Curable resin composition, dry film, and cured product

Abstract

[Problem] Provided are: a curable resin composition which exhibits excellent adhesion to a silicon substrate; a dry film comprising a resin layer that is formed from said curable resin composition; and a cured product which is obtained by curing said curable resin composition or the resin layer of said dry film. [Solution] The curable composition is a curable composition set forth in claim 1 comprising (A) a polyhydroxyamide compound, (B) a crosslinking agent, (C) a compound having a phenolic hydroxyl group and a reactive double bond, and (D) a photoacid generator, wherein the crosslinking agent (B) includes a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in the molecular structure, and the polyhydroxyamide compound (A) is a compound including structural units represented by formulae (1) and (2). {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 that does not include a hydroxyl group.}

Description

Curable resin composition, dry film, and cured product

[0001] This invention relates to a curable resin composition, a dry film, and a cured product.

[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, the demand for higher performance and miniaturization of electronic components and electrical equipment has led to a need for further integration of semiconductor devices. To meet these demands, high-performance and miniaturization technologies are being developed in the field of semiconductor device packaging, such as wafer-level packages (WLPs). In addition, in insulating films used in redistribution layers, it is necessary to have sufficient adhesion to the silicon substrate in order to achieve further miniaturization of pattern formation.

[0007] Therefore, the object of this disclosure is to provide a curable resin composition that exhibits excellent adhesion to a silicon substrate; a dry film having a resin layer formed by the curable resin composition; and a cured product obtained by curing the curable resin composition or the resin layer of the dry film.

[0008] The inventors have discovered that the above-mentioned problems can be solved by combining a polyhydroxyamide compound, a crosslinking agent, a specific compound, and a photoacid generator, and have completed the present invention. That is, the embodiments of the present invention are as follows.

[0009] One aspect of the present invention is a curable resin composition. The curable resin composition comprises (A) a polyhydroxyamide compound, (B) a crosslinking agent, (C) a compound having a phenolic hydroxyl group and a reactive double bond, and (D) a photoacid generator, wherein the (B) crosslinking agent comprises a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in its molecular structure, and the (A) polyhydroxyamide compound comprises a compound containing structural units represented by the following formulas (1) and (2). {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 curable resin composition according to the above embodiment, the (B) crosslinking agent preferably contains a heterocycle.

[0011] In the curable resin composition according to the above embodiment, the compound having a phenolic hydroxyl group and a reactive double bond is preferably represented by the following formula (3). {In formula (3), R ５ It is a group that has a reactive double bond.

[0012] In the curable resin composition according to the above embodiment, it is preferable to further include (E) a photoradical generator.

[0013] 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.

[0014] Another aspect of the present invention is a cured product. This cured product is obtained by curing the resin layer of the curable resin composition or dry film according to the above aspect.

[0015] According to the present invention, there can be provided a curable resin composition that exhibits excellent adhesion to a silicon substrate; a dry film including a resin layer formed from the curable resin composition; and a cured product obtained by curing the curable resin composition or the resin layer of the dry film.

[0016] 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.

[0017] 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 from these upper limit values and lower limit values are described in this specification.

[0018] In this specification, when a certain compound is described, its stereoisomers are also described simultaneously unless otherwise specified.

[0019] In this specification, the "substituent" is not particularly limited, and unless otherwise specified, examples include a hydroxyl group, a phenol group, a phenyl group, a halogen group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, a thioester group, an aldehyde group, an acetyl group, and the like.

[0020] In this specification, "(meth)acryl" means including both "acryl" and "methacryl". Also, "(meth)acrylate" means including both "acrylate" and "methacrylate".

[0021] In this specification, the solid content means a component other than a solvent (particularly an organic solvent) among the curable resin composition or the components constituting each raw material, and is based on mass unless otherwise specified.

