Compound, polyhydroxyamide compound, photosensitive resin composition, dry film, cured product, and electronic component

Abstract

Provided are: a new compound usable for a resin composition such as a photosensitive resin composition; and a polyhydroxyamide compound. Also provided are: a photosensitive resin composition containing the polyhydroxyamide compound; a dry film having a resin layer formed from the photosensitive resin composition; a cured product obtained by curing the photosensitive resin composition or curing the resin layer of the dry film; and an electronic component including the cured product. The present invention provides a compound represented by formula (1). (In formula (1), R represents a divalent organic group.)

Description

Compound, polyhydroxyamide compound, photosensitive resin composition, dry film, cured product, and electronic component

[0001] The present invention relates to a compound, a polyhydroxyamide compound, a photosensitive resin composition, a dry film, a cured product, and an electronic component.

[0002] Photosensitive resin compositions containing polyhydroxyamide compounds, which are polybenzoxazole precursors, exhibit excellent properties such as insulating properties, heat resistance, and mechanical strength, and are therefore widely used as insulating films in various fields such as semiconductors and electronic components.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing a polybenzoxazole precursor, a compound that generates an acid upon irradiation with actinic rays in a specific wavelength range, a crosslinkable or polymerizable compound, and a compound that generates an acid upon heating. According to the disclosure of Patent Document 1, a negative-type photosensitive resin composition is provided that exhibits good sensitivity and resolution and provides good chemical resistance, heat resistance, and mechanical properties.

[0004] Japanese Patent Application Laid-Open No. 2012-203359

[0005] In recent years, the demand for higher performance and smaller size of electronic components and electrical equipment has led to a demand for even higher integration of semiconductor elements. To meet these demands, technologies for higher performance and smaller size have been developed in the field of semiconductor element packaging, such as wafer level packaging (WLP). In addition to further miniaturization of pattern formation, insulating films used in rewiring layers are also required to have various properties that are compatible with these higher performance and smaller size technologies.

[0006] Therefore, an object of the present disclosure is to provide a novel compound and a novel polyhydroxyamide compound using the compound.

[0007] One aspect of the present invention is a compound represented by the following formula (1): (R in formula (1) is a divalent organic group.)

[0008] The compound of the above embodiment is preferably represented by the following formula (2). (R in formula (2) is a divalent organic group.)

[0009] The compound of the above embodiment is preferably represented by the following formula (3). (R in formula (3) is a divalent organic group.)

[0010] In the compound of the above embodiment, it is preferable that R has an aromatic ring or an aliphatic ring.

[0011] In the compound of the above aspect, R is preferably any one selected from the following formula (4): (* in formula (4) indicates a binding site.)

[0012] Another aspect of the present invention is a polyhydroxyamide compound having a structural unit represented by the following formula (5): (R in formula (5) １ , R ２ are each independently a divalent organic group.

[0013] Another aspect of the present invention is a photosensitive resin composition, which contains the polyhydroxyamide compound of the above aspect.

[0014] Another aspect of the present invention is a dry film, which includes a resin layer formed from the photosensitive resin composition of the above aspect.

[0015] Another aspect of the present invention is a cured product obtained by curing the photosensitive resin composition of the above aspect or the resin layer of the dry film of the above aspect.

[0016] Another aspect of the present invention is an electronic component, which has the cured product of the above aspect.

[0017] The present invention provides a novel compound and a novel polyhydroxyamide compound using the compound. It also provides a photosensitive resin composition containing the polyhydroxyamide compound, a dry film having a resin layer formed from the photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition or the resin layer of the dry film, and an electronic component having the cured product.

[0018] Compound (A-1) synthesized in Synthesis Example 1 １ The results of H-NMR measurement (NMR chart) are shown below. １ The H-NMR measurement results (NMR chart) of the compound (A-3) synthesized in Synthesis Example 3 are shown below. １ The results of H-NMR measurement (NMR chart) of compound (A-4) synthesized in Synthesis Example 4 are shown below. １ The H-NMR measurement results (NMR chart) of the compound (A-5) synthesized in Synthesis Example 5 are shown below. １ The results of H-NMR measurement (NMR chart) of compound (A-6) synthesized in Synthesis Example 6 are shown below. １ The results of H-NMR measurement (NMR chart) of compound (A-7) synthesized in Synthesis Example 7 are shown below. １ The H-NMR measurement results (NMR chart) are shown.

[0019] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expression "a to b" in the description of a numerical range means a to b, unless otherwise specified.

[0020] In this specification, when multiple upper limit values ​​and multiple lower limit values ​​are separately described, all numerical ranges that can be set by freely combining these upper limit values ​​and lower limit values ​​are considered to be described in this specification.

[0021] In this specification, when a compound is described, its isomers are also described unless otherwise specified.

[0022] The "substituent" is not particularly limited, and unless otherwise specified, examples thereof include a hydroxyl group, a phenol group, a phenyl group, a halogen group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, a thioester group, an aldehyde group, an acetyl group, and the like.

[0023] The term "aromatic ring" is not particularly limited, and unless otherwise specified, also includes heterocycles.

[0024] In this specification, the solid content means the components constituting the photosensitive resin composition or each raw material other than the solvent (particularly the organic solvent), and is based on mass unless otherwise specified.

[0025] 1. Compound The compound (hydroxycarboxylic acid compound) of this embodiment is represented by the following formula (1). (R in formula (1) is a divalent organic group.)

[0026] The compound of this embodiment is preferably represented by the following formula (2). (R in formula (2) is a divalent organic group.)

[0027] Furthermore, the compound of this embodiment is preferably represented by the following formula (3). (R in formula (3) is a divalent organic group.)

[0028] R in the formulas (1) to (3) is not particularly limited as long as it is a divalent organic group, and may be, for example, a divalent organic group including an aromatic hydrocarbon group (arylene group), an aliphatic hydrocarbon group (alkylene group, cycloalkylene group), an ether group, a ketone group, an ester group, a sulfonyl group, or the like.

[0029] Among the divalent organic groups mentioned above, R preferably has an aromatic ring or an aliphatic ring. Examples of the divalent organic group having an aromatic ring include biphenyl skeleton, diphenyl ether skeleton, diphenyl thioether skeleton, benzophenone skeleton, diphenylmethane skeleton, diphenylpropane skeleton, diphenylhexafluoropropane skeleton, diphenyl sulfoxide skeleton, diphenyl sulfone skeleton, benzene skeleton, etc. Examples of the divalent organic group having an aliphatic ring include cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cycloundecane skeleton, cyclododecane skeleton, dicyclopentadiene skeleton, etc.

