Polyhydroxyamide compound, negative photosensitive resin composition, dry film, cured product, and electronic component

Abstract

To provide a polyhydroxyamide compound with which it is possible to obtain a new negative photosensitive resin composition that does not include a resin component which may be targeted by PFAS regulations.SOLUTION: Provided is a polyhydroxyamide compound including: a structural unit represented by formula (1); and a structural unit wherein a fluorene group in the structure of (1) is replaced with a sulfonyl group.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] A photosensitive resin composition containing a polyimide 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 have been developed in the field of semiconductor element packages such as wafer-level packages. In the insulating film used for the rewiring 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 photosensitive resin composition is provided that exhibits good sensitivity and resolution and imparts 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] However, in recent years, forever chemicals such as perfluoroalkyl compounds (PFAS) have been under international consideration for restrictions on their use due to reasons such as reported associations with health hazards. The negative photosensitive resin composition of Patent Document 1 may contain a perfluoroalkyl group in the polybenzoxazole precursor from the viewpoints of the transparency of exposure light and developability, and may be subject to PFAS regulations. In the future, there is a demand for a negative photosensitive resin composition that can comply with PFAS regulations and has properties equivalent to those of conventional negative photosensitive resin compositions.

[0007] The present invention is in view of the above problems, and an object thereof is to provide a polyhydroxyamide compound capable of obtaining a new negative photosensitive resin composition that does not contain a resin component that may be subject to PFAS regulations. Another object is to provide a dry film having a resin layer formed by the negative photosensitive resin composition; a cured product formed by the negative photosensitive resin composition or the resin layer of the dry film; and an electronic component having the cured product.

Means for Solving the Problems

[0008] One aspect of the present invention is a polyhydroxyamide compound. The polyhydroxyamide compound is a polyhydroxyamide compound containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

Chemical formula

Chemical formula

[0009] In the polyhydroxyamide compound of the above aspect, the number n 1 of the structural units represented by the formula (1) 2The number n of the structural units represented by the formula (1) in the total with 1 The ratio [n 1 / (n 1 +n 2 )] is preferably 0.35 to 0.80.

[0010] In the negative photosensitive resin composition of the above aspect, the weight average molecular weight of the polyhydroxyamide compound is preferably 2,000 to 20,000.

[0011] Another aspect of the present invention is a negative photosensitive resin composition. The negative photosensitive resin composition contains the polyhydroxyamide compound of the above aspect.

[0012] Another aspect of the present invention is a dry film. The dry film includes a resin layer formed by the negative photosensitive resin composition of the above aspect.

[0013] Another aspect of the present invention is a cured product. The cured product is formed by the negative photosensitive resin composition of the above aspect or the resin layer of the dry film of the above aspect.

[0014] 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

[0015] According to the present invention, a polyhydroxyamide compound capable of obtaining a new negative photosensitive resin composition containing no resin component that may be subject to PFAS regulations can be provided. Further, a dry film having a resin layer formed by the negative photosensitive resin composition; a cured product formed by the negative photosensitive resin composition or the resin layer of the dry film; an electronic component having the cured product; can be provided.

Embodiments for Carrying Out the Invention

[0016] 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.

[0017] In this specification, when a plurality of upper limit values and a plurality of lower limit values are separately described, all numerical ranges that can be freely combined and set from these upper limit values and lower limit values are considered to be described in this specification.

[0018] In this specification, when a certain compound is described, its isomers are also considered to be described simultaneously.

[0019] In this specification, the solid content means the components constituting the photosensitive resin composition or the composition other than the solvents (especially organic solvents) of each raw material, and is based on mass unless otherwise specified.

[0020] 1. Polyhydroxyamide compound The polyhydroxyamide compound of this embodiment contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). It is preferable that the polyhydroxyamide compound of this embodiment does not have a perfluoroalkyl group in its structure.

Chemical formula

Chemical formula

[0021] R in formula (1) 1 and R in formula (2) 2is not particularly limited as long as it is a divalent organic group, and examples thereof include an alkylene group, a cycloalkylene group, an arylene group, an alkyl ether group, a ketone group, an ester group, and the like. Among these, a divalent aromatic hydrocarbon group having a skeleton such as benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl propane, benzophenone, or a divalent aliphatic hydrocarbon group having a skeleton such as butane or cyclobutane is preferable. From the viewpoints of the resolution of the negative photosensitive resin composition and the insulation reliability of the cured product, R 1 and R 2 each preferably has 4 to 30 carbon atoms, and phenyl, biphenyl, and diphenyl ether are preferable. In addition, two or more of the groups exemplified above as R 1 and R 2 can be contained in the molecule of the polyhydroxyamide compound, respectively. Further, R 1 and R 2 may have the same structure or different structures.

[0022] The polyhydroxyamide compound may have an alkali-soluble group at its terminal. The alkali-soluble group at the terminal is not particularly limited, and examples thereof 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. From the viewpoint of solubility in the developer, it preferably has a carboxyl group or a phenolic hydroxyl group.

