馬來酸酐、衣康酸酐等。 Examples of monomers having unsaturated carboxylic acids of the component (A1) include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-( 2-(Methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxybenzene) Base) acrylamide, etc., and as a monomer having an unsaturated carboxylic anhydride, maleic anhydride, itaconic anhydride, etc. can be cited.

作為(A2)成分之具有酚性羥基與聚合性不飽和基之單體，例如可列舉p-羥基苯乙烯、α-甲基-p-羥基苯乙烯、N-羥基苯基馬來醯亞胺、N-羥基苯基丙烯醯胺、N-羥基苯基甲基丙烯醯胺、p-羥基苯基丙烯酸酯、p-羥基苯基甲基丙烯酸酯等，此等可單獨或組合2種以上使用。其中，較佳為選自p-羥基苯基丙烯酸酯與p-羥基苯基甲基丙烯酸酯之單體。 The monomer having a phenolic hydroxyl group and a polymerizable unsaturated group of the component (A2) includes, for example, p-hydroxystyrene, α-methyl-p-hydroxystyrene, and N-hydroxyphenylmaleimide , N-hydroxyphenyl acrylamide, N-hydroxyphenyl methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, etc., these can be used alone or in combination of two or more . Among them, preferred are monomers selected from p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate.

作為(A3)具有羥烷基與聚合性不飽和基之單體，例如可列舉2-羥基乙基丙烯酸酯、2-羥基丙基丙烯酸酯、4-羥基丁基丙烯酸酯、2,3-二羥基丙基丙烯酸酯、2-羥基乙基甲基丙烯酸酯、2-羥基丙基甲基丙烯酸酯、4-羥 基丁基甲基丙烯酸酯、2,3-二羥基丙基甲基丙烯酸酯、甘油單甲基丙烯酸酯、5-丙烯醯氧基-6-羥基降莰烯-2-羧酸基(Carboxylic)-6-內酯等。 (A3) The monomer having a hydroxyalkyl group and a polymerizable unsaturated group includes, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-di Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxy Butyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid (Carboxylic)-6 -Lactone etc.

作為(A4)N取代馬來醯亞胺化合物，例如可列舉N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、及N-環己基馬來醯亞胺等。 (A4) The N-substituted maleimide compound includes, for example, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

又，在本發明，得到(A)成分之丙烯酸聚合物時，可併用可與上述單體(A1)~(A4)共聚合之其他單體。作為如此之單體的具體例，可列舉丙烯酸酯化合物、甲基丙烯酸酯化合物、馬來醯亞胺、丙烯醯胺化合物、丙烯腈、苯乙烯化合物及乙烯化合物等。以下，雖列舉該其他單體的具體例，但並非被限定於此等者。 Moreover, in the present invention, when obtaining the acrylic polymer of the component (A), other monomers copolymerizable with the above-mentioned monomers (A1) to (A4) may be used in combination. Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Although specific examples of the other monomers are listed below, they are not limited to these.

作為前述丙烯酸酯化合物，例如可列舉甲基丙烯酸酯、乙基丙烯酸酯、異丙基丙烯酸酯、苄基丙烯酸酯、萘基丙烯酸酯、蒽基丙烯酸酯、蒽基甲基丙烯酸酯、苯基丙烯酸酯、環氧丙基丙烯酸酯、苯氧基乙基丙烯酸酯、2,2,2-三氟乙基丙烯酸酯、tert-丁基丙烯酸酯、環己基丙烯酸酯、異莰基丙烯酸酯、2-甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、2-乙氧基乙基丙烯酸酯、2-胺基乙基丙烯酸酯、四氫糠基丙烯酸酯、3-甲氧基丁基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、2-丙基-2-金剛烷基丙烯酸酯、8-甲基-8-三環癸基丙烯酸酯、及、8-乙基-8-三環癸基丙烯酸酯、二乙二醇單丙烯酸酯、己內酯2-(丙烯醯氧基)乙基酯、聚(乙二醇)乙基醚丙烯酸酯等。 Examples of the aforementioned acrylate compounds include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate. Ester, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2- Methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutane Acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl -8-Tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, etc.

作為前述甲基丙烯酸酯化合物，例如可列舉甲基甲基丙烯酸酯、乙基甲基丙烯酸酯、異丙基甲基丙烯酸酯、苄基甲基丙烯酸酯、萘基甲基丙烯酸酯、蒽基甲基丙烯酸酯、蒽基甲基甲基丙烯酸酯、苯基甲基丙烯酸酯、環氧丙基甲基丙烯酸酯、苯氧基乙基甲基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、tert-丁基甲基丙烯酸酯、環己基甲基丙烯酸酯、異莰基甲基丙烯酸酯、2-甲氧基乙基甲基丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、2-乙氧基乙基甲基丙烯酸酯、2-胺基甲基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、3-甲氧基丁基甲基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、γ-丁內酯甲基丙烯酸酯、2-丙基-2-金剛烷基甲基丙烯酸酯、8-甲基-8-三環癸基甲基丙烯酸酯、及、8-乙基-8-三環癸基甲基丙烯酸酯、二乙二醇單甲基丙烯酸酯、己內酯2-(甲基丙烯醯氧基)乙基酯、聚(乙二醇)乙基醚甲基丙烯酸酯等。 As the aforementioned methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and anthrylmethacrylate can be cited. Methyl acrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethylmethacrylate Methyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantine Alkyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloxy) ethyl ester, poly(ethylene glycol) ethylene Base ether methacrylate and so on.

作為前述丙烯醯胺化合物，例如可列舉N-甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、N-甲氧基甲基丙烯醯胺、N-甲氧基甲基甲基丙烯醯胺、N-丁氧基甲基丙烯醯胺、N-丁氧基甲基甲基丙烯醯胺等。 Examples of the aforementioned acrylamide compound include N-methacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, and N,N-dimethylmethacrylamide. Amine, N-methoxymethacrylamide, N-methoxymethylmethacrylamide, N-butoxymethacrylamide, N-butoxymethylmethacrylamide, etc. .

作為前述乙烯化合物，例如可列舉甲基乙烯基醚、苄基乙烯基醚、環己基乙烯基醚、乙烯萘、乙烯蒽、乙烯基咔唑、烯丙基環氧丙基醚、3-乙烯基-7-氧雜雙環[4.1.0]庚烷、1,2-環氧-5-己烯、及、1,7-辛二烯單環氧 化合物等。 Examples of the aforementioned vinyl compounds include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-vinyl -7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxy Compound etc.

作為前述苯乙烯化合物，係不具有羥基之苯乙烯，例如可列舉苯乙烯、α-甲基苯乙烯、氯苯乙烯、溴苯乙烯等。 As the aforementioned styrene compound, styrene which does not have a hydroxyl group, and examples thereof include styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

得到本發明所用之鹼可溶性丙烯酸聚合物之方法雖並未特別限定，但例如在使鹼可溶性單體(A1)~(A4)、其以外之可共聚合之單體及依所期望之聚合起始劑等共存之溶劑中，藉由於50~110℃之溫度下使其聚合反應，而得到。此時，所用之溶劑若為溶解構成鹼可溶性丙烯酸聚合物之單體及具有特定官能基之丙烯酸聚合物者，則並未特別限定。作為具體例，可列舉後述(D)溶劑所記載之溶劑。 Although the method for obtaining the alkali-soluble acrylic polymer used in the present invention is not particularly limited, for example, the alkali-soluble monomers (A1) to (A4), other copolymerizable monomers, and polymerization as desired It is obtained by polymerization reaction at a temperature of 50~110℃ in a coexisting solvent such as a starting agent. At this time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. As a specific example, the solvent described in (D) Solvent mentioned later can be mentioned.

如此進行所得之具有特定官能基之丙烯酸聚合物通常為溶解於溶劑之溶液的狀態。 The acrylic polymer having a specific functional group obtained in this manner is usually in a state of a solution dissolved in a solvent.

又，將如上述進行所得之特定共聚物的溶液，於二乙基醚或水等之攪拌下投入並使其再沉澱，過濾．洗淨經生成之沉澱物後，於常壓或減壓下，藉由常溫或是加熱乾燥，可成為特定共聚物之粉體。藉由如此之操作，可去除與特定共聚物共存之聚合起始劑或未反應單體，其結果，得到經純化之特定共聚物的粉體。以一次之操作無法充分純化的情況下，將所得之粉體再溶解於溶劑，重複進行上述之操作即可。 In addition, the solution of the specific copolymer obtained as described above is poured into diethyl ether or water under stirring, and reprecipitated, and filtered. After washing the formed precipitate, it can be dried under normal pressure or reduced pressure at normal temperature or by heating to become a powder of a specific copolymer. Through such an operation, the polymerization initiator or unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If it is not possible to fully purify by one operation, re-dissolve the obtained powder in the solvent and repeat the above operation.

在本發明，可直接使用上述特定共聚物的粉體、或是將該粉體例如再溶解於後述之(D)溶劑而作為溶液的狀態 使用亦可。 In the present invention, the powder of the above-mentioned specific copolymer can be used as it is, or the powder can be re-dissolved in the solvent (D) described later to form a solution. It can also be used.

