Polyhydroxyamide compound, curable resin composition, dry film, and cured product

Abstract

Provided are: a polyhydroxyamide compound that is capable of complying with PFAS regulations and exhibits excellent i-line transmittance; a curable resin composition containing the polyhydroxyamide compound; a dry film comprising a resin layer formed of the curable resin composition; and a cured product formed of the curable resin composition or the resin layer of the dry film. One embodiment of the present invention is a polyhydroxyamide compound containing structural units represented by formulas (1) and (2) and not having a perfluoroalkyl skeleton. (In formula (1), R1 is a divalent organic group, and R2 is a tetravalent organic group.) (In formula (2), R3 is a divalent organic group, and R4 is a divalent organic group not containing a hydroxyl group.)

Description

Polyhydroxyamide compounds, curable resin compositions, dry films, and cured products

[0001] This invention relates to polyhydroxyamide compounds, curable resin compositions, dry films, and cured products.

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

[0003] Conventionally, the increasing performance and miniaturization of electronic components and electrical equipment have necessitated the high integration of semiconductor devices. To meet this demand, high-performance and miniaturization technologies have been developed in the field of semiconductor device packaging, such as wafer-level packages. In insulating films used in redistribution layers, excellent resolution is required for the miniaturization of pattern formation.

[0004] Patent Document 1 discloses a photosensitive resin composition containing a polybenzoxazole precursor, a compound that generates acid upon irradiation with active light in a specific wavelength range, a crosslinkable or polymerizable compound, and a compound that generates acid upon heat. According to the disclosure in Patent Document 1, a negative-type photosensitive resin composition is provided that exhibits good sensitivity and resolution and provides chemical resistance, heat resistance, and mechanical properties.

[0005] Japanese Patent Publication No. 2012-203359

[0006] In recent years, perfluoroalkyl compounds (PFAS) and other permanent chemicals have been linked to health problems, leading to international discussions about regulating their use. The negative-type photosensitive resin composition described in Patent Document 1 may contain a perfluoroalkyl skeleton in its polybenzoxazole precursor and may be subject to PFAS regulations. In the future, there will be a need for photosensitive resin compositions that can comply with PFAS regulations.

[0007] However, the perfluoroalkyl skeleton can improve the i-ray transmittance of polybenzoxazole precursors due to its high electron-withdrawing properties and bulky structure. Photosensitive resins that can comply with PFAS regulations tend to have lower i-ray transmittance compared to photosensitive resins with a perfluoroalkyl skeleton, and when used as a photosensitive resin composition, they tend to make it difficult to form patterned resin films of the desired shape.

[0008] The present invention addresses the above-mentioned problems and aims to provide a polyhydroxyamide compound that can comply with PFAS regulations and exhibits excellent i-ray permeability; a curable resin composition containing the polyhydroxyamide compound; a dry film having a resin layer formed by the curable resin composition; and a cured product formed by the curable resin composition or the resin layer of the dry film.

[0009] One aspect of the present invention is a polyhydroxyamide compound. This polyhydroxyamide compound comprises the structural units of the following formulas (1) and (2) and does not have a perfluoroalkyl skeleton. {In formula (1), R １ R is a divalent organic group. ２ It is a tetravalent organic group. {In formula (2), R ３ R is a divalent organic group. ４ It is a divalent organic group that does not contain a hydroxyl group.

[0010] In the polyhydroxyamide compound of the above embodiment, the R ４ However, it is preferable that it contains an aromatic ring or an aliphatic ring.

[0011] Another aspect of the present invention is a curable resin composition. This curable resin composition comprises the polyhydroxyamide compound of the above aspect, a crosslinking agent, and a photoacid generator.

[0012] Another aspect of the present invention is a dry film, which comprises a resin layer formed from the curable resin composition of the above aspect.

[0013] Another aspect of the present invention is a cured product. The cured product is formed by the curable resin composition of the above aspect or the resin layer of the dry film of the above aspect.

[0014] Another aspect of the present invention is an electronic component. The electronic component has the cured product of the above aspect.

[0015] According to the present invention, a polyhydroxyamide compound that can comply with PFAS regulations and exhibits excellent i-line transparency; a curable resin composition containing the polyhydroxyamide compound; a dry film having a resin layer formed by the curable resin composition; a cured product formed by the curable resin composition or the resin layer of the dry film; can be provided.

[0016] 1H-NMR measurement results (NMR charts) of the polyhydroxyamide compounds (A-1) to (A-2) synthesized in Synthesis Examples 1 to 2 and the polyhydroxyamide compound (A-8) synthesized in Synthesis Example 8. １ 1H-NMR measurement results (NMR charts) of the polyhydroxyamide compounds (A-3) to (A-5) synthesized in Synthesis Examples 3 to 5 and the polyhydroxyamide compound (A-8) synthesized in Synthesis Example 8 are shown. １ 1H-NMR measurement results (NMR charts) of the polyhydroxyamide compounds (A-6) to (A-7) synthesized in Synthesis Examples 6 to 7 and the polyhydroxyamide compound (A-8) synthesized in Synthesis Example 8 are shown. １ 1H-NMR measurement results (NMR charts) are shown.

[0017] Hereinafter, embodiments of the disclosed technology will be described in detail. In this specification, the notation "a to b" in the description of a numerical range represents a to b unless otherwise specified.

[0018] In this specification, when a plurality of upper limit values and a plurality of lower limit values are separately described, all numerical ranges that can be freely combined and set by these upper limit values and lower limit values are described in this specification.

