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

Abstract

The present invention provides a curable resin composition that can comply with PFAS regulations and has improved resolution; 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. [Solution] A polyhydroxyamide compound is provided, comprising a polyhydroxyamide compound having the structure of the following formula (1), a crosslinking agent, a photoacid generator, and a phenol compound, wherein the polyhydroxyamide compound does not have a perfluoroalkyl skeleton, and the weight-average molecular weight of the phenol compound is 5,000 or less. [Formula 1] TIFF2026054862000024.tif34170{In formula (1), R 1 R is a divalent organic group. 2 It is a tetravalent organic group.

Description

[Technical Field]

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

[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. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2012-203359 [Overview of the project] [Problems that the invention aims to solve]

[0006] In recent years, persistent chemicals (forever chemicals) such as perfluoroalkyl compounds (PFAS) have been under international consideration for regulation of their use due to reasons such as being reported to be associated with health hazards. The negative photosensitive resin composition of Patent Document 1 may contain a perfluoroalkyl skeleton in a polybenzoxazole precursor and can be subject to PFAS regulation. In the future, there is a need for a photosensitive resin composition that can respond to PFAS regulation.

[0007] However, a photosensitive resin composition using a photosensitive resin containing a perfluoroalkyl skeleton tends to exhibit excellent resolution due to containing fluorine atoms. Therefore, while responding to PFAS regulation, it is required to simultaneously achieve an improvement in resolution.

[0008] The present invention is in view of the above problems, and aims to provide a curable resin composition that can respond to PFAS regulation and has improved resolution; 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.

Means for Solving the Problems

[0009] One aspect of the present invention is a curable resin composition. The curable resin composition includes a polyhydroxyamide compound having a structure of the following formula (1), a crosslinking agent, a photoacid generator, and a phenol compound, the polyhydroxyamide compound does not have a perfluoroalkyl skeleton, and the weight average molecular weight of the phenol compound is 5,000 or less.

Chemical Formula

[0010] In the curable resin composition of the above aspect, it is preferable that the weight average molecular weight of the phenol compound is 1,000 or less.

[0011] In the curable resin composition of the above aspect, it is preferable that the polyhydroxyamide compound further contains the structure of the following formula (2). [Chemical formula] {In formula (2), R 3 is a divalent organic group, and R 4 is a divalent organic group not containing a hydroxyl group.}

[0012] In the curable resin composition of the above aspect, it is preferable that the phenol compound has a fluorene structure.

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

[0014] 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.

[0015] Another aspect of the present invention is an electronic component. The electronic component has the cured product of the above aspect. [Advantages of the Invention]

[0016] According to the present invention, it is possible to provide a curable resin composition that can comply with PFAS regulations and has improved resolution; 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. [Embodiments for Carrying Out the Invention]

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

[0018] In this specification, if multiple upper limits and multiple lower limits are described separately, all numerical ranges that can be set by freely combining these upper and lower limits are described herein.

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

[0020] "Substituents" are not particularly limited and, unless otherwise specified, include, for example, hydroxyl groups, phenol groups, phenoxy groups, alkoxy groups, phenyl groups, halogen groups, thiol groups, sulfo groups, amino groups, imino groups, hydroxyamino groups, nitro groups, nitroso groups, carboxyl groups, thiocarboxyl groups, ester groups, thioester groups, aldehyde groups, acetyl groups, etc.

[0021] The term "aromatic ring" is not particularly limited and, unless otherwise specified, includes heterocycles.

[0022] In this specification, "solids" refers to the components of a curable resin composition, or a composition other than the solvents (especially organic solvents) of each raw material, and is measured by mass unless otherwise specified.

[0023] In this specification, the weight-average molecular weight can be measured using known measurement methods, such as the polystyrene-based molecular weight, by gel permeation chromatography (GPC). In the case of low-molecular-weight compounds that do not exhibit a molecular weight distribution, the theoretical molecular weight calculated from their chemical formula can be considered the weight-average molecular weight.

[0024] 1. Curable resin composition The curable resin composition of this embodiment preferably contains a polyhydroxyamide compound, a crosslinking agent, a photoacid generator, and a phenol compound. It may also further contain basic compounds, etc.