[0030] Among the divalent organic groups having an aromatic ring or an aliphatic ring described above, R is more preferably any one selected from the group represented by the following formula (4). (* in formula (4) indicates a binding site.)

[0031] As shown in the above formulas (1) to (3), the compound of this embodiment has alkali-soluble groups, a phenolic hydroxyl group and a carboxyl group, and therefore can be preferably used in the synthesis of alkali-soluble resins. An alkali-soluble resin is a resin that allows a resin composition to be dissolved in an alkaline developer, i.e., to be developed with an alkali. Therefore, an alkali-soluble resin synthesized using the compound of this embodiment is preferably used in the production of a photosensitive resin composition or a cured product obtained by curing the photosensitive resin composition. The compound of this embodiment can be particularly preferably used in the synthesis of a polyhydroxyamide compound.

[0032] From the viewpoints of the resolution of the photosensitive resin composition containing the polyhydroxyamide compound obtained using the compound of this embodiment and the insulation reliability of the cured product, the number of carbon atoms in R is preferably 1 to 30, 5 to 20, or 5 to 15.

[0033] An example of a method for producing the compound of this embodiment is a method of reacting an aromatic carboxylic acid compound represented by the following formula (1-1) with a dicarbonyl dichloride compound represented by the following formula (1-2), which are used as raw materials. That is, the compound represented by formula (1) can be obtained by reacting the aromatic carboxylic acid compound represented by formula (1-1) with the dicarbonyl dichloride compound represented by formula (1-2). (R in formula (1-2) is as described above.)

[0034] The aromatic carboxylic acid compound represented by the above formula (1-1) is preferably 4-amino-3-hydroxybenzoic acid (4A3HBA) represented by the following formula (2-1) or 3-amino-4-hydroxybenzoic acid (3A4HBA) represented by the following formula (3-1):

[0035] The compound represented by the formula (2) is obtained by reacting 4-amino-3-hydroxybenzoic acid represented by the formula (2-1) with the dicarbonyl dichloride compound represented by the formula (1-2). The compound represented by the formula (3) is obtained by reacting 3-amino-4-hydroxybenzoic acid represented by the formula (3-1) with the dicarbonyl dichloride compound represented by the formula (1-2).

[0036] The dicarbonyl dichloride compound represented by the above formula (1-2) is not particularly limited, and known dicarbonyl dichloride compounds can be used, such as isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), 4,4'-oxybis(benzoyl chloride) (DEDC), and 1,4-cyclohexanedicarbonyl chloride (CHDC), which are represented by the following formula (1-3):

[0037] In this embodiment, the dicarbonyl dichloride compounds represented by the above formulas (1-2) and (1-3) are used, but the present invention is not limited thereto, and dicarboxylic acids such as phthalic acid and terephthalic acid, or their halides may also be used. Examples of halogens used in halides include chlorine, fluorine, bromine, and iodine.

[0038] In the reaction between the aromatic carboxylic acid compound represented by the formula (1-1) and the dicarbonyl dichloride compound represented by the formula (1-2), an organic solvent may be used, if necessary.

[0039] The organic solvent is not particularly limited, and known organic solvents can be used. Examples include amide organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide; alcohol organic solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester organic solvents such as ethyl acetate, butyl acetate, and ethyl lactate; ether organic solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and tetrahydrofuran (THF); and aromatic hydrocarbon compound organic solvents such as benzene, toluene, and xylene. Among the above, amide organic solvents are preferred.

[0040] The amount of the organic solvent is not particularly limited as long as it allows the reaction to proceed efficiently, and is preferably about 50 to 500% by mass relative to 100% by mass of the total amount of the aromatic carboxylic acid compound represented by the formula (1-1) and the dicarbonyl dichloride compound represented by the formula (1-2).

[0041] The reaction temperature and reaction time for the above reaction can be appropriately selected from conventionally known reaction conditions. For example, the reaction can be carried out in the presence of a base such as pyridine at 0° C. to 30° C. for 5 to 25 hours.

[0042] Furthermore, as a method for producing the compound of this embodiment, for example, a method of subjecting an aromatic carboxylic acid compound represented by (1-1) and a dicarboxylic acid compound as raw materials to a condensation reaction can be mentioned. The conditions for the condensation reaction can be appropriately selected from the same conditions as those for the polycondensation reaction for obtaining a polyhydroxyamide compound described below.

[0043] 2. Polyhydroxyamide Compound The polyhydroxyamide compound of this embodiment has a structural unit of the following formula (5). (R in formula (5) １ , R ２ are each independently a divalent organic group.

[0044] R in formula (5) １ is not particularly limited as long as it is a divalent organic group, and may contain, for example, an aromatic hydrocarbon group (arylene group), an aliphatic hydrocarbon group (alkylene group, cycloalkylene group), an ether group, a ketone group, an ester group, a sulfonyl group, or the like.

[0045] R １ Among the above-mentioned divalent organic groups, it is preferable that the divalent organic group has an aromatic ring or an aliphatic ring. Examples of the divalent organic group having an aromatic ring include a biphenyl skeleton, a diphenyl ether skeleton, a diphenyl thioether skeleton, a benzophenone skeleton, a diphenylmethane skeleton, a diphenylpropane skeleton, a diphenylhexafluoropropane skeleton, a diphenyl sulfoxide skeleton, a diphenyl sulfone skeleton, a benzene skeleton, etc. Examples of the divalent organic group having an aliphatic ring include a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cycloundecane skeleton, a cyclododecane skeleton, a dicyclopentadiene skeleton, etc.

[0046] Furthermore, R １ is more preferably at least one selected from the divalent organic groups having an aromatic ring or an aliphatic ring described above, represented by the following formula (4): (* in formula (4) indicates a binding site.)

