Positive type photosensitive resin composition, positive type photosensitive resin sheet, cured product, cured product manufacturing method, semiconductor device, and display device

Abstract

The purpose of the present invention is to provide a highly sensitive positive type photosensitive resin composition that exhibits less amount of film reduction during alkaline developing, and that can shorten the exposure time. A positive type photosensitive resin composition according to the present invention contains a heat-resistant resin including nitrogen atoms, and (B) a photoacid generator. The (A) resin includes a structural unit represented by formula (1). When the total amount of all resins contained in the composition is defined as 100 mass%, the contained amount of fluorine atoms in all resins is 15 mass% or less. (In formula (1), R1 represents an organic group having a valence of 3-12 and having 3-30 carbon atoms, and R2 represents a monovalent acid degradable group having 3-20 carbon atoms. m represents an integer of 0-4 and n represents an integer of 1-4. * represents a binding site, and a and b each independently represent an integer of 1 or 2.)

Description

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

[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.

[0002] Polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance, electrical insulation properties, and mechanical properties, are widely used in surface protection films and interlayer insulating films used in semiconductor devices, insulating layers in organic electroluminescent devices, and planarizing films for TFT (thin film transistor) substrates. In recent years, photosensitive resin compositions in which these resins themselves or their precursors are given photosensitivity have been used (hereinafter, these photosensitive resin compositions will be referred to as polyimide-based photosensitive resin compositions). The use of polyimide-based photosensitive resin compositions can simplify the pattern processing step and shorten the complicated manufacturing process.

[0003] As polyimide-based photosensitive resin compositions, positive-type compositions in which the exposed area becomes readily soluble in a developer and can be patterned, and negative-type compositions in which the composition itself is readily soluble and the exposed area becomes insoluble in a developer have been proposed. Generally, positive-type compositions have superior resolution compared to negative-type compositions, and therefore positive-type polyimide-based photosensitive resin compositions are used in applications requiring fine processing.

[0004] Known positive-type polyimide-based photosensitive resin compositions include those in which a quinone diazide compound is added to a polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor (see, for example, Patent Document 1), and those in which a photoacid generator is added to a polyamide containing a protecting group that can be cleaved in the presence of an acid (see, for example, Patent Document 2).

[0005] JP 2011-180473 A JP 2011-221173 A

[0006] In recent years, due to factors such as the increasing size of substrates being used and increased productivity, it has become necessary to shorten the exposure time and to reduce the amount of film loss in unexposed areas during development in order to improve the aperture ratio and in-plane uniformity of film thickness after development.

[0007] The technology described in Patent Document 1 combines an alkali-soluble resin with a quinone diazide compound. The quinone diazide compound interacts with the alkali-soluble resin, reducing the solubility of the composition in an alkaline developer. On the other hand, the quinone diazide compound undergoes a photochemical reaction upon exposure to form an indene carboxylic acid compound, which acts as a dissolution promoter in an alkaline developer. This creates a dissolution rate difference (dissolution contrast) between the unexposed and exposed areas, enabling pattern processing. Therefore, sensitivity depends on the amount of quinone diazide compound added. However, increasing the amount of quinone diazide compound reduces the photochemical reaction rate due to the light absorption of the quinone diazide compound itself. Therefore, it is difficult to achieve both a short exposure time and minimal film loss.

[0008] The technology disclosed in Patent Document 2 involves substituting the hydrogen atoms of hydroxy groups in an alkali-soluble polyamide with tert-butoxycarbonyl groups (hereinafter also referred to as t-Boc groups) to produce an alkali-insoluble resin, which is then combined with a photoacid generator. This technology generates an acid from the photoacid generator in the exposed area, which reacts with the t-Boc group, eliminating the t-Boc group from the polyamide (hereinafter referred to as deprotection), converting the polyamide from alkali-insoluble to alkali-soluble. As a result, a dissolution contrast is created between the exposed and unexposed areas, enabling positive-tone pattern processing. However, this technology suffers from the issues of being unable to shorten the exposure time due to the low reactivity of the t-Boc group with the acid and the low dissolution contrast between the exposed and unexposed areas, as well as the generation of residues at the pattern openings.

[0009] An object of the present invention is to provide a positive photosensitive composition which has high sensitivity due to a shortened exposure time, which reduces the amount of film loss during development, and which leaves little residue in pattern openings.

[0010] The present invention is as follows: (1) A positive photosensitive resin composition comprising (A) a heat-resistant resin containing a nitrogen atom and (B) a photoacid generator, the resin (A) containing a structural unit represented by formula (1), and a fluorine atom content in all the resins in the composition being 15% by mass or less, where the total amount of all the resins in the composition is 100% by mass.

[0011]

[0012] In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ is a monovalent acid-decomposable group having 3 to 20 carbon atoms. m is an integer of 0 to 4, and n is 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 (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 (1) or (2), wherein the acid-decomposable group is an oxymethyl group. (4) The OR of formula (1) ２ (5) The positive photosensitive resin composition according to any one of (1) to (3), wherein the pKa of the phenolic hydroxyl group-containing structure generated by decomposition of the R ２ (5) The positive photosensitive resin composition according to any one of (1) to (4), wherein at least one of the following is a group represented by formula (2) or a group represented by formula (3):

[0013]

[0014] 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. 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. 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. (6) The R ２ (5) The positive photosensitive resin composition according to any one of (1) to (5), wherein at least one of the following is a group represented by formula (4) or a group represented by formula (5):

[0015]

[0016] In formula (4) and formula (5), R ６ and R ７R 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. (7) The positive photosensitive resin composition according to any one of (1) to (5), wherein the formula (1) is formula (6).

[0017]

[0018] In formula (6), R ２ , a, and b have the same meanings as the same symbols in the formula (1). L is a direct bond, —C(CH ３ ) ２ -, 9H-fluorene-9,9-diyl group. １ and m ２ Each of n independently represents an integer of 0 to 2. １ and n ２ are each independently an integer of 0 to 2, provided that 1≦(n １ +n ２ )≦4. * indicates a bonding site. (8) The positive photosensitive resin composition according to (2), wherein the resin (A) contains a structural unit represented by formula (7) and / or a structural unit represented by formula (8).

[0019]

[0020] In formula (7), X １ represents a tetravalent organic group having 4 to 50 carbon atoms or a structural unit of the formula (1). １ represents a divalent organic group having 6 to 30 carbon atoms or a structural unit of the formula (1). １ and Y １ At least one of the structural units is the structural unit of the formula (1), and X １ When the structural unit of the formula (1) is used, a=b=2, and Y １ However, when the structural unit of the formula (1) is used, a+b=2. * indicates a bonding site.

[0021]

[0022] In formula (8), X ２represents a divalent organic group having 4 to 50 carbon atoms or a structural unit of the formula (1). ２ represents a divalent organic group having 6 to 30 carbon atoms or a structural unit of the formula (1). ２ and Y ２ At least one of the units is a structural unit of the formula (1), and a=b=1. * indicates a bonding site. (9) In the formula (7), X １ 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), X ２ is a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. ２ The total number of groups is M1, and the number of OH groups and OR groups from the structure of formula (9) is ２ When the molecular weight of the remaining structural portion excluding the group is defined as N1, the value of M1 / N1 is 0.004075 or more, and / or the resin (A) has a structural unit represented by formula (10), and the OH group and OR group contained in formula (10) ２ The total number of groups is M2, and the number of OH groups and OR groups from the structure of formula (10) is ２ (2) The positive photosensitive resin composition according to (2), wherein the value of M2 / N2 is 0.004075 or more, where N2 is the molecular weight of the remaining structural portion excluding the group.

[0023]

[0024] In formula (9) and formula (10), R １ , R ２ , m, and n have the same meanings as the same symbols in the formula (1). ３ represents a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. ４represents a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. (11) The positive photosensitive resin composition according to any one of (1) to (10), wherein the (B) photoacid generator comprises a nonionic photoacid generator. (12) The positive photosensitive resin composition according to any one of (1) to (11), 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 any one of (1) to (12), wherein the (B) photoacid generator comprises an oxime sulfonate compound and / or an imide sulfonate compound. (14) The positive photosensitive resin composition according to any one of (1) to (13), further comprising (C) an amine compound whose conjugate acid has a pKa of 4.5 to 10.8. (15) The positive photosensitive resin composition according to any one of (1) to (14), further comprising a solvent (D), 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. (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 shape on a support. (17) A cured product obtained by curing the positive photosensitive resin composition according to any one of (1) to (15). (18) A method for producing a cured product, comprising the steps of: a) applying the positive photosensitive resin composition according to any one of (1) to (15) onto a substrate and drying it to form a positive photosensitive resin film; or b) using the positive photosensitive resin sheet according to (16) to thermocompression bond the positive photosensitive resin composition of the present invention onto a substrate, b) exposing the positive photosensitive resin film or the thermocompression-bonded positive photosensitive resin composition to light, c) developing the exposed portion of the exposed positive photosensitive resin film or the exposed portion of the thermocompression-bonded positive photosensitive resin composition by eluting or removing it with an alkaline aqueous solution, and d) heat-treating the developed positive photosensitive resin film or the developed thermocompression-bonded positive photosensitive resin composition. (19) A semiconductor device in which the cured product according to (17) is arranged as a protective film for a semiconductor or an interlayer insulating film between rewirings. (20) A display device comprising 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 disposed opposite the first electrode, wherein the insulating layer comprises the cured product described in (17).(21) A display device comprising a planarization film provided in a state of covering irregularities on a substrate on which a thin film transistor (TFT) is formed, wherein the planarization film comprises the cured product according to (17).

