Resin composition, cured product, and semiconductor device

Abstract

To provide a resin composition capable of obtaining a cured product excellent in adhesion to a silicon base material, a cured product obtained by curing the resin composition, and a semiconductor device having the cured product.SOLUTION: A resin composition according to an embodiment contains a polyhydroxyamide compound containing a repeating structure represented by the following formula (1) and a phenol resin, wherein the content of the phenol resin is 12 to 90% by mass based on 100% by mass of the total amount of the polyhydroxyamide compound and the phenol resin. {In the formula (1), R1 is a 2-valent organic group, and R2 is a 4-valent organic group. } SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product, and a semiconductor device. [Background technology]

[0002] Photosensitive resin compositions containing polybenzoxazole precursors exhibit excellent properties such as insulating properties, heat resistance, and mechanical strength, and are therefore widely used as insulating films in various fields such as semiconductor devices and electronic components.

[0003] For example, Patent Document 1 describes that a photosensitive resin composition containing a polybenzoxazole precursor is used to control the ring closure ratio of the polybenzoxazole precursor, thereby obtaining a cured product having excellent chemical resistance, elongation, and adhesion to metallic copper. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 122623 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when used as an insulating film in a semiconductor device, good adhesion to not only copper but also silicon is required. The cured product of Patent Document 1 may not have sufficient adhesion to a silicon substrate, which may result in defects such as peeling of the insulating film from the substrate.

[0006] The problem to be solved by the present invention is to provide a resin composition that can give a cured product that has excellent adhesion to a silicon substrate; a cured product obtained by curing the resin composition; and a semiconductor device that includes the cured product. [Means for solving the problem]

[0007] One aspect of the present invention is a resin composition comprising a polyhydroxyamide compound having a repeating unit represented by the following formula (1) and a phenolic resin having a repeating unit represented by the following formula (2), wherein the content of the phenolic resin is 12 to 90% by mass, where the total amount of the polyhydroxyamide compound and the phenolic resin is 100% by mass. [ka] {In formula (1), R 1 is a divalent organic group, R 2 is a tetravalent organic group. [ka] {In formula (2), R 3 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms which may have an unsaturated double bond.}

[0008] In the resin composition of the above embodiment, the polyhydroxyamide compound preferably contains a repeating structure represented by the following formula (1-1). [ka]

[0009] In the resin composition of the above aspect, the repeating unit structure of the phenol resin is preferably a structure having a phenol skeleton derived from cashew nut shell liquid.

[0010] The resin composition of the above embodiment preferably further contains a photoacid generator and / or a crosslinking agent.

[0011] Another aspect of the present invention is a cured product obtained by curing the resin composition of the above aspect.

[0012] Another aspect of the present invention is a semiconductor device, which includes the cured product of the above aspect. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a resin composition that can give a cured product that has excellent adhesion to a silicon substrate; a cured product obtained by curing the resin composition; and a semiconductor device that includes the cured product. DETAILED DESCRIPTION OF THE INVENTION

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

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

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

[0017] In this specification, the term "substituent" is not particularly limited, and unless otherwise specified, examples thereof include a hydroxyl 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, and the like.

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

[0019] 1.Resin composition The resin composition of this embodiment contains a polyhydroxyamide compound containing a repeating unit represented by the following formula (1) and a phenolic resin containing a repeating unit represented by the following formula (2). The resin composition of this embodiment may further contain a photoacid generator and / or a crosslinking agent. Each component of the resin composition will be described in detail below. [ka] {In formula (1), R 1 is a divalent organic group, R 2 is a tetravalent organic group. [ka] {In formula (2), R 3 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms which may have an unsaturated double bond.}

[0020] 1-1. Polyhydroxyamide compounds As described above, the polyhydroxyamide compound of this embodiment contains the repeating structure represented by the following formula (1). [ka] {In formula (1), R 1 is a divalent organic group, R 2 is a tetravalent organic group.

