Polyamide resin, photosensitive resin composition, cured product, method for producing same, and electronic component

Abstract

A polyamide resin (A) having a dicarboxylic acid residue and a diamine residue, which contains a specific molecular chain terminal. The present invention provides a photosensitive resin composition having excellent alkali developability, low dielectric tangent and low dielectric constant, a cured product obtained from the photosensitive resin composition, an insulating film, and an electronic component.

Description

Technical Field

[0001] This invention relates to polyamide resins, photosensitive resin compositions, cured products, methods for manufacturing the same, and electronic components. More specifically, it relates to photosensitive resin compositions that are well-suited for use as surface protective films, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like in electronic components such as semiconductor elements. Background Technology

[0002] Representative materials used as surface protective films or interlayer insulating films for semiconductor devices, insulating layers for organic electrolytic devices, or planarization films for TFT substrates include polyimide resins, which exhibit excellent heat resistance or electrical insulation properties. Furthermore, to improve productivity, polyimides and their precursors that impart negative or positive photosensitivity have also been investigated.

[0003] In recent years, with the expansion of semiconductor applications and the improvement of performance, efforts have been made to reduce costs and achieve high integration through the efficiency of manufacturing processes. Therefore, semiconductor devices with multilayered metal rewiring have attracted much attention. For such multilayered metal rewiring insulating films, multiple high-temperature processing steps are required in the manufacturing process. Furthermore, to improve productivity, patterning capabilities using photolithography are required. In patterning, development with organic solvents (organic development) is used, but due to the high environmental impact of VOCs (volatile organic compounds), development with alkaline solutions (alkaline development) with low environmental impact is required. Moreover, in high-frequency communication equipment applications for high-speed wireless communication, reducing transmission loss requires lowering the dielectric tangent (also known as the "dielectric loss tangent") in the insulating film.

[0004] As a positively photosensitive polyimide material for alkaline development, a positive resin composition containing hydroxystyrene resin, polyamic acid, and quinone diazo compound has been proposed (Patent Document 1). Additionally, a negatively photosensitive polyimide resin composition using an alkaline aqueous solution as the developing solution has been proposed (Patent Document 2). As a method for low dielectric tangent reduction, a soluble polyimide using a dimeric diamine with a low polarity structure can be cited (Patent Document 3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2007-156243

[0008] Patent Document 2: International Publication No. 2004 / 109403

[0009] Patent Document 3: Japanese Patent Application Publication No. 2018-203959 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] In the application of existing technologies for multilayer wiring insulation films used in high-frequency communication equipment for high-speed wireless communication, for example in Patent Documents 1 and 2, functional groups such as phenolic hydroxyl groups are required to impart solubility in alkaline aqueous solutions, which greatly increases the dielectric tangent. Furthermore, in Patent Document 3, the low-polarity structure significantly reduces solubility in alkaline aqueous solutions, making alkaline development difficult.

[0012] Problem-solving methods

[0013] To address the aforementioned issues, the present invention has the following configuration.

[0014] [1] A (A) polyamide resin, which is a polyamide resin having dicarboxylic acid residues and diamine residues, the (A) polyamide resin comprising the molecular chain ends shown in formula (1),

[0015]

[0016] In equation (1), Y 1 Z represents a divalent organogroup with 2 to 70 carbon atoms, Z represents a monovalent monocarboxylic acid residue with 1 to 20 carbon atoms, and R represents a divalent organogroup with 2 to 70 carbon atoms. 1 and R 2 Each of the following groups independently represents a monovalent organic group with 1 to 10 carbon atoms, p and q represent integers from 0 to 3, and * represents the binding site with the amide bond.

[0017] [2] The polyamide resin of (A) as described in [1], wherein the dicarboxylic acid residues contain an aliphatic chain structure having 1 to 30 carbon atoms.

[0018] [3] The polyamide resin (A) as described in [1] or [2], wherein Z in formula (1) is a monovalent monocarboxylic acid residue containing 1 to 20 carbon atoms in an unsaturated carbon-carbon double bond.

[0019] [4] A photosensitive resin composition comprising (A) a polyamide resin and (B) a photosensitizer as described in any one of [1] to [3], wherein the (B) photosensitizer is one or more compounds selected from (b-1) naphthoquinone diazo compound, (b-2) photoradical polymerization initiator and (b-3) photoacid generator.

[0020] [5] The photosensitive resin composition as described in any of [1] to [4] further contains (C) a heat-generating acid agent.

[0021] [6] The photosensitive resin composition as described in [5], wherein the (C) thermal acid-producing agent is a thermal acid-producing agent having a sulfonate structure.

[0022] [7] A cured product formed by curing the photosensitive resin composition described in any one of [4] to [6].

[0023] [8] A cured product comprising a resin having the structure shown in formula (2),

[0024]

[0025] In equation (2), * represents a chemical bond.

[0026] [9] A cured product derived from hexafluoroisopropanol at a wavelength of 1350–1450 cm⁻¹ -1 Peak intensity I a The wavelength of the cyclized structure derived from hexafluoroisopropanol and amide groups is 1050–1150 cm. -1 Peak intensity I b The ratio is I a / I b It is below 1.

[0027]

[10] A method for manufacturing a cured product, comprising the following steps:

[0028] The process of coating the photosensitive resin composition described in any one of [4] to [6] onto a substrate and drying it to form a resin film.

[0029] The process of exposing the resin film.

[0030] The process of developing the exposed resin film, and

[0031] The process of heating the developed resin film.

[0032]

[11] An electronic component having the cured material described in any one of [7] to [9].

[0033]

[12] The electronic component as described in

[11] is an electronic component that at least includes a semiconductor package, the semiconductor package comprising a semiconductor element, a rewiring layer, a sealing resin, a grounding portion, and antenna wiring.

[0034] The insulation layer of the rewiring layer and / or the sealing resin contain the cured material.

[0035] The sealing resin is located between the grounding part and the antenna wiring.

[0036] Invention Effects

[0037] According to the present invention, it is possible to provide a photosensitive resin composition with excellent alkaline developability and low dielectric tangent, a cured product obtained from the photosensitive resin composition, electronic components, antenna elements, and semiconductor packages. Attached Figure Description

[0038] Figure 1 This is a schematic cross-sectional view of an example of a semiconductor package having an IC chip (semiconductor element), a rewiring layer, a sealing resin, and an antenna element. Detailed Implementation

[0039] The present invention will be described in detail below.

[0040] The present invention is a (A) polyamide resin having dicarboxylic acid residues and diamine residues, the (A) polyamide resin comprising the molecular chain ends shown in formula (1).

[0041]

[0042] In equation (1), Y 1 Z represents a divalent organogroup with 2 to 70 carbon atoms, Z represents a monovalent monocarboxylic acid residue with 1 to 20 carbon atoms, and R represents a divalent organogroup with 2 to 70 carbon atoms. 1 and R 2 Each of the following groups independently represents a monovalent organic group with 1 to 10 carbon atoms. p and q represent integers from 0 to 3. * indicates the bonding site with the amide bond.

[0043] <(A) Polyamide resin>

[0044] This invention relates to a (A) polyamide resin having dicarboxylic acid residues and diamine residues, wherein the (A) polyamide resin comprises the molecular chain ends shown in formula (1). Here, a dicarboxylic acid residue refers to a group other than a carboxyl group or a functional group derived from a carboxylic acid in a dicarboxylic acid or dicarboxylic acid derivative, and a diamine residue refers to a group other than an amino group or a functional group derived from an amino group in a diamine or diamine derivative. Furthermore, for example, a diamine having an amide bond obtained by reacting and reducing a diamine with 3-nitrobenzoyl chloride is considered as a diamine derivative. Additionally, in the case of a diamine or diamine derivative having an amide bond obtained by reacting a diamine with a carboxylic acid, groups other than an amino group or a functional group derived from an amino group are considered as diamine residues. Similarly, in the case of a dicarboxylic acid or dicarboxylic acid derivative having an amide bond obtained by reacting a diamine with a carboxylic acid, groups other than a carboxyl group or a functional group derived from a carboxylic acid are considered as dicarboxylic acid residues. Similarly, in the case of diamines or diamine derivatives having amide bonds obtained by reacting dicarboxylic acids with amines, their groups other than the amino group or functional groups derived from the amino group are treated as diamine residues.