[0025] The positive photosensitive composition of the present invention has high sensitivity, allowing the exposure time to be shortened, and the amount of film loss during development is small, leaving little residue in the pattern openings.

[0026] The present invention provides a positive photosensitive resin composition comprising (A) a heat-resistant resin containing a nitrogen atom and (B) a photoacid generator, wherein the resin (A) contains a structural unit represented by formula (1), and the fluorine atom content of all the resins contained in the composition is 15% by mass or less, where the total amount of all the resins contained in the composition is 100% by mass.

[0027]

[0028] In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ represents 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.

[0029] The positive photosensitive resin composition of the present invention contains a photoacid generator (B), and thus can generate an acid in the composition by irradiating the composition with exposure light corresponding to the photoacid generator contained therein. The generated acid is generated by reacting the R １ -O-R ２ O-R in the structure ２ It acts on the bond between R １ -OH. １ The —OH group acts as a soluble group in an alkaline aqueous solution, and therefore the positive photosensitive resin composition of the present invention can exhibit a solubility contrast in an alkaline aqueous solution between the unexposed and exposed areas, thereby forming a positive relief pattern in which the exposed areas are soluble.

[0030] For this reason, in this specification, R ２ is referred to as an acid-decomposable group. ２can be converted to a hydroxyl group by the action of an acid, ２ The structure of R １ -O-R ２ is R １ The conversion to —OH is sometimes referred to as “deprotection.”

[0031] <(A) Heat-resistant resin containing a nitrogen atom> The heat-resistant resin containing a nitrogen atom refers to a resin having a group containing a nitrogen atom, such as an amide group or a urea group, or a heterocycle containing a nitrogen atom, 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.

[0032] It also includes precursor resins that, through chemical ring closure or thermal ring closure, become resins having a nitrogen atom-containing heterocycle such as an imide ring or an oxazole ring and a 5% weight loss temperature of 200° C. or higher.

[0033] Examples of heat-resistant resins containing nitrogen atoms include polyimide, polyamide, polyurea, polyamideimide, polyazole (polybenzimidazole, polybenzoxazole, polybenzothiazole), etc. Among these, polyamide includes polyimide precursor and polyazole precursor.

[0034] More preferred examples of the heat-resistant resin containing a nitrogen atom (A) include one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof.

[0035] Polyimides are polymers containing imide bonds in their repeating units. Polyimides can be synthesized by known methods. For example, polyimides can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and then dehydrating and cyclizing the resulting reaction product through heating or a reaction using a catalyst such as an acid or a base. Therefore, polyimides contain residues of tetracarboxylic acid and / or its derivatives, and residues of diamine and / or its derivatives.

[0036] The reaction product before dehydration and ring closure is called a polyimide precursor, and the process of dehydration and ring closure to form imide bonds is called imidization. The rate at which groups capable of forming imide bonds in the polyimide precursor are imidized is called the imidization rate.

[0037] The imidization rate of the polyimide is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and particularly preferably 80% or more. An imidization rate of 30% or more is preferable because it is possible to reduce the amount of outgassing at high temperatures and improve the reliability of the cured product described below.

[0038] Polybenzoxazole is a polymer containing a benzoxazole structure in its repeating unit. It can be synthesized by a known method. For example, it can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid activated ester, or the like, and then dehydrating and cyclizing the resulting reaction product by heating or by reaction with an acid, a base, acetic anhydride, or a carbodiimide compound. Therefore, it contains a dicarboxylic acid residue and a bisaminophenol residue.

[0039] Polyamide is a polymer containing amide bonds in its repeating unit and can be synthesized by known methods.

[0040] The polyamide is preferably a polyimide precursor or a polybenzoxazole precursor. The polyimide precursor is a polyamide that can be converted into a polyimide by heating. Because the polyamide is a polyimide precursor, a highly heat-resistant resin film can be formed. The polyimide precursor can be synthesized by a known method. For example, it can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. The polybenzoxazole precursor is a polyamide that can be converted into a polybenzoxazole by heating. Because the polyamide is a polybenzoxazole precursor, a highly heat-resistant resin film can be formed. The polybenzoxazole precursor can be synthesized by a known method. For example, it can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, or a dicarboxylic acid activated ester.

[0041] The copolymer refers to a copolymer of two or more types selected from the group consisting of polyimide, polybenzoxazole, and polyamide.

[0042] The resin (A) contained in the positive photosensitive resin composition of the present invention is preferably a copolymer of two or more resins selected from the group consisting of polyimide, polybenzoxazole, and polyamide. By using a copolymer, it becomes easier to achieve both heat resistance, solvent solubility, and alkali solubility.

[0043] The main chain terminals of the resin (A) contained in the positive photosensitive resin composition of the present invention are preferably capped with a terminal-capping agent such as a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Capping the main chain terminals with the terminal-capping agent can improve the storage stability of the positive photosensitive resin composition. The proportion of the monoamine used as the terminal-capping agent relative to the total amine components is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 60 mol% or less, and particularly preferably 50 mol% or less. The proportion of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the terminal-capping agent relative to the diamine components is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 100 mol% or less, and particularly preferably 90 mol% or less. Multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0044] The weight-average molecular weight of the (A) resin, as determined by gel permeation chromatography in terms of polystyrene, is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 60,000. By setting the weight-average molecular weight within the above range, it is possible to easily achieve good solvent solubility, good solubility in a developer, and high mechanical strength. In the present invention, the weight-average molecular weight is determined by the method described below.

[0045] <Resin (A) Contains a Structural Unit Represented by Formula (1)> In the positive photosensitive resin composition of the present invention, the resin (A) contains a structural unit represented by formula (1).

[0046]

[0047] In formula (1), R １ represents a trivalent to dodecavalent organic group having 3 to 30 carbon atoms, and R ２ is a monovalent acid-decomposable group having 3 to 20 carbon atoms.

[0048] R １ has an aromatic ring, and the aromatic ring group is an OH group or an OR ２It is preferable that the aromatic ring is directly bonded to a group. The aromatic ring is more preferably a phenyl group or a naphthyl group. １ By adopting such a structure, OR ２ The alkali solubility of the OH groups after deprotection is improved, which makes it easier to obtain a positive relief pattern with little residue.

[0049] R １ has a phenyl group or a naphthyl group, and the phenyl group or the naphthyl group is an OH group or an OR ２ Specific examples of the preferred structure of formula (1) directly bonded to the group include the following structures:

[0050]

[0051] In the above structure, R ２ , a, and b have the same meanings as the same symbols in the formula (1). ３ , m ４ , n ３ are each independently an integer of 0 to 2, n ４ represents an integer of 1 or 2. ３ +m ４ = m, n ３ +n ４ = n, and m and n have the same meanings as the same symbols in the formula (1).

[0052] In formula (1), m represents an integer of 0 to 4, and n represents an integer of 1 to 4. From the viewpoint of the heat resistance of the resin, the value of m+n is preferably an integer of 1 to 4, more preferably an integer of 1 or 2, and even more preferably 2.

[0053] In formula (1), * represents a bonding site, and a and b each independently represent an integer of 1 or 2. From the viewpoint of the heat resistance of the resin, it is preferable that a=b=1 or a=b=2, and it is more preferable that a=b=1.

[0054] The structure represented by formula (1) can be obtained by, for example, synthesizing one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide and copolymers thereof using a hydroxyl group-containing acid dianhydride or a hydroxyl group-containing diamine, and converting some or all of the OH groups of the resin into OR２ It can be obtained by modifying the group.

[0055] Examples of hydroxy group-containing acid dianhydrides include, but are not limited to, 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), N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide).

[0056] Examples of hydroxy group-containing diamines include, but are not limited to, 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.

[0057] More preferred structures of formula (1) include OR ２ The pKa of the phenolic hydroxyl group-containing structure produced by decomposition of the group with an acid is at least 11. The pKa value is preferably at least 11.5, more preferably at least 12, and even more preferably at least 12.5.

[0058] At this time, the OR ２ The structure having a pKa of 11 or more, which is a phenolic hydroxyl group-containing structure produced by decomposition of the group with an acid, must account for 50 mol % or more of the structure of formula (1) contained in the composition, assuming that the structure is 100 mol.

[0059] Here, OR of Equation (1) ２ The pKa of the phenolic hydroxyl group-containing structure produced by decomposition of the group with an acid is the OR ２It is a calculated value representing an index of the acidity of the phenolic hydroxyl group in the structure of the following general formula (11) in which all groups have been deprotected. It can be said that the higher the pKa, the lower the acidity of the phenolic hydroxyl group. In principle, the higher the acidity of the phenolic hydroxyl group, the better the solubility in an alkaline developer. However, by intentionally keeping the acidity low by setting the pKa to 11 or more, OR reaction due to the acid generated by exposure can be prevented. ２ This improves the deprotection of the hydroxyl group from the unexposed group to the OH group, and the solubility contrast in an alkaline aqueous solution between the exposed and unexposed areas is significantly increased. As a result, there is an advantage in that the exposure sensitivity is higher than when the alkaline solubility is simply improved.