[0022] 1. Curable Resin Composition The curable resin composition of this embodiment preferably contains (A) a polyhydroxyamide compound, (B) a crosslinking agent, (C) a compound having a phenolic hydroxyl group and a reactive double bond, and (D) a photoacid generator. Further, the curable resin composition of this embodiment preferably further contains (E) a photo radical generator, and may further contain a basic compound or the like.

[0023] 1-1. (A) Polyhydroxyamide Compound The (A) polyhydroxyamide compound contains structural units represented by the following formulas (1) and (2). {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 not containing a hydroxyl group.}

[0024] R １ in formula (1) is not particularly limited as long as it is a divalent organic group. 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, or the like.

[0025] 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 hexafluoropropane 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. 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 (A) polyhydroxyamide compound contains R 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, diphenylhexafluoropropane 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 (4) below is more preferred from the viewpoint of obtaining a curable resin composition with excellent resolution. {In equation (4), * 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) ３It 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 diphenylhexafluoropropane 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 the curable resin composition and adhesion of the cured product, R ３ The number of carbon atoms is preferably 4 to 30, R ３ It is preferable that the group has a benzene skeleton, a biphenyl skeleton, a diphenyl ether skeleton, or a diphenylhexafluoropropane 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, and that it does not contain a perfluoroalkyl group. 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 (5) below. {In equation (5), * 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 structures may be the same or different. The polyhydroxyamide compound of this embodiment has the structure of formula (2) in addition to the structure of formula (1), and therefore tends to exhibit excellent sensitivity in curable resin compositions.

[0035] From the viewpoint of complying with PFAS regulations, the polyhydroxyamide compound of this embodiment preferably does not have a perfluoroalkyl skeleton. 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 represented by a dash (where n is an integer of 1 or more), and an example is a trifluoromethyl group.

[0036] (A) The polyhydroxyamide compound may have an alkali-soluble group at its terminus. The alkali-soluble group at the terminus is not particularly limited and may include functional groups such as an alcoholic hydroxyl group, a phenolic hydroxyl group, an acid anhydride group, a carboxyl group, a sulfonic acid group, a sulfonamide group, or an active methylene group. From the viewpoint of solubility in the developer, it is preferable to have a carboxyl group or a phenolic hydroxyl group.

[0037] When the (A) polyhydroxyamide compound of this embodiment is used as a negative-type photosensitive resin composition, phenolic hydroxyl groups are particularly preferred among these alkali-soluble groups. When the (A) polyhydroxyamide compound has phenolic hydroxyl groups at its terminals, the solubility of the (A) polyhydroxyamide compound in the developer can be improved. Furthermore, since phenolic hydroxyl groups are less reactive than carboxyl groups, when used in combination with the (B) crosslinking agent, etc., described later, as a curable resin composition, excessive reaction with the (B) crosslinking agent, etc., is suppressed, and the solubility of the unexposed areas in the developer can be maintained even when the PEB process described later is performed. It is presumed that this makes it possible to provide a curable resin composition with excellent resolution.

[0038] The alkali-soluble groups at the ends of these (A) polyhydroxyamide compounds may be present as residues of monomers constituting the (A) polyhydroxyamide compound, or as terminal structures introduced by a terminal encapsulant having alkali-soluble groups. Preferably, the alkali-soluble groups at the ends of the (A) polyhydroxyamide compound are present as terminal structures introduced by a terminal encapsulant having alkali-soluble groups.

[0039] 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.

[0040] (A) The polyhydroxyamide compound may contain two or more repeating structural units of formula (1) or (2) above. It may also contain structural units other than the repeating structures of formula (1) or (2) above, for example, it may contain repeating structural units of polyamic acid. (A) It is more preferable that the repeating structure of the polyhydroxyamide compound consists substantially only of the repeating structures of formula (1) and (2) above.

[0041] 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.

[0042] (A) The weight-average molecular weight (Mw) of the polyhydroxyamide compound can be, for example, 2,000 to 40,000, preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 10,000. By setting the molecular weight within this range, it becomes possible to form an L / S pattern that is finer and has a higher aspect ratio.