[0023] Among these alkali-soluble groups, a phenolic hydroxyl group is particularly preferable. When the polyhydroxyamide compound has a phenolic hydroxyl group at its terminal, the solubility of the polyhydroxyamide compound in the developer can be improved. Further, since the phenolic hydroxyl group has a lower reactivity than the carboxyl group, an excessive reaction with the crosslinking agent is suppressed, and the solubility of the unexposed portion in the developer can be maintained even when the PEB process is performed. It is presumed that a negative photosensitive resin composition capable of forming an L / S pattern that is finer and has a higher aspect ratio can be provided because the resolution can be maintained.

[0024] Further, the alkali-soluble group contained at the terminal of these polyhydroxyamide compounds may be one possessed as a residue of the monomer constituting the polyhydroxyamide compound, or may be one possessed as a terminal structure introduced by a terminal capping agent having an alkali-soluble group. It is preferable that the alkali-soluble group contained at the terminal of the polyhydroxyamide compound is one possessed as a terminal structure introduced by a terminal capping agent having an alkali-soluble group.

[0025] The terminal capping agent is not particularly limited, and examples include compounds having one amino group and one hydroxyl group such as aminophenol compounds, hydroxybenzylamine compounds, aminobenzyl alcohol compounds, and alcoholamine compounds; compounds having one carboxyl group and one 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; acid anhydride compounds such as phthalic anhydride and 5-norbornene-2,3-dicarboxylic anhydride.

[0026] The number n of structural units represented by the above formula (1) 1 and the number n of structural units represented by the above formula (2) 2 The ratio [n of the number n of structural units represented by the above formula (1) in the total with 1 / (n 1 +n 1 +n 2 )] (hereinafter referred to as L) can be, for example, 0.10 to 0.90. L can be determined from the integrated intensity ratio of the peak derived from the structural unit represented by formula (1) and the peak derived from the structural unit represented by formula (2) by performing H-NMR measurement of the polyhydroxyamide compound.

[0027] From the viewpoint of obtaining a polyhydroxyamide compound more suitable for use as a negative photosensitive resin composition, L is preferably from 0.35 to 0.80. Since the structural unit represented by formula (1) has a highly hydrophobic fluorene skeleton, it has excellent solubility in organic solvents and can moderately suppress alkali solubility. Further, the structural unit represented by formula (2) has excellent i-line transmittance and has a highly hydrophilic sulfonyl group, so that alkali solubility can be improved. By setting L within the above range, a polyhydroxyamide compound with an excellent balance of various properties can be obtained, and it is presumed that a polyhydroxyamide compound more suitable for use as a negative photosensitive resin composition can be obtained.

[0028] From the viewpoint of obtaining a negative photosensitive resin composition that is more likely to form a finer pattern by the same mechanism, L is more preferably from 0.40 to 0.75, and even more preferably from 0.45 to 0.60. In addition, the polyhydroxyamide compound of this embodiment may contain other structural units other than the structural units of the above formula (1) and the above formula (2).

[0029] Here, the structural unit refers to, for example, a structural unit derived from a monomer that is a raw material when a raw material is polymerized or copolymerized to obtain a polyhydroxyamide compound (such as the structural unit of the above formula (1) or the above formula (2)). The structural unit derived from a monomer includes a case where structural units derived from a plurality of different monomers are combined to form one structural unit.

[0030] The value of L can be adjusted by the blending of raw materials (such as monomers) when producing the polyhydroxyamide compound. As a method for producing the polyhydroxyamide compound, for example, a method of copolymerizing using a hydroxyamino compound represented by the following formula (3) and the following formula (4) and a dicarbonyldichloride compound represented by the following formula (5) as raw materials can be used. By adjusting the blending amounts of these raw materials, the value of L can be adjusted.

Chemical formula

Chemical formula

[0031] The dicarbonyldichloride compound represented by the above formula (5) is not particularly limited, and examples thereof include terephthalic acid dichloride, 1,1'-biphenyl-4,4'-dicarbonyldichloride, or a compound represented by the following formula (6), 4,4'-oxybis(benzoyl chloride) (DEDC), etc. In this embodiment, it is preferably DEDC. [Chemical formula]

[0032] Other compounds copolymerizable with the above-described compounds may be copolymerized. Examples of other copolymerizable compounds include diol compounds, acid dianhydrides, diisocyanate compounds, diamine compounds different from the hydroxyamino compounds represented by the above formula (3) or the above formula (4), etc.

[0033] The weight average molecular weight (Mw) of the polyhydroxyamide compound can be 2,000 to 20,000, preferably 2,000 to 15,000, more preferably 3,000 to 15,000, and even more preferably 4,000 to 10,000. By setting it within such a range, it becomes possible to form a finer and higher aspect ratio L / S pattern.

[0034] The number average molecular weight (Mn) of the polyhydroxyamide compound is preferably 1,000 to 10,000, and more preferably 1,500 to 6,000.