[0060]

[0061] m and n have the same meanings as the same symbols in the formula (1).

[0062] The pKa is calculated as follows. The structure of general formula (11) is used as the target, and calculations are made using a method for calculating the electronic state of a molecule in accordance with the Schrodinger equation in quantum mechanics. Specifically, the calculations were made using the following calculation software and basis functions, taking into account the solvation energy with water. That is, a uniform dielectric was placed around the molecule, and the interaction between the molecule and the dielectric was calculated. In this study, the calculations were made with a dielectric constant of ε = 78.39. Calculation software: Gaussian 16 Calculation level: B3LYP / 6-31+G(d,p) Solvation method: PCM-UAHF-G03 (Solvent = water) OR of formula (1) ２ The following structures are preferred examples of structures that produce a phenolic hydroxyl group-containing structure having a pKa of 11 or more when the group is decomposed with an acid.

[0063]

[0064] A more preferred structure of formula (1) is the structure of formula (6).

[0065]

[0066] In formula (6), R ２ , a, and b have the same meanings as the same symbols in the formula (1). L is a direct bond, —C(CH ３ )２ -, 9H-fluorene-1,9-diyl group. More preferably, -C(CH ３ ) ２ - is. １ , m ２ , n １ and n ２ are each independently an integer of 0 to 2, provided that 1≦(n １ +n ２ )≦4. * indicates a binding site.

[0067] The 9H-fluorene-1,9-diyl group is a group represented by the following formula:

[0068]

[0069] In formula (1), R ２ is a monovalent acid-decomposable group having 3 to 20 carbon atoms.

[0070] Examples of the acid-decomposable group include organic groups that do not contain a carbonyl group, such as a tertiary alkyl group like a t-butyl group, and an oxymethyl group, with an oxymethyl group being more preferred.

[0071] The oxymethyl group referred to here is a monovalent group having a structure in which carbon and oxygen are bonded together by a single bond in order from the bonding site. The monovalent oxymethyl group having 3 to 20 carbon atoms can be specifically represented by the following structure:

[0072]

[0073] In the above structure, R １１ ~R １６ , R １８ represents a monovalent organic group, and R １７ and R １９indicates a divalent organic group. * indicates a bonding site. The number of carbon atoms in the structure is 3 to 20. Examples of monovalent organic groups include alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 5 to 10 carbon atoms, alkoxyalkyl groups having 2 to 8 carbon atoms, and alkoxycyclic alkyl groups having 6 to 16 carbon atoms. Examples of divalent organic groups include propane-1,3-diyl groups, butane-1,3-diyl groups, pentane-1,3-diyl groups, and groups in which a hydrogen atom of a group selected from the group consisting of propane-1,3-diyl groups, butane-1,3-diyl groups, and pentane-1,3-diyl groups has been substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkoxyalkyl groups having 2 to 8 carbon atoms.

[0074] The R ２ is the monovalent oxymethyl group having 3 to 20 carbon atoms, the OR ２ This improves the deprotection property from the R group to the OH group, and increases the dissolution contrast in an alkaline aqueous solution between the unexposed and exposed areas. As a result, there is an advantage in that it has high exposure sensitivity. ２ At least one of the above is preferably a group represented by formula (2) or a group represented by formula (3).

[0075]

[0076] 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. 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. 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.

[0077] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups.

[0078] Specific examples of alkoxyalkyl groups having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, and a propoxybutyl group.

[0079] Specific examples of the cyclic alkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclopentylethyl group, a cyclohexylethyl group, a cycloheptylethyl group, a cyclopentylpropyl group, a cyclohexylpropyl group, and a cycloheptylpropyl group.

[0080] Specific examples of alkoxy cyclic alkyl groups having 6 to 16 carbon atoms include a methoxypentyl group, an ethoxypentyl group, a propoxypentyl group, a dimethoxypentyl group, a diethoxypentyl group, a dipropoxypentyl group, a trimethoxypentyl group, a triethoxypentyl group, a tripropoxypentyl group, a methoxyhexyl group, an ethoxyhexyl group, a propoxyhexyl group, a dimethoxyhexyl group, a diethoxyhexyl group, a dipropoxyhexyl group, a trimethoxyhexyl group, a triethoxyhexyl group, a tripropoxyhexyl group, a methoxyheptyl group, an ethoxyheptyl group, a propoxyheptyl group, a dimethoxyheptyl group, a diethoxyheptyl group, a dipropoxyheptyl group, a trimethoxyheptyl group, a triethoxyheptyl group, and a tripropoxyheptyl group.

[0081] 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 pentoxy group, and a hexoxy group.

[0082] The R ２ At least one of R is a group represented by formula (2) or a group represented by formula (3), １ -O-R ２ is R １The organic group released when converted to --OH is less likely to remain during development, resulting in a pattern with less residue.

[0083] From the viewpoint of obtaining a pattern with less residue, the R ２ is more preferably a group represented by formula (2).

[0084] From the viewpoint of obtaining a pattern with less residue, the R ２ is more preferably a group represented by formula (4) or a group represented by formula (5).

[0085]

[0086] In formula (4) and formula (5), R ６ and R ７ R 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.

[0087] 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).

[0088] Formula (4) or (5) is R １ -O-R ２ O-R in the structure ２ The α-position of O-R is branched. ２ When the α-position of １ -O-R ２ is R １ The organic group eliminated when converted to --OH is less likely to remain during development, resulting in a pattern with even less residue.

[0089] In particular, the structure of formula (1) is OR ２ The structure of formula (1) contained in the composition is 50 mol % or more of a structure having a pKa of 12.5 or more, which is generated by decomposition of the R group with an acid, and２ When is a group represented by formula (4) or a group represented by formula (5), the organic group is further prevented from remaining during development, and a pattern with less residue can be obtained.

[0090] Furthermore, from the viewpoint of obtaining a pattern with less residue, it is preferable that the phenolic hydroxyl group in the resin (A) and the OR ２ When the total number of groups is 100 moles, OR ２ It is most preferred that the proportion of groups is 40 mol % or less.

[0091] In addition, from the viewpoint of suppressing a decrease in film thickness during development, the phenolic hydroxyl group in the resin (A) and the OR ２ When the total number of groups is 100 moles, OR ２ The proportion of the group is preferably 15 mol % or more, and more preferably 20 mol % or more.

[0092] Of the resins (A), at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof preferably contains a structural unit represented by the following general formula (7) and / or a structural unit represented by the following general formula (8):

[0093]

[0094] In formula (7), X １ represents a tetravalent organic group having 4 to 50 carbon atoms or a structural unit of the formula (1). １ represents a divalent organic group having 6 to 30 carbon atoms or a structural unit of the formula (1). １ and Y １ At least one of the structural units is the structural unit of the formula (1), and X １ When the structural unit of the formula (1) is used, a=b=2, and Y １ However, when the structural unit of the formula (1) is used, a+b=2. * indicates a bonding site.

[0095] The structural unit represented by formula (7) has an imide structure with high heat resistance, and therefore a resin film with high heat resistance can be obtained.

[0096] In formula (8), X ２represents a divalent organic group having 4 to 50 carbon atoms or a structural unit of the formula (1). ２ represents a divalent organic group having 6 to 30 carbon atoms or a structural unit of the formula (1). ２ and Y ２ At least one of the above is a structural unit of the formula (1), where a = b = 1. * indicates a binding site.

[0097] The structural unit represented by formula (8) has a precursor structure of polybenzoxazole, which has high heat resistance. Therefore, by subjecting the structural unit represented by formula (8) to heat treatment to cause oxazole ring closure, a resin film with high heat resistance can be obtained.

[0098] From the viewpoint of reducing the film thickness reduction due to heat treatment, it is more preferable that the resin (A) contains a structural unit represented by formula (7).

[0099] In the formula (7), X １ is preferably a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. ２ 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 advantage of increasing the change in solubility of the resin before and after deprotection, increasing the contrast between the unexposed and exposed areas, and achieving high sensitivity. Examples of 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 include the following structures:

[0100]

[0101] * indicates the binding site.

[0102] From the viewpoint of increasing the contrast between the unexposed area and the exposed area and increasing the sensitivity, X １ and / or, in the formula (8), X ２ In the above, the proportion of aliphatic skeletons having 4 or more carbon atoms is preferably 50 mol % or more, more preferably 70 mol % or more.

[0103] Furthermore, in terms of increasing the change in solubility of the resin before and after deprotection, increasing the contrast between the unexposed area and the exposed area, and achieving high sensitivity, it is preferable that the resin (A) is one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyamide, and copolymers thereof, which have a structural unit represented by formula (9), and the OH group and OR group contained in formula (9) are ２ The total number of groups is M1, and the number of OH groups and OR groups from the structure of formula (9) is ２ When the molecular weight of the remaining structural portion excluding the group is defined as N1, the value of M1 / N1 is 0.004075 or more, and / or the resin (A) has a structural unit represented by formula (10) and the OH group and OR group contained in formula (10) ２ The total number of groups is M2, and the number of OH groups and OR groups from the structure of formula (10) is ２ When the molecular weight of the remaining structural portion excluding the group is N2, the value of M2 / N2 is preferably 0.004075 or more.

[0104] The values ​​of M1 / N1 and M2 / N2 are more preferably 0.004501, and even more preferably 0.005001.