[0045] Polyamides are polymers containing amide bonds. Examples of such polymers include those obtained by reacting a dicarboxylic acid, a diacyl chloride of the corresponding dicarboxylic acid, or an active diester of a dicarboxylic acid with a diamine, a corresponding diisocyanate compound, or a trimethylsilyl diamine, which contain "dicarboxylic acid and / or its derivative residues" and "diamine and / or its derivative residues".

[0046] (A) The polyamide resin comprises the molecular chain ends shown in Formula (1). Formula (1) has a hexafluoroisopropanol group. Since the hexafluoroisopropanol group is an acidic alcohol, it is alkali-soluble. In addition, this polyamide resin can be thermally derivatized into a polyamide cyclizer, exhibiting excellent dielectric properties.

[0047] In this invention, alkali solubility refers to the process of coating a silicon wafer with a solution of resin dissolved in γ-butyrolactone, pre-baking it at 120°C for 3 minutes to form a pre-baked film with a thickness of 10μm±0.5μm, immersing the pre-baked film in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23±1°C for 1 minute, and then rinsing it with pure water. The dissolution rate, calculated based on the reduction in film thickness at this time, is above 50nm / min.

[0048] As diamine compounds that can form the end of the molecular chain shown in formula (1), the following compounds can be listed, but are not limited to these. As commercially available products, “HFA-mTB”, “HFA-MDA”, “HFA-ODA”, “HFA-BIS-A-EF” and other products manufactured by Central Glass Co., Ltd. can be listed.

[0049] The (A) polyamide resin exhibits excellent dielectric properties due to the presence of an amide structure at the ends of its molecular chains, which can also derive cyclizations. Furthermore, although the reason is not yet certain, it exhibits excellent alkali-developable properties by forming the molecular chain ends shown in formula (1). Here, a monocarboxylic acid residue refers to a group other than a carboxyl group or a functional group derived from a carboxylic acid in a monocarboxylic acid or its derivative. As a method for forming the molecular chain ends shown in formula (1), methods such as sealing the resin ends with end-capping agents such as monocarboxylic acids, monoacyl chloride compounds, or monoactive ester compounds can be cited.

[0050] As monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds, known monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds can be used. Examples of end-capping agents include: acetyl chloride, propionyl chloride, cyclopropaneformyl chloride, cyclobutaneformyl chloride, cyclopentaneformyl chloride, cyclohexaneformyl chloride, isobutyryl chloride, n-butyryl chloride, isovaleryl chloride, n-valeryl chloride, hexanoyl chloride, heptayl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, 2-ethylhexanoyl chloride, 2-propylvaleryl chloride, 3,3-dimethylbutyryl chloride, 4-methylvaleryl chloride, 2,2-dimethylbutyryl chloride, methoxyacetyl chloride, 2-ethoxyacetyl chloride, chloroacetyl chloride, and 2-chloroacetyl chloride. Propionyl chloride, 3-chloropropionyl chloride, 2-furanoyl chloride, 3-(methylthio)propionyl chloride, 2-thiophenecarboxyl chloride, benzoyl chloride, o-methylbenzoyl chloride, m-methylbenzoyl chloride, p-methylbenzoyl chloride, phenylacetyl chloride, 3-phenylpropionyl chloride, 3,5-dimethylbenzoyl chloride, phenoxyacetyl chloride, methoxybenzoyl chloride, 4-ethoxybenzoyl chloride, naphthyl chloride, acryloyl chloride, methacryloyl chloride, crotonyl chloride, 2-methyl-but-2-enoyl chloride (tigloyl chloride), 3-ethoxyacryloyl chloride, cinnamoyl chloride, trans-8-methyl-6-nonenoyl chloride, linoleoyl chloride, norbornenecarboxyl chloride, and their corresponding monocarboxylic acids and monocarboxylic anhydrides, but not limited to these. Here, a monocarboxylic anhydride refers to a compound obtained by condensing two molecules of a monocarboxylic acid. Examples of active esters of monocarboxylic acids used as capping agents include, for instance, active ester compounds of monocarboxylic acids obtained by reacting the aforementioned acyl chloride with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

[0051] In formula (1), Z is preferably a monovalent monocarboxylic acid residue containing 1 to 20 carbon atoms with an unsaturated carbon-carbon double bond. By containing an unsaturated carbon-carbon double bond, the carbon-carbon unsaturated double bond undergoes a cross-linking reaction during thermosetting, which can improve the elongation of the cured product. In addition, since the unsaturated carbon-carbon double bond is non-polar, its cured product is less likely to affect the dielectric tangent compared to other cross-linking groups.

[0052] Examples of end-capping agents containing carbon-carbon unsaturated double bonds include acryloyl chloride, methylpropionyl chloride, chloride, crotonyl chloride, 2-methyl-but-2-enoyl chloride (tigloyl chloride), 3-ethoxyacryloyl chloride, cinnamoyl chloride, trans-8-methyl-6-nonenoyl chloride, linoleoyl chloride, norbornene carboxyl chloride, and their corresponding monocarboxylic acids and monocarboxylic anhydrides, but are not limited to these.

[0053] When using monocarboxylic acids, monoacyl chloride compounds, or monoactive ester compounds, the proportion of these compounds introduced is preferably 0.1 moles or more, and particularly preferably 5 moles or more, when all carboxylic acid compounds contained in (A) polyamide resin are set to 100 moles. On the other hand, from the viewpoint of maintaining a high molecular weight of the resin, when all carboxylic acid compounds contained in (A) polyamide resin are set to 100 moles, the proportion of the end-capping agent introduced is preferably 50 moles or less, and particularly preferably 30 moles or less. By reacting multiple end-capping agents, multiple different terminal groups can be introduced. Here, "all carboxylic acid compounds" refers to the total content of compounds containing carboxyl groups, such as monocarboxylic acids and dicarboxylic acids.

[0054] Furthermore, in this invention, the capping agent introduced into the (A) polyamide resin can be easily detected by gas chromatography (GC), pyrolysis gas chromatography (PGC), infrared spectroscopy and / or NMR determination.

[0055] In this invention, any diamine compound can be used to form copolymers. Examples of diamine residues and their derivative residues include, for example, residues of aromatic diamines, bisaminophenol compounds, alicyclic diamines, alicyclic dihydroxydiamines, aliphatic diamines, or aliphatic dihydroxydiamines. These diamine residues and their derivative residues may contain heteroatoms in addition to the nitrogen and oxygen atoms present in amino groups and their derivatives.

[0056] Examples of diamine residues and residues in diaminophenol compounds and their derivatives include, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3'-dimethylbenzidine, and 3,3'-dimethoxybenzidine. o-Toluidine, 4,4'-Diaminoterphenyl, 1,5-Diaminonaphthalene, 2,5-Diaminopyridine, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 1,2-Cyclohexanediamine, 1,4-Cyclohexanediamine, bis(4-aminocyclohexyl)methane, 3,6-Dihydroxy-1,2-Cyclohexanediamine, 2,5-Dihydroxy-1,4-Cyclohexanediamine, bis(3-hydroxy-4-aminocyclohexyl)methane, 4,4'-bis(p-amino... 2,2-Bis[4-(p-aminophenoxy)phenyl]propane, hexahydro-4,7-methanolide, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4- Compounds such as amino-3-hydroxyphenyl) sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or their diisocyanate compounds or residues of trimethylsilyldiamine, but not limited to these.

[0057] The polyamide resin of the present invention (A) contains dicarboxylic acid residues. Examples of dicarboxylic acid residues and their derivative residues include, but are not limited to, residues of phthalic acid, isophthalic acid, terephthalic acid, 4,4'-dicarboxybiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-dicarboxybiphenyl, 4,4'-benzophenone dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, malonic acid, itaconic acid, maleic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, or acyl chlorides of these dicarboxylic acids, active esters of dicarboxylic acids, or dicarboxylic acid compounds.