[0035] The molecular weight dispersity (PDI) of the polyhydroxyamide compound is preferably 1.5 to 5.0, and more preferably 1.5 to 4.5.

[0036] When the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight dispersity (PDI) of the polyhydroxyamide compound are within such ranges, the solubility in the developer in the unexposed area and the reaction with the crosslinking agent in exposure achieve a suitable balance, and a negative photosensitive resin composition with excellent resolution can be obtained.

[0037] In this specification, the weight average molecular weight and number average molecular weight are values measured by gel permeation chromatography (GPC) (GL7700 manufactured by GL Sciences Inc.) and converted using standard polystyrene. The specific measurement conditions are as follows.

[0038] Column: TSKgel αM (manufactured by Tosoh Corporation) Column internal temperature: 40 °C Eluent composition: 100 mmol / L of H 3 PO 4 (H 3 PO 4 85% aqueous solution used as a raw material) and an NMP solution containing 10 mmol / L of LiBr Eluent flow rate: 0.5 mL / min Calibration standard reagent: Polystyrene Detector wavelength: 260 nm and 300 nm Detector temperature: Room temperature (about 25 °C) Baseline range during analysis: 15 minutes to 40 minutes Molecular weight calculation range during analysis: 20 to 35 minutes

[0039] Also, in this specification, the molecular weight dispersity (PDI) is calculated by the following formula. PDI = Mw / Mn

[0040] The chlorine atom concentration (or chloride ion concentration) contained in the molecular structure of the polyhydroxyamide compound is not particularly limited, and is preferably 5 mass ppm or less with respect to the mass of the entire polyhydroxyamide compound. The lower the chlorine atom concentration (or chloride ion concentration) contained in the molecular structure of the negative photosensitive resin composition, the easier it is to obtain a cured product with more excellent insulation reliability.

[0041] The alkali dissolution rate of the polyhydroxyamide compound is not particularly limited and can be, for example, 10 to 1000 nm / sec, more preferably 50 to 700 nm / sec, and even more preferably 100 to 500 nm / sec, from the viewpoint of obtaining a negative photosensitive resin composition excellent in developability and sensitivity. If the alkali dissolution rate is too low, the unexposed portion may not be sufficiently dissolved, making pattern formation difficult. If the alkali dissolution rate is too high, the sensitivity may decrease or the pattern may swell during development. The alkali dissolution rate of the polyhydroxyamide compound can be measured by the method described in the examples below.

[0042] 2. Negative photosensitive resin composition The negative photosensitive resin composition of this embodiment contains the above-described polyhydroxyamide compound. Further, the negative photosensitive resin composition of this embodiment preferably further contains a crosslinking agent, a photoacid generator, a basic compound, etc. The negative photosensitive resin composition of this embodiment preferably does not substantially contain a compound having a perfluoroalkyl group from the viewpoint of compliance with PFAS regulations for the entire negative photosensitive resin composition.

[0043] 2-1. Crosslinking agent The crosslinking agent is not particularly limited and known ones can be used. Examples include melamine compounds, guanamine compounds, triazine compounds, epoxy compounds, oxetane compounds, isocyanate compounds, oxazoline compounds, etc. The crosslinking agent is preferably a compound having at least one or more selected from the group consisting of a methoxymethyl group and a methylol group. These functional groups cause a crosslinking reaction with phenolic hydroxyl groups and carboxyl groups contained in the polyhydroxyamide compound, etc. using the acid generated from the photoacid generator described below as an active species by heating, so that negative photolithography (pattern formation) is realized by exposure, PEB, and development processing. Further, after pattern formation, by further heating, the curing reaction of the negative photosensitive resin composition proceeds, and excellent properties as a cured product are exhibited.

[0044] In addition, since the crosslinking agent improves the resolution of the negative photosensitive resin composition and the insulation reliability after curing, it preferably contains a heterocyclic ring. The heterocyclic ring is not particularly limited and contains one or more heteroatoms such as boron, nitrogen, oxygen, phosphorus, sulfur, antimony, arsenic, bismuth, selenium, silicon, tellurium, tin, etc., and includes a saturated or unsaturated ring of 3-membered, 4-membered, 5-membered, 6-membered, 7-membered or 8-membered rings. From the viewpoints of the resolution of the negative photosensitive resin composition and the insulation reliability of the cured product, a heterocyclic ring containing nitrogen is preferable, and a heterocyclic ring containing a plurality of nitrogens is more preferable.

[0045] Specifically, compounds having a triazine structure such as hexamethylol melamine and hexamethoxymethyl melamine, compounds having a guanamine structure such as tetramethylol benzoguanamine and tetramethoxymethyl benzoguanamine, compounds having a glycoluril structure such as tetramethylol glycoluril and tetramethoxyglycoluril, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone are more preferable. Among these, particularly from the viewpoint of providing a negative photosensitive resin composition capable of forming an L / S pattern with finer and higher aspect ratio, compounds having a triazine structure containing a triazine ring and compounds having a guanamine structure can be preferably used.