[0019] In this specification, when a certain compound is described, its stereoisomers are also described unless otherwise specified.

[0020] The "substituent" is not particularly limited, and unless otherwise specified, for example, it may be a hydroxyl group, a phenol group, a phenoxy group, an alkoxy 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, etc.

[0021] The "aromatic ring" is not particularly limited, and unless otherwise specified, it includes heterocyclic rings.

[0022] In this specification, the solid content means the components constituting the curable resin composition or the composition other than the solvent (especially organic solvent) of each raw material, and is based on mass unless otherwise specified.

[0023] 1. Polyhydroxyamide compound The polyhydroxyamide compound of this embodiment contains structural units of the following formulas (1) and (2) and does not have a perfluoroalkyl skeleton. {In formula (1), R １ is a divalent organic group, and R ２ is a tetravalent organic group.} {In formula (2), R ３ is a divalent organic group, and R ４ is a divalent organic group that does not contain a hydroxyl group.}

[0024] R in formula (1) １ is not particularly limited as long as it is a divalent organic group, and for example, it may be a divalent organic group containing an aromatic hydrocarbon group (arylene group), an aliphatic hydrocarbon group (alkylene group, cycloalkylene group), an ether group, a ketone group, an ester group, etc.

[0025] R in formula (1) １Among the divalent organic groups described above, it is preferable that the group has an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of divalent organic groups having an aromatic hydrocarbon group include divalent organic groups having structures such as a biphenyl skeleton, a diphenyl ether skeleton, a benzophenone skeleton, a diphenylethane skeleton, a diphenylpropane skeleton, a diphenyl sulfone skeleton, and a benzene skeleton. Examples of divalent organic groups having an aliphatic hydrocarbon group include divalent organic groups having structures such as 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, and a dicyclopentadiene skeleton. These skeletons may or may not have substituents.

[0026] From the viewpoint of resolution of curable resin compositions, R １ The number of carbon atoms is preferably 4 to 30, R １ It is preferable that the polyhydroxyamide compound has a benzene skeleton, a biphenyl skeleton, or a diphenyl ether skeleton and is a divalent organic group without substituents. １ It is also possible to include two or more of the groups exemplified above.

[0027] R in equation (1) ２ The organic group is not particularly limited as long as it is a tetravalent organic group, for example, a tetravalent aromatic hydrocarbon group is preferred. Examples of tetravalent aromatic hydrocarbon groups include tetravalent aromatic hydrocarbon groups having structures such as a biphenyl skeleton, diphenyl ether skeleton, diphenyl thioether skeleton, benzophenone skeleton, diphenylmethane skeleton, diphenylpropane skeleton, diphenyl sulfoxide skeleton, diphenyl sulfone skeleton, and benzene skeleton. These skeletons may or may not have substituents. Among these, an organic group having the structure shown in formula (3) below is more preferred from the viewpoint of obtaining a curable resin composition with excellent resolution. {In equation (3), * indicates a bonding site.}

[0028] The hydroxyl group in formula (1) is not particularly limited, but is preferably an alcoholic hydroxyl group or a phenolic hydroxyl group. From the viewpoint of improving the developability of the curable resin composition, it is more preferably a phenolic hydroxyl group.

[0029] R in equation (2) ３ The divalent organic group is not particularly limited and may include, 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, and the like.

[0030] R in equation (2) ３ It is preferable that the divalent organic group has an aromatic hydrocarbon group or an aliphatic hydrocarbon group among the divalent organic groups described above. Examples of divalent organic groups having an aromatic hydrocarbon group include divalent organic groups having structures such as a biphenyl skeleton, a diphenyl ether skeleton, a benzophenone skeleton, a diphenylethane skeleton, a diphenylpropane skeleton, a diphenyl sulfone skeleton, and a benzene skeleton. Examples of divalent organic groups having an aliphatic hydrocarbon group include divalent organic groups having structures such as 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, and a dicyclopentadiene skeleton. These skeletons may or may not have substituents. R in formula (2) ３ It is preferable that the group is a divalent organic group that does not contain a hydroxyl group. In other words, it is preferable that formula (2) as a whole does not contain a hydroxyl group.

[0031] From the viewpoint of resolution of curable resin compositions, R ３ The number of carbon atoms is preferably 4 to 30, R ３ It is preferable that the polyhydroxyamide compound has a benzene skeleton, a biphenyl skeleton, or a diphenyl ether skeleton and is a divalent organic group without substituents. ３ It is also possible to include two or more of the groups exemplified above.

[0032] R in equation (2) ４The group is not particularly limited as long as it is a divalent organic group that does not contain a hydroxyl group, and may include, for example, aromatic hydrocarbon groups (arylene groups), aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups), ether groups, ketone groups, ester groups, sulfonyl groups, triazine rings, triazole rings, siloxane bonds, etc. Among the above, it is preferable that it contains an aromatic ring or an aliphatic ring. More specifically, it is preferable that it has a structure such as fluorene, biphenyl, diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenyl sulfoxide, diphenyl sulfone, benzene, 2-methyl-1,3,5-triazine, 2-phenyl-1,3,5-triazine, bicyclohexyl, dicyclohexylmethane, 1,1,3,3-tetramethyl-1,3-dipropyldisiloxane, etc. Each structure may or may not have substituents.