[0058] The dicarboxylic acid residues preferably contain an aliphatic chain structure with 1 to 30 carbon atoms. The aliphatic chain structure exhibits a low dielectric tangent due to its low polarity. Furthermore, the presence of an aliphatic chain structure improves the polymer's mobility, allowing for a lower temperature for the derived polyamide cyclization (low-temperature curing). By enabling low-temperature curing, excellent dielectric tangent is exhibited even after heating at low temperatures. While further reasons have not yet been determined, the aliphatic chain structure contributes to improved alkali developability and elongation. From the viewpoint of low-temperature curing, the number of carbon atoms in the aliphatic chain structure is more preferably 4 or more, and from the viewpoint of alkali developability, it is more preferably 15 or less. Examples of dicarboxylic acid residues containing an aliphatic chain structure with 1 to 30 carbon atoms include malonic acid, itaconic acid, maleic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, or their dicarboxylic acid acyl chlorides, active esters of dicarboxylic acids, or diformyl compounds, but are not limited to these. When the total amount of dicarboxylic acid residues in (A) polyamide resin is set to 100 mol%, the total content of dicarboxylic acid residues with an aliphatic chain structure is preferably 15 mol% or more and 100 mol% or less, preferably 30 mol% or more and 100 mol% or less. Within this range, excellent performance is observed in low-temperature curing, low dielectric tangent, elongation, and alkali developability.

[0059] The polyamide resin of the present invention (A) may contain tricarboxylic acid residues and / or derivative residues thereof. Here, a tricarboxylic acid residue refers to a group other than a carboxyl group or a functional group derived from a carboxylic acid in a tricarboxylic acid or its derivative. Examples of tricarboxylic acid residues include, for example, residues of aromatic tricarboxylic acids, alicyclic tricarboxylic acids, or aliphatic tricarboxylic acids. In addition to the oxygen atom of the carboxyl group, the tricarboxylic acid residue may also have heteroatoms other than the oxygen atom.

[0060] Examples of tricarboxylic acid residues and their derivative residues include, but are not limited to, residues of 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2,4,5-benzophenonetricarboxylic acid, 2,4,4'-biphenyltricarboxylic acid or 3,3',4'-tricarboxylic acid diphenyl ether, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid or triformyl chloride, active esters of tricarboxylic acid, or diformyl monocarboxylic acids.

[0061] In this invention, it is also possible to simultaneously have polyphenylene oxide other than (A) polyamide resin. The structure of azoles, and the structure of polyimides or polyimide precursors (polyamic acid or polyamic acid esters).

[0062] (A) The weight-average molecular weight of the polyamide resin is preferably 3,000 or more and 100,000 or less. If the weight-average molecular weight is 5,000 or more, the mechanical properties of the cured product can be improved. More preferably, the weight-average molecular weight is 7,000 or more. On the other hand, if the weight-average molecular weight is 100,000 or less, the solubility in organic solvents can be improved, and if the weight-average molecular weight is 50,000 or less, it is easy to satisfy all of these conditions, including good solvent solubility, good solubility in developer, and high mechanical strength, and is therefore preferred.

[0063] The weight-average molecular weight (Mw) can be confirmed using GPC (gel permeation chromatography). For example, it can be determined using N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) as the developing solvent and converted from polystyrene. In addition, when the polyamide resin (A) contains two or more resins, it is sufficient that the weight-average molecular weight of at least one of them is within the above range.

[0064] The polyamide resin (A) used in this invention is preferably polymerized using a solvent. The polymerization solvent is not particularly limited in type, as long as it can dissolve the dicarboxylic acids and diamines used as raw material monomers. Examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolium ketone, N,N-dimethylacrylamide, N,N-dimethylisobutyramide, and methoxy-N,N-dimethylpropionamide; cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; diols such as triethylene glycol; phenols such as m-cresol and p-cresol; acetophenone, 1,3-dimethyl-2-imidazolium ketone, sulfolane, and dimethyl sulfoxide.

[0065] <(B) Photosensitive agent>

[0066] The photosensitive resin composition of the present invention contains the above-mentioned polyamide resin (A) and photosensitizer (B).

[0067] The photosensitive resin composition of the present invention can form embossed patterns by containing a (B) photosensitizer.

[0068] (B) The photosensitizer is preferably one or more compounds selected from (b-1) naphthoquinone diazo compound, (b-2) photoradical polymerization initiator, and (b-3) photoacid generator. By containing (b-1) naphthoquinone diazo compound, acid can be generated in the light-irradiated area, increasing the solubility of the light-irradiated area in the alkaline aqueous solution, resulting in a positive relief pattern that is soluble in the light-irradiated area. Alternatively, by containing (b-2) photoradical polymerization initiator and a radical polymerizable compound, the active free radicals generated in the light-irradiated area cause the olefinic unsaturated bonds in the radical polymerizable compound to undergo radical polymerization, resulting in a negative relief pattern that is insoluble in the light-irradiated area. Furthermore, by containing (b-3) photoacid generator, from the viewpoint of promoting cationic polymerization, it is suitable for negative pattern formation; and from the viewpoint of freeing alkali-soluble groups by exposure when the resin or other materials have acidic groups protected by acid-dissociable groups, it is suitable for positive pattern formation. (b-1), (b-2), and (b-3) can also be combined as needed.

[0069] Examples of (b-1)naphthoquinone diazo compounds include compounds formed by ester bonding of quinone diazo sulfonic acid and a polyhydroxy compound, compounds formed by sulfonamide bonding of quinone diazo sulfonic acid and a polyamino compound, and compounds formed by ester bonding and / or sulfonamide bonding of quinone diazo sulfonic acid and a polyhydroxy-polyamino compound. Preferably, at least 50 mol% of the functional groups of these polyhydroxy and polyamino compounds are replaced by quinone diazo compounds. Furthermore, it is preferable to contain two or more (b-1)naphthoquinone diazo compounds, thus obtaining a highly sensitive photosensitizing resin composition. From the viewpoint of high sensitivity, the content of (b-1)naphthoquinone diazo compound is preferably 3 to 40 parts by mass relative to 100 parts by mass of (A) polyamide resin.

[0070] In this invention, the quinone diazonium preferably uses either 5-diazonaphthoquinone sulfonyl or 4-diazonaphthoquinone sulfonyl. The 4-diazonaphthoquinone sulfonyl ester compound exhibits absorption in the i-line region of the mercury lamp, making it suitable for i-line exposure. The absorption of the 5-diazonaphthoquinone sulfonyl ester compound extends to the g-line region of the mercury lamp, making it suitable for g-line exposure. In this invention, the 4-diazonaphthoquinone sulfonyl ester compound or the 5-diazonaphthoquinone sulfonyl ester compound is preferably selected according to the exposure wavelength. Alternatively, it may contain a diazononaphthoquinone sulfonyl ester compound having both 4-diazonaphthoquinone sulfonyl and 5-diazonaphthoquinone sulfonyl groups in the same molecule, or it may contain both 4-diazonaphthoquinone sulfonyl and 5-diazonaphthoquinone sulfonyl ester compounds.

[0071] (b-2) As a specific example of a photopolymerization initiator, photopolymerization initiators described in, for example, International Publication Nos. 2019 / 087985,

[0223] to

[0276] , can be used. Among these, from the viewpoint of enabling high sensitivity, oxime ester-based photopolymerization initiators are preferred. Two or more of these may be included.

[0072] In this invention, the content of the photopolymerization initiator (b-2) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyamide resin (A). If it is 0.1 parts by mass or more, sufficient free radicals will be generated by light irradiation, thus improving sensitivity. In addition, if it is 20 parts by mass or less, the alkaline developability can be improved without curing the unirradiated part due to excessive free radical generation.

[0073] (b-3) Photoacid-generating agents are compounds that produce acids by causing bond breaking or reaction through exposure. Examples of (b-3) include, for instance, ionic or nonionic compounds. Ionic compounds are preferably triorganosulfonium salts. Nonionic compounds are preferably halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, sulfonylimide compounds, phosphate ester compounds, or sulfonylbenzotriazole compounds.

[0074] (b-3) As a photoacid generator, known photoacid generators can be used, but from the viewpoint of cationic curing and copper corrosion resistance, (b-3) preferably contains a sulfonium salt having at least one selected from borate ions, phosphate ions, and gallate ions as a relative anion. Here, borate ions are complex ions having boron as a central atom, phosphate ions are complex ions having phosphorus as a central atom, and gallate ions are complex ions having gallium as a central atom.

