TW201100966A - Positive photosensitive composition and method for forming cured film using the same - Google Patents

Abstract

The present invention provides a positive photosensitive composition and a method for forming a cured film using the same, wherein the positive photosensitive composition has excellent sensitivity, retention of film thickness and storage stability and a method for forming a cured film, and the positive photosensitive composition is capable of obtaining a cured film having excellent heat endurance, adhesiveness and transmittance by means of curing thereof. The present invention provides a positive photosensitive composition and a method for forming a cured film using the same. The positive photosensitive composition comprises a resin obtained by reacting a specific styrene-based constitution unit of a carboxyl group which is produced by dissociating from a dissociative group with a carboxyl group to form a functional group constitution unit of a covalent bon, and meanwhile the resin does not dissolve in alkali or difficultly dissolve in alkali and dissolve in alkali while a dissociative group is dissociated; a compound has more than two of epoxy groups in the molecular; and an acid compound can be produced by irradiating 300 nm of active ray.

Description

[Technical Field] The present invention relates to a positive photosensitive resin composition and a method of forming a cured film using the same. More specifically, the present invention relates to a positive type of a planarizing film, a protective film or an interlayer insulating film suitable for forming electronic parts of liquid crystal display elements, integrated circuit elements, solid-state imaging elements, organic EL elements, and the like. A photosensitive resin composition and a method of forming a cured film using the same. [Prior Art] Conventionally, in electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and organic EL elements, generally, planarizing films and electronic parts for imparting flatness to the surface of electronic parts are formed. When a protective film which deteriorates or damages or an interlayer insulating film for maintaining insulation is used, a photosensitive resin composition is used. For example, a TFT-type liquid crystal display device can be provided with a polarizing plate on a glass substrate, and a transparent conductive circuit layer such as ITO or a thin film transistor (TFT) can be formed, and an interlayer insulating film can be used as a further Q side of the back surface plate. A polarizing plate is disposed on the glass substrate, and a pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as an upper panel, and the back panel is passed through the spacer. The panel is formed by sealing liquid crystal between the two sheets, and the photosensitive resin composition used for forming the interlayer insulating film is required to have excellent residual film ratio, heat resistance, adhesion, and transparency. Further, the photosensitive resin composition is required to have excellent stability over time when stored. As a photosensitive resin composition, for example, Patent Document 1 proposes a photosensitive resin composition comprising: (A) a resin soluble in an aqueous alkaline solution, which is (a) an unsaturated carboxylic acid. Or a unsaturated carboxylic acid anhydride, (b) a radical polymerizable compound having an epoxy group, and (c) a polymer of another radical polymerizable compound; and (B) a radiation-sensitive acid generating compound. Patent Document 2 proposes a photosensitive resin composition comprising a photosensitive resin composition comprising an alkali-soluble acrylic polymer binder, a quinonediazide-containing compound, a crosslinking agent, and a photoacid generator. . However, in any of these systems, the sensitivity, the residual film rate in the unexposed portion, the resolution, and the stability over time are insufficient, and it is not possible to satisfy the manufacture of a high-quality liquid crystal display device. Patent Document 3 proposes a positive-type chemically amplified photoresist composition characterized by a crosslinking agent, an acid generator and itself which are insoluble or poorly soluble in an alkaline aqueous solution, but contain a resin having a resin The action of the acid will cleave the protecting group, which will become soluble in the aqueous alkaline solution after cleavage. However, it is not possible to satisfy the manufacture of high-quality liquid crystal display elements because of insufficient adhesion or transmittance. Patent Document 4 proposes a radiation sensitive Q resin composition characterized by containing a resin and an acid generator containing an acetal structure and/or a ketal structure and an epoxy group, and having low sensitivity and transmittance. Unable to meet. Patent Document 5 proposes a radiation sensitive resin composition characterized by: a hydroxystyrene resin protected by an acetal or a ketal; a compound which generates an acid due to an active light having an irradiation wavelength of 300 nm or more; Joint agent; but the transmittance is low and cannot be satisfied. [PATENT DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei No. Hei. [Patent Document 4] JP-A-2004-264623 [Patent Document 5] JP-A-2008-3 04902 SUMMARY OF INVENTION [Problems to be Solved by the Invention] _ Therefore, the subject of the present invention is to provide a sensitivity A positive photosensitive resin composition excellent in degree of resilience, residual film, and stability, and a method for forming a cured film using the same, which are cured to obtain a cured film excellent in heat resistance, adhesion, transmittance, and the like. A positive photosensitive resin composition and a method of forming a cured film using the same. Further, a cured film obtained by using the cured film forming method is provided, and a liquid crystal display element, an integrated circuit element, a solid-state imaging element or an organic EL element having the cured film is provided. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have completed the present invention as a result of concentration. The present invention is as follows. [1] A positive-type photosensitive resin composition characterized by comprising: (A) a resin comprising a constituent unit represented by the following formula (1) and having a reactivity with a thiol group to form a covalent bond a constituent unit of a functional group of a bond, and is alkali-insoluble or alkali-insoluble and dissociable-base dissociates to become alkali-soluble; and (B) 201100966 a compound which generates an acid by irradiation with active light.

(1) In the formula (1), R1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group. However, except when R2 and R3 are simultaneously a hydrogen atom. R4 represents a linear, branched or cyclic alkyl group or an aralkyl group which may also be substituted. R2 or R3 may also be bonded to R4 to form a cyclic ether. [2] The positive photosensitive resin composition of [1], which further contains (C) a compound having two or more epoxy groups in the molecule (except for the above A). [3] The positive photosensitive resin composition according to [1] or [2], wherein the component (B) contains Q having an acid which generates an acid by irradiation with an active light having a wavelength of 300 nm or more. [4] The positive photosensitive resin composition according to any one of [1] to [3] wherein the component (B) contains an oxime sulfonate group represented by the following formula (2). Compound. 201100966 In the formula (2), R5 represents a linear, branched, cyclic alkyl group which may be substituted, or an aryl group which may be substituted. [5] The positive photosensitive resin composition of [4], wherein the compound containing a sulfonic acid sulfonium group represented by the formula (2) is a compound represented by the following formula (2-1).

In the general formula (2-1), R5 is the same as R5 in the formula (2). The x system represents a linear or branched alkyl group, an alkoxy group or a halogen atom. The m system represents an integer of 〇~3. When m is 2 or 3, a plurality of Xs may be the same or different. [6] The positive photosensitive resin composition of [4], wherein the compound containing a sulfonic acid sulfonium group represented by the formula (2) is a compound represented by the following formula (2-2).

In the formula (2-2), the R5 group is the same as R5 in the formula (2). R6 represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cyano group or a nitro group. 201100966 1 is an integer from 0 to 5. When 1 is 2 or more, a plurality of R6s may be different. [7] The positive-type photosensitive resin composition according to any one of [1] to [6], wherein the functional group-based epoxy which can react with a carboxyl group to form a covalent bond [8] is positive photosensitive of [7] In the resin composition, the constituent unit having the functional group which forms a covalent bond by the reaction is derived from the radical polymerizable monomer represented by any one of the formulas (3) to (5). 〇 can be the same as the front base. It can form a single R7 〇 H2C=4 - a R1 with the carboxylic acid. I | (3) R® R8

〇 In the general formulae (3) to (5), R7 represents a hydrogen atom, a methyl group or a halogen atom. R8 to R15 each independently represent a hydrogen atom or an alkyl group. X represents a divalent linking group. η is an integer from 1 to 10 0. And a positive type photosensitive resin composition of any one of [1] to [6], wherein the functional group oxygen capable of reacting with a thiol group to form a covalent bond

201100966 [ι〇] The positive photosensitive resin composition of [9], wherein the constituent unit having a functional group capable of reacting with a carboxyl group to form a covalent bond is derived from a radical represented by the following general formula (6) A constituent unit of a polymerizable monomer.

R7 represents a hydrogen atom, a methyl group or a halogen atom. R8 to R12 each independently represent a hydrogen atom or an alkyl group. X represents a divalent linking group. η is an integer from 1 to 10 0. [11] The positive photosensitive resin composition according to any one of [1] to [1], which further comprises (D) an adhesion aid. Q [12] A method for forming a cured film, comprising the steps of: coating a positive photosensitive resin composition according to any one of [1] to [11] on a substrate and drying to form a coating film; a step of performing exposure by passing through a photomask and using active light; a step of developing a pattern using an alkaline developing solution; and a step of heat-treating the obtained pattern. [1] The method for forming a cured film according to [1 2], wherein after the image is formed by development using an alkaline developing solution, the step of comprehensively exposing is further performed before the step of heat-treating the obtained pattern. • 10-201100966 [14] A cured film formed by a method of forming a cured film such as [12] or [13]. [15] A liquid crystal display element having a cured film as [14]. [16] An integrated circuit component having a cured film as in [14]. [17] A solid-state photographic element having a cured film as in [14]. [18] An organic EL element having a cured film as [14]. Hereinafter, preferred embodiments of the present invention will be described. [1] The positive photosensitive resin composition of any one of [1] to [1 1], wherein 〇 is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the component (A) (B) ingredient. [2] The positive photosensitive resin composition 任 according to any one of [1] to [1 1], wherein the total amount of the component (A) is 100 parts by mass, and contains 1 to 50. Parts by mass (C). [21] The positive photosensitive resin composition according to any one of [1] to [11], wherein the content of the component (A) is 0.1 part by mass based on 100 parts by mass of the total amount of the component (A). Q 20 parts by mass (D). According to the present invention, it is possible to provide a positive photosensitive resin composition and a method for forming a cured film using the same, which are a positive photosensitive resin composition excellent in sensitivity, residual film ratio, and storage stability, and use thereof In the method of forming a cured film, the positive photosensitive resin composition is cured to obtain a cured film excellent in heat resistance, adhesion, transmittance, and the like. [Embodiment] Hereinafter, the present invention will be described in detail. Further, the label of the group (atomic group) of the present specification does not include a substituted or unsubstituted label, and includes a substituent having a substituent and a substituent. For example, the "alkyl group" is not limited to an alkyl group having no substituent (unsubstituted alkyl group), and also includes a substituent (substituted alkyl group). (A) Resin component The positive photosensitive resin composition of the present invention contains a resin (also referred to as "(A) component)), and the resin contains a composition represented by the following general formula (1): f) _ ^ unit And a constituent unit having a functional group capable of reacting with a carboxyl group to form a covalent bond, and is insoluble in alkali or insoluble in alkali, and is dissolvable in the dissociative group to be alkali-soluble, and may further contain other resins. Here, the acid dissociable group means a functional group which can be dissociated in the presence of an acid.

