Photosensitive resin composition, cured product, method for producing cured product, semiconductor device, and display device

Abstract

The present invention addresses the problem of providing a photosensitive resin composition that has good solvent solubility and high sensitivity, retains a pattern shape during heat treatment, and makes it possible to obtain a cured product having high elongation at breakage. The solution to the problem is a photosensitive resin composition that comprises a polyimide resin (A1) containing a diamine residue having a specific structure, a phenol resin (A2), a photosensitizer (B), and a solvent (C).

Description

Photosensitive resin composition, cured product, method for producing the cured product, semiconductor device and display device.

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

[0002] Conventionally, polyimide resins and polybenzoxazole resins, which have excellent heat resistance, electrical insulation, and mechanical properties, have been widely used for surface protective films and interlayer insulating films of semiconductor devices, insulating layers of display devices such as organic light-emitting elements, and planarization films of thin-film transistors (hereinafter sometimes referred to as TFTs). Furthermore, the polyimide resins and polybenzoxazole resins used must be soluble in organic solvents and alkaline aqueous solutions used in the processing steps.

[0003] Furthermore, in addition to the above-mentioned properties, polyimide resins and polybenzoxazole resins require increased sensitivity to the g-line (436 nm), h-line (405 nm), and i-line (365 nm) used as exposure light sources in order to improve productivity. To date, methods have been used to introduce specific structures into the resin to improve solvent solubility (see Patent Document 1). Other methods for increasing sensitivity include those containing 101 parts by weight or more of novolac resin and / or polyhydroxystyrene resin per 100 parts by weight of polyimide precursor or polybenzoxazole precursor (see Patent Document 2), and those containing a phenol resin with a specific structure in addition to the polyimide precursor or polybenzoxazole precursor (see Patent Documents 3 and 4).

[0004] International Publication No. 2009 / 081950, Japanese Patent Publication No. 2005-352004, Japanese Patent Publication No. 2018-22171, Japanese Patent Publication No. 2018-55124

[0005] However, applying resins containing specific structures to improve solvent solubility as described in the above literature presented a challenge: insufficient sensitivity. Furthermore, adding large amounts of the phenolic resin described in the above literature to improve sensitivity resulted in a deterioration of pattern shape retention and elongation at break during heat treatment. In short, the challenge was to achieve a balance between solvent solubility, sensitivity, pattern shape, and elongation at break.

[0006] To solve the above problems, the present invention has the following configuration: [1] A photosensitive resin composition comprising one or more resins (A1) selected from the group consisting of polyimide, polybenzoxazole and copolymers thereof, a phenolic resin (A2), a photosensitive agent (B), and a solvent (C), wherein component (A1) contains at least one diamine residue represented by any of formulas (1) to (3) described later. [2] The photosensitive resin composition according to [1], wherein the content of component (A2) is 101 parts by weight or more and 500 parts by weight or less per 100 parts by weight of component (A1). [3] The photosensitive resin composition according to [1] or [2], wherein component (B) comprises a compound represented by formula (7) described later. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the (A2) component contains a novolac resin (A2-1), the (A2-1) component does not contain an aromatic aldehyde residue and / or an aromatic ketone residue, and when the molar amount of m-cresol residues in the (A2-1) component is m and the molar amount of p-cresol residues is p, the molar ratio p / m is 0 or more and 5 / 9 or less. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (A2) component contains a phenol resin (A2-2) having repeating structural units represented by formula (8) and formula (9), which will be described later. [6] The photosensitive resin composition according to [5], wherein the content of the (A2-2) component is greater than 0% by weight and 50% by weight or less, based on 100% by weight of the (A2) component. [7] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [6]. A method for producing a cured product comprising, in this order: applying a photosensitive resin composition according to any one of [1] to [6] to a substrate, then drying it to form a resin film; exposure of the dried resin film; development of the exposed resin film; and heat treatment of the developed resin film. [9] A cured product comprising a resin-derived skeleton selected from polyimide and polybenzoxazole, a phenol resin-derived skeleton, and a photosensitive agent-derived skeleton, each containing at least one diamine residue represented by any one of formulas (1) to (3).

[10] The cured product according to [9], wherein the phenol resin-derived skeleton contains a phenol resin-derived skeleton having repeating structural units represented by formula (8) and repeating structural units represented by formula (9).

[11] The cured product according to

[10] , wherein the content of the phenol resin-derived skeleton having repeating structural units represented by formula (8) and repeating structural units represented by formula (9) is greater than 0% by weight and 50% by weight or less, based on 100% by weight of the phenol resin-derived skeleton.

[12] A semiconductor device having the cured product according to any one of [7], [9] to

[11] .

[13] A display device having the cured product according to any one of [7], [9] to

[11] .

[0007] According to the present invention, a photosensitive resin composition can be obtained that has good solvent solubility, high sensitivity, maintains its pattern shape during heat treatment, and has high elongation at break.

[0008] These are schematic cross-sectional and plan views representing an example of a display device 100A having a stepped shape in which the pixel division layer has a thick film portion and a thin film portion. This is a schematic cross-sectional view representing an example of a display device 30A having an interlayer insulating layer, a partition layer, and a planarization layer. This is a schematic cross-sectional view representing an example of a pad portion of a semiconductor device 10A having bumps.

[0009] The present invention will now be described in detail. The present invention is a photosensitive resin composition comprising one or more resins (A1) selected from the group consisting of polyimides, polybenzoxazoles and copolymers thereof, a phenolic resin (A2), a photosensitive agent (B), and a solvent (C), wherein component (A1) contains at least one diamine residue represented by any of formulas (1) to (3).

[0010]

[0011] In equations (1), (2), and (3), X １ 、 X ３ and X ４ Each of these is independently a divalent group represented by a direct bond or formula (4), R １ 、 R ２ and R ３each independently represents an alkyl group having 1 to 4 carbon atoms, and X ２ is a divalent group represented by the formula (5) or the formula (6), i each independently represents 0 or 1, and * represents a bonding point bonded to a nitrogen atom contained in an imide structure, a hydroxyamide structure or an amido acid structure.

[0012]

[0013] In the formula (4), * represents a bonding point bonded to a nitrogen atom contained in an imide structure, a hydroxyamide structure or an amido acid structure. ** represents a bonding point bonded to an aromatic ring.

[0014]

[0015] In the formulas (5) and (6), R ４ each independently represents an alkyl group having 1 to 4 carbon atoms, a represents 1 or 2, b represents any integer from 1 to 3, R ５ and R ６ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents a bonding point bonded to an aromatic ring. However, R ５ and R ６ do not have the same structure.

[0016] <One or more resins (A1) selected from the group consisting of polyimide, polybenzoxazole and their copolymers (hereinafter sometimes referred to as component (A1))> The photosensitive resin composition of the present invention contains component (A1). Polyimide contains a repeating structural unit having a polyimide ring and / or a repeating structural unit having a structure before ring closure of an imide ring. Here, the structure before ring closure of the imide ring has a structure of an amido acid (or amic acid) or an ester of the acid. The ratio of the repeating structural unit having a polyimide ring and the repeating structural unit having a structure before ring closure of the imide ring in the polyimide is not particularly limited, and the ratio may be changed according to the properties required for various applications.

[0017] A polybenzoxazole is a compound containing repeating structural units having a polybenzoxazole ring and / or repeating structural units having a structure before cyclization to the oxazole ring. Here, the structure before cyclization to the oxazole ring is a structure having a hydroxyamide structure. There are no particular restrictions on the ratio of repeating structural units having a polybenzoxazole ring to repeating structural units having a structure before cyclization to the oxazole ring in a polybenzoxazole, and the ratio may be changed according to the properties required for various applications.

[0018] These copolymers, namely the copolymers of polyimide and polybenzoxazole, refer to those containing at least one of the repeating structural units of polyimide and at least one of the repeating structural units of polybenzoxazole.

[0019] There are no particular restrictions on the ratio of repeating structural units of polyimide to polybenzoxazole in a copolymer of polyimide and polybenzoxazole; the ratio may be changed according to the properties required for various applications.

[0020] Polyimides contain tetracarboxylic acid residues and diamine residues in their repeating structural units. Polybenzoxazoles contain dicarboxylic acid residues and diamine residues in their repeating structural units. Preferably, polyimides contain repeating structural units represented by formula (10) and / or formula (11).

[0021]

[0022] In equations (10) and (11), Y １ and Y ２ Each of these independently represents a tetravalent tetracarboxylic acid residue with 2 to 40 carbon atoms. １ and Z ２ Each of these independently represents a diamine residue represented by one of the formulas (1) to (3). １８ * represents a hydrogen atom, a C1-C20 alkyl group, or a C2-C20 monovalent group having an ethylenically unsaturated double bond. * represents a bond.

[0023] A tetracarboxylic acid residue refers to a structure obtained by removing four carboxyl groups from a tetracarboxylic acid, or a structure obtained by removing four groups derived from carboxyl groups from a tetracarboxylic acid derivative. Specific examples of tetracarboxylic acid derivatives include acid dianhydrides.

[0024] Examples of tetravalent tetracarboxylic acid residues having 2 to 40 carbon atoms include, specifically, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, and bicyclo[2.2.2]octo-7-ene-2,3,5 ,6-tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, residues of alicyclic tetracarboxylic acid dianhydrides such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid Rubonic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, Residues of aromatic tetracarboxylic dianhydrides such as bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, as well as bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 2,2-bis(3,Examples of aromatic acid dianhydrides include 4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorendiohydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorendiohydride, or compounds in which the aromatic ring of these compounds is substituted with alkyl groups or halogen atoms, and residues of aromatic acid dianhydrides such as acid dianhydrides having an amide group.

[0025] Polyimides may have multiple different repeating structural units by freely combining tetracarboxylic acid residues having the specific structures described above with diamine residues represented by any of formulas (1) to (3).

[0026] The polybenzoxazole preferably contains repeating structural units represented by formula (12) and / or formula (13).

[0027]

[0028] In equations (12) and (13), Y ３ and Y ４ Each independently represents a dicarboxylic acid residue having 2 to 40 carbon atoms, Z ３ and Z ４ Each of these independently removes two hydroxyl groups from a diamine residue represented by any of formulas (1) to (3), and X １ , X ３ and X ４ * represents a structure where the bond is direct. * represents a bonding site.

[0029] A dicarboxylic acid residue refers to a structure obtained by removing two carboxyl groups from a dicarboxylic acid, or a structure obtained by removing two groups derived from carboxyl groups from a dicarboxylic acid derivative. Specific examples of dicarboxylic acid derivatives include dicarboxylic acid chlorides and dicarboxylic acid esters.

[0030] Examples of dicarboxylic acid residues having 2 to 40 carbon atoms include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl etherdicarboxylic acid, and itaconic acid.