[0046] 2-2. Photoacid Generator The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light. Examples thereof include naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyamidosulfonates, aromatic N-oxymidosulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimides, benzoquinonediazosulfonic acid esters, and the like. These can be used alone or in combination of two or more in any ratio. The photoacid generator is preferably an oxime sulfonate compound from the viewpoint of achieving better resolution and insulation reliability, and more preferably one containing the structure of the following formula (7). [Chemical formula] (In the formula, X is a hydrocarbon group or a halogen atom, m is an integer of 0 to 3, and R 3 is a hydrogen atom, a hydrocarbon group, an organic group containing a ketone group, or a halogen atom.)

[0047] X in the above formula (7) is not particularly limited and can be, for example, a hydrocarbon group (e.g., an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) or a halogen atom. The hydrocarbon group may have a substituent and can have a linear, branched, or cyclic structure. The hydrocarbon group is preferably a linear or branched one having 1 to 4 carbon atoms. As the halogen atom, a chlorine atom or a fluorine atom is preferably used.

[0048] m in the above formula (7) represents an integer of 0 to 3, and 0 or 1 is preferred. When m is 2 or 3, the plurality of Xs may be the same or different.

[0049] R in the above formula (7) 3It is preferably a hydrogen atom, a hydrocarbon group, an organic group containing a ketone group, or a halogen atom. The hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) may be unsubstituted or may be substituted with a halogen atom.

[0050] The hydrocarbon group is preferably a linear, branched or cyclic one having 1 to 20 carbon atoms, and more preferably a linear, branched or cyclic one having 1 to 10 carbon atoms. The halogen atom may be a chlorine atom or a fluorine atom.

[0051] Examples of commercially available oxime sulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, Irgacure PAG203, etc. manufactured by BASF.

[0052] 2-3. Basic Compound The negative photosensitive resin composition of this embodiment preferably contains a basic compound. In particular, when the negative photosensitive resin composition of this embodiment contains a basic compound, it is possible to suppress the diffusion of the acid generated from the photoacid generator to the unexposed portion by exposure, so that the resolution can be improved and the generation of development residues in the unexposed portion after development can be prevented.

[0053] The basic compound is not particularly limited. For example, amine compounds such as 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, 4,4’-diaminodiphenylamine; amide compounds such as formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide; lactams such as pyrrolidone, N-methylpyrrolidone; urea compounds such as methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea; nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, 4-methylimidazole, 8-hydroxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine; morpholine compounds such as morpholine, 4-methylmorpholine; etc. can be mentioned. These can be used alone or in combination of a plurality at any ratio. Among these, amine compounds are preferred, alcohol amines such as N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine are more preferred, and diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine are even more preferred.

[0054] 2-4. Solvent The negative photosensitive resin composition of this embodiment can contain a solvent. The solvent is not particularly limited, and examples thereof include ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethyl sulfone, pyridine, and the like.

[0055] 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, dipropylene glycol monoethyl ether, and the like.

[0056] 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, ethyl 2-ethoxypropionate, and the like.

[0057] Examples of ketones include methyl ethyl ketone; methyl isobutyl ketone (4-methyl-2-pentanone); 2-heptanone; Cycloalkanones that are monoketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, 2,2-dimethylcyclopentanone; Cycloalkanones such as diketones including 1,3 - cyclopentanedione, 3 - methyl - 1,2 - cyclopentanedione, 1,2 - cyclohexanedione, 1,3 - cyclohexanedione, 1,4 - cyclohexanedione, 2 - methyl - 1,3 - cyclopentanedione, etc.; Cycloalkenones such as 4 - methyl - 2 - cyclopentenone, 2 - cyclohexenone, 2 - cyclopentene - 1 - one, 2 - cyclohexene - 1 - one, etc.; Cyclic ketones having a heterocyclic skeleton such as 2 - azetidinone, 4,5 - dihydro - 3(2H) - thiophenone, 4 - oxothiane, dihydroreboglucosen, etc. can be mentioned. etc.;

[0058] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, ethylene glycol monoethyl ether acetate, etc.

[0059] Examples of lactones include γ - butyrolactone, etc., examples of lactams include N - methylpyrrolidone, N - methylcaprolactam, etc., and examples of sulfoxides include dimethyl sulfoxide, hexamethyl sulfoxide, etc.

[0060] These solvents can be used alone or in any ratio combination of a plurality. Among these solvents, from the viewpoint of excellent affinity with each component in the negative - type photosensitive resin composition, lactones or cyclic ketones are preferred, and γ - butyrolactone or cyclopentanone is preferred. Also, from the viewpoint of excellent solvent removability during drying of the negative - type photosensitive resin composition and compatibility with the edge rinse process in semiconductor manufacturing, cyclic ketones are preferred, cycloalkanones which are monoketones are more preferred, and cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2 - norbornanone, 2 - methylcyclohexanone, 4 - methylcyclohexanone, 3 - methylcyclohexanone, 2,2 - dimethylcyclopentanone are even more preferred, and cyclopentanone is particularly preferred.

