Resins, photosensitive resin compositions, dry films, cured products, and electronic components

Abstract

The present invention provides: a resin exhibiting excellent i-ray transparency; a photosensitive resin composition containing the resin; a dry film having a resin layer formed by the photosensitive resin composition; and a cured product obtained by curing the photosensitive resin composition or the resin layer of the dry film. [Solution] A resin having the structural unit of the following formula (1) is provided. TIFF2026119656000013.tif45170 {In formula (1), R1 is a tetravalent organic group, and R2 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.}

Description

Technical Field

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

Background Art

[0002] A photosensitive resin composition containing a polybenzoxazole precursor exhibits excellent properties such as insulation, heat resistance, and mechanical strength, and thus is widely used as an insulating film in various fields such as semiconductors and electronic components.

[0003] Conventionally, with the improvement in performance and miniaturization of electronic components and electrical devices, higher integration of semiconductor elements has been demanded. To meet this requirement, high-performance and miniaturization technologies in the field of semiconductor element packages such as wafer-level packages have been developed. In the insulating film used for the redistribution layer, excellent resolution is required for miniaturization of pattern formation.

[0004] Patent Document 1 discloses a photosensitive resin composition containing a polybenzoxazole precursor, a compound that generates an acid upon irradiation with actinic rays in a specific wavelength region, a compound that can be crosslinked or polymerized, and a compound that generates an acid by heat. According to the disclosure of 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

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, in order to further miniaturize semiconductor devices, there has been a demand for even better properties in the resins used in photosensitive resin compositions such as polybenzoxazole precursors, and in particular, excellent transmittance of the i-line (light with a wavelength of 365 nm) used for pattern formation.

[0007] Furthermore, perfluoroalkyl compounds (PFAS) and other permanent chemicals are being considered for international regulation due to reports of their association with health hazards. The negative-type photosensitive resin composition described in Patent Document 1 may contain a perfluoroalkyl skeleton in its polybenzoxazole precursor and may be subject to PFAS regulations. In the future, there may be a need for photosensitive resin compositions that can comply with PFAS regulations.

[0008] The perfluoroalkyl skeleton can improve the i-ray permeability of resins such as polybenzoxazole precursors due to its high electron-withdrawing properties and bulky structure. Therefore, the inventors have found that photosensitive resin compositions that do not have a perfluoroalkyl skeleton and can comply with PFAS regulations tend to have particularly low i-ray permeability and are difficult to form patterned resin films of desired shapes.

[0009] The present invention addresses the above-mentioned problems and aims to provide a resin exhibiting excellent i-ray transparency; a photosensitive resin composition containing the resin; a dry film having a resin layer formed by the photosensitive resin composition; and a cured product obtained by curing the photosensitive resin composition or the resin layer of the dry film. [Means for solving the problem]

[0010] One aspect of the present invention is a resin, which has the structural unit of the following formula (1). [ka] {In formula (1), R1 is a tetravalent organic group, and R2 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.}

[0011] In the resin of the above aspect, it is preferable that the structural unit represented by the formula (1) is a structural unit represented by the following formula (2).

Chemical formula

[0012] Another aspect of the present invention is a photosensitive resin composition. The photosensitive resin composition contains the resin of the above aspect, a crosslinking agent, and a photoacid generator.

[0013] In the photosensitive resin composition of the above aspect, it is preferable to further contain any one or more selected from the group consisting of alcoholamine compounds and alkoxyamine compounds.

[0014] Another aspect of the present invention is a dry film. The dry film includes a resin layer formed by the photosensitive resin composition of the above aspect.

[0015] Another aspect of the present invention is a cured product. The cured product is obtained by curing the resin layer of the photosensitive resin composition of the above aspect or the dry film of the above aspect.

[0016] Another aspect of the present invention is an electronic component. The electronic component has the cured product of the above aspect.

Advantages of the Invention

[0017] According to the present invention, it is possible to provide a resin exhibiting excellent i-line transparency; a photosensitive resin composition containing the resin; a dry film having a resin layer formed by the photosensitive resin composition; and a cured product obtained by curing the photosensitive resin composition or the resin layer of the dry film.

Brief Description of the Drawings

[0018] [Figure 1] The 1H-NMR measurement results (NMR chart) of the resin (A-1) synthesized in Synthesis Example 1 are shown.