[0025] 1-1. Polyhydroxyamide compounds The polyhydroxyamide compound of the present embodiment includes the structure of the following formula (1) and does not have a perfluoroalkyl skeleton. [Chemical formula] {In formula (1), R 1 is a divalent organic group, and R 2 is a tetravalent organic group.}

[0026] R 1 in formula (1) is not particularly limited as long as it is a divalent organic group, and may be, for example, 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.

[0027] R 1 in formula (1) preferably has an aromatic hydrocarbon group or an aliphatic hydrocarbon group among the above-mentioned divalent organic groups. Examples of the divalent organic group having an aromatic hydrocarbon group include divalent organic groups having structures such as a biphenyl skeleton, a diphenyl ether skeleton, a benzophenone skeleton, a diphenyl ethane skeleton, a diphenyl propane skeleton, a diphenyl sulfone skeleton, and a benzene skeleton. Examples of the divalent organic group 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.

[0028] From the viewpoint of the resolution of the curable resin composition, the carbon number of R 1 is preferably 4 to 30, and phenyl, biphenyl, and diphenyl ether are preferred. In addition, two or more of the groups exemplified above as R 1 can also be contained in the molecule of the polyhydroxyamide compound.

[0029] R 2The 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. Among these, an organic group having the structure shown in formula (3) below is more preferred. [ka] {In equation (3), * indicates a bonding site.}

[0030] 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.

[0031] 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 -(CF2) structure in which all hydrogen atoms on the alkyl chain (alkyl skeleton) are replaced with fluorine atoms. n The hyphen (where n is an integer greater than or equal to 1) represents a skeleton, for example, a trifluoromethyl group.

[0032] The polyhydroxyamide compound of this embodiment may further include the structure of formula (2) below. When the structure of formula (2) is included, the i-ray permeability of the polyhydroxyamide compound tends to improve, and the sensitivity of the curable resin composition tends to improve. [ka] {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.

[0033] R in equation (2) 3The group is not particularly limited as long as it is a divalent organic group, 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.

[0034] R in equation (2) 3 Among 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.

[0035] From the viewpoint of resolution of curable resin compositions, R 3 The number of carbon atoms is preferably 4 to 30, and phenyl, biphenyl, and diphenyl ethers are preferred. Furthermore, the polyhydroxyamide compound contains R 3 It is also possible to include two or more of the groups exemplified above.

[0036] 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.

[0037] 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. [ka] {In equation (4), * indicates a binding site.}

[0038] 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.

[0039] 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.

[0040] Of these alkali-soluble groups, phenolic hydroxyl groups are particularly preferred. When the polyhydroxyamide compound has phenolic hydroxyl groups at its terminals, 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 curable resin composition with excellent resolution.

[0041] 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.

[0042] 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.

[0043] 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. It is more preferable that the polyhydroxyamide compound consists substantially only of the repeating structures of formula (1) and (2) above.

[0044] The weight-average molecular weight (Mw) of the polyhydroxyamide compound is 2,000 to 20,000, preferably 2,000 to 15,000, more preferably 3,000 to 15,000, and even more preferably 4,000 to 12,000. This range allows for the formation of finer L / S patterns with a higher aspect ratio.

[0045] 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.

[0046] 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

[0047] 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.

[0048] In this specification, the weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC) (GL7700, GL Sciences) and converted to standard polystyrene values. The specific measurement conditions are as follows:

[0049] Column: TSKgelαM (manufactured by Tosoh Corporation) Column temperature: 40℃ Eluent composition: NMP solution containing 100 mmol / L H3PO4 (using an 85% aqueous solution of H3PO4 as the raw material) and 10 mmol / L LiBr. Eluent flow rate: 0.5mL / min Calibration standard reagent: Polystyrene Detector wavelengths: 260nm and 300nm Detector temperature: Room temperature (approximately 25°C) Baseline range during analysis: 15-40 minutes Molecular weight calculation range during analysis: 20-35 minutes

[0050] The alkali dissolution rate of the polyhydroxyamide compound is not particularly limited and can be, for example, 10 to 1000 nm / sec, or 50 to 700 nm / sec or 100 to 500 nm / sec. The alkali dissolution rate of the polyhydroxyamide compound can be measured by the method described in the examples below.

[0051] Polyhydroxyamide compounds may be used individually or in combination of two or more.

