Photosensitive resin composition, dry film, cured product, and electronic component

Abstract

To provide a new photosensitive resin composition having superior adhesion to a Si wafer.SOLUTION: A photosensitive resin composition in one form of the present disclosure comprises a polyhydroxyurea compound having a structural unit represented by formula (1), a photoacid generator, and a crosslinking agent.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Photosensitive resin compositions that utilize a ring-closure reaction of polyhydroxyamide, a polybenzoxazole precursor, are widely used in various fields such as semiconductors and electronic components.

[0003] Patent Document 1 discloses a polyhydroxyamide-based photosensitive resin composition containing a polybenzoxazole precursor, a compound that generates an acid when irradiated with actinic rays in a specific wavelength range, a crosslinkable or polymerizable compound, and a compound that generates an acid when heated. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-203359 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the demand for higher performance and smaller size of electronic components and electrical devices, there has been a demand for even higher integration of semiconductor elements. To meet these demands, technologies for higher performance and smaller size in the field of semiconductor elements, such as wafer-level packaging (WLP), have been developed, and photosensitive resin compositions used in semiconductor elements are required to have improved adhesion to substrates such as Si wafers. However, with polyhydroxyamide-based photosensitive resin compositions such as those disclosed in Patent Document 1, there is a risk that sufficient adhesion to Si wafers cannot be obtained.

[0006] Therefore, an object of the present invention is to provide a novel photosensitive resin composition that has excellent adhesion to Si wafers. [Means for solving the problem]

[0007] One embodiment of the present invention is a photosensitive resin composition. The photosensitive resin composition contains a polyhydroxyurea compound having a structural unit represented by the following formula (1), a photoacid generator, and a crosslinking agent. [ka]

[0008] The crosslinking agent is preferably a compound having one or more groups selected from the group consisting of a methoxymethyl group and a methylol group. The photoacid generator preferably contains an oxime sulfonate compound. It is preferable that R1 contains the polyhydroxyurea compound represented by the following formula (2). [ka] (In formula (2), R3 is a single bond or a divalent organic group. * is a bonding site.) It is preferable to include the polyhydroxyurea compound in which R2 is an alkylene group having 1 to 10 carbon atoms or a divalent group having an aromatic ring or an aliphatic ring. It is preferable that the polyhydroxyurea compound contains the polyhydroxyurea compound in which R2 is any one selected from the following formulae (a) to (d). [ka] (In formulas (a) to (d), * indicates a binding site.)

[0009] Another aspect of the present invention is a dry film comprising a resin layer formed from the photosensitive resin composition.

[0010] Another aspect of the present invention is a cured product obtained by curing the photosensitive resin composition.

[0011] Another aspect of the present invention is an electronic component having the cured product. [Effects of the Invention]

[0012] According to the present invention, a novel photosensitive resin composition having excellent adhesion to a Si wafer can be provided. [Brief explanation of the drawings]

[0013] [Figure 1] 1H-NMR spectra of polyhydroxyurea compounds A-1, A-2, and A-3. [Figure 2] 1 is a 1H-NMR spectrum of polyhydroxyurea compound B-1. [Figure 3] 1 is a 1H-NMR spectrum of polyhydroxyurea compound B-2. [Figure 4] 1 is a 1H-NMR spectrum of polyhydroxyurea compound B-3. [Figure 5] 1H-NMR spectrum of polyhydroxyurea compound B-4. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expression "a to b" in the description of a numerical range means a to b, unless otherwise specified.

[0015] In this specification, when multiple upper limit values ​​and multiple lower limit values ​​are separately described, all numerical ranges that can be set by freely combining these upper limit values ​​and lower limit values ​​are considered to be described in this specification.

[0016] In this specification, when a compound is described, its isomers are also described.

[0017] The "substituent" is not particularly limited, and unless otherwise specified, examples thereof include a hydroxyl group, a phenol group, a phenyl group, a halogen group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, a thioester group, an aldehyde group, an acetyl group, and the like.

[0018] In this specification, the solid content means the components other than the solvent (solvent) among the components constituting the photosensitive resin composition or each raw material, and is based on mass unless otherwise specified.

[0019] The composition, production method, and uses of the photosensitive resin composition according to the present disclosure will be described below.

[0020] <<<Composition of photosensitive resin composition>>> The photosensitive resin composition according to the present disclosure includes a polyhydroxyurea compound, a photoacid generator, and a crosslinking agent. The photosensitive resin composition according to the present disclosure may also include other components. Each component will be described below.

[0021] <<Polyhydroxyurea compounds>> <Structure> The polyhydroxyurea compound has a structural unit represented by the following formula (1).

[0022] [ka]

[0023] In formula (1), R1 is a tetravalent organic group, and R2 is a divalent organic group.

[0024] In a polyhydroxyurea compound containing the structural unit represented by formula (1) as a repeating unit, R 1、 Each R2 may be the same or different.

[0025] R1 and R2 may be organic groups containing fluorine or organic groups not containing fluorine.