[0061] 2-5. Other components The negative photosensitive resin composition of this embodiment can contain other components as long as the effects of the present disclosed technology are not impaired. As the other components, known components that can be contained in the negative photosensitive resin composition can be used. For example, fillers, adhesives, surfactants, plasticizers, thermal acid generators, sensitizers, leveling agents, colorants, fibers, fine particles, etc. can be mentioned.

[0062] The surfactant is not particularly limited, and examples thereof include fluorine-based surfactants and silicone-based surfactants. Commercially available products of fluorine-based surfactants include the "Megafac" series manufactured by DIC Corporation (for example, 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 products of silicone-based surfactants include the surface conditioner series of BYK Chemie GmbH (for example, 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 can be used alone or in combination of two or more.

[0063] 3. Preparation of negative photosensitive resin composition The negative photosensitive resin composition of this embodiment can be obtained by mixing arbitrary components including components such as a crosslinking agent, a photoacid generator, and a basic compound in addition to the polyhydroxyamide compound described above. The mixing of each component can be carried out under heating as necessary.

[0064] 3-1. Polyhydroxyamide compound The content of the polyhydroxyamide compound can be 50 to 80% by mass when the total mass of the solid content of the negative photosensitive resin composition is 100% by mass. Here, the solid content mass in this specification refers to the mass of the residue after completely volatilizing the volatile components.

[0065] 3-2. Crosslinking agent The content of the crosslinking agent can be 10 to 40% by mass when the total mass of the solid content of the negative photosensitive resin composition is 100% by mass. When the crosslinking agent has a methoxymethyl group and / or a methylol group, the content of the crosslinking agent can be such that the ratio of the number of methoxymethyl groups and / or methylol groups contained in the crosslinking agent to the number of phenolic hydroxyl groups contained in the negative photosensitive resin composition (methoxymethyl group and / or methylol group: phenolic hydroxyl group) is 120:100 to 200:100. By setting such a ratio, the resolution of the negative photosensitive resin composition and the insulation reliability after curing can be made more excellent.

[0066] 3-3. Photoacid generator The content of the photoacid generator can be 0.5 to 10% by mass when the total mass of the solid content of the negative photosensitive resin composition is 100% by mass, and preferably 1 to 5% by mass.

[0067] 3-4. Basic compound When adding a basic compound, the content can be 0.01 to 0.50% by mass when the total mass of the solid content of the negative photosensitive resin composition is 100% by mass, and preferably 0.08 to 0.40% by mass. By setting such a range, it becomes easier to suppress the generation of development residues in the unexposed areas after developing the negative photosensitive resin composition.

[0068] 4. Dry film The dry film of this embodiment includes a base material and a resin layer formed on this base material using the negative photosensitive resin composition of this embodiment. Further, for the protection of the resin layer, a protective film may be laminated on the surface of the resin layer.

[0069] The resin layer can be obtained, for example, by applying a negative photosensitive resin composition onto a substrate, using a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc. to adjust the thickness of the resin layer, 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.

[0070] The substrate is not particularly limited, and examples thereof include metal foils such as copper foils; films such as polyimide films, polyester films, polyethylene naphthalate (PEN) films; and the like.

[0071] The protective film is not particularly limited, and a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, paper, etc. can be used. It is preferable to select a protective film having an adhesion between the protective film and the resin layer 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 peeling treatment can be used.

[0072] 5. Cured Product The cured product of the present embodiment is obtained by curing the resin layer of the above-described negative photosensitive resin composition or dry film. The cured product may be a patterned cured product. Examples of the method for manufacturing the patterned cured product include the following methods.

[0073] 5-1. Dry Coating Film Formation Step The dry coating film formation step is a step of applying the above-described negative photosensitive resin composition onto a substrate to form a coating film, and then drying it. In the dry coating film formation step, it is also possible to form a dry coating film on the substrate by transferring the resin layer of the dry film onto the substrate.

[0074] The method for applying the negative photosensitive resin composition onto a substrate is not particularly limited. For example, methods such as applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spraying with a spray coater, and inkjet method can be mentioned. The coating film thickness is not particularly limited and can be, for example, 10 μm or less, 5 μm or less, 3 μm or less. By making the film thickness thinner, it becomes possible to perform finer L / S patterning while maintaining the aspect ratio of the pattern.

[0075] The method for drying the coating film is not particularly limited. For example, air drying, heat drying using an oven or hot plate, vacuum drying, etc. can be mentioned. The conditions for heat drying are, for example, a heating temperature of 70 to 140 °C and a drying time of 1 to 30 minutes.

[0076] The transfer of the resin layer of the dry film onto the substrate is preferably performed under pressure and heating using a vacuum laminator or the like. The heating temperature can be, for example, 60 to 100 °C.