[0052] One method for producing polyhydroxyamide compounds is to polymerize a dihydroxydiamino compound represented by formula (5) and a dicarbonyl dichloride compound represented by formula (6) as raw materials. If necessary, a diamine compound represented by formula (7) may be further copolymerized. [ka] {In formula (5), R 2 This is as stated above. [ka] {In formula (6), R 1 , R 3 This is as stated above. [ka] {In formula (7), R4 This is as stated above.

[0053] 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.

[0054] The dicarbonyl dichloride compound represented by formula (6) above 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.

[0055] 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), 4,4'-methylenebis(2- Examples include 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), 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and tetramethyl-1,3-bis(3-aminopropyl)disiloxane. 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.

[0056] Among those mentioned above, it is preferable that it be one of DCHM, 2E6MA, or BTFL as shown in formula (8) below. [ka]

[0057] 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.

[0058] 1-2. Crosslinking agents The crosslinking agent is not particularly limited and any known agent can be used, such as melamine compounds, guanamine compounds, triazine compounds, epoxy compounds, oxetane compounds, isocyanate compounds, oxazoline compounds, etc.

[0059] The crosslinking agent preferably contains a compound having at least one selected from the group consisting of methoxymethyl groups and methylol groups. These functional groups, using the acid generated from the photoacid generator described later as an active species, undergo a crosslinking reaction with phenolic hydroxyl groups and carboxyl groups contained in polyhydroxyamide compounds, etc., upon heating. 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 of the cured product are exhibited.

[0060] The crosslinking agent preferably contains a heterocycle to improve the resolution and insulation reliability of the curable resin composition 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, and tin, and includes saturated or unsaturated rings of 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, or 8-membered rings. From the viewpoint of the resolution of the curable resin composition and the insulation reliability of the cured product, a heterocycle containing nitrogen is preferred, and a heterocycle containing multiple nitrogen atoms is more preferred.

[0061] 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.

[0062] 1-3. 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 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-oxiamide sulfonates, aromatic N-oxiimide 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 and insulation reliability, the photoacid generator is preferably an oxime sulfonate compound. Examples of oxime sulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF, with those containing the structure of formula (9) below being particularly preferred. [ka] {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.

[0063] 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. A chlorine atom or a fluorine atom is preferably used as the halogen atom.

[0064] In formula (9) above, m represents an integer between 0 and 3, preferably 0 or 1. When m is 2 or 3, the multiple X values ​​may be the same or different.

[0065] R in equation (9) above 5 It is preferable that this be an organic group containing a hydrogen atom, a hydrocarbon group, 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.

[0066] 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.

[0067] 1-4. Phenol compounds The phenol compound of this embodiment is a compound having at least one phenolic hydroxyl group, and is a different compound from the polyhydroxyamide compound, crosslinking agent, and photoacid generator described above.

[0068] The resolution of a curable resin composition is improved by the inclusion of a phenolic compound. This is presumed to be due to an increase in phenolic hydroxyl groups in the curable resin composition, which improves its affinity with the developer, and the promotion of crosslinking reactions with the crosslinking agent in the exposed area by a phenolic compound with an appropriate molecular weight. However, the detailed mechanism remains unclear because the resolution improvement is significantly greater than expected.

[0069] The upper limit of the weight-average molecular weight of the phenol compound is 5,000 or less, and from the viewpoint of excellent compatibility with other components in the curable resin composition, it is preferably 1,000 or less, 800 or less, 700 or less, 600 or less, etc. The lower limit of the weight-average molecular weight of the phenol compound is preferably 150 or more, 200 or more, 300 or more, etc.

[0070] Phenolic compounds are not particularly limited as long as they have at least one phenolic hydroxyl group. Phenolic compounds may have multiple phenolic hydroxyl groups, or hydroxyl groups other than phenolic hydroxyl groups. The hydroxyl groups other than phenolic hydroxyl groups are not particularly limited. Examples of phenolic compounds include the following compounds.

[0071] Examples of compounds having multiple phenolic hydroxyl groups on a single aromatic ring include hydroquinone, catechol, resorcinol, hydroxyquinol, phloroglucinol, pyrogallol, and hexahydroxybenzene.