[0026] Preferred examples of R1 and R2 in formula (1) will be described.

[0027] R1 preferably has 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and preferably has 30 or less, 25 or less, or 20 or less carbon atoms.

[0028] Examples of R1 include a tetravalent organic group having an aliphatic hydrocarbon skeleton or a tetravalent organic group having an aromatic ring skeleton. Examples of aromatic rings include benzene, diphenyl, diphenylmethane, diphenylpropane (2,2-diphenylpropane, 1,3-diphenylpropane, etc.), biphenyl, etc. The aromatic ring may also contain a heteroatom, such as diphenyl ether, diphenyl thioether, benzophenone, diphenylhexafluoropropane, diphenyl sulfoxide, or diphenyl sulfone.

[0029] R1 is preferably a tetravalent organic group represented by the following formula (2).

[0030] [ka]

[0031] In formula (2), R3 is a single bond or a divalent organic group. Examples of the divalent organic group include an ether bond, a sulfonyl group, a group having a fluorene skeleton, and an alkylene group. * denotes a bonding site.

[0032] Regarding the bonding site * in formula (2), typically, a hydroxyl group and an amine group are bonded to the aromatic ring bonded to one side of R3, and a hydroxyl group and an amine group are bonded to the aromatic ring bonded to the other side of R3. In this case, it is preferable that the amine group is bonded to the meta position and the hydroxyl group is bonded to the para position of each aromatic ring, with the position to which R3 is bonded being considered the ipso position.

[0033] In formula (2), R3 is preferably an alkylene group having 1 to 10 carbon atoms, 2 to 5 carbon atoms, or 3 to 5 carbon atoms.

[0034] R3 is preferably an organic group represented by the following formula (2-1).

[0035] [ka]

[0036] In formula (2-1), a is an integer of 0 to 3. * is a bonding site.

[0037] In formula (1), R2 is preferably an alkylene group having 1 to 10 carbon atoms or a divalent group having an aromatic ring or an aliphatic ring.

[0038] The alkylene group preferably has 2 to 8 carbon atoms or 4 to 8 carbon atoms.

[0039] The number of carbon atoms in the divalent group having an aromatic ring or an aliphatic ring is preferably 6 or more, and is preferably 30 or less, 25 or less, 20 or less, or 15 or less. Examples of the aromatic ring include benzene, diphenyl, diphenylmethane, and diphenylpropane. The aromatic ring may also contain a heteroatom, such as diphenyl ether, diphenyl thioether, benzophenone, diphenylhexafluoropropane, diphenyl sulfoxide, and diphenyl sulfone. The divalent group having an aromatic ring or an aliphatic ring preferably does not contain a heteroatom.

[0040] R2 is preferably any one of the following formulae (a) to (f), and more preferably any one of the following formulae (a) to (d). In particular, from the viewpoint of obtaining a photosensitive resin composition with excellent resolution, it is even more preferably any one of (a), (c), or (d).

[0041] [ka]

[0042] R2 can also be expressed as a structure in which the isocyanate group of a conventionally known isocyanate compound (for example, the isocyanate compound described below) is substituted with a bonding site (*).

[0043] The polyhydroxyurea compound may have an alkali-soluble group at its terminal, which 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, and an active methylene group.

[0044] From the viewpoint of solubility in a developer, the polyhydroxyurea compound preferably has a carboxyl group or a phenolic hydroxyl group at its terminal, and particularly preferably has a phenolic hydroxyl group at its terminal. Since the phenolic hydroxyl group has lower reactivity than the carboxyl group, excessive reaction with the crosslinker is suppressed, and the solubility of the unexposed area in the developer can be maintained even after the PEB process. This allows the resolution to be maintained, and it is presumed that a photosensitive resin composition capable of forming a finer L / S pattern with a high aspect ratio can be provided.

[0045] The alkali-soluble group contained at the terminal of the polyhydroxyurea compound may be a residue of a monomer constituting the polyhydroxyurea compound, or may be introduced by a terminal-capping agent having an alkali-soluble group. Terminal-capping agents will be described later.

[0046] <Physical properties> The weight-average molecular weight (Mw) of the polyhydroxyurea compound is preferably 1,000 or more, 2,000 or more, or 3,000 or more, and is preferably 50,000 or less, 40,000 or less, or 30,000 or less. By setting the weight-average molecular weight within this range, it becomes possible to form a finer L / S pattern with a higher aspect ratio.

[0047] The number average molecular weight (Mn) of the polyhydroxyurea compound is preferably 1,000 or more, 1,5000 or more, or 2,000 or more, and is preferably 10,000 or less, 8,000 or less, or 6,000 or less.

[0048] The polyhydroxyurea compound preferably has a molecular weight dispersity index (PDI) of 1.5 to 25.0, more preferably 1.5 to 10.0. The molecular weight dispersity index (PDI) is calculated by the following formula. PDI=Mw / Mn

[0049] When the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight dispersity (PDI) of the polyhydroxyurea compound are within the above ranges, a favorable balance is achieved between the solubility in a developer in the unexposed area and the reaction with a crosslinker during exposure, making it easier to obtain a photosensitive resin composition with excellent resolution.