[0031] Furthermore, the (A1) component contains at least one diamine residue represented by any of formulas (1) to (3). In formulas (1) to (3), R １ ~R ３ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. In particular, R is chosen because it can improve the heat resistance of component (A1) and reduce developing residue. １ ~R ３ It is preferable that the group is a methyl group. In formula (1), i independently represents either 0 or 1. It is preferable that i is 0 because it is possible to reduce the amount of developing residue. It is also preferable that i = 1 because it is possible to obtain a photosensitive resin composition with good solvent solubility and to reduce the dielectric constant of the cured product obtained by curing the photosensitive resin composition.

[0032] Since the diamine residues represented by any of formulas (1) to (3) all have phenolic hydroxyl groups, they can impart solubility to alkaline developers and reduce development residue.

[0033] In equations (1) to (3), X １ , X ３ and X ４ Each of these is independently a divalent group, either directly bonded or represented by formula (4). １ , X ３ and X４ However, because it is a direct bond, it is possible to increase the hydroxyl group concentration of component (A1), and thus it is preferable because it is possible to reduce the residue after development. Also, X １ , X ３ and X ４ However, because it is a divalent organic group represented by formula (4), the structure of hydroxyamide is introduced into the structure of formula (1), so in the curing process the hydroxyamide ring closes to form an oxazole ring, and a cured product with low water absorption can be obtained, which is preferable.

[0034] X ２ R is a divalent organic group represented by formula (5) or formula (6). ４ Each of these is an alkyl group having 1 to 4 carbon atoms, but a methyl group is preferred because it can increase the heat resistance of component (A1) and reduce developing residue. a represents 1 or 2, and b represents any integer from 1 to 3. R in formula (6) ５ and R ６ Each of these independently represents a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms, but R can improve the heat resistance of component (A1) and reduce developing residue. ５ and R ６ Each of these is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms. Also, in formula (6), R ５ The number of carbon atoms and R ６ It is more preferable, from the viewpoint of balancing solvent solubility and elongation at break, that the total number of carbon atoms is 1 or more and 9 or less. Even more preferable, R ５ The number of carbon atoms and R ６ The total number of carbon atoms is 3 or more and 8 or less. However, R ５ and R ６ They do not have the same structure.

[0035] The phrase "does not take the same structure" used here means R ５ and R ６ This relationship includes not only those with different empirical formulas, but also structural isomers that have the same empirical formula but different interatomic bonding states. ５ and R６ Because the structures are asymmetric and do not have the same structure, intermolecular packing is suppressed, making it possible to improve the solvent solubility of component (A1).

[0036] Specific examples of diamine residues represented by any of formulas (1) to (3) include, for example, diamine residues represented by any of formulas (14) to (31).

[0037]

[0038]

[0039] In particular, component (A1) contains a diamine residue represented by formula (1), and in formula (5), the R ４ The total number of carbon atoms is 1 or more and 5 or less, and in formula (6), the R ５ The number of carbon atoms and the R ６ It is preferable that the total number of carbon atoms be between 3 and 10, from the viewpoint of obtaining a photosensitive resin composition with good solvent solubility without worsening developing residue or sensitivity.

[0040] In this context, in equation (5), the R ４ The total number of carbon atoms is 1 or more and 5 or less, for example, in formula (5), R ４ If there are multiple R ４ This means that the sum of the number of carbon atoms in each of these is between 1 and 5. Also, in formula (6) as used here, ５ The number of carbon atoms and the R ６ The total number of carbon atoms is 3 or more and 10 or less, which means R ５ and R ６ This means that the number of carbon atoms in each element is counted individually, and the sum of these numbers is between 3 and 10.

[0041] Furthermore, component (A1) contains a diamine residue represented by formula (1), and the X ２ However, it is preferable that the group is a divalent group represented by any of formulas (32) to (37).

[0042]

[0043] In formulas (32) to (37), * represents a bond point attached to an aromatic ring. From the viewpoint of further improving solvent solubility, if component (A1) contains a repeating structural unit represented by formula (10) and / or a repeating structural unit represented by formula (11), Z １ and Z ２ Preferably, is a diamine residue of any of formulas (14) to (19) or formulas (23) to (28). From the viewpoint of further improving solvent solubility, if component (A1) contains a repeating structural unit represented by formula (12) and / or a repeating structural unit represented by formula (13), Z ３ and Z ４ It is preferable that the structure is obtained by removing two amino groups and two hydroxyl groups from any of the diamines of formulas (14) to (19).

[0044] Furthermore, component (A1) may have other known diamine residues other than the diamine residue represented by any of formulas (1) to (3).

[0045] Other known specific examples of diamine residues include, for example, aliphatic diamine residues and aromatic diamine residues. Aliphatic diamine residues refer to diamine residues that do not have an aromatic ring. Examples of aliphatic diamine residues include aliphatic alkyldiamines containing alkylene groups such as alkylene groups, polyethylene ether groups, polyoxypropylene groups, and tetramethylene ether groups, as well as alicyclic diamines and aliphatic diamines having a siloxane structure.

[0046] Examples of aliphatic alkyldiamine residues include polymethylenediamine, diamines containing polyethylene ether groups, polyoxypropylenediamine, diamines containing tetramethylene ether groups such as RT-1000 and HT-1100, amino group-containing alkylene etherdiamines, and dimer amines.

[0047] Examples of alicyclic diamine residues include cyclohexyldiamine, methylenebiscyclohexylamine, norbornanediamine, and PRO-NBDA (trade name, manufactured by Mitsui Chemicals Fine, Inc.).

[0048] Examples of aliphatic diamine residues having a siloxane structure include 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) and bis(p-aminophenyl)octamethylpentasiloxane. When aliphatic groups having a siloxane structure are copolymerized within a range that does not reduce heat resistance, adhesion to the substrate can be improved.

[0049] Furthermore, examples of aromatic diamine residues include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (AZ-FDA), 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane (HB), bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)sulfone, and 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]- Examples of residues include hydroxyl group-containing diamine residues such as 1,1,1-trifluoroethane and 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, sulfonic acid-containing diamine residues such as 3-sulfonic acid-4,4'-diaminodiphenyl ether, thiol group-containing diamine residues such as dimercaptophenylenediamine, aromatic diamine residues such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylmethane, as well as residues of compounds in which some of the hydrogen atoms of these aromatic rings are substituted with C1-C10 alkyl groups or fluoroalkyl groups.

[0050] It is preferable to include structures represented by formulas (38) to (43) as other known diamine residues other than the diamine residue represented by any one of formulas (1) to (3).

[0051]

[0052] In equations (38) to (43), * represents a bond point attached to an aromatic ring.

[0053] Diamine residues containing the structures represented by formulas (38) to (43) include the diamine residues represented by formulas (44) to (55).

[0054]

[0055]

[0056] Furthermore, it is also preferable to include a structure represented by formula (56) or formula (57) as another known diamine residue other than the diamine residue represented by any one of formulas (1) to (3).

[0057]

[0058] In formula (56), X ６ is a direct bond or -C(CH) ３ ) ２ This represents a minus sign. In equation (57), t represents an integer between 0 and 2. * represents a connection point.

[0059] Since the structure of formula (56) or formula (57) has a phenyl ether substructure, it is possible to impart flexibility to component (A1) by including a diamine residue containing the structure represented by formula (56) or formula (57), and as a result, it is possible to improve the elongation at break of the cured product of the photosensitive resin composition.

[0060] Examples of diamine residues containing the structure represented by formula (56) or formula (57) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)benzene (APB), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis[4-(3-aminophenoxy)phenyl]propane. In particular, from the viewpoint of improving the elongation at break of the cured product and reducing the residue of the photosensitive resin composition, it is preferable to include a diamine residue of any of TPE-Q, TPE-R, or APB.

[0061] From the viewpoint of improving the elongation at break of the cured product obtained by curing the photosensitive resin composition without worsening the residue or sensitivity of the photosensitive resin composition, when the total amount of diamine residues contained in component (A1) is 100 mol%, the total content of the diamine residues represented by formula (56) and the diamine residues represented by formula (57) is preferably 1 to 30 mol%, and more preferably 1 to 25 mol%. Component (A1) may contain the above-mentioned residues individually or in combination of two or more. By including multiple repeating structural units with different structures, aggregation of resins is suppressed when a photosensitive resin composition is formed, thereby improving the storage stability of the photosensitive resin composition.

[0062] Furthermore, the ends of component (A1) may be sealed with known end-sealing agents such as monoamines, acid anhydrides, monoacid chlorides, monocarboxylic acids, and monoactive esters. By sealing the ends of the resin with an end-sealing agent, the dissolution rate of the resin in an alkaline aqueous solution can be easily adjusted to a desirable range. In particular, it is preferable to use an end-sealing agent having phenolic hydroxyl groups or crosslinking groups. By using an end-sealing agent having phenolic hydroxyl groups, alkali solubility is imparted to the resin, thereby reducing residue. In addition, by using an end-sealing agent having crosslinking groups, the crosslinking reaction proceeds during the heat curing process, making it possible to obtain a cured film with excellent chemical resistance and elongation at break.

[0063] Specific examples of the monoamines mentioned above include those having a phenolic hydroxyl group, such as 2-aminophenol (hereinafter referred to as OAP), 3-aminophenol (hereinafter referred to as MAP), and 4-aminophenol (hereinafter referred to as PAP). Furthermore, examples of monoamines having a photocrosslinkable group include 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, and others such as aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid.

[0064] Among the acid anhydrides, monocarboxylic acids, monoacid chloride compounds, or monoactive ester compounds, those having a phenolic hydroxyl group include 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, and 1-hydroxy-5-carboxynaphthalene. Furthermore, those having a photocrosslinkable group include maleic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter, Na), itaconic acid anhydride, itaconic acid, maleic acid, acrylic acid, methacrylic acid, 3-phenylacrylic acid, crotonic acid, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 7-oxabicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylic acid anhydride, and 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride. Other examples include acetic anhydride, succinic anhydride, phthalic anhydride, cyclohexanedicarboxylic acid anhydride, 3-carboxythiophenol, 4-carboxythiophenol, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, trimellitic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Furthermore, with respect to the above monocarboxylic acids, mono-acid chloride compounds in which the carboxyl groups of these monocarboxylic acids have been acid-chlorinated may be used, mono-acid chloride compounds in which only one carboxyl group of the above dicarboxylic acids has been acid-chlorinated may be used, or active ester compounds obtained by the reaction of a mono-acid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide may be used.

[0065] Furthermore, multiple different end groups may be introduced by reacting the above-mentioned multiple end-capturing agents.

[0066] When a monoamine is used as the end-capturing agent, its introduction ratio is preferably 1 mol% to 60 mol% relative to 100 mol% of the total amine compounds contained in component (A1). By setting the introduction ratio of the monoamine to preferably 1 mol% or more, and more preferably 5 mol% or more, an effective effect of reducing residue after development can be obtained. Furthermore, by setting the introduction ratio of the monoamine to preferably 60 mol% or less, and more preferably 50 mol% or less, the molecular weight of the resin can be kept high, and high chemical resistance and elongation at break can be maintained.