[0047] R in formula (5) ２ is a residue of a diamine compound described below, and is not particularly limited as long as it is a divalent organic group, and may contain, for example, an aliphatic hydrocarbon group (alkylene group, cycloalkylene group), an aromatic hydrocarbon group (arylene group), an ether group, a ketone group, an ester group, a sulfonyl group, a triazine ring, a triazole ring, a siloxane bond, etc. More specifically, it is preferable that the diamine compound has a skeleton such as biphenyl, diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfoxide, diphenyl sulfone, or benzene, or 2-methyl-1,3,5-triazine, 2-phenyl-1,3,5-triazine, or 1,1,3,3-tetramethyl-1,3-dipropyldisiloxane.

[0048] From the viewpoint of the resolution of the photosensitive resin composition and the insulation reliability of the cured product, R １ The number of carbon atoms in R is preferably 1 to 30, 5 to 20, or 5 to 15. ２ The number of carbon atoms in R is preferably 1 to 30, 5 to 20, or 5 to 15. １ and R ２ It is also possible to have two or more of the groups exemplified above contained as R １ and R ２ may be of the same structure or of different structures.

[0049] The polyhydroxyamide compound of the present embodiment has a phenolic hydroxyl group, which is an alkali-soluble group, and therefore can be used as an alkali-soluble resin. As will be described later, when the polyhydroxyamide compound of the present embodiment is used as a photosensitive resin composition, it can be made into an alkali-developable negative-type photosensitive resin composition or a positive-type photosensitive resin composition.

[0050] The polyhydroxyamide compound of this embodiment may have an alkali-soluble group at its terminal. The alkali-soluble group at the terminal is not particularly limited, and examples thereof include functional groups such as an alcoholic hydroxyl group, a phenolic hydroxyl group, an acid anhydride group, a carboxyl group, a sulfonic acid group, a sulfonamide group, and an active methylene group. From the viewpoint of solubility in a developer, it is preferable that the polyhydroxyamide compound have a carboxyl group or a phenolic hydroxyl group.

[0051] When the polyhydroxyamide compound of this embodiment is used as a negative-tone photosensitive resin composition, among these alkali-soluble groups, a phenolic hydroxyl group is particularly preferred. When the polyhydroxyamide compound has a terminal phenolic hydroxyl group, the solubility of the polyhydroxyamide compound in a developer can be improved. Furthermore, since the phenolic hydroxyl group has lower reactivity than a carboxyl group, when the compound is used in combination with a crosslinking agent or the like to form a photosensitive resin composition, excessive reaction with the crosslinking agent or the like is suppressed, and the solubility of the unexposed area in the developer can be maintained even after a PEB process is performed. This is presumably what allows for the provision of a photosensitive resin composition with excellent resolution.

[0052] The alkali-soluble group at the end of these polyhydroxyamide compounds may be a residue of a monomer constituting the polyhydroxyamide compound, or may be a terminal structure introduced by a terminal-capping agent having an alkali-soluble group. The alkali-soluble group at the end of the polyhydroxyamide compound is preferably a terminal structure introduced by a terminal-capping agent having an alkali-soluble group.

[0053] The end-capping agent is not particularly limited, and examples thereof include compounds having one amino group and a hydroxyl group, such as aminophenol compounds, hydroxybenzylamine compounds, aminobenzyl alcohol compounds, and alcoholamine compounds; compounds having one carboxyl group and a hydroxyl group, such as hydroxy acids; acid anhydride compounds having a hydroxyl group, such as hydroxy acid anhydrides; compounds having an amino group and a carboxyl group, such as aminobenzoic acid and amino acids; and acid anhydride compounds, such as phthalic anhydride and 5-norbornene-2,3-dicarboxylic anhydride.

[0054] Examples of methods for producing a polyhydroxyamide compound include a method of polycondensing raw materials, which are a compound represented by the above-mentioned formula (1) (a hydroxycarboxylic acid compound) and a diamine compound represented by the following formula (6), using a condensing agent described below. (R in formula (6) ２ is as described above.)

[0055] The hydroxycarboxylic acid compound represented by formula (1) is the same as the above-mentioned "1. Compound," and therefore, description thereof will be omitted here.

[0056] The diamine compound represented by the above formula (6) is not particularly limited, and known diamine compounds can be used, for example, 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diaminodiphenyl ether, 3,3'-oxydianiline, 4,4'-oxydianiline, 2,7-diaminofluorene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-ethylenedianiline, diethylenetriamine, 1,12-diaminododecane, 1,11 1,10-diaminodecane, 1,9-diaminononane, 1,8-diaminooctane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diaminopropane, ethylenediamine, 3,5-diamino-1,2,4-triazole, benzoguanamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-methylenebis(2,6-diethylaniline), etc. As described above, there are many types of diamine compounds represented by formula (6), and therefore, according to this embodiment, a wide variety of polyhydroxyamide compounds can be produced, and polyhydroxyamide compounds having a variety of properties can be obtained.

[0057] Other copolymerizable compounds may be copolymerized with the above-mentioned compounds, such as diol compounds, acid dianhydrides, and diisocyanate compounds.

[0058] In the polycondensation reaction described above, the carboxy group of the hydroxycarboxylic acid compound represented by formula (1) is activated with an activator as needed, and then bonded to the amino group portion of the diamine compound represented by formula (6) through a condensation reaction with a condensing agent to form an amide bond. As this condensation reaction progresses, the polycondensation reaction proceeds. The polycondensation reaction proceeds in a suitable liquid medium. Examples of the liquid medium include water, aqueous buffer solutions (e.g., acidic buffer solutions), and organic solvents such as N-methylpyrrolidone (NMP).

[0059] Examples of the activator include N-hydroxypolycarboxylic acid imides such as N-hydroxysuccinimide (NHS) and n-hydroxy-5-norbornene-2,3-dicarboxylic acid imide (HONB), N-hydroxytriazoles such as 1-hydroxybenzotriazole (HOBt), N-hydroxytriazines such as 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOBt), 2-hydroxyimino-2-cyanoacetic acid ethyl ester, and pentafluorophenol. Of these, HOBt is preferred.

[0060] Examples of condensing agents include carbodiimide condensing agents such as diisopropylcarbodiimide (DIPC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDAC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC), and dicyclohexylcarbodiimide (DCC), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM), and carbonyldiimidazole. Among these, EDAC and DMT-MM are preferred.

[0061] The reaction temperature and reaction time for the polycondensation reaction can be appropriately selected from conventionally known reaction conditions, and for example, the reaction can be carried out at -20°C to 100°C for 5 minutes to 24 hours.

