Positive photosensitive resin composition, positive photosensitive resin sheet, cured product, method for producing cured product, semiconductor device, and display device

Abstract

The purpose of the present invention is to provide a high-sensitivity positive photosensitive resin composition which has a small amount of film reduction during alkali development and is capable of shortening the exposure time. The present invention is a positive photosensitive resin composition containing a heat-resistant resin containing a nitrogen atom and a photoacid generator (B), the resin (A) containing a constituent unit represented by formula (1), and the fluorine atom content in the whole resin being 15 mass% or less, with the total amount of the whole resin contained in the composition being 100 mass%. (In formula (1), R1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, and R2 represents a monovalent acid-decomposable group having 3 to 20 carbon atoms; m represents an integer of 0-4; n represents an integer of 1-4; * represents a bonding site, and a and b each independently represent an integer of 1 or 2. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition, a positive photosensitive resin sheet, a cured product, a method for producing the cured product, a semiconductor device, and a display device. Background Art

[0002] For surface protection films or interlayer insulating films used in semiconductor devices, insulating layers of organic electric field light-emitting elements, or planarizing films of thin film transistor (TFT) substrates, polyimide resins or polybenzoxazole resins with excellent heat resistance, electrical insulation, and mechanical properties are widely used. In recent years, photosensitive resin compositions that impart photosensitivity to these resins themselves or their precursors (hereinafter, these photosensitive resin compositions are referred to as polyimide-based photosensitive resin compositions) have been used. By using polyimide-based photosensitive resin compositions, the pattern processing process can be simplified and the complicated manufacturing process can be shortened.

[0003] Regarding polyimide-based photosensitive resin compositions, there are proposed positive materials in which the exposed portion is easily soluble in a developer and pattern processing is possible, and negative materials in which the composition itself is easily soluble and the exposed portion is insoluble in a developer. Generally speaking, positive-type materials have better resolution than negative-type materials, so positive-type polyimide-based photosensitive resin compositions are used in applications requiring fine processability.

[0004] As positive-type polyimide photosensitive resin compositions, there are known polyimide photosensitive resin compositions obtained by adding a quinonediazide compound to polyimide, polybenzoxazole, a polyimide precursor or a polybenzoxazole precursor (for example, refer to Patent Document 1), or polyimide photosensitive resin compositions obtained by adding a photoacid generator to a polyamide containing a protective group that can be detached in the presence of an acid (for example, refer to Patent Document 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2011-180473

[0008] Patent Document 2: Japanese Patent Application Publication No. 2011-221173 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In recent years, due to the increase in the size of substrates used and the improvement in productivity, in order to shorten the exposure time and further improve the aperture ratio and in-plane uniformity of film thickness after development, it has become a problem to reduce the amount of film reduction in the unexposed part during development.

[0011] The technology described in Patent Document 1 is a technology that combines an alkali-soluble resin with a quinonediazide. The quinonediazide compound interacts with the alkali-soluble resin to reduce the solubility of the composition relative to the alkaline developer. On the other hand, since it becomes an indene carboxylic acid compound due to the photochemical reaction caused by exposure, it acts as a dissolution promoter relative to the alkaline developer, so that the difference in dissolution rate (dissolution contrast) is shown between the unexposed part and the exposed part, so that pattern processing can be performed. Therefore, the sensitivity depends on the amount of quinonediazide compound added. However, if the amount of quinonediazide compound added is increased, the photochemical reaction rate is reduced due to the light absorption of the quinonediazide compound itself. Therefore, it is difficult to take into account the shortening of the exposure time and the less film reduction.

[0012] The technology of Patent Document 2 is a technology that replaces the hydrogen atoms of the hydroxyl groups in the alkali-soluble polyamide with a tert-butoxycarbonyl group (hereinafter, also referred to as a t-Boc group) to make an alkali-insoluble resin, and combines it with a photoacid generator. The technology can generate an acid from the photoacid generator in the exposed part, and the acid reacts with the t-Boc group to release the t-Boc group from the polyamide (hereinafter, referred to as deprotection), thereby changing the polyamide from alkali-insoluble to alkali-soluble. As a result, the following technology is obtained: a dissolution contrast is generated between the exposed part and the unexposed part, and a positive pattern processing can be performed. In the technology, there are problems that the exposure time cannot be shortened due to the low reaction rate of the t-Boc group with the acid and the small dissolution contrast between the exposed part and the unexposed part, and a problem of residue being generated in the pattern opening.

[0013] An object of the present invention is to provide a positive photosensitive composition having high sensitivity to shorten exposure time, small film reduction during development, and small residue in pattern openings.

[0014] Technical means of solving problems

[0015] The present invention is as follows.

[0016] (1) A positive photosensitive resin composition comprising: (A) a heat-resistant resin containing nitrogen atoms; and (B) a photoacid generator, wherein the resin (A) contains a constituent unit represented by formula (1), and the total amount of all resins contained in the composition is set to 100% by mass, and the fluorine atom content in all resins is not more than 15% by mass.

[0017] [Chemistry 1]

[0018]

[0019] In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2It is a monovalent acid-decomposable group having 3 to 20 carbon atoms. m represents an integer of 0 to 4, and n represents an integer of 1 to 4. * represents a bonding site, and a and b each independently represent an integer of 1 or 2.

[0020] (2) The positive photosensitive resin composition according to (1), wherein the heat-resistant resin (A) containing a nitrogen atom is one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof.

[0021] (3) The positive photosensitive resin composition according to (1) or (2), wherein the acid-decomposable group is an oxymethyl group.

[0022] (4) The positive photosensitive resin composition according to any one of (1) to (3), wherein OR 2 The pKa of the phenolic hydroxyl group-containing structure generated by acid decomposition of the hydroxyl group is 11 or more.

[0023] (5) The positive photosensitive resin composition according to any one of (1) to (4), wherein the R 2 At least one of is a group represented by formula (2) or a group represented by formula (3).

[0024] [Chemistry 2]

[0025]

[0026] In formula (2) and formula (3), R 3 R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. 4 R represents an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. 5 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms. p represents an integer of 0 to 2, and q represents an integer of 0 to 2. * represents a bonding site.

[0027] (6) The positive photosensitive resin composition according to any one of (1) to (5), wherein the R 2 At least one of is a group represented by formula (4) or a group represented by formula (5).

[0028] [Chemistry 3]

[0029]

[0030] In formula (4) and formula (5), R 6 and R 7 Each independently represents an alkyl group having 1 to 6 carbon atoms. 8represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms. r represents an integer of 0 to 2, and s represents an integer of 0 to 2. * represents a bonding site.

[0031] (7) The positive photosensitive resin composition according to any one of (1) to (5), wherein the formula (1) is the formula (6).

[0032] [Chemistry 4]

[0033]

[0034] In formula (6), R 2 , a and b represent the same meanings as the same symbols in the formula (1). L represents a direct bond, -C(CH3)2-, 9H-fluorene-9,9-diyl. m1 and m2 each independently represent an integer of 0 to 2. n1 and n2 each independently represent an integer of 0 to 2. Wherein 1≤(n1+n2)≤4 is satisfied. * represents a bonding site.

[0035] (8) The positive photosensitive resin composition according to claim 2, wherein the resin (A) contains a structural unit represented by formula (7) and / or a structural unit represented by formula (8).

[0036] [Chemistry 5]

[0037]

[0038] In formula (7), X1 represents a tetravalent organic group having 4 to 50 carbon atoms, or a constituent unit of formula (1). Y1 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X1 and Y1 is a constituent unit of formula (1), and when X1 is a constituent unit of formula (1), a=b=2, and when Y1 is a constituent unit of formula (1), a+b=2. * represents a bonding site.

[0039] [Chemistry 6]

[0040]

[0041] In formula (8), X2 represents a divalent organic group having 4 to 50 carbon atoms, or a constituent unit of formula (1). Y2 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X2 and Y2 is a constituent unit of formula (1), and a=b=1. * represents a bonding site.

[0042] (9) A positive photosensitive resin composition according to (8), wherein in the formula (7), X1 is a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms; and / or in the formula (8), X2 is a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms.

[0043] (10) The positive photosensitive resin composition according to (2), wherein the resin (A) has a structural unit represented by formula (9), and when the OH group and OR 2 The total number of groups is defined as M1, and the OH group and OR group are removed from the structure of formula (9). 2 When the molecular weight of the remaining structural part after the group is defined as N1, the value of M1 / N1 is 0.004075 or more, and / or

[0044] The resin (A) has a structural unit represented by formula (10). When the OH group and OR 2 The total number of the groups is defined as M2, and the OH group and the OR group are removed from the structure of formula (10). 2 When the molecular weight of the remaining structural part after the group is defined as N2, the value of M2 / N2 is 0.004075 or more.

[0045] [Chemistry 7]

[0046]

[0047] In formula (9) and formula (10), R 1 , R 2 , m and n have the same meanings as the same symbols in the above formula (1). X3 represents a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. X4 represents a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms.

[0048] (11) The positive photosensitive resin composition according to any one of (1) to (10), wherein the (B) photoacid generator comprises a nonionic photoacid generator.

[0049] (12) The positive photosensitive resin composition according to any one of (1) to (11), wherein the (B) photoacid generator contains a photoacid generator having an acid dissociation constant (pKa) of an acidic group generated by light in the range of -14 to 2.

[0050] (13) The positive photosensitive resin composition according to any one of (1) to (12), wherein the (B) photoacid generator comprises an oxime sulfonate compound and / or an imide sulfonate compound.

[0051] (14) The positive photosensitive resin composition according to any one of (1) to (13), further comprising (C) an amine compound having a conjugate acid having a pKa in the range of 4.5 to 10.8.

[0052] (15) The positive photosensitive resin composition according to any one of (1) to (14), further comprising (D) a solvent, wherein the solvent (D) comprises an aprotic solvent having 3 to 12 carbon atoms and a relative dielectric constant in the range of 5 to 20.

[0053] (16) A positive photosensitive resin sheet obtained by forming the positive photosensitive resin composition according to any one of (1) to (15) into a sheet on a support.

[0054] (17) A cured product obtained by curing the positive photosensitive resin composition according to any one of (1) to (15).

[0055] (18) A method for producing a cured product, comprising: a) a step of coating the positive photosensitive resin composition according to any one of (1) to (15) on a substrate and drying it to form a positive photosensitive resin film, or a step of using the positive photosensitive resin sheet according to (16) to thermally press-bond the positive photosensitive resin composition of the present invention to a substrate; b) a step of exposing the positive photosensitive resin film or the positive photosensitive resin composition after thermal pressing; c) a step of eluting or removing the exposed portion of the exposed positive photosensitive resin film or the exposed portion of the positive photosensitive resin composition after thermal pressing using an alkaline aqueous solution to perform development; and d) a step of heating the developed positive photosensitive resin film or the positive photosensitive resin composition after thermal pressing.