In the general formula (1),

R1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group. However, except when R2 and R3 are simultaneously a hydrogen atom. R4 represents a linear, branched or cyclic alkyl group or an aralkyl group which may also be substituted. -12- 201100966 R2 or R3 may also be bonded to R4 to form a cyclic ether. R1 of the formula (1) is preferably a hydrogen atom or a methyl group. R2 or R3 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. R4 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted. Here, as the substituent, an alkoxy group having 1 to 5 carbon atoms or a halogen atom is preferred. The aralkyl group of R4 is preferably an aralkyl group having 7 to 10 carbon atoms. When R2 or R3 is bonded to R4 to form a cyclic ether, it is preferred that R2 or R3 is bonded to R4^ to form an alkylene chain having 2 to 5 carbon atoms. The radical polymerizable monomer used for forming the structural unit represented by the formula (1) includes, for example, o-(1-oxoalkoxycarbonyl)styrene, m-(1-alkoxyalkane). Oxycarbonyl)styrene, p-(1-alkoxyalkoxycarbonyl)styrene, o-(1-alkyl-1-alkoxyoxycarbonyl)styrene, m-(1-alkyl-1-ampleoxy) Base oxycarbyl) phenylethylene, p-(1-hospital-1-indolyloxyxy) styrene, o-(1-alkoxyalkoxycarbonyl)-α-methylstyrene, (1-Alkoxy Q-alkyloxycarbonyl)-α-methylstyrene, p-(1-alkoxyalkoxycarbonyl)-α-methylstyrene, o-[1-(aralkyloxy)alkoxy Carbonyl]styrene, m-[1-(aralkyloxy)alkoxycarbonyl]styrene, p-[1-(aralkyloxy)alkoxycarbonyl]styrene, o-(2-oxocycloalkoxycarbonyl) Styrene, m-(2-oxocycloalkoxycarbonyl)styrene, p-(2-oxecyclooxycarbonyl)styrene, and the like. Among these, m-(1-alkoxyalkoxycarbonyl)styrene, p-(1-alkoxyalkoxycarbonyl)styrene, m-(2-oxocycloalkoxycarbonyl)styrene, p-( 2-Oxoheterocyclooxycarbonyl)styrene is preferred. Preference is given to (1-alkoxyalkoxycarbonyl)styrene and p-(2-oxocyclohexane-13-201100966 oxycarbonyl)styrene. Specific examples of the radical polymerizable monomer used to form the structural unit represented by the general formula (1) include o-(1-methoxyethoxycarbonyl)styrene and m-(1-_A) Oxyethoxyethoxycarbonyl)styrene, p-(1-methoxyethoxycarbonyl)styrene, o-(1ethoxypropoxycarbonyl)styrene-(1-ethoxyethoxycarbonyl)styrene , p-(1-ethoxyethoxycarbonyl)styrene, o-(1-n-propoxyethoxycarbonyl)styrene, m-(p-α-n-propoxyethoxycarbonyl)styrene, p-(1-n-propyl) Oxyethoxycarbonyl)benzene

G olefin, p-(1-isopropoxyethoxycarbonyl)styrene, o-(1-n-butoxyethoxycarbonyl)styrene, m-(1-n-butoxyethoxycarbonyl)styrene, p-( 1-n-butoxyethoxycarbonyl)styrene, p-(1-isobutoxyethoxycarbonyl)styrene, o-(1-benzylethoxycarbonyl)styrene, m-(1-benzylethoxycarbonyl) Styrene, p-(1·benzylethoxycarbonyl)styrene, o-(2-oxohexyloxycarbonyl)styrene, p-(2-oxocyclooxycarbonyl)styrene, m-(2-oxo) Heterocyclic hexyloxycarbonyl) styrene, p-(2-oxohexyloxycarbonyl)styrene, m-(1-ethoxyethoxy Q-carbonyl)α-methylstyrene, p-(1-ethoxyB) Oxycarbonyl)α-methylstyrene, m-(1-methyl-1-ethoxyethoxycarbonyl)styrene, p-(1-methyl-1-ethoxyethoxycarbonyl)styrene, etc. It can be used individually or in combination of 2 or more types. The radical polymerizable monomer used for forming the structural unit represented by the formula (1) may be a commercially available product or may be synthesized by a known method. For example, it can be synthesized by reacting vinyl benzoic acid with vinyl ether in the presence of an acid catalyst as described below. -14- 201100966

Here, R1 'R3 and R4 correspond to R1, R3 and R' of the formula (1), and R13 and R14 correspond to -CH(R13)(R14) and correspond to R2 of the formula (1). The photosensitive composition of the present invention comprises the steps of: forming a hardened film by coating and drying on a substrate to form a coating film; passing the mask and using active light to perform exposure; using alkaline a step of forming a pattern like a liquid; a step of performing full exposure as necessary; and a step of heat-treating the obtained pattern; and an acid dissociable group (-C(R2) (in the step of total exposure or heat treatment) R3)OR4) is dissociated from the structural unit represented by the formula (1) of the component (A), and a carboxyl group is formed in the side chain of the component (A). The structural unit containing a functional group capable of forming a covalent bond by reacting with a carboxyl group in the component (A) of the present invention, the "functional group capable of reacting with a carboxyl group to form a covalent bond" means The heat treatment can react with the carboxyl group formed in the side chain of the component (A) as described above to form a functional group of the covalent bond. As described above, the carboxyl group formed in the side chain of the component A and the "functional group which reacts with the carboxyl group to form a covalent bond" in the component (A) are formed by heat treatment to form a covalent bond, and are formed by crosslinking. Good hardened film. As a functional group capable of reacting with such a carboxyl group to form a covalent bond, for example, -15-201100966 may, for example, be an epoxy group or an oxetanyl group, and the epoxy group may have a reactivity with a carboxyl group to form a covalent bond. The constituent unit of the bond is preferably a constituent unit composed of a radical polymerizable monomer of any of the following general formulas (3) to (5), and is used in combination of two or more kinds. The molecular weight of the polymerizable monomer represented by the formula (3) to (10) is preferably 10 to 500, particularly preferably 12 Å. The structure of the functional group can be expressed alone or in groups of free radicals.

G In the general formulae (3) to (5), x represents an organic group such as a divalent linking group, _〇, -s- or -coo-, -〇CH2C〇〇. χ is better. R' represents a hydrogen atom, a methyl group or a halogen atom, preferably hydrogen. R8 to Rl5 each independently represent a hydrogen atom or an alkyl group. Methyl is preferred. For example, an integer of 1 to 3 may be used as an integer of -COO- atoms or a methyl group, or a hydrogen atom or -16-201100966 η. Specifically, when a radical polymerizable monomer used for forming a constituent unit containing an epoxy group (which is a functional group capable of forming a covalent bond with a carboxyl group) is used, examples thereof include glycidyl acrylate and A. Glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4 epoxy methacrylate, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate, etc. (Methyl) ^ acrylates; o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl epoxypropyl ether, α-methyl-o-vinyl Vinylbenzyl epoxypropyl ether, such as agglomerated epoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether Vinyl phenylepoxypropyl ethers such as o-vinylphenylepoxypropyl ether, m-vinylphenylepoxypropyl ether, p-vinylphenylepoxypropyl ether, etc. Oxypropyl propyl ester, Glycidyl methacrylate, p-vinylphenyl Q epoxy propyl ether, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methacrylate, preferably acrylic acid Glycidyl propyl ester and glycidyl methacrylate are particularly preferred. A constituent unit having a functional group capable of reacting with a carboxyl group to form a covalent bond, and a constituent unit composed of a radical polymerizable monomer represented by the following general formula (6) or (7) For the best 'can be used alone or in combination with two types of 50 pass ~ ο ο ο with 1 to make 'on the amount to sub 7 (good m for

Subdivided by unilaterality.聚佳聚更基为由 ο From 2 ～ 50 50 Table 1 -17- 201100966

(7) In the general formulae (6) and (7), X represents a divalent linking group, for example, an organic group such as 0-, -S-o or -COO-, or -OCH2C00-. The X system is preferably -coo-. R7 represents a hydrogen atom, a methyl group or a halogen atom, and preferably a hydrogen atom or a methyl group. R8 to R15 each independently represent a hydrogen atom or an alkyl group. A hydrogen atom or a methyl group is preferred. The integer of η is 1 to 10, and preferably an integer of 1 to 3. The above-mentioned specific example of the radically polymerizable monomer containing an epoxy group is exemplified as an example of the radical polymerizable monomer used for forming the structural unit having an oxetane group. A compound obtained by substituting an epoxy group into an oxetanyl group, or a (meth) acrylate having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A-2001-330953. The radical polymerizable monomer used for forming a constituent unit having a functional group capable of reacting with a carboxyl group to form a covalent bond can also be used commercially, or can be synthesized by a known method. -18- 201100966 元 Ο Ο 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The constituent unit of the following.