Modes for Carrying Out the Invention

[0019] Hereinafter, embodiments of the disclosed technology will be described in detail. In this specification, the notation "a~b" in the description of a numerical range represents a to b, unless otherwise specified.

[0020] In this specification, when a plurality of upper limit values and a plurality of lower limit values are separately described, all numerical ranges that can be freely combined and set from these upper limit values and lower limit values are described in this specification.

[0021] In this specification, when a certain compound is described, unless otherwise specified, its stereoisomers are also described at the same time.

[0022] The "substituent" is not particularly limited, and unless otherwise specified, for example, a hydroxyl group, a phenol group, a phenoxy group, an alkoxy group, a phenyl group, a halogen group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, a thioester group, an aldehyde group, an acetyl group, etc. can be mentioned.

[0023] The "aromatic" is not particularly limited, and unless otherwise specified, it includes heterocycles.

[0024] In this specification, the solid content means the components constituting the photosensitive resin composition or the composition other than the solvent (especially the organic solvent) of each raw material, and is based on mass unless otherwise specified.

[0025] 1. A resin having a structural unit of formula (1) (hereinafter, also simply referred to as "resin") The resin of this embodiment has a structural unit of the following formula (1).

Chemical formula

[0026] From the viewpoint of complying with PFAS regulations, it is preferable that the resin of this embodiment does not have a perfluoroalkyl skeleton in its structure. 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, and examples include a trifluoromethyl group.

[0027] In formula (1), R1 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. From the viewpoint of excellent resolution when used as a photosensitive resin composition, a tetravalent aromatic hydrocarbon group having a diphenylpropane skeleton or a diphenylhexafluoropropane skeleton is preferred, and an organic group having the structure shown in formula (3) below is more preferred. [ka] {In equation (3), * indicates a bonding site.}

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

[0029] In formula (1), R2 is not particularly limited as long as it is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. R2 is preferably hydrogen. If R2 is a hydrocarbon group having 1 to 10 carbon atoms, R2 may be linear, branched, or cyclic, and is preferably linear. R2 may be saturated or unsaturated, and is preferably saturated.

[0030] The resin of this embodiment has a triazine structure in formula (1) above. This is thought to result in excellent i-line transparency. Although the mechanism is not clear, it is presumed that the presence of an electron-withdrawing triazine skeleton changes the energy levels of the HOMO and LUMO, causing the absorption band to shift to a lower wavelength, thus improving i-line transparency.

[0031] The resin of this embodiment may have alkali-soluble groups at its ends. The alkali-soluble groups at the ends are not particularly limited and include functional groups such as alcoholic hydroxyl groups, phenolic hydroxyl groups, acid anhydride groups, carboxyl groups, sulfonic acid groups, sulfonamide groups, and active methylene groups. From the viewpoint of solubility in developing solutions, it is preferable to have carboxyl groups or phenolic hydroxyl groups.

[0032] When the photosensitive resin composition of this embodiment is a negative-type photosensitive resin composition, it is particularly preferable that the resin of this embodiment has phenolic hydroxyl groups at its terminals among these alkali-soluble groups. When the resin has phenolic hydroxyl groups at its terminals, the solubility of the resin in the developer can be improved. Furthermore, since phenolic hydroxyl groups have lower reactivity compared to carboxyl groups, when used in combination with crosslinking agents, etc., described later, excessive reactions with crosslinking agents, etc. are 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 photosensitive resin composition with excellent resolution.

[0033] The alkali-soluble groups located at the ends of the resin may be present as residues of the monomers constituting the resin, or as end structures introduced by an end-capturing agent having alkali-soluble groups. Preferably, the alkali-soluble groups located at the ends of the resin are end structures introduced by an end-capturing agent having alkali-soluble groups.

[0034] 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.

[0035] The resin of this embodiment may contain two or more repeating structures of formula (1) above. Furthermore, the resin may contain structures other than the repeating structure of formula (1) above, for example, polyhydroxyamides, polyamic acids, and repeating structures of polyamides that do not have hydroxyl groups or carboxyl groups. Preferably, the resin consists substantially only of the repeating structure of formula (1) above.

[0036] In this embodiment, it is preferable that the structural unit represented by formula (1) is the structural unit represented by the following formula (2). [ka]

[0037] The weight-average molecular weight (Mw) of the resin in this embodiment 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 becomes possible to form a finer L / S pattern with a higher aspect ratio.