[0056] (19) A semiconductor device in which the hardened material according to (17) is arranged as a protective film of a semiconductor or an interlayer insulating film between redistribution wirings.

[0057] (20) A display device comprising: a first electrode formed on a substrate, an insulating layer formed on the first electrode in a manner that partially exposes the first electrode, and a second electrode arranged opposite to the first electrode, wherein the insulating layer includes the cured product according to (17).

[0058] (21) A display device including a planarizing film provided so as to cover the unevenness on a substrate on which a thin film transistor (TFT) is formed, wherein the planarizing film includes the cured product according to (17).

[0059] Effects of the Invention

[0060] Since the positive photosensitive composition of the present invention has high sensitivity, the exposure time can be shortened, and the film reduction amount during development is small, and the residue in the pattern opening portion is small. DETAILED DESCRIPTION

[0061] The present invention is a positive photosensitive resin composition, comprising: (A) a heat-resistant resin containing nitrogen atoms; (B) a photoacid generator,

[0062] The resin (A) comprises a structural unit represented by formula (1), and the fluorine atom content in the total resin is 15% by mass or less, with the total amount of the total resins contained in the composition being 100% by mass.

[0063] [Chemistry 8]

[0064]

[0065] In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 It is a monovalent acid-decomposable group having 3 to 20 carbon atoms. m represents an integer of 0 to 4, and n represents an integer of 1 to 4. * represents a bonding site, and a and b each independently represent an integer of 1 or 2.

[0066] The positive photosensitive resin composition of the present invention contains (B) a photoacid generator, and an acid can be generated in the composition by irradiating exposure light corresponding to the contained photoacid generator. The generated acid can act on R in the heat-resistant resin (A) containing a nitrogen atom and containing a structural unit represented by formula (1). 1 -OR 2 OR in the structure 2 The key between them is converted to R 1 -OH.R 1 -OH functions as a solubility group in an alkaline aqueous solution. Therefore, the positive photosensitive resin composition of the present invention can show a solubility contrast in an alkaline aqueous solution between an unexposed portion and an exposed portion, and thus can form a positive relief pattern in which the exposed portion is dissolved.

[0067] Therefore, in this specification, R 2 In addition, since OR can be decomposed by acid 2 The structure is converted to hydroxyl, so sometimes OR 2 The structure of is called "a hydroxyl group protected by an acid-decomposable group". 1 -OR 2 is converted to R 1 The -OH case is called "deprotection".

[0068] <(A) Heat-resistant resin containing nitrogen atoms>

[0069] The heat-resistant resin containing nitrogen atoms refers to a resin having a nitrogen atom-containing group such as an amide group or a urea group, or a nitrogen atom-containing heterocyclic ring such as an imide ring or an oxazole ring in the repeating structure of the polymer, and having a 5% weight loss temperature of 200° C. or higher.

[0070] Furthermore, a precursor resin that becomes a resin having a heterocyclic ring containing a nitrogen atom such as an imide ring or an oxazole ring by chemical ring closure or thermal ring closure and having a 5% weight loss temperature of 200° C. or higher is also included.

[0071] Examples of the heat-resistant resin containing a nitrogen atom include polyimide, polyamide, polyurea, polyamideimide, polyazole (polybenzimidazole, polybenzoxazole, polybenzothiazole), etc. Among them, polyamide includes a polyimide precursor and a polyazole precursor.

[0072] As more preferred (A) heat-resistant resin containing a nitrogen atom, at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof is preferred.

[0073] The so-called polyimide is a polymer containing an imide bond in a repeating unit. The polyimide can be synthesized using a known method. For example, it can be obtained by the following method: for the reaction product obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride or tetracarboxylic diester dichloride, etc. with diamine, corresponding diisocyanate compound or trimethyl silylated diamine, etc., it is dehydrated and ring-closed by heating or reaction using a catalyst such as an acid or base. Therefore, the polyimide has a tetracarboxylic acid and / or its derivative residue, and a diamine and / or its derivative residue.

[0074] The reaction product before dehydration and ring closure is called a polyimide precursor, and the formation of imide bonds by dehydration and ring closure is called imidization. The ratio of imidization of the groups capable of forming imide bonds in the polyimide precursor is called imidization rate.

[0075] The imidization rate of the polyimide is preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 80% or more. An imidization rate of 30% or more is preferred because it can reduce the amount of degassing at high temperatures and improve the reliability of the cured product described later.

[0076] The so-called polybenzoxazole is a polymer containing a benzoxazole structure in a repeating unit. The polybenzoxazole can be synthesized using a known method. For example, it can be obtained by the following method: the reaction product obtained by reacting a bisaminophenol compound with a dicarboxylic acid, or a corresponding dicarboxylic acid chloride or a dicarboxylic acid active ester, etc., is dehydrated and ring-closed by heating or by reacting an acid, a base, acetic anhydride or a carbodiimide compound, etc. Therefore, it has a dicarboxylic acid residue and a bisaminophenol residue.

[0077] Polyamide is a polymer having an amide bond in a repeating unit. Polyamide can be synthesized by a known method.

[0078] The polyamide is preferably a polyimide precursor or a polybenzoxazole precursor. A polyimide precursor is a polyamide that can be converted into a polyimide by heating. By using a polyamide as a polyimide precursor, a resin film with high heat resistance can be made. The polyimide precursor can be synthesized using a known method. For example, it can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride or a tetracarboxylic diester dichloride, etc. with a diamine, a corresponding diisocyanate compound or a trimethylsilylated diamine, etc. The polybenzoxazole precursor is a polyamide that can be converted into a polybenzoxazole by heating. By using a polyamide as a polybenzoxazole precursor, a resin film with high heat resistance can be made. The polybenzoxazole precursor can be synthesized using a known method. For example, it can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, or a corresponding dicarboxylic acid chloride or a dicarboxylic acid active ester, etc.

[0079] These copolymers refer to copolymers of two or more selected from the group consisting of polyimide, polybenzoxazole, and polyamide.

[0080] The resin (A) contained in the positive photosensitive resin composition of the present invention is preferably a copolymer of two or more selected from the group consisting of polyimide, polybenzoxazole, and polyamide. By using a copolymer, it is easy to achieve a balance between heat resistance, solvent solubility, and alkali solubility.

[0081] The (A) resin contained in the positive photosensitive resin composition of the present invention is preferably sealed at the main chain end with a known monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, monoactive ester compound or other end-capping agent. By sealing the main chain end with an end-capping agent, the storage stability of the positive photosensitive resin composition can be improved. The introduction ratio of the monoamine used as an end-capping agent is preferably 0.1 mol% or more relative to the total amine components, particularly preferably 5 mol% or more, and preferably 60 mol% or less, particularly preferably 50 mol% or less. The introduction ratio of the anhydride, monocarboxylic acid, monoacyl chloride compound or monoactive ester compound used as an end-capping agent is preferably 0.1 mol% or more relative to the diamine component, particularly preferably 5 mol% or more, and preferably 100 mol% or less, particularly preferably 90 mol% or less. Multiple different end groups can be introduced by reacting multiple end-capping agents.

[0082] The weight average molecular weight of the resin (A) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and still more preferably 7,000 to 60,000, in terms of polystyrene obtained by gel permeation chromatography. By setting the weight average molecular weight to the above range, it is easy to satisfy all of good solvent solubility, good solubility in a developer, and high mechanical strength. In the present invention, the weight average molecular weight is obtained by the method described below.

[0083] <(A) Resin contains a structural unit represented by formula (1)>

[0084] In the positive photosensitive resin composition of the present invention, the resin (A) contains a structural unit represented by the formula (1).

[0085] [Chemistry 9]

[0086]

[0087] In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 It is a monovalent acid-decomposable group having 3 to 20 carbon atoms.

[0088] R 1 Preferably, it has an aromatic ring, and the aromatic ring is connected to the OH group or OR 2 The aromatic ring is more preferably phenyl or naphthyl. 1 Take this structure, OR 2 The alkaline solubility of the OH group after the deprotection of the group is improved, so that a positive relief pattern with less residue can be easily obtained.

[0089] R 1 A phenyl group or a naphthyl group is present, wherein the phenyl group or the naphthyl group and the OH group or the OR 2Specific examples of preferred structures of formula (1) in which the groups are directly linked include the following structures.

[0090] [Chemistry 10]

[0091]

[0092] In the structure, R 2 , a and b represent the same meanings as the same symbols in the formula (1). m3, m4, and n3 each independently represent an integer of 0 to 2, and n4 represents an integer of 1 to 2. And m3+m4=m, n3+n4=n, and m and n represent the same meanings as the same symbols in the formula (1).

[0093] In formula (1), m represents an integer of 0 to 4, and n represents an integer of 1 to 4. From the viewpoint of heat resistance of the resin, the value of m+n is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and still more preferably 2.

[0094] In formula (1), * represents a bonding site, and a and b each independently represent an integer of 1 or 2. From the viewpoint of heat resistance of the resin, a=b=1 or a=b=2 is preferred, and a=b=1 is more preferred.

[0095] The structure represented by formula (1) can be obtained, for example, by synthesizing one or more resins selected from the group consisting of the polyimide, polybenzoxazole, polyamide and copolymers thereof using a hydroxyl-containing acid dianhydride or a hydroxyl-containing diamine, and modifying a part or all of the OH groups of the resin to OR 2 base.

[0096] Examples of the hydroxyl-containing acid dianhydride include 6,6'-methylenebis(5-hydroxyisobenzofuran-1,3-dione), N,N'-(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diyl)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N,N'-(propane-2,2'-diylbis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), and N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), but are not limited thereto.

[0097] Examples of the hydroxyl-containing diamine include 2,4-diaminophenol, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)propane, and bis(3-amino-4-hydroxyphenyl)fluorene, but are not limited thereto.

[0098] As a more preferred structure of formula (1), OR of formula (1) 2 The pKa of the phenolic hydroxyl group-containing structure generated by acid decomposition of the group is 11 or more. The pKa value is preferably 11.5 or more, more preferably 12 or more, and even more preferably 12.5 or more.

[0099] At this time, when the structure of formula (1) contained in the composition is set to 100 mol, the OR 2 The structure containing a phenolic hydroxyl group generated by acid decomposition of the group needs to contain 50 mol % or more of a structure having a pKa of 11 or more.

[0100] Here, the so-called OR in formula (1) 2 The pKa of the structure containing a phenolic hydroxyl group generated by acid decomposition of the group is represented by OR 2 The calculated value of the index of the acidity of the phenolic hydroxyl group of the structure of the following general formula (11) in which all the groups are deprotected. It can be said that the higher the pKa, the lower the acidity of the phenolic hydroxyl group. Originally, the higher the acidity of the phenolic hydroxyl group, the higher the solubility in the alkaline developer. However, the following characteristics are shown: by setting the pKa to 11 or more and deliberately suppressing the acidity to a low level, the acid generated by exposure from OR 2 The deprotection property of the OH group is improved, and the solubility contrast between the unexposed part and the exposed part with respect to the alkaline aqueous solution is significantly increased. As a result, there is an advantage of having a higher exposure sensitivity than simply improving the alkaline solubility.