又，在本發明，(A)成分之丙烯酸聚合物可為複數種之特定共聚物的混合物。 Furthermore, in the present invention, the acrylic polymer of the component (A) may be a mixture of a plurality of specific copolymers.

<(B)成分> <(B) Ingredient>

作為(B)成分之1,2-醌二疊氮化合物，係具有羥基或胺基之任一者、或羥基及胺基雙方之化合物，此等之羥基或胺基(具有羥基與胺基雙方時，係該等之合計量)當中，較佳為可使用10~100莫耳%，特佳為20~95莫耳%以1,2-醌二疊氮磺酸經酯化、或醯胺化之化合物。 The 1,2-quinonediazide compound as the component (B) is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group. When it is the total amount of these), preferably 10-100 mol% can be used, particularly preferably 20-95% mol%, esterified with 1,2-quinonediazide sulfonic acid, or amide Chemical compound.

作為前述具有羥基之化合物，例如可列舉酚、o-甲酚、m-甲酚、p-甲酚、氫醌、間苯二酚、鄰苯二酚、沒食子酸甲酯、沒食子酸乙酯、1,3,3-參(4-羥基苯基)丁烷、2,2-雙(4-羥基苯基)丙烷、1,1-雙(4-羥基苯基)環已烷、4,4’-二羥基苯基碸、4,4-六氟異亞丙基二酚、1,1,1-參(4-羥基苯基)乙烷、4,4’-[1-[4-[1-(4-羥基苯基)-1-甲基乙基]苯基]亞乙基]雙酚、2,4-二羥基二苯甲酮、2,3,4-三羥基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,3,4,4’-四羥基二苯甲酮、2,2’,3,4,4’-五羥基二苯甲酮、2,5-雙(2-羥基-5-甲基苄基)甲基等之酚化合物、乙醇、2-丙醇、4-丁醇、環己醇、乙二醇、丙二醇、二乙二醇、二丙二醇、2-甲氧基乙醇、2-丁氧基乙醇、2-甲氧基丙醇、2-丁氧基丙醇、乳酸乙酯、乳酸丁酯等之脂肪族醇類。 As the aforementioned compound having a hydroxyl group, for example, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, gallate Ethyl acid, 1,3,3-ginseng(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane , 4,4'-dihydroxyphenyl sulfide, 4,4-hexafluoroisopropylene diphenol, 1,1,1-ginseng (4-hydroxyphenyl)ethane, 4,4'-[1- [4-[1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxy Benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'- Phenol compounds such as pentahydroxybenzophenone, 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol , Propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate, etc. Aliphatic alcohols.

又，作為前述含有胺基之化合物，可列舉苯 胺、o-甲苯胺、m-甲苯胺、p-甲苯胺、4-胺基二苯基甲烷、4-胺基二苯基、o-苯二胺、m-苯二胺、p-苯二胺、4,4’-二胺基苯基甲烷、4,4’-二胺基二苯基醚、等之苯胺類、胺基環已烷。 Also, as the aforementioned amine group-containing compound, benzene can be cited Amine, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine Amines, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, anilines, and aminocyclohexane.

進而，作為含有羥基與胺基雙方之化合物，例如可列舉o-胺基酚、m-胺基酚、p-胺基酚、4-胺基間苯二酚、2,3-二胺基酚、2,4-二胺基酚、4,4’-二胺基-4”-羥基三苯基甲烷、4-胺基-4’,4”-二羥基三苯基甲烷、雙(4-胺基-3-羧基-5-羥基苯基)醚、雙(4-胺基-3-羧基-5-羥基苯基)甲烷、2,2-雙(4-胺基-3-羧基-5-羥基苯基)丙烷、2,2-雙(4-胺基-3-羧基-5-羥基苯基)六氟丙烷等之胺基酚類、2-胺基乙醇、3-胺基丙醇、4-胺基環己醇等之烷醇胺類。 Furthermore, examples of compounds containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, and 2,3-diaminophenol , 2,4-diaminophenol, 4,4'-diamino-4”-hydroxytriphenylmethane, 4-amino-4',4”-dihydroxytriphenylmethane, bis(4- Amino-3-carboxy-5-hydroxyphenyl) ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5 -Hydroxyphenyl)propane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane and other aminophenols, 2-aminoethanol, 3-aminopropanol , 4-aminocyclohexanol and other alkanolamines.

此等之1,2-醌二疊氮化合物可單獨或以2種以上的組合使用。 These 1,2-quinonediazide compounds can be used alone or in combination of two or more kinds.

在本發明之正型感光性樹脂組成物之(B)成分之含量，相對於(A)成分之100質量份，較佳為5~100質量份，更佳為8~50質量份，再更佳為10~40質量份。未滿5質量份時，有正型感光性樹脂組成物之曝光部與未曝光部對顯影液的溶解速度差縮小，藉由顯影之圖型化困難的情況。又，超過100質量份時，有由於以短時間的曝光無法充分分解1,2-醌二疊氮化合物故感度降低的情況、或有(B)成分吸收光導致硬化膜的透明性降低的情況。 The content of the component (B) in the positive photosensitive resin composition of the present invention is preferably 5-100 parts by mass, more preferably 8-50 parts by mass relative to 100 parts by mass of the component (A), and still more Preferably, it is 10-40 parts by mass. When it is less than 5 parts by mass, the difference in the dissolution rate of the developer with the exposed part and the unexposed part of the positive photosensitive resin composition may be reduced, and patterning by development may be difficult. In addition, when it exceeds 100 parts by mass, the 1,2-quinonediazide compound cannot be sufficiently decomposed by exposure for a short time, and the sensitivity may decrease, or the (B) component may absorb light and decrease the transparency of the cured film. .

<(C)成分> <(C) Ingredients>

(C)成分為交聯劑，更具體而言，係具有藉由與(A)成分進行熱反應而可形成交聯構造之構造的化合物。以下雖列舉具體例，但並非被限定於此等者。熱交聯劑，例如較佳為選自(C1)具有2個以上選自烷氧基甲基及羥基甲基之取代基的交聯性化合物或(C2)後述之式(2)表示之交聯性化合物者。此等之交聯劑可單獨或以2種以上之組合使用。 The component (C) is a crosslinking agent, and more specifically, a compound having a structure capable of forming a crosslinked structure by thermally reacting with the component (A). Although specific examples are given below, they are not limited to these. The thermal crosslinking agent is preferably selected from (C1) crosslinkable compounds having two or more substituents selected from the group consisting of alkoxymethyl and hydroxymethyl, or (C2) the cross-linking compound represented by the following formula (2) Linked compounds. These crosslinking agents can be used alone or in combination of two or more kinds.

(C1)成分之具有2個以上選自烷氧基甲基及羥基甲基之取代基的交聯性化合物，係曝露於熱硬化時之高溫時，藉由脫水縮合反應進行交聯反應者。作為如此之化合物，例如可列舉烷氧基甲基化乙炔脲、烷氧基甲基化苯代三聚氰胺、及烷氧基甲基化三聚氰胺等之化合物、及酚醛樹脂(Phenoplast)系化合物。 (C1) The crosslinkable compound having two or more substituents selected from the group consisting of alkoxymethyl and hydroxymethyl, which is the component, is one that undergoes a crosslinking reaction through a dehydration condensation reaction when exposed to a high temperature during thermal curing. As such a compound, for example, compounds such as alkoxymethylated acetylene carbamide, alkoxymethylated benzomelamine, and alkoxymethylated melamine, and phenolic resin (Phenoplast)-based compounds can be cited.

作為烷氧基甲基化乙炔脲的具體例，例如可列舉1,3,4,6-肆(甲氧基甲基)乙炔脲、1,3,4,6-肆(丁氧基甲基)乙炔脲、1,3,4,6-肆(羥基甲基)乙炔脲、1,3-雙(羥基甲基)尿素、1,1,3,3-肆(丁氧基甲基)尿素、1,1,3,3-肆(甲氧基甲基)尿素、1,3-雙(羥基甲基)-4,5-二羥基-2-咪唑啉酮、及1,3-雙(甲氧基甲基)-4,5-二甲氧基-2-咪唑啉酮等。作為市售品，可列舉三井Cytec(股)製乙炔脲化合物(商品名：Cymel(註冊商標)1170、Powder link(註冊商標)1174)等之化合物、甲基化尿素樹脂(商品名：UFR(註冊商標)65)、丁基化尿素樹脂(商品名：UFR(註冊商標)300、U-VAN10S60、U-VAN10R、U-VAN11HV)、DIC(股)製尿素/甲醯胺系樹脂(高縮合型、商品名：BECKAMINE(註冊商 標)J-300S、同P-955、同N)等。 As specific examples of alkoxymethylated acetylene carbamides, for example, 1,3,4,6-tetrakis (methoxymethyl) acetylene carbamide, 1,3,4,6-tetrakiss (butoxymethyl) )Acetylene carbamide, 1,3,4,6-4-(hydroxymethyl)acetylene carbamide, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-4-(butoxymethyl)urea , 1,1,3,3-four (methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis( Methoxymethyl)-4,5-dimethoxy-2-imidazolinone and the like. As commercially available products, acetylene carbamide compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 1170, Powder link (registered trademark) 1174), etc., and methylated urea resins (trade name: UFR ( Registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock) urea/formamide resin (high condensation Model, trade name: BECKAMINE (registrar Standard) J-300S, same as P-955, same as N), etc.