[0038] The number-average molecular weight (Mn) of the resin in this embodiment is preferably 1,000 to 15,000, more preferably 1,500 to 10,000, and particularly preferably 1,500 to 6,000.

[0039] The molecular weight dispersion (PDI) of the resin in this embodiment is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5. The molecular weight dispersion (PDI) is calculated by the following formula. PDI = Mw / Mn

[0040] When the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight dispersion (PDI) of the resin in this embodiment fall within a specified range, a suitable balance is achieved between solubility in the developer and reaction with the crosslinking agent, resulting in a photosensitive resin composition with superior resolution.

[0041] 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:

[0042] 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

[0043] The resin of this embodiment may be used individually or in combination of two or more types.

[0044] As a method for producing the resin of this embodiment, for example, a method of copolymerizing a dihydroxydiamino compound represented by formula (4), a dichlorotriazine compound represented by formula (5), and other compounds that can copolymerize with these as raw materials is included. Examples of other copolymerizable compounds include diol compounds, acid dianhydrides, diisocyanate compounds, dicarboxylic acid compounds, dicarboxylic acid dichlorides, and diamine compounds different from the dihydroxydiamino compound represented by formula (4). [ka] {In equation (4), R1 is as described above.} [ka] {In equation (5), R2 is as described above.}

[0045] The dihydroxydiamino compound represented by formula (4) 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.

[0046] The dichlorotriazine compound represented by formula (5) above is not particularly limited, and examples include 2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-methyl-1,3,5-triazine, 2,4-dichloro-6-ethyl-1,3,5-triazine, and 2,4-dichloro-6-phenyl-1,3,5-triazine.

[0047] The reaction between the dihydroxydiamino compound represented by formula (4) and the dichlorotriazine compound represented by formula (5) can be carried out in an organic solvent. The organic solvent is not particularly limited, and known ones can be used. Examples include amide organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF); alcohol organic solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester organic solvents such as ethyl acetate, butyl acetate, and ethyl lactate; ether organic solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and tetrahydrofuran (THF); and aromatic hydrocarbon organic solvents such as benzene, toluene, and xylene.

[0048] The reaction between the dihydroxydiamino compound represented by formula (4) and the dichlorotriazine compound represented by formula (5) can be carried out, for example, in an organic solvent at 0 to 90°C for 1 to 48 hours with stirring.

[0049] 2. Photosensitive resin composition The photosensitive resin composition of this embodiment comprises the resin according to the embodiment, a crosslinking agent, and a photoacid generator. It is also preferable that it further contains one or more compounds selected from the group consisting of alcoholamine compounds and alkoxyamine compounds. The resin according to the embodiment can be used in both negative and positive type photosensitive resin compositions.

[0050] From the viewpoint of complying with PFAS regulations for the photosensitive resin composition as a whole, it is preferable that the photosensitive resin composition of this embodiment does not substantially contain compounds having a perfluoroalkyl skeleton.

[0051] 2-1. Crosslinking agents The crosslinking agent is not particularly limited and any known agent can be used, such as melamine compounds, guanamine compounds, triazine compounds, epoxy compounds, oxetane compounds, isocyanate compounds, and oxazoline compounds. The crosslinking agent is preferably a compound having at least one selected from the group consisting of methoxymethyl groups and methylol groups. These functional groups undergo a crosslinking reaction with phenolic hydroxyl groups and carboxyl groups contained in the resin etc. according to the embodiment by heating, using the acid generated from the photoacid generator described later as the active species. As a result, negative-type photolithography (pattern formation) is achieved by exposure, PEB and development treatment. Furthermore, by heating after pattern formation, the curing reaction of the photosensitive resin composition proceeds, and excellent properties of the cured product are exhibited.

[0052] The crosslinking agent is preferably heterocyclic in order to improve the resolution of the photosensitive resin composition. The heterocyclic is not particularly limited and may contain one or more heteroatoms such as boron, nitrogen, oxygen, phosphorus, sulfur, antimony, arsenic, bismuth, selenium, silicon, tellurium, or tin, and may be a saturated or unsaturated ring of three, four, five, six, seven, or eight members. From the viewpoint of the resolution of the photosensitive resin composition, heterocyclics containing nitrogen are preferred, and heterocyclics containing multiple nitrogen atoms are more preferred.