[0077] The substrate is not particularly limited and can be, for example, a printed wiring board with a circuit formed, a flexible printed wiring board, or a wafer on which a semiconductor element is formed.

[0078] 5-2. Exposure process The exposure process is a process in which radiation is irradiated onto the dry coating film formed in the dry coating film forming process through a photomask capable of forming a desired pattern, thereby sensitizing the photoacid generator in the exposed portion and generating active species. When patterning is not required, it is not necessary to use a photomask. Also, a pattern may be directly drawn with a laser using a direct drawing apparatus.

[0079] As the wavelength of the radiation, one having a wavelength capable of activating the photoacid generator is used. For performing miniaturized patterning, those having a maximum wavelength of 410 nm or less are preferable. The irradiation energy can be adjusted according to the thickness of the formed dry coating film, etc., and is, for example, 10 to 1500 mJ / cm 2It can be used. 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.

[0080] 5-3. PEB Process The PEB process is a process of heat-treating the dry coating film exposed in the exposure process and imparting developability resistance to the exposed portion of the dry coating film (hereinafter, may be abbreviated as the exposed portion). In the PEB process, using the acid generated from the photoacid generator at the exposed portion as an active species, the cross-linking reaction between the polyhydroxyamide compound or the compound containing a phenolic hydroxyl group and the cross-linking agent proceeds, and the exposed portion becomes 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 performed by a known method such as a hot plate or a heating furnace.

[0081] 5-4. Development Process The development process is a process of obtaining a patterned coating film by treating the dry coating film heated in the PEB process with a developer and dissolving and removing the unexposed portion of the dry coating film with the developer. As the development method, a known method can be used, for example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, etc. can be mentioned.

[0082] As the developer, a known one can be used, for example, aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc. can be mentioned. If necessary, water-soluble organic solvents such as methanol, ethanol, isopropyl alcohol, and surfactants can be added.

[0083] After the treatment with the developer, the coating film can be washed with a rinsing solution as needed to obtain a patterned coating film. The rinsing solution is not particularly limited, and examples thereof include pure water, methanol, ethanol, isopropyl alcohol, and the like. These can be used alone or in combination of a plurality at an arbitrary ratio.

[0084] 5-5. Post-development heating step The post-development heating step is a step of heating the patterned coating film formed in the development step to complete the 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. The heating can be performed by a known method such as a hot plate or an inert oven, and it is desirable to perform the heating in a nitrogen atmosphere.

[0085] 6. Use of the negative photosensitive resin composition The negative photosensitive resin composition of the present embodiment can be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like. The forming material for the semiconductor element is, for example, a resist material, a buffer coat film, or an insulating film for a redistribution layer of a wafer-level package (WLP). Further, examples of the forming material for the electronic component include a printed wiring board, an interlayer insulating film, and a wiring coating film.

Examples

[0086] Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Each component used in the Examples and Comparative Examples is as follows.

[0087] <Polyhydroxyamide compound> Polyhydroxyamide compounds A-1 to A-8 were synthesized as follows. The compounding components, addition molar ratios, and the [n 1 / (n 1 +n 2 )] values, weight average molecular weights, number average molecular weights, and molecular weight dispersities of the obtained polyhydroxyamide compounds A-1 to A-8 are shown in Table 1. Note that [n 1 / (n1 +n 2 )] The value of ] was measured by 1H-NMR, and the value of each molecular weight was measured by GPC according to the method described above.

[0088] (Synthesis Example 1: Polyhydroxyamide Compound (A-1)) (Mn: 2,400, Mw: 6,300) In a 120 mL vial equipped with a stirrer and a thermometer (room temperature), 4.63 g (12.2 mmol) of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF) and 0.5 g (4.6 mmol) of 3-aminophenol (3AP) were dissolved by stirring in 20.8 g of N-methylpyrrolidone (NMP) for 15 minutes. Then, the vial was immersed in an ice bath, and while maintaining the inside of the vial at 0 to 5 °C, 3.79 g (12.8 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added in solid form 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 poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 33 g of cyclopentanone. 5 g of an anion exchange resin (Amberlyst B-20 from Organo) was added thereto, and the mixture was vigorously stirred for 1 hour. After concentrating the stirred solution, it was poured into a large amount of ion-exchanged water, and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyhydroxyamide compound (A-1).

[0089] (A-1) Polyhydroxyamide compound [Chemical formula]

[0090] (Synthesis Example 2: Copolymer Polyhydroxyamide Compound (A-2)) (Mn: 4,900, Mw: 12,100)(n 1 = 25, n 2 = 75) In a 120 mL vial equipped with a stirrer and a thermometer (room temperature), 1.16 g (3.1 mmol) of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF), 2,2-bis(3-amino-4-hydroxyphenyl)sulfone (SO2 2.57 g (9.16 mmol) of (AP) and 0.45 g (4.44 mmol) of 3-aminophenol (3AP) were stirred and dissolved in 18.6 g of N-methylpyrrolidone (NMP). After that, the vial was immersed in an ice bath, and while maintaining the temperature inside the vial at 0 to 5 °C, 3.78 g (12.8 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added. In the same manner as in Synthesis Example 1 except for this, a polyhydroxyamide compound (A-2) was obtained.