作為烷氧基甲基化苯代三聚氰胺的具體例，可列舉四甲氧基甲基苯代三聚氰胺等。作為市售品，可列舉三井Cytec(股)製(商品名：Cymel(註冊商標)1123)、(股)三和化工製(商品名：NIKALAC(註冊商標)BX-4000、同BX-37、同BL-60、同BX-55H)等。 As a specific example of alkoxymethylated benzo melamine, tetramethoxymethyl benzo melamine etc. are mentioned. As commercially available products, Mitsui Cytec (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) BX-4000, the same as BX-37, Same as BL-60, same as BX-55H) etc.

作為烷氧基甲基化三聚氰胺的具體例，例如可列舉六甲氧基甲基三聚氰胺等。作為市售品，可列舉三井Cytec(股)製甲氧基甲基型三聚氰胺化合物(商品名：Cymel(註冊商標)300、同301、同303、同350)、丁氧基甲基型三聚氰胺化合物(商品名：My coat(註冊商標)506、同508)、三和化工製甲氧基甲基型三聚氰胺化合物(商品名：NIKALAC(註冊商標)MW-30、同MW-22、同MW-11、同MW-100LM、同MS-001、同MX-002、同MX-730、同MX-750、同MX-035)、丁氧基甲基型三聚氰胺化合物(商品名：NIKALAC(註冊商標)MX-45、同MX-410、同MX-302)等。 As a specific example of alkoxymethylated melamine, hexamethoxymethyl melamine etc. are mentioned, for example. As commercially available products, methoxymethyl melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 300, the same 301, the same 303, the same 350), butoxymethyl melamine compounds (Trade name: My coat (registered trademark) 506, the same as 508), Sanhe Chemical's methoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MW-30, the same MW-22, the same MW-11 , Same MW-100LM, same MS-001, same MX-002, same MX-730, same MX-750, same MX-035), butoxymethyl type melamine compound (trade name: NIKALAC (registered trademark) MX -45, same as MX-410, same as MX-302) etc.

又，可為使如此胺基之氫原子以羥甲基或烷氧基甲基取代之三聚氰胺化合物、尿素化合物、乙炔脲化合物及苯代三聚氰胺化合物縮合所得之化合物。例如，可列舉由美國專利第6323310號所記載之三聚氰胺化合物及苯代三聚氰胺化合物所製造之高分子量化合物。作為前述三聚氰胺化合物之市售品，可列舉商品名：Cymel(註冊商標)303(三井Cytec(股)製)等，作為前述苯代三聚氰胺化合 物之市售品，可列舉商品名：Cymel(註冊商標)1123(三井Cytec(股)製)等。 In addition, it may be a compound obtained by condensing a melamine compound, a urea compound, an acetylene urea compound, and a benzomelamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high-molecular-weight compounds produced from melamine compounds and benzene-substituted melamine compounds described in U.S. Patent No. 6,323,310 can be cited. As a commercially available product of the aforementioned melamine compound, a trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), etc., can be cited as the aforementioned benzoyl melamine compound Examples of commercially available products include trade name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.) and the like.

作為酚醛樹脂系化合物的具體例，例如可列舉2,6-雙(羥基甲基)酚、2,6-雙(羥基甲基)甲酚、2,6-雙(羥基甲基)-4-甲氧基酚、3,3’,5,5’-肆(羥基甲基)聯苯基-4,4’-二醇、3,3’-伸甲基雙(2-羥基-5-甲基苯甲醇)、4,4’-(1-甲基亞乙基)雙[2-甲基-6-羥基甲基酚]、4,4’-伸甲基雙[2-甲基-6-羥基甲基酚]、4,4’-(1-甲基亞乙基)雙[2,6-雙(羥基甲基)酚]、4,4’-伸甲基雙[2,6-雙(羥基甲基)酚]、2,6-雙(甲氧基甲基)酚、2,6-雙(甲氧基甲基)甲酚、2,6-雙(甲氧基甲基)-4-甲氧基酚、3,3’,5,5’-肆(甲氧基甲基)聯苯基-4,4’-二醇、3,3’-伸甲基雙(2-甲氧基-5-甲基苯甲醇)、4,4’-(1-甲基亞乙基)雙[2-甲基-6-甲氧基甲基酚]、4,4’-伸甲基雙[2-甲基-6-甲氧基甲基酚]、4,4’-(1-甲基亞乙基)雙[2,6-雙(甲氧基甲基)酚]、4,4’-伸甲基雙[2,6-雙(甲氧基甲基)酚]等。亦可作為市售品取得，作為其具體例，可列舉26DMPC、46DMOC、DM-BIPC-F、DM-BIOC-F、TM-BIP-A、BISA-F、BI25X-DF、BI25X-TPA(以上為旭有機材工業(股)製)等。 As specific examples of phenolic resin compounds, for example, 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4- Methoxyphenol, 3,3',5,5'-tetrakis (hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methyl Benzyl alcohol), 4,4'-(1-methylethylene) bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6 -Hydroxymethylphenol], 4,4'-(1-methylethylene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6- Bis(hydroxymethyl)phenol), 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl) -4-methoxyphenol, 3,3',5,5'-tetrakis (methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2- Methoxy-5-methylbenzyl alcohol), 4,4'-(1-methylethylene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylidene Bis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylene)bis[2,6-bis(methoxymethyl)phenol], 4 , 4'-Methylenebis[2,6-bis(methoxymethyl)phenol] and so on. It can also be obtained as a commercially available product. Specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (above It is manufactured by Asahi Organic Materials Industry Co., Ltd.) and so on.

進而，作為(C1)成分，亦可使用：使用以N-羥基甲基丙烯醯胺、N-甲氧基甲基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺、N-丁氧基甲基甲基丙烯醯胺等之羥基甲基或烷氧基甲基取代之丙烯醯胺化合物或甲基丙烯醯胺化合物而製造之聚合物。 Furthermore, as component (C1), it is also possible to use: N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, N-butyl It is a polymer produced from hydroxymethyl or alkoxymethyl substituted acrylamide compounds or methacrylamide compounds such as oxymethylmethacrylamide.

作為如此之聚合物，例如可列舉聚(N-丁氧基甲基丙烯醯胺)、N-丁氧基甲基丙烯醯胺與苯乙烯的共聚物、N-羥基甲基甲基丙烯醯胺與甲基甲基丙烯酸酯的共聚物、N-乙氧基甲基甲基丙烯醯胺與苄基甲基丙烯酸酯的共聚物、及N-丁氧基甲基丙烯醯胺與苄基甲基丙烯酸酯與2-羥基丙基甲基丙烯酸酯的共聚物等。如此之聚合物的重量平均分子量為1,000~50,000，較佳為、1,500~20,000，更佳為2,000~10,000。 Examples of such polymers include poly(N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacrylamide Copolymer with methacrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethacrylamide and benzylmethyl Copolymers of acrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

此等之交聯性化合物可單獨或組合2種以上使用。 These crosslinkable compounds can be used alone or in combination of two or more kinds.

作為在本發明之正型感光性樹脂組成物之交聯劑，選擇(C1)成分時的含量，係相對於(A)成分之100質量份，較佳為5~50質量份，更佳為10~40質量份。未滿5質量份時，有金屬濺鍍後之耐熱性降低、或段差平坦化性降低的情況。又，超過50質量份時，有顯影時之密著性降低、或感度降低之可能性。 As the crosslinking agent of the positive photosensitive resin composition of the present invention, the content when selecting the component (C1) is relative to 100 parts by mass of the component (A), preferably 5-50 parts by mass, more preferably 10-40 parts by mass. If it is less than 5 parts by mass, the heat resistance after metal sputtering may decrease, or the step flatness may decrease. In addition, when it exceeds 50 parts by mass, the adhesion during development may decrease or the sensitivity may decrease.

又本發明之正型感光性樹脂組成物，作為(C2)成分，可含有式(2)表示之交聯性化合物。 In addition, the positive photosensitive resin composition of the present invention may contain a crosslinkable compound represented by formula (2) as the component (C2).

Figure 104140780-A0202-12-0015-1
Figure 104140780-A0202-12-0015-1

(式中，k表示2~10之整數，m表示0~4之整數， R1表示k價之有機基)。 (In the formula, k represents an integer from 2 to 10, m represents an integer from 0 to 4, and R 1 represents an organic group with k valence).

(C2)成分若為具有式(2)表示之環烯氧化物構造之化合物，則並未特別限定。作為其具體例，可列舉下述式C2-1及C2-2、或以下所示之市售品等。 (C2) If the component is a compound having the cycloalkylene oxide structure represented by formula (2), it is not particularly limited. As the specific example, the following formula C2-1 and C2-2, or the commercial item shown below, etc. are mentioned.