[0062] The weight-average molecular weight (Mw) of the polyhydroxyamide compound can be set to 2,000 to 21,000, preferably 3,000 to 20,000, more preferably 3,500 to 15,000, and even more preferably 5,000 to 12,000. By setting the weight-average molecular weight within such a range, it becomes possible to form a finer L / S pattern with a higher aspect ratio.

[0063] The number average molecular weight (Mn) of the polyhydroxyamide compound is preferably 800 to 10,000, more preferably 900 to 2,000.

[0064] The polydispersity index (PDI) of the polyhydroxyamide compound is preferably 1.5 to 25.0, more preferably 1.5 to 16.0. The polydispersity index (PDI) is calculated by the following formula: PDI=Mw / Mn

[0065] When the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI) of the polyhydroxyamide compound are within the above ranges, a favorable balance is achieved between the solubility in a developer and the reactivity with a crosslinking agent, and a photosensitive resin composition exhibiting favorable dissolution contrast can be obtained.

[0066] In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) (GL7700 manufactured by GL Science) and converted into standard polystyrene. Specific measurement conditions are as follows:

[0067] Column: TSKgel αM (manufactured by Tosoh Corporation) Column temperature: 40°C Eluent composition: 100 mmol / L H ３ P.O. ４ (H ３ P.O. ４ NMP solution containing 85% aqueous solution as raw material) and 10 mmol / L LiBr Eluent flow rate: 0.5 mL / min Calibration standard reagent: polystyrene Detector wavelength: 260 nm and 300 nm Detector temperature: room temperature (approximately 25°C) Baseline range during analysis: 15 to 40 minutes Molecular weight calculation range during analysis: 20 to 35 minutes

[0068] The alkaline dissolution rate of the polyhydroxyamide compound is not particularly limited and can be, for example, 10 to 3000 nm / sec, 50 to 1000 nm / sec, or 100 to 500 nm / sec. If the alkaline dissolution rate is too low, the photosensitive resin composition may not dissolve sufficiently during development, making pattern formation difficult. If the alkaline dissolution rate is too high, sensitivity may decrease or the pattern may swell during development. The alkaline dissolution rate of the polyhydroxyamide compound can be measured by the method described in the Examples below.

[0069] 3. Photosensitive Resin Composition The photosensitive resin composition of this embodiment contains the polyhydroxyamide compound described above. The polyhydroxyamide compound of this embodiment can be used in both negative-working and positive-working photosensitive resin compositions.

[0070] The photosensitive resin composition of the present embodiment may further contain a crosslinking agent, a photoacid generator, a basic compound, and the like.

[0071] 3-1. Crosslinking Agent The crosslinking agent is not particularly limited and can be any known crosslinking agent, such as a melamine compound, a guanamine compound, a triazine compound, an epoxy compound, an oxetane compound, an isocyanate compound, or an oxazoline compound. The crosslinking agent is preferably a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group. These functional groups undergo a crosslinking reaction with phenolic hydroxyl groups or carboxyl groups contained in polyhydroxyamide compounds or the like upon heating, using the acid generated from a photoacid generator (described below) as the active species. Negative photolithography (pattern formation) can be achieved by exposure, PEB, and development. Furthermore, further heating after pattern formation promotes the curing reaction of the photosensitive resin composition, resulting in the development of excellent properties as a cured product.

[0072] Furthermore, the crosslinking agent preferably contains a heterocycle in order to improve the resolution of the photosensitive resin composition and the insulating reliability after curing. The heterocycle is not particularly limited and contains one or more heteroatoms such as boron, nitrogen, oxygen, phosphorus, sulfur, antimony, arsenic, bismuth, selenium, silicon, tellurium, or tin, and includes a 3-, 4-, 5-, 6-, 7-, or 8-membered saturated or unsaturated ring. From the viewpoint of the resolution of the photosensitive resin composition and the insulating reliability of the cured product, the heterocycle is preferably a nitrogen-containing heterocycle, and more preferably a heterocycle containing multiple nitrogen atoms.

[0073] Specifically, from the viewpoint of providing a negative-type photosensitive resin composition capable of forming a finer L / S pattern with a high aspect ratio, compounds having a triazine structure including a triazine ring and compounds having a guanamine structure including a triazine ring are more preferred, as are compounds having a glycoluril structure including tetramethylol glycoluril and tetramethoxyglycoluril, and compounds having an imidazolidinone structure including 1,3-bis(methoxymethyl)-2-imidazolidinone. Of these, compounds having a triazine structure including a triazine ring and compounds having a guanamine structure are particularly preferred from the viewpoint of providing a negative-type photosensitive resin composition capable of forming a finer L / S pattern with a high aspect ratio.

[0074] 3-2. Photoacid Generator The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light, and examples thereof include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyamidosulfonates, aromatic N-oxyimidosulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimides, benzoquinone diazosulfonic acid esters, etc. These can be used alone or in combination in any desired ratio.

[0075] When the polyhydroxyamide compound of this embodiment is used as a negative-type photosensitive resin composition, the photoacid generator is preferably used in combination with the above-mentioned crosslinking agent, and the photoacid generator is preferably an oxime sulfonate compound. Examples of the oxime sulfonate compound include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF, and those having the structure of the following formula (7) are particularly preferred. (In formula (7), X represents a hydrocarbon group or a halogen atom, m represents an integer of 0 to 3, and R ３ is a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom.

[0076] X in the above formula (7) is not particularly limited and can be, for example, a hydrocarbon group (e.g., an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) or a halogen atom. The hydrocarbon group may have a substituent and can have a linear, branched, or cyclic structure. A linear or branched hydrocarbon group having 1 to 4 carbon atoms is preferably used. A chlorine atom or a fluorine atom is preferably used as the halogen atom.

[0077] In the above formula (7), m represents an integer of 0 to 3, and is preferably 0 or 1. When m is 2 or 3, multiple Xs may be the same or different.

[0078] R in the above formula (7) ３ is preferably a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom. The hydrocarbon group (e.g., an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) may be unsubstituted or may be substituted with a halogen atom.

[0079] The hydrocarbon group is preferably a linear, branched or cyclic group having 1 to 20 carbon atoms, more preferably a linear, branched or cyclic group having 1 to 10 carbon atoms. The halogen atom may be a chlorine atom or a fluorine atom.