[0050] <Content> The content of the polyhydroxyurea compound represented by formula (1) in the photosensitive resin composition is preferably 50 to 80 mass % when the total mass of the solid content of the photosensitive resin composition is taken as 100 mass %.

[0051] <Synthesis method> An example of a method for synthesizing the polyhydroxyurea compound represented by formula (1) will be described below.

[0052] The polyhydroxyurea compound represented by formula (1) can be obtained by reacting an amine compound represented by the following formula (I) with an isocyanate compound represented by the following formula (II).

[0053] [ka]

[0054] In formula (I), R1 is the same as R1 in formula (1), and therefore a description thereof will be omitted.

[0055] [ka]

[0056] In formula (II), R2 is the same as R2 in formula (1), and therefore a description thereof will be omitted.

[0057] Specific examples of the compound represented by formula (I) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene.

[0058] Examples of the compound represented by formula (II) include diisocyanate compounds having an alkylene group (alkylene diisocyanate compounds), diisocyanate compounds having an aromatic ring (aromatic diisocyanate compounds), and diisocyanate compounds having an aliphatic ring (alicyclic diisocyanate compounds).

[0059] Examples of the alkylene diisocyanate compound include butane-1,4-diisocyanate, hexamethylene diisocyanate, and isopropylene diisocyanate.

[0060] Examples of aromatic diisocyanate compounds include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate (XDI), and tetramethylxylene diisocyanate (TMXDI).

[0061] Examples of the alicyclic diisocyanate compound include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexane-1,3-diylbismethylene diisocyanate, and methylcyclohexane diisocyanate.

[0062] The compound represented by formula (II) is preferably any of the compounds represented by the following formulae (a1) to (f1), more preferably any of the compounds represented by the following formulae (a1) to (d1), and even more preferably any of the compounds represented by the following formulae (a1), (c1) or (d1).

[0063] [ka]

[0064] By using a compound represented by formula (I) and a compound represented by formula (II) as monomers, an amino group and an isocyanate group react to form a urea bond, thereby synthesizing a polyhydroxyurea compound represented by formula (1). The conditions for synthesizing the polyhydroxyurea compound (such as temperature, reaction time, type of solvent and concentration of each monomer in the solvent, and the presence or absence of a catalyst) can be appropriately adjusted depending on the type of monomer used, etc.

[0065] As described above, the polyhydroxyurea compound represented by formula (1) may have an alkali-soluble group introduced as a terminal structure by an end-capping agent. In other words, an end-capping agent may be used in the synthesis of the polyhydroxyurea compound represented by formula (1).

[0066] The end-capping agent is, for example, a compound having a group capable of reacting with an amino group or a hydroxyl group derived from the compound represented by formula (I), or a group capable of reacting with an isocyanate group derived from the compound represented by formula (II), and an alkali-soluble group.

[0067] The end-capping agent is not particularly limited, and examples thereof include aminophenol compounds such as 2-aminophenol, 3-aminophenol, and 4-aminophenol; compounds having one amino group and a hydroxyl group such as hydroxybenzylamine compounds, aminobenzyl alcohol compounds, and alcoholamine compounds; compounds having one carboxyl group and a hydroxyl group such as hydroxy acids; compounds having an amino group and a carboxyl group such as aminobenzoic acid and amino acids; acid anhydride compounds such as phthalic anhydride and 5-norbornene-2,3-dicarboxylic anhydride; and acid anhydride compounds having a hydroxyl group such as hydroxy acid anhydrides.

[0068] For example, when an aminophenol compound such as 2-aminophenol, 3-aminophenol, or 4-aminophenol is used as the end-capping agent, the isocyanate group derived from the isocyanate compound and the amino group of the aminophenol compound are bonded to obtain a polyhydroxyurea compound having a terminal structure represented by the following formula (1-1):

[0069] [ka]

[0070] In formula (1-1), R1 and R2 are the same as R1 and R2 in formula (1), respectively.

[0071] The amount of the end-capping agent used in the synthesis of the polyhydroxyurea compound can be adjusted appropriately taking into consideration the amount of each monomer, the molecular weight of the desired polyhydroxyurea compound, the introduction ratio of the end structure of the polyhydroxyurea compound, and the like.

[0072] In the synthesis of the polyhydroxyurea compound, the end-capping agent may be mixed simultaneously with each monomer, or the end-capping agent may be additionally mixed during the reaction of each monomer or after the reaction is completed.

[0073] Unlike polyhydroxyamide compounds, the polyhydroxyurea compound according to the present disclosure can be synthesized without using a carboxylic acid dichloride derivative, and therefore it is possible to obtain a composition that is free of or contains very little impurities such as chlorine. Furthermore, by using such a polyhydroxyurea compound in combination with a photoacid generator and a crosslinking agent, which will be described later, it is possible to obtain a cured product that has excellent adhesion to a Si wafer.