Figure 104140780-A0202-12-0016-2
Figure 104140780-A0202-12-0016-2

Figure 104140780-A0202-12-0016-3
Figure 104140780-A0202-12-0016-3

作為市售品，可列舉Epolead GT-401、同GT-403、同GT-301、同GT-302、CELLOXIDE 2021、CELLOXIDE 3000(Daicel化學工業(股)製 商品名)、脂環式環氧樹脂即Denacol EX-252(Nagase ChemteX(股)製 商品名)、CY175、CY177、CY179(以上、CIBA-GEIGY A.G製 商品名)、Araldite CY-182、同CY-192、同CY-184(以上、CIBA-GEIGY A.G製 商品名)、Epiclon 200、同400(以上、DIC(股)製 商品名)、Epikote 871、同872(以上、油化殼環氧(股)製 商品名)、ED-5661、ED-5662(以上、Celanese coating(股)製 商品名)等。又，此等之交聯 性化合物可單獨或組合2種類以上使用。 Commercial products include Epolead GT-401, GT-403, GT-301, GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (trade name manufactured by Daicel Chemical Industry Co., Ltd.), and alicyclic epoxy resin Namely Denacol EX-252 (Nagase ChemteX (stock) product name), CY175, CY177, CY179 (above, CIBA-GEIGY AG product name), Araldite CY-182, the same as CY-192, the same as CY-184 (above, CIBA-GEIGY AG product name), Epiclon 200, the same 400 (above, DIC (stock) product name), Epikote 871, the same 872 (above, oily shell epoxy (stock) product name), ED-5661 , ED-5662 (above, Celanese coating (stock) system trade name), etc. Also, this kind of cross-linking The sex compound can be used alone or in combination of two or more kinds.

此等當中，從耐熱性、耐溶劑性、耐長時間燒成耐性等之耐製程性、及透明性的觀點來看，較佳為具有環己烯氧化物構造之上述式C2-1及式C2-2表示之化合物、Epolead GT-401、同GT-403、同GT-301、同GT-302、CELLOXIDE 2021、CELLOXIDE 3000。 Among these, from the viewpoints of process resistance such as heat resistance, solvent resistance, long-term firing resistance, etc., and transparency, the above-mentioned formulas C2-1 and formulas having a cyclohexene oxide structure are preferred. The compound represented by C2-2, Epolead GT-401, the same GT-403, the same GT-301, the same GT-302, CELLOXIDE 2021, CELLOXIDE 3000.

作為上述交聯劑，選擇(C2)成分時的含量，係相對於(A)成分之100質量份為3~50質量份，較佳為7~40質量份，更佳為10~30質量份。交聯性化合物的含量少時，由於藉由交聯性化合物所形成之交聯密度不夠充分，有得不到使圖型形成後之耐熱性、耐溶劑性、對於長時間燒成之耐性等提昇的效果的情況。另外，超過50質量份時，有存在未交聯之交聯性化合物，降低圖型形成後之耐熱性、耐溶劑性、對於長時間燒成之耐性等，又，感光性樹脂組成物之保存安定性惡化的情況。 As the above-mentioned crosslinking agent, the content when selecting component (C2) is 3-50 parts by mass relative to 100 parts by mass of component (A), preferably 7-40 parts by mass, more preferably 10-30 parts by mass . When the content of the cross-linkable compound is small, the cross-link density formed by the cross-linkable compound is not sufficient, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation cannot be obtained. The situation of the enhanced effect. In addition, when it exceeds 50 parts by mass, there are uncrosslinked crosslinkable compounds, which reduce the heat resistance, solvent resistance, and resistance to long-term firing after pattern formation. In addition, the preservation of the photosensitive resin composition Deteriorating stability.

<(D)溶劑> <(D) Solvent>

本發明所用之(D)溶劑，係溶解(A)成分、(B)成分及(C)成分，且溶解依所期望而添加之後述(E)成分~(F)成分等者，若為具有這樣溶解能之溶劑，則其種類及構造等並未特別限定。 The (D) solvent used in the present invention dissolves component (A), component (B), and component (C), and dissolves as desired and adds components (E) to (F), etc. described later, if it has The type and structure of the solvent capable of dissolving in this way are not particularly limited.

作為這樣的(D)溶劑，例如可列舉乙二醇單甲基醚、乙二醇單乙基醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二 醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-丁酮、3-甲基-2-戊酮、2-戊酮、2-己酮、γ-丁內酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、及N-甲基吡咯啶酮等。 As such (D) solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, propylene glycol Alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3 -Methyl-2-pentanone, 2-pentanone, 2-hexanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate Ester, 3-ethoxy methyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N , N-dimethylacetamide, and N-methylpyrrolidone, etc.

此等之溶劑可一種單獨、或以二種以上之組合使用。 These solvents can be used alone or in combination of two or more.

此等(D)溶劑當中，丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、2-庚酮、丙二醇丙基醚、丙二醇丙基醚乙酸酯、乳酸乙酯、乳酸丁酯等以塗膜性良好且安全性高的觀點來看更佳。此等溶劑一般而言係用作用於光阻材料之溶劑。 Among these (D) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. It is more preferable from the viewpoint of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.

<(E)成分> <(E) Ingredient>

(E)成分係界面活性劑。當本發明之正型感光性樹脂組成物，以使其塗佈性提昇為目的，在不損害本發明之效果的範圍下，可進一步含有界面活性劑。 (E) The component is a surfactant. When the positive photosensitive resin composition of the present invention aims to improve its coatability, it may further contain a surfactant within a range that does not impair the effects of the present invention.

作為(E)成分之界面活性劑，雖並未特別限制，但例如可列舉氟系界面活性劑、矽氧系界面活性劑、非離子系界面活性劑等。作為此種界面活性劑，例如可使 用住友3M(股)製、DIC(股)製或者AGC清美化工(股)製等之市售品。此等市售品由於容易取得，故很方便。作為其具體例，可列舉Poly Fox PF-136A、151、156A、154N、159、636、6320、656、6520(Omnova公司製)、Megafac R30、R08、R40、R41、R43、F251、F477、F552、F553、F554、F555、F556、F557、F558、F559、F560、F561、F562、F563、F565、F567、F570(DIC(股)製)、FC4430、FC4432(住友3M(股)製)、Asahi guard AG710、Surflon S-386、S-611、S-651、(AGC清美化工(股)製)、FtergentFTX-218、DFX-18、220P、251、212M、215M((股)Neos製)等之氟系界面活性劑、BYK-300、302、306、307、310、313、315、320、322、323、325、330、331、333、342、345、346、347、348、349、370、377、378、3455(BYK Chemie日本(股)製)、SH3746、SH3749、SH3771、SH8400、SH8410、SH8700、SF8428(東麗道康寧．矽氧(股)製)、KF-351、KF-352、KF-353、KF-354L、KF-355A、KF-615A、KF-945、KF-618、KF-6011、KF-6015(信越化學工業(股)製)等之矽氧系界面活性劑。 The surfactant of the (E) component is not particularly limited, but examples thereof include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. As such a surfactant, for example, Use Sumitomo 3M (shares) system, DIC (shares) system or AGC Qingmei Chemical (shares) system and other commercially available products. These commercially available products are very convenient because they are easy to obtain. Specific examples include Poly Fox PF-136A, 151, 156A, 154N, 159, 636, 6320, 656, 6520 (manufactured by Omnova), Megafac R30, R08, R40, R41, R43, F251, F477, F552 , F553, F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 (DIC (share) system), FC4430, FC4432 (Sumitomo 3M (share) system), Asahi guard AG710, Surflon S-386, S-611, S-651, (AGC Qingmei Chemical Co., Ltd.), FtergentFTX-218, DFX-18, 220P, 251, 212M, 215M ((stock) Neos), etc. System surfactant, BYK-300, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 , 378, 3455 (manufactured by BYK Chemie Japan Co., Ltd.), SH3746, SH3749, SH3771, SH8400, SH8410, SH8700, SF8428 (manufactured by Toray Dow Corning Silicon Oxide Co., Ltd.), KF-351, KF-352, KF- 353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.) and other silica-based surfactants.

(E)成分之界面活性劑可一種單獨、或以二種以上之組合使用。 (E) The surfactant of component (E) can be used alone or in combination of two or more.

使用界面活性劑時，其含量根據(A)成分100質量份，通常為0.01~1.0質量份，較佳為0.02~0.8質量份。即使(E)成分之界面活性劑的使用量設定在超過1.0 質量份的量，上述塗佈性的改良效果變得遲鈍，變不經濟。為0.01質量份以下時，有未表現塗佈性改善之效果的情況。 When a surfactant is used, its content is based on 100 parts by mass of the component (A), and is usually 0.01 to 1.0 parts by mass, preferably 0.02 to 0.8 parts by mass. Even if the amount of surfactant used in component (E) is set to exceed 1.0 In the amount of parts by mass, the effect of improving the coating properties becomes dull and uneconomical. When it is 0.01 parts by mass or less, the effect of improving coatability may not be exhibited.