The content ratio of the constituent unit represented by the formula (1) is preferably 10 to 90 mol%, more preferably 20 mol%, based on the total repeating unit of the resin constituting (Α). The constituent unit content of the functional group having a functional group capable of reacting with a carboxyl group to form a covalent bond is preferably 5 to 50 mol% with respect to the total repeating unit of the resin constituting the (Α) component, and is preferably 1 〇 to 4 0 0 Ear % is better. In the (Α) component, a constituent unit represented by the formula (1) and a constituent unit other than a moiety having a functional group capable of reacting with a carboxyl group to form a covalent bond may be uniformly added as necessary. The structural unit represented by the formula (1) and the constituent unit other than the constituent unit having a functional group capable of forming a covalent bond with a carboxyl group may be ethylene, tert-butoxystyrene, methylstyrene or hydroxyl group. Phenylethyl α-methylstyrene, ethoxylated styrene, α-methylethyloxybenzene, methoxystyrene, ethoxystyrene, chlorostyrene, vinyl-19- 201100966 benzoic acid Methyl ester, ethyl vinyl benzoate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, methyl propyl acrylate Vinegar, isopropyl acrylate isopropyl acrylate, butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyl acrylate a constituent unit of propyl ester, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, isodecyl acrylate, isodecyl methacrylate, glycidyl methacrylate, acrylonitrile, etc. It can be used alone or in combination of two kinds of mosses. The content of the constituent units is preferably 85 mol% or less, more preferably 60 mol% or less, based on the total amount of the total repeating unit of the resin constituting the component (A). The molecular weight of the component (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of the weight average molecular weight of the polystyrene. The Q (A) component may be used by mixing two or more kinds of resins containing different constituent units, or may be used by mixing two or more kinds of resins which are composed of the same constituent unit and have different compositions. Further, various methods are known for the method of synthesizing the component (A). When an example is given, the free use of at least the constituent unit represented by the formula (1) can be used. Mixing of a radical polymerizable monomer and a radical polymerizable monomer used for forming a constituent unit having a functional group capable of reacting with a carboxyl group to form a covalent bond, -20-201100966 The solvent is synthesized by polymerization using a radical polymerization initiator. (B) a compound which generates an acid by irradiation with active light or radiation. A compound which is used in the present invention to generate an acid by irradiation with active light or radiation (also referred to as "(B) component") or a photoacid generator) For example, a phosphonium salt or an iodine salt, a diazomethane compound, an imidosulfonate compound, an oxime sulfonate compound, etc. can be used, and it can use individually or in combination of 2 or more types. The photoacid generator is preferably a compound which sensitizes an active light having a wavelength of 3,000 nm or more and generates an acid, and more preferably contains a compound of the oxime sulfonate group represented by the formula (2). Ο p»N—Ο—S—R5 (2) / sw In the formula (2), R5 represents a linear, branched, cyclic alkyl group which may also be substituted, or may be substituted Aryl. Q is preferably an alkyl group of R5, and a linear or branched alkyl group having 1 to 10 carbon atoms is preferred. The alkyl group of R5 includes an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 1 carbon number, or an alicyclic group (having a bridge such as 7,7-dimethyl-2-oxooxanyl group) The alicyclic group is preferably substituted by a bicycloalkyl group or the like. The aryl group of R5 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group, and the aryl group of R5 is also preferred. It may be substituted by an alkyl group, an aryloxy group or a halogen atom having 1 to 5 carbon atoms. The photoacid generator containing the oxime sulfonate group represented by the formula (2) 'in a -21 - 201100966 aspect' is as follows The compound represented by the formula (2-1) is more preferably.

In the formula (2-1), the r5 group is the same as the R5 in the formula (2). 〇 X represents a linear or branched alkyl group, an alkoxy group, or a halogen atom. The m system represents an integer of 0 to 3. When m is 2 or 3, the plural X may be the same or different. The alkyl group of X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group of X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom of X is preferably a chlorine atom or a fluorine atom. 〇 m is better than 〇 or 1. In particular, in the general formula (3), a compound in which m is 1 'X is a methyl group and a substitution position of X is an ortho position, and R5 is a linear alkyl group having a carbon number of 1 to 10, 7, 7 A compound of -dimethyl-2-oxomethoxymethyl or p-tolyl is particularly preferred. Specific examples of the oxime sulfonate compound include, for example, the following compound (i), compound (ii), and compound (ϋ〇, compound (iv), compound (v), etc., which may be used alone or in combination of two or more types. It can also be used with other types of -22- 201100966 (B).

The compounds (i) to (v) can be obtained as commercially available products. In the other aspect, the photoacid generator containing the oxime sulfonate group represented by the formula (2) is more preferably a compound represented by the following formula (2-2).