[0021] R in formula (1) 1 is not particularly limited as long as it is a divalent organic group, and may be, for example, a divalent organic group including an aromatic hydrocarbon group (arylene group), an aliphatic hydrocarbon group (alkylene group, cycloalkylene group), an ether group, a ketone group, an ester group, or the like.

[0022] R in formula (1) 1Among the divalent organic groups mentioned above, it is preferable that the divalent organic group has an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of the divalent organic group having an aromatic hydrocarbon group include divalent organic groups having a structure such as a biphenyl skeleton, a diphenyl ether skeleton, a benzophenone skeleton, a diphenylethane skeleton, a diphenylpropane skeleton, a diphenylhexafluoropropane skeleton, a diphenylsulfone skeleton, and a benzene skeleton. Examples of the divalent organic group having an aliphatic hydrocarbon group include divalent organic groups having a structure such as a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cycloundecane skeleton, a cyclododecane skeleton, and a dicyclopentadiene skeleton.

[0023] From the viewpoint of the resolution of the resin composition and the insulation reliability of the cured product, R 1 The carbon number of R is preferably 4 to 30, and phenyl, biphenyl, diphenyl ether, and diphenylhexafluoropropane are preferred. 1 It is also possible to contain two or more of the groups exemplified above as .

[0024] R in formula (1) 2 is not particularly limited as long as it is a tetravalent organic group, and for example, a tetravalent aromatic hydrocarbon group is preferred. Examples of the tetravalent aromatic hydrocarbon group include tetravalent aromatic hydrocarbon groups having a structure such as a biphenyl skeleton, a diphenyl ether skeleton, a diphenyl thioether skeleton, a benzophenone skeleton, a diphenylmethane skeleton, a diphenylpropane skeleton, a diphenylhexafluoropropane skeleton, a diphenyl sulfoxide skeleton, a diphenyl sulfone skeleton, and a benzene skeleton. Among these, an organic group having a structure represented by the following formula (3) is more preferred. [ka] {In formula (3), a is an integer of 0 to 3, and * is a bonding site.}

[0025] The polyhydroxyamide compound of this embodiment 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 a developer, it is preferable that the polyhydroxyamide compound have a carboxyl group or a phenolic hydroxyl group.

[0026] Of these alkali-soluble groups, the polyhydroxyamide compound of this embodiment preferably has a phenolic hydroxyl group. When the polyhydroxyamide compound has a terminal phenolic hydroxyl group, the solubility of the polyhydroxyamide compound in a developer can be improved. Furthermore, since the phenolic hydroxyl group has lower reactivity than a carboxyl group, when used in combination with a crosslinking agent, etc., described below, excessive reaction with the crosslinking agent, etc., is suppressed, and the solubility of the unexposed area in a developer can be maintained even when a PEB process, described below, is performed. This is thought to make it possible to provide a resin composition with excellent resolution.

[0027] The alkali-soluble group located at the terminal of the polyhydroxyamide compound may be a residue of a monomer constituting the polyhydroxyamide compound, or may be a terminal structure introduced by a terminal-capping agent having an alkali-soluble group. The alkali-soluble group located at the terminal of the polyhydroxyamide compound is preferably a terminal structure introduced by a terminal-capping agent having an alkali-soluble group.

[0028] The end-capping agent is not particularly limited, and examples thereof 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 anhydride and 5-norbornene-2,3-dicarboxylic anhydride.

[0029] The polyhydroxyamide compound of the present embodiment may contain two or more repeating units of the above formula (1). Alternatively, the polyhydroxyamide compound may contain a structure other than the repeating unit of the above formula (1), such as a repeating unit of polyamide having no polyamic acid, hydroxy group, carboxyl group, or the like.

[0030] The polyhydroxyamide compound of this embodiment preferably contains a repeating structure represented by the following formula (1-1). [ka]

[0031] The weight-average molecular weight (Mw) of the polyhydroxyamide compound of 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 setting the weight-average molecular weight within such a range, it becomes possible to form a finer L / S pattern with a higher aspect ratio.

[0032] The number average molecular weight (Mn) of the polyhydroxyamide compound of the present embodiment is preferably from 1,000 to 15,000, more preferably from 1,500 to 10,000, and particularly preferably from 1,500 to 6,000.