[0043] (A) The number-average molecular weight (Mn) of the polyhydroxyamide compound is preferably 1,000 to 15,000, more preferably 1,500 to 10,000, and particularly preferably 1,500 to 6,000.

[0044] (A) The molecular weight dispersibility (PDI) of the polyhydroxyamide compound is preferably 1.5 to 4.0, and more preferably 1.5 to 3.5. The molecular weight dispersibility (PDI) is calculated by the following formula: PDI = Mw / Mn

[0045] (A) When the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight dispersion (PDI) of the polyhydroxyamide compound are within the specified range, a suitable balance is achieved between solubility in the developer and (B) reaction with the crosslinking agent, resulting in a curable resin composition with superior resolution.

[0046] In this specification, the weight-average molecular weight and number-average molecular weight were measured by gel permeation chromatography (GPC) (GL7700, GL Sciences) and converted to standard polystyrene values. The specific measurement conditions are as follows.

[0047] Column: TSKgelαM (Tosoh Corporation) Column temperature: 40°C Eluent composition: 100 mmol / L H ３ PO ４ (H ３ PO ４ (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

[0048] (A) Polyhydroxyamide compounds may be used individually or in combination of two or more.

[0049] (A) As a method for producing the polyhydroxyamide compound, for example, a method can be used in which a dihydroxydiamino compound represented by formula (6), a dicarbonyl dichloride compound represented by formula (7), and a diamine compound represented by formula (8) are copolymerized as raw materials. Alternatively, a method can be used in which other compounds copolymerizable with these compounds are copolymerized. Examples of other copolymerizable compounds include diol compounds, acid dianhydrides, diisocyanate compounds, and diamine compounds different from those represented by formula (6) or formula (8). {In formula (6), R ２ This is as stated above. {In formula (7), R １ , R ３ This is as stated above. {In formula (8), R ４ This is as stated above.

[0050] The dihydroxydiamino compound represented by formula (6) above is not particularly limited, and includes 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl)sulfone, and the like.

[0051] The dicarbonyl dichloride compound represented by formula (7) 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.

[0052] The diamine compound represented by formula (8) 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 (8). Therefore, according to this embodiment, a wide variety of polyhydroxyamide compounds can be produced, and polyhydroxyamide compounds with various properties can be obtained.

[0053] Among those mentioned above, it is preferable that it be one of DCHM, 2E6MA, or BTFL as shown in formula (9) below.

[0054] 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.

[0055] 1-2. (B) Crosslinking agent (B) Known crosslinking agents can be used. Examples include melamine compounds, guanamine compounds, triazine compounds, epoxy compounds, oxetane compounds, isocyanate compounds, oxazoline compounds, etc.

[0056] (B) The crosslinking agent preferably contains a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in its molecular structure. These functional groups, with the acid generated from the photoacid generator described later as an active species, undergo a crosslinking reaction with phenolic hydroxyl groups, carboxyl groups, etc. contained in (A) polyhydroxyamide compounds, etc., upon heating. As a result, pattern formation is achieved by exposure, PEB, and development treatment, and the curable resin composition of this embodiment can be preferably used as a negative-type photosensitive resin composition. Furthermore, by further heating after pattern formation, the curing reaction of the curable resin composition proceeds, and excellent properties as a cured product are exhibited.

[0057] (B) 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, tin, etc., and includes saturated or unsaturated rings of three-membered, four-membered, five-membered, six-membered, seven-membered, or eight-membered rings. 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.

[0058] 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 tetramethylolglycoluryl and tetramethoxyglycoluryl, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone are more preferred. Of these, compounds having a triazine structure containing a triazine ring and compounds having a guanamine structure are particularly preferred from the viewpoint of providing a curable resin composition that can form a finer L / S pattern with a higher aspect ratio.