[0033] From the viewpoint of resolution of curable resin compositions, R ４ The carbon number is preferably 1 to 30. In particular, it is more preferable that it be one of the organic groups shown in formula (4) below. {In equation (4), * indicates a bonding site.}

[0034] Furthermore, within the molecule of the polyhydroxyamide compound, R １ , R ２ , R ３ and R ４ It is also possible to include two or more of the groups exemplified above. １ , R ２ , R ３ and R ４ These may have the same structure or different structures.

[0035] The polyhydroxyamide compound of this embodiment is thought to have excellent i-ray transmittance because it has the structure of formula (2) in addition to the structure of formula (1). The mechanism is not clear, but it is presumed to be as follows. The structure represented by formula (1) has a hydroxyl group and therefore tends to have low i-ray transmittance. In particular, when the hydroxyl group is a phenolic hydroxyl group, the conjugation length of the structure shown in formula (1) becomes longer, causing the light absorption to shift to longer wavelengths, which tends to lower i-ray transmittance. On the other hand, the R of formula (2) ４ The structure represented by formula (2) does not have a hydroxyl group, so it tends to have relatively high i-ray permeability. Therefore, it is presumed that having the structure represented by formula (2) improves the i-ray permeability of polyhydroxyamide compounds.

[0036] The polyhydroxyamide compound of this embodiment does not have a perfluoroalkyl skeleton in its structure. Therefore, it can comply with PFAS regulations. In this embodiment, the perfluoroalkyl skeleton is defined as a structure in which all hydrogen atoms on the alkyl chain (alkyl skeleton) are replaced with fluorine atoms. ２ ) ｎ This represents a skeleton (where n is an integer greater than or equal to 1), such as a trifluoromethyl group.

[0037] Polyhydroxyamide compounds may have alkali-soluble groups at their terminal ends. The alkali-soluble groups at the terminal ends are not particularly limited and include functional groups such as alcoholic hydroxyl groups, phenolic hydroxyl groups, acid anhydride groups, carboxyl groups, sulfonic acid groups, sulfonamide groups, and active methylene groups. From the viewpoint of solubility in developing solutions, it is preferable to have carboxyl groups or phenolic hydroxyl groups.

[0038] Of these alkali-soluble groups, phenolic hydroxyl groups are particularly preferred. When the polyhydroxyamide compound has phenolic hydroxyl groups at its termini, the solubility of the polyhydroxyamide compound in the developer can be improved. Furthermore, since phenolic hydroxyl groups are less reactive than carboxyl groups, excessive reaction with the crosslinking agent is suppressed, and the solubility of the unexposed areas in the developer can be maintained even after the PEB process. This is presumed to provide a negative-type curable resin composition with excellent resolution.

[0039] The alkali-soluble groups contained at the ends of these polyhydroxyamide compounds may be present as residues of the monomers constituting the polyhydroxyamide compound, or as terminal structures introduced by a terminal encapsulant having alkali-soluble groups. Preferably, the alkali-soluble groups contained at the ends of the polyhydroxyamide compounds are present as terminal structures introduced by a terminal encapsulant having alkali-soluble groups.

[0040] Examples of end-capturing agents are not particularly limited and 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 anhydrides and 5-norbornene-2,3-dicarboxylic acid anhydrides.

[0041] The polyhydroxyamide compound may contain two or more repeating structures of formula (1) or (2) above. It may also contain structures other than the repeating structures of formula (1) or (2) above. For example, it may contain a repeating structure of polyamic acid. Preferably, the polyhydroxyamide compound consists substantially only of the repeating structures of formula (1) and (2) above.

[0042] The molar ratio of the structure represented by formula (1) to the structure represented by formula (2) can be, for example, 1:99 to 99:1. From the viewpoint of obtaining a polyhydroxyamide compound with excellent solvent solubility, it is preferably 99:1 to 50:50, and from the viewpoint of obtaining a polyhydroxyamide compound with excellent alkali solubility, it is preferably 99:1 to 80:20.

[0043] The weight-average molecular weight (Mw) of the polyhydroxyamide compound is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 3,000 to 12,000, and particularly preferably 4,000 to 10,000. By setting the molecular weight within this range, it becomes possible to form a finer L / S pattern with a higher aspect ratio.

[0044] The number-average molecular weight (Mn) of the polyhydroxyamide compound is preferably 1,000 to 10,000, and more preferably 1,500 to 6,000.

[0045] The molecular weight dispersibility (PDI) of the polyhydroxyamide compound is preferably 1.5 to 5.0, and more preferably 1.5 to 4.5. The molecular weight dispersibility (PDI) is calculated by the following formula: PDI = Mw / Mn

[0046] When the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight dispersion (PDI) of the polyhydroxyamide compound fall within a specified range, a suitable balance is achieved between solubility in the developer in the unexposed area and reaction with the crosslinking agent during exposure, resulting in a curable resin composition with superior resolution.

[0047] In this specification, the weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC) (GL7700, GL Sience, Inc.) and converted to standard polystyrene values. The specific measurement conditions are as follows:

[0048] Column: TSKgelαM (manufactured by Tosoh Corporation) Column temperature: 40°C Eluent composition: 100 mmol / L H ３ PO ４ (H ３ PO４ (85% aqueous solution used as raw material) and NMP solution containing 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 (approx. 25°C) Baseline range during analysis: 15-40 minutes Molecular weight calculation range during analysis: 20-35 minutes

[0049] Polyhydroxyamide compounds may be used individually or in combination of two or more.