[0067] When using an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound as the end-capturing agent, the total introduction ratio of these compounds is preferably 1 mol or more and 100 mol or less per 100 mol of the total amine compound contained in component (A1). By setting the introduction ratio to preferably 1 mol or more, more preferably 5 mol or more, an effective effect of reducing residue after development can be obtained. On the other hand, by setting the introduction ratio to preferably 100 mol or less, more preferably 90 mol or less, the molecular weight of the resin can be kept high, and high chemical resistance and elongation at break can be maintained.

[0068] In this context, "total amine compounds" refers to the sum of the content of compounds containing an amino group, such as monoamines, diamines, and triamines.

[0069] The weight-average molecular weight (Mw) of component (A1) is preferably 3,000 to 100,000 in polystyrene terms, as determined by gel permeation chromatography (GPC). By setting the Mw to 100,000 or less, more preferably 80,000, and even more preferably 60,000 or less, good solvent solubility and good solubility in developing solutions can be effectively obtained. Furthermore, by setting the weight-average molecular weight to 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, high elongation at break can be effectively obtained.

[0070] Component (A1) can be synthesized by known methods. When component (A1) is polyimide, for example, it can be synthesized by reacting a tetracarboxylic dianhydride with a diamine compound having the structure of a diamine residue represented by any of formulas (1) to (3) at low temperature in a polymerization solvent; by obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with an amine in the presence of a condensing agent; or by obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with an amine. Alternatively, the resin obtained by the above methods may be dehydrated and cyclized by heating or chemical treatment with an acid or base. When component (A1) is polybenzoxazole, for example, it can be synthesized by reacting a diamine compound having the structure of a diamine residue represented by any of formulas (1) to (3) with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, or a dicarboxylic acid active ester.

[0071] It is desirable to isolate component (A1), polymerized by the above method, by immersing it in a large amount of deionized water or a methanol / deionized water mixture, allowing it to precipitate, then filtering and drying it. This precipitation process removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties and chemical resistance after thermal curing. The polymerization solvent can be any solvent that can dissolve the raw material monomers, such as acidic dianhydrides and diamines, and is not particularly limited in type. For example, amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide (MPA), 3-butoxy-N,N-dimethylpropanamide (BPA), N,N'-dimethylpropyleneurea (DMPU), N,N-dimethylisobutylamide (DMIB), N,N-dimethylpropionamide (DMPA), 3-methyl-2-oxazolidinone, and γ-butyrolact. Examples of polymers include chlorofluorocarbons (hereinafter referred to as GBL), cyclic esters such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, esters such as methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, ethylpropylene glycol ketal levulinate, and ethylglycerol ketal levulinate, acetophenone, sulfolane, dimethyl sulfoxide (hereinafter referred to as DMSO), and dihydrolevoglucocenone (Cyrene, manufactured by Circa). The amount of polymerization solvent used is preferably 100 to 1,900 parts by weight, and more preferably 150 to 950 parts by weight, per 100 parts by weight of component (A1).

[0072] <Phenol resin (A2) (hereinafter sometimes referred to as component (A2))> The photosensitive resin composition of the present invention contains phenol resin (A2). Component (A2) is a resin synthesized from phenols and aldehydes and / or ketones. Component (A2) is obtained by polycondensation of phenols and aldehydes and / or ketones by known methods. Component (A2) may also contain a combination of two or more novolac resins.

[0073] Examples of phenols include alkylphenols such as phenol, m-cresol, p-cresol, o-cresol, xylenol, ethylphenol, butylphenol, octylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, and 2,3,6-trimethylphenol; examples of polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol, and catechol; and examples of other phenols such as halogenated phenols, phenylphenol, and aminophenol. Component (A2) may be obtained by combining two or more of these phenols.

[0074] Furthermore, examples of the above-mentioned aldehydes and / or ketones include formaldehyde, paraformaldehyde, acetaldehyde, chloroacetaldehyde, aromatic aldehydes, aromatic ketones, etc. Of these, the use of formaldehyde is particularly preferred. Component (A2) may be obtained by combining two or more of these aldehydes and / or ketones. The polycondensation ratio of phenols and aldehydes and / or ketones is preferably 0.6 moles or more, and more preferably 0.7 moles or more, of aldehydes and / or ketones per mole of phenols. Furthermore, the polycondensation ratio of phenols and aldehydes and / or ketones is preferably 3 moles or less, and more preferably 1.5 moles or less, of aldehydes and / or ketones per mole of phenols.

[0075] It is preferable that component (A2) contains a novolac resin (A2-1) (hereinafter sometimes referred to as component (A2-1)) which does not contain aromatic aldehyde residues and / or aromatic ketone residues, and has a molar ratio p / m of 0 to 5 / 9 when the molar amount of m-cresol residues in the resin is m and the molar amount of p-cresol residues is p. That is, it is preferable that component (A2) contains a novolac resin (A2-1), that component (A2-1) does not contain aromatic aldehyde residues and / or aromatic ketone residues, and that the molar ratio p / m of 0 to 5 / 9 when the molar amount of m-cresol residues in component (A2-1) is m and the molar amount of p-cresol residues is p.

[0076] Here, aromatic aldehyde residues represent structures obtained by removing the oxo group from aromatic aldehydes, and aromatic ketone residues represent structures obtained by removing the oxo group from aromatic ketones. m-cresol residues represent structures derived from m-cresol, and p-cresol residues represent structures derived from p-cresol.

[0077] The inclusion of component (A2-1) in component (A2) reduces the absorbance of the resin and improves sensitivity. Furthermore, from the viewpoint of alkali solubility and sensitivity improvement, component (A2-1) preferably contains m-cresol residues and p-cresol residues, with a molar ratio p / m of 0 to 5 / 9 and more preferably 1 / 4 or less.

[0078] The content of component (A2) is preferably 101 parts by weight or more and 500 parts by weight or less per 100 parts by weight of component (A1). By keeping it within this range, high sensitivity can be achieved while ensuring the retention of the pattern shape during heat treatment.

[0079] (A2) The component is synthesized by polycondensation reaction of phenols with aldehydes and / or ketones, and an acidic catalyst is usually used. Examples of acidic catalysts include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and p-toluenesulfonic acid. The amount of these acidic catalysts used is usually 1 × 10⁻¹⁶ per mole of phenols. －５ ~5 x 10 －１ The unit is moles. In polycondensation reactions, water is usually used as the reaction medium, but if a heterogeneous system is formed from the initial stages of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of hydrophilic solvents include alcohols such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. Examples of lipophilic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw materials.

[0080] The reaction temperature for polycondensation can be adjusted as appropriate depending on the reactivity of the raw materials, but is usually between 10 and 200°C. The polycondensation reaction method can be appropriately employed, such as charging phenols, aldehydes, and an acidic catalyst all at once and reacting them, or adding phenols, aldehydes, etc., as the reaction progresses in the presence of an acidic catalyst. After the polycondensation reaction is complete, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc., the reaction temperature is generally raised to 130-230°C, volatile components are removed under reduced pressure, and the novolac resin is recovered.

[0081] In the present invention, the polystyrene-equivalent weight-average molecular weight (hereinafter referred to as "Mw") of component (A2) is preferably 1,000 or more, more preferably 2,000 or more. Furthermore, it is preferably 20,000 or less, and more preferably 15,000 or less. Within this range, the photosensitive resin composition of the present invention exhibits excellent workability when applied to a substrate and excellent solubility in alkaline developing solutions.

[0082] <Phenolic resin (A2-2) having repeating structural units represented by formula (8) and formula (9) (hereinafter sometimes referred to as component (A2-2))> Component (A2) preferably contains phenolic resin (A2-2) having repeating structural units represented by formula (8) and formula (9).

[0083]

[0084] In formula (8), R １２ Each of these independently represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. １３ R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １４ Each of these independently represents a monovalent organic group with 1 to 10 carbon atoms. d1 and d3 independently represent integers from 0 to 3, and d2 represents an integer from 1 to 3, provided that 1 ≤ d2 + d3 ≤ 5. * represents a bond.

[0085]

[0086] In formula (9), R １５Each of these independently represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. １６ R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １７ Each of these independently represents a monovalent organic group with 1 to 10 carbon atoms. d4 and d5 independently represent integers from 0 to 3. * represents a bond.

[0087] The inclusion of component (A2-2) in component (A2) allows the pattern shape to be maintained during heat treatment, and an excellent pattern shape can be obtained after heat curing.

[0088] Furthermore, it is preferable that the ratio of the number of repeating structural units represented by formula (8) to the number of repeating structural units represented by formula (9) is formula (8):formula (9) = 60:40 to 90:10.

[0089] By setting the above range, appropriate developability is provided, and an excellent pattern shape can be obtained after heat treatment. Also, in formulas (8) and (9), each R １２ ~R １７ Regarding R １２ ~R １７ If it is a hydrocarbon group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. Component (A2-2) can be synthesized from phenols and aromatic aldehydes and / or aromatic ketones.

[0090] Examples of phenols include the alkylphenols, polyhydric phenols, and other phenols mentioned above. Among these, phenols represented by formula (58) are more preferred. These phenols may be used individually or in combination with other phenols.

[0091]

[0092] Examples of aromatic aldehydes used in the repeating structural unit represented by formula (8) include salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methylsalicyaldehyde, 4-methylsalicyaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, and 2,3,4-trihydroxybenzaldehyde. Among these, aromatic aldehydes represented by the following formula (59) are more preferred. These aromatic aldehydes may be used individually or in combination of multiple aromatic aldehydes.

[0093]

[0094] Examples of aromatic aldehydes used in the repeating structural unit represented by formula (9) include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, and 4-isobutylbenzaldehyde. Among these, aromatic aldehydes represented by the following formula (60) are more preferred. These aromatic aldehydes may be used individually or in combination of multiple aromatic aldehydes.

[0095]

[0096] Aromatic ketones used in the repeating structural unit represented by formula (8) include, for example, p-hydroxyacetophenone, m-hydroxyacetophenone, 3',5'-dihydroxyacetophenone, p-hydroxypropiophenone, m-hydroxypropiophenone, p-hydroxyvalerophenone, 1'-hydroxy-2'-acetonaphthone, 2'-hydroxy-1'-acetonaphthone, 2'-hydroxy-5'-methylacetophenone, 4'-hydroxy-2'-methylacetophenone, 4'-hydroxy-3'-methylacetophenone, 2'-hydroxy-4',5'-dimethylacetophenone, 2'-hydroxy-4'-methoxyacetophenone, 2'-hydroxy-5'-methoxyacetophenone, Examples include 2'-hydroxy-6'-methoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2'-hydroxy-3-phenylpropiophenone, o-hydroxybenzophenone, p-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-5-methylbenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and the like. Among these, aromatic ketones represented by the following formula (61) are more preferred. These aromatic ketones may be used individually or in combination of multiple aromatic ketones.