[0053] Specifically, compounds having a triazine structure such as hexamethylolmelamine and hexamethoxymethylmelamine, compounds having a guanamine structure such as tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanamine, compounds having a glycoluryl structure such as tetramethylol glycoluryl and tetramethoxyglycoluryl, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone are more preferred.

[0054] 2-2. Photoacid Generator The photoacid generator is not particularly limited as long as it is a compound that generates acid upon irradiation with light such as ultraviolet or visible light. Examples include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyamide sulfonates, aromatic N-oxyimide sulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimide, and benzoquinone diazosulfonic acid esters. These can be used individually or in combination in any ratio. From the viewpoint of achieving better resolution, the photoacid generator is preferably an oxime sulfonate compound. Examples of oxime sulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF, and those containing the structure of the following formula (6) are particularly preferred. [ka] {In formula (6), X is a hydrocarbon group or halogen atom, m is an integer from 0 to 3, and R3 is an organic group containing a hydrogen atom, a hydrocarbon group, a ketone group, or a halogen atom.}

[0055] In formula (6) 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.

[0056] In formula (6) 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.

[0057] In formula (6) above, R3 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 it may be substituted with a halogen atom.

[0058] 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.

[0059] 2-3. Alcoholamine compounds / alkoxyamine compounds The photosensitive resin composition of this embodiment preferably contains one or more compounds selected from the group consisting of alcoholamine compounds and alkoxyamine compounds.

[0060] Alcoholamine compounds are compounds having an alcoholic hydroxyl group and an amine skeleton. Examples of amine skeletons include primary, secondary, or tertiary amine skeletons. Alcoholamine compounds are not particularly limited and include, for example, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine.

[0061] Alkoxyamine compounds are compounds having an alkoxy group and an amine skeleton. The amine skeleton is the same as that of the alcoholamine compounds described above. Alkoxyamine compounds are not particularly limited, and examples include tris(2-methoxy)amine, bis(2-methoxy)amine, tris(2-ethoxy)amine, and bis(2-ethoxy)amine.

[0062] If the mixture contains one or more compounds selected from the group consisting of alcoholamine compounds and alkoxyamine compounds, the diffusion of acid generated from the photoacid generator to the unexposed areas during exposure can be suppressed, thereby improving resolution and preventing the formation of development residue in the unexposed areas after development. From a similar viewpoint, the inclusion of alcoholamine compounds is particularly preferable.

[0063] These can be used individually or in combination in any ratio.

[0064] 2-4. Solvents The photosensitive resin composition of this embodiment may contain a solvent. The solvent is not particularly limited and can include, for example, ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethyl sulfone, pyridine, and the like.

[0065] 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.

[0066] 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.

[0067] Ketones include methyl ethyl ketone; methyl isobutyl ketone (4-methyl-2-pentanone); 2-heptanone; Cycloalkanones, which are monoketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone; 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.

[0068] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0069] 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.

[0070] 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 photosensitive resin composition, and γ-butyrolactone or cyclopentanone are preferred. Furthermore, from the viewpoint of excellent solvent removal during drying of the photosensitive 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.

[0071] 2-5. Other ingredients The photosensitive 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 photosensitive resin composition, such as fillers, adhesives, surfactants, plasticizers, thermoacid generators, sensitizers, leveling agents, colorants, fibers, fine particles, and the like.

[0072] The surfactant is not particularly limited and examples include fluorine-based surfactants and silicone-based surfactants. Examples of commercially available fluorine-based surfactants include DIC's "MegaFac" series (e.g., MegaFac F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-569, etc.). Examples of commercially available silicone-based surfactants include the surface modifier series from BIK-Chemie Co., Ltd. (e.g., BYK-302, BYK-307, BYK-310, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK-348, BYK-349, BYK-377, BYK-378, BYK-3455, BYK-3760, etc.). These may be used individually or in combination of two or more types.

[0073] 3. Preparation of photosensitive resin composition The photosensitive resin composition of this embodiment can be obtained by mixing the resin according to the embodiment with any other components, including a crosslinking agent, a photoacid generator, and an alcoholamine compound. The mixing of each component can be carried out under heating as needed.

[0074] 3-1. Resin The resin content according to the embodiment can be 50 to 80% by mass, when the total mass of the solid content of the photosensitive resin composition is 100% by mass.