[0101] [Chemistry 11]

[0102]

[0103] m and n have the same meanings as the same symbols in the above formula (1).

[0104] The calculation method of pKa is as follows. Taking the structure of general formula (11) as the object, the calculation is performed by following the Schrödinger equation in quantum mechanics and using the method of calculating the electronic state of the molecule. Specifically, the calculation is performed using the following calculation software and basis functions, taking into account the solubility energy with water. That is, a uniform dielectric is arranged around the molecule, and the interaction between the molecule and the dielectric is calculated. In this study, the dielectric constant is set to ε = 78.39 for calculation.

[0105] Computation software: Gaussian 16

[0106] Calculation level: B3LYP / 6-31+G(d,p)

[0107] Solvation method: PCM-UAHF-G03 (Solvent = water)

[0108] As the OR of formula (1) 2 Preferred structures in which the pKa of the phenolic hydroxyl group-containing structure generated by acid decomposition of the group is 11 or more include the following structures.

[0109] [Chemistry 12]

[0110]

[0111] As a more preferable structure of formula (1), the structure of formula (6) can be mentioned.

[0112] [Chemistry 13]

[0113]

[0114] In formula (6), R 2 , a and b represent the same meanings as the same symbols in the formula (1). L represents a direct bond, -C(CH3)2-, 9H-fluorene-1,9-diyl. More preferably, it is -C(CH3)2-. m1, m2, n1 and n2 each independently represent an integer of 0 to 2. Wherein 1≤(n1+n2)≤4 is satisfied. * represents a bonding site.

[0115] The 9H-fluorene-1,9-diyl group is a group represented by the following formula.

[0116] [Chemistry 14]

[0117]

[0118] In formula (1), R 2 It is a monovalent acid-decomposable group having 3 to 20 carbon atoms.

[0119] Examples of the acid-decomposable group include a tertiary alkyl group such as a tert-butyl group and an organic group not containing a carbonyl group such as an oxymethyl group, and more preferably an oxymethyl group.

[0120] The oxymethyl group referred to herein is a monovalent group having a structure in which carbon and oxygen are bonded in order from a bonding site by single bonds. The monovalent oxymethyl group having 3 to 20 carbon atoms can be specifically represented by the following structure.

[0121] [Chemistry 15]

[0122]

[0123] In the structure, R 11 ~R 16 , R 18Represents a monovalent organic group, R 17 and R 19 Indicates a divalent organic group. * indicates a bonding site. The number of carbon atoms in the structure is 3 to 20.

[0124] Examples of the monovalent organic group include an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, and an alkoxycyclic alkyl group having 6 to 16 carbon atoms.

[0125] Examples of the divalent organic group include propane-1,3-diyl, butane-1,3-diyl, pentane-1,3-diyl, or a group in which a hydrogen atom of a group selected from the group consisting of propane-1,3-diyl, butane-1,3-diyl and pentane-1,3-diyl is substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxyalkyl group having 2 to 8 carbon atoms.

[0126] Through the R 2 is the monovalent oxymethyl group having 3 to 20 carbon atoms, and the acid generated by exposure to light is 2 The deprotection property of the OH group is improved, and the dissolution contrast between the unexposed part and the exposed part with respect to the alkaline aqueous solution is increased. As a result, there is an advantage of having a high exposure sensitivity. 2 At least one of the groups is preferably a group represented by formula (2) or a group represented by formula (3).

[0127] [Chemistry 16]

[0128]

[0129] In formula (2) and formula (3), R 3 R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. 4 R represents an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. 5 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms. p represents an integer of 0 to 2, and q represents an integer of 0 to 2.

[0130] Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.

[0131] Specific examples of the alkoxyalkyl group having 2 to 8 carbon atoms include methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxymethyl, propoxyethyl, propoxypropyl, and propoxybutyl.

[0132] Specific examples of the cyclic alkyl group having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclopentylethyl, cyclohexylethyl, cycloheptylethyl, cyclopentylpropyl, cyclohexylpropyl and cycloheptylpropyl.

[0133] Specific examples of the alkoxycyclic alkyl group having 6 to 16 carbon atoms include methoxypentyl, ethoxypentyl, propoxypentyl, dimethoxypentyl, diethoxypentyl, dipropoxypentyl, trimethoxypentyl, triethoxypentyl, tripropoxypentyl, methoxyhexyl, ethoxyhexyl, propoxyhexyl, dimethoxyhexyl, diethoxyhexyl, dipropoxyhexyl, trimethoxyhexyl, triethoxyhexyl, tripropoxyhexyl, methoxyheptyl, ethoxyheptyl, propoxyheptyl, dimethoxyheptyl, diethoxyheptyl, dipropoxyheptyl, trimethoxyheptyl, triethoxyheptyl, tripropoxyheptyl, and the like.

[0134] Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.

[0135] Through the R 2 At least one of the groups is a group represented by formula (2) or a group represented by formula (3), and in R 1 -OR 2 Convert to R 1 The organic group released in the case of -OH is less likely to remain during development, and as a result, a pattern with less residue can be obtained.

[0136] From the viewpoint of obtaining a pattern with less residue, the R 2 More preferred is a group represented by formula (2).

[0137] From the viewpoint of obtaining a pattern with less residue, the R 2 More preferably, it is a group represented by formula (4) or a group represented by formula (5).

[0138] [Chemistry 17]

[0139]

[0140] In formula (4) and formula (5), R 6 and R 7 Each independently represents an alkyl group having 1 to 6 carbon atoms. 8 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms. r represents an integer of 0 to 2, and s represents an integer of 0 to 2. * represents a bonding site.

[0141] Specific examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the alkoxyalkyl group having 2 to 8 carbon atoms are the same as the specific examples of the corresponding groups in formula (2) and formula (3).

[0142] Formula (4) or formula (5) is R 1 -OR 2 OR in the structure 2 The structure after the α position branch. If it is OR 2 The structure after the α-branching, then in R 1 -OR 2 Convert to R 1 The organic group released in the case of -OH is less likely to remain during development, resulting in a pattern with less residue.

[0143] In particular, when the structure of formula (1) is 100 mol, the composition contains 50 mol% or more of OR 2 The pKa of the structure containing a phenolic hydroxyl group generated by acid decomposition is 12.5 or more, and R 2 In the case of a group represented by formula (4) or a group represented by formula (5), the residual organic group during development can be further suppressed, and a pattern with less residue can be obtained.

[0144] From the viewpoint of obtaining a pattern with less residue, when the phenolic hydroxyl group in the resin (A) is combined with OR 2 When the total number of groups is 100 mol, OR 2 The ratio of the groups is most preferably 40 mol% or less.

[0145] In addition, from the viewpoint of suppressing the film thickness reduction during development, when the phenolic hydroxyl group in the resin (A) is combined with OR 2 When the total number of groups is 100 mol, OR 2 The ratio of the group is preferably 15 mol% or more, more preferably 20 mol% or more.

[0146] The resin (A) preferably contains one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof, which contain a structural unit represented by the following general formula (7) and / or a structural unit represented by the following general formula (8).

[0147] [Chemistry 18]

[0148]

[0149] In formula (7), X1 represents a tetravalent organic group having 4 to 50 carbon atoms, or a constituent unit of formula (1). Y1 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X1 and Y1 is a constituent unit of formula (1), and when X1 is a constituent unit of formula (1), a=b=2, and when Y1 is a constituent unit of formula (1), a+b=2. * represents a bonding site.

[0150] Since the structural unit represented by the formula (7) has an imide structure having high heat resistance, a resin film having high heat resistance can be obtained.

[0151] In formula (8), X2 represents a divalent organic group having 4 to 50 carbon atoms, or a constituent unit of formula (1). Y2 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of formula (1). At least one of X2 and Y2 is a constituent unit of formula (1), and a=b=1. * represents a bonding site.

[0152] The structural unit represented by formula (8) has a precursor structure of a polybenzoxazole having high heat resistance. Therefore, by subjecting the structural unit represented by formula (8) to heat treatment to close the oxazole ring, a resin film having high heat resistance can be obtained.

[0153] From the viewpoint of reducing the reduction in film thickness due to heat treatment, it is more preferred that the resin (A) contains the structural unit represented by formula (7).

[0154] In the formula (7), X1 is preferably a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. And / or in the formula (8), X2 is preferably a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. This has the advantages of increasing the change in solubility of the resin before and after deprotection, improving the contrast between the unexposed part and the exposed part, and achieving high sensitivity. The tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms, and the divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms can be exemplified by the following structures.

[0155] [Chemistry 19]

[0156]

[0157] *Indicates the bonding site.

[0158] From the viewpoint of improving the contrast between the unexposed portion and the exposed portion and achieving high sensitivity, the proportion of the aliphatic skeleton having 4 or more carbon atoms in X1 in the formula (7) and / or X2 in the formula (8) is preferably 50 mol % or more, more preferably 70 mol % or more.

[0159] Furthermore, in terms of increasing the solubility change of the resin before and after deprotection, improving the contrast between the unexposed part and the exposed part, and realizing high sensitivity, it is preferred that at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof in the resin (A) has a structural unit represented by formula (9), and when the OH group and OR contained in formula (9) are 2 The total number of groups is defined as M1, and the OH group and OR group are removed from the structure of formula (9). 2 When the molecular weight of the remaining structural part after the group is set to N1, the value of M1 / N1 is 0.004075 or more, and / or the (A) resin has a structural unit represented by formula (10), when the OH group and OR contained in formula (10) are 2 The total number of groups is defined as M2, and the OH group and OR group are removed from the structure of formula (10). 2 When the molecular weight of the remaining structural part after the group is defined as N2, the value of M2 / N2 is 0.004075 or more.

[0160] The values ​​of M1 / N1 and M2 / N2 are more preferably 0.004501, and still more preferably 0.005001.

[0161] In formula (9) and formula (10), R 1 , R 2 , m and n have the same meanings as the same symbols in the above formula (1). X3 represents a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. X4 represents a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms.

[0162] For example, as a specific example of the formula (9), in the case of the following structure, since M1=2.000 and N1=512.5, M1 / N1=0.003902.

[0163] [Chemistry 20]

[0164]

[0165] In addition, as a specific example of the formula (10), in the case of the following structure, since M2=2.000 and N2=532.9, M1 / N1=0.003753.

[0166] [Chemistry 21]

[0167]

[0168] In the general formula (1), R 1 -OR 2 is by making R 1For example, by reacting a resin having R -OH with a protective agent in a solvent-free state or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, cyclopentanone, etc., in the presence of an acid or a base at a reaction temperature of -20°C to 50°C. 1 -OH resin reacts with a protective agent to obtain R 1 -OR 2 Resin, that is, (A) resin.

[0169] As the protecting agent, a known protecting agent capable of protecting a hydroxyl group can be used.