[0097]

[0098] Aromatic ketones used in the repeating structural unit represented by formula (9) include, for example, acetophenone, propiophenone, butyrophenone, isobutyrophenone, valerophenone, cyclohexylphenyl ketone, p-methylacetophenone, m-methylacetophenone, o-methylacetophenone, p-ethylacetophenone, p-propylacetophenone, 2',4'-dimethylacetophenone, 3',4'-dimethylacetophenone, 2',4',6'-trimethylacetophenone, p-methylpropiophenone, p-ethylpropiophenone, 1'-acetonaphthone, 2'-acetonaphthone, 4-acetylbiphenyl, p-methoxyacetophenone, m-methoxyacetophenone, o-methoxyacetophenone, and p-ethoxyacetophenone. Examples include non, p-phenoxyacetophenone, 2',4'-dimethoxyacetophenone, 2',5'-dimethoxyacetophenone, 3',4'-dimethoxyacetophenone, 6'-methoxy-2'-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 3',5'-dimethoxy-4'-hydroxyacetophenone, benzophenone, anthraquinone, p-methylbenzophenone, m-methylbenzophenone, o-methylbenzophenone, 4,4'-dimethylbenzophenone, p-morpholinobenzophenone, p-phenylbenzophenone, p-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like. Among these, aromatic ketones represented by the following formula (62) are more preferred. These aromatic ketones may be used individually or in combination of multiple aromatic ketones.

[0099]

[0100] In the present invention, the aromatic aldehydes and aromatic ketones may be used individually or in combination. Furthermore, the ratio of phenols to aromatic aldehydes and / or aromatic ketones is preferably in the range of [aromatic aldehydes and / or aromatic ketones] / [phenols], where the molar ratio is 0.5 to 2.0, as this results in fewer unreacted phenols and a sufficiently high molecular weight novolac-type phenolic resin is obtained, and more preferably in the range of 0.7 to 1.8.

[0101] The content of component (A2-2) is preferably greater than 0% by weight and 50% by weight or less, relative to 100% by weight of component (A2). Furthermore, it is more preferable that it is greater than 0% by weight and 25% by weight or less. By keeping it within the above range, a cured product with good fracture elongation and pattern shape after heat curing can be obtained. From another viewpoint, the content of component (A2-2) is preferably 1% by weight or more, 10% by weight or more, 15% by weight or more, and 30% by weight or more, relative to 100% by weight of component (A2), in that order, the higher the content, the better. Also, from the viewpoint of chemical resistance, the content of component (A2-2) is preferably 48% by weight or less, relative to 100% by weight of component (A2).

[0102] <(A1) component and (A2) component other than resin (A3) containing phenol as a structural unit (hereinafter sometimes referred to as (A3) component)> The resin component other than (A1) component and (A2) component may contain resin (A3) containing phenol as a structural unit. Specifically, examples of (A3) component include polyhydroxystyrene, phenol resin-containing epoxy resin, and phenol group-containing acrylic resin. The content is preferably 30 parts by weight or less when the total amount of resin components is 100 parts by weight. High sensitivity can be achieved by keeping it within this range.

[0103] <Photosensitive agent (B) (hereinafter sometimes referred to as component (B))> The photosensitive resin composition of the present invention contains a photosensitive agent (B). Component (B) is a photoacid generator that generates acid upon exposure. Acid is generated in the exposed area, increasing the solubility of the exposed area in an alkaline aqueous solution, and a positive-type photosensitive resin composition in which the light-irradiated area dissolves can be obtained. Examples of photoacid generators include onium salt-type ionic photoacid generators such as sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts, and quinone diazide compounds, with quinone diazide compounds being preferred.

[0104] Examples of onium salt-type ionic photoacid generators include methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate of triphenylsulfonium; 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.

[0105] As the quinone diazide compound, a compound in which the sulfonic acid of the quinone diazide is esterified to a polyhydroxy compound is preferred. The polyhydroxy compounds used here include Bis-Z, TekP-4HBPA, TekOC-4HBPA, TrisP-HAP, TrisP-PA, BisP-AP, BisP-3MZ, Bis25X-F, BisOC-FL, BisP-MIBK, DML-PC, DML-POP, TML-BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP- Examples of compounds include PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, and methylenebisphenol. In addition to polyhydroxy compounds to which the sulfonic acid of quinone diazide is bonded by an ester, other examples include polyamino compounds to which the sulfonic acid of quinone diazide is bonded by a sulfonamide bond, and polyhydroxypolyamino compounds to which the sulfonic acid of quinone diazide is bonded by an ester bond and / or a sulfonamide bond.

[0106] Component (B) may contain either or both of a 5-naphthoquinone diazidosulfonyl ester compound having a 1,2-naphthoquinone-2-diazide-5-sulfonyl group (hereinafter sometimes referred to as a 5-naphthoquinone diazidosulfonyl group) and a 4-naphthoquinone diazidosulfonyl ester compound having a 1,2-naphthoquinone-2-diazide-4-sulfonyl group (hereinafter sometimes referred to as a 4-naphthoquinone diazidosulfonyl group). The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, depending on the wavelength of exposure, it is possible to appropriately select whether to include the 4-naphthoquinone diazidosulfonyl ester compound or the 5-naphthoquinone diazidosulfonyl ester compound, or the ratio if used in combination. Furthermore, component (B) may also contain a quinone diazide compound having both a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in the same molecule.

[0107] Specific examples of quinone diazide compounds include those represented by formulas (63) and (64).

[0108]

[0109] In formulas (63) and (64), Q independently represents a 5-naphthoquinone diazidosulfonyl group, a 4-naphthoquinone diazidosulfonyl group, or a hydrogen atom. However, not all of Q can be hydrogen atoms.

[0110] Quinone diazide compounds, in which a quinone diazide sulfonic acid is esterified to a polyhydroxy compound, can be synthesized by known methods through an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. In the above esterification reaction, a mixture with various esterification numbers and positions can be obtained. In this invention, the esterification rate (the ratio of naphthoquinone diazide sulfonyl groups to all Qs) is defined as the average value of this mixture. The esterification rate defined in this way can be adjusted by the mixing ratio of the starting material polyhydroxy compound and 1,2-naphthoquinone-2-diazide-5-(and / or -4-)sulfonyl chloride. That is, since substantially all of the added 1,2-naphthoquinone-2-diazide-5-(and / or -4-)sulfonyl chloride undergoes an esterification reaction, to obtain a mixture with a desired esterification rate, the molar ratio of the starting materials should be adjusted. In this invention, the esterification rate is preferably 50% or more, and more preferably 75% or more. This range is preferable because it allows for good contrast between exposed and unexposed areas, resulting in good sensitivity and pattern shape.

[0111] The molecular weight of the quinone diazide compound is preferably 2500 or less, and more preferably 1600 or less. If the molecular weight is 2500 or less, the quinone diazide compound will decompose sufficiently during heat treatment after pattern formation, resulting in a cured film with excellent heat resistance, mechanical properties, and adhesion. On the other hand, a molecular weight of 300 or more is preferable, and more preferably 350 or more. A molecular weight of 300 or more prevents the photosensitive agent from volatilizing during drying after coating, resulting in good developability.

[0112] The content of component (B) is preferably 1 part by weight or more, more preferably 3 parts by weight or more, preferably 50 parts by weight or less, and more preferably 40 parts by weight or less, based on 100 parts by weight of the total amount of components (A1) and (A2), from the viewpoint of pattern processability.

[0113] Component (B) preferably contains a compound represented by formula (7). By containing a compound represented by formula (7), sensitivity can be increased while maintaining elongation at break and heat resistance.

[0114]

[0115] (In formula (7), R ７ ~R １０ each independently represents a monovalent organic group having 1 to 10 carbon atoms. R １１ represents a divalent organic group having 1 to 20 carbon atoms. Also, Q each independently represents a 5-naphthoquinonediazidosulfonyl group, a 4-naphthoquinonediazidosulfonyl group, or a hydrogen atom. However, not all of Q can be hydrogen atoms. c1, c2, c3, and c4 each independently represent an integer of 0 to 4.) In formula (7), R ７ ~R １０ each independently represents a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. More specifically, as the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group is preferable. As the alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an isobutoxy group, an n-butoxy group, a sec-butoxy group, or a t-butoxy group is preferable. As the alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, or a butenyl group is preferable.)

[0116] Also, R １１ represents a divalent organic group having 1 to 20 carbon atoms. Examples of the divalent organic group having 1 to 20 carbon atoms include an alkylene group such as a methylene group, an ethylene group, or a tetramethylene group; an arylene group such as a phenylene group; a group in which one or more carbon atoms of the alkylene group or arylene group are substituted with an oxygen atom, a nitrogen atom, or a sulfur atom; and a group in which one or more hydrogen atoms of these groups are substituted with a substituent, etc. A hydrocarbon group having 1 to 20 carbon atoms is preferable.)

[0117] Examples of hydrocarbon groups having 1 to 20 carbon atoms include the methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, cyclopentylene group, cycloheptylene group, phenylene group, and the following compounds.

[0118]

[0119] * indicates a connection point.

[0120] R １１ Because the group is a hydrocarbon group having 1 to 20 carbon atoms, the sensitivity and storage stability can be improved by enhancing the anti-dissolution effect.

[0121] In formula (7) above, Q represents a 5-naphthoquinone diazidosulfonyl group, a 4-naphthoquinone diazidosulfonyl group, or a hydrogen atom. However, not all of Q can be hydrogen atoms.

[0122] Specifically, the following compounds can be listed as polyhydroxy compounds that are raw materials for the compound represented by formula (7). Component (B) may contain two or more compounds represented by formula (7) based on these polyhydroxy compounds.

[0123]

[0124] <Solvent (C)> The photosensitive resin composition of the present invention contains solvent (C). Examples of solvent (C) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, and diacetone alcohol; esters such as ethyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate; and aromatic hydrocarbons such as toluene and xylene. The photosensitive resin composition may contain two or more of these solvents. The content of solvent (C) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 2,000 parts by weight or less, and more preferably 1,500 parts by weight or less, based on 100 parts by weight of the total amount of resin of component (A1) and component (A2).

[0125] <Thermal Crosslinking Agent (D)> The photosensitive resin composition of the present invention preferably contains a thermal crosslinking agent (D). The thermal crosslinking agent (D) preferably contains an alkoxymethyl group-containing compound. Since alkoxymethyl groups undergo a crosslinking reaction in a temperature range of 150°C or higher, the inclusion of this compound allows for crosslinking during the curing process, resulting in a good pattern shape. The thermal crosslinking agent (D) preferably contains two or more alkoxymethyl groups to increase the crosslinking density, and more preferably contains four or more alkoxymethyl groups to further increase the crosslinking density and improve chemical resistance. In the present invention, the alkoxymethyl group-containing compound is preferably a compound having a group represented by formula (65) or a compound represented by formula (66), and these may be used in combination.