[0074] <<Photoacid generator>> The photoacid generator is not particularly limited as long as it is a compound that generates an acid when irradiated with light such as ultraviolet light or visible light.

[0075] Examples of photoacid generators include naphthoquinone diazide compounds, diaryl sulfonium salts, triaryl sulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryl diazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonate esters, nitrobenzyl esters, aromatic N-oxyamidosulfonates, aromatic N-oxyimidosulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimides, benzoquinone diazosulfonate esters, etc. These can be used alone or in combination in any ratio.

[0076] The photoacid generator is preferably an oxime sulfonate compound from the viewpoint of achieving better resolution and insulation reliability, and more preferably one having a structure of the following formula (3).

[0077] [ka]

[0078] In formula (3), X is a monovalent organic group, m is an integer of 0 to 3, R A is a monovalent organic group.

[0079] In the above formula (3), m is preferably 0 or 1. When m is 2 or 3, multiple Xs may be the same or different.

[0080] R in the above formula (3) A is preferably 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 may be substituted with a halogen atom. The halogen atom is, for example, a chlorine atom or a fluorine atom.

[0081] R AWhen contains a hydrocarbon group, the hydrocarbon group is preferably a linear, branched or cyclic group having 1 to 20 carbon atoms, and more preferably a linear, branched or cyclic group having 1 to 10 carbon atoms.

[0082] The oxime sulfonate compound may be a commercially available product such as Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, or Irgacure PAG203 manufactured by BASF.

[0083] The content of the photoacid generator in the photosensitive resin composition is preferably 0.1 to 20 parts by mass, or 0.5 to 10 parts by mass, relative to 100 parts by mass of the solid content of the polyhydroxyurea compound in the photosensitive resin composition.

[0084] <<Crosslinking agent>> The crosslinking agent is not particularly limited, and known crosslinking agents can be used.

[0085] Examples of the crosslinking agent include melamine compounds, guanamine compounds, triazine compounds, epoxy compounds, oxetane compounds, isocyanate compounds, and oxazoline compounds.

[0086] The crosslinking agent is preferably a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group. These functional groups, using the acid generated from the photoacid generator described below as the active species, undergo a crosslinking reaction with phenolic hydroxyl groups or carboxyl groups contained in polyhydroxyurea compounds and the like upon heating, thereby achieving negative photolithography (pattern formation) through exposure, PEB, and development. Furthermore, by further heating after pattern formation, the curing reaction of the photosensitive resin composition progresses, and the cured product exhibits excellent properties.

[0087] Furthermore, the crosslinking agent preferably contains a heterocycle, which improves the resolution of the photosensitive resin composition and the insulating reliability after curing. The heterocycle is not particularly limited and contains one or more heteroatoms such as boron, nitrogen, oxygen, phosphorus, sulfur, antimony, arsenic, bismuth, selenium, silicon, tellurium, or tin, and includes a 3-, 4-, 5-, 6-, 7-, or 8-membered saturated or unsaturated ring. From the viewpoints of the resolution of the photosensitive resin composition and the insulating reliability of the cured product, the heterocycle is preferably a nitrogen-containing heterocycle, and more preferably a heterocycle containing multiple nitrogen atoms.

[0088] Specific examples of the crosslinking agent include compounds having a triazine structure such as hexamethylolmelamine and hexamethoxymethylmelamine, compounds having a guanamine structure such as tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanamine, compounds having a glycoluril structure such as tetramethylolglycoluril and tetramethoxyglycoluril, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone. From the viewpoint of being able to provide a photosensitive resin composition capable of forming an L / S pattern that is finer and has a higher aspect ratio, the crosslinking agent is preferably a compound having a triazine structure containing a triazine ring or a compound having a guanamine structure.

[0089] The content of the crosslinking agent in the photosensitive resin composition is preferably 5 to 80 parts by mass, assuming that the mass of the solid content of the polyhydroxyurea compound in the photosensitive resin composition is 100 parts by mass. Furthermore, when the crosslinking agent has a methoxymethyl group and / or a methylol group, the content of the crosslinking agent is preferably such that the ratio of the number of methoxymethyl groups and methylol groups contained in the crosslinking agent to the number of phenolic hydroxyl groups contained in the photosensitive resin composition (total of methoxymethyl groups and methylol groups:phenolic hydroxyl groups) is 120:100 to 200:100. By achieving such a ratio, the resolution of the photosensitive resin composition and the insulation reliability after curing can be improved.

[0090] <<Other ingredients>> The photosensitive resin composition of the present disclosure may contain other components as long as the effects of the present disclosure are not impaired. Examples of other components include known components that can be contained in photosensitive resin compositions. More specifically, examples of other components include basic compounds, surfactants, fillers, adhesion agents, plasticizers, thermal acid generators, sensitizers, leveling agents, colorants, fibers, and fine particles.