[0170] As a protective agent, for example in R 2 In the case of 1-ethoxyethyl, ethyl vinyl ether can be used. 2 In the case of 2-tetrahydropyranyl, 3,4-dihydro-2H-pyran and the like can be used.

[0171] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. In addition, organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.

[0172] Examples of the base include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0173] <Fluorine atom content>

[0174] In the positive photosensitive resin composition of the present invention, the total amount of all resins contained in the composition is set to 100 mass%, and the fluorine atom content in the total resin is 15 mass% or less. Preferably, it is 8.5 mass% or less. When the fluorine atom content is 15 mass% or less, the reason is unclear, but during exposure, R 1 -OR 2 Convert to R 1 -OH, that is, the reaction rate of deprotection. Therefore, when compared with the same exposure amount, the deprotection rate can be increased, so a highly sensitive positive photosensitive resin composition can be prepared.

[0175] From the viewpoint of reducing pattern residues after development, the fluorine atom content is more preferably 3.5 mass % or less.

[0176] The fluorine atom content in all the resins contained in the composition can be analyzed by the following method, assuming that the total amount of all the resins contained in the composition is 100 mass %.

[0177] First, separate the resin from the composition. Accurately weigh the separated resin as a sample. Use an automatic sample combustion device to burn it in the combustion tube of the analysis device, absorb the generated gas into the solution, and analyze part of the absorption liquid by ion chromatography. As the absorption liquid, H2O2 0.036 mass% can be used.

[0178] <(B) Photoacid generator>

[0179] The positive photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator is a compound that has the function of generating an acid by exposure. The photoacid generator (B) can be a known photoacid generator within a range that does not impair the effects of the present invention.

[0180] As the (B) photoacid generator, an onium salt-type ionic photoacid generator or a nonionic photoacid generator can be cited. The so-called onium salt refers to a compound having an electron pair that is not related to a chemical bond, which is generated by a coordination bond with other cationic compounds through the electron pair. In the ionic photoacid generator, the cationic part of the onium salt determines the photochemical properties (molar absorptivity, absorption wavelength, quantum yield), and the anionic part determines the strength of the generated acid. On the other hand, a nonionic photoacid generator is a photoacid generator in which the light-absorbing part is ester-bonded with the acid.

[0181] As the ionic compound, as the ionic compound, it is preferably an ionic compound that does not contain heavy metals or halogen ions, and more preferably a triorganosulfonium salt compound. Specific examples of the triorganosulfonium salt compound include: triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, perfluoro-1-butanesulfonate ("SP-056", trade name, manufactured by ADEKA); dimethyl-1-naphthylsulfonium sulfonate; dimethyl (4-hydroxy-1-naphthyl) sulfonium sulfonate; dimethyl (4,7-dihydroxy-1-naphthyl) sulfonium sulfonate; diphenyliodonium sulfonate, etc.

[0182] As the nonionic photo-acid generator, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, a sulfonimide compound, a phosphate compound, a sulfonebenzotriazole compound, or the like can be used.

[0183] Specific examples of the diazomethane compound include bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Co., Ltd. and Koho Pure Chemical Industries, Ltd.).

[0184] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred sulfone compounds include 2-(p-toluenesulfonyl)acetophenone, bis(phenylsulfonyl)methane, and the like.

[0185] Specific examples of the sulfonate compound include alkyl sulfonate, halogenated alkyl sulfonate, aryl sulfonate, and iminosulfonate compounds. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenyl sulfonate.

[0186] Specific examples of the carboxylic acid ester compound include 2-nitrobenzyl carboxylate and the like.

[0187] The photoacid generator (B) preferably includes a nonionic photoacid generator. When the photoacid generator (B) includes a nonionic photoacid generator, the solubility of the unexposed portion is suppressed, and the film thickness reduction during development is suppressed.

[0188] The photoacid generator (B) is more preferably a photoacid generator having an acid dissociation constant (pKa) of an acidic group generated by light in the range of -14 to 2. The photoacid generator (B) has an acid dissociation constant (pKa) of an acidic group generated by light in the range, so that the acidic group generated by light can act efficiently on R as an acid. 1 -OR 2 structure. Therefore, further deprotection can be performed to prepare a highly sensitive positive photosensitive resin composition. Specific examples of photoacid generators whose acid dissociation constant (pKa) of the acidic group generated by light is in the range of -14 to 2 include trifluoromethanesulfonic acid (pKa=-14), nonafluorobutanesulfonic acid (pKa=-3.57), p-toluenesulfonic acid (pKa=-2.8), methanesulfonic acid (pKa=-2.6), benzenesulfonic acid (pKa=0.7), 10-camphorsulfonic acid (pKa=1.2), ethanesulfonic acid (pKa=1.83), 1-propanesulfonic acid (pKa=1.92), and the like.

[0189] The (B) photoacid generator preferably comprises an oxime sulfonate compound and / or an imide sulfonate compound. Oxime sulfonate compounds and imide sulfonate compounds are nonionic photoacid generators, and the acidic group generated by light is a sulfonic group, so the acid dissociation constant (pKa) is high, and not only can a positive photosensitive resin composition with higher sensitivity be prepared, but also the interaction with polar functional groups such as carbonyl or amide groups contained in polyimide, polybenzoxazole, and polyamide is enhanced, thereby suppressing the solubility of the unexposed part and suppressing the reduction of the film thickness during development.

[0190] The oxime sulfonate compound can be represented by the following structure.

[0191] [Chemistry 22]

[0192]

[0193] R 21 It is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, trifluoromethanesulfonyl, nonafluorobutyl, perfluorooctyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-yl)methyl, benzyl, phenyl, tosyl, and naphthyl.

[0194] R 22 and R 23 It is a monovalent organic group having 1 to 30 carbon atoms. 22 and R 23 Specific examples of the monovalent organic group having 1 to 30 carbon atoms include cyano, trifluoromethyl, hexafluoropropyl, pentafluorobutyl, dodecafluorohexyl, phenyl, 4-methoxyphenyl, 2-fluorenyl, 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl, and the like.

[0195] R 24 It is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the monovalent organic group having 3 to 30 carbon atoms include the following structures.

[0196] [Chemistry 23]

[0197]

[0198] *Indicates the bonding site.

[0199] Specific examples of the oxime sulfonate esters include: "Irgacure" (registered trademark) PAG-103 (benzyl cyanide, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylene), PAG-121 (benzyl cyanide, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylene), PAG-108 (benzyl cyanide, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylene), PAG-203 (all manufactured by BASF, Japan), and PAI-101 ((Z)-4-methoxy-N-(toluenesulfonyloxy)iminobenzyl cyanide, manufactured by Midori Kagaku Co., Ltd.).

[0200] The imidosulfonate compound can be represented by the following structure.

[0201] [Chemistry 24]

[0202]

[0203] R 25 It is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include: 21 The bases listed as specific examples are as follows.

[0204] R 26 and R 27 It is a monovalent organic group having 1 to 30 carbon atoms. 26 and R 27 Specific examples of the monovalent organic group having 1 to 30 carbon atoms include: 22 and R 23 The bases listed as specific examples are as follows.

[0205] R 28 It is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the divalent organic group having 3 to 30 carbon atoms include the following structures.

[0206] [Chemistry 25]

[0207]

[0208] R 29 It is a monovalent organic group having 1 to 12 carbon atoms. t represents an integer of 0 to 2. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include methyl, ethyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, 1-(hex-1-en-1-yl) group, and 1-(4-butoxyphenethyl) group. * represents a bonding site.

[0209] Examples of the imide sulfonate compound include N-hydroxynaphthalene imide trifluoromethanesulfonate, "ADEKA ARKLS" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalene imide trifluoromethanesulfonate, manufactured by ADEKA), NA-101 (N-hydroxynaphthalene imide p-toluenesulfonate), and NA-106 (N-hydroxynaphthalene imide camphorsulfonate, all manufactured by Midori Kagaku Co., Ltd.).

[0210] In the present invention, the content of the photoacid generator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of all resins in the positive photosensitive resin composition. When the photoacid generator (B) is within the above range, a highly sensitive positive photosensitive resin composition can be obtained.

[0211] <(C) Amine compound having a conjugate acid pKa in the range of 4.5 to 10.8>

[0212] The positive photosensitive resin composition of the present invention preferably further contains (C) an amine compound having a conjugate acid pKa in the range of 4.5 to 10.8. By containing the (C) amine compound, deprotection is suppressed during the prebaking described later. Therefore, a positive photosensitive resin composition with a small reduction in the developed film can be prepared.

[0213] The (C) amine compound is more preferably an amine compound containing a conjugated acid with a pKa of 5.0 to 10.0, and further preferably an amine compound containing a conjugated acid with a pKa of 6.0 to 9.0. When the (C) amine compound contains an amine compound with a conjugated acid pKa in the above range, deprotection during prebaking is suppressed, and the acid generated during exposure is not easily neutralized, so that a positive photosensitive resin composition with a small reduction in developed film can be prepared.

[0214] As amine compounds whose conjugate acid pKa is within the above range, there are listed: aniline (pKa=4.6), dimethylaniline (pKa=5.20), pyridine (pKa=5.25), 2-methylpyridine (pKa=5.97), 2,6-lutidine (pKa=6.75), imidazole (pKa=6.95), N-methylmorpholine (pKa=7.38), morpholine (pKa=8.36), dicyclohexylamine (pKa=10.4), cyclohexylamine (pKa=10.6), etc.

[0215] From the viewpoint of enhancing the interaction with polar functional groups such as carbonyl groups and amide groups contained in polyimide, polybenzoxazole and polyamide and reducing the film thickness reduction during development, a conjugated acid having a pyridine skeleton is preferred, and lutidine is more preferred.

[0216] In the present invention, the content of the amine compound (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the resin (A). When the content of the amine compound (C) is within the above range, a positive photosensitive resin composition with a small film reduction and high sensitivity can be obtained.

[0217] <(D) Solvent>

[0218] The positive photosensitive resin composition of the present invention preferably further contains (D) a solvent. By containing a solvent, coating properties become good and a homogeneous positive photosensitive resin film can be obtained. The solvent (D) can be a known solvent within a range that does not impair the effects of the present invention.

[0219] The solvent (D) is not particularly limited, and preferably used are amide solvents, ester solvents, alcohol solvents, ether solvents, ketone solvents, dimethyl sulfoxide, and the like.

[0220] Specific examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropyleneurea.

[0221] Specific examples of the ester solvent include γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate.

[0222] Specific examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, and the like.

[0223] Specific examples of the ether solvent include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether.

[0224] Specific examples of the ketone solvent include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.

[0225] As the solvent (D), an aprotic solvent having a relative dielectric constant in the range of 5 to 20 is preferred, a relative dielectric constant in the range of 6 to 19 is more preferred, and a relative dielectric constant in the range of 7 to 19 is further preferred.