[0080] When the polyhydroxyamide compound of this embodiment is used as a positive-tone photosensitive resin composition, the photoacid generator is preferably a dissolution inhibitor, and is preferably a naphthoquinone diazide compound. Examples of naphthoquinone diazide compounds that can be used include naphthoquinone diazide adducts of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (e.g., TKF-520, TKF-528, TKF-420, and TKF-428 manufactured by Sanbo Chemical Research Institute) and naphthoquinone diazide adducts of tetrahydroxybenzophenone (e.g., BS550, BS570, and BS599 manufactured by Sanbo Chemical Research Institute). The addition of naphthoquinone diazide can be achieved by, for example, reacting o-quinone diazide sulfonyl chlorides with a hydroxy compound or an amino compound. These compounds can be used alone or in combination in any ratio.

[0081] 3-3. Basic Compound The photosensitive resin composition of this embodiment may contain a basic compound. In particular, when the photosensitive resin composition of this embodiment contains a basic compound, it is possible to prevent the acid generated from the photoacid generator upon exposure from diffusing into unexposed areas, thereby improving resolution and preventing development residues from being generated in unexposed areas after development.

[0082] The basic compound is not particularly limited, and examples thereof include trimethylamine, diethylamine, triethylamine, N,N-diisopropylethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, tris(2-methoxy)amine, bis(2-methoxy)amine, tris(2-ethoxy)amine, bis(2-ethoxy)amine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4, Amine compounds such as 4'-diaminodiphenylamine; amide compounds such as formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide; lactams such as pyrrolidone and N-methylpyrrolidone; methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3-diphenyl Examples of suitable amine compounds include urea and other urea compounds; nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and pyridine; and morpholine compounds such as morpholine and 4-methylmorpholine. These compounds can be used alone or in combination in any ratio. Among these, amine compounds are preferred, and alcoholamines such as N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine are more preferred, with diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine being even more preferred.

[0083] The photosensitive resin composition of the present embodiment may contain a solvent. The solvent is not particularly limited, and examples thereof include ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethyl sulfone, and pyridine.

[0084] Examples of ethers include 2-methoxy-1-methylethyl acetate (PGMEA), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0085] Examples of esters include ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, and ethyl 2-ethoxypropionate.

[0086] Examples of ketones include methyl ethyl ketone; methyl isobutyl ketone (4-methyl-2-pentanone); 2-heptanone; monoketone cycloalkanones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone; diketone cycloalkanones such as 1,3-cyclopentanedione, 3-methyl-1,2-cyclopentanedione, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, and 2-methyl-1,3-cyclopentanedione; Examples include cycloalkenones such as 4-methyl-2-cyclopentenone, 2-cyclohexenone, 2-cyclopenten-1-one, and 2-cyclohexen-1-one; and cyclic ketones having a heterocyclic skeleton such as 2-azetidinone, 4,5-dihydro-3(2H)-thiophenone, 4-oxothiane, and dihydrolevogluconocene.

[0087] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0088] Examples of lactones include γ-butyrolactone, examples of lactams include N-methylpyrrolidone and N-methylcaprolactam, and examples of sulfoxides include dimethyl sulfoxide and hexamethyl sulfoxide.

[0089] These solvents can be used alone or in combination of two or more in any ratio. Among these solvents, lactones or cyclic ketones are preferred, and γ-butyrolactone or cyclopentanone is preferred, from the viewpoint of excellent affinity with each component in the negative photosensitive resin composition. Furthermore, from the viewpoint of excellent solvent removability during drying of the negative photosensitive resin composition and suitability for the edge rinse step in semiconductor manufacturing, cyclic ketones are preferred, and monoketone cycloalkanones are more preferred, with cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone being even more preferred, and cyclopentanone being particularly preferred.

[0090] 3-5. Other Components The photosensitive resin composition of the present embodiment may contain other components as long as the effects of the disclosed technology are not impaired. Examples of other components include known components that can be contained in photosensitive resin compositions, such as fillers, adhesives, surfactants, plasticizers, thermal acid generators, sensitizers, leveling agents, colorants, fibers, and fine particles.

[0091] The surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, etc. Commercially available fluorine-based surfactants include the "Megafac" series manufactured by DIC Corporation (e.g., Megafac F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-569, etc.). Commercially available silicone surfactants include the BYK-Chemie surface conditioner series (e.g., BYK-302, BYK-307, BYK-310, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK-348, BYK-349, BYK-377, BYK-378, BYK-3455, BYK-3760, etc.). These may be used alone or in combination of two or more.

[0092] 4. Preparation of Photosensitive Resin Composition The photosensitive resin composition of the present embodiment can be obtained by mixing the polyhydroxyamide compound described above with optional components including a crosslinking agent, a photoacid generator, a basic compound, etc. The components can be mixed under heating, if necessary.

[0093] 4-1. Polyhydroxyamide Compound The content of the polyhydroxyamide compound can be 50 to 80% by mass, assuming that the total mass of the solid content of the photosensitive resin composition is 100% by mass.

[0094] 4-2. Crosslinking Agent The content of the crosslinking agent can be 5 to 80 parts by mass, assuming the solid mass of the polyhydroxyamide compound in the photosensitive resin composition is 100 parts by mass. Furthermore, when the crosslinking agent has methoxymethyl groups and / or methylol groups, the content of the crosslinking agent can be such that the ratio of the number of methoxymethyl groups and / or methylol groups contained in the crosslinking agent to the number of phenolic hydroxyl groups contained in the photosensitive resin composition (methoxymethyl groups and / or methylol groups:phenolic hydroxyl groups) is 120:100 to 200:100. By achieving such a ratio, the photosensitive resin composition can have better resolution and insulating reliability after curing.

[0095] The content of the photoacid generator can be 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the solid content of the polyhydroxyamide compound in the photosensitive resin composition.

[0096] 4-4. Basic Compound When a basic compound is added, the content thereof can be 0.01 to 1.0 part by mass, and preferably 0.05 to 0.50 part by mass, relative to 100 parts by mass of the solid content of the polyhydroxyamide compound in the photosensitive resin composition. By setting the content within this range, it becomes easier to suppress the generation of development residues in unexposed areas after development of the photosensitive resin composition.

[0097] 5. Dry Film The dry film of the present embodiment includes a substrate and a resin layer formed on the substrate using the photosensitive resin composition of the present embodiment. In addition, a protective film may be further laminated on the surface of the resin layer to protect the resin layer.