[0126]

[0127] In formula (65), R １９ and R ２０ Each of these independently represents an alkyl group having 1 to 20 carbon atoms. * represents a bond. From the viewpoint of solubility with the resin composition, R １９ and R ２０Each is independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

[0128] In formula (66), R ２１ and R ２２ represent CH ２ OR ４７ represents R ４７ represents an alkyl group having 1 to 6 carbon atoms. From the viewpoint of solubility with the resin composition, R ４７ is more preferably an alkyl group having 1 to 3 carbon atoms. R ２３ represents a hydrogen atom, a methyl group or an ethyl group. R ２４ is represented by formula (67), and R ２５ to R ４６ each independently represent a hydrogen atom, an organic group having 1 to 20 carbon atoms, Cl, Br, I or F. k represents an integer of 1 to 4. In formula (67), * represents a bonding site.

[0129] Specific examples of the compound containing the group represented by formula (65) include, but are not limited to, the following compounds. [[ID=?]]

[0130] [[ID=?]] [[ID=?]] [[ID=?]]

[0131] Specific examples of the compound represented by formula (66) include, but are not limited to, the following compounds.

[0132]

[0133] In addition to the alkoxymethyl group-containing compound, it is also preferable to contain a cyclic ether group-containing compound. The cyclic ether group-containing compound refers to a compound containing an epoxy group or an oxetanyl group. It is preferable to contain a cyclic ether group-containing compound because the elongation at break is improved. Specific examples of the cyclic ether group-containing compound include, but are not limited to, structures such as the following formula.

[0134]

[0135] It should be noted that there are some question marks in the translation as the original text has some unclear or incomplete tags in lines 28, 29, 30, 31 which are retained as is in the translation.From the viewpoint of increasing the crosslinking density and further improving the pattern shape, the content of the thermal crosslinking agent (D) is preferably 3 parts by weight or more per 100 parts by weight of the total amount of resins of components (A1) and (A2). A better pattern shape can be obtained if it is 10 parts by weight or more. Furthermore, from the viewpoint of pattern processability, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 20 parts by weight or less.

[0136] By staying within the above range, the elongation at break and chemical resistance of the cured film can be improved.

[0137] <Adhesion-improving agent (E)> The photosensitive resin composition of the present invention may contain an adhesion-improving agent (E). The presence of an adhesion-improving agent (E) improves adhesion to the substrate. Examples of adhesion-improving agents (E) include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, as well as titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy group-containing silicon compounds. It is preferable to contain a silane coupling agent as the adhesion-improving agent (E).

[0138] The adhesion improver (E) described above is preferably contained in an amount of 0.001 parts by weight or more, more preferably 0.005 parts by weight or more, and even more preferably 0.01 parts by weight or more, based on 100 parts by weight of the total amount of resins of component (A1) and component (A2). Furthermore, it is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less. Within this range, it is possible to achieve both the heat resistance of the composition and adhesion to the substrate.

[0139] <Surfactant (F)> The photosensitive resin composition of the present invention preferably contains a surfactant (F). A surfactant is a compound having both a hydrophilic structure and a hydrophobic structure. By including an appropriate amount of the surfactant (F), the surface tension of the photosensitive resin composition can be arbitrarily adjusted, improving the leveling properties during application and improving the uniformity of the film thickness of the coating.

[0140] As the surfactant (F), fluororesin-based surfactants, silicone-based surfactants, polyoxyalkylene ether-based surfactants, or acrylic resin-based surfactants are preferred. In particular, it is more preferable that the surfactant (F) includes a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant, as this can suppress contamination of the opening after curing. As specific examples of the surfactant (F), the surfactants described in

[0419] to

[0420] of International Publication No. 2019 / 087985 can be used.

[0141] The content ratio of surfactant (F) in the photosensitive resin composition of the present invention is preferably 0.001% by weight or more, and more preferably 0.005% by weight or more, of the total photosensitive resin composition. A content ratio of 0.001% by weight or more can improve the leveling properties during application. On the other hand, the content ratio of surfactant is preferably 1% by weight or less, and more preferably 0.5% by weight or less. A content ratio of 1% by weight or less can reduce defects that occur during application and make it possible to obtain a cured product with high heat resistance.

[0142] <Dissolution Accelerator> The photosensitive resin composition of the present invention may further contain a dissolution accelerator. The dissolution accelerator can supplement the alkali developability of the photosensitive resin composition, reduce residue, and improve sensitivity in the positive-type photosensitive resin composition. The aforementioned dissolution accelerator is preferably a compound having a phenolic hydroxyl group, for example, Bis-z, BisOC-Z, BisOCR-CP, BisP-MZ, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, TrisOCRPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Mirex HBPX, Mirex PIRM, Mirex MDPR (trade name, manufactured by Mitsui Chemicals, Inc.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOCF, 4PC, B Examples of compounds having phenolic hydroxyl groups include IR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), bisphenol A, bisphenol AF (hereinafter referred to as BPAF), bisphenol B, bisphenol C, bisphenol S, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,8,9-triol, and 8-quinolinol. The content of the dissolution accelerator is preferably 1 to 40 parts by weight when the total of components (A1) and (A2) is 100 parts by weight, in order to maintain a good pattern shape while improving sensitivity.

[0143] <Method for producing the photosensitive resin composition of the present invention> Methods for producing the photosensitive resin composition of the present invention include, for example, placing components (A1), (A2), (B), solvent (C), and other components as needed into a glass flask or stainless steel container and stirring and dissolving them using a mechanical stirrer, dissolving them using ultrasonic waves, or stirring and dissolving them using a planetary stirring and defoaming device.

[0144] The obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dirt and particles. The pore size of the filtration filter is 0.5 to 0.02 μm, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but is not limited to these. The material of the filtration filter is polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., but polyethylene and nylon are preferred. If the photosensitive resin composition contains inorganic particles or pigments, it is preferable to use a filtration filter with a larger pore size than these.

[0145] <Cured Product> The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. Methods for curing the photosensitive resin composition include, for example, heating the photosensitive resin composition or irradiating it with activated light. Specifically, methods of curing with heat or light include heating at 150°C to 500°C for 5 minutes to 5 hours, or irradiating with 365 nm i-line, 405 nm h-line, and 432 nm g-line of a high-pressure mercury lamp at 50 mJ / cm². ２ More than 3000mJ / cm ２ Known methods include curing by exposure, as described below. By curing the photosensitive resin composition of the present invention, the heat resistance and chemical resistance of the cured product can be improved. The cured product is preferably one that has the shape of a film, i.e., a cured film.

[0146] <Method for manufacturing a cured product> The method for manufacturing a cured product of the present invention includes, in this order: applying a photosensitive resin composition to a substrate and then drying it to form a resin film; an exposure step of exposing the dried resin film to light; a developing step of developing the exposed resin film; and a heat treatment step of heat treating the developed resin film.

[0147] In the process of applying a photosensitive resin composition to a substrate and then drying it to form a resin film, the photosensitive resin composition of the present invention is applied to the substrate by methods such as spin coating, slit coating, dip coating, spray coating, and printing. Substrates used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, metals, glass, metal oxide insulating films, silicon nitride, and ITO. The coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the composition, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

[0148] After application, it dries to form a resin film. Drying may be performed by vacuum drying if necessary, followed by heat treatment using a hot plate, oven, infrared, etc., at a temperature of 50°C to 180°C for 1 minute to several hours.

[0149] In the exposure process for exposing a dried resin film, a chemical beam is irradiated onto the resin film through a photomask having a desired pattern. Chemical beams used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in this invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

[0150] In the development process, which involves developing an exposed resin film, the exposed resin film is developed using a developer solution to remove the exposed areas. Preferred developers include aqueous solutions of alkaline compounds such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. 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 to these alkaline aqueous solutions, either individually or in combination. After development, the film is rinsed with water. Here too, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0151] In the heat treatment process for developing the resin film, heat treatment is performed using a hot plate, oven, infrared radiation, etc. Heat treatment removes residual solvents and components with low heat resistance, thereby improving heat resistance and chemical resistance. The photosensitive resin composition of the present invention can improve heat resistance and chemical resistance because component (A1) can form imide rings and / or oxazole rings by heat treatment. Furthermore, if a crosslinking agent (D) is included, heat treatment can promote a thermal crosslinking reaction, improving mechanical properties, heat resistance, and chemical resistance. This heat treatment is performed by selecting a temperature and gradually increasing it, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, heat treatment may be performed at 150°C, 250°C, and 350°C for 30 minutes each. Alternatively, the temperature may be linearly increased from room temperature to 320°C over 2 hours.

[0152] The heat-resistant resin film formed using the photosensitive resin composition of the present invention is suitably used in applications such as passivation films for semiconductors, protective films for semiconductor devices, interlayer insulating films for multilayer wiring for high-density mounting, and insulating layers for organic electroluminescent devices.

[0153] <Semiconductor Device> The semiconductor device of the present invention has a cured product of the present invention. The semiconductor device of the present invention further has a semiconductor chip and a encapsulating material covering the semiconductor chip, wherein the conductive inorganic layer is a redistribution layer and the insulating resin layer is an interlayer insulating layer of the redistribution layer. Furthermore, from the viewpoint of improving integration density and suppressing transmission loss between wirings, it is preferable that the area of ​​the redistribution layer is larger than the area of ​​the semiconductor chip in a plan view. It is preferable that the encapsulating material covering the semiconductor chip is in direct contact with the interlayer insulating layer of the redistribution layer. Furthermore, from the viewpoint of improving heat resistance and reliability, it is preferable that the encapsulating material covering the semiconductor chip contains an epoxy resin, and more preferably contains a cured epoxy resin. Examples of semiconductor devices include a fan-out wafer-level package structure, a fan-out panel-level package structure, or an antenna-in-package structure. These package structures in the semiconductor device of the present invention may be single-die or multi-die structures, and from the viewpoint of improving integration density and suppressing transmission loss between wirings, a multi-die structure is preferred. The multi-die structure preferably has a chiplet structure, more preferably includes one or more dies selected from the group consisting of logic, memory, analog IC (analog integrated circuit), RF circuit (high-frequency circuit), and power semiconductor, and even more preferably includes two or more dies.

[0154] <Display Device> The display device of the present invention has the cured product of the present invention.

[0155] Examples of display devices include LCDs, ECDs, ELDs, and organic EL displays. Specifically, an organic EL display device having at least a TFT substrate, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, wherein the planarization layer or insulating layer, etc., has the cured film of the present invention. The display device of the present invention can be suitably used in various electronic devices. Examples of electronic devices include smartphones, tablet PCs, and smart glasses.