[0105] In formula (9) and formula (10), R １ , R ２ , m, and n have the same meanings as the same symbols in the formula (1). ３ represents a tetravalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms. ４ represents a divalent organic group having 4 to 50 carbon atoms and containing an aliphatic skeleton having 4 or more carbon atoms.

[0106] For example, in the case of the following structure as a specific example of formula (9), M1 = 2.000 and N1 = 512.5, so M1 / N1 = 0.003902.

[0107]

[0108] Furthermore, in the case of the following structure, which is a specific example of formula (10), M2 = 2.000 and N2 = 532.9, so M1 / N1 = 0.003753.

[0109]

[0110] In general formula (1), R１ -O-R ２ is R １ It can be obtained by reacting a resin having —OH with a protecting agent. For example, it can be obtained by reacting a resin having —OH with a protecting agent without solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, or cyclopentanone. １ By reacting a resin having —OH with a protecting agent in the presence of an acid or a base at a reaction temperature of −20 to 50° C., R １ -O-R ２ In this way, a resin having the formula (A), i.e., resin (A), can be obtained.

[0111] As the protecting agent, a known protecting agent capable of protecting a hydroxyl group can be used. ２ When the alkyl group is a 1-ethoxyethyl group, ethyl vinyl ether can be used, and when the alkyl group is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran, etc. can be used.

[0112] Examples of acids 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. Organic acid salts such as pyridinium p-toluenesulfonate are also preferably used. Examples of bases include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0113] <Fluorine Atom Content> In the positive photosensitive resin composition of the present invention, the fluorine atom content in all resins is 15% by mass or less, preferably 8.5% by mass or less, where the total amount of all resins contained in the composition is 100% by mass. When the fluorine atom content is 15% by mass or less, it is possible that, although the reason is not clear, R １ -O-R ２ is R １ Therefore, when compared at the same exposure dose, the deprotection rate can be made high, and a highly sensitive positive photosensitive resin composition can be obtained.

[0114] From the viewpoint of reducing pattern residue after development, the fluorine atom content is more preferably 3.5 mass % or less.

[0115] The fluorine atom content of all resins contained in the composition can be analyzed by the following method, where the total amount of all resins contained in the composition is taken as 100% by mass. First, the resin is separated from the composition. The separated resin is precisely weighed as a sample. Using an automatic sample combustion device, the resin is burned in the combustion tube of an analyzer, and the generated gas is absorbed into a solution. After that, a portion of the absorbed solution is analyzed by ion chromatography. The absorbed solution is H ２ O ２ 0.036% by weight can be used.

[0116] <(B) Photoacid Generator> The positive photosensitive resin composition of the present invention contains (B) a photoacid generator. A photoacid generator is a compound that has the function of generating an acid upon exposure to light. Any known photoacid generator (B) can be used as long as it does not impair the effects of the present invention.

[0117] Examples of the (B) photoacid generator include onium salt-type ionic photoacid generators and nonionic photoacid generators. An onium salt refers to a compound generated when a compound having an electron pair not involved in a chemical bond forms a coordinate bond with another cationic compound via the electron pair. In the ionic photoacid generator, the cationic portion of the onium salt determines the photochemical properties (molar absorption coefficient, absorption wavelength, quantum yield), and the anionic portion determines the strength of the acid generated. On the other hand, nonionic photoacid generators are photoacid generators in which the light-absorbing portion and the acid are connected via an ester bond.

[0118] The ionic compound is preferably one 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, and perfluoro-1-butanesulfonate ("SP-056", product name, manufactured by ADEKA Corporation); the sulfonate of dimethyl-1-naphthylsulfonium; the sulfonate of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the sulfonate of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the sulfonate of diphenyliodonium.

[0119] As the nonionic photoacid 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.

[0120] Specific examples of diazomethane compounds include bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0121] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred examples of the sulfone compound include 2-(p-toluenesulfonyl)acetophenone, bis(phenylsulfonyl)methane, etc.

[0122] Specific examples of the sulfonate ester compound include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, iminosulfonate ester compounds, etc. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, 2,6-(dinitrobenzyl)phenyl sulfonate, etc.

[0123] Specific examples of carboxylic acid ester compounds include carboxylic acid 2-nitrobenzyl ester.

[0124] The photoacid generator (B) preferably contains a nonionic photoacid generator, which inhibits the solubility of unexposed areas and suppresses film thickness reduction during development.

[0125] It is more preferable that the (B) photoacid generator contains a photoacid generator in which the acid dissociation constant (pKa) of the acidic group generated by light is in the range of −14 to 2. When the (B) photoacid generator contains an acid dissociation constant (pKa) of the acidic group generated by light in the above range, the acidic group generated by light can be efficiently converted into an acid. １ -O-R ２ This allows the photoacid generator to act on the structure of the compound represented by the formula (1). As a result, deprotection proceeds more rapidly, resulting in a highly sensitive positive photosensitive resin composition. Specific examples of the photoacid generator in which the acid dissociation constant (pKa) of the acidic group generated by light is in the range of -14 to 2 include photoacid generators in which the acid generated by light is 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), or the like.

[0126] It is more preferable that the photoacid generator (B) contains an oxime sulfonate compound and / or an imide sulfonate compound. The oxime sulfonate compound and the imide sulfonate compound are nonionic photoacid generators, and the acidic group generated by light is a sulfo group, which not only has a high acid dissociation constant (pKa) and can provide a positive photosensitive resin composition with higher sensitivity, but also strengthens the interaction with polar functional groups such as carbonyl groups and amide groups contained in polyimide, polybenzoxazole, and polyamide, thereby further suppressing the solubility of unexposed areas and preventing film thickness reduction during development.

[0127] The oxime sulfonate compound can be represented by the following structure:

[0128]

[0129] R ２１ 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a trifluoromethanesulfonic acid group, a nonafluorobutyl group, a perfluorooctyl group, a (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl group, a benzyl group, a phenyl group, a tosyl group, and a naphthyl group.

[0130] R ２２ and R ２３ is a monovalent organic group having 1 to 30 carbon atoms. ２２ and R ２３ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include a cyano group, a trifluoromethyl group, a hexafluoropropyl group, a pentafluorobutyl group, a dodecafluorohexyl group, a phenyl group, a 4-methoxyphenyl group, a 2-fluorenyl group, and a 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl group.

[0131] R ２４ 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.

[0132]

[0133] * indicates the binding site.

[0134] Specific examples of the oxime sulfonate include "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (benzeneacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (benzeneacetonitrile, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylidene), and PAG-203 (all manufactured by BASF Japan Ltd.), and PAI-101 ((Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Co., Ltd.).

[0135] The imidosulfonate compound can be represented by the following structure:

[0136]

[0137] R ２５ 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 R ２１ Examples of the groups include those given as specific examples of the above.

[0138] R ２６ and R ２７ is a monovalent organic group having 1 to 30 carbon atoms. ２６ and R ２７ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include R ２２ and R ２３ Examples of the groups include those given as specific examples of the above.

[0139] R ２８ is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of divalent organic groups having 3 to 30 carbon atoms include the following structures:

[0140]

[0141] R ２９is a monovalent organic group having 1 to 12 carbon atoms. t is an integer of 0 to 2. Specific examples of monovalent organic groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecanyl group, a 1-(hex-1-en-1-yl) group, and a 1-(4-butoxyphenethyl) group. * indicates a bonding site.

[0142] Examples of the imide sulfonate compound include N-hydroxynaphthalimide triflate, "ADEKA ARCLES" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalimide triflate, manufactured by ADEKA Corporation), NA-101 (N-hydroxynaphthalimide-p-toluenesulfonate), and NA-106 (N-hydroxynaphthalimide camphorsulfonate, all manufactured by Midori Chemical Industry Co., Ltd.).

[0143] In the present invention, the content of (B) the photoacid generator 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 the total resin in the positive-type photosensitive resin composition. By setting the content of (B) the photoacid generator in the above range, a highly sensitive positive-type photosensitive resin composition can be obtained.

[0144] <(C) Amine Compound Having a Conjugated Acid pKa in the Range of 4.5 to 10.8> The positive photosensitive resin composition of the present invention preferably further contains (C) an amine compound having a conjugated acid pKa in the range of 4.5 to 10.8. By containing the amine compound (C), deprotection is suppressed during pre-baking, which will be described later. Therefore, a positive photosensitive resin composition with little loss of developed film can be obtained.

[0145] The amine compound (C) more preferably contains an amine compound whose conjugate acid has a pKa of 5.0 to 10.0, and even more preferably contains an amine compound whose conjugate acid has a pKa of 6.0 to 9.0. When the amine compound (C) contains an amine compound whose conjugate acid has a pKa within the above range, deprotection during prebaking is suppressed and acid generated during exposure is less likely to be neutralized, making it possible to provide a positive photosensitive resin composition with little film loss upon development.

[0146] Examples of amine compounds having a conjugate acid with a pKa in the above range include aniline (pKa=4.6), dimethylaniline (pKa=5.20), pyridine (pKa=5.25), 2-picoline (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), and cyclohexylamine (pKa=10.6).

[0147] Conjugated acids having a pyridine skeleton are preferred, and lutidine is more preferred, from the viewpoint of strengthening the interaction with polar functional groups such as carbonyl groups and amide groups contained in polyimide, polybenzoxazole, and polyamide, thereby reducing the film thickness reduction during development.