<(F)成分> <(F) Ingredients>

(F)成分係密著促進劑。本發明之正型感光性樹脂組成物以使與顯影後之基板的密著性提昇為目的，可添加密著促進劑。作為如此之密著促進劑的具體例，可列舉三甲基氯矽烷、二甲基乙烯基氯矽烷、甲基二苯基氯矽烷、氯甲基二甲基氯矽烷等之氯矽烷類、三甲基甲氧基矽烷、二甲基二乙氧基矽烷、甲基二甲氧基矽烷、二甲基乙烯基乙氧基矽烷、二苯基二甲氧基矽烷、苯基三乙氧基矽烷、乙烯基三氯矽烷、γ-胺基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-(N-哌啶基)丙基三乙氧基矽烷、3-脲丙基三乙氧基矽烷、3-脲丙基三甲氧基矽烷等之烷氧基矽烷類、六甲基二矽氮烷、N,N‘-雙(三甲基矽烷基)尿素、二甲基三甲基矽烷基胺、三甲基矽烷基咪唑等之矽氮烷類、苯并***、苯并咪唑、吲唑、咪唑、2-巰基苯并咪唑、2-巰基苯并噻唑、2-巰基苯并噁唑、尿唑、硫脲嘧啶、巰基咪唑、巰基嘧啶等之雜環狀化合物、或1,1-二甲基尿素、1,3-二甲基尿素等之尿素、或硫脲化合物。 The component (F) is an adhesion promoter. The positive photosensitive resin composition of the present invention can add an adhesion promoter for the purpose of improving the adhesion to the substrate after development. As specific examples of such adhesion promoters, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, three Methyl methoxy silane, dimethyl diethoxy silane, methyl dimethoxy silane, dimethyl vinyl ethoxy silane, diphenyl dimethoxy silane, phenyl triethoxy silane , Vinyl trichlorosilane, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(N-piperidyl)propyltriethoxysilane, 3-ureapropyltriethoxysilane, 3-ureapropyltrimethoxysilane Alkoxysilanes such as silyl silanes, hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, etc. Silazanes, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercapto Heterocyclic compounds such as imidazole and mercaptopyrimidine, or urea such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

上述之密著促進劑，例如亦可使用信越化學 工業(股)製、Momentive Performance Materials Worldwide Inc.製或東麗道康寧．矽氧(股)製等之市售品之化合物，此等之市售品可輕易取得。 The adhesion promoter mentioned above, for example, Shin-Etsu Chemical Industrial (stock) system, Momentive Performance Materials Worldwide Inc. system or Toray Dow Corning. Silicone (stock) compounds and other commercially available products, these commercially available products can be easily obtained.

作為(F)成分，可前述密著性促進劑當中之1種或組合2種類以上使用。 As the (F) component, one of the aforementioned adhesion promoters or a combination of two or more of them can be used.

此等之(F)成分之中，以烷氧基矽烷類(亦即矽烷偶合劑)可得到良好之密著性的點來看較佳。 Among these (F) components, alkoxysilanes (that is, silane coupling agents) are preferred from the viewpoint that good adhesion can be obtained.

此等之密著促進劑的添加量，相對於(A)成分之100質量份，通常為0.1~20質量份，較佳為0.5~10質量份。使用20質量份以上時有感度降低的情況，又，未滿0.1質量份時，有得不到密著促進劑之充分效果的情況。 The addition amount of these adhesion promoters is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the component (A). When using 20 parts by mass or more, the sensitivity may decrease, and when it is less than 0.1 parts by mass, the sufficient effect of the adhesion promoter may not be obtained.

<其他添加劑> <Other additives>

進而本發明之正型感光性樹脂組成物，在不損害本發明之效果下，如有必要可含有流變調整劑、顏料、染料、保存安定劑、消泡劑、或多元酚、多元羧酸等之溶解促進劑等。 Furthermore, the positive photosensitive resin composition of the present invention may contain rheology modifiers, pigments, dyes, preservation stabilizers, defoamers, or polyphenols and polycarboxylic acids if necessary without impairing the effects of the present invention. And other dissolution promoters.

<正型感光性樹脂組成物> <Positive photosensitive resin composition>

本發明之正型感光性樹脂組成物係將(A)成分之使(A1)~(A4)共聚合而得之共聚物、(B)成分之1,2-醌二疊氮化合物、(C)成分之交聯劑溶解於(D)溶劑者，且各自依期望，可進一步含有(E)成分之界面活性劑、(F)成分之密著 促進劑、及其他添加劑當中之一種以上的組成物。 The positive photosensitive resin composition of the present invention is a copolymer obtained by copolymerizing (A1) to (A4) of component (A), 1,2-quinonediazide compound of component (B), and (C) ) The cross-linking agent of the component is dissolved in the solvent of (D), and each of them may further contain the surfactant of the component (E) and the adhesion of the component (F) as desired. A composition consisting of more than one type of accelerator and other additives.

其中，本發明之正型感光性樹脂組成物之較佳例係如以下。 Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows.

[1]：根據(A)成分100質量份，含有5~100質量份之(B)成分、5~50質量份之(C)成分，此等成分溶解於(D)溶劑之正型感光性樹脂組成物。 [1]: Based on 100 parts by mass of component (A), containing 5-100 parts by mass of component (B) and 5-50 parts by mass of component (C), these components are dissolved in (D) solvent for positive photosensitive Resin composition.

[2]：在上述[1]之組成物，根據(A)成分100質量份，進一步將(E)成分含有0.01~1.0質量份之正型感光性樹脂組成物。 [2]: In the composition of the above-mentioned [1], based on 100 parts by mass of the (A) component, the (E) component further contains 0.01 to 1.0 parts by mass of a positive photosensitive resin composition.

[3]：在上述[1]或[2]之組成物，根據(A)成分100質量份，進一步將(F)成分含有0.1~20質量份之正型感光性樹脂組成物。 [3]: In the composition of the above-mentioned [1] or [2], based on 100 parts by mass of the component (A), the component (F) further contains 0.1 to 20 parts by mass of a positive photosensitive resin composition.

在本發明之正型感光性樹脂組成物之固含量的比例，只要各成分為均勻溶解於溶劑，雖並非特別限定者，但例如為1~80質量%，又例如為5~60質量%、或10~50質量%。於此所謂固含量，係指從正型感光性樹脂組成物之全成分去除(D)溶劑者。 The solid content ratio of the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but it is, for example, 1 to 80% by mass, or, for example, 5 to 60% by mass, Or 10-50% by mass. The term “solid content” here refers to the removal of the (D) solvent from all components of the positive photosensitive resin composition.

本發明之正型感光性樹脂組成物之調製方法雖並未特別限定，但作為其調製法，例如可列舉將(A)成分(鹼可溶性樹脂)溶解於(D)溶劑，於此溶液將(B)成分之1,2-醌二疊氮化合物、(C)成分之交聯劑以特定比例混合，而成為均勻溶液之方法、或者在此調製法之適當階段，如有必要可進一步添加(E)成分(界面活性劑)、(F)成分(密著促進劑)及其他添加劑來進行混合之方法。 Although the preparation method of the positive photosensitive resin composition of the present invention is not particularly limited, as the preparation method, for example, the component (A) (alkali-soluble resin) is dissolved in the solvent (D), and the solution is ( ( E) Method of mixing component (surfactant), component (F) (adhesion promoter) and other additives.

在本發明之正型感光性樹脂組成物的調製時，可直接使用藉由在(D)溶劑中之聚合反應所得之共聚物的溶液，此情況下，於此(A)成分之溶液與前述相同加入(B)成分、(C)成分等而成為均勻溶液時，將濃度調整作為目的，可進一步追加投入(D)溶劑。此時，於特定共聚物之形成過程所用之(D)溶劑、與於正型感光性樹脂組成物之調製時為了濃度調整所用之(D)溶劑，可為相同亦可為相異。 In the preparation of the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (D) can be directly used. In this case, the solution of the component (A) and the aforementioned When the (B) component, (C) component, etc. are added in the same manner to form a uniform solution, the concentration adjustment is the purpose, and the (D) solvent can be further added. At this time, the (D) solvent used in the formation process of the specific copolymer and the (D) solvent used for concentration adjustment during the preparation of the positive photosensitive resin composition may be the same or different.

而且，經調製之正型感光性樹脂組成物的溶液，較佳為使用孔徑為0.2μm左右之濾器等進行過濾後再使用。 Furthermore, the prepared solution of the positive photosensitive resin composition is preferably filtered with a filter having a pore diameter of about 0.2 μm or the like before use.

<塗膜及硬化膜> <Coating film and hardened film>

將本發明之正型感光性樹脂組成物於半導體基板(例如矽/二氧化矽被覆基板、氮化矽基板、被覆金屬例如鋁、鉬、鉻等之基板、玻璃基板、石英基板、ITO基板等)之上，藉由旋轉塗佈、流動塗佈、輥塗佈、裂縫塗佈、裂縫接著旋轉塗佈、噴墨塗佈等來進行塗佈。之後，藉由以熱板或烤箱等進行預備乾燥，可形成塗膜。之後，將此塗膜藉由進行加熱處理，而形成正型感光性樹脂膜。 Apply the positive photosensitive resin composition of the present invention to semiconductor substrates (e.g., silicon/silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates, etc. ) Above, coating is performed by spin coating, flow coating, roll coating, slit coating, slit followed by spin coating, inkjet coating, and the like. After that, by pre-drying with a hot plate or oven, etc., a coating film can be formed. After that, this coating film is heated to form a positive photosensitive resin film.