[0226] When the (D) solvent contains an aprotic solvent having a relative dielectric constant in the range of 5 to 20, the stability of the positive photosensitive resin composition during storage is improved.

[0227] Examples of aprotic solvents having a relative dielectric constant in the range of 5 to 20 include tetrahydrofuran (relative dielectric constant 7.6), propylene glycol monomethyl ether acetate (relative dielectric constant 8.3), methyl isobutyl ketone (relative dielectric constant 13.1), cyclopentanone (relative dielectric constant 14.5), cyclohexanone (relative dielectric constant 18.3), and methyl ethyl ketone (relative dielectric constant 18.5).

[0228] The (D) solvent is preferably an aprotic solvent containing 3 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. The aprotic solvent containing 3 to 12 carbon atoms has excellent solubility in the (A) resin contained in the positive photosensitive resin composition of the present invention. Therefore, the positive photosensitive resin composition of the present invention can be made into a high-concentration positive photosensitive resin composition by containing an aprotic solvent containing 3 to 12 carbon atoms. By coating the composition, for example, not only a positive photosensitive resin film with a large film thickness of more than 1 μm can be easily obtained, but also a resin film with a strong resin network is formed during film formation, thereby reducing the amount of film reduction during development.

[0229] The solvent (D) is preferably a cyclic ketone, more preferably cyclopentanone, from the viewpoint of enhancing the interaction with polar functional groups such as carbonyl groups and amide groups contained in polyimide, polybenzoxazole and polyamide, and reducing the film thickness reduction during development.

[0230] When the total mass of the aprotic solvent having a relative dielectric constant in the range of 5 to 20 is 100 mass%, the cyclic ketone solvent preferably accounts for 20 mass% or more.

[0231] The positive photosensitive resin composition of the present invention preferably further comprises a (D) solvent, wherein the (D) solvent comprises an aprotic solvent having 3 to 12 carbon atoms and having a relative dielectric constant in the range of 5 to 20. In the present invention, the content of the (D) solvent is preferably 100 parts by mass or more relative to 100 parts by mass of the (A) resin in order to dissolve the composition, and the content of the (D) solvent is preferably 1,500 parts by mass or less in order to form a coating film having a film thickness of 1 μm or more.

[0232] In particular, from the viewpoint of enhancing the interaction with polar functional groups such as carbonyl groups or amide groups contained in polyimide, polybenzoxazole, and polyamide, and reducing the film thickness reduction during development, it is further preferred that (B) the photoacid generator contains an oxime sulfonate compound and / or an imide sulfonate compound, and (C) the amine compound is a conjugated acid having a pyridine skeleton, and (D) the solvent is an aprotic solvent with a relative dielectric constant in the range of 5 to 20, and when the aprotic solvent with a relative dielectric constant in the range of 5 to 20 is taken as 100 mass%, 20 mass% or more is a cyclic ketone solvent. In addition, in order to make the interaction stronger, it is most preferred that the structure of formula (1) is contained, when the structure of formula (1) contained in the composition is taken as 100 mol, 50 mol% or more of OR of formula (1) is contained. 2 The pKa of the phenolic hydroxyl group-containing structure generated by acid decomposition of the group is 12.5 or more.

[0233] The photosensitive resin composition of the present invention may contain other additives than those described above. Examples of other additives include a dissolution accelerator, a sensitizer, a silane coupling agent, and a surfactant.

[0234] <Hardened article, method for producing the cured article>

[0235] The cured product of the present invention is a cured product obtained by curing the positive photosensitive resin composition of the present invention.

[0236] As a curing condition, a temperature of 150°C to 320°C is applied to carry out a thermal crosslinking reaction to improve heat resistance and chemical resistance. The heat treatment can be carried out by selecting a temperature and heating it in stages, or by selecting a certain temperature range and carrying out the heating for 5 minutes to 5 hours while continuously heating it. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. The lower limit of the curing condition in the present invention is preferably above 170°C, but in order to fully carry out the curing, it is more preferably above 180°C. In addition, the upper limit of the curing condition is preferably below 280°C.

[0237] The method for producing a cured product of the present invention comprises: applying the positive photosensitive resin composition of the present invention on a substrate and drying the coating to form a positive photosensitive resin film;

[0238] A step of exposing the positive photosensitive resin film;

[0239] A step of washing or removing the exposed portion of the positive photosensitive resin film after exposure with an alkaline aqueous solution to perform development; and

[0240] A step of heat-treating the positive photosensitive resin film after development.

[0241] The cured product obtained in this manner mainly contains polyimide or polybenzoxazole, and therefore has excellent heat resistance, electrical insulation, and mechanical properties.

[0242] The method for producing a cured product according to the embodiment of the present invention includes a step of applying the positive photosensitive resin composition of the present invention on a substrate to form a positive photosensitive resin film.

[0243] The substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafer, ceramic stacked substrate, metal-plated substrate, sapphire, and gallium arsenide.

[0244] The method of coating the positive photosensitive composition of the present invention on the substrate can be a known method. As the device used for coating, there can be listed: a full coating device such as spin coating, dip coating, curtain coating, spray coating or slit coating, or a printing device such as screen printing, roller coating, micro gravure coating or inkjet.

[0245] After coating, drying is performed to form a positive photosensitive resin film. Drying is performed using a vacuum drying device or a heating device such as a hot plate or an oven. When a heating device is used, it is preferably performed at a temperature range of 50° C. to 150° C. for 30 seconds to 30 minutes. The thickness of the positive photosensitive resin film is preferably 0.1 μm to 100 μm.

[0246] The method for producing a cured product according to the embodiment of the present invention includes a step of exposing the positive photosensitive resin film.

[0247] In the exposure process, the positive photosensitive resin film is exposed through a mask having a desired pattern. The wavelength of the exposure light irradiated is not particularly limited, and examples thereof include: g-rays (436nm), i-rays (365nm), and h-rays (405nm) with a wavelength of 300nm to 450nm. Among them, it is preferred to irradiate light with a wavelength of 365nm. As the light source used in the exposure process, for example, there are: various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and metal halide lamps. In addition, as needed, the wavelength of the irradiated light can be adjusted by spectral filters such as long wavelength cutoff filters, short wavelength cutoff filters, and bandpass filters.

[0248] After exposure, post-exposure baking may be performed as required. By performing post-exposure baking, effects such as improved resolution after development or increased allowable range of development conditions can be expected. Post-exposure baking may use an oven, hot plate, infrared, flash annealing device, laser annealing device, etc. The post-exposure baking temperature is preferably 50°C to 180°C, more preferably 60°C to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.

[0249] The method for producing a cured product according to the embodiment of the present invention includes a step of washing or removing the exposed portion of the positive photosensitive resin film after exposure with an alkaline aqueous solution and performing development.

[0250] In order to form a pattern of a positive photosensitive resin composition, after exposure, a developer is used to remove the exposed part. The developer used for development is a solution that dissolves and removes the polymer soluble in the alkaline aqueous solution, typically an alkaline aqueous solution in which an alkaline compound is dissolved. As the alkaline compound, tetramethylammonium hydroxide, potassium hydroxide, sodium carbonate, etc. can be listed. In addition, depending on the circumstances, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc., alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc., or a combination of the above can be added to these alkaline aqueous solutions.

[0251] After development, it is preferred to perform rinsing with an organic solvent or water. When an organic solvent is used, in addition to the developer, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. may also be mentioned. When water is used, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may also be added to water for rinsing.

[0252] The method for producing a cured product according to the embodiment of the present invention includes a step of heat-treating the positive photosensitive resin film after development.

[0253] After development, a temperature of 150°C to 320°C is applied to carry out a thermal crosslinking reaction to improve heat resistance and chemical resistance. The heat treatment is performed by selecting a temperature and heating it in stages, or by selecting a certain temperature range and performing it for 5 minutes to 5 hours while continuously heating it. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. As the lower limit of the curing conditions in the present invention, it is preferably above 170°C, but in order to fully perform the curing, it is more preferably above 180°C. In addition, as the upper limit of the curing conditions, it is preferably below 280°C.

[0254] <Positive photosensitive resin sheet and method for producing cured product>

[0255] The shape of the positive photosensitive resin composition of the present invention is not limited, and may be, for example, a paste or a sheet.

[0256] In addition, the positive photosensitive resin sheet of the present invention is a positive photosensitive resin sheet obtained by forming the positive photosensitive resin composition of the present invention into a sheet on a support. The positive photosensitive resin sheet of the present invention refers to a sheet-shaped resin sheet in which the positive photosensitive resin composition of the present invention is applied to a support, dried at a temperature and for a time within a range in which the solvent can be volatilized, and the positive photosensitive resin composition of the present invention is not completely cured, and the positive photosensitive resin composition of the present invention is soluble in an organic solvent.

[0257] The support is not particularly limited, and various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. In order to improve adhesion and peelability, surface treatments such as silicone, silane coupling agent, aluminum chelating agent, polyurea, etc. may be applied to the joint surface between the support and the positive photosensitive resin composition. In addition, the thickness of the support is not particularly limited, and from the perspective of workability, it is preferably in the range of 10μm to 100μm. Furthermore, in order to protect the film surface of the positive photosensitive resin composition obtained by coating, a protective film may also be provided on the film surface. In this way, the surface of the positive photosensitive resin composition can be protected from pollutants such as dust or dirt in the atmosphere.

[0258] Examples of methods for coating the positive photosensitive resin composition on a support include spin coating using a spinner, spray coating, roll coating, screen printing, knife coater, die coater, calendar coater, meniscus coater, rod coater, roll coater, notch wheel roll coater, gravure coater, screen coater, slot die coater, etc. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but generally, from the viewpoint of uniformity of the coating film, the film thickness after drying is preferably 0.5 μm or more and 100 μm or less.

[0259] An oven, a hot plate, infrared rays, etc. can be used for drying. The drying temperature and drying time can be set within the range that allows the solvent to volatilize, and are preferably set appropriately such that the photosensitive resin composition is in an uncured or semi-cured state. Specifically, it is preferably carried out within the range of 40°C to 150°C for 1 minute to several tens of minutes. In addition, these temperatures can also be combined to increase the temperature in stages, for example, heat treatment can be performed at 80°C and 90°C for 2 minutes each.

[0260] The cured product of the present invention is obtained by curing the positive photosensitive resin composition of the present invention. One embodiment of the method for producing the cured product of the present invention includes:

[0261] a) applying the positive photosensitive resin composition of the present invention on a substrate and drying it to form a positive photosensitive resin film;

[0262] b) exposing the positive photosensitive resin film to light;

[0263] c) a step of washing or removing the exposed portion of the positive photosensitive resin film after exposure with an alkaline aqueous solution to perform development; and

[0264] d) a step of heating the positive photosensitive resin film after development. Another aspect of the method for producing a cured product of the present invention is to use the positive photosensitive resin sheet of the present invention, comprising:

[0265] a) a step of thermally pressing the positive photosensitive resin composition of the present invention onto a substrate;

[0266] b) exposing the positive photosensitive resin composition after thermal compression bonding;

[0267] c) a step of washing or removing the exposed portion of the positive photosensitive resin composition after thermal compression bonding with an alkaline aqueous solution to perform development; and

[0268] d) a step of heating the developed positive photosensitive resin composition.