-23- 201100966 In the formula (2-2), the R5 group is the same as the R5 of the formula (2). R6 represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group 'cyano group or a nitro group. The 1 series represents an integer of 0 to 5. When 1 is 2 or more, a plurality of R6s may be the same or different. The general formula (2-2) will be explained in more detail. Preferred examples of r5 include an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy group having 1 to 5 carbon atoms, which may be substituted by W. A phenyl group, a naphthyl group which may be substituted by W, or a fluorenyl group which may be substituted by | Here, the 'W system" means a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 1 carbon atom, a halogenated alkyl group having 1 to 5 carbon atoms or a carbon atom. A halogenated alkoxy group having 1 to 5 is used. As R5 of the formula (2-2), methyl 'ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n-butyl The group, Q benzyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl is preferred, and methyl, ethyl, n-propyl, n-butyl, benzyl or p-tolyl is particularly preferred. The halogen atom represented by R6 is preferably a fluorine atom, a chlorine atom or a bromine atom. The alkyl group represented by R6 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. The alkoxy group represented by R6 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. -24- 201100966 As 1 ', 0~2 is better, and 〇 or 1 is especially good. A preferred aspect of the compound contained in the photoacid generator represented by the formula (2-2) 'R5 means methyl, ethyl, n-propyl, n-butyl or 4-tolyl' R6 represents A hydrogen atom or a methoxy group, and 1 is a quinone or a 1 state. The following is a particularly preferred example of the compound contained in the photoacid generator represented by the formula (2-2), but the present invention is not limited thereto. Α-(methylsulfonyloxyimino)benzyl cyanide (R3A=methyl, r4A = hydrogen atom) α-(ethylsulfonyloxyimino)benzyl cyanide (R3A=ethyl, r /a = hydrogen atom) 〇, α-(n-propylsulfonyloxyimino)benzyl cyanide (R3A = n-propyl, r " = hydrogen atom) α-(n-butyl sulfonyloxyimide Benzyl cyanide (R3A = n-butyl, R4A = hydrogen atom) α-(4-toluenesulfonyloxyimino)benzyl cyanide (R3A = 4-tolyl, 11^=hydrogen atom) α- (phenylsulfonyloxyimino)benzyl cyanide (R3A = phenyl, R4A = hydrogen atom) Q α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile ( R3A=methyl, R4A=methoxy) α-[(ethylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R3A=ethyl, R4A=methoxy) α- [(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R3A = n-propyl, R4A = methoxy) α-[(n-butylsulfonyloxyimino) -4_methoxyphenyl]acetonitrile (R3A = n-butyl, R4A = methoxy) -25- 201100966 α-[(4-tolylsulfonyloxyimino)_4_methoxybenzene Acetonitrile (R3A = 4_ tolyl, R4A = A α)[(phenylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (r3a=phenyl, r4A=methoxy) In the photosensitive resin composition of the present invention, photoacid generation The agent (B) is preferably contained in an amount of from 1 to 10 parts by mass, more preferably from 0,5 to 10 parts by mass, per 100 parts by mass of the copolymer (A). 0 The photosensitive resin composition of the invention A photoacid generator other than the photoacid generator of the oxime sulfonate group represented by the formula (2), if necessary, as a photoacid generator for inducing active light. (C) In the molecule Specific examples of the compound having two or more epoxy groups as a compound having two or more epoxy groups in the molecule (also referred to as "(C) component") include bisphenol A type epoxy resin and double Phenol f-type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, and the like. Q These can be obtained as a commercial product. For example, examples of the bisphenol A type epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, JAPAN EPOXY RESINS), EPICLON 860, and EPICLON 1050. EPICLON1051, EPICLON 1055 (above, Dainippon INK Chemical Industry Co., Ltd., etc.; as bisphenol F-type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, JAPAN EPOXY RESINS) System, -26- 201100966 EPICLON830, EPICLON835 (above, Dainippon INK Chemical Industry Co., Ltd., LCE-21, RE-602S (above, Nippon Chemical Co., Ltd.), etc.: as phenol novolak type epoxy resin Examples include JER152, JER154, JER1 57S70 (above, JAPAN EPOXY RESINS), EPICLON-740, EPICLON-740, EPICLON-770, EPICLON-775 (above, Dainippon INK Chemical Industry Co., Ltd.); Examples of the cresol novolac type epoxy resin include EPICLON-N-660, EPICLON-N665, EPICLON-N670, EPICLON-N673, EPICLON-N680, and 〇EPICLON-N690 ' EPICLON-N695 ( , Japan's INK Chemical Industry Co., Ltd., EOCN- 1 020 (above, Nippon Chemical Co., Ltd.), etc.; as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP -4088S (above, ADEKA (share) system), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE2083, CELLOXIDE 2085, EHPE3 1 50, EPOLE AD PB 3 600, same as PB 4700 (above, DAICEL chemical (share)), etc. For example, Q ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-401 1 S (above, ADEKA), NC-2000, NC-3000, NC-7300, XD-1000 , EPPN-501, EPPN-502 (above, ADEKA (share) system). These can be used individually or in combination of 2 or more types. Among these, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolac type epoxy resin are preferable. It is particularly preferred to use bisphenol A type epoxy resin. The content of the component (C) is preferably from 1 to 50 parts by mass, more preferably from 5 to 30 parts by mass, per 100 parts by mass of the component (A), from -27 to 201100966 parts. The component (C) is effective for adhesion improvement to a metal layer of chromium, molybdenum, aluminum, giant, or titanium 'copper, cobalt, tungsten, nickel, or the like. When these metal layers are formed by sputtering, the effect is remarkable. (D) Adhesive Aid The positive photosensitive resin composition of the present invention may further contain (D) an adhesion aid. The adhesion aid (D) which can be used in the present invention is an inorganic substance such as ruthenium, iridium oxide or tantalum nitride, or a metal such as gold, copper or aluminum, and an insulating film. Adhesively elevated compound. Specifically, a decane coupling agent, a thiol compound, or the like can be given. The decane coupling agent which is an adhesion aid which can be used in the present invention is not particularly limited as long as it is modified by an interface, and those skilled in the art can be used. Preferred decane coupling agents include, for example, γ-glycidoxypropyl Q trialkoxydecane, γ-glycidoxypropylalkyldialkoxydecane, and γ-methylpropene oxime. Oxypropyl propyl alkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl trialkoxy decane, γ-hydrothiopropyltrialkoxy Decane, β·(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. Γ-glycidoxypropyl ethoxide oxalate or γ-methyl propyl methoxypropyltrialkoxy decane is preferred, γ-glycidoxypropyl trialkoxy The base decane is more preferred. -28- 201100966 These can be used alone or in combination of two or more. These are effective for adhesion improvement to the substrate, and are also effective for adjusting the taper angle with the substrate. The mixing ratio of the component (A), the component (B), the component (C), and the component (D) of the positive photosensitive resin composition of the present invention is 1 part by mass based on the total amount of the component (A). The component (B) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass. Further, the component (C) is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass. Further, the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. <Other components> In addition to the components (A), (B), (C), and (D), the positive photosensitive resin composition of the present invention may be added with a basic compound as necessary. Surfactant, ultraviolet absorber, sensitizer, plasticizer, tackifier, organic solvent, adhesion promoter, organic or inorganic anti-precipitation agent, etc. <Basic compound> Q As the basic compound, it can be arbitrarily selected and used from among users of the chemical amplification type resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a carboxylic acid quaternary ammonium salt, or the like can be given. The aliphatic amine may, for example, be trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine or bicyclod. Hexylamine, dicyclohexylmethylamine, and the like. The aromatic amine may, for example, be aniline, benzylamine, N,N-dimethylaniline or diphenylamine. -29- 201100966 The heterocyclic amine may, for example, be pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine or 4-phenylene. Pyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4·methylimidazole, diphenylbenzimidazole, 2,4,5-triphenylimidazole ,nicotine,nicotinic acid,nicotinamide,quinoline, 8-hydroxyquinoline, pyridinium, pyrazole, argon, guanidine, pyrrolidine, piperidine, piperene, porphyrin, 4-methyl Porphyrin, 1,5-diazabicyclo[4,3,0]-5-pinene, 1,8-diazabicyclo[5,3,fluorene]-7-undecene, and the like. 〇 As the ammonium oxyhydroxide, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide or the like can be given. Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate. The compounding ratio of the basic compound is preferably 0.001 to 1 part by mass per part by mass of the component (A), and more preferably 0.005 to 0.2 part by mass. <Interactive Agent> G As the surfactant, any of anionic, cationic, nonionic or amphoteric may be used, and a surfactant is preferably a nonionic surfactant. As examples of the nonionic surfactant, polyoxyethylene can be used as a high-grade polyetherether, a polyoxyethylene higher alkylphenyl ether, a higher fatty acid diester of polyoxyethylene propylene glycol, a lanthanide, or a fluorine. Is a surfactant. In addition, the following product names, κρ (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), eft〇p (manufactured by JEMC), and MEGAFAC (manufactured by Otsuka ΝΚ Chemical Industry Co., Ltd.), 'Fur〇rad' (Sumitomo 3M system), -30- 201100966 ASAHI GUARD, SURFLON (made by Asahi Glass), PolyFox (made by OMNOVA), FTERGENT (made by NEOS). In addition, as a surfactant, a structural unit A and a structural unit B represented by the following general formula (1) are used, and the gel permeation chromatograph measured by tetrahydrofuran (THF) is used. The polystyrene has a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less. 〇 constituent unit A constituent unit B ί ΐ L ^ -CH 2 — 0 - -CH 2 — 0 — (I) 〇 -) j - R 4 In the formula (1), R 1 and R 3 each independently represent a hydrogen atom or a R2 is a linear alkylene group having a carbon number of 1 or more and 4 or less. R4 is a hydrogen atom or an alkyl group having a carbon number of 1 or more and 4 or less. The alkyl group "L" represents an alkylene group having 3 or more and 6 or less carbon atoms. , p and q are mass ratios, and P is a number 1 of 10% by mass or more and 80% by mass or less, and q is a number 2'r of 20% by mass or more and 90% by mass or less. An integer of 1 or more and 18 or less is represented, and η represents an integer of 1 or more and below. The above L is preferably a branch extending from the following formula (II). R5 of the formula (Π) represents an alkyl group having 1 or more and 4 or less carbon atoms, and is preferably an alkyl group having 1 or more and 3 or less carbon atoms in terms of compatibility and wettability to a surface to be coated. An alkyl group having 2 or 3 carbon atoms is more preferred. The sum (p + q) of Ρ and q is P + q = 100, that is, preferably 100% by mass. -31- 201100966 —CH2CH— (") The weight average molecular weight (M w) of the copolymer is converted to polystyrene by a gel permeation chromatograph using THF as a solvent, and is 1000 or more and 100,000 or less. Preferably, it is more preferably 1 500 or more and 500 or less. The surfactants may be used singly or in combination of two or more. The blending ratio of the surfactant is usually ❹1 〇 by mass or less per 1 part by mass of the component (A), preferably 0.01 to 10 parts by mass, more preferably 0.01 to 1 part by mass. <Plasticizer> Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, dodecyl decanoate, polyethylene glycol, glycerin, dimethyl glyceryl phthalate, tartaric acid. Dibutyl ester, dioctyl adipate, triethylene glyceryl, and the like. The compounding ratio of the plasticizer is preferably 20 parts by mass or less per 100 parts by mass of the component (A), and more preferably 10 parts by mass or less. <Sensitizer> The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof when combined with the photoacid generator (B). The sensitizer absorbs active light or radiation and becomes an electron-excited state. The sensitizer which becomes an electron-excited state acts in contact with the photo-acid generator to cause movement of electrons, energy movement, heat generation and the like. Thereby, the photoacid generator undergoes a chemical change to decompose and generate an acid. Further, as an example of a preferred sensitizer, a compound which belongs to the following compound and has an absorption wavelength at any wavelength in the region of 350 nm to 450 nm can be mentioned. Polynuclear aromatics (eg, ruthenium, osmium, tri-o-phenylene, anthracene, 9,10,-dibutoxyanthracene, 9,10,-diethoxyanthracene, 3,7-dimethoxyanthracene, 9, 10, -dipropoxy fluorene), xanthene (such as luciferin, eosin, erythrosine, rhodamine B, rose red), xanthone (xanthone) Classes (eg, oxime ketone, 9-oxosulfonium, dimethyl-9-oxopurine, diethyl-9-oxo-sulphur), anthocyanins (eg, thiocarbonate, Oxygen-carbonated cyanine), merocyanoids (eg, anthocyanins, carbonaceous anthocyanins), rhodacyanines, oxonols, thiazolines (eg thiazide) (thionine), methylene blue, toluidine blue), acridine (eg acridine orange, chlorferrin, acridine yellow), acridone (eg acridone ' 10-butyl-2-chloropurine) Pyridone), terpenoids (such as hydrazine), squalium (such as squalene), styryl, basetyryl (eg 2-[2-[4 -(dimethylamino)phenyl]vinyl]benzoxazole), coumarins (eg 7-two Amino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyran [ 6,7,8-ij]porphyrin-11-one). Among these sensitizers, polycyclic aromatics, acridones, styrenes, alkali styrenes, and coumarins are preferred, and polycyclic aromatics are more preferred. Among the polycyclic aromatics, anthracene derivatives are preferred. <Solvent> The positive photosensitive resin composition of the present invention can be used by dissolving the above-mentioned component in a solvent as a solution. Examples of solvents that can be used in the positive photosensitive resin composition of the present invention are: - (1) ethyl alcohol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monopropyl ether, ethylene Ethylene glycol monoalkyl ethers such as alcohol monobutyl ether; (2) ethylene glycol dialkyl groups such as ethylene glycol dimethyl acid, ethylene glycol diethyl ether, ethylene glycol dipropyl ether Ethers; (3) Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, etc. Ethylene glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol (4) propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; a propylene glycol dialkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; (6) propylene glycol monomethyl ether Propylene glycol monoalkyl ether acetates such as acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; Q (7) diethylene glycol Methyl ether Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; (8) diethylene glycol monomethyl ether acetate, Diethylene glycol monoalkyl ether acetate such as diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate (9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; -34 - 201100966 (10) dipropylene glycol dialkyl ether acetate such as dipropylene glycol dimethyl acetate acetate, dipropylene glycol diethyl acetate acetate, dipropylene glycol ethyl methyl acetate; (11) Dipropylene glycol propylene glycol monomethyl acetate, dipropylene glycol monoethyl ketone acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate Monoalkyl ether acetates; (12) methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactic acid, n-amyl lactate, a lactate such as isoamyl acetate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, N-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate , an aliphatic carboxylic acid ester such as n-butyl butyrate or isobutyl butyrate; (14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, 2·hydroxy-3-methyl Q Ethyl butyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, butyric acid Other esters such as 3-methyl-3-methoxybutyl ester, methyl acetonitrile acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate; (15) methyl ethyl ketone, A Ketopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc. Ketones; -35- 201100966 (16) n-Methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-A A guanamine such as a pyrrolidone; (17) a lactone such as γ-butyrolactone. Further, these solvents may also be added with benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, if necessary. Ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate A solvent such as an ester, ethylene carbonate or propylene carbonate. The solvent may be used singly or in combination of two or more. The blending ratio of the solvent is usually 50 to 3,000 parts by mass per 100 parts by mass of the component, more preferably 100 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass. By using a positive photosensitive resin composition containing a (Α) component and a (Β) component, it is possible to provide a positive photosensitive resin composition which is excellent in sensitivity, Q residual film ratio, and stability over time. When the photosensitive resin composition is cured, a cured film excellent in heat resistance, adhesion, transparency, and the like can be obtained. <Method of Forming Cured Film> Subsequently, a method of forming a cured film using the positive photosensitive resin composition of the present invention will be described. By coating the positive photosensitive resin composition of the present invention on a substrate and heating it, a coating film can be formed on the substrate. -36- 201100966 By irradiating the obtained coating film with active light, the component (B) is decomposed and generates an acid. The acid-dissociable group in the structural unit represented by the formula (1) contained in the component (A) is decomposed by hydrolysis to form a carboxyl group by the action of the acid which is generated by the acid. Subsequently, a positive image was formed by removing the exposed portion (which contains a resin having a carboxyl group which is easily dissolved in the alkaline developing solution) by using an alkaline developing solution. The reaction formula of the hydrolysis reaction is shown below.