[0059] 1-3. (C) Compounds having a phenolic hydroxyl group and a reactive double bond {Hereinafter, these may simply be referred to as (C) phenolic compounds} (C) Phenolic compounds are compounds having a phenolic hydroxyl group and a reactive double bond, and are not particularly limited as long as they are different from the (A) polyhydroxyamide compounds, (B) crosslinking agents, and (D) photoacid generators described later. (C) Phenolic compounds may have a monocyclic or polycyclic structure. (C) Phenolic compounds may have one or more phenolic hydroxyl groups and one or more reactive double bonds. Examples include monomers described in International Publication No. WO2021 / 153545, and compounds obtained by (meth)acrylicating one of the hydroxyl groups of a compound having two phenolic hydroxyl groups. Examples of compounds having two phenolic hydroxyl groups include biphenols, bisphenol compounds, and dihydroxynaphthalene. (C) Phenolic compounds are preferably represented by the following formula (3). {In formula (3), R ５ It is a group that has a reactive double bond.

[0060] R in equation (3) ５The group is not particularly limited as long as it has a reactive double bond, and examples include (meth)acrylate groups, (meth)acrylamide groups, allyl groups, vinyl groups, allyl ether groups, vinyl ether groups, etc. Of these, (meth)acrylate groups and (meth)acrylamide groups are preferred.

[0061] (C) Phenolic compounds have a phenolic hydroxyl group. Also, (C) phenolic compounds are R ５ With respect to the position of , the phenolic hydroxyl group may be located at the ortho, meta, or para position.

[0062] Although the detailed mechanism is unknown, it is presumed that the curable resin composition of this embodiment, by containing a phenolic compound (C), has improved flexibility and therefore possesses excellent adhesion to a silicon substrate.

[0063] (C) Phenolic compounds have reactive double bonds. Therefore, (C) phenolic compounds can introduce other functional groups and structures using the reactive double bond as a reaction site, thereby imparting various properties to the curable resin composition. In particular, when used in combination with (E) photoradical generators described later, exposure causes the reactive double bonds of (C) phenolic compounds to crosslink by radical polymerization, which tends to reduce the alkali solubility of the exposed area, thus potentially improving the sensitivity of the curable resin composition. Furthermore, as mentioned above, they can also react with (A) polyhydroxyamide compounds and (B) crosslinking agents, so each component from (A) to (C) is firmly incorporated into the structure of the cured product, which can further improve various physical properties of the cured product. For example, the elongation and adhesion of the cured product can be further improved. In addition, curing shrinkage of the cured product can be reduced.

[0064] (C) Among the phenolic compounds, examples of compounds represented by formula (3) above include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 4-hydroxyphenyl methacrylate, and 4-hydroxyphenyl methacrylamide. Among these, 4-hydroxyphenyl methacrylate {formula (10) below} and 4-hydroxyphenyl methacrylamide {formula (11) below} are preferred.

[0065] (C) Phenolic compounds may be used alone or in combination of several.

[0066] 1-4. (D) Photoacid Generator (D) 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, benzoquinone diazosulfonic acid esters, etc. These can be used individually or in combination in any ratio.

[0067] When (A) the polyhydroxyamide compound of this embodiment is used as a curable resin composition, (D) the photoacid generator is preferably used in combination with the crosslinking agent (B) described above, and (D) the photoacid generator is preferably an oxime sulfonate compound. Examples of oxime sulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, Irgacure PAG203, etc., manufactured by BASF, and those containing the structure of the following formula (12) are particularly preferred. {In formula (12), X is a hydrocarbon group or halogen atom, m is an integer from 0 to 3, R ６ This is an organic group containing a hydrogen atom, a hydrocarbon group, a ketone group, or a halogen atom.

[0068] In formula (12) 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.

[0069] In formula (12) 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.

[0070] R in the above formula (12) ６ 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.

[0071] 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.

[0072] Examples of commercially available oximesulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203, all manufactured by BASF.