[0091] (A-2) Copolymer polyhydroxyamide compound [Chemical formula] ※ Copolymer polyhydroxyamide compound containing the above formula (1) and formula (2)

[0092] (Synthesis Examples 3 to 5: Copolymer polyhydroxyamide compounds (A-3) to (A-5)) 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF), 2,2-bis(3-amino-4-hydroxyphenyl)sulfone (SO 2 Except that the molar ratio of addition of (AP), 3-aminophenol (3AP), and 4,4'-oxybis(benzoyl chloride) (DEDC) was as shown in Table 1, in the same manner as in Synthesis Example 2, polyhydroxyamide compounds (A-3) to (A-5) were obtained.

[0093] (Synthesis Example 6: Polyhydroxyamide compound (A-6)) (Mn: 2,500, Mw: 9,800) Instead of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF), 2,2-bis(3-amino-4-hydroxyphenyl)sulfone (SO 2 6.85 g (24.4 mmol) of (AP) was used, and in the same manner as in Synthesis Example 1 except that 0.86 g (7.87 mmol) of 3-aminophenol (3AP), 35 g of N-methylpyrrolidone (NMP), and 7.54 g (25.5 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) were used, a polyhydroxyamide compound (A-7) was obtained.

[0094] (A-6) Polyhydroxyamide compound

Chemical formula

[0095] (Synthesis Example 7: Polyhydroxyamide compound (A-7)) (Mn: 3,200, Mw: 9,500) Instead of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF), 16.3 g (44.5 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was used, and 1.80 g (22.0 mmol) of 3-aminophenol (3AP), 80 g of N-methylpyrrolidone (NMP), and 16.4 g (55.5 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) were used. In the same manner as in Synthesis Example 1, a polyhydroxyamide compound (A-8) was obtained.

[0096] (A-7) Polyhydroxyamide compound

Chemical formula

[0097] The following evaluations were performed on each polyhydroxyamide compound. The evaluation results are shown in Table 1.

[0098] (Evaluation of i-line transmittance) Using the polyhydroxyamide compound obtained in the above synthesis example, a cyclopentanone solution with a solid content concentration of 20% by mass was prepared, spin-coated on a quartz glass so that the film thickness after drying would be 3 μm, and heated and dried at 90 °C for 3 minutes using a hot plate to form a dry coating film of the polyhydroxyamide compound. The transmission spectrum of the dry coating film was measured using an ultraviolet-visible spectrophotometer (Jasco V-570, manufactured by JASCO Corporation). The above transmission spectrum was measured under the conditions of a bandwidth of 5 nm, a scanning speed of 400 nm / min, and a data reading interval of 1 nm. The transmittance of i-line (wavelength 365 nm), which is the exposure wavelength, was evaluated according to the following evaluation criteria. (Evaluation Criteria) A: The i-line transmittance is 70% or more and less than 80%. B: The i-line transmittance is 40% or more and less than 70%. C: The i-line transmittance is less than 40%.

[0099] (Evaluation of Alkali Solubility) Using the polyhydroxyamide compound obtained in the above synthesis example, a 20% by mass cyclopentanone solution was prepared, spin-coated on a silicon substrate, and heated and dried at 90 °C for 3 minutes using a hot plate to form a dry coating film of the polyhydroxyamide compound. After measuring the initial film thickness of the dry coating film using an optical interference film thickness meter, it was developed using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 25 °C, the dissolution time of the dry coating film was measured, and the alkali dissolution rate was calculated from the following formula. Alkali dissolution rate (nm / s) = Initial film thickness (nm) / Dissolution time (s) (Evaluation Criteria) A: The dissolution rate is 50 nm / s or more and 500 nm / s or less. B: The dissolution rate exceeds 500 nm / s and is 1000 nm / s or less. C: The dissolution rate exceeds 1000 nm / s. D: It has no alkali solubility, or the alkali dissolution rate is extremely slow (less than 50 nm / s) and the dissolution time cannot be measured.

[0100] (Evaluation of Solvent Solubility) The solubility of the polyhydroxyamide compound obtained in the above synthesis example in cyclopentanone and propylene glycol monomethyl ether (PGME) was confirmed. When preparing a negative photosensitive resin composition using a polyhydroxyamide compound with low solubility in cyclopentanone, it was prepared using a mixed solvent of cyclopentanone and dimethyl sulfoxide. (Evaluation Criteria) A: Soluble in both cyclopentanone and PGME B: Insoluble in cyclopentanone, soluble in PGME, or soluble in cyclopentanone, insoluble in PGME C: Insoluble in both cyclopentanone and PGME

[0101] [Table 1] Note that the added molar ratio in Table 1 represents the molar percentage when the charged amount of DEDC is 100 mol%.