[0075] Examples of cations that form the aforementioned sulfonium salts include triphenylsulfonium, tri-p-tolylsulfonium, 1-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tris(1-naphthyl)sulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(2-thioxanthonethio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonyl)phenyl]sulfonium, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonium}phenyl]sulfonium, bis{ 4-[bis(4-fluorophenyl]sulfonium]phenyl} sulfide, bis{4-[bis(4-methylphenyl]sulfonium]phenyl} sulfide, bis{ 4-[bis(4-methoxyphenyl]sulfonium]phenyl}sulfide, 4-(4-benzoyl2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl2-chlorophenylthio)phenyl diphenylsulfonium, 4-(4-benzoylphenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 2-[(di-p-tolyl)sulfonium]thioxanthone, 5-(4-ethoxyphenyl)thianthracene and 5-(2,4,6-trimethylphenyl)thiathane Triarylsulfonium; diphenylbenzoylmethylsulfonium, diphenyl-4-nitrobenzoylmethylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium, etc., diarylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetylcarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylbenzoylmethylsulfonium, 4-methoxyphenylmethylbenzoylmethylsulfonium, 4-acetylcarbonyloxyphenylmethylbenzoylmethylsulfonium, 2-naphthylmethylbenzoylmethylsulfonium, 2-naphthyloctadecylbenzoylmethylsulfonium and 9-anthraylmethylbenzoylmethylsulfonium, etc., monoarylsulfonium; dimethylbenzoylmethylsulfonium, benzoylmethyltetrahydrothiophene Dimethylbenzylsulfonium and benzyltetrahydrothiophene However, these are not the only ones.

[0076] Examples of borate ions include, but are not limited to, pentafluorophenylborate, trifluorophenylborate, tetrafluorophenylborate, trifluoromethylphenylborate, bis(trifluoromethyl)phenylborate, pentafluoroethylphenylborate, bis(pentafluoroethyl)phenylborate, fluoro-bis(trifluoromethyl)phenylborate, fluoro-pentafluoroethylphenylborate, and fluoro-bis(pentafluoroethyl)phenylborate.

[0077] Examples of phosphate ions include, but are not limited to, hexafluorophosphate and tris(pentafluoroethyl)trifluorophosphate.

[0078] Examples of gallium ions include tetra(pentafluorophenyl) gallate, tetra(3,5-bis(trifluoromethyl)phenyl) gallate, etc., but are not limited to these.

[0079] (b-3) The content of photoacid generator is preferably 0.5 to 20 parts by weight relative to 100 parts by weight of (A) polyamide resin.

[0080] <(C) Thermal acid-producing agent>

[0081] The photosensitive resin composition of the present invention preferably contains (C) a thermally generating acid agent. The thermally generating acid agent is a compound that produces acid upon heating, and the thermal decomposition start temperature of (C) is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. Setting the thermal decomposition temperature to 120°C or higher prevents acid generation during the pre-baking process in pattern processing. Furthermore, the thermal decomposition start temperature of (C) is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. By setting the thermal decomposition temperature to 250°C or lower, sufficient acid can be generated during the heating process. In the present invention, by generating acid during the heating process, the cyclization reaction of (A) polyamide resin can be promoted, enabling low-temperature curing, and exhibiting excellent dielectric tangent even during heating at low temperatures.

[0082] In this invention, the (C) thermal acid-producing agent only needs to have the function of producing acid upon heating. Compounds that have the function of producing acid through light such as ultraviolet light are also included in the definition of (C) thermal acid-producing agent. However, quinone diazo compounds are not included in the definition of (C) thermal acid-producing agent.

[0083] The acid produced from the (C) heat-generating acid agent is preferably a strong acid, such as aryl sulfonic acids like p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids like methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or camphorsulfonic acid.

[0084] Examples of heat-generating acid agents (C) include sulfonate salts and sulfonates, as shown below. Two or more of these substances may be present. From the viewpoint of generating heat upon heating, it is preferable that the sulfonate salt contains a compound selected from monoaryl sulfonate salts and trialkyl sulfonate salts.

[0085] In the (C) thermal acid-generating agent, since it has little effect on the dielectric tangent and can promote the cyclization reaction of polyamide resin with a small amount of addition, the (C) thermal acid-generating agent is preferably a thermal acid-generating agent with a sulfonate structure. Sulfonate esters can be exemplified by structures represented by, for example, formula (3) or formula (4).

[0086]

[0087] In equation (3), R 3 and R 4 Each can independently represent a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms that may have substituents, or an aryl group having 6 to 20 carbon atoms that may have substituents. Examples of substituents include hydroxyl, halogen atom, cyano, vinyl, ethynyl, and straight-chain or cyclic alkyl groups having 1 to 10 carbon atoms.

[0088]

[0089] In equation (4), R 5 This refers to a monovalent organogroup with 1 to 20 carbon atoms. As described above, R... 5 The acceptable monovalent organic groups with 1 to 20 carbon atoms can be CF3, alkyl, aryl, perfluoroalkyl, and structures shown in formula (5).

[0090]

[0091] In equation (5), * represents the joint.

[0092] Examples of compounds described in formula (3) above include methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, phenyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, butyl ethanesulfonate, phenyl ethanesulfonate, methyl propanesulfonate, ethyl propanesulfonate, propyl propanesulfonate, butyl propanesulfonate, phenyl propanesulfonate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, phenyl butyrate, methyl octyl sulfonate, ethyl octyl sulfonate, propyl octyl sulfonate, and butyl octyl sulfonate. Examples of compounds described in formula (4) above include phenyl octyl sulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, methoxyphenyl methanesulfonate, methoxyethyl methanesulfonate, 1,4-butanediol dimethanesulfonate, methoxyethyl p-toluenesulfonate, and 1,3-propanediol di-p-toluenesulfonate. Other examples include "Irgacure" (registered trademark) PAG103 and PAG121 (trade name, BASF). Products manufactured by JAPAN (Co., Ltd.), PA-411, PA-480 (trade name: Hereus (Co., Ltd.), etc. In addition, as other heat-generating acid agents with sulfonate structures, examples include PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, PAI-1004 (trade name: Midori Kagaku (Co., Ltd.), SP-082, SP-601, SP-606, SP-607, SP-612 (trade name: ADEKA (Co., Ltd.), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade name: Hereus (Co., Ltd.), NAI-105, NAI-106, NAI-109 (trade name: Midori Kagaku (Co., Ltd.)). manufactured by Kagaku Co., Ltd.), etc.

[0093] From the viewpoint of promoting the cyclization reaction of polyamide resin, the content of (C) thermal acid-generating agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, relative to 100 parts by mass of (A) polyamide resin. Furthermore, from the viewpoint of imparting high heat resistance to the cured product, the content of (C) thermal acid-generating agent is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of (A) polyamide resin.

[0094] <Free radical polymeric compounds>

[0095] The photosensitive resin composition of the present invention may also contain a free radical polymerizable compound. By containing a compound having two or more olefinic unsaturated bonds, the exposure sensitivity is further improved in the case of negative photosensitivity due to the increased crosslinking density during exposure. In addition, in both negative and positive photosensitivity, the chemical resistance of the cured film after curing is further improved. Specific examples of free radical polymerizable compounds include, for example, the free radical polymerizable compounds described in International Publication Nos. 2019 / 087985

[0189] to

[0222] .

[0096] The molecular weight of the free radical polymerizable compound is preferably 5000 or less, more preferably 2000 or less. If it is 5000 or less, it can maintain compatibility with (A) polyamide resin and reduce phenomena such as film whitening, so it is preferred.

[0097] The amount of the free radical polymerizable compound added is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of polyamide resin (A). Within this range, it is easy to obtain improved exposure sensitivity and chemical resistance of the cured film while maintaining the target properties.

[0098] <Catonic polymeric compounds>

[0099] The photosensitive resin composition of the present invention may also contain cationic polymeric compounds. By containing cationic polymeric compounds, the exposure sensitivity is improved due to the increased crosslinking density during exposure in the case of negative photosensitivity. Examples of cationic polymeric compounds include, for instance, epoxy compounds, oxetane compounds, olefinically unsaturated compounds (such as vinyl ethers and styrene derivatives), bicyclic orthoesters, spirocyclic orthocarbonates, and spirocyclic orthoesters.

[0100] Well-known epoxy compounds can be used as epoxides, such as aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0101] Examples of aromatic epoxy compounds include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenolic varnishes and their oxidized olefinic adducts) having at least one aromatic ring.

[0102] Examples of alicyclic epoxides include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (such as 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexylmethyl) ester).