[0148] In the present invention, the content of the (C) amine compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the (A) resin. By having the content of the (C) amine compound in the above range, a positive-type photosensitive resin composition with low film loss and high sensitivity can be obtained.

[0149] <(D) Solvent> The positive photosensitive resin composition of the present invention preferably further contains (D) a solvent. By containing a solvent, the coating property is improved and a homogeneous positive photosensitive resin film can be obtained. Any known solvent can be used as the (D) solvent as long as it does not impair the effects of the present invention.

[0150] The solvent (D) is not particularly limited, but suitable examples include amide solvents, ester solvents, alcohol solvents, ether solvents, ketone solvents, and dimethyl sulfoxide.

[0151] Specific examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropylene urea.

[0152] Specific examples of ester solvents 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.

[0153] Specific examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-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-t-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, and propylene glycol.

[0154] Specific examples of ether solvents 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.

[0155] Specific examples of ketone solvents include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.

[0156] The solvent (D) preferably contains an aprotic solvent having a relative dielectric constant in the range of 5 to 20, more preferably 6 to 19, and even more preferably 7 to 19.

[0157] When the solvent (D) contains an aprotic solvent having a relative dielectric constant in the range of 5 to 20, the storage stability of the positive photosensitive resin composition as a solution is improved.

[0158] Examples of aprotic solvents having a dielectric constant in the range of 5 to 20 include tetrahydrofuran (dielectric constant 7.6), propylene glycol monomethyl ether acetate (dielectric constant 8.3), methyl isobutyl ketone (dielectric constant 13.1), cyclopentanone (dielectric constant 14.5), cyclohexanone (dielectric constant 18.3), and methyl ethyl ketone (dielectric constant 18.5).

[0159] The (D) solvent preferably contains an aprotic solvent having 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. An aprotic solvent having 3 to 12 carbon atoms has excellent solubility for the (A) resin contained in the positive photosensitive resin composition of the present invention. Therefore, by including an aprotic solvent having 3 to 12 carbon atoms in the positive photosensitive resin composition of the present invention, a high-concentration positive photosensitive resin composition can be obtained. By applying the composition, not only can a large positive photosensitive resin film having a thickness of, for example, 1 μm or more be easily obtained, but also a resin film with a strong resin network can be formed during film formation, thereby minimizing film thickness reduction during development.

[0160] From the viewpoint of strengthening the interaction with polar functional groups such as carbonyl groups and amide groups contained in polyimide, polybenzoxazole, and polyamide, and thereby reducing the film thickness reduction during development, the solvent (D) is preferably a cyclic ketone, and more preferably cyclopentanone.

[0161] These cyclic ketone solvents preferably account for 20% by mass or more when the total mass of the aprotic solvents having a relative dielectric constant in the range of 5 to 20 is taken as 100%.

[0162] The positive photosensitive resin composition of the present invention further contains a (D) solvent, and the (D) solvent preferably contains an aprotic solvent having 3 to 12 carbon atoms and 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 is preferably 1,500 parts by mass or less in order to form a coating film with a thickness of 1 μm or more.

[0163] In particular, from the viewpoint of strengthening the interaction with polar functional groups such as carbonyl groups and amide groups contained in polyimide, polybenzoxazole, and polyamide, and thereby reducing the film thickness reduction during development, it is more preferable that (B) the photoacid generator contains an oxime sulfonate compound and / or an imide sulfonate compound, (C) the amine compound is a conjugated acid having a pyridine skeleton, and (D) the solvent is an aprotic solvent having a relative dielectric constant in the range of 5 to 20, and when the total weight of the aprotic solvent having a relative dielectric constant in the range of 5 to 20 is taken as 100 weight percent, 20 weight percent or more of the aprotic solvent is a cyclic ketone solvent, and in addition, in order to further strengthen the interaction, the structure of formula (1) contains an OR ２ It is most preferable that the structure having a pKa of 12.5 or more, which is a phenolic hydroxyl group-containing structure produced by decomposition of the group with an acid, accounts for 50 mol % or more of the structure of formula (1) contained in the composition, where the structure is 100 mol.

[0164] The photosensitive resin composition of the present invention may contain other additives in addition to those described above, such as a dissolution promoter, a sensitizer, a silane coupling agent, a surfactant, etc.

[0165] <Cured Product, Method for Producing Cured Product> The cured product of the present invention is a cured product obtained by curing the positive photosensitive resin composition of the present invention. The curing conditions include applying a temperature of 150°C to 320°C to promote a thermal crosslinking reaction and improve heat resistance and chemical resistance. This heat treatment can be carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. The lower limit of the curing conditions in the present invention is preferably 170°C or higher, but more preferably 180°C or higher to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0166] The method for producing a cured product of the present invention includes the steps of: applying the positive photosensitive resin composition of the present invention onto a substrate and drying it to form a positive photosensitive resin film; exposing the positive photosensitive resin film to light; developing the exposed portion of the positive photosensitive resin film by dissolving or removing it with an alkaline aqueous solution; and heat-treating the developed positive photosensitive resin film.

[0167] The cured product obtained in this manner is a cured product mainly composed of polyimide or polybenzoxazole, and therefore has excellent heat resistance, electrical insulation properties, and mechanical properties.

[0168] A method for producing a cured product according to an embodiment of the present invention includes a step of applying the positive photosensitive resin composition of the present invention onto a substrate to form a positive photosensitive resin film.

[0169] The substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafer, ceramic deposition substrate, metal plated substrate, sapphire, and gallium arsenide.

[0170] The positive photosensitive composition of the present invention can be applied to a substrate by any known method, including full-surface coating devices such as spin coating, dip coating, curtain flow coating, spray coating, and slit coating, and printing devices such as screen printing, roll coating, microgravure coating, and inkjet printing.

[0171] After coating, the coating is dried to form a positive photosensitive resin film. Drying is performed using a vacuum dryer or a heating device such as a hot plate or oven. When using a heating device, drying 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 to 100 μm.

[0172] The method for producing a cured product according to an embodiment of the present invention includes a step of exposing the positive photosensitive resin film to light.

[0173] In the exposure step, the positive photosensitive resin film is exposed through a mask having a desired pattern. The wavelength of the exposure light to be irradiated is not particularly limited, and examples thereof include light having a wavelength of 300 to 450 nm, such as g-line (436 nm), i-line (365 nm), and h-line (405 nm). Of these, light having a wavelength of 365 nm is preferred. Examples of light sources used in the exposure step include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, and metal halide lamps. Furthermore, the wavelength of the irradiated light may be adjusted, if necessary, through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a bandpass filter.

[0174] After exposure, post-exposure baking may be performed as necessary. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance for development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like can be used. The post-exposure baking temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.

[0175] The method for producing a cured product according to an embodiment of the present invention includes a step of developing the exposed portion of the positive photosensitive resin film by dissolving or removing it with an alkaline aqueous solution.

[0176] To form a pattern of a positive-type photosensitive resin composition, after exposure, the exposed area is removed using a developer. The developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution containing an alkaline compound dissolved therein. Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added, either alone or in combination, to these alkaline aqueous solutions.

[0177] After development, it is preferable to perform a rinse treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, examples of the solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may also be added to the water for rinsing treatment.

[0178] The method for producing a cured product according to an embodiment of the present invention includes a step of heat treating the developed positive photosensitive resin film.

[0179] After development, a temperature of 150°C to 320°C is applied to promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0180] <Method for Producing Positive Photosensitive Resin Sheet and Cured Product> The positive photosensitive resin composition of the present invention is not limited in shape, and may be, for example, in the form of a paste or a sheet.

[0181] The positive photosensitive resin sheet of the present invention is a sheet-shaped positive photosensitive resin sheet obtained by forming the positive photosensitive resin composition of the present invention on a support. The positive photosensitive resin sheet of the present invention refers to a sheet-shaped sheet obtained by applying the positive photosensitive resin composition of the present invention to a support and drying it at a temperature and for a time within a range that allows the solvent to volatilize, in which the positive photosensitive resin composition of the present invention is not completely cured and is soluble in an organic solvent.

[0182] The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the positive photosensitive resin composition may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and releasability. The thickness of the support is also not particularly limited, but from the viewpoint of workability, a thickness in the range of 10 to 100 μm is preferred. Furthermore, to protect the film surface of the positive photosensitive resin composition obtained by coating, a protective film may be provided on the film surface. This protects the surface of the positive photosensitive resin composition from contaminants such as dust and dirt in the atmosphere.

[0183] Examples of methods for applying the positive photosensitive resin composition to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and methods using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The coating film thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity, etc.

[0184] For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and drying time may be within a range that allows the solvent to volatilize, and it is preferable to appropriately set a range that allows the photosensitive resin composition to be in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 40°C to 150°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 80°C and 90°C for 2 minutes each.