[0156] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these embodiments. The names of the compounds used that are abbreviated are shown below. ODPA: 4,4'-oxydiphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Wakayama Seika Kogyo Co., Ltd.) SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) MAP: 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) GBL: γ-butyrolactone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) TMAH: tetramethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.) HMOM-TPHAP: Thermal crosslinking agent containing a methoxymethyl group (manufactured by Honshu Chemical Industry Co., Ltd.). It is represented by the following formula (75).VG-3101L: Thermal crosslinking agent containing epoxy groups (manufactured by Printec) NAC-5: 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (manufactured by Toyo Gosei Kogyo Co., Ltd.) NAC-4: 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (manufactured by Toyo Gosei Kogyo Co., Ltd.) TrisP-PA: α,α-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)-ethylbenzene (manufactured by Honshu Chemical Industry Co., Ltd.) TekP-4HBPA: 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexanyl-1-ylidene]tetrakisphenol (manufactured by Honshu Chemical Industry Co., Ltd.) TekOC-4HBPA: 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexanyl-1-ylidene]tetrakis[2-methylphenol] (manufactured by Honshu Chemical Industry Co., Ltd.) BisP-3MZ: 4,4'-(3-methylcyclohexane-1,1-diyl)diphenol (manufactured by Honshu Chemical Industry Co., Ltd.) BisP-HTG: 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.) BisP-IOTD: 4,4'-(2-ethylhexylidene)diphenol (manufactured by Honshu Chemical Industry Co., Ltd.) BisP-IBTD: 4,4'-(2-methylpropane-1,1-diyl)diphenol (manufactured by Honshu Chemical Industry Co., Ltd.) BIOC-E: 1,1'-bis(4-hydroxy-3-methylphenyl)ethane (manufactured by Asahi Organic Chemicals Co., Ltd.) SPI: 3,3,3',3'-tetramethyl-1,1'-spirobiindan-6,6'-diol (manufactured by JFE Chemical Corporation) TMHI: 3-(4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol (manufactured by JFE Chemical Corporation) ODB-HBT: A mixture of dicarboxylic acid derivatives obtained by reacting bis(4-carboxyphenyl) ether (manufactured by Tokyo Chemical Industries, Ltd.) and 1-hydroxy-1,2,3-benzotriazole (manufactured by Tokyo Chemical Industries, Ltd.) in a molar ratio of 1:2 BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Tokyo Chemical Industries, Ltd.) MPA: 3-methoxy-N,N-dimethylpropanamide.

[0157] [Measurement and Evaluation Method] (1) Weight-average molecular weight (Mw) of component (A1) and component (A2) The resins obtained in each synthesis example were measured for weight-average molecular weight (Mw) in polystyrene equivalent using a gel permeation chromatography (GPC) analyzer under the following conditions. Analyzer: Waters 2695 (Waters Inc.) 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% lithium chloride and 0.48% phosphoric acid by weight) Guard column: TOSOH TSK guard column (Tosoh Corporation) Column: TOSOH TSK-GEL a-2500 and TOSOH TSK-GEL a-4000 (both manufactured by Tosoh Corporation) in series. Number of measurements: 2 (the average value was used as the weight-average molecular weight of component (A1) and component (A2)).

[0158] (2) Esterification rate of polyamic acid esters Using a nuclear magnetic resonance (NMR) spectrometer (EX-270, manufactured by JEOL Ltd.), a mixed solution of 10 mg of the resin obtained in each synthesis example and 0.8 g of deuterated DMSO (DMSO-d6) was obtained. １ ¹H-NMR was measured, and the integral value of the peak originating from aromatic protons in the resin was determined. The esterification rate of the polyamic acid ester was calculated from the area ratio of the peak originating from methyl protons of the carboxylic acid ester. Since resins other than polyamic acid esters do not contain carboxylic acid esters, the esterification rate is considered unmeasurable and is represented by "-".

[0159] (3) Imide ring closure rate and benzoxazole closure rate The resins obtained in each synthesis example were dissolved in GBL to a concentration of 35% by weight. This solution was applied to a 4-inch silicon wafer by spin coating using a spinner (Mikasa Corporation 1H-DX), and then pre-baked on a hot plate at 120°C for 3 minutes to produce a resin film with a thickness of 4-5 μm. The wafer with this resin film was divided into two, and one half was cured in a clean oven (Koyo Thermo Systems Co., Ltd. CLH-21CD-S) under a nitrogen stream (oxygen concentration of 20 ppm or less) at 140°C for 30 minutes, and then further heated to 320°C for 1 hour to completely close the imide ring. The transmitted infrared absorption spectra of the resin film before and after curing were measured using an infrared spectrophotometer (Horiba, Ltd. FT-720), and the absorption peak of the imide structure due to polyimide (1,780 cm⁻¹) was observed. －１ Nearby, 1,377 cm －１ After confirming its presence (in the vicinity), 1,377 cm －１ The peak intensities in the vicinity (before curing: S, after curing: T) were determined. The peak intensity ratio, obtained by dividing the peak intensity (S) by the peak intensity (T), was calculated using the following formula and represented as the imide group content in the polymer before heat treatment, i.e., the imide ring closure rate. Imide ring closure rate [%] = (S / T) × 100.

[0160] Regarding the benzoxazole ring closure rate, a resin film with a thickness of 4-5 μm was prepared using the same method as described above. The prepared resin film-coated silicon wafer was divided into two parts. One part was heated at 320°C for 30 minutes using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation) to completely close the benzoxazole ring (resin film after heating). The other part was used as is without heat treatment (resin film before heating). The transmitted infrared absorption spectra of the resin film before and after heating were measured using an infrared spectrophotometer (FT-720; manufactured by Horiba, Ltd.). The absorption peak of the benzoxazole structure due to polybenzoxazole was 1,570 cm⁻¹. －１ After confirming the presence of a peak (caused by C=C (C=N) stretching vibration) in the vicinity, the measurement was taken at 1,570 cm before heating. －１ Nearby peak intensity (P), 1,570 cm after heating. －１The peak intensity (Q) in the vicinity was determined for each. The benzoxazole cyclization rate in the resin film before heating was calculated using the following formula: Benzoxazole cyclization rate [%] = (P / Q) × 100.

[0161] (4) Film Thickness Measurement The film thickness after pre-baking and development was measured using a Lambda Ace STM-602 optical interference film thickness measuring device manufactured by Dainippon Screen Mfg. Ltd., with a refractive index of 1.629. (5) Solvent Solubility The photosensitive resin compositions of each example and comparative example were applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Corporation), and then pre-baked on a hot plate at 120°C for 2 minutes to produce a resin film with a thickness of 2 μm. The wafer with this resin film was immersed in 100 g of PGME (propylene glycol monomethyl ether) at 23°C for 5 minutes and rinsed with pure water. Dissolution of the resin film was confirmed by visual inspection and film thickness measurement. The following judgments were made, with A being a pass and B being a fail. A: Film thickness after 5 minutes of immersion is less than 1.0 μm. B: Film thickness after 5 minutes of immersion is 1.0 μm or more.

[0162] (6) Sensitivity Evaluation A photosensitive resin composition was applied to an 8-inch silicon wafer using a spin-coating method with a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.) to produce a pre-baked film with a film thickness of 7 μm after heat treatment. Pre-baking was performed at 120°C for 3 minutes. Subsequently, 100 to 1500 mJ / cm was applied using an i-line stepper (manufactured by Nikon Corporation, NSR-2205i14). ２ Within the range of 20 mJ / cm², the exposure dose is 20 mJ / cm². ２ Exposure was performed by gradually changing the exposure level. The size of the concave line pattern used for exposure was 20 μm in line width. After exposure, development was performed using a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (manufactured by Tama Chemical Industry Co., Ltd.) under conditions such that the change in film thickness of the unexposed areas before and after development was 0.4 μm to 0.6 μm. Then, the film was rinsed with pure water, shaken dry, and a pattern-forming film was obtained. The minimum exposure level at which the 20 μm line width pattern opened with a width of 19.95 μm or more was defined as the optimal exposure level (Eop), and was evaluated in six stages from A to F as follows. Note that a smaller optimal exposure level (Eop) indicates higher sensitivity. A: 250 mJ / cm ２Less than B: 250 mJ / cm ２ More than 600mJ / cm ２ Less than C: 600 mJ / cm ２ More than 800mJ / cm ２ Less than D: 800 mJ / cm ２ 900mJ / cm or more ２ Less than E: 900 mJ / cm² ２ More than 1000mJ / cm ２ Less than F: 1000 mJ / cm ２ The above or pattern processing is not possible.

[0163] (7) Evaluation of elongation at break The resin compositions obtained in each example and comparative example were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 so that the film thickness after heat treatment was 7 μm, and then pre-baked. The wafer was then heated to 320°C at a rate of 3.5°C / min with an oxygen concentration of 20 ppm by volume or less using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), and heated at 320°C for 30 minutes. When the temperature fell below 50°C, the silicon wafer was removed and the cured film of the resin composition was peeled off the wafer by immersion in 45% by weight hydrofluoric acid for 1 minute. This film was cut into strips 1 cm wide and 9 cm long, and the elongation at break was measured by pulling it at a tensile speed of 50 mm / min using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at a room temperature of 23.0°C and a humidity of 45.0% RH. Measurements were taken on 10 strips per sample, and the average of the top 5 scores was calculated. The results were evaluated in three stages, A to C, as shown below. Note that a higher elongation at break indicates higher elongation. A: 8% or more B: 5% or more but less than 8% C: Less than 5%.

[0164] (8) Evaluation of the pattern shape of the photosensitive resin composition (evaluation of the cross-sectional shape) A pattern-forming film was obtained under the same conditions as in (6) above, except that the pattern used for exposure was a convex line pattern with a line width of 10 μm.

[0165] After development, the wafer was divided into two. One half was heated in an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream with an oxygen concentration of 20 ppm by volume or less, from 50°C to 320°C at a rate of 3.5°C / min, and then heated at 320°C for 30 minutes to harden the pattern-forming film and obtain a cured film. The wafer was removed when the temperature dropped below 50°C. Subsequently, both the developed and cured wafers were cut, and the cross-sectional shape of the 10 μm linewidth convex pattern in Eop was observed and measured using a scanning electron microscope S-4800 (manufactured by Hitachi High-Tech).

[0166] When L1 is the line width at the bottom of the convex pattern after development, L2 is the line width at 1% of the pattern height from the surface after development, L3 is the line width at the bottom of the pattern after curing, and L4 is the line width at 1% of the pattern height from the surface after curing, the value of (L2 / L1) / (L4 / L3) was used to evaluate the results in five stages from A+ to D, as shown below. Pattern height represents the highest part of the convex pattern. Note that A+ is the most desirable result. A+: 0.97 or more and less than 1.03 A: 0.95 or more and less than 0.97, 1.03 or more and less than 1.05 B: 0.6 or more and less than 0.95, 1.05 or more and less than 1.4 C: Less than 0.6, 1.4 or more D: Unmeasurable.