[0073] 1-5. (E) Photoradical Generator The curable resin composition of this embodiment may further contain (E) a photoradical generator. (E) A photoradical generator is a compound that generates radicals upon light irradiation (exposure). In this embodiment, compounds that generate radicals and acids upon light irradiation are treated as (E) photoradical generators.

[0074] If the curable resin composition of this embodiment contains (E) a photoradical generator, the generated radicals can radically polymerize the above-mentioned (C) phenolic compound, thereby improving the developability of the exposed area.

[0075] (E) As the photoradical generator, known and conventional photoradical generators can be used. Examples include benzoin ethers, acetophenones, α-ketols, aromatic sulfonyl chlorides, oxime esters, benzoin, benzyls, benzophenones, ketals, thioxanthones, acylphosphine oxides, etc.

[0076] Examples of benzoin ether-based photoradical generators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisoine.

[0077] Examples of acetophenone-based photoradical generators include 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and methoxyacetophenone.

[0078] Examples of α-ketol-based photoradical generators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one.

[0079] Examples of aromatic sulfonyl chloride-based photoradical generators include 2-naphthalene sulfonyl chloride.

[0080] Examples of oxime ester-based photoradical generators include oxime ester compounds having a carbazole skeleton, such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime, 1,2-propanedione, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-2-(O-benzoyl oxime), 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], the compound represented by formula (13) below {2-(acetyloxyiminomethyl)thioxanthene-9-one}, and the compound represented by formula (14) below {e.g., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime)}.

[0081] In formula (14), R ７ R represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group. ８ 、 R １０ Each of these independently represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group. ９ This represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, a C2-C12 alkanoyl group, a C2-C12 alkoxycarbonyl group (if the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbone group.

[0082] Examples of benzoin-based photoradical generators include benzoin.

[0083] Examples of benzyl-based photoradical generators include benzyl.

[0084] Examples of benzophenone photoradical generators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenyl ketone.

[0085] Examples of ketal-based photoradical generators include benzyldimethyl ketal.

[0086] Examples of thioxanthone-based photoradical generators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0087] Examples of acylphosphine oxide-based photoradical generators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, and bis(2,6-dimethyl (Xybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop Pan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 - Phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-Trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethitoxybenzoyl-2,4,6-trimeth Examples include benzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide, etc.

[0088] These (E) photoradical generators may be used individually or in combination of two or more types.

[0089] 1-6. Basic Compounds The curable resin composition of this embodiment may further 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 (D) photoacid generator to the unexposed areas by exposure, thereby improving resolution and preventing the formation of development residue in the unexposed areas after development.

[0090] 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.

[0091] 1-7. 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0096] 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.

[0097] 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.

[0098] 1-8. 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.

[0099] 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.

[0100] The curable resin composition of this embodiment may further contain, as other components, compounds containing phenolic hydroxyl groups other than the (C) phenolic compounds described above. The compounds containing phenolic hydroxyl groups other than the (C) phenolic compounds may be monomers or polymers. Examples of compounds containing phenolic hydroxyl groups other than the (C) phenolic compounds include polyhydroxystyrene copolymers obtained by copolymerizing hydroxystyrene (which may be o-, m-, or p-) with styrene.

[0101] 2. Preparation of the Curable Resin Composition The curable resin composition of this embodiment can be obtained by mixing the above-mentioned (A) polyhydroxyamide compound, (B) crosslinking agent, (C) phenolic compound, and (D) photoacid generator with any component including (E) photoradical generator, basic compound, etc. The mixing of each component can be carried out under heating as necessary.

[0102] 2-1. (A) Polyhydroxyamide compound The content of (A) the polyhydroxyamide compound can be 30 to 80% by mass, when the total mass of the solids of the curable resin composition is 100% by mass.