[0185] 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 the steps of: a) applying the positive photosensitive resin composition of the present invention to a substrate and drying it to form a positive photosensitive resin film; b) exposing the positive photosensitive resin film; c) developing the exposed portion of the exposed positive photosensitive resin film by eluting or removing it with an alkaline aqueous solution; and d) heat-treating the developed positive photosensitive resin film. Another embodiment of the method for producing the cured product of the present invention includes the steps of using the positive photosensitive resin sheet of the present invention, and a) thermocompression-bonding the positive photosensitive resin composition of the present invention onto a substrate; b) exposing the thermocompression-bonded positive photosensitive resin composition; c) developing the exposed portion of the thermocompression-bonded positive photosensitive resin composition by eluting or removing it with an alkaline aqueous solution; and d) heat-treating the developed positive photosensitive resin composition.

[0186] The cured product obtained in this manner is a cured product mainly composed of polyimide or polybenzoxazole, and therefore has excellent heat resistance, electrical insulation properties, and mechanical properties.

[0187] Examples of the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and circuit components arranged on these substrates. Examples of organic circuit boards include glass substrate copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth / epoxy copper-clad laminates, heat-resistant thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards 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 components include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low-dielectric materials containing glass-based materials and / or resins; high-dielectric materials containing resins or high-dielectric-constant inorganic particles; and insulators containing glass-based materials.

[0188] The step of thermocompression bonding the positive photosensitive resin sheet onto the substrate is not particularly limited, and known methods can be used. For example, when the positive photosensitive resin sheet has a protective film, the protective film is peeled off, and the positive photosensitive resin sheet and the substrate are placed opposite each other and bonded by thermocompression. The support may be peeled off from the positive photosensitive resin sheet before or after thermocompression bonding, or before or after exposure. Thermocompression bonding can be performed by heat pressing, thermal lamination, thermal vacuum lamination, etc. Among these, thermal lamination is preferred. The bonding temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, the bonding temperature is preferably 150°C or lower to prevent the resin composition film from curing during bonding, which would deteriorate the resolution of pattern formation in the exposure and development steps.

[0189] There are no particular limitations on the step of exposing the positive photosensitive resin sheet, the step of developing the exposed portion of the exposed positive photosensitive resin sheet by eluting or removing it with an alkaline aqueous solution, and the step of heat-treating the developed positive photosensitive resin sheet, but it is preferable that these steps be carried out in the same manner as in the method for producing a cured product using the positive photosensitive resin composition.

[0190] The cured product obtained by curing the positive-type photosensitive resin composition of the present invention can be used in electronic components such as semiconductor devices. In this invention, the term "semiconductor device" refers to any device that can function by utilizing the characteristics of a semiconductor element. Semiconductor devices include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these. Semiconductor devices also include electronic components such as multilayer wiring boards for connecting semiconductor elements. Specifically, the composition is suitable for applications such as semiconductor passivation films, surface protection films for semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between multiple semiconductor elements, interlayer insulating films between wiring layers in multilayer wiring for high-density packaging, and insulating layers in organic electroluminescent devices, but is not limited thereto and can be used for a variety of applications.

[0191] The semiconductor device of the present invention is a semiconductor device in which the cured product of the present invention is disposed as a protective film for a semiconductor or an interlayer insulating film between rewirings. By disposing a cured film of the positive photosensitive composition as a protective film for a semiconductor or an interlayer insulating film between rewirings, a highly reliable semiconductor device can be obtained.

[0192] The semiconductor device of the present invention is preferably a semiconductor device in which the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. The semiconductor device in which the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers is a semiconductor device in which the cured product of the present invention is formed on the rewiring to form an interlayer insulating film, and each set of this rewiring and interlayer insulating film constitutes one layer, and this set is repeatedly arranged in 2 to 10 layers. By repeatedly arranging the rewiring and the interlayer insulating film in 2 to 10 layers, the semiconductor device can be made smaller.

[0193] The display device of the present invention is a display device comprising 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 disposed opposite the first electrode, wherein the insulating layer comprises the cured product of the present invention.

[0194] Another embodiment of the display device of the present invention is a display device comprising a planarization film provided in a state of covering irregularities on a substrate on which thin film transistors (TFTs) are formed, wherein the planarization film comprises the cured product of the present invention.

[0195] Specifically, the display device preferably has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, with the planarization layer and / or insulating layer containing the cured product. Taking an active matrix display device as an example, a display device may have a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or a resin film, a planarization layer disposed thereon to cover the irregularities, and a display device further disposed on the planarization layer. The display device and the wiring are connected via contact holes formed in the planarization layer. The cured product obtained by curing the positive photosensitive resin composition of the present invention has excellent planarization properties and pattern dimensional stability, and is therefore preferably provided as a planarization layer in a display device. In particular, flexible display devices have become mainstream in recent years, and the display device may have a substrate having the driving circuit described above made of a resin film.

[0196] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The names of the compounds used, for which abbreviations are used, are shown below. Regarding the diamine compound, the OR of formula (1) when it is resin (A) is used. ２ The pKa of the phenolic hydroxyl group-containing structure produced by decomposition of the group with an acid is also shown.

[0197] (Acid dianhydride compounds) TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride CHDA: 1,2,4,5-cyclohexane tetracarboxylic dianhydride (Diamine compounds) BAP (pKa=12.76): 2,2-bis(3-amino-4-hydroxyphenyl)propane 6FAP (pKa=10.43): 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane HA: N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide) ABPS (pKa=8.24): bis(3-amino-4-hydroxyphenyl)sulfone BAHF (pKa=11.12): 9,9-bis(3-amino-4-hydroxyphenyl)fluorene CPPS (pKa=12.22): 1,1-bis(3-amino-4-hydroxyphenyl)cyclopentane CHPS (pKa=13.27): 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane (acid dicompound) ODBC: 4,4'-oxybis(benzoyl chloride) BPDC: 4,4'-dicyclohexyldicarboxylic acid chloride CHDC: 4,4'-cyclohexanedicarboxylic acid chloride (cis, trans mixture) (End-capping agent having an amino group) mAP: 3-aminophenol.

[0198] ((B) Photoacid Generator) (Oxime sulfonate compound) PAG-103: "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene, manufactured by BASF Japan Ltd.) PAI-101: (Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Co., Ltd. (Imidosulfonate compound) SP-606: "ADEKA ARKLES" (registered trademark) SP-606 (4-butoxy-N-hydroxy-naphthalimide triflate, manufactured by ADEKA Corporation) (Ionic photoacid generator) SP-056: "ADEKA ARKLES" (registered trademark) SP-056 (triphenylsulfonium perfluoro-1-butanesulfonate, manufactured by ADEKA Corporation).

[0199] ((C) Amine compound) Lutidine: 2,6-lutidine ((D) Solvent) CP: Cyclopentanone GBL: γ-butyrolactone (Others) IPVE: Isopropyl vinyl ether CHVE: Cyclohexyl vinyl ether NPVE: n-propyl vinyl ether DHP: Dihydropyran Boc ２ O: di-tert-butyl dicarbonate NQD-1: diester of 4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol and naphthoquinone diazide sulfonic acid.

[0200] (1) Weight-average molecular weight of polyimide, polybenzoxazole, and polyamide The weight-average molecular weight (Mw) in terms of polystyrene was measured using a GPC analyzer. The weight-average molecular weight of polyimide resin and polybenzoxazole resin was measured under the following conditions. Measurement device: Waters 2695 (manufactured by Waters Corporation) Column temperature: 50°C Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21 wt% lithium chloride and 0.48 wt% phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).

[0201] (2) Imidization rate (%) of PI-01 to PI-20 and PAA-01 The polyimides (PI-01 to PI-20, PAA-01) obtained in the synthesis examples were dissolved in GBL to a concentration of 35% by mass. This 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 produce a resin film with a thickness of 4 to 5 μm. This resin-coated wafer was divided into two, and one was cured in a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 20 ppm or less) at 140 ° C for 30 minutes, then further heated to 320 ° C for 1 hour to completely close the imide ring (Sample IM02). The other was used as is (Sample IM01). The transmission infrared absorption spectra of the resin films (IM01, IM02) before and after curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak (1,780 cm ) of the imide structure due to polyimide was observed. －１ Near 1,377 cm －１ After confirming the existence of the 1,377 cm －１ Peak intensity (S) near 1,377 cm of IM02 －１The peak intensity ratio was calculated by dividing the peak intensity (S) by the peak intensity (T), and this was taken as the content of imide groups in the polyimide before heat treatment, i.e., the imidization rate.

[0202] (3) Fluorine Atom Content in Total Resin in Positive Photosensitive Resin Composition A resin or resin solution was precisely weighed as a sample. Using the automatic sample combustion apparatus described below, the resin or resin solution was burned in the combustion tube of an analyzer, and the generated gas was absorbed into a solution. A portion of the absorbed solution was then analyzed by ion chromatography. In the case of a resin solution, the total fluorine atom content (% by mass) in the obtained sample was divided by the solid content (%) to determine the fluorine atom content in the resin.

[0203] <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C Outlet 1000°C Gas: Ar / O ２ 200mL / min :O ２ / 400 mL / min Absorption liquid: H ２ O ２ 0.036 mass%, internal standard P 4 μg / mL Amount of absorption solution: 20 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DINONEX Co., Ltd.) Mobile phase: 2.7 mmol / L Na ２ CO ３ / 0.3 mmol / L NaHCO ３ Flow rate: 1.5 mL / min. Detector: electrical conductivity detector. Injection volume: 20 μL.