R4oh 〇 In order to accelerate the decomposition of the water, it is necessary to perform post-exposure heat treatment as necessary: Post Exposure Bake (hereinafter referred to as PEB). When the heating temperature is high, the generated carboxyl group may crosslink with the epoxy group, resulting in failure to develop. In fact, when the third butoxycarbonyl styrene is used in place of the repeating unit represented by the general formula (1), since the activation energy of the acid dissociation reaction becomes high, in order to dissociate the acid dissociable group, it is necessary to PEB is carried out at a high temperature, but at the same time a cross-linking reaction occurs, resulting in no image acquisition. On the other hand, since the acid dissociable group acid represented by the general formula (1) of the present invention has low activation energy, it can be easily dissolved to produce a carboxyl group by the acid derived from the exposed acid generator. The necessity of PEB, by -37- 201100966, can form a positive image by visualization. Further, the decomposition of the acid dissociable group can be promoted by the PEB' at a lower temperature without causing a crosslinking reaction. The PEB temperature is 1300. (: The following is preferable, preferably 1 to 10 ° C or less is more preferably 80 ° C or less. Subsequently, the acid dissociation in the general formula (1) is obtained by heating the obtained positive image. The base thermally decomposes to form a carboxyl group 'and crosslinks it with the epoxy group' to form a cured film. The heating is preferably performed at a high temperature of 150 ° C or higher ' Ο preferably 180 to 250 ° C. It is particularly preferable to heat at 200 to 250 ° C. The heating time can be appropriately set according to the heating temperature or the like 'usually 10 to 90 minutes. When the step of increasing the total irradiation of the active light before the heating step is performed, the active light is irradiated The acid produced can promote the crosslinking reaction. Subsequently, a method of forming a cured film using the cured film of the positive photosensitive resin composition of the present invention will be specifically described. Q A method of preparing a composition solution: (A) component, B) the component, the component (C), and other formulation agents are mixed at a predetermined ratio and in any manner, and stirred and dissolved to prepare a composition solution. For example, the components may be dissolved in a solvent beforehand, and the components may be dissolved in a solvent. Prescribed ratio mixing to modulate The solution of the composition prepared as described above can also be used after filtration using a filter having a pore size of 0.2 μm. &lt;Manufacturing method of coating film&gt; Coating the composition solution on a predetermined substrate by using Heat-removed -38 - 201100966 Solvent (hereinafter referred to as pre-baking), a desired coating film can be formed. As the substrate, for example, a liquid crystal display element is provided, and a polarizing plate is provided and a black matrix is provided as necessary. A layer, a color filter layer, and a glass plate in which a transparent conductive circuit layer is further provided. The method of applying the substrate is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, a slit coating method, or the like can be used. In addition, the heating condition at the time of pre-baking is such that the repeating unit represented by the formula (1) in the component (A) of the unexposed portion does not dissociate, and the component (A) is formed in the alkaline smear liquid. The range of the solubility varies depending on the type of each component or the mixing ratio, and is preferably about 80 to 130 ° C and about 30 to 120 seconds. <Pattern forming method> On the substrate provided with the coating film, After the active light is applied to the mask of the fixed pattern, heat treatment (PEB) is performed as necessary, and the exposed portion is removed by using a developing solution to form an image pattern. For the emission of active light, a low-pressure mercury lamp, a high-pressure mercury lamp, or a Q ultra-high pressure mercury lamp can be used. For chemical light, excimer laser generating device, etc., it is preferable to use active light having a wavelength of 300 nm or more, such as g-ray, i-ray, or h-ray. Further, it is also possible to pass, for example, a long-wavelength cut filter and a short-wavelength cut filter as necessary. The illuminating light is adjusted by a spectroscopic filter of a band pass filter. As the developing liquid, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; or sodium carbonate or potassium carbonate can be used. Alkali metal carbonates; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, etc. -39-201100966; An aqueous solution of sodium or sodium decanoate. Further, an aqueous solution obtained by adding a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkali may be used as a developing solution. The pH of the developing solution is preferably 10.0 or more. The development time is usually 30 to 180 seconds, and the development method may be any of a liquid filling method and a dipping method. After the development, the water is washed for 30 to 90 seconds to form the desired pattern. &lt;Crosslinking step&gt; 〇When a pattern having an unexposed portion obtained by development is used, a heating device such as a hot plate or an oven is used to heat the predetermined time, for example, a hot plate at a predetermined temperature, for example, 180 to 250 ° C. 5 to 30 minutes, 30 to 90 minutes in the oven, the acid dissociable group of the component A is removed and carboxyl groups are generated, and the carboxyl group is reacted and crosslinked with the crosslinked functional group to form heat resistance and hardness. Such as an excellent protective film or interlayer insulating film. Further, by performing heat treatment in a nitrogen atmosphere, transparency can be improved. Further, it is preferable to cause the acid to be generated from the component (B) which is present in the unexposed portion by irradiating the active light to the substrate on which the pattern is formed before the heat treatment. [Examples] Subsequently, the present invention will be more specifically described by way of examples. However, the invention is not limited by such embodiments. [Synthesis Example 1: Synthesis of A-1] In a 500 ml 3-necked flask, 89.4 g (0.36 mol) of (1-n-butyr-40-201100966 oxyethoxycarbonyl)styrene, 34.lg (〇. 24 moles of glycidyl methacrylate and 300 ml of methyl isobutyl ketone, and a catalytic amount of 2,2,-azobis(methyl 2-methylpropionate) was added as a radical polymerization. The initiator was polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After cooling the reaction liquid, a large amount of heptane was injected to precipitate a polymer. After the crystals were obtained by filtration, the product was dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain a polymer A-1. (1-n-Butoxyethoxycarbonyl)styrene/glycidyl methacrylate] as a solution of diethylene glycol ethyl methyl oxime ether. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw/Mn) was 1.8. [Synthesis Example 2: Synthesis of A-2] In a 500 ml 3-necked flask, 66.1 g (0.3 mol) of (1-ethoxyethoxycarbonyl)styrene, 25.6 g (0.18 mol) of methacrylic acid ring was added. Oxypropyl propyl ester, 〇21.lg (0.12 mol) benzyl methacrylate and 300 ml of methyl isobutyl ketone, and a catalytic amount of 2,2'-azobis(2-methylpropionic acid) is added here. The methyl ester) was used as a radical polymerization initiator, and was polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After cooling the reaction liquid, a large amount of heptane was injected to precipitate a polymer. After crystallization was obtained by filtration, it was dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain a polymer A-2. (1-Ethoxyethoxycarbonyl)styrene/glycidyl methacrylate/benzyl methacrylate] as a solution of diethylene glycol ethyl methyl ether. -41 - 201100966 The molecular weight and molecular weight distribution of the obtained polymer were GPC measurement results based on phenethyl hydrazine, and the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw/Mn) was 1.8. [Synthesis Example 3: Synthesis of A-3] In a 500-neck 3-necked flask, 101.6 g (0.36 mol) of (1-hydroxyethoxycarbonyl)styrene, 23.1 g (0.18 mol) of acrylic epoxy was added. Propyl ester, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and 30 ml of methyl isobutyl ketone, and the amount of catalyst added 2,2'-azobis(2-methyl) Methyl propionate was used as a radical polymerization initiator and polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After cooling the reaction liquid, a large amount of heptane was injected to precipitate a polymer. After crystallization is obtained by filtration, it is dissolved in ethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain a polymer A-3. (1-Benzyloxyethoxycarbonyl)styrene/glycidyl acrylate/2-hydroxyethyl methacrylate] as a solution of diethylene glycol ethyl methyl ether. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 7,000, and the molecular weight distribution (Mw/Mn) was 1.8. [Synthesis Example 4: Synthesis of A-4] 66.1 g (0.3 mol) of (1-ethoxyethoxycarbonyl)styrene, 25.6 g (0.18 mol) of methacrylic acid was added to a 500-neck 3-neck flask. Glycidyl acrylate, 21. lg (0.12 mol) benzyl methacrylate and 300 ml of methyl isobutyl ketone, and a catalytic amount of 2,2'-azobis(2-methylpropionic acid) is added here. The methyl ester) was used as a radical polymerization initiator and was polymerized at 80 ° C under a nitrogen atmosphere for 6 hours - 42 - 201100966. After cooling the reaction liquid, a large amount of heptane was injected to precipitate a polymer. After crystallization is obtained by filtration, it is dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain a polymer A-4. (1-Ethoxyethoxycarbonyl)styrene/glycidyl methacrylate/benzyl methacrylate] as a solution of diethylene glycol ethyl methyl ether. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 5,000, and the molecular weight distribution (Mw/Mn) was 1.6. 〇 [Synthesis Example 5: Synthesis of A_5] In a 500 ml 3-necked flask, 79.3 g (0.36 mol) of (1-ethoxyethoxycarbonyl)styrene, 35.3 § (0.18 mol) of methacrylic acid 3 were added. 4-epoxycyclohexylmethyl ester (CYLCOMER 100 manufactured by DAICEL Chemical Co., Ltd.), 7.8 g (〇.〇6 mol) 2-hydroxyethyl methacrylate and 30 ml methyl isobutyl ketone, and a catalyst was added thereto. The amount of 2,2'-azobis(methyl 2-methylpropionate) was used as a radical polymerization initiator, and it was polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After the reaction solution was cooled, a large amount of heptane was injected to precipitate a polymer. After crystallization was obtained by filtration, it was dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain a polymer A-5. (1-Ethoxyethoxycarbonyl)styrene/3,4-epoxycyclohexylmethyl methacrylate/2-hydroxyethyl methacrylate] was used as a solution of diethylene glycol ethyl methyl ether. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC measurement using styrene as a standard, and the weight average molecular weight was about 9000, and the molecular weight distribution (Mw/Mn) of the molecule -43 to 201100966 was 1.8. [Synthesis Example 6: Synthesis of Α-6] In a 500 ml 3-necked flask, 84.3 g (0.36 mol) of (1-ethoxyethoxycarbonyl)-α-methylstyrene, 31.7 g (0.18 mol) was added. p-Vinylphenylepoxypropyl ether, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and 300 ml of methyl isobutyl ketone, and the amount of catalyst added 2,2'- Azobis(methyl 2-methylpropionate) was used as a radical polymerization initiator, and polymerization was carried out at 80 ° C for 6 hours under a nitrogen atmosphere. After cooling the reaction liquid, a large amount of heptane was injected to precipitate a polymer. After crystallization is obtained by filtration, it is dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain a polymer A-6. (1-ethoxyethoxycarbonyl)-α-methylstyrene/p-vinylphenylepoxypropyl ether/2-hydroxyethyl methacrylate] as diethylene glycol ethyl methyl ether Solution. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 5,000, and the molecular G amount distribution (Mw/Mn) was 1.7. [Synthesis Example 7: Synthesis of A-7] In a 500 ml 3-necked flask, 69.7 g (0.3 mol) of p-(2-oxocyclohexyl)hydroxycarbonylstyrene, 21.3 g (0.15 mol) of methacrylic acid ring was added. Oxypropyl propyl ester, 15.9 g (0.09 mol) benzyl methacrylate, 5.2 g (0 〇 6 mol) methacrylic acid and 300 ml methyl isobutyl ketone, and the amount of catalyst added 2, 2' -Azobis(methyl 2-methylpropionate) was used as a radical polymerization initiator, and it was polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After the reaction solution was cooled, -44 to 201100966 was injected into a large amount of heptane to precipitate a polymer. After crystallization is obtained by filtration, it is dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain a polymer A-7. (2-oxocyclohexyl)hydroxycarbonylstyrene/glycidyl methacrylate/benzyl methacrylate/methacrylic acid] as a solution of diethylene glycol ethyl methyl ether. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 7,000, and the molecular weight distribution (Mw/Mn) was 1.8. 〇V [Synthesis Example 8: Synthesis of A-8] In a 500 ml 3-necked flask, 66.1 g (0.3 mol) of (1-ethoxyethoxycarbonyl)styrene, 33.2 g (0.18 mol) of methyl group was added. (1-ethyl-3-oxetanyl)methyl acrylate, 21.1 g (0.12 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone, and the amount of catalyst added 2, 2 '-Azobis(methyl 2-methylpropionate) was used as a radical polymerization initiator, and it was polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After the reaction solution was cooled, it was poured into a large amount of G-yard to precipitate a polymer. After crystallization is obtained by filtration, it is dissolved in diethylene glycol ethyl ether, and the heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain a polymer A-8. (1-ethoxyethoxycarbonyl)styrene/(1-ethyl-3-oxetanyl)methyl methacrylate/benzyl methacrylate] as diethylene glycol ethyl methyl ether Solution. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 8 Å, and the molecular weight distribution (Mw/Mn) was 1.7. -45-201100966 [Synthesis of Polymers A-9 to A-15] Polymers A-9 to A-15 which will be disclosed later were obtained by the same method as the above production method. [Synthesis Comparative Example 1: Synthesis of A'_16] In a 500 ml 3-necked flask, 61.3 g (0.3 mol) of p-butoxycarbonylstyrene, 21.3 g (0.15 mol) of glycidyl methacrylate, 26.4 g (0.15 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone, and a catalytic amount of 2,2'-azobis(methyl 2-methylpropionate) was added thereto as a self-tanning agent. The initiator was polymerized from the base and polymerized at 80 ° C for 6 hours under a nitrogen atmosphere. After cooling the reaction liquid, a large amount of heptane was injected to precipitate a polymer. After crystallization was obtained by filtration, it was dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain a polymer A'-16 [ For the third butoxycarbonylstyrene/glycidyl methacrylate/benzyl methacrylate] as a solution of diethylene glycol ethyl methyl ether. The molecular weight and molecular weight distribution of the obtained polymer were measured by GPC using styrene as a standard, and the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw/Mn) was 1.8. [Synthesis Comparative Example 2: Synthesis of A' -1 7] 72 g of 4-hydroxystyrene (VP-8000, manufactured by Nippon Soda Co., Ltd.), 16.4 g of ethyl vinyl ether and 300 ml of acetic acid were placed in a 500 ml 3-neck flask. Ethyl ester, and a catalytic amount of p-toluenesulfonic acid was added thereto, and it was polymerized at room temperature for 3 hours under a nitrogen atmosphere. After adding a small amount of triethylamine, it was washed with pure water. Further, diethylene glycol ethyl ether was added to the ethyl acetate layer, and ethyl acetate contained in the solution was distilled off under reduced pressure to obtain polymer A'-17 (p. 1-ethoxyethoxystyrene/p-hydroxystyrene) was used as a solution of diethylene glycol ethyl methyl ether. The composition ratio of the obtained polymer to -1·ethoxyethoxystyrene unit and p-hydroxystyrene unit was determined to be about 3 5:65 from NMR. Further, as a result of GPC measurement using phenethylamine as a standard, the weight average molecular weight was about 9000, and the molecular weight distribution (Mw/Mn) was 1.2. [Synthesis of Comparative Example 3: Synthesis of A'-l 8] 合成 Synthesis A, -18 was carried out in accordance with Synthesis Example I of JP-A-2004-264623. 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile)' 200 parts by weight of diethylene glycol ethyl methyl ether in a 3-neck flask, followed by addition of 40 parts by weight of methacrylic acid 1-(cyclohexyloxy)ethyl ester, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, and 3 parts by weight of α-methylstyrene After the polymer is replaced by nitrogen, slowly start Q and stir. The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A, -12). The molecular weight of the obtained polymer was determined by GPC measurement using styrene as a standard, the weight average molecular weight was about 1 000, and the molecular weight distribution (Mw/Mn) was 1.9. [Examples 1 to 19 and Comparative Examples 1 to 4] (1) Preparation of Positive Photosensitive Resin Composition Solution As shown in Table 1 below, each component was mixed to obtain a uniform solution, and then a polytetrafluoroethylene having a pore diameter of 0.2 μm was used. The filter was filtered to prepare a positive photosensitive tree-47-201100966 lipid composition solution. (2) Evaluation of preservation stability The viscosity of the positive photosensitive resin composition solution at 23 ° C was measured using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. The viscosity of the composition after storage in a thermostat at 23 ° C for one month was measured. For the viscosity after the preparation, the viscosity after the room temperature was stored for one month was increased to less than 5%, and it was evaluated as 〇, and when it was 5% or more, it was X. The results are shown in Table 2 below. (3) Evaluation of sensitivity and residual film rate during development ^ After spin coating a positive photosensitive resin composition solution on a silicon wafer having a tantalum oxide film, preheating on a hot plate at 10 ° C Bake for 60 seconds to form a coating film having a film thickness of 3 μm. • Subsequently, an i-ray stepper (FPA-3 000 i5+ manufactured by CANON Corporation) was used to perform exposure through a prescribed mask. Then, after baking at 50 ° C for 60 seconds, the image was visualized at 23 ° C for 60 seconds using an alkaline developing solution (2.38 mass% or 0.4% by mass aqueous tetramethylammonium hydroxide solution) shown in Table 2. Wash with ultrapure water for 1 minute. By these operations, the optimum exposure amount (Eopt) when the line of 5 μm is resolved with a gap of 1:1 is taken as the sensitivity. The film thickness of the unexposed portion after the development was measured, and the ratio of the film thickness after coating (the thickness of the unexposed film after development + the film thickness after coating χΐ00 (%)) was evaluated. The residual film rate at the time of development. The evaluation results of the sensitivity and the residual film rate at the time of development are shown in Table 2. (4) The heat resistance is the above (3), except that a transparent substrate (manufactured by CORNING-48-) is used. 201100966 CORNING 1 73 7) In addition to the tantalum wafer having a tantalum oxide film, a coating film is formed in the same manner as in the above (3), and a proximity exposure apparatus (UX-1 000SM manufactured by USHIO Electric Co., Ltd.) is used and adhered. The photomask was exposed to ultraviolet light having a light intensity of 18 mW/cnx2 at 3 65 nm. Subsequently, the alkaline developing solution (2.38 mass% or 0.4 mass% aqueous solution of tetramethylammonium hydroxide) described in Table 2 was used. After exposure at 23 ° C for 60 seconds, it was rinsed with ultrapure water for 10 seconds. By these operations, the line and the gap of ΙΟμηη were made into a 1:1 pattern.

