Curable resin composition, dry film, and cured product

Abstract

The present invention provides: a curable resin composition exhibiting excellent adhesion to a silicon substrate; a dry film comprising 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. [Solution] 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 is a compound containing a structural unit represented by the following formula (1) and a specific structure. TIFF2026054861000027.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 a curable resin composition, a dry film, and a cured product. [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, with the requirements for higher performance and miniaturization of electronic components and electrical equipment, further high integration of semiconductor elements has been demanded. To meet these requirements, high-performance and miniaturization technologies in the field of semiconductor element packages such as wafer-level packages (WLPs) have been developed. In the insulating film used for the rewiring layer, it is also necessary to have sufficient adhesion to the silicon substrate in particular in order to achieve further miniaturization of pattern formation.

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

Means for Solving the Problems

[0008] The inventors of the present invention have found that the above 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, aspects of the present invention are as follows.

[0009] One aspect of the present invention is a curable resin composition. The curable resin composition includes (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. The (B) crosslinking agent includes a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in its molecular structure. The (A) polyhydroxyamide compound is a compound including structural units represented by the following formulas (1) and (2).

Chemical formula

Chemical formula

[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 the (C) phenolic hydroxyl group and reactive double bond is preferably represented by the following formula (3). [ka] {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. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide: a curable resin composition exhibiting excellent adhesion to a silicon substrate; a dry film comprising 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. [Modes for carrying out the invention]

[0016] Embodiments of the disclosed technology will be described in detail below. In this specification, unless otherwise specified, the notation "a to b" in descriptions of numerical ranges means a or greater and b or less.

[0017] 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.

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

[0019] In this specification, "substituent" is not particularly limited and, unless otherwise specified, includes, for example, hydroxyl groups, phenol 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, and the like.

[0020] In this specification, "(meth)acrylic" means both "acrylic" and "methacrylic." Similarly, "(meth)acrylate" means both "acrylate" and "methacrylate."

[0021] In this specification, "solids content" refers to components other than solvents (especially organic solvents) among the components constituting the curable resin composition or each raw material, and unless otherwise specified, it is based on mass.

[0022] 1. Curable resin composition The curable resin composition of this embodiment preferably 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. Furthermore, the curable resin composition of this embodiment preferably further comprises (E) a photoradical generator, and may further comprise basic compounds or the like.

[0023] 1-1. (A) Polyhydroxyamide compounds (A) Polyhydroxyamide compounds contain structural units represented by the following formulas (1) and (2). [Chemistry] {In formula (1), R 1 is a divalent organic group, and R 2 is a tetravalent organic group.} [Chemistry] {In formula (2), R 3 is a divalent organic group, and R 4 is a divalent organic group that does not contain a hydroxyl group.}

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

[0025] R 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.

[0026] From the viewpoint of the resolution of the curable resin composition, the number of carbon atoms of R 1 is preferably 4 to 30, and phenyl, biphenyl, diphenyl ether, and diphenyl hexafluoropropane are preferred. In addition, two or more of the groups exemplified above as R <00​

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

[0030] R in equation (2) 3Among the divalent organic groups mentioned 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 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.

[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, and phenyl, biphenyl, diphenyl ether, and diphenylhexafluoropropane are preferred. In addition, the polyhydroxyamide compound contains R 3 It is also possible to include two or more of the groups exemplified above.

[0032] R in equation (2) 4 The 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.

[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. [ka] {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 compounds of this embodiment preferably do not have a perfluoroalkyl skeleton. 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.

[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 termini, 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 compounds 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 using this range, it is possible to form a finer L / S pattern with 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 are 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 (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

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

[0049] (A) As a method for producing polyhydroxyamide compounds, 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 other compounds copolymerizable with these are copolymerized as raw materials. Examples of other copolymerizable compounds include diol compounds, acid dianhydrides, diisocyanate compounds, and diamine compounds different from the dihydroxydiamino compound represented by formula (6). [ka] {In formula (6), R 2 This is as stated above. [ka] {In formula (7), R 1 , R 3 This is as stated above. [ka] {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), 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 (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. [ka]

[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 undergo a crosslinking reaction with phenolic hydroxyl groups and carboxyl groups contained in (A) polyhydroxyamide compounds, etc., upon heating, using the acid generated from the photoacid generator described later as an active species. 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 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, 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.

[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) The phenolic compound is a compound having a phenolic hydroxyl group and a reactive double bond, and is not particularly limited as long as it is a different compound from the (A) polyhydroxyamide compound, (B) crosslinking agent, and (D) photoacid generator described later. (C) The phenolic compound may have a monocyclic or polycyclic structure. (C) The phenolic compound 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) The phenolic compound is preferably represented by the following formula (3). [ka] {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 group, (meth)acrylamide group, allyl group, vinyl group, allyl ether group, vinyl ether group, etc. Of these, (meth)acrylate group and (meth)acrylamide group 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 (C) phenolic compound, 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 (2) 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. [ka] [ka]

[0065] (C) Phenolic compounds may be used individually or in combination.

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

[0069] In formula (12) 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.