[0050] One example of a method for producing polyhydroxyamide compounds is a copolymerization of a dihydroxydiamino compound represented by formula (5), a dicarbonyl dichloride compound represented by formula (6), and a diamine compound represented by formula (7) as raw materials. {In formula (5), R ２ This is as stated above. {In formula (6), R １ , R ３ This is as stated above. {In formula (7), R ４ This is as stated above.

[0051] The dihydroxydiamino compound represented by formula (5) above is not particularly limited, and examples include 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, and bis(3-amino-4-hydroxyphenyl)sulfone.

[0052] The dicarbonyl dichloride compound represented by formula (6) is not particularly limited and includes isophthalic acid chloride, terephthalic acid chloride, phthaloyl chloride, 4,4'-oxybis(benzoyl chloride), 4,4'-biphenyl dicarbonyl chloride, dodecanedioyl chloride, suberic acid chloride, succinate chloride, adipic acid chloride, and the like.

[0053] The diamine compound represented by formula (7) above is not particularly limited and any known diamine compound can be used, for example, 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diaminodiphenyl ether, 4,4'-diaminodicyclohexylmethane (DCHM), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3,3'-oxydianiline, 2,7-diaminofluorene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-methylenebis(2,6-dimethylaniline). Examples include 4,4'-methylenebis(2-ethyl-6-methylaniline) (2E6MA), 4,4'-ethylenedianiline, diethylenetriamine, 1,12-diaminododecane, 1,11-diaminoundecane, 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, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene (BTFL), and 1,3-bis(3-aminopropyl)tetramethyldisiloxane. As described above, there are many types of diamine compounds represented by formula (7). Therefore, according to this embodiment, a wide variety of polyhydroxyamide compounds can be produced, and polyhydroxyamide compounds with various properties can be obtained.

[0054] The diamine compound represented by formula (7) above is preferably one of DCHM, 2E6MA, or BTFL, as shown in formula (8) below, among those mentioned above.

[0055] Other compounds that can copolymerize with the above-mentioned compounds may also be copolymerized. Examples of other copolymerizable compounds include diol compounds, acid dianhydrides, and diisocyanate compounds.

[0056] 2. Curable Resin Composition The curable resin composition of this embodiment contains the polyhydroxyamide compound described above. The polyhydroxyamide compound of this embodiment can be used in both negative and positive curable resin compositions.

[0057] The curable resin composition of this embodiment preferably contains a crosslinking agent and a photoacid generator. It may also further contain a basic compound.

[0058] 2-1. Crosslinking Agent The crosslinking agent is not particularly limited and any known agent can be used, for example, melamine compounds, guanamine compounds, triazine compounds, epoxy compounds, oxetane compounds, isocyanate compounds, oxazoline compounds, etc. The crosslinking agent is preferably a compound having at least one selected from the group consisting of methoxymethyl groups and methylol groups. These functional groups undergo a crosslinking reaction with phenolic hydroxyl groups and carboxyl groups contained in polyhydroxyamide compounds, etc., upon heating, using the acid generated from the photoacid generator described later as the active species. As a result, negative-type photolithography (pattern formation) is achieved by exposure, PEB, and development. Furthermore, by heating after pattern formation, the curing reaction of the curable resin composition proceeds, and excellent properties as a cured product are exhibited.

[0059] The crosslinking agent preferably contains a heterocycle to improve the resolution of the curable resin composition. 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, and tin, and includes saturated or unsaturated rings of three, four, five, six, seven, or eight members. From the viewpoint of the resolution of the curable resin composition, a heterocycle containing nitrogen is preferred, and a heterocycle containing multiple nitrogen atoms is more preferred.

[0060] Specifically, compounds having a triazine structure such as hexamethylolmelamine and hexamethoxymethylmelamine, compounds having a guanamine structure such as tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanamine, compounds having a glycoluryl structure such as tetramethylol glycoluryl and tetramethoxyglycoluryl, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone are more preferred.

[0061] 2-2. Photoacid Generator The photoacid generator is not particularly limited as long as it is a compound that generates acid upon irradiation with light such as ultraviolet light or visible light. Examples 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-oxyamide sulfonates, aromatic N-oxyimide sulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimide, and benzoquinone diazosulfonic acid esters. These can be used individually or in combination in any ratio. From the viewpoint of achieving better resolution, the photoacid generator is preferably an oxime sulfonate compound. Examples of oximesulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF, with those containing the structure of the following formula (9) being particularly preferred. {In formula (9), X is a hydrocarbon group or halogen atom, m is an integer from 0 to 3, R ５ This is an organic group containing a hydrogen atom, a hydrocarbon group, a ketone group, or a halogen atom.

[0062] In formula (9) above, X is not particularly limited and can be, for example, a hydrocarbon group (e.g., alkyl group, alkenyl group, alkynyl group, aryl group, etc.) or a halogen atom. The hydrocarbon group may have substituents and can have a linear, branched, or cyclic structure. Linear or branched hydrocarbon groups having 1 to 4 carbon atoms are preferably used. As the halogen atom, a chlorine atom or a fluorine atom is preferably used.

[0063] In formula (9) above, m represents an integer from 0 to 3, preferably 0 or 1. When m is 2 or 3, the multiple X values ​​may be the same or different.

[0064] R in equation (9) above ５ It is preferable that the halogen atom be a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom. The hydrocarbon group (e.g., alkyl group, alkenyl group, alkynyl group, aryl group, etc.) may be unsubstituted, or it may be substituted with a halogen atom.