[0103] Examples of aliphatic epoxides include polyglycidyl ethers of aliphatic polyols or their epoxide adducts (such as 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether), polyglycidyl esters of aliphatic polyacids (such as diglycidyl tetrahydrophthalate), and epoxides of long-chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

[0104] As the oxetane compound, known oxetane compounds can be used, such as 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl(3-ethyl-3-oxetanemethyl) ether, 2-hydroxyethyl(3-ethyl-3-oxetanemethyl) ether, 2-hydroxypropyl(3-ethyl-3-oxetanemethyl) ether, 1,4-bis[(3-ethyl-3-oxetanemethoxy)methyl]benzene, oxetane sesquioxane, and phenolic varnish oxetane, etc.

[0105] As olefinic unsaturated compounds, known cationic polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationic polymerizable nitrogen-containing monomers.

[0106] Examples of aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0107] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0108] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0109] Examples of styrene-based products include styrene, α-methylstyrene, p-methoxystyrene, and 4-tert-butoxystyrene.

[0110] Examples of cationic polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

[0111] Examples of bicyclic orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane.

[0112] Examples of spirocyclic orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0113] Examples of spirocyclic orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0114] The amount of cationic polymerizable compound added is preferably 5 parts by mass or more and 200 parts by mass or less relative to 100 parts by mass of (A) polyamide resin, more preferably 10 parts by mass or more and 150 parts by mass or less. Within this range, it is easy to obtain improved exposure sensitivity and chemical resistance of the cured film while maintaining the target properties.

[0115] <Thermal Crosslinking Agent>

[0116] The photosensitive resin composition of the present invention may also contain a thermal crosslinking agent that crosslinks by heat. By containing a thermal crosslinking agent, the heat resistance of the cured film at high temperatures can be further improved. The thermal crosslinking agent can be any compound that can crosslink by heat, such as compounds having an alkoxymethyl structure.

[0117] As compounds having an alkoxymethyl structure, they may contain known compounds. Examples include, for instance, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, and DML-BPC.

[0118] DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF,

[0119] TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all of the above are trade names and can be obtained from Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" (registered trademark) MX-280, "NIKALAC" (registered trademark) MX-270, "NIKALAC" (registered trademark) MX-279, "NIKALAC" (registered trademark) MW-100LM, "NIKALAC" (registered trademark) MX-750LM (all of the above are trade names and can be obtained from Sanwa Chemical Co., Ltd.).

[0120] Among these compounds, from the viewpoint of the heat resistance of the cured film obtained after heat curing, compounds selected from any one of "NIKALAC" (registered trademark) MX-290, "NIKALAC" (registered trademark) MX-280, "NIKALAC" (registered trademark) MX-270, "NIKALAC" (registered trademark) MX-279, "NIKALAC" (registered trademark) MW-100LM, and "NIKALAC" (registered trademark) MX-750LM are preferred from the viewpoint of storage stability.

[0121] From the viewpoint of obtaining a cured film with high chemical resistance, the amount of thermal crosslinking agent added is preferably 1 part by weight or more, more preferably 5 parts by weight or more, relative to 100 parts by weight of (A) polyamide resin. Furthermore, from the viewpoint of reducing degassing, it is preferably 100 parts by weight or less, more preferably 80 parts by weight or less.

[0122] <Sealing Improver>

[0123] The photosensitive resin composition of the present invention may also contain a binding modifier. Examples of binding modifiers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, silane coupling agents such as titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds. Trimethoxyvinylsilane, triethoxyvinylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and p-styryltrimethoxysilane are particularly preferred, and p-styryltrimethoxysilane is more preferred. As a sealant improver, it may contain two or more of these.

[0124] The content of the adhesion modifier in the photosensitive resin composition is preferably 0.1 to 10% by mass in 100% of the total resin. By setting it within this range, a photosensitive resin composition with high adhesion to the substrate and excellent resistance to oxygen plasma or UV ozone treatment can be provided.

[0125] <surfactants>

[0126] The photosensitive resin composition of the present invention may contain a surfactant. By containing a surfactant, the wettability with the substrate can be improved, and the film thickness uniformity of the coated film can also be improved. Commercially available compounds can be used as surfactants. Specifically, examples of silicone-based surfactants include the SH, SD, and ST series from DuPont Toray Specialty Materials Co., Ltd., the BYK series from BYK Japan Co., Ltd., the KP series from Shin-Etsu Chemical Industry Co., Ltd., the DISFOAM series from Nippon Oil Co., Ltd., and the TSF series from Momentive Performance Materials Japan Co., Ltd. Examples of fluorinated surfactants include the "MEGAFACE" (registered trademark) series from DIC Co., Ltd., the Fluorad series from 3M Japan Co., Ltd., the "Surflon" (registered trademark) series and the "AsahiGuard" (registered trademark) series from AGC Co., Ltd., the EF series from Mitsubishi Materials Electronic Chemicals Co., Ltd., and the PolyFox series from OMNOVA Solutions Co., Ltd. Surfactants derived from acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd., and the "DISPARLON" series from Kusumoto Chemical Co., Ltd.

[0127] The surfactant content is preferably 0.001% by mass and 1% by mass or less in 100% of the total resin. Within this range, defects such as bubbles or pinholes will not occur, thereby improving the wettability of the photosensitive resin composition to the substrate and improving the uniformity of the coating film thickness.

[0128] <Antioxidants>

[0129] The photosensitive resin composition of the present invention may also contain an antioxidant. By containing an antioxidant, it is possible to suppress the yellowing of the cured film and the reduction of mechanical properties such as breaking strength during subsequent heat treatment processes. In addition, it is preferred because it inhibits the oxidation of metal materials by preventing rust.

[0130] As antioxidants, hindered phenolic antioxidants or hindered amine antioxidants are preferred. Furthermore, the amount of phenolic or amino groups in one molecule is preferably 2 or more, and more preferably 4 or more, as this readily yields an antioxidant effect.

[0131] Specific examples of antioxidants include, for example, the antioxidants described in

[0063] to

[0070] of Japanese Patent Application Publication No. 2018-165819.

[0132] The amount of antioxidant added is preferably 0.1 parts by weight or more and 10.0 parts by weight or less relative to 100 parts by weight of (A) polyamide resin, more preferably 0.3 parts by weight or more and 5.0 parts by weight or less. Within this range, the developability and the effect of inhibiting discoloration caused by heat treatment can be appropriately maintained.

[0133] <Solvent>

[0134] The photosensitive resin composition of the present invention may also contain a solvent. Examples of solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolium ketone, N,N-dimethylacrylamide, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionic acid amide; tetrahydrofuran, dimethyl... Ethers such as alkanes, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. It may also contain two or more of these.

[0135] The solvent content is preferably 100 parts by weight or more relative to 100 parts by weight of polyamide resin (A) in order to dissolve the composition, and preferably 1500 parts by weight or less in order to form a coating film with a film thickness of 1 μm or more.

[0136] <Methods for manufacturing solidified products>

[0137] In the process of coating the photosensitive resin composition of the present invention onto a substrate and drying it to form a resin film, the photosensitive resin composition of the present invention is first coated onto the substrate to obtain a coated film of the photosensitive resin composition. Examples of substrates include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and substrates on which circuit components are disposed.

[0138] Examples of coating methods include spin coating, slot coating, dip coating, spray coating, and printing. Furthermore, the coating thickness varies depending on the coating method, the concentration of solid components in the composition, and the viscosity, but typically the dried film thickness ranges from 0.1 to 150 μm.

[0139] Before coating, the substrate to be coated with the photosensitive resin composition can be pretreated with the aforementioned adhesion modifier. Examples of pretreatment methods include dissolving the adhesion modifier in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate at 0.5–20% by mass, and then treating the substrate surface using methods such as spin coating, die coating, rod coating, dip coating, spray coating, or steam treatment. After treating the substrate surface, vacuum drying can be performed as needed. Alternatively, the substrate can be reacted with the adhesion modifier by heat treatment at 50°C to 280°C. Drying is preferably performed using an oven, heating plate, infrared radiation, etc., at a temperature between 50°C and 140°C for 1 minute to 2 hours.

[0140] In the process of exposing a photosensitive resin film, a mask with a desired pattern is placed between the photosensitive resin film and a chemical irradiation. Examples of chemical rays used for exposure include ultraviolet light, visible light, electron beams, and X-rays. However, in this invention, chemical rays containing gamma rays (436 nm), h-rays (405 nm), or i-rays (365 nm), which are typical exposure wavelengths, are preferred.