[0072] Examples of compounds having one phenolic hydroxyl group and one hydroxyl group other than a phenolic hydroxyl group include 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 3-hydroxy-α-methylbenzyl alcohol, 2-hydroxybenzyl alcohol, vanillyl alcohol, 2-hydroxy-3-methoxybenzyl alcohol, and other compounds having one phenolic hydroxyl group and one hydroxyl group other than a phenolic hydroxyl group.

[0073] Compounds having two phenolic hydroxyl groups include bisphenol F, dimethylbisphenol F, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(2,3,5-trimethyl-4-hydroxyphenyl)methane, bis(3,5,6-trimethyl-4-hydroxyphenyl)methane, bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)methane, bis(3,5-diethyl-4-hydroxyphenyl)methane, and bis(3-t-butyl-4-hydroxyphenyl)methane. Xyphenyl)methane, bis(3,5-dibutyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxy-5-phenylphenyl)methane, bis(3-methyl-4-hydroxy-5-benzylphenyl)methane, bis(3-phenyl-4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(3-methyl-4-hydroxyphenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1, 1-Bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)ethane, bisphenol A, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-diethyl Bis(hydroxyphenyl) alkanes such as 2,2-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, and 2,2-bis(4-hydroxyphenyl)hexane; Bis(hydroxyphenyl)phenylalkanes such as bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-phenylpropane, and 2,2-bis(4-hydroxyphenyl)-1,3-diphenylpropane; Bis(hydroxyphenyl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane; Bis(hydroxyphenyl) sulfones such as bis(4-hydroxyphenyl) sulfone and bis(3,5-dimethyl-4-hydroxyphenyl) sulfone; Bis(hydroxyphenyl) sulfides such as bis(4-hydroxyphenyl) sulfide and bis(3,5-dimethyl-4-hydroxyphenyl) sulfide; Bis(hydroxyphenyl) ethers such as bis(4-hydroxyphenyl) ether and bis(3,5-dimethyl-4-hydroxyphenyl) ether; Bis(hydroxyphenyl) ketones such as bis(4-hydroxyphenyl)ketone and bis(3,5-dimethyl-4-hydroxyphenyl)ketone; Biphenols such as biphenol, 3,3'-dimethylbiphenyl-4,4'-diol, 3,3'-di-tert-butylbiphenyl-4,4'-diol, and 3,3',5,5'-tetramethylbiphenyl-4,4'-diol; Examples include bis(hydroxyphenyl)fluorenes such as 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis(4-hydroxyphenyl)fluorene (BPF); and so on.

[0074] Examples of compounds having two phenolic hydroxyl groups and other hydroxyl groups include 2-[bis(4-hydroxyphenyl)methyl]benzyl alcohol.

[0075] Examples of compounds having three phenolic hydroxyl groups include 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (THP), 1,1,1-tris(4-hydroxyphenyl)ethane, and 4,4',4''-trihydroxytriphenylmethane.

[0076] Examples of compounds having four phenolic hydroxyl groups include tetrakis(4-hydroxyphenyl)ethylene, 4,4',4'',4'''-methanetetrayltetraphenol, 9,9-bis(3,4-dihydroxyphenyl)fluorene, 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexanyl-1-ylidene]tetrakis[2-methylphenol] (TekOC-4HBPA), 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexanyl-1-ylidene]tetrakisphenol (TekP-4HBPA), and 9,9-bis(3,4-dihydroxyphenyl)fluorene.

[0077] Examples of polymers include phenolic resins such as resol-type phenolic resins and novolac-type phenolic resins; polyphenolic polymers such as polyhydroxystyrene polymers obtained by polymerizing hydroxystyrene (which may be o-, m-, or p-); and polyphenolic copolymers such as polyhydroxystyrene copolymers obtained by copolymerizing hydroxystyrene (which may be o-, m-, or p-) with other polymerizable compounds such as styrene.

[0078] The phenol compounds exemplified above can be used individually or in combination of several in any ratio. Of these, those having two or more phenolic hydroxyl groups are preferred. It is preferable that the phenol compound has 2 to 4 phenolic hydroxyl groups.

[0079] 1-5. Basic Compounds The curable resin composition of this embodiment preferably contains a basic compound, from the viewpoint of improving dissolution contrast and resolution, as well as improving the stability of the coating film during the setting time from application of the curable resin composition to exposure.