[0065] The hydrocarbon group is preferably linear, branched, or cyclic with 1 to 20 carbon atoms, and more preferably linear, branched, or cyclic with 1 to 10 carbon atoms. The halogen atom may be a chlorine atom or a fluorine atom.

[0066] 2-3. Basic Compounds The curable resin composition of this embodiment may contain basic compounds. In particular, when the curable resin composition of this embodiment contains basic compounds, it is possible to suppress the diffusion of acid generated from the photoacid generator to the unexposed areas due to exposure, thereby improving resolution and preventing the formation of development residue in the unexposed areas after development.

[0067] The basic compounds are not particularly limited, and include, for example, trimethylamine, diethylamine, triethylamine, N,N-diisopropylethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, trybenzylamine, 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 include urea compounds such as urea; 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 can be used individually or in combination in any ratio. Among these, amine compounds are preferred, alcohol amines such as N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine are more preferred, and diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine are even more preferred.

[0068] 2-4. Solvents The curable resin composition of this embodiment may contain a solvent. The solvent is not particularly limited and examples include ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethyl sulfone, pyridine, and the like.

[0069] 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.

[0070] 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.

[0071] Ketones include methyl ethyl ketone; methyl isobutyl ketone (4-methyl-2-pentanone); 2-heptanone; cycloalkanones, which are monoketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone; and cycloalkanones, which are diketones 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-oxotiane, and dihydrolevogluconocene.

[0072] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0073] 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.

[0074] These solvents can be used individually or in combination in any ratio. Among these solvents, lactones or cyclic ketones are preferred from the viewpoint of excellent affinity with each component in the curable resin composition, and γ-butyrolactone or cyclopentanone are preferred. Furthermore, from the viewpoint of excellent solvent removal during drying of the curable resin composition and suitability for the edge rinsing process in semiconductor manufacturing, cyclic ketones are preferred, monoketone cycloalkanones are more preferred, and cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone are even more preferred, and cyclopentanone is particularly preferred.

[0075] 2-5. Other Components The curable resin composition of this embodiment may contain other components as long as they do not impair the effects of the disclosed technology. Other components may include known components that can be included in a curable resin composition, such as fillers, adhesives, surfactants, plasticizers, thermoacid generators, sensitizers, leveling agents, colorants, fibers, fine particles, etc.

[0076] The surfactant is not particularly limited and examples include fluorine-based surfactants and silicone-based surfactants. Commercially available fluorine-based surfactants include the "MegaFac" series from 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.). Examples of commercially available silicone-based surfactants include the surface modifier series from BYK-Chemie Co., Ltd. (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 individually or in combination of two or more types.

[0077] 3. Preparation of Curable Resin Composition The curable resin composition of this embodiment can be obtained by mixing the polyhydroxyamide compound described above with any other components, including crosslinking agents, photoacid generators, and basic compounds. The mixing of each component can be carried out under heating as needed.

[0078] 3-1. Polyhydroxyamide Compounds The content of polyhydroxyamide compounds can be 50 to 80% by mass, when the total mass of the solids in the curable resin composition is taken as 100% by mass.

[0079] 3-2. Crosslinking Agent The crosslinking agent content can be 5 to 80 parts by mass, based on 100 parts by mass of the solid content of the polyhydroxyamide compound in the curable resin composition. Furthermore, if the crosslinking agent has methoxymethyl groups and / or methylol groups, the ratio of the number of methoxymethyl groups and / or methylol groups in the crosslinking agent to the number of phenolic hydroxyl groups in the curable resin composition (methoxymethyl groups and / or methylol groups: phenolic hydroxyl groups) can be set to 120:100 to 200:100. By using such a ratio, the resolution of the curable resin composition can be improved.

[0080] 3-3. Photoacid Generator The amount of photoacid generator can be 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, when the solid content mass of the polyhydroxyamide compound in the curable resin composition is 100 parts by mass.

[0081] 3-4. Basic Compounds When basic compounds are added, the content can be 0.01 to 1.0 parts by mass, and preferably 0.05 to 0.50 parts by mass, based on 100 parts by mass of the solid content of the polyhydroxyamide compound in the curable resin composition. By setting the content within this range, it becomes easier to suppress the generation of development residue in the unexposed areas after developing the curable resin composition.

[0082] 4. Dry Film The dry film of this embodiment comprises a substrate and a resin layer formed on the substrate using the curable resin composition of this embodiment. Furthermore, a protective film may be laminated on the surface of the resin layer to protect the resin layer.

[0083] The resin layer can be obtained, for example, by applying a curable 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, or spray coater, and then drying it. The thickness of the resin layer is not particularly limited and can be 1 to 150 μm depending on the application.

[0084] The substrate is not particularly limited and examples include metal foils such as copper foil; and films such as polyimide film, polyester film, and polyethylene naphthalate (PEN) film.

[0085] 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 in which the adhesion between the protective film and the resin layer is lower than the adhesion between the substrate and the resin layer. 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 with a release treatment applied to its surface can be used.

[0086] 5. Cured Product The cured product of this embodiment is obtained by curing the resin layer of the curable resin composition or dry film described above. The cured product may be a patterned cured product. A method for manufacturing a patterned cured product will be described below, using the case of a negative-type curable resin composition as an example.

[0087] 5-1. Drying Film Formation Process The drying film formation process involves applying the above-mentioned curable resin composition onto a substrate to form a film, and then drying it. The drying film formation process can also be carried out by laminating a resin layer of dry film onto the substrate to form a dried film on the substrate.