[0141] As needed, the electronic components of the present invention may include a post-exposure baking (PEB) step. As a PEB process, it is preferable to use an oven, heating plate, infrared light, etc., to bake the exposed photosensitive resin film at a temperature of 50°C to 150°C for 1 minute to 2 hours.

[0142] In the process of developing the photosensitive resin film, after exposure, the exposed or unexposed areas are removed using a developing solution. Preferably, the developing solution is an aqueous solution of an alkaline compound such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. Additionally, depending on the circumstances, one or more of the following can be added to the aqueous solution of these alkaline compounds: 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. After development, rinsing is generally performed with organic solvents or water. Alcohols such as ethanol and isopropanol, as well as esters such as ethyl lactate and propylene glycol monomethyl ether acetate, can also be added for rinsing.

[0143] Dry etching can also be used as a method for patterning the photosensitive resin composition. Specifically, it includes: a step of coating the photosensitive resin composition of the present invention onto a substrate; a step of evaporating it at a temperature of 80°C or higher and below 150°C; a step of curing it at a temperature of 150°C or higher and below 350°C; and a step of ablation processing using a carbonic acid laser or a UV laser. There are no particular limitations on the irradiation conditions for the UV laser; excimer lasers such as ArF (193nm), KrF (248nm), XeCl (308nm), and XeCl (351nm), as well as YAG lasers (355nm), are commonly used. While carbonic acid lasers have lower resolution compared to UV lasers, they are also used in applications where high precision is not required due to their lower equipment cost and better economic efficiency.

[0144] Next, in the process of heat-treating the developed resin film, the patterned photosensitive resin film is heat-treated using an oven. After development, a temperature of 150°C to 350°C is applied to induce a thermal crosslinking reaction, thereby curing the film. This heat treatment can be performed by selectively increasing the temperature in stages, or by continuously increasing the temperature within a certain range for 5 minutes to 5 hours. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. As the lower limit of the curing conditions in this invention, 170°C or higher is preferred, but 180°C or higher is more preferred to ensure sufficient curing. Furthermore, there is no particular limitation on the upper limit of the curing conditions, but from the viewpoint of suppressing film shrinkage and stress, 280°C or lower is preferred, 250°C or lower is more preferred, and 230°C or lower is even more preferred.

[0145] <Cured product>

[0146] In this invention, curing refers to heat treatment of the resin or photosensitive resin composition at a temperature of 150°C or higher, and the cured product refers to the substance obtained by heat treatment of the resin or photosensitive resin composition at a temperature of 150°C or higher. Through the above-mentioned heat treatment, cross-linking reactions, ring-closing reactions of the polyamide resin, etc., are carried out.

[0147] The cured product of the present invention has any one of the first to third forms.

[0148] The first form of the cured product of the present invention is formed by curing the photosensitive resin composition of the present invention. The cured product of the present invention is characterized by a low dielectric tangent.

[0149] Furthermore, the second form of the cured product of the present invention contains a resin having the structure shown in formula (2).

[0150]

[0151] In equation (2), * represents a chemical bond.

[0152] The cured product of a resin containing a structure shown in formula (2) has a low dielectric tangent.

[0153] Furthermore, the third form of the cured product of the present invention contains a wavelength of 1350–1450 cm⁻¹ derived from hexafluoroisopropanol groups. -1 The peak intensity (Ia) and the wavelength of the cyclized structure derived from the hexafluoroisopropanol group and amide group are 1050–1150 cm⁻¹. -1 The resin has a peak intensity (Ib) ratio (Ia / Ib) of less than 1. By making the Ia / Ib ratio less than 1, there are fewer highly polar hexafluoroisopropanol groups and more cyclized structures of hexafluoroisopropanol groups and amide groups, resulting in a low dielectric tangent of the cured product. The cyclized structure of hexafluoroisopropanol groups and amide groups is the structure shown in formula (2).

[0154]

[0155] In equation (2), * represents chemical bonding.

[0156] The Ia / Ib ratio is preferably 0.6 or less, more preferably 0.3 or less. These peak intensities can be calculated by infrared absorption spectroscopy measurements.

[0157] <Manufacturing Methods for Electronic Components>

[0158] The cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or protective film for constructing electronic components.

[0159] Here, electronic components can include active components with semiconductors such as transistors, diodes, integrated circuits (ICs), and memory, as well as passive components such as resistors, capacitors, and inductors. Furthermore, electronic components using semiconductors are also called semiconductor devices.

[0160] As a specific example of a solidified material in electronic components, it is suitable for use as a passivation film for semiconductors, a surface protective film for semiconductor elements, TFTs (Thin Film Transistors), an interlayer insulating film between rewiring in multilayer wiring for high-density mounting of 2 to 10 layers, an insulating film for touch panel displays, a protective film, an insulating layer for organic electroluminescent elements, etc., but is not limited to these, and can be used in various structures.

[0161] In addition, the substrate surface on which the cured material is formed can be appropriately selected according to the application and process. Examples include silicon, ceramics, glass, metal, epoxy resin, etc., and multiple of these materials can be configured on the same surface.

[0162] In the electronic components of this invention, examples of semiconductor devices include, for instance, chip-first fan-out wafer-level packaging or chip-first fan-out panel-level packaging. Chip-first fan-out wafer-level packaging or chip-first fan-out panel-level packaging refers to a semiconductor package in which an extension portion is formed around a semiconductor chip using a sealing resin such as epoxy resin, rewiring is performed from the electrodes on the semiconductor chip to the extension portion, and solder balls are also provided on the extension portion to ensure the necessary number of terminals. In chip-first fan-out wafer-level packaging or chip-first fan-out panel-level packaging, the wiring is arranged to cross the boundary formed by the main surface of the semiconductor chip and the main surface of the sealing resin, and the cured material is configured as an insulating film between the wirings.

[0163] As an example of the manufacturing method of the electronic component of the present invention, a method for manufacturing a semiconductor device using a re-distribution layer (RDL) preliminary process is shown. A barrier metal such as Ti is formed on a support substrate such as a glass substrate or a silicon wafer by sputtering, and then a Cu seed crystal (seed layer) is formed on it by sputtering. Electrode pads made of Cu are then formed by plating. Next, the photosensitive resin composition of the present invention is coated onto the entire surface of the support substrate on which the electrode pads are formed, and dried to form a photosensitive resin film. A pattern of "lines and spacings," squares, or holes is formed on the obtained photosensitive resin film as needed. Then, a cured layer is formed by heat treatment. This layer becomes an insulating film. Next, a seed layer is formed again by sputtering, and metal wiring (redistribution) made of Cu is formed by plating. Afterward, the process from seed layer formation to metal wiring formation is repeated to form a multilayer wiring structure. Next, the photosensitive resin composition of the present invention is coated again to form a pattern, and then cured by heat treatment to form an insulating film. Then, Cu pillars are formed on the metal wiring using a plating method at the openings of the insulating film. Here, the spacing of the Cu pillars is equal to the spacing of the conductive portions of the semiconductor chip. That is, when the spacing of the conductive portions of the semiconductor chip is finer than the spacing of the electrode pads, the rewiring layers constituting the multilayer wiring structure gradually refine the spacing from the electrode pads to the Cu pillars, thus multiplying the wiring. The thickness of adjacent insulating films in the multilayer wiring structure also becomes the same as or thinner as they approach the semiconductor chip. Next, the semiconductor chip is connected to the Cu pillars via solder bumps. Thus, the electrode pads and the semiconductor chip are electrically connected via metal wiring and solder bumps. Afterward, the semiconductor chip is sealed with sealing resin to form a semiconductor package, and then the support substrate and the rewiring layers are peeled off to separate the semiconductor package. This allows a semiconductor device with a multilayer wiring structure formed using the RDL (Reinforcing Layer) process to be obtained.

[0164] The electronic component of the present invention is an electronic component comprising at least a semiconductor package having semiconductor elements, a rewiring layer, a sealing resin, and antenna wiring.

[0165] The insulating layer of the rewiring layer and / or the sealing resin contain the cured product of the present invention.

[0166] The sealing resin is preferably located between the grounding portion and the antenna wiring. The cured product of this invention, due to its low dielectric constant and dielectric tangent, can suppress transmission loss and improve antenna characteristics.