[0091] The photosensitive resin composition preferably contains a basic compound, which can prevent the acid generated from the photoacid generator upon exposure from diffusing into the unexposed area, thereby improving the resolution and preventing development residues from being generated in the unexposed area after development.

[0092] The basic compound is not particularly limited, and examples thereof include trimethylamine, diethylamine, triethylamine, N,N-diisopropylethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, tris(2-methoxy)amine, bis(2-methoxy)amine, tris(2-ethoxy)amine, bis(2-ethoxy)amine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4, Amine compounds such as 4'-diaminodiphenylamine; amide compounds such as formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide; lactams such as pyrrolidone and N-methylpyrrolidone; methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3-diphenyl Examples of suitable amine compounds include urea and other urea compounds; nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and pyridine; and morpholine compounds such as morpholine and 4-methylmorpholine. These compounds can be used alone or in combination in any ratio. Among these, amine compounds are preferred, with alcoholamines such as N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine being more preferred, and diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine being even more preferred.

[0093] When a basic compound is added, the content thereof can be 0.01 to 1.0 parts by mass, and preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the solid content of the polyhydroxyurea compound in the photosensitive resin composition.

[0094] The surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, etc. Commercially available fluorine-based surfactants include the "Megafac" series manufactured by DIC Corporation (e.g., Megafac F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-569, etc.). Commercially available silicone surfactants include the BYK-Chemie surface conditioner series (e.g., BYK-302, BYK-307, BYK-310, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK-348, BYK-349, BYK-377, BYK-378, BYK-3455, BYK-3760, etc.). These may be used alone or in combination of two or more.

[0095] The photosensitive resin composition may also contain an appropriate solvent.

[0096] The solvent is not particularly limited, and examples thereof include ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethyl sulfone, and pyridine.

[0097] 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.

[0098] 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.

[0099] Ketones include methyl ethyl ketone; methyl isobutyl ketone (4-methyl-2-pentanone); 2-heptanone; cycloalkanones such as monoketones, such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone; 1,3-cyclopentanedione, 3-methyl-1,2-cyclopentanedione, and 2-methyl-2-pentanone; Examples of the cycloalkanones include diketone cycloalkanones such as 4-methyl-2-cyclopentenone, 2-cyclohexenone, 2-cyclopenten-1-one, and 2-cyclohexen-1-one; cycloalkenones such as 4-methyl-2-cyclopentenone, 2-cyclohexenone, 2-cyclopenten-1-one, and 2-cyclohexen-1-one; and cyclic ketones having a heterocyclic skeleton such as 2-azetidinone, 4,5-dihydro-3(2H)-thiophenone, 4-oxothiane, and dihydrolevogluconocene.

[0100] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0101] Examples of lactones include γ-butyrolactone (GBL), lactams include N-methylpyrrolidone and N-methylcaprolactam, and sulfoxides include dimethyl sulfoxide and hexamethyl sulfoxide.

[0102] These solvents can be used alone or in combination in any ratio. Among these solvents, lactones or cyclic ketones are preferred, and γ-butyrolactone or cyclopentanone is more preferred, from the viewpoint of excellent affinity with each component in the photosensitive resin composition.

[0103] Furthermore, from the viewpoints of excellent solvent removability during drying of the photosensitive resin composition and suitability for the edge rinse step in semiconductor manufacturing, cyclic ketones are preferred, and monoketone cycloalkanones are more preferred, with cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone being even more preferred, and cyclopentanone being particularly preferred.

[0104] <<<Method for producing photosensitive resin composition>>> The photosensitive resin composition according to the present disclosure can be obtained by mixing the polyhydroxyurea compound represented by formula (1), a crosslinking agent, a photoacid generator, and other components as needed. The mixing of the components can be carried out under heating as needed.

[0105] <<<Applications / Methods of Use of Photosensitive Resin Compositions>>> The photosensitive resin composition according to the present disclosure is preferably used as a negative photosensitive resin composition. Hereinafter, a dry film and a cured product obtained using the photosensitive resin composition according to the present disclosure will be described.

[0106] <<Dry film>> The dry film of the present embodiment includes a substrate and a resin layer formed on the substrate using the photosensitive resin composition of the present embodiment. In addition, a protective film may be further laminated on the surface of the resin layer to protect the resin layer.

[0107] The resin layer can be obtained, for example, by applying a photosensitive resin composition onto a substrate, adjusting the thickness of the resin layer using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., and drying the resin layer. The thickness of the resin layer is not particularly limited and can be set to 1 to 150 μm depending on the application.

[0108] The substrate is not particularly limited, and examples thereof include metal foils such as copper foils; and films such as polyimide films, polyester films, and polyethylene naphthalate (PEN) films.

[0109] The protective film is not particularly limited, and polyethylene film, polytetrafluoroethylene film, polypropylene film, paper, etc. can be used. It is preferable to select a protective film such that the adhesion between the protective film and the resin layer is lower than the adhesion between the substrate and the resin layer. In order to make the adhesion between the protective film and the resin layer lower than the adhesion between the substrate and the resin layer, a protective film whose surface has been subjected to a release treatment can be used.