作為此加熱處理之條件，例如採用從溫度70℃~160℃、時間0.3~60分鐘之範圍當中經適當選擇之加熱溫度及加熱時間。加熱溫度及加熱時間較佳為80℃~140℃、0.5~10分鐘。 As the conditions of this heating treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70°C to 160°C and a time of 0.3 to 60 minutes are used. The heating temperature and heating time are preferably 80°C to 140°C, 0.5 to 10 minutes.

又，由正型感光性樹脂組成物形成之正型感光性樹脂膜的膜厚，例如為0.1~30μm，又例如為0.2~10μm，進而例如為0.3~8μm。 In addition, the film thickness of the positive photosensitive resin film formed of the positive photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and for example, 0.3 to 8 μm.

於上述所得之塗膜上，裝著具有特定圖型之遮罩而照射紫外線等之光，藉由以鹼顯影液進行顯影，洗出曝光部而得到端面銳利之浮雕圖型。 The coating film obtained above is equipped with a mask with a specific pattern, irradiated with light such as ultraviolet rays, and developed with an alkali developer to wash out the exposed part to obtain a sharp-end relief pattern.

作為可被使用之鹼性顯影液，例如可列舉碳酸鉀、碳酸鈉、氫氧化鉀、氫氧化鈉等之鹼金屬氫氧化物之水溶液、氫氧化四甲基銨、氫氧化四乙基銨、膽鹼等之氫氧化第四級銨之水溶液、乙醇胺、丙基胺、乙二胺等之胺水溶液等之鹼性水溶液。進而，亦可於此等之顯影液加入界面活性劑等。 As the alkaline developer that can be used, for example, aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium hydroxide such as choline, aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants etc. can also be added to these developing solutions.

上述當中，氫氧化四乙基銨0.1~2.38質量%水溶液一般係作為光阻之顯影液使用，即使在本發明之感光性樹脂組成物，使用此鹼性顯影液，亦不會引起膨潤等之問題可成為良好的顯影。 Among the above, a 0.1~2.38% by mass aqueous solution of tetraethylammonium hydroxide is generally used as a developer for photoresist. Even if the photosensitive resin composition of the present invention is used, this alkaline developer will not cause swelling, etc. The problem can be a good development.

又，作為顯影方法，液池法、浸塗法、搖動浸漬法等皆可使用。此時之顯影時間通常為15~180秒。 In addition, as the development method, a bath method, a dip coating method, a shaking dipping method, etc. can be used. The developing time at this time is usually 15 to 180 seconds.

顯影後，對於正型感光性樹脂膜，藉由流水之洗淨，例如進行20~120秒，接著藉由使用壓縮空氣或是壓縮氮或藉由旋轉進行風乾，去除基板上之水分，然後得到經圖型形成之膜。 After development, the positive photosensitive resin film is washed with running water, for example, for 20 to 120 seconds, and then dried by using compressed air or compressed nitrogen or by rotating to remove the moisture on the substrate, and then obtain Film formed by pattern.

接著，對於該圖型形成膜，為了熱硬化藉由進行後烘烤，具體而言，藉由使用熱板、烤箱等進行加 熱，而得到耐熱性、透明性、平坦化性、低吸水性、耐化學性等優異，且具有良好之浮雕圖型之膜。 Next, for the pattern-forming film, post-baking is performed for thermal curing, specifically, by using a hot plate, an oven, etc. Heat to obtain a film with excellent heat resistance, transparency, planarization, low water absorption, chemical resistance, etc., and with a good relief pattern.

作為後烘烤，一般係採用在選自溫度140℃~270℃範圍當中之加熱溫度，於熱板上的情況為5~30分鐘，於烤箱中的情況為30~90分鐘進行處理之方法。 As post-baking, generally a heating temperature selected from the range of 140°C to 270°C is used, with 5 to 30 minutes on a hot plate, and 30 to 90 minutes in an oven.

然後，藉由該後烘烤，可得到作為目的且具有良好圖型形狀之硬化膜。 Then, by this post-baking, a cured film with a good pattern shape can be obtained for the purpose.

如以上，藉由本發明之正型感光性樹脂組成物，可形成保存安定性高，有充分高感度且於顯影時，未曝光部之膜減非常小，具有微細圖型之塗膜。 As described above, the positive photosensitive resin composition of the present invention can form a coating film with high storage stability, sufficiently high sensitivity, and a very small film loss in the unexposed area during development, with a fine pattern.

又，從此塗膜所得之硬化膜係具有圖型殘渣少之特徵。因此，可適合使用在液晶顯示器或有機EL顯示器之各種膜，例如適合與層間絕緣膜、保護膜、絕緣膜等一起，使用在TFT型液晶元件之陣列平坦化膜等之用途。 In addition, the cured film obtained from this coating film is characterized by less pattern residues. Therefore, it can be suitably used in various films of liquid crystal displays or organic EL displays. For example, it is suitable for use with interlayer insulating films, protective films, insulating films, etc., in array flattening films of TFT-type liquid crystal elements.

[實施例] [Example]

以下，雖列舉實施例，更詳細說明本發明，但本發明並非被限定於此等實施例者。 Hereinafter, the present invention will be explained in more detail by citing examples, but the present invention is not limited to these examples.

[實施例所用之簡稱] [Abbreviations used in Examples]

以下之實施例所用之簡稱之意義係如以下。 The meanings of the abbreviations used in the following embodiments are as follows.

MAA：甲基丙烯酸 MAA: Methacrylic acid

MMA：甲基甲基丙烯酸酯 MMA: Methmethacrylate

HEMA：2-羥基乙基甲基丙烯酸酯 HEMA: 2-hydroxyethyl methacrylate

PQMA：4-羥基苯基甲基丙烯酸酯 PQMA: 4-hydroxyphenyl methacrylate

CHMI：N-環己基馬來醯亞胺 CHMI: N-cyclohexylmaleimide

AIBN：偶氮雙異丁腈 AIBN: Azobisisobutyronitrile

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 PGME: Propylene glycol monomethyl ether

QD：藉由α,α,α‘-參(4-羥基苯基)-1-乙基-4-異丙基苯1mol與1,2-萘醌-2-二疊氮化物-5-磺醯基氯1.5mol之縮合反應所合成之化合物 QD: By using 1mol of α,α,α'-(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfonate Compound synthesized by condensation reaction of 1.5 mol of acyl chloride

CEL-2021P：3,4-環氧環己基甲基-3’,4’-環氧環已烷羧酸酯 CEL-2021P: 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexane carboxylate

GT-401：丁烷四羧酸 四(3,4-環氧環己基甲基)修飾ε-己內酯 GT-401: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone

MPTS：γ-甲基丙烯醯氧基丙基三甲氧基矽烷 MPTS: γ-methacryloxypropyl trimethoxysilane

R30：DIC(股)製Megafac R-30(商品名) R30: Megafac R-30 (trade name) manufactured by DIC (shares)

[數平均分子量及重量平均分子量之測定] [Determination of number average molecular weight and weight average molecular weight]

將依以下之合成例所得之特定共聚物及特定交聯體之數平均分子量及重量平均分子量，使用日本分光(股)製GPC裝置(Shodex(註冊商標)管柱KF803L及KF804L)，將溶出溶劑四氫呋喃依以流量1ml/分鐘流入管柱中(管柱溫度40℃)而使其溶離之條件測定。尚，下述之數平均分子量(以下稱為Mn)及重量平均分子量(以下稱為Mw)係以聚苯乙烯換算值表示。 The number-average molecular weight and weight-average molecular weight of the specific copolymer and specific cross-linked body obtained according to the following synthesis examples are eluted using GPC equipment (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation Tetrahydrofuran was measured under the condition that it flows into the column at a flow rate of 1 ml/min (column temperature is 40°C) to dissolve it. Note that the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<合成例1> <Synthesis Example 1>

作為構成特定共聚物之單體成分，係使用MAA 12.0g、CHMI 21.0g、MMA 27.0g，作為自由基聚合起始劑係使用AIBN 3.8g，將此等在溶劑PGMEA 95.8g中，藉由以溫度60℃~100℃使其進行聚合反應，而得到Mn4,500、Mw7,800之鹼可溶性丙烯酸聚合物成分(特定共聚物)的溶液(特定共聚物濃度：40.0質量%)。(P1) As the monomer components constituting the specific copolymer, MAA 12.0g, CHMI 21.0g, MMA 27.0g are used, and AIBN 3.8g is used as a radical polymerization initiator. These are used in the solvent PGMEA 95.8g. The polymerization reaction was performed at a temperature of 60°C to 100°C to obtain a solution of an alkali-soluble acrylic polymer component (specific copolymer) of Mn4,500 and Mw7,800 (specific copolymer concentration: 40.0% by mass). (P1)