[0080] 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.

[0081] These can be used individually or in combination in any ratio. Of 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.

[0082] 1-6. solvent 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.

[0083] 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.

[0084] 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.

[0085] 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-norbornone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone; Cycloalkanones of 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; Cycloalkenones such as 4-methyl-2-cyclopentenone, 2-cyclohexenone, 2-cyclopenten-1-one, and 2-cyclohexen-1-one; Examples include cyclic ketones with a heterocyclic skeleton, such as 2-azetidinone, 4,5-dihydro-3(2H)-thiophenone, 4-oxotiane, and dihydrolevogluconocene.

[0086] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0087] 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.

[0088] 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.

[0089] 1-7. Other ingredients 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, and the like.

[0090] The surfactant is not particularly limited and examples include fluorine-based surfactants and silicone-based surfactants. Examples of commercially available fluorine-based surfactants include DIC's "MegaFac" series (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 BIK-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.

[0091] 2. 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, phenol compounds, and basic compounds. The mixing of each component can be carried out under heating as needed.

[0092] 2-1. Polyhydroxyamide compounds The polyhydroxyamide compound content 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.

[0093] 2-2. Crosslinking agents 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 contains 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. Such a ratio can improve the resolution and insulation reliability of the curable resin composition after curing.

[0094] 2-3. 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.

[0095] 2-4. Phenol Compounds The phenol compound content is preferably 1 to 40 parts by mass, more preferably 3 to 35 parts by mass, and even more preferably 5 to 25 parts by mass, based on 100 parts by mass of the solid content of the polyhydroxyamide compound in the curable resin composition.

[0096] The mass ratio of the crosslinking agent content to the phenol compound content can be 40:0.1 to 40:30, preferably 40:0.5 to 40:25, and more preferably 40:0.5 to 40:15.

[0097] 2-5. Basic Compounds When adding a basic compound, the amount can be 0.01 to 1.0 parts by mass, 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. This range makes it easier to suppress the generation of development residue in the unexposed areas after developing the curable resin composition.

[0098] 3. 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 it.

[0099] 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.

[0100] The substrate is not particularly limited and can include, for example, metal foils such as copper foil; films such as polyimide film, polyester film, and polyethylene naphthalate (PEN) film.

[0101] 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.

[0102] 4.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.

[0103] 4-1. Dry coating film formation process The drying film formation process involves applying the above-mentioned curable resin composition onto a substrate to form a coating 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.

[0104] The method for applying the curable resin composition to the substrate is not particularly limited and can include methods 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.

[0105] The drying method for 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.

[0106] 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.

[0107] 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.

[0108] 4-2. Exposure Process The exposure process involves irradiating the dried coating formed in the drying coating 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.

[0109] 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. 2 This 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.

[0110] 4-3.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 phenol compound and the 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.

[0111] 4-4.Developing process The developing 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.

[0112] 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 used as developers.

[0113] 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.

[0114] 4-5. Post-development heating process The post-development heating step involves heating the pattern coating film formed in the development step 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.

[0115] 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.

[0116] 5. Uses of curable resin compositions 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, and the like. Examples of forming materials for semiconductor elements include resist materials, buffer coating films, and insulating films for redistribution layers of wafer-level packages (WLPs). Examples of forming materials for electronic components include printed circuit boards, interlayer insulating films, and wiring coating films. [Examples]

[0117] 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.

[0118] <<Raw materials for curable resin compositions>> <Polyhydroxyamide compound (A)> Polyhydroxyamide compounds A-1 to A-2 were synthesized as described below. Table 1 shows 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-2.