[0098] The resin layer can be obtained, for example, by applying a photosensitive resin composition onto a substrate, adjusting the thickness of the resin layer using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., and drying the resin layer. The thickness of the resin layer is not particularly limited and can be set to 1 to 150 μm depending on the application.

[0099] The substrate is not particularly limited, and examples thereof include metal foils such as copper foils; and films such as polyimide films, polyester films, and polyethylene naphthalate (PEN) films.

[0100] The protective film is not particularly limited, and polyethylene film, polytetrafluoroethylene film, polypropylene film, paper, etc. can be used. It is preferable to select a protective film such that the adhesion between the protective film and the resin layer is lower than the adhesion between the substrate and the resin layer. In order to make the adhesion between the protective film and the resin layer lower than the adhesion between the substrate and the resin layer, a protective film whose surface has been subjected to a release treatment can be used.

[0101] 6. Cured Product The cured product of this embodiment is obtained by curing the above-described photosensitive resin composition or the resin layer of the dry film. The cured product may be a patterned cured product. A method for producing a patterned cured product will be described below using a negative photosensitive resin composition as an example.

[0102] 6-1. Dry Coating Film Forming Step The dry coating film forming step is a step of applying the above-described photosensitive resin composition onto a substrate to form a coating film, and then drying the coating film. In the dry coating film forming step, it is also possible to form a dry coating film on a substrate by laminating a resin layer of a dry film onto the substrate.

[0103] The method for applying the photosensitive resin composition onto a substrate is not particularly limited, and examples thereof include a method of applying the composition using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., a method of spraying the composition using a spray coater, and an inkjet method. The thickness of the applied film is not particularly limited, and can be, for example, 10 μm or less, 5 μm or less, or 3 μm or less. By reducing the film thickness, finer L / S patterning becomes possible while maintaining the aspect ratio of the pattern.

[0104] The method for drying the coating film is not particularly limited, and examples thereof include air drying, heat drying in an oven or on a hot plate, vacuum drying, etc. Conditions for heat drying include, for example, a heating temperature of 70 to 140°C and a drying time of 1 to 30 minutes.

[0105] The resin layer of the dry film is preferably laminated onto the substrate under pressure and heat using a vacuum laminator, etc. The heating temperature can be, for example, 60 to 100°C.

[0106] The substrate is not particularly limited, and may be, for example, a printed wiring board on which a circuit is formed, a flexible printed wiring board, or a wafer on which a semiconductor element is formed.

[0107] 6-2. Exposure Step In the exposure step, the dried coating film formed in the dried coating film formation step is irradiated with radiation through a photomask capable of forming a desired pattern, thereby sensitizing the photoacid generator in the exposed area and generating active species. If patterning is not required, there is no need to use a photomask. Alternatively, a pattern may be directly written with a laser using a direct writing device.

[0108] The wavelength of the radiation used is one that can activate the photoacid generator, and in order to perform fine patterning, a maximum wavelength of 410 nm or less is preferred. The irradiation energy can be adjusted depending on the thickness of the formed dry coating film, and is, for example, 10 to 1500 mJ / cm. ２ As the exposure light source, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, a KRF laser, or the like can be used.

[0109] 6-3. PEB Process The PEB process is, for example, a process in which a dried coating film made of a photosensitive resin composition exposed in the exposure process is heat-treated to impart development resistance to the exposed portion of the dried coating film (hereinafter, sometimes abbreviated as "exposed portion"). In the PEB process, an acid generated from a photoacid generator in the exposed portion serves as an active species to promote a crosslinking reaction between the polyhydroxyamide compound or the compound containing a phenolic hydroxyl group and the crosslinking agent, thereby making the exposed portion insoluble in a developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be performed using a known method such as a hot plate or a heating furnace.

[0110] 6-4. Development Step The development step is a step in which the dried coating film heated in the PEB step is treated with a developer to obtain a patterned coating film. More specifically, the unexposed areas of the dried coating film are dissolved and removed in the developer to obtain a patterned coating film. As the development method, a known method can be used, and examples thereof include a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment.

[0111] Known developers can be used, and examples of such developers include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, water-soluble organic solvents such as methanol, ethanol, and isopropyl alcohol, and surfactants can be added.

[0112] After treatment with the developer, the coating film can be washed with a rinse solution as needed to obtain a patterned coating film. The rinse solution is not particularly limited, and examples thereof include pure water, methanol, ethanol, and isopropyl alcohol. These can be used alone or in combination in any ratio.

[0113] 6-5. Post-development heating step The post-development heating step is a step in which the patterned coating film formed in the development step is heated to complete curing of the patterned coating film and obtain a cured patterned coating film (cured product). The heating temperature can be 150 to 200°C, and the heating time can be 1 to 120 minutes. Heating can be performed by a known method such as a hot plate or an inert oven, and heating is preferably performed under a nitrogen atmosphere.

[0114] When the photosensitive resin composition of the present embodiment is a positive photosensitive resin composition, a dissolution inhibitor is used as a photoacid generator, and the coating film is treated with a developer in the development step, whereby the exposed areas of the dried coating film are dissolved and removed in the developer, thereby obtaining a patterned coating film.

[0115] 7. Uses of Compound and Photosensitive Resin Composition The compound, polyhydroxyamide compound, and photosensitive resin composition of this embodiment can be suitably used as materials for forming displays, semiconductor elements, electronic components, optical components, building materials, and the like. Materials for forming semiconductor elements include, for example, resist materials, buffer coating films, and insulating films for rewiring layers in wafer-level packages (WLP). Materials for forming electronic components include, for example, printed wiring boards, interlayer insulating films, and wiring coating films.

[0116] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the following. The components used in the examples and comparative examples are as follows.

[0117] <Compounds (hydroxycarboxylic acid compounds)> Compounds (hydroxycarboxylic acid compounds) were synthesized as follows: The raw material components, molar ratios added, and yields of each compound are shown in Table 1 below.

[0118] Synthesis Example 1: Compound (A-1) In a 120 mL vial equipped with a stirrer and a thermometer (room temperature), 6.13 g (40 mmol) of 4-amino-3-hydroxybenzoic acid (4A3HBA) was dissolved in 70.96 g of tetrahydrofuran (THF) and 3.48 g of pyridine with stirring for 15 minutes. The vial was then immersed in an ice bath, and while maintaining the temperature inside the vial at 0 to 5°C, 4.06 g (20 mmol) of isophthaloyl chloride (IPC) was added over 15 minutes, followed by stirring in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, water (100 ml) was added and the mixture was filtered to obtain compound (A-1).