[0110] <<Cured product>> The cured product according to the present disclosure is a product obtained by curing a photosensitive resin composition or a resin layer of a dry film. The cured product may be patterned.

[0111] An example of a method for producing a patterned cured product using a negative photosensitive resin composition will be described below.

[0112] <Dry coating formation process> The dry coating film forming step is a step of applying the above-mentioned photosensitive resin composition onto a substrate to form a coating film, and then drying the coating film. In the dry coating film forming step, it is also possible to form a dry coating film on a substrate by laminating a resin layer of a dry film onto the substrate.

[0113] The method for applying the photosensitive resin composition to a substrate is not particularly limited, and examples thereof include application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spray application using a spray coater, and inkjet printing. The thickness of the applied film is not particularly limited, and can be, for example, 10 μm or less, 5 μm or less, or 3 μm or less. By reducing the film thickness, finer L / S patterning becomes possible while maintaining the aspect ratio of the pattern.

[0114] The drying method of the coating film is not particularly limited, and examples thereof include blow drying, heat drying using an oven or a hot plate, vacuum drying, etc. When performing heat drying, the conditions are, for example, a heating temperature of 70 to 140 °C and a drying time of 1 to 30 minutes.

[0115] Lamination of the resin layer of the dry film onto the substrate is preferably carried out under pressure and heating using a vacuum laminator or the like. The heating temperature can be, for example, 60 to 100 °C.

[0116] The substrate is not particularly limited, and examples thereof can be a printed wiring board on which a circuit is formed, a flexible printed wiring board, and a wafer on which a semiconductor element is formed.

[0117] <Exposure process> In the exposure process, an active energy ray is irradiated through a photomask capable of forming a desired pattern on the dry coating film formed in the dry coating film forming process, thereby sensitizing the photoacid generator in the exposed portion and generating active species. When patterning is not required, there is no need to pass through a photomask. Also, a pattern may be directly drawn with a laser using a direct drawing apparatus.

[0118] As the wavelength of the active energy ray, one having a wavelength capable of activating the photoacid generator is used, and in order to perform miniaturized patterning, one having a maximum wavelength of 410 nm or less is preferable. The irradiation energy can be adjusted according to the thickness of the formed dry coating film, etc., and can be, for example, 10 to 1500 mJ / cm 2 and can be set. As the exposure light source, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, a KRF laser, etc., can be used.

[0119] <PEB process> The PEB process is a process in which the dried coating film exposed in the exposure process is heat-treated to impart development resistance to the exposed area of ​​the dried coating film (hereinafter sometimes abbreviated as "exposed area"). In the PEB process, an acid generated from a photoacid generator in the exposed area acts as an active species to promote a crosslinking reaction between a polyhydroxyurea compound or a compound containing a phenolic hydroxyl group and a crosslinking agent, thereby making the exposed area insoluble in a developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be performed using a known method such as a hot plate or a heating furnace.

[0120] <Developing process> The developing step is a step in which the dried coating film heated in the PEB step is treated with a developer to dissolve and remove the unexposed areas of the dried coating film in the developer, thereby obtaining a patterned coating film. As the developing method, a known method can be used, such as a rotary spray method, a paddle method, or an immersion method accompanied by ultrasonic treatment.

[0121] Known developers can be used, and examples of such developers include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, water-soluble organic solvents such as methanol, ethanol, and isopropyl alcohol, and surfactants can be added.

[0122] After treatment with the developer, the coating film can be washed with a rinse solution as needed to obtain a patterned coating film. The rinse solution is not particularly limited, and examples thereof include pure water, methanol, ethanol, and isopropyl alcohol. These can be used alone or in combination in any ratio.

[0123] <Post-development heating process> The post-development heating step is a step in which the patterned coating film formed in the development step is heated to complete curing of the patterned coating film and obtain a cured patterned coating film (cured product). The heating temperature can be 150 to 200°C, and the heating time can be 1 to 120 minutes. Heating can be performed by a known method such as a hot plate or an inert oven, and heating is preferably performed under a nitrogen atmosphere.

[0124] <<Applications>> The photosensitive resin composition and its cured product can be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, etc. Examples of forming materials for semiconductor elements include resist materials, buffer coating films, and insulating films for rewiring layers in wafer-level packages (WLPs). Examples of forming materials for electronic components include printed wiring boards, interlayer insulating films, and wiring coating films. [Example]

[0125] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the following.

[0126] <<Polyhydroxyurea compounds>> Polyhydroxyurea compounds A-1 to A-3 and polyhydroxyurea compounds B-1 to B-4 were synthesized as follows.