[0070] R in equation (12) above 6 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.

[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) The 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, benzyl, benzophenones, ketals, thioxanthones, and acylphosphine oxides.

[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 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)], compounds represented by the following formula (13) {2-(acetyloxyiminomethyl)thioxanthene-9-one}, compounds represented by the following formula (14) {e.g., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime)}, and other oxime ester compounds having a carbazole skeleton. [ka] [ka]

[0081] In formula (14), R 7R 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 a basic compound. In particular, when the curable resin composition of this embodiment contains a basic compound, it is possible to suppress the diffusion of the acid generated from the (D) photoacid generator to the unexposed areas upon 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-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.

[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 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.

[0099] 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 BICK CHEMI Corporation (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 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 needed.

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

[0103] 2-2. (B) Crosslinking agent (B) The crosslinking agent content can be 5 to 80 parts by mass when the total solid content of (A) polyhydroxyamide compound and (C) phenolic compound in the curable resin composition is 100 parts by mass. Furthermore, if the crosslinking agent (B) has methoxymethyl groups and / or methylol groups, the ratio of the number of methoxymethyl groups and / or methylol groups contained in the crosslinking agent (B) to the number of phenolic hydroxyl groups contained in the curable resin composition (methoxymethyl groups and / or methylol groups: phenolic hydroxyl groups) can be 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 a phenolic hydroxyl group and a reactive double bond {(C) Phenolic compounds} (C) The content of the phenolic compound can be such that the solid content mass ratio of (A) polyhydroxyamide compound to (C) phenolic compound in the curable resin composition (solid content mass of polyhydroxyamide compound: solid content mass of phenolic compound) 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 compound to (C) phenolic compound 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 (D) The content of the 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 (E) The content of 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 adding a basic compound, the amount can be 0.01 to 1.00 parts by mass, preferably 0.05 to 0.50 parts by mass, based on a total solid content of (A) polyhydroxyamide compound and (C) phenolic compound in the curable resin composition of 100 parts by mass. This range makes it easier to suppress the generation of development residue in 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. 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.

[0114] 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.

[0115] 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.

[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 process with light such as ultraviolet 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 fine patterning, a maximum wavelength of 410 nm or less is preferred. The irradiation energy can be adjusted depending on the thickness of the formed dry coating, 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.

[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 acts as an active species in the exposed portion, and a crosslinking reaction proceeds between (A) a polyhydroxyamide compound, (C) a phenolic compound, and (B) a crosslinking agent, making the exposed portion insoluble in the developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be carried out by known methods such as a hot plate or a heating furnace.

[0121] 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.

[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 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.

[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 (D) photoacid generator and treating the coating with a developer in the above development step, thereby dissolving and removing the exposed parts of the dried coating in the developer.

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

[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 (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-1) (BAP-2E6MA-DEDC-3AP). [ka]

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

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

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

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

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

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

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

[0136] <Preparation of curable resin composition> Each component was blended in the amounts shown in Table 1, and by dissolving each component in a solvent, varnishes of the curable resin compositions for each example and comparative example were obtained. Note that, except for the solvent, the amounts of each component in Table 1 represent the solid content by mass.

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

[0138] (Resolution evaluation) • Line / space (L / S) measurement 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 3.0 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, followed by 60 seconds of post-exposure heating (PEB) on a hot plate. The heating temperatures for the PEB process were as shown in Table 1. Subsequently, the films were developed using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, rinsed with ultrapure water for 30 seconds, and spin-dried for 30 seconds to obtain samples with patterns.

[0139] The samples of each example and comparative example 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 (magnification 10,000x), and the film thickness, the smallest 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.

[0140] (Evaluation of adhesion) A varnish was applied to a silicon wafer using a spin coater, and then dried on a hot plate at 90°C for 3 minutes to obtain a dried film (approximately 5 μm thick) of the resin composition. The resulting dried film was exposed to an exposure dose of 1,000 mJ / cm². 2 The entire surface was exposed to UV (365nm) light, then heated at 120°C for 1 minute, and finally heated in an inert gas oven {Koyo Thermo Systems Co., Ltd., CLH-21CD-S} 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 1mm squares, and the number of squares that remained intact after being peeled off with cellophane tape (registered trademark) was measured.

[0142] [Table 1] [Industrial applicability]

[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.

Claims

1. (A) Polyhydroxyamide compounds, (B) Crosslinking agent and (C) Compounds having a phenolic hydroxyl group and a reactive double bond, (D) A photoacid generator, The crosslinking agent (B) comprises a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in its molecular structure. The (A) polyhydroxyamide compound is a curable resin composition comprising structural units represented by the following formulas (1) and (2). 【Chemistry 1】 {In formula (1), R １ R is a divalent organic group. ２ It is a tetravalent organic group. 【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.

2. The curable resin composition according to claim 1, wherein the crosslinking agent (B) comprises a heterocycle.

3. The (C) compound having a phenolic hydroxyl group and a reactive double bond is represented by the following formula (3), the curable resin composition according to claim 1. 【Transformation 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 from 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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