[0119] (Synthesis Example 2: Compound (A-2)) Compound (A-2) was obtained in the same manner as in Synthesis Example 1, except that terephthaloyl chloride (TPC) was used instead of isophthaloyl chloride (IPC) and the molar ratios of the raw material components added were as shown in Table 1 below.

[0120] (Synthesis Example 3: Compound (A-3)) Compound (A-3) was obtained in the same manner as in Synthesis Example 1, except that 4,4′-oxybis(benzoyl chloride) (DEDC) was used instead of isophthaloyl chloride (IPC) and the molar ratios of the raw material components added were as shown in Table 1 below.

[0121] Synthesis Example 4: Compound (A-4) Compound (A-4) was obtained in the same manner as in Synthesis Example 1, except that 1,4-cyclohexanedicarbonyl chloride (CHDC) was used instead of isophthaloyl chloride (IPC) and the molar ratios of the raw material components added were as shown in Table 1 below.

[0122] Synthesis Example 5: Compound (A-5) Compound (A-5) was obtained in the same manner as in Synthesis Example 1, except that 3-amino-4-hydroxybenzoic acid (3A4HBA) was used instead of 4-amino-3-hydroxybenzoic acid (4A3HBA) and the molar ratios of the raw material components added were as shown in Table 1 below.

[0123] Synthesis Example 6: Compound (A-6) Compound (A-6) was obtained in the same manner as in Synthesis Example 1, except that 3-amino-4-hydroxybenzoic acid (3A4HBA) was used instead of 4-amino-3-hydroxybenzoic acid (4A3HBA), 4,4′-oxybis(benzoyl chloride) (DEDC) was used instead of isophthaloyl chloride (IPC), and the molar ratios of the raw material components added were as shown in Table 1 below.

[0124] Synthesis Example 7: Compound (A-7) Compound (A-7) was obtained in the same manner as in Synthesis Example 1, except that 3-amino-4-hydroxybenzoic acid (3A4HBA) was used instead of 4-amino-3-hydroxybenzoic acid (4A3HBA), 1,4-cyclohexanedicarbonyl chloride (CHDC) was used instead of isophthaloyl chloride (IPC), and the molar ratios of the raw material components added were as shown in Table 1 below.

[0125] The compounds (hydroxycarboxylic acid compounds) (A-1) to (A-7) obtained in the above synthesis examples were subjected to the following measurements and evaluations.

[0126] ( １ H-NMR Measurement) For the compounds (hydroxycarboxylic acid compounds) (A-1) to (A-7) obtained in the above Synthesis Examples, １ H-NMR measurement was carried out. A nuclear magnetic resonance spectrometer (JNM-ECA400II, manufactured by JEOL Ltd.) was used for the measurement. Figures 1 to 7 show the H-NMR spectra of each of the compounds (A-1) to (A-7). １ The H-NMR measurement results (NMR charts) and the positions of hydrogen atoms corresponding to the peaks in the NMR charts of the compounds (A-1) to (A-7) are shown.

[0127] As shown in Figs. １From the results of H-NMR measurement, it was possible to confirm that the compounds (A-1) to (A-7) were compounds having the structures of the respective chemical formulas (A-1) to (A-7).

[0128] (Evaluation of Solvent Solubility) Each of the compounds (hydroxycarboxylic acid compounds) (A-1) to (A-7) obtained in the above Synthesis Examples was mixed with N-methylpyrrolidone (NMP) or N,N-dimethylformamide (DMF) as a solvent to a concentration of 20% by mass, and the mixture was allowed to stand at 70°C for 1 hour, after which its solubility in the solvent was confirmed. The evaluation results are shown in Table 1 below. (Evaluation Criteria) A: Soluble in both NMP and DMF B: Insoluble in NMP and soluble in DMF, or soluble in NMP and insoluble in DMF C: Insoluble in both NMP and DMF

[0129] The molar ratios added in Table 1 represent the molar amounts when the amount of 4A3HBA or 3A4HBA charged is taken as 100 moles.

[0130] <Polyhydroxyamide Compounds> Polyhydroxyamide compounds (B-1) to (B-7) were synthesized as follows. The components and molar ratios of each polyhydroxyamide compound, as well as the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI) of the resulting polyhydroxyamide compounds (B-1) to (B-7) are shown in Table 2 below.

[0131] Synthesis Example 8: Polyhydroxyamide Compound (B-1) In a 50 mL vial equipped with a stirrer and a thermometer (room temperature), 2.15 g (4.07 mmol) of compound (A-6), 0.79 g (3.93 mmol) of 3,4'-diaminodiphenyl ether (3,4'-ODA), and 0.03 g (0.29 mmol) of 3-aminophenol (3AP) were dissolved in 11.6 g of N-methylpyrrolidone (NMP) with stirring for 30 minutes. The flask was then immersed in an ice bath, and while maintaining the temperature inside the flask at 0 to 5°C, 1.33 g (8.55 mmol) of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (EDAC) was added over 15 minutes, followed by stirring in the ice bath for 1 hour. After stirring for 18 hours at room temperature, the solution was poured into a large amount of methanol, and the precipitate was collected. The precipitated solid was collected and then dried under reduced pressure at 100° C. for 5 hours to obtain a polyhydroxyamide compound (B-1).

[0132] (Condensing agent) 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (EDAC)

[0133] (Polyhydroxyamide compound (B-1))

[0134] Regarding the polyhydroxy compound (B-1) and the components used in the synthesis of the polyhydroxy compound (B-1) {compound (A-6), 3,4'-ODA}, １ H-NMR measurement was carried out using the same apparatus as described above.

[0135] the above １ By H-NMR measurement, it was confirmed that in the NMR chart of polyhydroxy compound (B-1), the peaks corresponding to the amino group of 3,4′-ODA and the carboxy group of compound (A-6) disappeared, and peaks corresponding to the hydroxy group, amide group, and aromatic ring derived from compound (A-6) were present.