The obtained pattern was further exposed to full exposure for 100 seconds, and heated in an oven at 220 ° C for 1 hour to form a heat-cured film on the glass substrate. The heat resistance was evaluated by measuring the rate of change of the bottom size before and after heat curing (1 - the bottom size of the heat-cured film + the bottom size after development) xl 〇〇 (%). The evaluation results of heat resistance are shown in Table 2. (5) Transmittance and Adhesiveness A coating film was formed in the same manner as in the above (4), and an alkaline developing solution (2.3% by mass or 0.4% by mass) of Q shown in Table 2 was used without exposure. After the image was developed at 23 ° C for 60 seconds, it was rinsed with ultrapure water for 1 〇 second. Subsequently, using a proximity exposure apparatus (UX-1000SM manufactured by USHIO Electric Co., Ltd.), full exposure was performed for 100 seconds using ultraviolet rays having a light intensity of 18 mW/cm 2 at 3 65 nm. Subsequently, a heat-cured film was formed on the glass substrate by heating at 240 ° C for 1 hour in an oven. The obtained heat-cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer (U-3 000: manufactured by Konica Minolta Co., Ltd.). -49- 201100966 In the heat-cured film, a cutter was used, and the cutter was cut at intervals of 1 mm in the longitudinal and lateral directions, and the adhesive tape peeling test was performed using a Scotch Tape. The adhesion of the cured film to the stomach was evaluated from the area of the cured film transferred to the adhesive tape surface. When the area is less than 1%, it is evaluated as 〇, and when it is less than 5%, it is X when it is Δ' 5% or more. The evaluation results of transmittance and adhesion are shown in Table 2. [Example 20] The composition of Example 18 was used and patterned as follows.感光 A photosensitive resin composition was slit-coated on a glass substrate of 2,16 Å x 2,460 mm, and pre-baked on a hot plate at 90 ° C for 90 seconds to remove the solvent to form a coating film having a film thickness of 3 μm. Subsequently, the most suitable exposure exposure was carried out using a FX_85S (manufactured by NIKON) and passing through a mask of a contact hole pattern having a diameter of 15 μm. After the exposure, spray development was carried out at 23 ° C for 60 seconds using a 4% by mass aqueous solution of tetramethylammonium hydroxide, and then rinsed with ultrapure water for 1 minute. By these operations, a pattern is obtained. Further, the obtained pattern was subjected to total exposure, and Q was heated at 220 ° C for 1 hour in an oven to form a heat-hardened film on the glass substrate. When viewed with an electron microscope, the cone-shaped perfect contact hole pattern having a bottom diameter of 15 μm was used. [Example 21] A contact hole pattern was produced in the same manner as in Example 20 except that the exposure was changed to a laser having a wavelength of 35 5 nm. A perfect contact hole pattern of 5 [) was obtained in the same manner as in Example 20. Further, the laser device uses "AEGIS" manufactured by V-Technology. -50- 201100966