[0269] The cured product obtained in this manner mainly contains polyamide or polybenzoxazole and is therefore excellent in heat resistance, electrical insulation, and mechanical properties.

[0270] The substrate may include, but is not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and substrates of constituent materials of circuits arranged on these substrates. Examples of organic circuit substrates include, but are not limited to, glass-based copper foil laminates such as glass cloth-epoxy copper foil laminates, composite copper foil laminates such as glass nonwoven fabric-epoxy copper foil laminates, heat-resistant-thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper foil film substrates and polyimide copper foil film substrates. In addition, examples of inorganic circuit substrates include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit constituent materials include: conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low dielectric materials containing glass materials and / or resins, high dielectric materials containing resins or high dielectric constant inorganic particles, insulators containing glass materials, etc.

[0271] The process of thermally pressing the positive photosensitive resin sheet onto the substrate is not particularly limited, and a known method can be used. For example, in the case where the positive photosensitive resin sheet has a protective film, the protective film is peeled off, the positive photosensitive resin sheet and the substrate are made to face each other, and they are bonded by thermal pressing. The support may be peeled off from the positive photosensitive resin sheet before or after thermal pressing, and before or after exposure. Thermal pressing can be performed by hot pressing, hot lamination, hot vacuum lamination, etc. Among them, hot lamination is preferred. In terms of adhesion and embeddability to the substrate, the bonding temperature is preferably above 40°C. In addition, in order to prevent the resin composition film from hardening during bonding and the resolution of the pattern formed in the exposure / development process from deteriorating, the bonding temperature is preferably below 150°C.

[0272] There are no particular restrictions on the steps of exposing the positive photosensitive resin sheet, developing the exposed portion of the positive photosensitive resin sheet by washing or removing it with an alkaline aqueous solution, and heating the developed positive photosensitive resin sheet, and they are preferably carried out in the same manner as the method for producing a cured product using the positive photosensitive resin composition.

[0273] The cured product obtained by curing the positive photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices. The so-called semiconductor device in the present invention refers to all devices that can function by utilizing the characteristics of semiconductor elements. An electro-optical device or a semiconductor circuit substrate in which a semiconductor element is connected to a substrate, a device in which a plurality of semiconductor elements are stacked, and an electronic device including these are all included in the semiconductor device. In addition, electronic parts such as a multilayer wiring board for connecting semiconductor elements are also included in the semiconductor device. Specifically, it is preferably used for a passivation film of a semiconductor, a surface protection film of a semiconductor element, an interlayer insulating film between a semiconductor element and wiring, an interlayer insulating film between a plurality of semiconductor elements, an interlayer insulating film between wiring layers of multilayer wiring for high-density mounting, an insulating layer of an organic electric field light-emitting element, etc., but it is not limited thereto and can be used for various purposes.

[0274] The semiconductor device of the present invention is a semiconductor device in which the cured product of the present invention is configured as a protective film for a semiconductor or an interlayer insulating film between redistribution wiring. By configuring the cured film of the positive photosensitive composition as a protective film for a semiconductor or an interlayer insulating film between redistribution wiring, a highly reliable semiconductor device can be manufactured.

[0275] The semiconductor device of the present invention is preferably a semiconductor device in which the redistribution wiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. The semiconductor device in which the redistribution wiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers is a semiconductor device in which the hardened material of the present invention is formed on the redistribution wiring as an interlayer insulating film, the combination of the redistribution wiring and the interlayer insulating film is regarded as one layer, and the combination is repeatedly arranged in 2 to 10 layers. By repeatedly arranging 2 to 10 layers of the redistribution wiring and the interlayer insulating film, the miniaturization of the semiconductor device can be achieved.

[0276] The display device of the present invention comprises a first electrode formed on a substrate, an insulating layer formed on the first electrode so as to partially expose the first electrode, and a second electrode arranged opposite to the first electrode, wherein the insulating layer contains the cured product of the present invention.

[0277] Another aspect of the display device of the present invention comprises a planarizing film provided to cover the unevenness on a substrate on which a thin film transistor (TFT) is formed, and in the display, the planarizing film comprises the cured product of the present invention.

[0278] Specifically, it is preferred that the substrate has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode, and the planarization layer and / or the insulating layer contain the hardened material. If an active matrix display device is taken as an example, a TFT, a wiring located on the side of the TFT and connected to the TFT, is provided on a substrate such as a glass or resin film, and a planarization layer is provided thereon in a manner covering the concave and convex, and a display device is further provided on the planarization layer. The display device and the wiring are connected via contact holes formed on the planarization layer. The hardened material obtained by hardening the positive photosensitive resin composition of the present invention is preferably provided as a planarization layer in the display device because of its excellent planarization property and pattern dimensional stability. In particular, the flexibility of display devices has become the mainstream in recent years, and it can also be a display device in which the substrate having the driving circuit contains a resin film.

[0279] Example

[0280] The present invention is further described in detail by way of examples and comparative examples below, but the present invention is not limited to these. In addition, the names of the compounds using abbreviations are shown below. In addition, for diamine compounds, the OR of formula (1) when used as resin (A) is also described. 2 The pKa of the structure containing a phenolic hydroxyl group generated by acid decomposition of the hydroxyl group.

[0281] (Acid dianhydride compound)

[0282] TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione

[0283] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

[0284] 6FDA: 4,4'-(hexafluoroisopropylidene) diphthalic anhydride

[0285] CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

[0286] CHDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

[0287] (Diamine compound)

[0288] BAP (pKa = 12.76): 2,2-bis(3-amino-4-hydroxyphenyl)propane

[0289] 6FAP (pKa = 10.43): 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0290] HA: N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide)

[0291] ABPS (pKa = 8.24): bis(3-amino-4-hydroxyphenyl)sulfone

[0292] BAHF (pKa = 11.12): 9,9-bis(3-amino-4-hydroxyphenyl)fluorene

[0293] CPPS (pKa = 12.22): 1,1-bis(3-amino-4-hydroxyphenyl)cyclopentane

[0294] CHPS (pKa = 13.27): 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane

[0295] (acid dicompound)

[0296] ODBC: 4,4'-oxybis(benzoyl chloride)

[0297] BPDC: 4,4'-Dicyclohexyldicarboxylic acid chloride

[0298] CHDC: 4,4'-cyclohexanedicarboxylic acid chloride (cis-trans mixture)

[0299] (Capping agent having amino group)

[0300] mAP: 3-aminophenol.

[0301] ((B) Photoacid generator)

[0302] (Oxime sulfonate compound)

[0303] PAG-103: "Irgacure" (registered trademark) PAG-103 (phenylacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylene, manufactured by BASF Japan)

[0304] PAI-101: (Z)-4-methoxy-N-(toluenesulfonyloxy)iminobenzyl cyanide, manufactured by Midori Kagaku Co., Ltd.

[0305] (Imidosulfonate compound)

[0306] SP-606: "ADEKA ARKLS" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalimide trifluoromethanesulfonate, manufactured by ADEKA Corporation)

[0307] (Ionic photoacid generator)

[0308] SP-056: "ADEKA ARKLS" (registered trademark) SP-056 (triphenylsulfonium perfluoro-1-butanesulfonate, manufactured by ADEKA Corporation).

[0309] ((C) Amine compound)

[0310] Lutidine: 2,6-lutidine

[0311] ((D)Solvent)

[0312] CP: Cyclopentanone

[0313] GBL: gamma-butyrolactone

[0314] (other)

[0315] IPVE: Isopropyl Vinyl Ether

[0316] CHVE: Cyclohexyl vinyl ether

[0317] NPVE: n-propyl vinyl ether

[0318] DHP: Dihydropyran

[0319] Boc2O: di-tert-butyl dicarbonate

[0320] NQD-1: diester of 4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol and naphthoquinonediazidesulfonic acid.

[0321] (1) Weight average molecular weight of polyimide, polybenzoxazole and polyamide

[0322] The weight average molecular weight (Mw) in terms of polystyrene was measured using a gel permeation chromatography (GPC) analyzer. The weight average molecular weights of the polyimide resin and the polybenzoxazole resin were measured under the following conditions.

[0323] Measurement device: Waters 2695 (manufactured by Waters Corporation)

[0324] Column temperature: 50℃

[0325] Flow rate: 0.4mL / min

[0326] Detector: 2489 UV / Vis detector (Detector) (measurement wavelength 260nm)

[0327] Developing solvent: N-Methylpyrrolidone (NMP) (containing 0.21 wt% lithium chloride and 0.48 wt% phosphoric acid)

[0328] Guard column: TOSOH TSK guard column (manufactured by Tosoh Co., Ltd.)

[0329] Column: TOSOH TSK-GEL a-2500,

[0330] TOSOH TSK-GEL a-4000 series (both manufactured by TOSOH Co., Ltd.).

[0331] (2) Imidization rate of PI-01 to PI-20 and PAA-01 (%)

[0332] The polyimide (PI-01 to PI-20, PAA-01) obtained in the synthesis example was dissolved in GBL in a concentration of 35% by mass. The solution was applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 3 minutes to prepare a resin film with a thickness of 4μm to 5μm. The wafer with the resin film was divided into two parts, one of which was cured at 140°C for 30 minutes under a nitrogen flow (oxygen concentration of less than 20ppm) using a clean oven (CLH-21CD-S manufactured by KOYO THERMOSYSTEM Co., Ltd.), and then further heated and cured at 320°C for 1 hour to completely close the imide ring (sample IM02). The other part was used as it is (sample IM01). The transmission infrared absorption spectra of the resin films (IM01 and IM02) before and after curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak of the imide structure (1,780 cm-1) due to polyimide was confirmed. -1 Nearby, 1,377cm -1 ) and then find the 1,377cm of IM01 -1 The peak intensity near (S), 1,377 cm of IM02 -1 The peak intensity ratio of the peak intensity (S) divided by the peak intensity (T) was calculated as the content of the imide groups in the polyimide before the heat treatment, that is, the imidization ratio.

[0333] (3) Fluorine atom content in all resins in the positive photosensitive resin composition

[0334] The resin or resin solution is accurately weighed as a sample. The sample is burned in the combustion tube of the analysis device using the automatic sample combustion device described below, and the generated gas is absorbed into the solution, and then part of the absorbed liquid is analyzed by ion chromatography. In the case of a resin solution, the total fluorine atom content (mass %) in the obtained sample is divided by the solid content concentration (%) to obtain the fluorine atom content in the resin.