[0119] (Synthesis Example 1: Polyhydroxyamide Compound (A-1)) (Mn: 2,600, Mw: 8,100) In a 120 mL vial (at room temperature) equipped with a stirrer and thermometer, 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 to maintain the temperature inside the vial at 0-5°C, and 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 solution, and the mixture was 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 the polyhydroxyamide compound (A-1) (BAP-DEDC-3AP). [ka]

[0120] (Synthesis Example 2: Polyhydroxyamide Compound (A-2)) (Mn: 2,800, Mw: 8,400) In a 120 mL vial (at room temperature) equipped with a stirrer and thermometer, 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. Then, 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 amount 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 amount of deionized water, and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain polyhydroxyamide compound (A-2) (BAP-2E6MA-DEDC-3AP). [ka]

[0121] <Crosslinking agent (B)> (B-1)MW-390 (manufactured by Nippon Carbide Industries, Ltd.: hexamethoxymethylmelamine compound) [ka]

[0122] <Photoacid Generator (C)> (C-1) PAG-103 (BASF: Oxime sulfonate compound) [ka]

[0123] <Phenol compound (D)> (D-1) BPF (manufactured by Tokyo Chemical Industry Co., Ltd.: 9,9-bis(4-hydroxyphenyl)fluorene) (molecular weight: 350) [ka] (D-2) THP (manufactured by Tokyo Chemical Industry Co., Ltd.: α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene) (molecular weight: 424) [ka] (D-3)TekOC-4HBPA (manufactured by Honshu Chemical Industry Co., Ltd.: 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexanyl-1-ylidene]tetrakis[2-methylphenol]) (molecular weight: 633) [ka]

[0124] (D-4) VPS-2515 (Manufactured by Nippon Soda Co., Ltd.: Polyhydroxystyrene-styrene copolymer) (Mw: 3,500)

[0125] <Basic compound (E)> (E-4) Triethanolamine (TEA) (manufactured by Mitsui Chemicals, Inc.) [ka]

[0126] <Surfactant (F)> (F-1) BYK-310 (manufactured by Big Chemie)

[0127] <Preparation of curable resin composition> Each component was blended in the amounts shown in Tables 1 and 2, and the varnishes of the curable resin compositions for each example and comparative example were obtained by dissolving and adjusting them with a solvent (cyclopentanone) so that the concentration of nonvolatile components in the varnish was 30%. The amounts of each component in Tables 1 and 2 are shown in parts by mass of solids.

[0128] <Rating> The following evaluations were performed using the curable resin compositions obtained for each example and comparative example. The results of each evaluation are shown in Table 1.

[0129] <Dissolution contrast evaluation (γ value measurement)> The varnishes obtained for each example and comparative example were applied to a silicon wafer using a spin coater to a cured thickness of 3.0 μm, and then soft-baked on a hot plate at 90°C for 180 seconds to obtain the dried coating films for each example and comparative example. The obtained dried coating films were then exposed to UV light (wavelength 365 nm) at an exposure dose of 0 to 100.0 mJ / cm². 2 Within the range of 10.0 mJ / cm² 2 Surface exposure was performed while gradually changing the exposure level, and then the surface was heated at 120°C for 60 seconds. After that, the dried coating was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution (developer) for 30 seconds and rinsed with pure water. The residual film percentage at each exposure level was measured, and a semi-logarithmic graph was created with the residual film percentage on the vertical axis, the exposure level on the horizontal axis, and the horizontal axis being logarithmic to obtain a sensitivity curve. In this sensitivity curve, an approximate straight line was calculated from the rising point of the sensitivity curve to the data point with the lowest exposure level where the residual film percentage was approximately 70%, and the dissolution contrast (γ value) was calculated from the slope of this approximate straight line. The results for each example and comparative example are shown in Tables 1 and 2.

[0130] <Evaluation of dissolution rate> The varnishes obtained for each example and comparative example were applied to a silicon wafer using a spin coater, and then heated and dried on a hot plate at 90°C for 3 minutes to obtain a coating film. The film thickness was measured using an optical interferometer. The obtained coating films were irradiated with broad light using a high-pressure mercury lamp (with i-line filter). The exposure dose was 50 mJ / cm². 2 Gradually increase the pressure to 100-1000 mJ / cm². 2 The experiment was conducted within the specified range. After exposure, the dried coating film was developed using a 2.38% TMAH aqueous solution, rinsed with water, and the dissolution time of the coating film was measured. The dissolution rate was calculated using the following formula. Dissolution rate (nm / s) = Film thickness (nm) / Dissolution time (s)

[0131] <Resolution Evaluation (1)> The varnishes of each example and comparative example were applied to a silicon wafer using a spin coater to a cured film thickness of approximately 3.5 μm. The cured films were then dried on a hot plate at 90°C for 3 minutes to obtain the curable resin compositions of each example and comparative example. Test patterns with L / S ratios of 2 / 2 μm to 10 / 10 μm were exposed to these dried films using a contact exposure machine (UVE-251S + EL-100 (manufactured by Sanei Electric Works Co., Ltd.)) at 1 μm intervals. Post-exposure heating (PEB) was performed on a hot plate for 60 seconds. The heating temperatures for the PEB process were as shown in Tables 1 and 2. Subsequently, the films were developed using a 2.38% TMAH aqueous solution for 30 seconds, rinsed with ultrapure water for 30 seconds, and spin-dried for 30 seconds to obtain samples with patterns.