[0103] 2-2. (B) Crosslinking agent The content of (B) crosslinking agent can be 5 to 80 parts by mass when the total solid content mass of (A) polyhydroxyamide compound and (C) phenolic compound in the curable resin composition is 100 parts by mass. Furthermore, if (B) crosslinking agent has methoxymethyl groups and / or methylol groups, the content of (B) crosslinking agent can be such that the ratio of the number of methoxymethyl groups and / or methylol groups contained in (B) crosslinking agent to the number of phenolic hydroxyl groups contained in the curable resin composition (methoxymethyl groups and / or methylol groups: phenolic hydroxyl groups) is 120:100 to 200:100. By using such a ratio, the resolution and adhesion of the curable resin composition can be made even better.

[0104] 2-3. (C) Compounds having phenolic hydroxyl groups and reactive double bonds {(C) Phenolic compounds} The content of (C) phenolic compounds can be such that the solid content mass ratio of (A) polyhydroxyamide compounds to (C) phenolic compounds in the curable resin composition (solid content mass of polyhydroxyamide compounds: solid content mass of phenolic compounds) is 99.9:0.1 to 0.1:99.9, preferably 99.0:1.0 to 40.0:60.0, more preferably 97.0:3.0 to 60.0:40.0, and particularly preferably 95.0:5.0 to 80.0:20.0. When the solid content mass ratio of (A) polyhydroxyamide compounds to (C) phenolic compounds in the curable resin composition is 95.0:5.0 to 80.0:20.0, a curable resin composition with excellent resolution can be obtained.

[0105] 2-4. (D) Photoacid Generator The content of (D) photoacid generator can be 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, when the total solid content mass of (A) polyhydroxyamide compound and (C) phenolic compound in the curable resin composition is 100 parts by mass.

[0106] 2-5. (E) Photoradical Generator The content of (E) the photoradical generator is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, when the total solid content mass of (A) polyhydroxyamide compound and (C) phenolic compound in the curable resin composition is 100 parts by mass.

[0107] 2-6. Basic Compounds When basic compounds are added, the content can be 0.01 to 1.00 parts by mass, and preferably 0.05 to 0.50 parts by mass, when the total solid content mass of (A) polyhydroxyamide compound and (C) phenolic compound in the curable resin composition is 100 parts by mass. 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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 using a curable resin composition as an example.

[0113] 4-1. 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 4-2. Exposure Process The exposure process involves irradiating the dried coating formed in the drying coating formation process with light such as ultraviolet light or visible light through a photomask capable of forming a desired pattern, thereby photosensitizing the (D) 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.

[0119] The wavelength of light used, such as ultraviolet or visible light, is one that can activate the (D) photoacid generator, and for finely patterned light, a maximum wavelength of 410 nm or less is preferred. The irradiation energy can be adjusted depending on the thickness of the formed dry coating, 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.

[0120] 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. In the PEB process, the acid generated from (D) a photoacid generator in the exposed portion acts as an active species, and a crosslinking reaction proceeds between (A) a polyhydroxyamide compound, (C) a phenolic compound and (B) a crosslinking agent, causing the exposed portion to become 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.

[0121] 4-4. 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.

[0122] 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.

[0123] 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.

[0124] 4-5. 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.

[0125] Furthermore, if the curable resin composition in this embodiment is a positive-type photosensitive resin composition, a patterned coating can be obtained by using a dissolution inhibitor as the photoacid generator and treating the coating with a developer in the development step, thereby dissolving and removing the exposed parts of the dried coating in the developer.

[0126] 5. 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), and can be particularly suitably used in redistribution layer formation processes using the damascene method. Furthermore, as forming materials for electronic components, examples include printed circuit boards, interlayer insulating films, and wiring coating films.

[0127] 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.

[0128] <(A) Polyhydroxyamide Compound> (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).