[0075] 3-2. Crosslinking agents The crosslinking agent content can be 5 to 80 parts by mass, based on a solid content mass of 100 parts by mass of the resin according to the embodiment in the photosensitive resin composition. Furthermore, if the crosslinking agent has methoxymethyl groups and / or methylol groups, the ratio of the number of methoxymethyl groups and / or methylol groups in the crosslinking agent to the number of phenolic hydroxyl groups in the photosensitive resin composition (methoxymethyl groups and / or methylol groups: phenolic hydroxyl groups) can be set to 120:100 to 200:100. Such a ratio can improve the resolution of the photosensitive resin composition.

[0076] 3-3. Photoacid Generator The amount of photoacid generator can be 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, when the solid content mass of the resin according to the embodiment in the photosensitive resin composition is 100 parts by mass.

[0077] 3-4. Alcoholamine compounds / alkoxyamine compounds When adding one or more compounds selected from the group consisting of alcoholamine compounds and alkoxyamine compounds, the total content of alcoholamine compounds and / or alkoxyamine compounds can be 0.01 to 1.0 parts by mass, and preferably 0.05 to 0.50 parts by mass, when the solid content mass of the resin according to the embodiment in the photosensitive resin composition is 100 parts by mass. By setting the content within this range, it becomes easier to suppress the generation of development residue in the unexposed areas after developing the photosensitive resin composition.

[0078] 4. Dry film The dry film of this embodiment comprises a substrate and a resin layer formed on the substrate using the photosensitive resin composition of this embodiment. Furthermore, a protective film may be laminated on the surface of the resin layer to protect it.

[0079] 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, 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.

[0080] The substrate is not particularly limited and can include, for example, metal foils such as copper foil; and films such as polyimide film, polyester film, and polyethylene naphthalate (PEN) film.

[0081] 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.

[0082] 5.Cured product The cured product of this embodiment is obtained by curing the resin layer of the photosensitive resin composition or dry film described above. The cured product may be a patterned cured product. A method for manufacturing a patterned cured product will be described below, using the case of a negative-type photosensitive resin composition as an example.

[0083] 5-1. Dry coating film formation process The drying film formation process involves applying the above-mentioned photosensitive 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.

[0084] The method for coating the photosensitive resin composition onto 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 5-2. Exposure Process The exposure process involves irradiating the dried coating formed in the drying coating process with active energy rays through a photomask capable of forming a desired pattern, thereby exposing the photoacid generator in the exposed area and generating active species. If patterning is not required, a photomask is not necessary. Alternatively, the pattern may be drawn directly with a laser using a direct drawing device.

[0089] The wavelength of the activation energy ray used is one that can activate the photoacid generator, and for fine patterning, a maximum wavelength of 410 nm or less is preferable. The irradiation energy can be adjusted depending on the thickness of the formed dry coating, for example, 10 to 1500 mJ / cm². 2This can be done. As the exposure light source, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, mercury short-arc lamps, KRF lasers, etc., can be used.

[0090] 5-3.PEB process The PEB process is a process in which a dried coating film made of a photosensitive resin composition exposed in the exposure process is heat-treated to impart developability to the exposed portion of the dried coating film (hereinafter sometimes abbreviated as the exposed portion). In the PEB process, the acid generated from the photoacid generator in the exposed portion acts as an active species, and a crosslinking reaction proceeds between a compound containing phenolic hydroxyl groups, such as the resin according to the embodiment, and a crosslinking agent, causing the exposed portion to become insoluble in the developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be carried out by known methods such as a hot plate or a heating furnace.

[0091] 5-4.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.

[0092] 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.

[0093] 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.

[0094] 5-5. 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.

[0095] Furthermore, if the photosensitive resin composition in this embodiment is a positive-type photosensitive resin composition, a patterned coating can be obtained by using a dissolution inhibitor as a photoacid generator and treating the coating with a developer in the development step, thereby dissolving and removing the exposed areas of the dried coating in the developer.

[0096] 6. Uses of photosensitive resin compositions The photosensitive resin composition of this embodiment exhibits excellent i-line transparency and can therefore be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like. Examples of forming materials for semiconductor elements include resist materials, buffer coating films, and insulating films for redistribution layers of wafer-level packages (WLPs). Examples of forming materials for electronic components include printed circuit boards, interlayer insulating films, and wiring coating films.

[0097] The electronic component of this embodiment has a cured product obtained by curing the resin layer of the photosensitive resin composition or dry film described above. Therefore, it can meet the demands for high performance, high integration, and high precision, which are important in modern electronic components. [Examples]

[0098] 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.