[0204] (4) Protection Rate The protection rate was measured using a 400 MHz, 1H-NMR (nuclear magnetic resonance) spectrometer (AL-400 manufactured by JEOL Ltd.). Specifically, the measurement was performed in a deuterated dimethyl sulfoxide solution with 16 integrations. The integral value of the proton of the methine group (>CH-) derived from the protecting group observed around 5-6 ppm and the integral value of the proton of the phenolic hydroxyl group observed around 9-11 ppm were calculated, and the ratio of the integral value of the proton of the methine group to the integral value of the proton of the phenolic hydroxyl group, when the sum of the integral values ​​of the protons of the methine group and the protons of the phenolic hydroxyl group was taken as 100%, was defined as the protection rate (%).

[0205] (5) Solid Content Concentration The solid content concentration was determined by the following method: 1.500 g of the solution was weighed into an aluminum cup and heated at 180°C for 30 minutes using a hot plate to evaporate the liquid. 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.

[0206] (6) Preparation of Relief Pattern The positive photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coater / developer (Tokyo Electron Ltd.), and heated at 100°C for 2 minutes to prepare a positive photosensitive resin film with a film thickness of 4.0 μm. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. Thereafter, using an i-line stepper NSR-2005i9C (Nikon Corporation), the film was exposed to light at an exposure dose of 5 to 300 mJ / cm through a mask having a 10 μm contact hole pattern. ２ in the range of 5 mJ / cm ２ After the exposure, the film was developed for 80 seconds using the ACT-8 developing device with 2.38% by mass of TMAH (manufactured by Tama Chemicals Co., Ltd.) as a developer, and then rinsed with distilled water and spun off to dry, thereby obtaining a relief pattern.

[0207] (6-1) Calculation of the amount of film reduction after development 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 － , B and C were considered to be acceptable. ＋ A: The amount of reduction in the developed film is less than 0.2 μm － A: The amount of reduction in the developed film is 0.2 μm or more and less than 0.3 μm. B: The amount of reduction in the developed film is 0.3 μm or more and less than 0.5 μm. C: The amount of reduction in the developed film is 0.5 μm or more and less than 1.0 μm. D: The amount of reduction in the developed film is 1.0 μm or more and less than 2.0 μm. E: The amount of reduction in the developed film is 2.0 μm or more.

[0208] (6-2) Sensitivity The resulting relief pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the sensitivity. The results were judged as follows, and a sensitivity of 100 mJ / cm was determined. ２ Less than A ＋ ~C － The result was a pass. ＋ : Sensitivity is 10 mJ / cm ２ A: Sensitivity is less than 10 mJ / cm ２ 15 mJ / cm or more ２ Less than A － : Sensitivity is 15 mJ / cm ２ 20mJ / cm or more ２ Less than B ＋ : Sensitivity is 20 mJ / cm ２ 30mJ / cm or more ２ B: Sensitivity is less than 30 mJ / cm ２ More than 40mJ / cm ２ Less than B － : Sensitivity is 40 mJ / cm ２ More than 50mJ / cm ２ Less than C ＋ : Sensitivity is 50 mJ / cm ２ 70mJ / cm or more ２ C: Sensitivity is less than 70 mJ / cm ２ 85mJ / cm or more ２ Less than C － : Sensitivity is 85 mJ / cm ２ More than 100mJ / cm ２ D: Sensitivity is less than 100 mJ / cm ２ More than 200mJ / cm ２ E: Sensitivity is less than 200 mJ / cm ２ That's all.

[0209] (6-3) Development Residues The development residues were observed by observing the contact holes formed in the obtained relief pattern at the minimum exposure dose, and observing the presence or absence of residues in the openings using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation).

[0210] The area of ​​the residue in the opening is judged as follows: A, B＋ , B -－ A: No residue in the opening (less than 1%), and C: Pass. ＋ B: The area of ​​residue in the opening is 1% or more but less than 2% － : The area of ​​the opening where the residue exists is 2% or more and less than 3%. C: The area of ​​the opening where the residue exists is 3% or more and less than 5%. D: The area of ​​the opening where the residue exists is 5% or more and less than 10%. E: The area of ​​the opening where the residue exists is 10% or more.

[0211] (7) Film Thickness Changes Due to Heat Treatment The positive photosensitive resin compositions obtained in each of the Examples and Comparative Examples were spin-coated onto an 8-inch silicon wafer using an ACT-8 coater / developer (Tokyo Electron Limited), and heated at 100°C for 2 minutes to produce a 4.0 μm-thick positive photosensitive resin film. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. The resin-coated wafer was heat-treated at 250°C for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less) using a clean oven (CLH-21CD-S, Koyo Thermo Systems Co., Ltd.), and the film thickness R (μm) was measured. The value of R / 4×100 was taken as the film thickness retention rate after heat treatment.

[0212] The film thickness was judged as follows, and A and B, which indicate a film thickness retention rate of 70% or more, were judged to be acceptable: A: Film thickness retention rate of 75% or more B: Film thickness retention rate of 70% or more but less than 75% C: Film thickness retention rate of less than 70%.

[0213] Synthesis Example 1 Synthesis of Polyimide (PI-01) Under a dry nitrogen stream, 30.03 g (100 mmol) of TDA-100 as an acid dianhydride and 200.0 g of NMP were weighed and dissolved in a three-neck flask. To this was added 1.860 g (20 mmol) of aniline as a monoamine along with 50.00 g of NMP, and the mixture was stirred at 40°C for 1 hour. Next, 23.25 g (90 mmol) of BAP as a diamine along with 50.00 g of NMP was added, and the mixture was reacted at 40°C for 1 hour, followed by stirring at 200°C for 4 hours. After stirring, the solution was poured into 2 L of pure water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of polyimide resin (PI-01). The resulting resin had an Mw of 24,900 and an imidization rate of 100%. The fluorine atom content in the resin was 0% by mass. The evaluation results are shown in Table 1.

[0214] Synthesis Examples 2 to 20 Synthesis of Polyimides (PI-02 to 20) Synthesis was performed in the same manner as in Synthesis Example 1, except that the types and amounts of the acid dianhydride, monoamine, and diamine used in Synthesis Example 1 were changed to those shown in Table 1. The evaluation results are shown in Table 1.

[0215]

[0216]

[0217] Synthesis Example 21 Synthesis of Polybenzoxazole Precursor (PBO-01) 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. The solution was then cooled to -15°C. After confirming that the solution temperature had reached -15°C, a solution of 26.56 g (90 mmol) of ODBC dissolved in 30 g of NMP was added dropwise so that the temperature in the reaction system did not exceed 0°C. After completion of the dropwise addition, stirring was continued for 6 hours at 20°C. After completion of the reaction, the above solution was added to 3 L of pure water containing 10 wt% methanol to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain polybenzoxazole resin (PBO-01). The resulting resin had an Mw of 23,400 and an oxazole ratio of 10%. The evaluation results are shown in Table 2-1.

[0218] Synthesis Examples 21 to 35 Synthesis of polybenzoxazole precursors (PBO-02 to 15) Synthesis was performed in the same manner as in Synthesis Example 21, except that the types and amounts of the dicarboxylic acid derivative, diamine, and terminal anhydride were changed to those shown in Table 2-1. The evaluation results are shown in Table 2-1.

[0219] Synthesis Example 36: Synthesis of Polyimide Precursor (PAA-01) Under a dry nitrogen stream, 31.02 g (100 mmol) of ODPA as an acid dianhydride and 200.0 g of NMP were weighed and dissolved in a three-necked flask. 1.860 g (20 mmol) of aniline as a monoamine was added together with 50.00 g of NMP, and the mixture was stirred at 40°C for 1 hour. Next, 54.41 g (90 mmol) of HFHA as a diamine was added together with 50.00 g of NMP, and the mixture was stirred at 40°C for 3 hours. After stirring, the solution was poured into 2 L of pure water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a powder of polyimide precursor (PAA-01). The resulting resin had an Mw of 27,000, an imidization rate of 5%, and a fluorine atom concentration of 18.3%. The evaluation results are shown in Table 2-2.

[0220]

[0221]

[0222] Synthesis Example 37 (A) Resin containing a structural unit represented by formula (1): In 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 was added as a protective agent, and the mixture was stirred at 0°C for 1 hour. Next, 1.000 x 10 pyridinium p-toluenesulfonate was added as a catalyst. －２ g was added and stirred at 0°C for 3 hours. After stirring was completed, the acid catalyst was neutralized with a saturated aqueous solution of sodium bicarbonate, and the water bath was then removed. The organic layer was further washed twice with water. Thereafter, low-boiling point residues were removed using a rotary evaporator in order to remove unreacted IPVE. The solids concentration of the solution was then measured, and CP was added so that the solids concentration was 40%, yielding a 40% solids solution of a resin (PI-01-IPVE10) in which hydroxyl groups were protected with 1-isopropoxyethyl groups, which are acid-decomposable groups. The proportion of phenolic hydroxyl groups protected with acid-decomposable groups was 10 mol%. The synthesis results are shown in Table 3.

[0223] Synthesis Examples 38 to 78 Synthesis was performed in the same manner as in Synthesis Example 37, except that the base polymer and protective agent were changed as shown in Table 3. The synthesis results are shown in Table 3.