[0102] <Crosslinking Agent> (B-1) MW-390 (Hexamethoxymethylmelamine compound manufactured by Nippon Carbide Industries Co., Ltd.) [Chemical Formula]

[0103] <Photoacid Generator> (C-1) PAG-103 (Oxime sulfonate compound manufactured by BASF) [Chemical Formula]

[0104] <Basic Compound> (D-1) Triethanolamine (TEA) [Chemical Formula]

[0105] <Solvent> Cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) Dimethyl sulfoxide (DMSO) (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0106] <Preparation of Negative-Type Photosensitive Resin Composition> Each component was blended in the amounts shown in Table 2 below, and dissolved and adjusted with a solvent so that the concentration of the non-volatile components in the varnish became 30%, thereby obtaining the varnishes of the negative-type photosensitive resin compositions of each example and comparative example. Note that, among the blending amounts of each component in Table 2, the amounts other than the blending amount of the solvent are shown in parts by mass of the solid content.

[0107] <Evaluation> The following evaluations were performed using the obtained negative-type photosensitive resin compositions of each example and comparative example. The results of each evaluation are shown in Table 2.

[0108] (Evaluation of Resolution and Sensitivity) The varnishes of each example and comparative example were applied onto a silicon wafer using a spin coater so that the film thickness after curing became 3.0 μm, dried at 90°C for 3 minutes using a hot plate, and dry coating films of the negative-type photosensitive resin compositions of each example and comparative example were obtained. A test pattern with an L / S of 2 / 2 μm to 10 / 10 μm at 1-μm intervals was exposed to this dry coating film using a contact exposure machine (UVE-251S + EL-100 (manufactured by San-Ei Electric Co., Ltd.)), and post-exposure baking (PEB) was performed on the hot plate for 60 seconds. The heating temperature in the PEB process was 120°C. Thereafter, development was performed for 30 seconds using a 2.38% TMAH aqueous solution, rinsing was performed with ultrapure water for 30 seconds, and spin drying was performed for 30 seconds to obtain a sample having a pattern.

[0109] Each sample was cut so that a cross-section perpendicular to the longitudinal direction of the pattern could be observed. The cut surface of the pattern was observed using a scanning electron microscope (observation magnification: 10,000 times), and the size of the minimum L / S that was normally patterned and the exposure amount at that time were described in Table 2. It shows that the smaller the size of the minimum L / S, the better the resolution, and the smaller the exposure amount, the better the sensitivity. In addition, a sample in which each pattern was vertically patterned without falling was judged to be normally patterned. The pattern shape was evaluated according to the following evaluation criteria. Note that the polyhydroxyamide compound used in Comparative Example 3 did not have alkali solubility or had extremely low alkali solubility as shown in Table 1, so pattern formation was not possible. (Evaluation Criteria) A: A substantially rectangular pattern is formed, and there is no development residue in the unexposed part. B: A substantially rectangular pattern is formed, but there is development residue in the unexposed part. C: A substantially rectangular pattern is not formed, or a pattern larger than the desired L / S width is formed due to swelling of the pattern, etc.

[0110] (Evaluation of PFAS Regulations) It was evaluated whether the polyhydroxyamide compounds A-1 to A-7 used in each example and comparative example could be subject to PFAS regulations. (Evaluation Criteria) PASS: Not subject to PFAS regulations FAIL: May be subject to PFAS regulations

[0111]

Table 2

Industrial Applicability

[0112] The polyhydroxyamide compound of the present invention can obtain a new negative-type photosensitive resin composition that does not contain resin components that can be subject to PFAS regulations. As a result, it is possible to comply with PFAS regulations and obtain a negative-type photosensitive resin composition having characteristics equivalent to those of conventional negative-type photosensitive resin compositions. Therefore, the polyhydroxyamide compound of the present invention can be widely used in various fields such as semiconductors and electronic components as an insulating film.

Claims

1. A polyhydroxyamide compound comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): 【Chemistry 1】 (In the formula R １ is a divalent organic group. 【Chemistry 2】 (In the formula R ２ is a divalent organic group.

2. The number of structural units represented by the formula (1), n １ and the number n of structural units represented by the formula (2) ２ The number of structural units represented by the formula 1 in the total of １ The proportion of [n １ / (n １ +n ２ 2. The polyhydroxyamide compound according to claim 1, wherein the molecular weight of the polyhydroxyamide compound is 0.35 to 0.

80.

3. A negative-type photosensitive resin composition comprising the polyhydroxyamide compound according to claim 1.

4. A dry film comprising a resin layer formed from the negative photosensitive resin composition according to claim 3.

5. A cured product formed from the negative photosensitive resin composition according to claim 3 or the resin layer of the dry film according to claim 4.

6. An electronic part comprising the cured product according to claim 5 .

Images