[0127] <Polyhydroxyurea compound A-1> In a 120 mL vial equipped with a stirrer and thermometer (room temperature), 23.0 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 8.18 mmol of 3-aminophenol (3AP) were dissolved in cyclopentanone with stirring to a concentration of 25 wt %. Then, 27.0 mmol of hexamethylene diisocyanate (HMNCO) was added, and the mixture was stirred at room temperature for 18 hours. The solution was then poured into a large amount of ion-exchanged water, and the precipitate was collected. The precipitated solid was collected and dried under reduced pressure to obtain polyhydroxyurea compound A-1.

[0128] The weight average molecular weight of the polyhydroxyurea compound A-1 is 17,900, and the number average molecular weight is 4,500.

[0129] Regarding the obtained polyhydroxyurea compound A-1 1 H-NMR measurement confirmed that the polyhydroxyurea compound A-1 had a structure represented by the following formula (A1). 1 The results of H-NMR measurement are shown in Figure 1.

[0130] [ka]

[0131] <Polyhydroxyurea compound A-2> Polyhydroxyurea compound A-2 was obtained in the same manner as polyhydroxyurea compound A-1, except that the raw materials used were changed to 26.1 mmol of hexamethylene diisocyanate (HMNCO), 23.9 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), and 4.26 mmol of 3-aminophenol (3AP).

[0132] The weight average molecular weight of the polyhydroxyurea compound A-2 is 26,300, and the number average molecular weight is 7,100.

[0133] Similar to polyhydroxyurea compound A-1, polyhydroxyurea compound A-2 1 H-NMR measurement was performed. 1 The results of H-NMR measurement are shown in Figure 1.

[0134] <Polyhydroxyurea compound A-3> Polyhydroxyurea compound A-2 was obtained in the same manner as polyhydroxyurea compound A-1, except that the raw materials used were changed to 25.5 mmol of hexamethylene diisocyanate (HMNCO), 24.5 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), and 2.09 mmol of 3-aminophenol (3AP).

[0135] The weight average molecular weight of the polyhydroxyurea compound A-3 is 42,100, and the number average molecular weight is 5,900.

[0136] Similar to polyhydroxyurea compound A-1, polyhydroxyurea compound A-3 1 H-NMR measurement was performed. 1 The results of H-NMR measurement are shown in Figure 1.

[0137] <Polyhydroxyurea compound B-1> In a 120 mL vial equipped with a stirrer and thermometer (room temperature), 4.60 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) and 1.48 mmol of 3-aminophenol (3AP) were dissolved in N-methylpyrrolidone (NMP) with stirring to a concentration of 20 wt %. Then, 5.40 mmol of isoboron diisocyanate was added, and the mixture was stirred at room temperature for 18 hours. The solution was then poured into a large amount of ion-exchanged water, and the precipitate was collected. The precipitated solid was collected and dried under reduced pressure to obtain polyhydroxyurea compound B-1.

[0138] The polyhydroxyurea compound B-1 has a weight average molecular weight of 18,600 and a number average molecular weight of 6,400.

[0139] Regarding the obtained polyhydroxyurea compound B-1 1 H-NMR measurement was performed. 1 The results of H-NMR measurement are shown in Figure 2.

[0140] <Polyhydroxyurea compound B-2> Polyhydroxyurea compound B-2 was obtained in the same manner as polyhydroxyurea compound B-1, except that the raw materials used were changed to 15.9 mmol of hexamethylene diisocyanate, 14.0 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and 7.96 mmol of 3-aminophenol (3AP).

[0141] The polyhydroxyurea compound B-2 has a weight average molecular weight of 46,700 and a number average molecular weight of 11,700.

[0142] Regarding the obtained polyhydroxyurea compound B-2 1 H-NMR measurement was performed. 1 The results of H-NMR measurement are shown in Figure 3.

[0143] <Polyhydroxyurea compound B-3> Polyhydroxyurea compound B-3 was obtained in the same manner as polyhydroxyurea compound B-1, except that the raw materials used were changed to 16.2 mmol of 4,4'-diphenylmethane diisocyanate, 13.8 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and 9.38 mmol of 3-aminophenol (3AP).

[0144] The polyhydroxyurea compound B-3 has a weight average molecular weight of 33,000 and a number average molecular weight of 11,200.

[0145] Regarding the obtained polyhydroxyurea compound B-3 1 H-NMR measurement was performed. 1 The results of H-NMR measurement are shown in Figure 4.

[0146] <Polyhydroxyurea compound B-4> Polyhydroxyurea compound B-4 was obtained in the same manner as polyhydroxyurea compound B-1, except that the raw materials used were changed to 16.0 mmol of 2,4-toluene diisocyanate, 14.0 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and 8.07 mmol of 3-aminophenol (3AP).

[0147] The weight average molecular weight of the polyhydroxyurea compound B-4 is 26,800, and the number average molecular weight is 9,300.

[0148] Regarding the obtained polyhydroxyurea compound B-4 1 H-NMR measurement was performed. 1 The results of H-NMR measurement are shown in Figure 5.