[0033] The polyhydroxyamide compound of the present embodiment preferably has a molecular weight dispersity index (PDI) of 1.0 to 4.0, more preferably 1.0 to 3.5. The molecular weight dispersity index (PDI) is calculated by the following formula. PDI=Mw / Mn

[0034] When the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI) of the polyhydroxyamide compound of the present embodiment are within the above ranges, a favorable balance is achieved between the solubility in the developer and the reaction with the crosslinker, making it possible to obtain a resin composition with superior resolution.

[0035] 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 Science) and converted into standard polystyrene. Specific measurement conditions are as follows:

[0036] Column: TSKgel αM {manufactured by Tosoh Corporation} Column temperature: 40℃ Eluent composition: NMP solution containing 100 mmol / L H3PO4 (85% aqueous H3PO4 solution used as raw material) and 10 mmol / L LiBr Eluent flow rate: 0.5mL / min Calibration standard: Polystyrene Detector wavelength: 260nm and 300nm Detector temperature: Room temperature (approx. 25°C) Baseline range during analysis: 15 to 40 minutes Molecular weight calculation range during analysis: 20 to 35 minutes

[0037] The polyhydroxyamide compounds of the present embodiment may be used singly or in combination of two or more.

[0038] A method for producing the polyhydroxyamide compound of this embodiment includes, for example, copolymerizing raw materials, a dihydroxydiamino compound represented by formula (4), a dicarbonyl dichloride compound represented by formula (5), and, if necessary, another compound copolymerizable therewith. Examples of the other copolymerizable compound include a diol compound, an acid dianhydride, a diisocyanate compound, and a diamine compound different from the dihydroxydiamino compound represented by formula (4). [ka] (In formula (4), R 2 is as described above.) [ka] (In formula (5), R 1is as described above.)

[0039] 1-2.Phenol resin As described above, the phenolic resin of this embodiment contains the repeating structure represented by the following formula (2). [ka] {In formula (2), R 3 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms which may have an unsaturated double bond.}

[0040] It is believed that the resin composition of this embodiment contains a predetermined amount of a phenolic resin having an aliphatic hydrocarbon group having 10 to 18 carbon atoms, as represented by formula (2), and thereby a cured product having excellent adhesion to a silicon substrate can be obtained. The mechanism of action is not clear, but is presumed to be as follows.

[0041] The resin composition of this embodiment contains the phenolic resin, which increases the hydroxyl group concentration in the resin composition, thereby improving the affinity between the resin composition and the silicon substrate. Furthermore, the phenolic resin contains a long-chain aliphatic hydrocarbon group, which improves the flexibility of the cured product obtained from the resin composition. Due to these synergistic effects, this embodiment is believed to be able to obtain a cured product with excellent adhesion to the silicon substrate.

[0042] R in equation (2) 3 However, when R has unsaturated double bonds, the number of unsaturated double bonds is not particularly limited and may be, for example, 1 to 5. 3 may be branched or unbranched, and is preferably unbranched.

[0043] R in equation (2) 3 Specific examples of the aliphatic hydrocarbon groups include the aliphatic hydrocarbon groups represented by the following formula (A): 3 It may contain two or more repeating structures with different repeat structures. [ka] {In formula (A), * represents a binding site.}

[0044] The repeating structure of the phenolic resin of this embodiment {the repeating structure represented by formula (2)} is preferably a structure having a phenolic skeleton derived from cashew nut shell liquid.

[0045] Cashew nut shell liquid is a component that can be obtained in high concentrations from cashew nut shells and contains multiple phenolic compounds, including cardanol. In this embodiment, the cashew nut shell liquid may be unrefined or refined. Cashew nut shell liquid is an easily available and highly reactive raw material. Furthermore, because it is not a fossil-derived raw material, it can also contribute to reducing carbon dioxide emissions.