[0335] <Combustion / Absorption Conditions>

[0336] System: AQF-2100H, GA-210 (Made by Mitsubishi Chemical Corporation)

[0337] Electric furnace temperature: Inlet 900℃ Outlet 1000℃

[0338] Gas: Ar / O2 200mL / min

[0339] :O2 / 400mL / min

[0340] Absorption liquid: H2O2 0.036 mass%, internal standard P 4μg / mL

[0341] Absorption liquid volume: 20mL

[0342] <Ion chromatography / anion analysis conditions>

[0343] System: ICS1600 (manufactured by DIONEX Corporation)

[0344] Mobile phase: 2.7mmol / L Na2CO3 / 0.3mmol / L NaHCO3

[0345] Flow rate: 1.5mL / min

[0346] Detector: Conductivity detector

[0347] Injection volume: 20 μL.

[0348] (4) Protection rate

[0349] The protection rate was measured using a 400MHz, 1H-NMR (Nuclear Magnetic Resonance) device (AL-400 manufactured by JEOL Ltd.). Specifically, the measurement was performed in a deuterated dimethyl sulfoxide solution with a cumulative number of 16 times. The integral value of the protons of the methine (>CH-) derived from the protecting group observed near 5ppm-6ppm and the integral value of the protons of the phenolic hydroxyl group observed near 9ppm-11ppm were calculated, and the ratio of the integral value of the methine protons when the sum of the integral value of the methine protons and the integral value of the protons of the phenolic hydroxyl group was set to 100% was taken as the protection rate (%).

[0350] (5) Solid content concentration

[0351] The solid content concentration was determined by the following method. 1.500 g of the solution was weighed in an aluminum cup and heated at 180°C for 30 minutes using a hot plate to evaporate the liquid content. The weight of the solid content remaining in the aluminum cup after heating was weighed and the solid content concentration was determined from the ratio to the weight before heating.

[0352] (6) Production of embossed patterns

[0353] Using a coating and developing device ACT-8 (manufactured by Tokyo Electron), the positive photosensitive resin composition obtained from each embodiment and comparative example was applied to an 8-inch silicon wafer by spin coating, and heated at 100°C for 2 minutes to produce a positive photosensitive resin film with a film thickness of 4.0μm. In addition, the film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings) under the condition of a refractive index of 1.629. Then, using an exposure machine i-ray stepper NSR-2005i9C (manufactured by Nikon), through a mask with a pattern of contact holes of 10μm, at an exposure amount of 5mJ / cm 2 ~300mJ / cm 2 Every 5mJ / cm 2 After exposure, the ACT-8 developing device was used, 2.38 mass % tetramethylammonium hydroxide (TMAH) (manufactured by Tama Chemical Industry Co., Ltd.) was used as a developing solution, and after developing for 80 seconds, it was rinsed with distilled water and spun off to dry to obtain a relief pattern.

[0354] (6-1) Calculation of the amount of reduction in developed film

[0355] The amount of film reduction after development was calculated by subtracting the film thickness after development from the film thickness before development. The results were judged as follows: A with a film reduction of less than 1.0 μm was considered + , A - , B and C are considered qualified.

[0356] A + :Development film reduction is less than 0.2μm

[0357] A - :The reduction of the developed film is 0.2μm or more and less than 0.3μm

[0358] B: The amount of reduction in developed film is 0.3 μm or more and less than 0.5 μm

[0359] C: The amount of reduction in developed film is 0.5 μm or more and less than 1.0 μm

[0360] D: The amount of reduction in developed film is 1.0 μm or more and less than 2.0 μm

[0361] E: The amount of reduction in developed film is 2.0 μm or more.

[0362] (6-2) Sensitivity

[0363] Regarding sensitivity, the embossed pattern obtained was observed using a flat panel display (FPD) microscope MX61 (manufactured by Olympus) at a magnification of 20 times to measure the opening diameter of the contact hole. The minimum exposure amount at which the opening diameter of the contact hole reached 10 μm was determined and used as the sensitivity. The results were judged as follows, and the sensitivity was less than 100 mJ / cm 2 A + ~C - Set as qualified.

[0364] A + : Sensitivity less than 10mJ / cm 2

[0365] A: Sensitivity is 10mJ / cm 2 Above and less than 15mJ / cm 2

[0366] A - : Sensitivity is 15mJ / cm 2 Above and less than 20mJ / cm 2

[0367] B + : Sensitivity is 20mJ / cm 2 Above and less than 30mJ / cm 2

[0368] B: Sensitivity is 30mJ / cm 2 Above and less than 40mJ / cm 2

[0369] B - : Sensitivity is 40mJ / cm 2 Above and less than 50mJ / cm 2

[0370] C + : Sensitivity is 50mJ / cm 2 Above and less than 70mJ / cm 2

[0371] C: Sensitivity is 70mJ / cm 2 Above and less than 85mJ / cm 2

[0372] C - : Sensitivity is 85mJ / cm 2 Above and less than 100mJ / cm 2

[0373] D: Sensitivity is 100mJ / cm 2 Above and less than 200mJ / cm2

[0374] E: Sensitivity is 200mJ / cm 2 above.

[0375] (6-3) Development residue

[0376] The development residue was observed by using a FPD / LSI (Large Scale Integrated Circuit) inspection microscope (Optiphot-300; manufactured by Nikon Corporation) to observe whether there was residue in the opening when the contact hole of the obtained embossed pattern was processed with the minimum exposure.

[0377] The following judgment was made: A and B with a residue in the opening less than 5% of the area were selected. + , B -- And C is set to be qualified.

[0378] A: No residue at the opening (less than 1%)

[0379] B + : The area of ​​the residue in the opening is 1% or more and less than 2%

[0380] B - : The area of ​​the residue in the opening is 2% or more and less than 3%

[0381] C: The area of ​​the residue in the opening is 3% or more and less than 5%

[0382] D: The area of ​​the residue in the opening is 5% or more and less than 10%

[0383] E: The area of ​​the residue in the opening is 10% or more.

[0384] (7) Changes in film thickness caused by heat treatment

[0385] Using a coating and developing device ACT-8 (manufactured by Tokyo Electron), the positive photosensitive resin composition obtained from each embodiment and comparative example was applied to an 8-inch silicon wafer by spin coating, and heated at 100°C for 2 minutes to produce a positive photosensitive resin film with a film thickness of 4.0 μm. In addition, the film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings) under the condition of a refractive index of 1.629. Using a clean oven (CLH-21CD-S manufactured by KOYO THERMO SYSTEM), the wafer with the resin film was heat-treated at 250°C for 30 minutes under a nitrogen flow (oxygen concentration of less than 20 ppm), and the film thickness R (μm) was measured. At this time, the value of R / 4×100 was taken as the film thickness retention rate after heat treatment.

[0386] The evaluation was performed as follows, and A and B having a film thickness retention rate of 70% or more were considered acceptable.

[0387] A: Film thickness retention rate is more than 75%

[0388] B: Film thickness retention rate is 70% or more and less than 75%

[0389] C: The film thickness retention rate is less than 70%.

[0390] Synthesis Example 1 Synthesis of polyimide (PI-01)

[0391] Under a dry nitrogen flow, 30.03g (100mmol) of TDA-100 and 200.0g of NMP as an acid dianhydride were weighed in a three-necked flask and dissolved. 50.00g of NMP and 1.860g (20mmol) of aniline as a monoamine were added thereto, and stirred at 40°C for 1 hour. Then, 50.00g of NMP and 23.25g (90mmol) of BAP as a diamine were added, reacted at 40°C for 1 hour, and then stirred at 200°C for 4 hours. After the stirring was completed, the solution was put into 2L of pure water to obtain a white precipitate. The precipitate was collected by filtration, washed with pure water 3 times, and dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of a polyimide resin (PI-01). The Mw of the obtained resin was 24,900, and the imidization rate was 100%. The fluorine atom content in the resin was 0% by mass. The evaluation results are shown in Table 1.

[0392] Synthesis of Polyimide (PI-02 to PI-20) in Synthesis Example 2 to Synthesis Example 20

[0393] The synthesis was carried out in the same manner as in Synthesis Example 1 except that the acid dianhydride, monoamine, and diamine were changed to the types and amounts described in Table 1. The evaluation results are described in Table 1.

[0394] [Table 1-1]

[0395]

[0396]

[0397] Synthesis Example 21 Synthesis of polybenzoxazole precursor (PBO-01)

[0398] Under a dry nitrogen stream, 25.83 g (100 mmol) of BAP and 2.960 g (20 mmol) of phthalic anhydride were dissolved in 75.00 g of NMP and stirred at 80°C for 2 hours. Then, the temperature of the solution was cooled to -15°C. After confirming that the temperature of the solution reached -15°C, a solution prepared by dissolving 26.56 g (90 mmol) of ODBC in 30 g of NMP was added dropwise so that the temperature in the reaction system did not exceed 0°C. After the addition was completed, stirring was continued at 20°C for 6 hours. After the reaction was completed, the solution was added to 3 L of pure water containing 10% by weight of methanol to precipitate a white precipitate. The precipitate was collected by filtration, washed with pure water 3 times, and dried in a vacuum dryer at 50°C for 72 hours to obtain a polybenzoxazole resin (PBO-01). The Mw of the obtained resin was 23,400, and the oxazolidinylation rate was 10%. The evaluation results are recorded in Table 2-1.

[0399] Synthesis Examples 21 to 35 Synthesis of Polybenzoxazole Precursors (PBO-02 to PBO-15)

[0400] Synthesis was carried out in the same manner as in Synthesis Example 21, except that the dicarboxylic acid derivative, diamine, and terminal acid anhydride were changed to the types and amounts described in Table 2-1. The evaluation results are described in Table 2-1.

[0401] Synthesis Example 36 Synthesis of polyimide precursor (PAA-01)

[0402] Under a dry nitrogen flow, 31.02 g (100 mmol) of ODPA and 200.0 g of NMP as an acid dianhydride were weighed and dissolved in a three-necked flask. 50.00 g of NMP and 1.860 g (20 mmol) of aniline as a monoamine were added thereto, and stirred at 40°C for 1 hour. Then, 50.00 g of NMP and 54.41 g (90 mmol) of HFHA as a diamine were added together, and reacted at 40°C for 3 hours. After the stirring was completed, the solution was put into 2 L of pure water to obtain a white precipitate. The precipitate was collected by filtration, washed with pure water 3 times, and dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of a polyimide precursor (PAA-01). The Mw of the obtained resin was 27,000, the imidization rate was 5%, and the fluorine atom concentration of the resin was 18.3%. The evaluation results are recorded in Table 2-2.