[0149] <<Polyhydroxyamide compounds>> As a comparative compound, polyhydroxyamide compound C-1 (weight average molecular weight 9,500, number average molecular weight 3,800) was prepared. The compound was synthesized using 4,4'-oxybis(benzoyl chloride) (DEDC) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and had the repeating structure represented by formula (C) below.

[0150] [ka]

[0151] <<Photosensitive resin composition>> Polyhydroxyurea compounds A-1 to A-3, B-1 to B-4, and polyhydroxyamide compound C-1 were used as resin components, and the components shown in Table 1 were further mixed in the ratios (parts by mass) shown in Table 1 to obtain varnishes of photosensitive resin compositions according to Examples 1 to 7 and Comparative Example 1. Note that, among the parts by mass of each component shown in Table 1, the parts by mass of the components other than the solvent represent the mass of the solid content.

[0152] The components shown in Table 1 are as follows:

[0153] <Photoacid generator> PAG-103 (oxime sulfonate compound manufactured by BASF) [ka]

[0154] <Crosslinking agent> MW-390 (Hexamethoxymethylmelamine compound manufactured by Nippon Carbide Industries Co., Ltd.)

[0155] <Surfactant> BYK-310 (BYK-Chemie polyester-modified silicone surfactant)

[0156] <Basic compounds> Triethanolamine

[0157] <<Evaluation>> <Resolution> The resolution of the varnishes of the photosensitive resin compositions according to Examples 1, 3-5, and 7, and Comparative Example 1 was evaluated according to the following evaluation method. The evaluation results are shown in Table 1.

[0158] (Evaluation method) The varnish was applied to a silicon substrate using a spin coater to a thickness of approximately 3 μm after curing. It was then soft-baked on a hot plate at 90°C for 3 minutes to obtain a dried coating. A test pattern with L / S of 2 / 2 μm to 10 / 10 μm at 1 μm intervals was exposed to the dried coating using a contact exposure machine (UVE-251S+EL-100 (Minae Electric Mfg. Co., Ltd.)) and post-exposure baked (PEB) for 60 seconds on a hot plate. The heating temperature for the PEB process was 120°C. The film was then developed for 30 seconds using a 2.38% TMAH aqueous solution and rinsed for 30 seconds with ultrapure water. This was followed by another 30-second development, 30-second rinse with ultrapure water, and 30-second spin-drying to obtain a patterned sample. The resulting sample was then cut so that a cross section perpendicular to the longitudinal direction of the pattern could be observed. The cut surface of the pattern is observed using a scanning electron microscope (at a magnification of 10,000 times), and the size of the smallest L / S that is properly patterned is evaluated as the resolution.

[0159] <Adhesion> The adhesion of the varnishes of the photosensitive resin compositions according to Examples 1 to 7 and Comparative Example 1 was evaluated according to the following evaluation method. The evaluation results are shown in Table 1.

[0160] (Evaluation method) The varnish was applied to a silicon wafer using a spin coater to a thickness of 10 μm after curing, and then soft-baked on a hot plate at 90°C for 180 seconds to obtain a dried coating. The resulting dried coating was then subjected to surface exposure using UV light (wavelength 365 nm) at an exposure dose of 300.0 mJ, and further dried in an inert oven at 220°C for 1 hour to obtain a silicon wafer with a cured film formed on its surface. A total of 100 1x1 mm squares were cut into the resulting cured film using a utility knife, with 10 rows and 10 columns. The squares were then peeled off with tape, and the number of squares peeled off from the silicon wafer was counted. The number of squares remaining on the silicon wafer (number of remaining cured films / 100) was used to evaluate adhesion.

[0161] [Table 1] [Industrial Applicability]

[0162] The photosensitive resin composition according to the present disclosure has excellent adhesion and can therefore be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like.

Claims

1. A photosensitive resin composition comprising a polyhydroxyurea compound having a structural unit represented by the following formula (1), a photoacid generator, and a crosslinking agent: 【Chemical 1】 (In formula (1), R １ is a tetravalent organic group. ２ is a divalent organic group.

2. The photosensitive resin composition according to claim 1 , wherein the crosslinking agent comprises a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group.

3. The photosensitive resin composition according to claim 1 , wherein the photoacid generator comprises an oxime sulfonate compound.

4. The R １ The photosensitive resin composition according to claim 1, comprising the polyhydroxyurea compound represented by the following formula (2): 【Chemistry 2】 (In formula (2), R ３ is a single bond or a divalent organic group. * is a bonding site.

5. The R ２ is an alkylene group having 1 to 10 carbon atoms, or a divalent group having an aromatic ring or an aliphatic ring.

6. The R ２ The photosensitive resin composition according to claim 1, wherein the polyhydroxyurea compound is any one selected from the following formulas (a) to (d): 【Chemistry 3】 (In formulas (a) to (d), * indicates a binding site.)

7. A dry film comprising a resin layer formed from the photosensitive resin composition according to any one of claims 1 to 6.

8. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.

9. An electronic component comprising the cured product according to claim 8.

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