[0046] The phenolic resin of this embodiment may further have a structure (hereinafter referred to as "other repeating structures") other than the repeating structure represented by the above formula (2). Examples of the other repeating structures include repeating structures having a phenol skeleton, a cresol skeleton, a resorcinol skeleton, a catechol skeleton, and a hydroquinone skeleton (the repeating structure represented by the following formula (2a)).

[0047] [ka] {In formula (2a), n is an integer of 1 or 2.}

[0048] When the phenolic resin of the present embodiment contains other repeating structures, the proportion of the repeating structures represented by formula (2) in the entire phenolic resin is preferably 50 mol % or more, more preferably 60 mol % or more, and even more preferably 70 mol % or more.

[0049] The weight average molecular weight (Mw) of the phenolic resin of the present embodiment is not particularly limited, and is, for example, preferably from 300 to 10,000, more preferably from 400 to 8,000, and even more preferably from 500 to 5,000.

[0050] The number average molecular weight (Mn) of the phenolic resin of this embodiment is preferably 100 to 5,000, more preferably 200 to 4,000, and particularly preferably 300 to 3,000.

[0051] The polydispersity index (PDI) of the phenolic resin of this embodiment is preferably 1.0 to 4.0, more preferably 1.0 to 3.5.

[0052] The conditions for measuring the weight average molecular weight and the number average molecular weight, and the method for calculating the molecular weight dispersity are as described above.

[0053] The viscosity of the phenolic resin of this embodiment is not particularly limited. For example, the viscosity at 25°C is preferably 50 Pa·s or less, and more preferably 30 Pa·s or less. The viscosity of the phenolic resin of this embodiment at 25°C is determined by multiplying the measured value (Pa·s) by a predetermined conversion factor (0.5) when rotating the resin at 10 revolutions per minute (10 rpm) at 25°C using an EHD rotational viscometer equipped with a cone rotor having a cone angle of 3° and a cone radius of 14 mm for 1 minute.

[0054] The hydroxyl equivalent of the phenolic resin of this embodiment is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0055] The phenolic resin of this embodiment can be produced, for example, by reacting a raw material phenolic compound, such as cashew nut shell liquid, with an aldehyde, such as formaldehyde, in the presence of an acid catalyst. Commercially available phenolic resins may also be used. Examples include Resitop ELP75 and Resitop ELP83H (manufactured by Gunei Chemical Industry Co., Ltd.).

[0056] 1-3. Photoacid generator The photoacid generator of this embodiment 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, and examples thereof 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-oxyamidosulfonates, aromatic N-oxyimidosulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimides, benzoquinone diazosulfonic acid esters, etc. These may be used alone or in combination in any ratio.

[0057] When the resin composition of this embodiment is used as a negative-type photosensitive resin composition, the photoacid generator is preferably used in combination with a crosslinking agent described below, and the photoacid generator is preferably an oxime sulfonate compound. Examples of the oxime sulfonate compound include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF, and those having the structure of the following formula (6) are particularly preferred. [ka]

[0058] X in the above formula (6) 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. A linear or branched hydrocarbon group having 1 to 4 carbon atoms is preferably used. A chlorine atom or a fluorine atom is preferably used as the halogen atom.

[0059] In the above formula (6), m represents an integer of 0 to 3, and is preferably 0 or 1. When m is 2 or 3, multiple Xs may be the same or different.

[0060] R in the above formula (6) 4 is preferably a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom. The hydrocarbon group (e.g., an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) may be unsubstituted or may be substituted with a halogen atom.

[0061] The hydrocarbon group is preferably a linear, branched or cyclic group having 1 to 20 carbon atoms, and more preferably a linear, branched or cyclic group having 1 to 10 carbon atoms. The halogen atom may be a chlorine atom or a fluorine atom.

[0062] 1-4. Crosslinking agent The crosslinking agent of the present embodiment may be a known compound, such as a melamine compound, a guanamine compound, a triazine compound, an epoxy compound, an oxetane compound, an isocyanate compound, or an oxazoline compound.