[0088] The method for applying the curable resin composition to the substrate is not particularly limited and can include, for example, application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, spray coating with a spray coater, or inkjet method. The coating film thickness 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, it becomes possible to create finer L / S patterning while maintaining the aspect ratio of the pattern.

[0089] The method for drying the coating film is not particularly limited and includes, for example, forced-air drying, heating drying using an oven or hot plate, and vacuum drying. When heating drying is performed, the conditions are, for example, a heating temperature of 70 to 140°C and a drying time of 1 to 30 minutes.

[0090] The lamination of the dry film resin layer onto the substrate is preferably carried out under pressure and heat using a vacuum laminator or the like. The heating temperature can be, for example, 60 to 100°C.

[0091] The substrate is not particularly limited and can be, for example, a printed circuit board, a flexible printed circuit board, or a wafer on which semiconductor elements are formed.

[0092] 5-2. Exposure Process The exposure process involves irradiating the dried coating formed in the drying coating formation process with active energy rays through a photomask capable of forming a desired pattern, thereby exposing the photoacid generator in the exposed area and generating active species. If patterning is not required, a photomask is not necessary. Alternatively, the pattern may be drawn directly with a laser using a direct drawing device.

[0093] The wavelength of the activation energy ray used is one that can activate the photoacid generator, and for fine patterning, a maximum wavelength of 410 nm or less is preferable. The irradiation energy can be adjusted depending on the thickness of the formed dry coating, for example, 10 to 1500 mJ / cm². ２This can be done. As the exposure light source, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, mercury short-arc lamps, KRF lasers, etc., can be used.

[0094] 5-3. PEB Process The PEB process is a process in which a dried coating film made of a curable resin composition exposed in the exposure process is heat-treated to impart developability to the exposed portion of the dried coating film (hereinafter sometimes abbreviated as the exposed portion). In the PEB process, the acid generated from the photoacid generator in the exposed portion acts as an active species, and a crosslinking reaction proceeds between the polyhydroxyamide compound or a compound containing a phenolic hydroxyl group and a crosslinking agent, making the exposed portion insoluble in the 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 carried out by known methods such as a hot plate or a heating furnace.

[0095] 5-4. Development Process The development process involves treating the dried coating film heated in the PEB process with a developer to obtain a patterned coating film. More specifically, the patterned coating film can be obtained by dissolving and removing the unexposed parts of the dried coating film with the developer. Known methods can be used for development, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment.

[0096] Known developers can be used, such as aqueous solutions of inorganic alkalis like sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia; organic amines like ethylamine, diethylamine, triethylamine, and triethanolamine; and quaternary ammonium salts like tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, water-soluble organic solvents or surfactants such as methanol, ethanol, and isopropyl alcohol can be added. Furthermore, organic solvents such as ketone solvents like cyclopentanone and cyclohexanone, ester solvents like propylene glycol monomethyl acetate and butyl acetate, and ether solvents like propylene glycol monomethyl ether can also be preferably used as developers.

[0097] After treatment with a developing solution, the coating can be washed with a rinsing solution as needed to obtain a patterned coating. The rinsing solution is not particularly limited and includes pure water, methanol, ethanol, isopropyl alcohol, etc. These can be used individually or in any combination in any ratio.

[0098] 5-5. Post-development heating step The post-development heating step is a step in which the pattern coating film formed in the development step is heated to complete the curing of the pattern coating film and obtain a cured pattern 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 carried out by known methods such as a hot plate or an inert oven, and it is preferable to heat under a nitrogen atmosphere.

[0099] Furthermore, if the curable resin composition in this embodiment is a positive-type curable resin composition, a patterned coating can be obtained by using a dissolution inhibitor as a photoacid generator and treating the coating film with a developer solution in the development step, thereby dissolving and removing the exposed areas of the dried coating film with the developer solution.

[0100] 6. Applications of the Curable Resin Composition The curable resin composition of this embodiment can be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, etc. Forming materials for semiconductor elements include, for example, resist materials, buffer coating films, and insulating films for redistribution layers of wafer-level packages (WLPs). Forming materials for electronic components include, for example, printed circuit boards, interlayer insulating films, and wiring coating films.

[0101] 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.

[0102] <Polyhydroxyamide Compounds (A)> Polyhydroxyamide compounds A-1 to A-8 were synthesized as described below. The constituent components, molar ratio of each polyhydroxyamide compound, and the weight-average molecular weight, number-average molecular weight, and molecular weight dispersion of the obtained polyhydroxyamide compounds A-1 to A-8 are shown in Table 1.

[0103] (Synthesis Example 1: Polyhydroxyamide Compound (A-1)) (Mn: 2,800, Mw: 8,400) In a 120 mL vial equipped with a stirrer and thermometer (at room temperature), 2.27 g (8.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 0.28 g (0.98 mmol) of 4,4'-methylenebis(2-ethyl-6-methylaniline) (2E6MA), and 0.33 g (3.05 mmol) of 3-aminophenol (3AP) were dissolved by stirring in 20.9 g of N-methylpyrrolidone (NMP) for 15 minutes. Subsequently, the vial was immersed in an ice bath, and while maintaining the temperature inside the vial at 0-5°C, 3.02 g (10.22 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over 10 minutes, and the mixture was stirred in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was added to a large volume of deionized water, and the precipitate was collected. The obtained solid was dissolved in 6.0 g of tetrahydrofuran. 2.5 g of anion exchange resin (Organo Amberlist B-20) was added, and the mixture was vigorously stirred for 1 hour. After concentrating the stirred solution, it was added to a large volume of deionized water, and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain polyhydroxyamide compound (A-1) (BAP-2E6MA-DEDC-3AP).