Sensitizer part by mass 1 1 1 t 1 1 1 1 1 &lt;N (N type 1 1 1 1 1 1 1 1 1 DBA DBA surfactant mass part CN 〇 &lt;S Ο CS 〇&lt;N 〇CS 〇 CS o fS 〇CN 〇CN 〇(N 〇CS o type (N &lt;N 13⁄4 mm cn Ph buried mass 0.02 0.02 0.02 i 0.02 0..01/0.02 1 ; 0.02 0.02 0.02 0.02 0.02 0.02 Type Ξ CN w W E1/E2 ww Ξ ω (N ω &lt; NWQ mass parts m cn ΓΛ cn m KD &lt;N yn cn 1 m Type 1 - Η (NQ s 1 * - H i - H 〇 mass parts Ο o 〇 o V £ &gt; O 〇1 oo Type cs G 3 i-1 1 GG mass scoop · cs &lt;N m 00 cn CO &lt;N 赛tlnrli Ξ (N PQ cn CQ 兮CQ B1/B4 s 5 &lt;N CQ CQ SO Ό CQ &lt; mass parts ο ooooo O 100 o O r«H o kind &lt; A-2 tn &lt; ! Λ. 1 A-5 A-6 A-7 A-8 &lt; A-9 A- 10 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 201100966

&lt;Ν (N , &lt; N tN (N (N &lt; N (N 1 1 1 1 &lt; ΠΊ &lt; m &lt;&lt; c &lt; 1 &lt;&lt;&lt; QQQWQWQ w QWQWQ CN Ο O (N 〇 &lt;N 〇(N 〇cs o CN 〇(N 〇&lt;N 〇(N o CN 〇m ro Ph m IXi mm Pl mm cn 5: s: sssss S gsssgg ο 〇oooooo 〇o 〇o cs ti] ω CN ω (N PJ CN (NW cs ω CN Ξ Ξ w Ξ mc〇ro mmmm 1 1 I—( T-^ TH F—H rH T—H 1 1 o OO ooooooo 1 1 QGGGGGGG f**~4 1— H 1 1 cN (N (N CN (N CN iTi (N (N m ΓΛ 〇Ό PQ v〇CQ so Ό CQ 0Q Ό CQ 00 PQ S s B, 9 B, 9 oooo F-H 100 o O TH o O 〇o ! 100 ΓΝ) »—H m inch ir> Os On m 00 00 &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; $ cs CO Ό Ό »—H 卜 00 Os (S m寸m 琢m 习 辑 辑 su su ; ; ; ; ; 蛔 蛔 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J The components, basic compounds, solvents, and surfactants are as follows. Component The number of the right side of the constituent unit indicates the molar ratio of the constituent unit. CH3

Mw: 8000 Mw/Mn: l.8 A-1 :

°°〇vW

00 Ο CHa Α一 2 : ί: CH5 CH3

Mw: 8000 Mw/Mn: K8 coo. .och2ch3 A· CHa

C〇〇v^s? 〇〇〇^〇aO

Mw: 7000 Mw/Mn: 1.8

COOv OCH

Coo-ch2\J

Mw: 5000 Mw/Mn: 1.6 C00v . OCH2CH3 CHa -53- 201100966 A-5 :

CH CH3 CH3 Red ♦ Today CH岵· 十吹〇* COO /- coov •0

OH

Mw: 9000 Mw/Mn: 1.8 coo 丫och2ch3 ch3 A-6 : CHa ❹

-CH ch3 c〇〇v/\

Mw: 5000 Mw/Mn: 1.7

OH C00n.0CH2CH3 ch3 A-7 : CH3 ch3 ch3 -CH^i Sc-Ch%5* *-fC-CH^5* ^°°N^S? COO-CH2-^^ Cl ΪΟΟΗ