[0132] <Resolution Evaluation (2)> The varnishes of Example 1 and Comparative Example 1 were applied to a silicon wafer using a spin coater to achieve a cured film thickness of approximately 3.0 μm. The films were then dried on a hot plate at 90°C for 3 minutes to obtain dried coatings of the curable resin compositions of Example 1 and Comparative Example 1. Test patterns with L / S values ​​of 0.5 / 0.5 μm, 0.6 / 0.6 μm, 0.7 / 0.7 μm, 0.8 / 0.8 μm, 1 / 1 μm, 1.2 / 1.2 μm, 1.5 / 1.5 μm, 1.7 / 1.7 μm, 2 / 2 μm, 3 / 3 μm, 4 / 4 μm, and 5 / 5 μm were exposed to this dried coating using an i-line stepper (reduction projection exposure system: NSR-2005i9C (Nikon Corporation: numerical aperture = 0.5, σ = 0.68, light source: high-pressure mercury lamp)). Post-exposure heating (PEB) was performed on a hot plate at 140°C for 60 seconds. Spin drying was performed for 30 seconds to obtain samples having the patterns of the curable resin compositions of each example and comparative example. The exposure conditions (exposure amount and focus) were selected to yield the best resolution for each curable resin composition of each example and comparative example.

[0133] Each sample obtained in resolution evaluations (1) and (2) 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 10,000x), and the film thickness, the minimum L / S size for normal patterning, and the exposure amount at that time are listed in Table 1. A smaller minimum L / S size indicates better resolution, and a lower exposure amount indicates better sensitivity. Samples in which each pattern was patterned vertically without tilting were judged to be normally patterned.

[0134] <Phase Separation Evaluation> The cross-section of the pattern was observed using a scanning electron microscope (magnification 10,000x), and phase separation was evaluated according to the following criteria based on whether a heterogeneous structure was observed in the cross-section of the sample. A: The entire cross-section of the sample is uniform (no heterogeneous structure is observed). B: A heterogeneous structure is observed in a portion of the sample cross-section. C: A heterogeneous structure is observed throughout the entire cross-section of the sample.

[0135] [Table 1]

[0136] [Table 2]

[0137] As shown in Tables 1 and 2, all of the curable resin compositions of this embodiment were shown to have improved resolution compared to those that do not contain phenolic compounds. In particular, the curable resin composition of Example 1 was able to form a pattern with an L / S ratio of 0.6 μm / 0.6 μm, and it was confirmed that it exhibited extremely excellent resolution. [Industrial applicability]

[0138] The curable resin composition of the present invention can comply with PFAS regulations and has improved resolution, making it suitable for use as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like.

Claims

1. The material comprises a polyhydroxyamide compound having the structure of the following formula (1), a crosslinking agent, a photoacid generator, and a phenol compound. The polyhydroxyamide compound does not have a perfluoroalkyl skeleton, A curable resin composition having a weight-average molecular weight of 5,000 or less of the phenol compound. 【Chemistry 1】 {In formula (1), R １ R is a divalent organic group. ２ It is a tetravalent organic group.

2. The curable resin composition according to claim 1, wherein the weight-average molecular weight of the phenol compound is 1,000 or less.

3. The curable resin composition according to claim 1, wherein the polyhydroxyamide compound further comprises the structure of the following formula (2). 【Chemistry 2】 {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.

4. The curable resin composition according to claim 1, wherein the phenol compound has a fluorene structure.

5. A dry film comprising a resin layer formed from the curable resin composition described in claim 1.

6. A cured product obtained by curing the resin layer of the curable resin composition according to claim 1 or the dry film according to claim 5.

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