[0167] (9) Chemical resistance of cured products The resin compositions obtained in each example and comparative example were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 and pre-baked so that the film thickness after heat treatment was 7 μm. Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 320°C at 3.5°C / min with an oxygen concentration of 20 volume ppm or less, and heat treatment was performed at 320°C for 30 minutes. After that, the silicon wafer was removed when the temperature fell below 50°C. The cured photosensitive resin compositions obtained by the above procedure were immersed in NMP at 23°C for 15 minutes, the film thickness before and after treatment was measured, the rate of change was determined and evaluated in four stages from A to D as shown below. Note that A is the most preferable result. A: Absolute value of the rate of change is less than 1%. B: Absolute value of the rate of change is 1% or more but less than 2%. C: Absolute value of the rate of change is 2% or more but less than 3%. D: Absolute value of the rate of change is 3% or more, or the hardened film has peeled off.

[0168] <Synthesis Example 1: Synthesis of Quinone Diazide Compound (QD-a)> Under a stream of dry nitrogen, 21.22 g (0.050 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of NAC-5 were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. A solution of 15.18 g of triethylamine dissolved in 50 g of 1,4-dioxane was added dropwise to the system so that the temperature was below 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The mixture was then filtered again, and the precipitated material was collected. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound QD-a represented by formula (68).

[0169]

[0170] In formula (68), * represents the bonding site with the oxygen atom.

[0171] <Synthesis Example 2: Synthesis of Quinone Diazide Compound (QD-b)> Except for using the raw materials listed in Table 1 in the molar ratios listed in Table 1, the compound (QD-b) represented by formula (69) was synthesized in the same manner as in Synthesis Example 1.

[0172]

[0173] In formula (69), * represents the bonding site with the oxygen atom.

[0174] <Synthesis Example 3: Synthesis of Quinone Diazide Compound (QD-c)> Under a stream of dry nitrogen, 57.67 g (0.1 mol) of TekP-4HBPA (manufactured by Honshu Chemical Industry Co., Ltd.) and 80.60 g (0.3 mol) of NAC-5 were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. A solution of 30.36 g of triethylamine dissolved in 50 g of 1,4-dioxane was added dropwise to the system so that the temperature was below 35°C. After addition, the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The mixture was then filtered again, and the precipitated material was collected. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound QD-c represented by formula (70).

[0175]

[0176] In formula (70), * represents the bonding site with the oxygen atom.

[0177] <Synthesis Examples 4-7: Synthesis of quinone diazide compounds (QD-d) to (QD-g)> Except for replacing TekP-4HBPA and NAC-5 in Synthesis Example 3 with the raw materials listed in Table 1 in the molar ratios listed in Table 1, the compounds (QD-d) to (QD-g) represented by formulas (71) to (74) were obtained.

[0178]

[0179]

[0180]

[0181]

[0182] In formulas (71) to (74), * represents the bonding site with the oxygen atom. The photosensitive materials obtained in Synthesis Examples 1 to 7 are summarized in Table 1.

[0183]

[0184] <Synthesis Example 8: Synthesis of Diamine (DAP-A)> In a 500 ml four-necked flask equipped with a stirrer, thermocouple, and dropping funnel, 24.28 g (0.086 mol) of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4'-(3-methylcyclohexane-1,1-diyl)diphenol) and 100 ml of glacial acetic acid were charged and stirred, and the internal temperature was raised to 50°C in a water bath. 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour, then cooled with ice to lower the internal temperature to 13°C, and another 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was then continued for 3 hours, the precipitated yellow crystals were filtered, washed sequentially with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain the dinitro compound.

[0185] Next, 50.27 g (0.135 mol) of the dinitro compound, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were placed in a 2 L four-necked flask equipped with a stirrer, thermocouple, Liebig condenser, and dropping funnel, and stirred under ice cooling. 0.9 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.), which had been soaked in 30 ml of ethanol, was added dropwise over 1 hour. After that, the solution was refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 ml of ethanol. All solvents were removed by heating under reduced pressure, and the residue was washed with 75 ml of ice-cooled ethanol, filtered, and then sequentially washed with 75 ml of deionized water and 150 ml of diethyl ether. The mixture was dried under reduced pressure to obtain the diamine (DAP-A).

[0186] <Synthesis Examples 9-16: Synthesis of Diamines (DAP-B) to (DAP-I)> Diamines (DAP-B) to (DAP-I) were obtained in the same manner as in Synthesis Example 8, except that the phenol compound raw material (0.086 mol) listed in Table 2 was used instead of BisP-3MZ in Synthesis Example 8.

[0187] <Synthesis Example 17: Synthesis of Diamine (HA)> 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 50 mL of acetone and 30 g (0.34 mol) of propylene oxide, and the mixture was cooled to -15°C. A solution of 11.2 g (0.055 mol) of isophthalic acid chloride dissolved in 60 mL of acetone was gradually added dropwise. After the addition was complete, the mixture was reacted at -15°C for 4 hours. The mixture was then returned to room temperature, and the precipitate was collected by filtration.

[0188] This precipitate was dissolved in 200 mL of γ-butyrolactone (GBL), and 3 g of 5% palladium-carbon was added and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached, and stirring continued at room temperature until the hydrogen gas balloon could no longer deflate, and then stirring was continued for another 2 hours with the hydrogen gas balloon attached. After stirring, the palladium compound was removed by filtration, and the solution was concentrated to half its volume using a rotary evaporator. Ethanol was added, and recrystallization was performed to obtain crystals of hydroxyl group-containing diamine (HA).

[0189] <Synthesis Example 18: Synthesis of Diamine Compound (HB)> 12.9 g (0.05 mol) of BAP was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 mL of acetone was added dropwise. After the addition was complete, the mixture was stirred at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and vacuum-dried at 50°C.

[0190] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve. 2.0 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen gas was then introduced using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon had not deflated any further. After the reaction was complete, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the diamine compound (HB).

[0191] <Synthesis Examples 19-21: Synthesis of Diamine Compounds (HC)-(HE)> Diamine compounds (HC)-(HE) were obtained in the same manner as in Synthesis Example 18, except that the phenol compound raw material (0.05 mol) listed in Table 2 was used instead of BAP in Synthesis Example 18.

[0192] The structures of the diamine compounds obtained in synthesis examples 8 to 21 are summarized below.

[0193]

[0194]

[0195]

[0196] <Synthesis Example 22: Synthesis of Polyamic Acid Ester (A1-1)> Under a stream of dry nitrogen, 13.0 g (0.0416 mol) of the diamine compound (DAP-A) obtained in Synthesis Example 8 and 0.62 g (0.0025 mol) of SiDA were dissolved in 95 g of MPa. 15.52 g (0.050 mol) of ODPA was added together with 10 g of MPa, and the mixture was stirred at 60°C for 2 hours. Then, 1.09 g (0.010 mol) of MAP was added together with 10 g of MPa as a terminal encapsulant, and the mixture was reacted at 60°C for 1 hour. After lowering the temperature from 60°C to 40°C, a solution of 11.9 g (0.100 mol) of DMFDMA (N,N-dimethylformamide dimethylacetal) diluted with 10 g of MPa was added dropwise. After the addition, stirring was continued at 40°C for 2 hours. After stirring, the solution was added to 2 L of deionized water, and the polymer solid precipitate was collected by filtration. The solution was then washed three times with 2 L of deionized water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain polyamic acid ester (A1-1), a form of polyimide.

[0197] <Synthesis Examples 23-40: Synthesis of Polyamic Acid Esters (A1-2) to (A1-19)> Polyamic acid esters (A1-2) to (A1-19) were obtained in the same manner as in Synthesis Example 22, except that the raw materials listed in Table 3 were used in the molar ratios listed in Table 3.

[0198] <Synthesis Example 41: Synthesis of Polybenzoxazole Precursor (A1-20)> Under a stream of dry nitrogen, 16.17 g (0.0475 mol) of the diamine compound (DAP-B) obtained in Synthesis Example 9 and 0.62 g (0.0025 mol) of SiDA were dissolved in 95 g of MPa. 19.70 g (0.040 mol) of ODB-HBT was added together with 10 g of MPa, and the mixture was stirred at 85°C for 1 hour. Then, 3.28 g (0.020 mol) of NA was added together with 10 g of MPa as a terminal encapsulant, and the mixture was reacted at 85°C for 30 minutes. After stirring, the solution was added to 2 L of deionized water, and the precipitate of the polymer solid was collected by filtration. The mixture was then washed three times with 2 L of deionized water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain polybenzoxazole precursor (A1-20).

[0199] <Synthesis Example 42: Synthesis of Polybenzoxazole Precursor (A1-21)> Polybenzoxazole precursor (A1-21) was obtained in the same manner as in Synthesis Example 41, except that the raw materials listed in Table 3 were used in the molar ratios listed in Table 3.

[0200] <Comparative Synthesis Example 1: Synthesis of Polyamic Acid Ester (A1-22)> Polyamic acid ester (A1-22) was obtained in the same manner as in Synthesis Example 22, except that the raw materials listed in Table 3 were used in the molar ratios listed in Table 3. <Comparative Synthesis Example 2: Synthesis of Polybenzoxazole Precursor (A1-23)> Polybenzoxazole precursor (A1-23) was obtained in the same manner as in Synthesis Example 41, except that the raw materials listed in Table 3 were used in the molar ratios listed in Table 3. The resins obtained in Synthesis Examples 22 to 42, Comparative Synthesis Example 1, and Comparative Synthesis Example 2 are summarized in Table 3.

[0201]

[0202] <Synthesis Example 43: Synthesis of Phenolic Resin (A21-1)> Under a stream of dry nitrogen, 54 g (0.50 mol) of m-cresol, 54 g (0.50 mol) of p-cresol, 75.5 g (0.93 mol) of 37 wt% formaldehyde aqueous solution, 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were charged. The mixture was then immersed in an oil bath, and the polycondensation reaction was carried out for 4 hours while refluxing the reaction mixture. After that, the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 40-67 hPa to remove volatile components. The dissolved resin was then cooled to room temperature to obtain a polymer solid of novolac resin (A21-1). The weight-average molecular weight was 3,500 from GPC.

[0203] <Synthesis Examples 44-46: Synthesis of Phenolic Resins (A21-2) to (A21-4)> Phenolic resins (A21-2) to (A21-4) were obtained in the same manner as in Synthesis Example 43, except that the phenols and aldehydes listed in Table 4 were used in the molar ratios listed in Table 4. The weight-average molecular weights from GPC were as shown in Table 4.