Mw: 7000 Mw/Mn: 1.8 COO,

〇 A-8 : CH3

_c味;·十响 *会CHho·产^ coo p〇 coo-ch2-^^

Mw: 8000 Mw/Mn: 1.7 ch2ch3 CO〇v〇CH2CH3 ch3 54- 201100966 A-9

Mw: 8000 Mw/Mn: 1.9

A-10

Mw: 30000 Mw/Mn: 1.4 A-11

〇

Mw: 8000 Mw/Mn: 17 -55- 201100966 A-13

. People 〇^^OH

Mw: 8000 Mw/Mn: 2.1

A-14

〇人〇^/OH

Mw: 8000 Mw/Mn: 1.9 A-15

-56- 201100966 A'-16

Mw: 8000 Mw/Nto: l, 8 Α, · 17

Mw; 9000 Mw/Mn: 1.2 0-〒 h-och2ch3 〇h ch3 Α_·18

CH 3 COO. &gt;

Ch3

Mw: 11000 Mw/Mn: 1.9 (B) Component B 1 : IRGACURE PAG1 03 (manufactured by CIBA SPECIALTY CHEMICALS)

-57- 201100966 B2 : IRGACURE PAG1 08 (manufactured by CIB A SPECIALTY CHEMICALS)

CH3 CN Ο

It

N**0—S—n-CaHi7 O B3 : CGI 1 3 8 0 (manufactured by CIBA SPECIALTY CHEMICALS)

O o B4 : IRGACURE PAG121 (manufactured by CIBA SPECIALTY CHEMICALS)

B5: CGI 725 (manufactured by CIBA SPECIALTY CHEMICALS)

0 II • s- 11 o B6: PAI-1001 (manufactured by MIDORI Chemical Co., Ltd.) -58- 201100966

B7: PAI-1001 (manufactured by MIDORI Chemical Co., Ltd.)

B8: α-(4-toluenesulfonyloxyimino)benzyl cyanide (synthesis according to the method described in paragraph 0108 of JP-A-2002-52 845 1).

B'9: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate (C) component C1 : JER1 00 1 (JAPAN Ε Ρ Ο XY RE S IN S (share) C2: JER834 (JAPAN EPOXY RESINS) -59- 201100966 C3: JER157S70 (JAPAN EPOXY RESINS) C4: JER154 (JAPAN EPOXY RESINS) (D) Component D1 : γ- Glycidoxypropyltrimethoxydecane D2: β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane D3: γ-methylpropenyloxypropylmethoxydecane [alkaline Compound] Ε 1 : 4 -Dimethylaminopyridinium 2: 1,5-diazabicyclo[4,3,0]-5-nonene [surfactant] FI : Furorad F-430 (manufactured by 3M Company) F2 : MEGAFAC R-〇8 (made by Dainippon INK Chemical Industry Co., Ltd.) F3: P〇lyF〇xPF-6320 (made by OMNOVA) W-3 :

W-3

2〇Μ% βΟΧϋ% Mw: 1500 [sensitizer] DBA: 9,10-dibutoxy oxime -60- 201100966

[Table 2] Developing solution concentration (% by mass) Preservation stability sensitivity (Eopt) (mJ/cm2) Residual film rate (%) Heat resistance (%) Adhesive transmittance (%) (240% / hour heating After) Example 1 0.4 〇36 98 &lt;1 〇98 Example 2 2.38 〇46 99 &lt;1 〇97 Example 3 0.4 〇42 98 &lt;1 〇98 Example 4 2.38 〇38 98 &lt;1 〇98 Example 5 0.4 〇43 99 &lt;1 〇97 Example 6 0.4 〇40 98 &lt;1 〇97 Example 7 0.4 〇37 99 &lt;1 〇98 Example 8 0.4 〇43 99 &lt;1 〇97 Example 9 0.4 〇38 98 &lt;1 〇98 Example 10 0.4 〇32 98 &lt;1 〇97 Example 11 0.4 〇36 99 &lt;1 〇97 Example Π 0.4 〇29 98 &lt;1 〇97 Example 13 0.4 〇28 98 &lt;1 〇97 Example 14 0.4 〇28 98 &lt;1 〇97 Example 15 0.4 〇31 98 &lt;1 〇97 Example 16 0.4 〇35 99 &lt;1 〇97 Example 17 0.4 〇32 98 &lt;1 〇97 Example 18 0.4 〇27 98 &lt;1 〇97 Example 19 0.4 〇27 98 &lt;1 〇97 Comparative Example 1 0.4 〇 No image formation 〇97 Comparative Example 2 2.38 〇51 97 &lt;20 〇70 Comparative Example 3 2.38 〇&gt;800 99 &lt;1 X 85 Comparative Example 4 0.4 〇&gt;800 99 &lt;1 X 86 -61 - 201100966 From Table 2, it is clear that the positive photosensitive resin composition of the present invention is sensitive. The cured film having excellent heat resistance, adhesion, transmittance, and the like can be obtained by being excellent in storage, stability, and storage stability. [Simple description of the schema] Sister 〇 [Main component symbol description] 蛀.

-62-

Claims (1)

201100966 VII. Patent application scope: 1. A positive photosensitive resin composition characterized by: (A) a resin containing a constituent unit represented by the following general formula (1) and having a carboxyl group a constituent unit of a functional group which forms a covalent bond by reaction, and is alkali-insoluble or alkali-insoluble and dissociable-based dissociates to become alkali-soluble; and (B) a compound which generates an acid by irradiation with active light. In the formula (1), R1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, and R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group, but R2 and R3 are simultaneously hydrogen. In the case of an atom, R4 represents a linear, branched or cyclic alkyl group or an aralkyl group which may be substituted, and R2 or R3 may be bonded to R4 to form a cyclic ether. 2. The positive photosensitive resin composition according to the first aspect of the invention, which further comprises (C) a compound having two or more epoxy groups in the molecule (except for the above A). 3. A positive photosensitive resin composition as claimed in claim 1 or 2 wherein the component (B) contains a compound which generates an acid by an active light of -63 to 201100966 having a wavelength of 30 〇 11111 or more. 4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B) contains an oxime sulfonate represented by the following formula (2). a compound of the formula, 〇^C*N-0-S-R5 (2) 0 in the formula (2), R5 represents a linear, branched, cyclic alkyl group which may also be substituted, or An aryl group that can be substituted. 5. The positive photosensitive resin composition of claim 4, wherein the compound containing a sulfonic acid sulfonium group represented by the formula (2) is a compound represented by the following formula (2-1). In the formula (2-1), the R 5 group is the same as R5 in the formula (2). The X system represents a linear or branched alkyl group, an alkoxy group or a halogen atom. The m system represents an integer of 〇~3. When m is 2 or 3, the plurality of Xs may be the same or different. 6. The positive photosensitive resin composition of claim 4, wherein the compound containing a sulfonic acid sulfonium group represented by the general formula (2) is a compound of the following formula (2 _ 2) -64 - 201100966 a compound expressed, In the formula (2-2), R5 is the same as R5 in the formula (2), 0 R6 represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cyano group or a nitro group, and 1 represents a group of 0 to 5 Integer. When 1 is 2 or more, a plurality of R6s may be the same or different. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the functional group-based epoxy group capable of reacting with the carboxyl group to form a covalent bond. 8. The positive-type photosensitive resin composition of claim 7, wherein the functional group having a functional group capable of reacting with the carboxyl group to form a covalent bond is derived from the following general formula (3) to (5) a constituent unit of a radical polymerizable monomer represented by any one of -65- 201100966 In the general formulae (3) to (5), R7 represents a nitrogen atom, a methyl group or a halogen atom, and R8 to R15 each independently represent a hydrogen atom or an alkyl group, and X represents a divalent linking group. , η is an integer from 1 to 10 0. The positive photosensitive resin composition according to any one of claims 1 to 6, which has a 0-functional oxetane group which can react with the carboxyl group to form a covalent bond. The positive photosensitive resin composition of claim 9, wherein the constituent unit having a functional group capable of reacting with the carboxyl group to form a covalent bond is derived from the following formula (6) a constituent unit of a radical polymerizable monomer, In the formula, R7 represents a hydrogen atom, a methyl group or a halogen atom, and R·8 to R12 each independently represent a hydrogen atom or an alkyl group, X represents a divalent linking group, and η is an integer of 1 to 10; The positive photosensitive resin composition according to any one of claims 1 to 10, which further comprises (D) an adhesion aid. -66-201100966 12 - A method for forming a cured film, comprising: coating a positive photosensitive resin composition as in any one of claims 1 to 11 on a substrate and drying it to form a step of coating a film; a step of exposing through a photomask and using active light; a step of developing an image using an alkaline developing solution; and a step of heat-treating the obtained pattern. 13. The method for forming a cured film according to claim 12, wherein after the pattern is formed by development using an alkaline developing solution, the step of comprehensively exposing is further performed before the step of heat-treating the resulting pattern of Q to . 1 4 A cured film formed by a method of forming a cured film as disclosed in claim 12 or 13. A liquid crystal display element having a cured film as in claim 14 of the patent application. 16. An integrated circuit component having a cured film as in claim 14 of the patent application. 17. A solid-state photographic element having a sturdy film as in claim 14 of the patent application. 18. An organic EL device having a hardened film as in claim 14 of the patent application. -67- 201100966 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. ❹ 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 〇 〇