[0224]

[0225]

[0226]

[0227] Example 1 Under yellow light, (A) 2.500 g of a 40% solids CP solution of P1-01-IPVE10 as a resin, (B) 5.000 × 10 －２ g, (C) 5.000 x 10 lutidine as an amine compound －３ Thereafter, 1,500 g of CP was added to adjust the concentration, thereby obtaining a positive photosensitive resin composition.

[0228] The positive photosensitive resin composition thus prepared was subjected to (6) the formation of a relief pattern, and the composition was evaluated for (6-1) the amount of film loss upon development, (6-2) the sensitivity, and (6-3) the amount of residue. The evaluation results are shown in Table 4.

[0229] Examples 2 to 38 and Comparative Examples 1 to 4 Evaluations were carried out in the same manner as in Example 1, except that the composition 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 an excessively high fluorine atom content, and Comparative Example 3 used PI-01-tBOC25 and contained an organic group containing a carbonyl group as an acid-decomposable group.

[0230]

[0231]

[0232]

[0233] Examples 39 and 40 Evaluations were carried out in the same manner as in Example 14, except that the type of (B) photoacid generator in Example 14 was changed as shown in Table 5. The evaluation results are shown in Table 5.

[0234] Example 41 Evaluation was carried out in the same manner as in Example 7, except that the type of (B) photoacid generator in Example 7 was changed as shown in Table 5. The evaluation results are shown in Table 5.

[0235]

[0236] Example 42 Evaluation was carried out in the same manner as in Example 3, except that the amine compound (C) in Example 3 was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0237] Example 43 Evaluation was carried out in the same manner as in Example 14, except that the amine compound (C) in Example 14 was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0238]

[0239] Examples 44 and 45: 10.00 g of PI-01-IPVE25 (40% CP solution) was weighed out, 6.000 g of GBL was added, and solvent substitution was carried out using a rotary evaporator. After solvent substitution, the solid concentration was measured, and GBL was added so that the solid concentration became 40%, thereby obtaining PI-01-IPVE25 (40% GBL solution).

[0240] The evaluation was performed in the same manner as in Example 3, except that the (A) resin in Example 3 was changed to PI-01-IPVE25 (40% GBL solution) and the type of solvent was changed as shown in Table 7, resulting in 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.

[0241]

[0242] Comparative Examples 5 to 7 As shown in Table 8, compositions were prepared using unprotected resins and quinone diazide compounds. (6) Relief patterns were prepared using the prepared compositions, and (6-1) the amount of film loss after development, (6-2) sensitivity, and (6-3) residue were evaluated. The evaluation results are shown in Table 8. None of Comparative Examples 5, 6, and 7 contain a structure of general formula (1) (n = 1 to 4).

[0243]

Claims

1. (A) Heat-resistant resin containing nitrogen atoms (B) Contains a photoacid generator, The (A) resin contains a constituent unit represented by formula (1), and with the total amount of resin contained in the composition being 100% by mass, the fluorine atom content in the total resin is 15% by mass or less, and at least one of the R2 is a group represented by formula (4) or a group represented by formula (5). Positive-type photosensitive resin composition. 【Chemistry 1】 (In formula (1), R １ This represents a 3- to 12-valent organic group having 3 to 30 carbon atoms, R ２ This is a monovalent, acid-degradable group with 3 to 20 carbon atoms. m represents an integer from 0 to 4, and n represents an integer from 1 to 4. * indicates a bonding site, and a and b independently represent integers of 1 or 2. 【Chemistry 2】 (In formulas (4) and (5), R6 and R7 each independently represent an alkyl group having 1 to 6 carbon atoms. R8 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 from 0 to 2, and s represents an integer from 0 to 2. * indicates a bonding site.)

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

3. The positive-type photosensitive resin composition according to claim 1, wherein the acid-degradable group is an oxymethyl group.

4. OR of the above formula (1) ２ The positive-type photosensitive resin composition according to claim 1, wherein the pKa of the phenolic hydroxyl group-containing structure produced by the decomposition of the group with acid is 11 or more.

5. The aforementioned R ２ The positive-type photosensitive resin composition according to claim 1, wherein at least one of the groups is a group represented by formula (2) or a group represented by formula (3). 【Transformation 3】 In equations (2) and (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 from 0 to 2, and q represents an integer from 0 to 2. * represents a bonding site.

6. The positive-type photosensitive resin composition according to claim 1, wherein formula (1) is formula (6). 【Chemistry 4】 (In formula (6), R ２ , a, and b have the same meanings as the same symbols in the above formula (1). L represents a direct bond, -C(CH ３ ) ２ -, a 9H-fluorene-9,9-diyl group. m １ and m ２ each independently represent an integer of 0 to 2. n １ and n ２ each independently represent an integer of 0 to 2. However, 1 ≤ (n １ + n ２ ) ≤ 4 is satisfied. * indicates a bonding site.)

7. The positive-type 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). 【Transformation 5】 (In formula (7), X １ This represents a tetravalent organic group having 4 to 50 carbon atoms, or the constituent unit of formula (1) above. １ represents a divalent organic group having 6 to 30 carbon atoms, or the constituent unit of formula (1) above. However, X １ and Y １ At least one of them is a constituent unit of formula (1), and X １ However, when the constituent unit of formula (1) is taken, a = b = 2, and Y １ However, when the constituent units are those of formula (1) above, a + b = 2. (* indicates a bonding site.) 【Transformation 6】 (In formula (8), X ２ This represents a divalent organic group having 4 to 50 carbon atoms, or the constituent unit of formula (1) above. ２ represents a divalent organic group having 6 to 30 carbon atoms, or the constituent unit of formula (1) above. However, X ２ and Y ２ At least one of them is a constituent unit of formula (1) above, and a = b = 1. (* indicates a bonding site.)

8. In the above formula (7), X １ However, it is a tetravalent organic group having 4 to 50 carbon atoms, which includes an aliphatic skeleton with 4 or more carbon atoms, and / or, in formula (8), X ２ The positive-type photosensitive resin composition according to claim 7, wherein the divalent organic group has 4 to 50 carbon atoms and contains an aliphatic skeleton with 4 or more carbon atoms.

9. The resin (A) has a structural unit represented by formula (9), and the OH group and OR included in formula (9) ２ The total number of groups is M1, and from the structure of formula (9), the OH group and OR group ２ When the molecular weight of the remaining structural part after removing the group is N1, the value of M1 / N1 is 0.004075 or greater, and / or The resin (A) has a structural unit represented by formula (10), and the OH group and OR included in formula (10) ２ M2 is the total number of groups, and from the structure of formula (10), OH groups and OR groups ２ The positive-type photosensitive resin composition according to claim 2, wherein the value of M2 / N2 is 0.004075 or more, when the molecular weight of the remaining structural portion after removing the group is N2. 【Transformation 7】 (In formula (9) and formula (10), R １ , R ２ , m, and n have the same meaning as the same symbols in formula (1) above. ３ This represents a tetravalent organic group with 4 to 50 carbon atoms, containing an aliphatic skeleton with 4 or more carbon atoms. ４ This represents a divalent organic group with 4 to 50 carbon atoms, containing an aliphatic skeleton with 4 or more carbon atoms.

10. The positive-type photosensitive resin composition according to claim 1, wherein the (B) photoacid generator comprises a nonionic photoacid generator.

11. The positive-type photosensitive resin composition according to claim 1, wherein the (B) photoacid generator comprises a photoacid generator whose acid dissociation constant (pKa) of the acid group generated by light is in the range of -14 to 2.

12. The positive-type photosensitive resin composition according to claim 1, wherein the (B) photoacid generator comprises an oximesulfonate compound and / or an imidosulfonate compound.

13. Furthermore, the positive-type photosensitive resin composition according to claim 1, comprising (C) an amine compound having a conjugate acid pKa in the range of 4.5 to 10.

8.

14. Furthermore, the positive-type photosensitive resin composition according to claim 1, wherein the solvent (D) comprises a carbon-3 to carbon-12 aprotic solvent having a relative dielectric constant in the range of 5 to 20.

15. A positive-type photosensitive resin sheet obtained by forming a positive-type photosensitive resin composition according to any one of claims 1 to 14 in a sheet shape on a support.

16. A cured product obtained by curing a positive-type photosensitive resin composition according to any one of claims 1 to 14.

17. A method for producing a cured product comprising: a) a step of applying and drying a positive-type photosensitive resin composition according to any one of claims 1 to 14 onto a substrate to form a positive-type photosensitive resin film, or a step of using a positive-type photosensitive resin sheet according to claim 15 to heat-press the positive-type photosensitive resin composition of the present invention onto a substrate; b) a step of exposing the positive-type photosensitive resin film or the heat-pressed positive-type photosensitive resin composition; c) a step of developing the exposed portion of the exposed positive-type photosensitive resin film or the exposed portion of the heat-pressed positive-type photosensitive resin composition by dissolving or removing it with an alkaline aqueous solution; and d) a step of heat-treating the developed positive-type photosensitive resin film or the developed heat-pressed positive-type photosensitive resin composition.

18. A semiconductor device in which the cured product according to claim 16 is disposed as a protective film of a semiconductor or an interlayer insulating film between redistributions.

19. A display device comprising 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 provided opposite the first electrode, A display device comprising the cured product described in claim 16 for the insulating layer.

20. A display device comprising a planarization film provided in such a manner that it covers irregularities on a substrate on which thin-film transistors (TFTs) are formed, wherein the planarization film includes the cured product described in claim 16.

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