[0104] (Synthesis Example 2: Polyhydroxyamide Compound (A-2)) Polyhydroxyamide compound (A-2) was obtained in the same manner as in Synthesis Example 1, except that the molar ratios of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 4,4'-methylenebis(2-ethyl-6-methylaniline) (2E6MA), 3-aminophenol, and 4,4'-oxybis(benzoyl chloride) (DEDC) were as shown in Table 1.

[0105] (Synthesis Example 3: Polyhydroxyamide Compound (A-3)) (Mn: 4,000, Mw: 8,700) Polyhydroxyamide compound (A-3) (BAP-BTFL-DEDC-3AP) was obtained in the same manner as in Synthesis Example 1, except that 0.37 g (0.98 mmol) of 9,9-bis(4-amino-3-methylphenyl)fluorene (BTFL) was used instead of 4,4'-methylenebis(2-ethyl-6-methylaniline) (2E6MA), and 2.27 g (8.80 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 0.34 g (3.10 mmol) of 3-aminophenol (3AP), 11.2 g of N-methylpyrrolidone (NMP), and 3.02 g (10.22 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC).

[0106] (Synthesis Examples 4-5: Polyhydroxyamide Compounds (A-4) to (A-5)) Polyhydroxyamide compounds (A-4) to (A-5) were obtained in the same manner as in Synthesis Example 3, except that the molar ratios of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 9,9-bis(4-amino-3-methylphenyl)fluorene (BTFL), 3-aminophenol (3-AP), and 4,4'-oxybis(benzoyl chloride) (DEDC) were as shown in Table 1.

[0107] (Synthesis Example 6: Polyhydroxyamide Compound (A-6)) (Mn: 4,300, Mw: 11,000) In a 120 mL vial equipped with a stirrer and thermometer (at room temperature), 0.20 g (0.95 mmol) of 4,4'-diaminodicyclohexylmethane (DCHM) and 1.9 mL of pyridine were dissolved in 14.0 g of N-methylpyrrolidone (NMP) with stirring for 15 minutes. Then, the vial was immersed in an ice bath, and while maintaining the temperature inside the vial at 0-5°C, 3.10 g (10.52 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added in solid form over 10 minutes, and the mixture was stirred in the ice bath for 30 minutes. After stirring at room temperature for 5 hours, 0.79 g (7.28 mmol) of 3-aminophenol (3AP) and 2.20 g (8.53 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) dissolved in 4.7 g of N-methylpyrrolidone (NMP) were added. After stirring at room temperature for 18 hours, the solution was poured into a large volume of deionized water and the precipitate was collected. The obtained solid was dissolved in 6.0 g of tetrahydrofuran. 2.5 g of anion exchange resin (Organo Amberlist B-20) was added, and the mixture was vigorously stirred for 1 hour. After concentrating the stirred solution, it was poured into a large volume of deionized water and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain polyhydroxyamide compound (A-6) (BAP-DCHM-DEDC-3AP).

[0108] (Synthesis Example 7: Polyhydroxyamide Compound (A-7)) (Mn: 2,900, Mw: 7,400) Polyhydroxyamide compound (A-7) was obtained in the same manner as in Synthesis Example 6, except that the molar ratios of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 4,4'-diaminodicyclohexylmethane (DCHM), 3-aminophenol (3AP), and 4,4'-oxybis(benzoyl chloride) (DEDC) were as shown in Table 1.

[0109] (Synthesis Example 8: Polyhydroxyamide Compound (A-8)) (Mn: 2,600, Mw: 8,100) In a 120 mL vial equipped with a stirrer and thermometer (at room temperature), 6.32 g (24.5 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) and 0.83 g (7.58 mmol) of 3-aminophenol (3AP) were dissolved by stirring in 35 g of N-methylpyrrolidone (NMP) for 15 minutes. Then, the vial was immersed in an ice bath, and while maintaining the temperature inside the vial at 0-5°C, 7.54 g (25.5 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over 10 minutes, and the mixture was stirred in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was added to a large amount of deionized water, and the precipitate was collected. The obtained solid was dissolved in 30 g of tetrahydrofuran. 7.5 g of anion exchange resin (Organo Amberlist B-20) was added to this mixture and vigorously stirred for 1 hour. After concentrating the stirred solution, it was added to a large amount of deionized water and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyhydroxyamide compound (A-8) (BAP-DEDC-3AP).

[0110] The following measurements and evaluations were performed on each of the polyhydroxyamide compounds (A-1) to (A-8) obtained in the above synthesis example.

[0111] ( １ (H-NMR measurement) For each polyhydroxyamide compound (A-1) to (A-8) obtained in the above synthesis example, １ 1H-NMR measurements were performed. A nuclear magnetic resonance spectrometer (JEOL Ltd., JNM-ECA400II) was used for the measurements.

[0112] Figure 1 shows the respective polyhydroxyamide compounds (A-1) to (A-2) and (A-8). １ The 1H-NMR measurement results (NMR chart) are shown in Figure 2. １ The 1H-NMR measurement results (NMR charts) are shown. Figure 3 shows the 1H-NMR measurement results (NMR charts) for each polyhydroxyamide compound (A-6) to (A-7) and (A-8).

[0113] Figures 1-3 are shown below. １ From the 1H-NMR measurement results, it was confirmed that each polyhydroxyamide compound (A-1) to (A-8) is a compound having the structure of the chemical formula described above.