[0167] As an example of such electronic components, the use of Figure 1 This paper describes a semiconductor package that includes an IC chip (semiconductor element), a rewiring layer, sealing resin, and antenna wiring. Figure 1 This is a schematic cross-sectional view of a semiconductor package comprising an IC chip (semiconductor element), a rewiring layer, a sealing resin, and an antenna element. Copper wiring 109 is formed on the electrode pads 102 of the IC chip 101, and a rewiring layer (copper layer 2, insulating film layer 3) is formed from an insulating film 110 formed by the cured material of the present invention. Barrier metal 111 and solder bumps 112 are formed on the pads of the rewiring layer (copper wiring 109 and insulating film 110). To seal the IC chip, a first sealing resin 108 is formed from the cured material of the present invention, and then copper wiring 109, serving as a ground portion for the antenna, is formed thereon. A first via wiring 107 is formed through a through-hole formed within the first sealing resin 108, connecting the ground portion 106 and the rewiring layer (copper wiring 109 and insulating film 110). A second sealing resin 105, formed from the cured product of the present invention, is formed on the first sealing resin 108 and the grounding wiring 106, and a planar antenna wiring 104 is formed thereon. A second via wiring 103, connecting the planar antenna wiring 104 and the rewiring layer (copper wiring 109 and insulating film 110), is formed through through holes formed in the first sealing resin 108 and the second sealing resin 105. The thickness of each layer of the insulating film 110 is preferably 10 to 20 μm, and the thickness of the first sealing resin and the second sealing resin is preferably 50 to 200 μm and 100 to 400 μm, respectively.

[0168] Example

[0169] The present invention will now be described by way of examples, but the invention is not limited to these examples. First, the evaluation methods in each example and comparative example will be described. In the evaluation, a photosensitive resin composition (hereinafter referred to as "varnish") that has been filtered before curing through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore size of 1 μm was used. Varnish refers to (A) a liquid obtained by dissolving polyamide resin and (B) a photosensitive agent, (C) a heat-generating acid agent or crosslinking agent as needed, in a solvent.

[0170] (1) Molecular weight determination

[0171] The weight-average molecular weight (Mw) of the polyamide resin component (A) was confirmed using a Waters 2690-996 GPC (Gel Permeation Chromatography) apparatus (manufactured by Waters Corporation, Japan). The determination was performed using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent, and the weight-average molecular weight (Mw) and dispersity (PDI = Mw / Mn) were calculated using polystyrene conversion.

[0172] (2) Alkali-developable properties

[0173] A solution of a photosensitive resin composition dissolved in γ-butyrolactone (hereinafter referred to as GBL) was coated onto a 6-inch silicon wafer and pre-baked at 120°C for 3 minutes using a hot plate to form a resin film with a thickness of 10 μm ± 0.5 μm. The film was then immersed in a 2.38% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution at 23 ± 1°C for 1 minute. The thickness of the resin film dissolved per minute was determined based on the change in film thickness before and after immersion, and this was taken as the alkaline dissolution rate (ADR). Additionally, if the resin film completely dissolved in less than 1 minute, the time taken for dissolution was measured. Based on this time and the film thickness before immersion, the thickness dissolved per minute was determined, and this was taken as the alkaline dissolution rate (nm / min). The evaluation criteria for alkaline developability based on the alkaline dissolution rate are as follows.

[0174] A: ADR is above 10000 nm / min

[0175] B: ADR is above 5000nm / min and below 10000nm / min

[0176] C: ADR is above 2000nm / min and below 5000nm / min

[0177] D: ADR less than 2000 nm / min

[0178] (3) Determination of dielectric constant and dielectric tangent of resin-cured film

[0179] (A) A solution of polyamide resin dissolved in GBL was spin-coated onto a 6-inch silicon wafer using a TOKYO ELECTRON Mark-7 coating and developing apparatus, with a film thickness of 11 μm after pre-baking at 120°C for 3 minutes. After pre-baking, the wafer was heated in an inert oven (CLH-21CD-S, JTEKT Thermo Systems Corporation) at an oxygen concentration below 20 ppm, increasing the temperature to 200°C or 250°C at 3.5°C / min, and then heated for 1 hour at 200°C or 250°C. After cooling, the silicon wafer was removed when the temperature dropped below 50°C and immersed in 45% hydrofluoric acid for 5 minutes, thereby peeling off the cured resin film from the silicon wafer. The film was cut into strips 3 cm wide and 10 cm long. The dielectric constant and dielectric tangent of the resin-cured film at a frequency of 1 GHz were determined using the perturbation-mode cavity resonator method according to ASTM D2250 at room temperature (23.0℃) and humidity (45.0%RH). The dielectric properties are shown in Table 1 below, and are evaluated in five grades from A to E.

[0180]

[0181] (4) IR measurement

[0182] A solution of polyamide resin (A) dissolved in GBL was coated onto a 6-inch silicon wafer and pre-baked at 120°C for 3 minutes using a hot plate to form a resin film with a thickness of 5 μm ± 0.5 μm. The wafer was then divided into three sections, and two of these sections were heated to 200°C or 250°C at a rate of 3.5°C / min with an oxygen concentration below 20 ppm using an inert oven CLH-21CD-S (manufactured by JTEKT Thermo Systems Corporation). The heating was carried out at 200°C or 250°C for 1 hour. The transmission infrared absorption spectra of the resin films before and after curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba Corporation). The wavelength of the structure before hexafluoroisopropanol cyclization was confirmed to be 1350–1450 cm⁻¹. -1 The peak intensity (Ia) and the wavelength of the structure derived from the hexafluoroisopropanol cyclization are 1050–1150 cm⁻¹. -1 Given the peak intensity (Ib), calculate the value of (Ia / Ib).

[0183] (5) Determination of the elongation at the breaking point of the resin-cured film

[0184] Similar to the above-mentioned "(3) Determination of dielectric constant and dielectric tangent of resin-cured film", a resin-cured film was prepared and cut into strips 1.5 cm wide and 9 cm long. Using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the film was stretched at a speed of 50 mm / min (chuck interval = 2 cm) at room temperature of 23.0°C and humidity of 45.0%RH, and the elongation at break (%) was measured. Ten strips were measured for each test subject, and the average of the top 5 values ​​was calculated. The evaluation criteria are as follows: A higher elongation at break indicates better mechanical properties.

[0185] A: Elongation at break is above 40%.

[0186] B: The elongation at the breaking point is 20% or more but less than 40%.

[0187] C: Elongation at break is less than 20%.

[0188] (6) Pattern processing capability

[0189] (6) -1 Sensitivity

[0190] A varnish of the photosensitive resin composition was spin-coated onto a silicon wafer using a spin coater, and then pre-baked at 120°C for 3 minutes using a heated plate to produce a pre-baked film with a thickness of 11 μm. On the obtained pre-baked film, a grayscale mask (1-100 μm, with a 1:1 "line and spacing" pattern) for sensitivity measurement was contact-exposed using a parallel light mask aligner (hereinafter referred to as PLA) (Canon Corporation PLA-501F) with an ultra-high pressure mercury lamp as the light source. Then, after exposure at 120°C for 1 minute, it was baked, and in (3), the above-mentioned coating and developing apparatus MARK-7 was used to perform paddle development for 90 seconds with a 2.38% by mass TMAH aqueous solution as the developer, followed by rinsing with water for 30 seconds.

[0191] After development, the film thickness is measured. When the photosensitive resin composition is negative, the minimum exposure value at which the residual film rate of the exposed section (=[film thickness after development] / [film thickness after pre-baking]×100] exceeds 90% is taken as the sensitivity (mJ / cm). 2 When the photosensitive resin composition is positive, the minimum exposure amount with a film thickness of 5 nm or less (below the detection limit) is used as the sensitivity. The exposure amount is measured using an i-line illuminometer. If the pattern is not completely removed or there are residues, it is recorded as "not photolithographic".

[0192] (6) -2 resolution

[0193] The sensitivity calculated by (6)-1 is used as the minimum pattern size (μm) after development under the exposure amount, which is taken as the resolution.

[0194] (7) Determination of dielectric constant and dielectric tangent of the cured film obtained from the photosensitive resin composition

[0195] As the coating material used, except for the varnish of the photosensitive resin composition used instead of the solution prepared by dissolving (A) polyamide resin in GBL, the dielectric constant and dielectric tangent of the cured film obtained from the photosensitive resin composition were measured in the same manner as the "determination of dielectric constant and dielectric tangent of the resin-cured film" described in (3). However, in the case of a negative photosensitive resin composition, after pre-baking, the film was subjected to PLA at 1500 mJ / cm 2 The entire surface is exposed to the specified intensity. The dielectric properties are shown in Table 2 below and are judged in 5 levels.