[0099] <Resin> Resin A-1 according to the embodiment and resin A-2 of the comparative example were synthesized as follows. The constituent components, molar ratio of each resin, and the weight-average molecular weight, number-average molecular weight, and molecular weight dispersion of the obtained resins A-1 to A-2 are shown in Table 1.

[0100] (Synthesis Example 1: Resin (A-1)) (Mn: 2,300, Mw: 7,500) In a 20 mL vial (at room temperature) equipped with a stirrer and thermometer, 1.27 g (4.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) and 0.123 g (1.1 mmol) of 3-aminophenol (3-AP) were dissolved in 5.03 g of N-methylpyrrolidone (NMP) with stirring for 15 minutes. Then, the vial was immersed in an ice bath, and while maintaining the temperature inside the vial at 0-5°C, 0.76 g (5.1 mmol) of 2,4-dichloro-1,3,5-triazine (DCT) 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 24 hours, the solution was added to a large amount of deionized water, and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain the resin (A-1) of this embodiment.

[0101] (A-1) Resin [ka]

[0102] (Synthesis example 2: Resin (A-2)) (Mn: 3,700, Mw: 9,900) In a 120 mL vial (at room temperature) equipped with a stirrer and thermometer, 6.32 g (24.5 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) and 0.83 g (7.58 mmol) of 3-aminophenol (3-AP) were dissolved by stirring in 35 g of N-methylpyrrolidone (NMP) for 15 minutes. Then, the vial was immersed in an ice bath to maintain the temperature inside the vial at 0-5°C, and 7.54 g (25.5 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over 10 minutes, and the mixture was stirred in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was added to a large amount of deionized water, and the precipitate was collected. The obtained solid was dissolved in 30 g of tetrahydrofuran (THF). 7.5 g of anion exchange resin (Organo Amberlist B-20) was added to this mixture and vigorously stirred for 1 hour. After concentrating the stirred solution, it was added to a large amount of deionized water and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain a comparative example resin (A-2) that was different from the resin of this embodiment.

[0103] The following measurements and evaluations were performed on each resin obtained in Synthesis Example 1 and Synthesis Example 2 described above.

[0104] ( 1 H-NMR measurement) Regarding the resin (A-1) obtained in the above synthesis example 1, 1 1H-NMR measurements were performed. A nuclear magnetic resonance spectrometer (JNM-ECA400II, manufactured by JEOL Ltd.) was used for the measurements.

[0105] Figure 1 shows the resin (A-1) 1 The 1H-NMR measurement results (NMR chart) are shown.

[0106] As shown in Figure 1 1 From the 1H-NMR measurement results, it was confirmed that resin (A-1) is a compound having the structure of the chemical formula described above.

[0107] (Evaluation of i-line absorbance) The resins obtained in Synthesis Example 1 and Synthesis Example 2 were dissolved in a mixed solvent of water and tetrahydrofuran (THF) in a weight ratio of 1:10 to prepare a solution with a concentration of 2 mg / mL. The light absorbance (Abs) of the prepared solution at a wavelength of 365 nm was measured using ultraviolet-visible spectroscopy (UV / VIS / NIR Spectrometer V-570) (manufactured by JASCO Corporation) in a quartz cell (path length and path width of 10 mm). A smaller Abs value indicates better i-line transmittance.

[0108] [Table 1] The results in Table 1 show that resin A-1 of this embodiment has improved i-ray permeability compared to resin A-2 of the comparative example. Note that the molar ratio of additions in Table 1 represents the molar percentage when the amount of DEDC or DCT added is set to 100 mol%. [Industrial applicability]

[0109] Since the resin of this disclosure exhibits excellent i-ray transparency, it can be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like.

Claims

1. A resin having the structural unit of the following formula (1). 【Chemistry 1】 {R in equation (1) １ R is a tetravalent organic group, ２ This is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.

2. The resin according to claim 1, wherein the structural unit represented by formula (1) is the structural unit represented by formula (2) below. 【Chemistry 2】

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

4. The photosensitive resin composition according to claim 3, further comprising one or more compounds selected from the group consisting of alcoholamine compounds and alkoxyamine compounds.

5. A dry film comprising a resin layer formed from the photosensitive resin composition described in claim 3.

6. A cured product obtained by curing the resin layer of the photosensitive resin composition described in claim 3 or the dry film described in claim 5.

7. An electronic component having the cured product described in claim 6.

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