[0129] <(B) Crosslinking agent> (B-1) MW-390 (manufactured by Nippon Carbide Industries Co., Ltd., hexamethoxymethylmelamine compound)

[0130] <(C) Compounds having a phenolic hydroxyl group and a reactive double bond> (C-1) HQMA-H (manufactured by Osaka Organic Chemical Industry Co., Ltd., 4-hydroxyphenyl methacrylate)

[0131] <(D) Photoacid Generator> (D-1) PAG-103 (Oximesulfonate compound manufactured by BASF)

[0132] <(E) Photoradical Generator> (E-1) OXE-05 (BASF Corporation, oxime ester compound)

[0133] <(F) Basic Compounds> (F-1) Triethanolamine (manufactured by Mitsui Chemicals, Inc.)

[0134] <(G) Surfactants> (G-1) BYK-310 (Manufactured by Bic Chemie, polyester-modified silicone surfactant)

[0135] <(H) Solvent> (H-1) Cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0136] <Preparation of Curable Resin Compositions> Each component was blended in the amounts shown in Table 1, and each component was dissolved in a solvent to obtain the curable resin composition varnish for each example and comparative example. Note that in Table 1, the amounts of each component, except for the amount of solvent, are shown in parts by mass of solids.

[0137] <Evaluation> The following evaluations were performed using the varnishes of each example and comparative example obtained. The results of each evaluation are shown in Table 1.

[0138] (Resolution Evaluation) - Line / Space (L / S) Measurement The varnish of each example and comparative example was applied to a silicon wafer using a spin coater under conditions that would result in an expected cured film thickness of approximately 3.0 μm. It was then dried on a hot plate at 90°C for 3 minutes to obtain a dried coating of the curable resin composition 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 values ​​from 2 / 2 μm to 10 / 10 μm were exposed at 1 μm intervals, and post-exposure heating (PEB) was performed on a hot plate for 60 seconds. The heating temperature for the PEB process was as shown in Table 1. Subsequently, the sample was developed for 30 seconds using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, rinsed with ultrapure water for 30 seconds, and spin-dried for 30 seconds to obtain a sample with a pattern.

[0139] The samples of each example and comparative example obtained were 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 (observation magnification of 10,000x), and the film thickness and the smallest L / S size for properly patterned patterns are listed in Table 1. A smaller minimum L / S size indicates better resolution. Samples in which each pattern was patterned vertically without tilting were judged to be properly patterned.

[0140] (Adhesion Evaluation) Varnish was applied to a silicon wafer using a spin coater, and then dried at 90°C for 3 minutes using a hot plate to obtain a dried film of the resin composition (approximately 5 μm thick). The obtained dried film was exposed to an exposure dose of 1,000 mJ / cm². ２ The entire surface was exposed to UV (365 nm) light, then heated at 120°C for 1 minute, and finally heated in an inert gas oven {CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.} under a nitrogen atmosphere at 220°C for 60 minutes to obtain a cured film on a silicon wafer.

[0141] The hardened film obtained in this way was then cut with a single blade to create a grid pattern of 100 1 mm squares, and the number of squares that remained intact after being peeled off with cellophane tape (registered trademark) was measured.

[0142]

[0143] The curable resin composition, dry film, and cured product of the present invention exhibit excellent adhesion to silicon substrates, and can therefore be suitably used as forming materials for display devices, semiconductor elements, electronic components, optical components, building materials, and the like. Cross-reference of related applications

[0144] This application claims priority based on Japanese Patent Application No. 2024-160189, 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 curable resin composition comprising (A) a polyhydroxyamide compound, (B) a crosslinking agent, (C) a compound having a phenolic hydroxyl group and a reactive double bond, and (D) a photoacid generator, wherein the (B) crosslinking agent comprises a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in its molecular structure, and the (A) polyhydroxyamide compound is a compound containing structural units represented by the following formulas (1) and (2). {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 curable resin composition according to claim 1, wherein the crosslinking agent (B) comprises a heterocycle.

3. The curable resin composition according to claim 1, wherein the compound having a phenolic hydroxyl group and a reactive double bond is represented by the following formula (3). {In formula (3), R ５ It is a group that has a reactive double bond.

4. (E) The curable resin composition according to claim 1, further comprising a photoradical generator.

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

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

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