[0204] <Synthesis Example 47: Synthesis of Phenolic Resin (A22-1)> Under a stream of dry nitrogen, 108.1 g (1.00 mol) of m-cresol, 34.0 g (0.32 mol) of benzaldehyde, 90.4 g (0.74 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were charged into a reaction vessel and reacted at 65°C under reflux for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and the mixture was washed five times using a separatory solution. Methyl isobutyl ketone was removed by distillation under reduced pressure at 100°C using an evaporator to obtain phenolic resin (A22-1). The ratio of the number of repeating structural units represented by formulas (55) and (56) is formula (55): formula (56) = 70:30. The weight-average molecular weight was 3000 from GPC.

[0205] <Synthesis Examples 48-49: Synthesis of Phenolic Resins (A22-2) to (A22-3)> Phenolic resins (A22-2) to (A22-3) were obtained in the same manner as in Synthesis Example 47, using the phenols and aldehydes listed in Table 4 in the molar ratios listed in Table 4. The weight-average molecular weights from GPC were as shown in Table 4.

[0206] <Synthesis Example 50: Synthesis of Phenolic Resin (A22-4)> 108.1 g (1.00 mol) of m-cresol, 36.29 g (0.342 mol) of benzaldehyde, 97.45 g (0.798 mol) of salicylaldehyde, 250 g of methanol, and 65 g of hydrochloric acid were charged into a reaction vessel and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and the mixture was washed five times using a separatory solution. Methyl isobutyl ketone was removed by distillation under reduced pressure at 100°C using an evaporator to obtain novolac-type phenolic resin (A22-4). The weight-average molecular weight was 17,000 from GPC.

[0207] <Synthesis Example 51: Synthesis of Phenolic Resin (A22-5)> Phenolic resin (A22-5) was obtained in the same manner as in Synthesis Example 50, using the phenols and aldehydes listed in Table 4 in the molar ratios listed in Table 4. The weight-average molecular weight was 11,000 from GPC.

[0208] <Synthesis Example 52: Synthesis of Phenolic Resin (A23-1)> Phenolic resin (A23-1) was obtained in the same manner as in Synthesis Example 43, except that the phenols and aldehydes listed in Table 4 were used in the molar ratios listed in Table 4 and the polycondensation reaction time was set to 6 hours. The weight-average molecular weight was 8,000 from GPC.

[0209] <Synthesis Example 53: Synthesis of Phenolic Resin (A22-6)> Phenolic resin (A22-6) was obtained in the same manner as in Synthesis Example 47, using the phenols and aldehydes listed in Table 4 in the molar ratios listed in Table 4. The weight-average molecular weight was 3,100 from GPC. The phenolic resins obtained in Synthesis Examples 43 to 53 are summarized in Table 4.

[0210]

[0211] [Example 1] Under a yellow light, a 20% GBL solution was added to 11.4 g of GBL, which is the solvent (C). The solution consisted of 6.0 g of polyamic acid ester (A1-1) as component (A1), 4.0 g of (A21-1) as component (A2), 2.0 g of QD-a as the photosensitive agent (B), and 5.75 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; a compound represented by the following formula (75)) as the crosslinking agent (D). The mixture was stirred for 30 minutes to dissolve the components, resulting in a homogeneous solution with a solid content of 45.1% by weight.

[0212]

[0213] Subsequently, the obtained solution was filtered through a 0.45 μmφ filter to obtain photosensitive resin composition 1. Then, various evaluations were performed using the obtained photosensitive resin composition 1 according to measurement and evaluation methods (1) to (8).

[0214] [Examples 2-52 and Comparative Examples 1-4] Various evaluations were carried out in the same manner as in Example 1, except that the photosensitive resin compositions were prepared with the compositions listed in Tables 5 and 6. The results of these evaluations are summarized in Table 7.

[0215]

[0216]

[0217]

[0218]

[0219] 10A Semiconductor device having bumps 11 Silicon substrate 12 Al pad 13 Passivation layer 14 Insulating layer 15 Metal layer 16 Metal wiring 17 Insulating layer 18 Barrier metal layer 19 Scribe line 20 Solder bump 30A Display device having interlayer insulating layer, partition layer and planarization layer 31 Light-emitting element 32 Interlayer insulating layer 33, 33c Metal wiring 34 Opposing substrate 35 Electrode terminal 36 Light-emitting element driving substrate 37 Driving element 38 Barrier metal 39 Solder bump 40 Partition layer 41 Planarization layer 100A Display device having a stepped shape in which the pixel division layer has a thick film portion and a thin film portion 101 Substrate 102 Metal wiring 103 TFT element layer 104 Interlayer insulating layer 105 TFT planarization layer / TFT protective layer 106 Pixel division layer with stepped shape 106a Thin film portion in the pixel division layer 107 First electrode 108 Light-emitting layer 109 Second electrode 110 Sealing layer 111 Touch panel wiring / touch panel electrode 112 Color filter layer 113 Black matrix layer 114 Overcoat layer 115 Substrate 116 Thick film portion in the pixel division layer 100x Cross-sectional axis in plan view 112a Color filter layer portion 116a Thick film portion in the pixel division layer portion 117a Opening in the pixel division layer portion with stepped shape 118a Opening in the black matrix layer portion

Claims

1. A photosensitive resin composition containing one or more resins (A1) selected from the group consisting of polyimide, polybenzoxazole, and their copolymers, a phenolic resin (A2), a photosensitizer (B), and a solvent (C), wherein the component (A1) contains at least one or more diamine residues represented by any of formulas (1) to (3). (In formulas (1), (2), and (3), X １ 、 X ３ and X ４ are each independently a direct bond or a divalent group represented by formula (4), and R １ 、 R ２ and R ３ each independently represent an alkyl group having 1 to 4 carbon atoms, X ２ is a divalent group represented by formula (5) or formula (6), i is each independently 0 or 1, and * represents a bonding point bonded to a nitrogen atom contained in an imide structure, a hydroxyamide structure, or an amic acid structure.) (In formula (4), * represents a bonding point bonded to a nitrogen atom contained in an imide structure, a hydroxyamide structure, or an amic acid structure. ** represents a bonding point bonded to an aromatic ring.) (In formulas (5) and (6), R ４ each independently represent an alkyl group having 1 to 4 carbon atoms, a represents 1 or 2, b represents any integer from 1 to 3, R ５ and R ６ each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents a bonding point bonded to an aromatic ring. However, R ５ and R ６ do not have the same structure.) 2. The photosensitive resin composition according to claim 1, wherein the content of component (A2) is 101 parts by weight or more and 500 parts by weight or less per 100 parts by weight of component (A1).

3. The photosensitive resin composition according to claim 1, wherein component (B) comprises a compound represented by formula (7). (In formula (7), R ７ ~R １０ Each of these independently represents a monovalent organic group having 1 to 10 carbon atoms. １１ c1, c2, c3, and c4 each represent an integer from 0 to 4. (The first two characters represent a divalent organic group with 1 to 20 carbon atoms. The second character represents a 5-naphthoquinone diazidosulfonyl group, a 4-naphthoquinone diazidosulfonyl group, or a hydrogen atom. However, not all of the characters represent hydrogen atoms. The third characters represent an integer from 0 to 4.) 4. The photosensitive resin composition according to claim 1, wherein the (A2) component contains a novolac resin (A2-1), the (A2-1) component does not contain aromatic aldehyde residues and / or aromatic ketone residues, and when the molar amount of m-cresol residues in the (A2-1) component is m and the molar amount of p-cresol residues is p, the molar ratio p / m is 0 or more and 5 / 9 or less.

5. The photosensitive resin composition according to claim 1, wherein the (A2) component contains a phenolic resin (A2-2) having repeating structural units represented by formula (8) and repeating structural units represented by formula (9). (In formula (8), R １２ Each of these independently represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. １３ R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １４ Each of these independently represents a monovalent organic group with 1 to 10 carbon atoms. d1 and d3 independently represent integers from 0 to 3, and d2 represents an integer from 1 to 3. However, the condition 1 ≤ d2 + d3 ≤ 5 is satisfied. * represents a bond. (In formula (9), R １５ Each of these independently represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. １６ R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １７ Each of these independently represents a monovalent organic group with 1 to 10 carbon atoms. d4 and d5 independently represent integers from 0 to 3. * represents a bond.

6. The photosensitive resin composition according to claim 5, wherein the content of component (A2-2) is greater than 0% by weight and 50% by weight or less, relative to 100% by weight of component (A2).

7. A cured product obtained by curing the photosensitive resin composition according to claim 1.

8. A method for producing a cured product, comprising the steps of: applying a photosensitive resin composition according to any one of claims 1 to 6 to a substrate, then drying it to form a resin film; exposure of the dried resin film; development of the exposed resin film; and heat treatment of the developed resin film, in this order.

9. A cured product comprising a resin-derived skeleton selected from polyimide and polybenzoxazole, a phenol resin-derived skeleton, and a photosensitive agent-derived skeleton, each containing at least one diamine residue represented by any of formulas (1) to (3). (In equations (1), (2), and (3), X １ 、 X ３ and X ４ Each of these is independently a divalent group represented by a direct bond or formula (4), R １ 、 R ２ and R ３ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, X ２ (where i is a divalent group represented by formula (5) or formula (6), i independently represents 0 or 1, and * represents a bond site attached to a nitrogen atom contained in the imide, hydroxyamide, or amidic acid structure.) (In formula (4), * represents a bond site attached to a nitrogen atom contained in the imide, hydroxyamide, or amidic acid structure. ** represents a bond site attached to an aromatic ring.) (In equations (5) and (6), R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, where a represents 1 or 2, and b represents any integer from 1 to 3, R ５ and R ６ Each of these independently represents a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms, and * represents a bond point attached to an aromatic ring. However, R ５ and R ６ They do not have the same structure.

10. The cured product according to claim 9, wherein the phenol resin-derived skeleton contains a phenol resin-derived skeleton having repeating structural units represented by formula (8) and repeating structural units represented by formula (9). (In formula (8), R １２ Each of these independently represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. １３ R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １４ Each of these independently represents a monovalent organic group with 1 to 10 carbon atoms. d1 and d3 independently represent integers from 0 to 3, and d2 represents an integer from 1 to 3. However, the condition 1 ≤ d2 + d3 ≤ 5 is satisfied. * represents a bond. (In formula (9), R １５ Each of these independently represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. １６ R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １７ Each of these independently represents a monovalent organic group with 1 to 10 carbon atoms. d4 and d5 independently represent integers from 0 to 3. * represents a bond.

11. The cured product according to claim 10, wherein the content of the repeating structural unit represented by formula (8) and the phenol resin-derived skeleton having the repeating structural unit represented by formula (9) is greater than 0% by weight and 50% by weight or less, relative to 100% by weight of the phenol resin-derived skeleton.

12. A semiconductor device having a cured product according to any one of claims 7, 9 to 11.

13. A display device having a cured product according to any one of claims 7, 9 to 11.

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