[0114] (Evaluation of i-line transmittance) Using the polyhydroxyamide compound obtained in the above synthesis example, a cyclopentanone solution with a solid content of 20% by mass was prepared, and it was spin-coated onto quartz glass so that the film thickness after drying would be 3 μm. The solution was then heated and dried on a hot plate at 90°C for 3 minutes to form a dried coating of the polyhydroxyamide compound. The transmission spectrum of the dried coating was measured using a UV-Vis spectrophotometer (JASCO V-570, manufactured by JASCO Corporation). The above transmission spectrum was measured under the conditions of a bandwidth of 5 nm, a scanning speed of 400 nm / min, and a data reading interval of 1 nm. The transmittance of the i-line (wavelength 365 nm), which is the exposure wavelength, was evaluated according to the following evaluation criteria. (Evaluation criteria) A: i-line transmittance is 40% or more and less than 80% B: i-line transmittance is 25% or more and less than 40% C: i-line transmittance is less than 25%

[0115] (Evaluation of Solvent Solubility) The solubility of the polyhydroxyamide compound obtained in the above synthesis example in cyclopentanone and propylene glycol monomethyl ether (PGME) was confirmed. (Evaluation Criteria) A: Soluble in both cyclopentanone and PGME B: Insoluble in cyclopentanone, soluble in PGME, or soluble in cyclopentanone, insoluble in PGME C: Insoluble in both cyclopentanone and PGME

[0116] Note that the molar ratios in Table 1 represent the molar percentage when the amount of DEDC added is set to 100 mol%.

[0117] <Crosslinking agent (B)> MW-390 (Hexamethoxymethylmelamine compound manufactured by Nippon Carbide Industries, Ltd.)

[0118] <Photoacid Generator (C)> PAG-103 (Oximesulfonate compound manufactured by BASF)

[0119] <Basic compound (D)> Triethanolamine (TEA)

[0120] <Solvent> Cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0121] <Surfactant> BYK-310 (manufactured by Bic Chemie Co., Ltd.)

[0122] <Preparation of Curable Resin Compositions> Each component was blended in the amounts shown in Table 2 below, and the varnishes of the curable resin compositions for each example and comparative example were obtained by dissolving and adjusting them with a solvent so that the concentration of non-volatile components in the varnish was 30%. Note that, in Table 2, the amounts of each component, except for the amount of solvent, are shown in parts by mass of solids.

[0123] <Evaluation> The following evaluations were performed using the curable resin compositions of each example and comparative example obtained. The results of each evaluation are shown in Table 2.

[0124] (Evaluation of Resolution and Sensitivity) The varnishes of each example and comparative example were applied to a silicon wafer using a spin coater under conditions that resulted in an expected cured film thickness of approximately 3.5 μm. The varnishes were dried on a hot plate at 90°C for 3 minutes to obtain dried coatings of the curable resin compositions of each example and comparative example. Using a contact exposure machine (UVE-251S + EL-100 (manufactured by Sanei Electric Works Co., Ltd.)), test patterns with L / S ratios from 2 / 2 μm to 10 / 10 μm were exposed at 1 μm intervals using the exposure amounts shown in Table 2. Post-exposure heating (PEB) was performed on a hot plate for 60 seconds. The heating temperatures for the PEB process were as shown in Table 2. Subsequently, the samples were developed using the developer shown in Table 2, rinsed with ultrapure water for 30 seconds, and spin-dried for 30 seconds to obtain samples with patterns. When TMAH was used as the developer, development was performed once for 30 seconds, and when cyclopentanone was used as the developer, development was performed twice for 10 seconds each.

[0125] Each sample was cut so that a cross-section perpendicular to the longitudinal direction of the pattern could be observed. The cross-section of the pattern was observed using a scanning electron microscope (magnification of 10,000x), and the film thickness and the minimum L / S size for properly patterned samples are listed in Table 2. A smaller minimum L / S size indicates better resolution, and a lower exposure indicates better sensitivity. Samples in which each pattern was patterned vertically without tilting were judged to be properly patterned.

[0126] TMAH ＊１ : 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 25°C CPen ＊２ : Cyclopentanone at 25°C

[0127] The polyhydroxyamide compounds of the present invention can comply with PFAS regulations and exhibit excellent i-ray transmittance, making them suitable for use as forming materials for display devices, semiconductor elements, electronic components, optical components, building materials, and the like. Cross-reference of related applications

[0128] This application claims priority based on Japanese Patent Application No. 2024-160191, filed with the Japan Patent Office on 17 September 2024, all of which disclosures are incorporated herein by reference in their entirety.

Claims

1. A polyhydroxyamide compound containing the structural units of the following formulas (1) and (2), and lacking a perfluoroalkyl skeleton. {In formula (1), R １ R is a divalent organic group. ２ It is a tetravalent organic group. {In formula (2), R ３ R is a divalent organic group. ４ It is a divalent organic group that does not contain a hydroxyl group.

2. The aforementioned R ４ The polyhydroxyamide compound according to claim 1, wherein it includes an aromatic ring or an aliphatic ring.

3. A curable resin composition comprising the polyhydroxyamide compound described in claim 1, a crosslinking agent, and a photoacid generator.

4. A dry film comprising a resin layer formed by the curable resin composition described in claim 3.

5. A cured product obtained by curing the resin layer of the curable resin composition according to claim 3 or the dry film according to claim 4.

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