[0063] The crosslinking agent of this embodiment preferably contains a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group in its molecular structure. These functional groups, using the acid generated from the photoacid generator as the active species, undergo a crosslinking reaction with phenolic hydroxyl groups, carboxyl groups, etc. contained in polyhydroxyamide compounds, etc., upon heating. This allows pattern formation through exposure, PEB, and development, making the resin composition of this embodiment particularly suitable for use as a negative-tone photosensitive resin composition. Furthermore, further heating after pattern formation promotes the curing reaction of the resin composition, resulting in the development of excellent properties as a cured product.

[0064] The crosslinking agent of this embodiment preferably contains a heterocycle, since this improves the resolution of the resin composition and the insulating reliability after curing. The heterocycle 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 include a 3-, 4-, 5-, 6-, 7-, or 8-membered saturated or unsaturated ring. From the viewpoints of the resolution of the resin composition and the insulating reliability of the cured product, the heterocycle is preferably a nitrogen-containing heterocycle, and more preferably a heterocycle containing multiple nitrogen atoms.

[0065] Specifically, compounds having a triazine structure such as hexamethylolmelamine and hexamethoxymethylmelamine, compounds having a guanamine structure such as tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanamine, compounds having a glycoluril structure such as tetramethylolglycoluril and tetramethoxyglycoluril, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone are more preferred. Of these, compounds having a triazine structure containing a triazine ring and compounds having a guanamine structure are particularly preferred from the viewpoint of providing a resin composition capable of forming an L / S pattern that is finer and has a higher aspect ratio.

[0066] 1-5. Basic compounds The resin composition of the present embodiment may further contain a basic compound. In particular, when the resin composition of the present embodiment contains a basic compound, it is possible to prevent the acid generated from the photoacid generator upon exposure from diffusing into unexposed areas, thereby improving resolution and preventing development residues from being generated in unexposed areas after development.

[0067] The basic compound is not particularly limited, and examples thereof include trimethylamine, diethylamine, triethylamine, N,N-diisopropylethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, tris(2-methoxy)amine, bis(2-methoxy)amine, tris(2-ethoxy)amine, bis(2-ethoxy)amine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4, Amine compounds such as 4'-diaminodiphenylamine; amide compounds such as formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide; lactams such as pyrrolidone and N-methylpyrrolidone; methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3-diphenyl Examples of suitable compounds include urea and other urea compounds; nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and pyridine; and morpholine compounds such as morpholine and 4-methylmorpholine. These compounds can be used alone or in combination in any ratio. Among these, amine compounds are preferred, with alcoholamines such as N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine being more preferred, and diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanolamine being even more preferred.

[0068] 1-6.Solvents The resin composition of the present embodiment may contain a solvent. The solvent is not particularly limited, and examples thereof include ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethyl sulfone, and pyridine.

[0069] 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.

[0070] 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.

[0071] 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; Diketone cycloalkanones 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 having a heterocyclic skeleton such as 2-azetidinone, 4,5-dihydro-3(2H)-thiophenone, 4-oxothiane, and dihydrolevogluconocene; and the like.

[0072] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0073] 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.

[0074] These solvents can be used alone or in combination of two or more in any ratio. Among these solvents, lactones or cyclic ketones are preferred, and γ-butyrolactone or cyclopentanone is preferred, from the viewpoint of excellent affinity with each component in the resin composition. Furthermore, from the viewpoint of excellent solvent removability during drying of the resin composition and compatibility with the edge rinse process in semiconductor manufacturing, cyclic ketones are preferred, and monoketone cycloalkanones are more preferred, with cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone being even more preferred, and cyclopentanone being particularly preferred.

[0075] 1-7.Other ingredients The resin composition of the present embodiment may contain other components as long as the effects of the disclosed technology are not impaired. Examples of other components include known components that can be contained in resin compositions, such as fillers, adhesion agents, surfactants, plasticizers, thermal acid generators, sensitizers, leveling agents, colorants, fibers, and fine particles.

[0076] The surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, etc. Commercially available fluorine-based surfactants include the "Megafac" series manufactured by DIC Corporation (e.g., Megafac F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-569, etc.). Commercially available silicone surfactants include the BYK-Chemie surface conditioner series (e.g., BYK-302, BYK-307, BYK-310, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK-348, BYK-349, BYK-377, BYK-378, BYK-3455, BYK-3760, etc.). These may be used alone or in combination of two or more.