<合成例2> <Synthesis Example 2>

作為構成特定共聚物之單體成分，係使用MAA 4.2g、CHMI 21.0g、HEMA 27.6g、MMA 7.2g，作為自由基聚合起始劑係使用AIBN 3.8g，將此等在溶劑PGME 95.8g中，藉由以溫度60℃~100℃使其進行聚合反應，而得到Mn4,200、Mw7,500之鹼可溶性丙烯酸聚合物成分(特定共聚物)的溶液(特定共聚物濃度：40.0質量%)。(P2) As the monomer components constituting the specific copolymer, MAA 4.2g, CHMI 21.0g, HEMA 27.6g, MMA 7.2g are used, and AIBN 3.8g is used as a radical polymerization initiator, and these are used in the solvent PGME 95.8g A solution of alkali-soluble acrylic polymer component (specific copolymer) of Mn4,200 and Mw7,500 (specific copolymer concentration: 40.0% by mass) is obtained by performing polymerization reaction at a temperature of 60°C to 100°C. (P2)

<合成例3> <Synthesis Example 3>

作為構成特定共聚物之單體成分，係使用MAA 11.0g、CHMI 20.9g、PQMA 15.0g、MMA 12.9g，作為自由基聚合起始劑係使用AIBN 2.9g，將此等在溶劑PGMEA 95.4g中，藉由以溫度60℃~100℃使其進行聚合反應，而得到Mn5,400、Mw10,000之鹼可溶性丙烯酸聚合物成分(特定共聚物)的溶液(特定共聚物濃度：40.0質量 %)。(P3) As the monomer components constituting the specific copolymer, MAA 11.0g, CHMI 20.9g, PQMA 15.0g, MMA 12.9g are used, AIBN 2.9g is used as a radical polymerization initiator, and these are used in the solvent PGMEA 95.4g , By carrying out the polymerization reaction at a temperature of 60℃~100℃, a solution of alkali-soluble acrylic polymer component (specific copolymer) of Mn5,400 and Mw10,000 (specific copolymer concentration: 40.0 mass) is obtained %). (P3)

<合成例4> <Synthesis Example 4>

作為構成特定共聚物之單體成分，係使用MAA 7.8g、C HMI 21.0g、HEMA 15.0g、PQMA 1.2g、MMA 15.0g，作為自由基聚合起始劑係使用AIBN 3.8g，將此等在溶劑PGMEA 95.8g中，藉由以溫度60℃~100℃使其進行聚合反應，而得到Mn4,100、Mw7,600之鹼可溶性丙烯酸聚合物成分(特定共聚物)的溶液(特定共聚物濃度：40.0質量%)。(P4) As the monomer components constituting the specific copolymer, MAA 7.8g, C HMI 21.0g, HEMA 15.0g, PQMA 1.2g, MMA 15.0g are used, and AIBN 3.8g is used as a radical polymerization initiator. In 95.8 g of the solvent PGMEA, the polymerization reaction was carried out at a temperature of 60°C to 100°C to obtain a solution of an alkali-soluble acrylic polymer component (specific copolymer) of Mn4,100 and Mw7,600 (specific copolymer concentration: 40.0% by mass). (P4)

<實施例1> <Example 1>

作為鹼可溶性樹脂溶液，於從前述合成例4所得之特定共聚物溶液(P4)，加入QD(以下稱為感光劑)、交聯性化合物、界面活性劑、密著輔助劑、溶劑後，於室溫攪拌8小時調製表1所示組成之正型感光性組成物。 As an alkali-soluble resin solution, after adding QD (hereinafter referred to as sensitizer), crosslinking compound, surfactant, adhesion adjuvant, and solvent to the specific copolymer solution (P4) obtained from the aforementioned Synthesis Example 4, The positive photosensitive composition having the composition shown in Table 1 was prepared by stirring at room temperature for 8 hours.

<比較例1~比較例3> <Comparative example 1~Comparative example 3>

作為鹼可溶性樹脂溶液，於從前述合成例1~3所得之特定共聚物溶液(P1~P3)，加入感光劑、交聯性化合物、界面活性劑、密著輔助劑、溶劑後，於室溫攪拌8小時，調製表1所示組成之正型感光性組成物。 As an alkali-soluble resin solution, add photosensitizers, crosslinking compounds, surfactants, adhesion aids, and solvents to the specific copolymer solutions (P1 to P3) obtained from the aforementioned Synthesis Examples 1 to 3, and then at room temperature After stirring for 8 hours, a positive photosensitive composition having the composition shown in Table 1 was prepared.

Figure 104140780-A0202-12-0029-4
Figure 104140780-A0202-12-0029-4

對於所得之實施例1以及比較例1~比較例3之各正型感光性樹脂組成物，分別將感度、顯影時之密著性、熱硬化時之圖型內殘渣的評估以下述所示之方法進行。 For the obtained positive photosensitive resin compositions of Example 1 and Comparative Example 1 to Comparative Example 3, the sensitivity, adhesion during development, and residue in the pattern during thermal curing were evaluated as follows: Method to proceed.

[感度之評估] [Evaluation of Sensitivity]

將正型感光性樹脂組成物於矽晶圓上使用旋轉塗佈機進行塗佈後，於溫度110℃在熱板上進行預烘烤120秒，而形成膜厚4.0μm之塗膜。膜厚係使用FILMETRICS製F20測定。於此塗膜藉由佳能(股)製紫外線照射裝置PLA-600FA，一定時間照射在365nm之光強度為5.5mW/cm2之紫外線。之後藉由於0.4質量%之氫氧化四甲基銨(以下稱為TMAH)水溶液浸漬90秒，進行顯影後，以超純水進行20秒流水洗淨。將在曝光部，溶解殘餘殆盡之最低曝光量(mJ/cm2)作為感度。 After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, it is pre-baked on a hot plate at a temperature of 110° C. for 120 seconds to form a coating film with a thickness of 4.0 μm. The film thickness was measured using F20 manufactured by FILMETRICS. Here, the coating film is irradiated with ultraviolet rays with a light intensity of 5.5mW/cm 2 at 365nm for a certain period of time by using the PLA-600FA UV irradiation device manufactured by Canon (Stocks). Then, it was immersed in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 90 seconds to develop, and then washed with ultrapure water under running water for 20 seconds. The minimum exposure amount (mJ/cm 2 ) at the exposure part where the dissolved residue is exhausted is used as the sensitivity.

[密著性之評估] [Assessment of Adhesion]

將正型感光性樹脂組成物於矽晶圓上使用旋轉塗佈機進行塗佈後於溫度110℃在熱板上進行預烘烤120秒， 而形成塗膜。於此塗膜透過遮罩一定時間照射在365nm之光強度為5.5mW/cm2之紫外線。製作將10μm×10μm之接觸孔以130μm間隔配置之圖型。之後藉由於0.4質量%之氫氧化四甲基銨(以下稱為TMAH)水溶液浸漬90秒進行顯影後，以超純水進行90秒流水洗淨。之後，使用ESPEC(股)製CLEANOVENPVHC-210於230℃進行30分鐘後烘烤，形成膜厚約4.0μm之硬化膜。之後，將經製作之10μm×10μm之開放圖型的密著性使用日立場致發射型掃描電子顯微鏡S-4100評估。將開放圖型無裙擺漂浮完全密著者判斷為良好(○)，有裙擺漂浮者判斷為不佳(×)。 The positive photosensitive resin composition was coated on a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110° C. for 120 seconds to form a coating film. Here, the coating film is irradiated with ultraviolet rays with a light intensity of 5.5mW/cm 2 at 365nm for a certain period of time through the mask. A pattern in which the contact holes of 10 μm×10 μm are arranged at intervals of 130 μm is made. Then, it was developed by immersing in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 90 seconds, and then washed with ultrapure water under running water for 90 seconds. After that, it was post-baked at 230°C for 30 minutes using CLEANOVENPVHC-210 manufactured by ESPEC (Stocks) to form a cured film with a thickness of about 4.0 μm. After that, the adhesion of the produced open pattern of 10 μm×10 μm was evaluated using the S-4100 scanning electron microscope. Those with open pattern without skirt floating and completely densely attached are judged as good (○), and those with floating skirt are judged as bad (×).

[圖型內殘渣之評估] [Assessment of residues in the pattern]

上述，將於密著性之評估所製作之10μm×10μm之開放圖型內的殘渣藉由日立場致發射型掃描電子顯微鏡S-4100確認。此時，將開放圖型內未殘留殘渣者判斷為良好(○)，有殘留者判斷為不佳(×)。 As mentioned above, the residue in the open pattern of 10 μm×10 μm produced by the evaluation of the adhesion was confirmed by the Japanese-emission scanning electron microscope S-4100. At this time, those with no residue remaining in the open pattern were judged as good (○), and those with remaining residue were judged as unsatisfactory (×).

[評估的結果] [Result of evaluation]

將進行以上之評估的結果示於以下之表2。 The results of the above evaluation are shown in Table 2 below.

Figure 104140780-A0202-12-0030-5
Figure 104140780-A0202-12-0030-5

由表2所示之結果可判斷出，實施例1之正 型感光性樹脂組成物皆為高感度，顯影時之密著性亦充分。進而顯示圖型形成後之圖型內的殘渣完全沒有之優異特性。 From the results shown in Table 2, it can be judged that Example 1 is positive The photosensitive resin compositions are all highly sensitive and have sufficient adhesion during development. Furthermore, it shows the excellent characteristics that the residue in the pattern after the pattern formation is completely absent.