[0196]

[0197] Hereinafter, the abbreviations of the compounds used in the examples and comparative examples are recorded.

[0198] OBBOC: 4,4'-O-bisbenzoyl chloride

[0199] SucC: Succinyl chloride

[0200] ADC: Adipic acid chloride

[0201] SubC: Octyl chloride

[0202] DDC: Dodecanoic acid chloride

[0203] HFA-mTB: 5,5'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-2,2'-dimethylbenzidine

[0204] HFA-ODA: 3,3'-Bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'-oxodiphenylamine

[0205] HDA-MDA: 3,3'-Bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'-methylenediphenylamine

[0206] HFA-BIS-A-EF: 1,1,1-Trifluoro-2,2-bis(3-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4-aminophenyl)ethane

[0207] BC: Benzoyl chloride

[0208] OC: Methylpropionyl chloride

[0209] PA: Phthalic anhydride

[0210] NA: Nadic anhydride

[0211] NQD: The naphthoquinone diazo compound described in Synthetic Example 17 (equivalent to photosensitizer (b-1)).

[0212] NCI-831: A photoradical polymerization initiator manufactured by ADEKA (equivalent to photosensitizer (b-2)).

[0213] CPI-310B: A photoacid-producing agent manufactured by San-Apro Co., Ltd. (equivalent to photosensitizer (b-3)).

[0214] TA-100: Aromatic sulfonium salt compound (trade name, manufactured by San-Apro Co., Ltd.)

[0215] BTS: Butyl p-toluenesulfonate (a heat-generating acid agent with a sulfonate structure, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.)

[0216] DPHA: Dipentaerythritol pentaacrylate

[0217] TEPIC-VL: Isocyanuric acid modified epoxy compound (manufactured by Nissan Chemical Co., Ltd.)

[0218] GBL: γ-Butyrolactone

[0219] [Synthesis Example 1: Synthesis of polyamide resin (A-1)]

[0220] Under a dry nitrogen stream, 21.77 g (0.040 mol) of HFA-mTB and 50.00 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were weighed into a three-necked flask and dissolved.

[0221] Here, while maintaining the temperature at 0–5°C, solutions of 9.44 g (0.032 mol) OBBOC and 2.25 g (0.016 mol) BC dissolved in 20 g NMP were added separately to 40.00 g NMP over 10 minutes each. The mixture was then brought back to room temperature and stirred for 3 hours. After the reaction was complete, the reaction solution was added to 2 L of water, and the precipitated solid was filtered to obtain a solid. The obtained solid was washed three times with water and dried in a vacuum dryer at 50°C for 72 hours to obtain polyamide resin (A-1).

[0222] [Synthesis Examples 2-16: Synthesis of Polyamide Resins (A-2) to (A-16)]

[0223] Polyamide resins (A-2) to (A-16) were synthesized by reacting in the same manner as in Synthesis Example 1, using the molar ratios shown in Table 3 below.

[0224] [Synthetic Example 17: Synthesis of Naphthoquinone Diazo Compounds]

[0225] Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Co., Ltd.) and 37.62 g (0.14 mol) of 5-diazonaphthoquinone sulfonyl chloride were dissolved in 1,4-dioxane. Add 450g of alkylene to a solution and allow it to reach room temperature. Then, add 1,4-dialkylene dropwise to the system in a manner that prevents the system temperature from exceeding 35°C. The triethylamine was added dropwise to 15.58 g (0.154 mol) of a mixture of 50 g of alkyl groups. The mixture was stirred at 30 °C for 2 hours. The triethylamine salt was filtered off, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain a naphthoquinone diazo compound with the following chemical formula.

[0226]

[0227]

[0228]

[0229] The details of each component in Table 4 are as follows.

[0230] <Polyamide Resin (A)>

[0231] (A-1) to (A-16): These are the resins described in Synthetic Examples 1 to 16, respectively.

[0232] Among them, the polyamide resin (A) of A-1 to A-13 has the molecular chain end of formula (1).

[0233] <Photosensitive Agent (B)>

[0234] NQD

[0235] NCI-831

[0236] CPI-310B

[0237] <Heat-generating acid agent (C)>

[0238] TA-100

[0239] BTS

[0240] <Crosslinking agent (D)>

[0241] DPHA

[0242] TEPIC-VL

[0243] <Solvent>

[0244] GBL

[0245] According to the composition ratios described in Table 4, the varnishes of Examples 1-18 and Comparative Examples 1-6 were prepared under a yellow light, and evaluations (2)-(5) were carried out in Examples 1-13 and Comparative Examples 1-3, and evaluations (6)-(7) were carried out in Examples 14-18 and Comparative Examples 4-6.

[0246] The measurement results are shown in Tables 5 and 6, respectively.

[0247]

[0248]

[0249] Explanation of reference numerals in the attached figures

[0250] 101IC chip

[0251] 102 electrode pads

[0252] Wiring at 103 No. 2 via

[0253] 104 planar antenna wiring

[0254] 105 Second Sealing Resin

[0255] 106 Grounding Wiring

[0256] 107 First Via Wiring

[0257] 108 First Sealing Resin

[0258] 109 copper wiring

[0259] 110 insulating film

[0260] 111 blocking metal

[0261] 112 solder bump

[0262] Industry availability

[0263] The resin composition of the present invention can be well used in surface protective films for semiconductor elements, interlayer insulating films, insulating layers for display devices such as organic light-emitting elements, planarization films for thin film transistor (TFT) substrates, wiring protection insulating films for circuit boards, etc.

Claims

1. A (A) polyamide resin, which is a polyamide resin having dicarboxylic acid residues and diamine residues, the (A) polyamide resin comprising the molecular chain ends shown in formula (1), In equation (1), Y 1 Z represents a divalent organogroup with 2 to 70 carbon atoms, Z represents a monovalent monocarboxylic acid residue with 1 to 20 carbon atoms, and R represents a divalent organogroup with 2 to 70 carbon atoms. 1 and R 2 Each of the following groups independently represents a monovalent organic group with 1 to 10 carbon atoms, p and q represent integers from 0 to 3, and * represents the binding site with the amide bond.

2. The polyamide resin of claim 1 (A), wherein the dicarboxylic acid residue contains an aliphatic chain structure having 1 to 30 carbon atoms.

3. The polyamide resin of claim 1 or 2, wherein Z in formula (1) is a monovalent monocarboxylic acid residue containing 1 to 20 carbon atoms in an unsaturated carbon-carbon double bond.

4. A photosensitive resin composition comprising (A) a polyamide resin as described in claim 1 or 2 and (B) a photosensitizer, wherein the (B) photosensitizer is one or more compounds selected from (b-1) naphthoquinone diazo compounds, (b-2) photoradical polymerization initiators and (b-3) photoacid generators.

5. The photosensitive resin composition of claim 4, further comprising (C) a heat-generating acid agent.

6. The photosensitive resin composition of claim 5, wherein the (C) thermal acid-producing agent is a thermal acid-producing agent having a sulfonate structure.

7. A cured product formed by curing the photosensitive resin composition of claim 4.

8. A cured product comprising a resin having the structure shown in formula (2), In equation (2), * represents a chemical bond.

9. A cured product derived from hexafluoroisopropanol groups at wavelengths of 1350–1450 cm⁻¹ -1 Peak intensity I a The wavelength of the cyclized structure derived from hexafluoroisopropanol and amide groups is 1050–1150 cm. -1 Peak intensity I b The ratio is I a / I b It is below 1.

10. A method for manufacturing a cured material, comprising the following steps: The process of coating the photosensitive resin composition of claim 4 onto a substrate and drying it to form a resin film. The process of exposing the resin film. The process of developing the exposed resin film, and The process of heating the developed resin film.

11. An electronic component having the cured material as described in claim 7.

12. The electronic component of claim 11, further comprising at least a semiconductor package, said semiconductor package including a semiconductor element, a rewiring layer, a sealing resin, a grounding portion, and antenna wiring. The insulation layer of the rewiring layer and / or the sealing resin contain the cured material. The sealing resin is located between the grounding part and the antenna wiring.

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