[0136] Synthesis Example 9: Polyhydroxyamide compound (B-2) Polyhydroxyamide compound (B-2) was obtained in the same manner as in Synthesis Example 8, except that 4,4'-methylenebis(2-ethyl-6-methylaniline) (2E6MA) was used instead of 3,4'-diaminodiphenyl ether (3,4'-ODA) and the molar ratios of the components added were as shown in Table 2 below.

[0137] (Polyhydroxyamide compound (B-2))

[0138] (Synthesis Example 10: Polyhydroxyamide compound (B-3)) Polyhydroxyamide compound (B-3) was obtained in the same manner as in Synthesis Example 8, except that 4,4'-methylenebis(2,6-diethylaniline) (DEMA) was used instead of 3,4'-diaminodiphenyl ether (3,4'-ODA) and the molar ratios of the components added were as shown in Table 2 below.

[0139] (Polyhydroxyamide compound (B-3))

[0140] (Synthesis Example 11: Polyhydroxyamide compound (B-4)) Polyhydroxyamide compound (B-4) was obtained in the same manner as in Synthesis Example 8, except that 3,4'-methylenedianiline (3,4'-MDA) was used instead of 3,4'-diaminodiphenyl ether (3,4'-ODA) and the molar ratios of the components added were as shown in Table 2 below.

[0141] (Polyhydroxyamide compound (B-4))

[0142] Synthesis Example 12 Polyhydroxyamide Compound (B-5) Polyhydroxyamide compound (B-5) was obtained in the same manner as in Synthesis Example 8, except that compound (A-5) was used instead of compound (A-6), 3,4'-methylenedianiline (3,4'-MDA) was used instead of 3,4'-diaminodiphenyl ether (3,4'-ODA), and the molar ratios of the components added were as shown in Table 2 below.

[0143] (Polyhydroxyamide compound (B-5))

[0144] Synthesis Example 13: Polyhydroxyamide Compound (B-6) In a 120 mL vial equipped with a stirrer and a thermometer (room temperature), 2,2-bis(3-amino-4-hydroxyphenyl)sulfone (SO ２ Using 6.85 g (24.4 mmol) of 3-aminophenol (3AP), 0.860 g (7.87 mmol) of 3-aminophenol (3AP) was dissolved in 35 g of N-methylpyrrolidone (NMP) with stirring. The vial was then immersed in an ice bath, and while maintaining the temperature inside the vial at 0 to 5°C, 7.54 g (25.5 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over 10 minutes, followed by stirring in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was poured into a large amount of ion-exchanged water, and the precipitate was recovered. The resulting solid was dissolved in 33 g of cyclopentanone. 5 g of anion-exchange resin (Organo Corporation, Amberlyst B-20) was added, and the mixture was stirred vigorously for 1 hour. The stirred solution was concentrated and then poured into a large amount of ion-exchanged water, and the precipitate was recovered. The precipitated solid was recovered and then dried under reduced pressure to obtain polyhydroxyamide compound (B-6).

[0145] (Polyhydroxyamide compound (B-6))

[0146] The molar ratios added in Table 2 represent mole % when the amount of compound (A-5), (A-6) or DEDC charged is taken as 100 mole %.

[0147] <Crosslinking agent> (C) MW-390 (hexamethoxymethyl melamine compound manufactured by Nippon Carbide Industries Co., Ltd.)

[0148] <Photoacid Generator> (D) PAG-103 (oxime sulfonate compound manufactured by BASF)

[0149] <Solvent> N-methylpyrrolidone (NMP) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0150] <Surfactant> BYK-310 (polyester-modified silicone surfactant manufactured by BYK-Chemie)

[0151] <Preparation of Photosensitive Resin Composition> Varnishes of the photosensitive resin composition of each Example and Comparative Example were obtained by blending the components in the amounts shown in Table 3 below and dissolving and adjusting the concentration of non-volatile components in the varnish to 30%. Note that, of the blending amounts of each component in Table 3 below, the blending amount of each component, excluding the blending amount of the solvent, indicates the solid content parts by mass.

[0152] <Evaluation> The photosensitive resin compositions obtained in the examples and comparative examples were subjected to the following evaluations. The results of the evaluations are shown in Table 3 below.

[0153] (Dissolution Contrast) The varnishes prepared in the Examples and Comparative Examples were applied to a silicon wafer using a spin coater and dried at 90°C for 3 minutes to obtain a dried film with a thickness of approximately 3 μm. A mask was placed over the obtained dried film, and a high-pressure mercury lamp was used to irradiate it with light having a wavelength of 365 nm at the exposure dose shown in Table 3 below. After post-exposure baking (PEB) under the conditions shown in Table 3 below, the film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) and rinsed with ion-exchanged water. The dissolution contrast was evaluated based on the following evaluation criteria. (Evaluation Criteria) A: The unexposed area was completely dissolved, and a residual film was found in the exposed area. B: Part of the unexposed area was not dissolved, and a residue was found. C: Both the exposed and unexposed areas were completely dissolved.

[0154]

[0155] The compound and polyhydroxyamide compound of the present invention are novel compounds that can be used in resin compositions such as photosensitive resin compositions, and can therefore be suitably used as forming materials for display devices, semiconductor elements, electronic components, optical components, building materials, etc. CROSS-REFERENCE TO RELATED APPLICATIONS

[0156] This application claims priority based on Japanese Patent Application No. 2024-024991, filed with the Japan Patent Office on February 21, 2024, the entire disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A compound represented by the following formula (1): (R in formula (1) is a divalent organic group.) 2. The compound according to claim 1, which is represented by the following formula (2): (R in formula (2) is a divalent organic group.) 3. The compound according to claim 1, which is represented by the following formula (3): (R in formula (3) is a divalent organic group.) 4. The compound of any one of claims 1 to 3, wherein R has an aromatic ring or an aliphatic ring.

5. The compound according to claim 4, wherein R is any one selected from the following formula (4): (* in formula (4) indicates a binding site.) 6. A polyhydroxyamide compound having a structural unit of the following formula (5): (R in formula (5) １ , R ２ are each independently a divalent organic group.

7. A photosensitive resin composition comprising the polyhydroxyamide compound according to claim 6.

8. A dry film comprising a resin layer formed from the photosensitive resin composition according to claim 7.

9. A cured product obtained by curing the photosensitive resin composition according to claim 7 or the resin layer of the dry film according to claim 8.

10. An electronic component comprising the cured product according to claim 9.

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