[產業上之可利用性] [Industrial availability]

本發明所致之正型感光性樹脂組成物，係適合作為形成在薄膜電晶體(TFT)型液晶顯示元件、有機EL元件等之各種顯示器之保護膜、平坦化膜、絕緣膜等之硬化膜之材料，尤其是亦適合作為形成TFT型液晶元件之層間絕緣膜、彩色濾光片之保護膜、陣列平坦化膜、反射型顯示器之反射膜下側的凹凸膜、有機EL元件之絕緣膜等之材料，進而，亦適合作為微透鏡材料等之各種電子材料。 The positive photosensitive resin composition of the present invention is suitable as a hardened film for protective films, planarization films, insulating films, etc. formed on various displays such as thin film transistor (TFT) liquid crystal display elements and organic EL elements. The material is especially suitable for forming the interlayer insulating film of TFT type liquid crystal element, the protective film of color filter, the array flattening film, the uneven film under the reflective film of reflective display, the insulating film of organic EL element, etc. The material, in turn, is also suitable for various electronic materials such as microlens materials.

Claims (11)

一種正型感光性樹脂組成物，其係含有下述(A)成分、(B)成分、(C)成分、及(D)溶劑，(A)成分：使下述(A1)~(A4)進行共聚合所得之鹼可溶性丙烯酸共聚物(A1)不飽和羧酸及/或不飽和羧酸酐、(A2)具有酚性羥基與聚合性不飽和基之單體、(A3)具有羥烷基與聚合性不飽和基之單體、(A4)N取代馬來醯亞胺化合物(惟，N-羥基苯基馬來醯亞胺成為(A2)成分者)；(B)成分：1,2-醌二疊氮(Quinonediazide)化合物、(C)成分：交聯劑(D)溶劑。 A positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, and (D) solvent, (A) component: the following (A1) to (A4) Alkali-soluble acrylic copolymer obtained by copolymerization (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) monomer having phenolic hydroxyl group and polymerizable unsaturated group, (A3) having hydroxyalkyl group and The monomer of polymerizable unsaturated group, (A4) N-substituted maleimide compound (except that N-hydroxyphenyl maleimide becomes the component (A2)); (B) component: 1,2- Quinonediazide compound, (C) component: crosslinking agent (D) solvent. 如請求項1之正型感光性樹脂組成物，其中，(A2)具有酚性羥基與聚合性不飽和基之單體為p-羥基苯基(甲基)丙烯酸酯。 The positive photosensitive resin composition of claim 1, wherein (A2) the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth)acrylate. 如請求項1或2之正型感光性樹脂組成物，其中，(A)成分之鹼可溶性丙烯酸聚合物的數平均分子量以聚苯乙烯換算為2,000~30,000。 The positive photosensitive resin composition of claim 1 or 2, wherein the number average molecular weight of the alkali-soluble acrylic polymer of the component (A) is 2,000 to 30,000 in terms of polystyrene. 如請求項1或2之正型感光性樹脂組成物，其中，相對於(A)成分之100質量份，(B)成分為5~100質量份。 The positive photosensitive resin composition of claim 1 or 2, wherein the component (B) is 5-100 parts by mass relative to 100 parts by mass of the component (A). 如請求項1或2之正型感光性樹脂組成物，其中，相對於(A)成分之100質量份，(C)成分為5~50質量份。 The positive photosensitive resin composition of claim 1 or 2, wherein the (C) component is 5-50 parts by mass relative to 100 parts by mass of the (A) component. 如請求項1或2之正型感光性樹脂組成物，其中，作為(E)成分，係相對於(A)成分之100質量份，將界面活性劑進一步含有0.01~1.0質量份。 The positive photosensitive resin composition of claim 1 or 2, wherein, as the component (E), the surfactant further contains 0.01 to 1.0 part by mass relative to 100 parts by mass of the component (A). 如請求項1或2之正型感光性樹脂組成物，其中，作為(F)成分，係相對於(A)成分之100質量份，將密著促進劑進一步含有0.1~20質量份。 The positive photosensitive resin composition of claim 1 or 2, wherein, as the component (F), the adhesion promoter further contains 0.1 to 20 parts by mass relative to 100 parts by mass of the component (A). 一種硬化膜，其係硬化如請求項1~7中任一項之正型感光性樹脂組成物而成。 A cured film formed by curing the positive photosensitive resin composition according to any one of claims 1 to 7. 一種顯示元件，其係具有如請求項8之硬化膜。 A display element having a hardened film as claimed in claim 8. 一種顯示元件，其係具有如請求項8之硬化膜作為顯示器用陣列平坦化膜。 A display element having the cured film as claimed in Claim 8 as an array flattening film for a display. 一種顯示元件，其係具有如請求項8之硬化膜作為層間絕緣膜。 A display element having the cured film as in Claim 8 as an interlayer insulating film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI773645B (en) * 2015-07-30 2022-08-11 日商東京應化工業股份有限公司 Photosensitive composition, pattern forming method, permanent film, and color filter for CMOS image sensor

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102040224B1 (en) * 2016-08-09 2019-11-06 주식회사 엘지화학 Method for manufacturing insulating film and multilayered printed circuit board
KR101947150B1 (en) * 2016-08-09 2019-02-12 주식회사 엘지화학 Method for manufacturing insulating film and multilayered printed circuit board
WO2018088754A1 (en) * 2016-11-11 2018-05-17 주식회사 엘지화학 Insulating layer manufacturing method and multi-layered printed circuit board manufacturing method
KR102040225B1 (en) * 2016-11-11 2019-11-06 주식회사 엘지화학 Method for manufacturing insulating film and multilayered printed circuit board
KR102080079B1 (en) 2018-10-30 2020-02-21 인하대학교 산학협력단 Highly fluorinated monomolecular photoresist having solubility in high fluorine solvent and method of forming pattern using the same
WO2024024501A1 (en) * 2022-07-29 2024-02-01 日産化学株式会社 Positive photosensitive resin composition
CN115160495B (en) * 2022-08-15 2024-05-14 四川华造宏材科技有限公司 Photoresist film-forming resin containing maleimide structure and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201433883A (en) * 2013-01-16 2014-09-01 Jsr Corp Thermosetting resin composition for forming cured film, negative radiation-sensitive resin composition, positive radiation-sensitive resin composition, cured film, formation method thereof, semiconductor element and display element

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3241399B2 (en) 1991-05-30 2001-12-25 ジェイエスアール株式会社 Radiation-sensitive resin composition for microlenses
JP3959732B2 (en) 1998-09-29 2007-08-15 Ｊｓｒ株式会社 Thermosetting resin composition
JP4584487B2 (en) * 2001-05-08 2010-11-24 コダック株式会社 Positive type image forming material and positive image forming method using the same
JP2005097546A (en) * 2003-08-22 2005-04-14 Okamoto Kagaku Kogyo Kk Lithographic printing original plate
EP1577330B1 (en) * 2003-08-22 2012-02-15 Okamoto Chemical Industry Co., Ltd Copolymer, image-forming composition and plate for lithography
TWI424270B (en) * 2004-05-26 2014-01-21 Nissan Chemical Ind Ltd Positive-type photosensitive resin composition, and interlayer insulator and microlens produced from the composition
US8828651B2 (en) * 2005-07-25 2014-09-09 Nissan Chemical Industries, Ltd. Positive-type photosensitive resin composition and cured film manufactured therefrom
KR101280478B1 (en) * 2005-10-26 2013-07-15 주식회사 동진쎄미켐 Photosensitive resin composition
JP5019055B2 (en) * 2006-01-25 2012-09-05 日産化学工業株式会社 Positive photosensitive resin composition and cured film obtained therefrom
JPWO2007132890A1 (en) * 2006-05-16 2009-09-24 日産化学工業株式会社 Positive photosensitive resin composition and porous film obtained therefrom
CN101349865B (en) * 2007-07-17 2012-10-03 富士胶片株式会社 Photosensitive compositions, curable compositions, color filters, and method for manufacturing the same
JP5496482B2 (en) * 2007-08-27 2014-05-21 富士フイルム株式会社 Novel compound, photopolymerizable composition, photopolymerizable composition for color filter, color filter and method for producing the same, solid-state imaging device, and lithographic printing plate precursor
TWI505034B (en) * 2010-02-02 2015-10-21 Nissan Chemical Ind Ltd Positive type photosensitive resin composition and liquid-repellent coating
CN103229101B (en) * 2010-11-30 2017-05-10 日产化学工业株式会社 Photosensitive resin composition for microlenses
JP5585796B2 (en) * 2012-07-06 2014-09-10 日産化学工業株式会社 Positive photosensitive resin composition containing a compound having an unsaturated group at the terminal
JP6070203B2 (en) * 2013-01-16 2017-02-01 Jsr株式会社 Semiconductor element and display element
JP6157193B2 (en) * 2013-04-22 2017-07-05 昭和電工株式会社 (Meth) acrylate polymer, composition containing the polymer and use thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201433883A (en) * 2013-01-16 2014-09-01 Jsr Corp Thermosetting resin composition for forming cured film, negative radiation-sensitive resin composition, positive radiation-sensitive resin composition, cured film, formation method thereof, semiconductor element and display element

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI773645B (en) * 2015-07-30 2022-08-11 日商東京應化工業股份有限公司 Photosensitive composition, pattern forming method, permanent film, and color filter for CMOS image sensor

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