[0403] [Table 2-1]

[0404]

[0405]

[0406] Synthesis Example 37 (A) A resin comprising a structural unit represented by formula (1):

[0407] Under a dry nitrogen stream, 10.00 g of PI-01 synthesized in Synthesis Example 1 as a base polymer and 50.00 g of CP as a solvent were weighed and dissolved in a three-necked flask. 1.800 g of IPVE as a protective agent was added thereto, and the mixture was stirred at 0°C for 1 hour. Then, 1.000 × 10 pyridinium p-toluenesulfonate as a catalyst was added. -2 g, stirred at 0 ° C for 3 hours. After the stirring was completed, the acid catalyst was neutralized with a saturated sodium bicarbonate aqueous solution and the water tank was removed. The organic layer was then washed twice with water. Then, a rotary evaporator was used to remove low-boiling residues for the purpose of removing unreacted IPVE. Then, the solid content concentration of the solution was determined, and CP was added in a manner such that the solid content concentration became 40%, and a 40% by mass solution of the solid content of the resin (PI-01-IPVE10) in which the hydroxyl group was protected by 1-isopropoxyethyl as an acid-decomposable group was obtained. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups is 10 mol%. The synthesis results are shown in Table 3.

[0408] Synthesis Example 38 to Synthesis Example 78

[0409] The synthesis was carried out in the same manner as in Synthesis Example 37 except that the base polymer and the protective agent were changed as shown in Table 3. Table 3 shows the synthesis results.

[0410] [Table 3-1]

[0411]

[0412]

[0413]

[0414] Example 1

[0415] Under a yellow light, 2.500 g of a 40% CP solution of P1-01-IPVE10 as the resin (A) and 5.000 × 10 -2 g, (C) 5.000×10-dimethylpyridine as an amine compound -3 Then, 1.500 g of CP was added to adjust the concentration to prepare a positive photosensitive resin composition.

[0416] The prepared positive photosensitive resin composition was subjected to (6) formation of a relief pattern, and (6-1) reduction in developed film, (6-2) sensitivity, and (6-3) residue evaluation.

[0417] Example 2 to Example 38, Comparative Example 1 to Comparative Example 4

[0418] The evaluation was performed in the same manner as in Example 1 except that the formulation of each component of the positive photosensitive resin composition was changed as shown in Table 4. The evaluation results are shown in Table 4. Comparative Examples 1 and 2 had excessive fluorine atom contents, and Comparative Example 3 used PI-01-tBOC25 and contained a carbonyl-containing organic group as an acid-decomposable group.

[0419] [Table 4-1]

[0420]

[0421]

[0422]

[0423] Embodiment 39 to Embodiment 40

[0424] Evaluation was performed in the same manner as in Example 14, except that the type of the (B) photoacid generator was changed as shown in Table 5. Table 5 shows the evaluation results.

[0425] Embodiment 41

[0426] The evaluation was performed in the same manner as in Example 7, except that the type of the (B) photoacid generator was changed as shown in Table 5. Table 5 shows the evaluation results.

[0427] [Table 5]

[0428]

[0429] Embodiment 42

[0430] The evaluation was performed in the same manner as in Example 3 except that the (C) amine compound was changed as shown in Table 6 from Example 3. Table 6 shows the evaluation results.

[0431] Embodiment 43

[0432] The evaluation was performed in the same manner as in Example 14, except that the (C) amine compound was changed as described in Table 6 from Example 14. Table 6 shows the evaluation results.

[0433] [Table 6]

[0434]

[0435] Embodiment 44, Embodiment 45

[0436] 10.00 g of PI-01-IPVE25 (40% CP solution) was weighed, 6.000 g of GBL was added, and solvent replacement was performed using a rotary evaporator. After solvent replacement, the solid content concentration was measured, and GBL was added so that the solid content concentration became 40% to obtain PI-01-IPVE25 (40% GBL solution).

[0437] Evaluation was performed in the same manner as in Example 3 except that the resin (A) was changed to PI-01-IPVE25 (40% GBL solution) and the type of solvent was changed as shown in Table 7 to a composition in which 100% of the solvent was GBL and a composition in which 20% of the solvent was CP. The evaluation results are shown in Table 7.

[0438] [Table 7]

[0439]

[0440] Comparative Examples 5 to 7

[0441] As shown in Table 8, a composition was prepared using an unprotected resin and a quinonediazide compound. The prepared composition was subjected to (6) formation of a relief pattern, and (6-1) reduction in developed film, (6-2) sensitivity, and (6-3) residue evaluation. The evaluation results are shown in Table 8. Comparative Examples 5, 6, and 7 all did not contain the structure of the general formula (1) (n=1 to 4).

[0442] [Table 8]

[0443]

Table 8

[0444]

Claims

1. A positive photosensitive resin composition, comprising: (A) Heat-resistant resin containing nitrogen atoms (B) a photoacid generator, The resin (A) comprises a structural unit represented by formula (1), and the total amount of all resins contained in the composition is 100% by mass, and the fluorine atom content in all resins is 15% by mass or less, [Chemistry 1] (In formula (1), R 1 represents a trivalent to 12valent organic group having 3 to 30 carbon atoms, R 2 is a monovalent acid-decomposable group having 3 to 20 carbon atoms; m represents an integer of 0 to 4, n represents an integer of 1 to 4; * represents a bonding site, and a and b each independently represent an integer of 1 or 2). 2 . The positive photosensitive resin composition according to claim 1 , wherein (A) the heat-resistant resin containing a nitrogen atom is one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof. 3 . The positive photosensitive resin composition according to claim 1 , wherein the acid-decomposable group is an oxymethyl group.

4. The positive photosensitive resin composition according to claim 1, wherein the OR 2 The pKa of the phenolic hydroxyl group-containing structure generated by acid decomposition of the hydroxyl group is 11 or more.

5. The positive photosensitive resin composition according to claim 1, wherein the R 2 At least one of is a group represented by formula (2) or a group represented by formula (3), [Chemistry 2] In formula (2) and formula (3), R 3 represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms; R 4 represents an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms; R 5 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms; p represents an integer of 0 to 2, q represents an integer of 0 to 2; and * represents a bonding site.

6. The positive photosensitive resin composition according to claim 1, wherein the R 2 At least one of is a group represented by formula (4) or a group represented by formula (5), [Chemistry 3] (In formula (4) and formula (5), R 6 and R 7 Each independently represents an alkyl group having 1 to 6 carbon atoms; R 8 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms; r represents an integer of 0 to 2, s represents an integer of 0 to 2; and * represents a bonding site).

7. The positive photosensitive resin composition according to claim 1, wherein the formula (1) is the formula (6), [Chemistry 4] (In formula (6), R 2 , a and b represent the same meanings as the same symbols in the formula (1); L represents a direct bond, -C(CH3)2-, 9H-fluorene-9,9-diyl; m1 and m2 each independently represent an integer of 0 to 2; n1 and n2 each independently represent an integer of 0 to 2; wherein, Satisfying 1≤(n1+n2)≤4; * indicates the bonding site).

8. The positive photosensitive resin composition according to claim 2, wherein the resin (A) comprises a structural unit represented by formula (7) and / or a structural unit represented by formula (8), [Chemistry 5] (In formula (7), X1 represents a tetravalent organic group having 4 to 50 carbon atoms, or a constituent unit of the formula (1); Y1 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of the formula (1); wherein, At least one of X1 and Y1 is a constituent unit of the formula (1); when X1 is a constituent unit of the formula (1), a=b=2; when Y1 is a constituent unit of the formula (1), a+b=2; * represents a bonding site) [Chemistry 6] (In formula (8), X2 represents a divalent organic group having 4 to 50 carbon atoms, or a constituent unit of the formula (1); Y2 represents a divalent organic group having 6 to 30 carbon atoms, or a constituent unit of the formula (1); wherein at least one of X2 and Y2 is a constituent unit of the formula (1), and a=b=1; * represents a bonding site).

9. The positive photosensitive resin composition according to claim 8, wherein in the formula (7), X1 is a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms; and / or in the formula (8), X2 is a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms.

10. The positive photosensitive resin composition according to claim 2, wherein the resin (A) has a structural unit represented by formula (9), when the OH group and OR 2 The total number of groups is defined as M1, and the OH group and OR group are removed from the structure of formula (9). 2 When the molecular weight of the remaining structural part after the group is set to N1, the value of M1 / N1 is 0.004075 or more; and / or The resin (A) has a structural unit represented by formula (10). When the OH group and OR 2 The total number of the groups is defined as M2, and the OH group and the OR group are removed from the structure of formula (10). 2 When the molecular weight of the remaining structural part after the group is set to N2, the value of M2 / N2 is 0.004075 or more, [Chemistry 7] (In formula (9) and formula (10), R 1 , R 2 , m and n represent the same meanings as the same symbols in the formula (1); X3 represents a tetravalent organic group having 4 to 50 carbon atoms and an aliphatic skeleton having more than 4 carbon atoms; X4 represents a divalent organic group having 4 to 50 carbon atoms and an aliphatic skeleton having more than 4 carbon atoms). 11 . The positive photosensitive resin composition according to claim 1 , wherein the (B) photoacid generator comprises a nonionic photoacid generator. 12 . The positive photosensitive resin composition according to claim 1 , wherein the (B) photoacid generator comprises a photoacid generator having an acid dissociation constant (pKa) of an acidic group generated by light in the range of −14 to 2. 13 . The positive photosensitive resin composition according to claim 1 , wherein the (B) photoacid generator comprises an oxime sulfonate compound and / or an imide sulfonate compound. 14 . The positive photosensitive resin composition according to claim 1 , further comprising (C) an amine compound having a conjugate acid with a pKa in the range of 4.5 to 10.

8. 15 . The positive photosensitive resin composition according to claim 1 , further comprising (D) a solvent, wherein the (D) solvent comprises an aprotic solvent having 3 to 12 carbon atoms and a relative dielectric constant in the range of 5 to 20. 16 . A positive photosensitive resin sheet, obtained by forming the positive photosensitive resin composition according to claim 1 into a sheet on a support.

17. A cured product obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 15.

18. A method for manufacturing a hardened object, comprising: a) a process of coating the positive photosensitive resin composition described in any one of claims 1 to 15 on a substrate and drying it to form a positive photosensitive resin film, or a process of thermally pressing the positive photosensitive resin composition of the present invention onto a substrate using the positive photosensitive resin sheet described in claim 16; b) a process of exposing the positive photosensitive resin film or the positive photosensitive resin composition after thermal pressing; c) a process of eluting or removing the exposed part of the exposed positive photosensitive resin film or the exposed part of the positive photosensitive resin composition after thermal pressing using an alkaline aqueous solution to perform development; and d) a process of heating the developed positive photosensitive resin film or the positive photosensitive resin composition after thermal pressing.

19. A semiconductor device, wherein the cured product according to claim 17 is arranged as a protective film of a semiconductor or an interlayer insulating film between redistribution wirings.

20. A display device, comprising: A first electrode formed on a substrate, an insulating layer formed on the first electrode in a manner that the first electrode is partially exposed, and a second electrode disposed opposite to the first electrode, wherein the display device The insulating layer includes the hardener according to claim 17 . 21 . A display device comprising a planarizing film provided in a state of covering the unevenness on a substrate on which a thin film transistor (TFT) is formed, wherein the planarizing film comprises the cured product according to claim 17 .

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