[0077] The resin composition of the present embodiment may further contain, as other components, a compound containing a phenolic hydroxyl group other than the above-mentioned phenolic resin. The compound containing a phenolic hydroxyl group other than the phenolic resin may be a monomer or a polymer. Examples of the compound containing a phenolic hydroxyl group other than the phenolic resin include polyhydroxystyrene copolymers obtained by copolymerizing hydroxystyrene (which may be any of o-, m-, or p-) and styrene.

[0078] 2. Preparation of Resin Composition The resin composition of the present embodiment can be obtained by mixing the above-described polyhydroxyamide compound and phenolic resin with optional components such as a crosslinking agent, a photoacid generator, a basic compound, etc. The components can be mixed under heating as needed.

[0079] 2-1. Polyhydroxyamide compounds The content of the polyhydroxyamide compound can be set to 50 to 80% by mass when the total mass of the solid content of the resin composition is taken as 100% by mass.

[0080] 2-2.Phenol resin The content of the phenolic resin is 12 to 90% by mass, where the total solid mass (total amount) of the polyhydroxy compound and the phenolic resin is 100% by mass. The content of the phenolic resin is preferably 12 to 70% by mass, and more preferably 12 to 25% by mass. By setting the content of the phenolic resin to 25% by mass or less, a resin composition with better compatibility can be obtained.

[0081] 2-3. Photoacid generator The content of the photoacid generator can be 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total solid content (total amount) of the polyhydroxy compound and the phenolic resin.

[0082] 2-4. Crosslinking agent The content of the crosslinking agent can be 5 to 80 parts by mass per 100 parts by mass of the total solid content (total amount) of the polyhydroxy compound and the phenolic resin. When the crosslinking agent has a methoxymethyl group and / or a methylol group, the content of the crosslinking agent can be set 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 resin composition (methoxymethyl groups and / or methylol groups:phenolic hydroxyl groups) is 120:100 to 200:100. By setting such a ratio, the resolution of the resin composition and the insulation reliability after curing can be improved.

[0083] 2-5. Basic compounds The content of the basic compound can be 0.01 to 1.00 parts by mass, and preferably 0.05 to 0.50 parts by mass, relative to 100 parts by mass of the total solid content (total amount) of the polyhydroxy compound and the phenolic resin. By setting the content within this range, it becomes easier to suppress the generation of development residues in unexposed areas after the resin composition is developed.

[0084] 3. Dry film The resin composition of the present embodiment may be applied to a support and then dried to form a dry film. That is, the dry film of the present embodiment includes a support and a resin layer formed from the resin composition of the present embodiment. To protect the resin layer, a protective film may be further laminated on the surface of the resin layer.

[0085] The resin layer can be obtained, for example, by applying a resin composition onto a support, adjusting the thickness of the resin layer using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., and drying the resin layer. The thickness of the resin layer is not particularly limited and can be set to 1 to 150 μm depending on the application.

[0086] The support is not particularly limited, and examples thereof include metal foils such as copper foils; and films such as polyimide films, polyester films, and polyethylene naphthalate (PEN) films.

[0087] The protective film is not particularly limited, and polyethylene film, polytetrafluoroethylene film, polypropylene film, paper, etc. can be used. It is preferable to select a protective film such that the adhesion between the protective film and the resin layer is lower than the adhesion between the support and the resin layer. In order to make the adhesion between the protective film and the resin layer lower than the adhesion between the support and the resin layer, a protective film whose surface has been subjected to a release treatment can be used.

[0088] 4.Cured product The cured product of this embodiment is formed from the resin composition described above. Alternatively, it is formed by curing the resin layer of the dry film described above. The cured product may be a patterned cured product. A method for producing a patterned cured product will be described below using an example in which a resin composition that is a negative photosensitive resin composition is used.

[0089] 4-1. Dry coating film formation process The dry coating film forming step is a step of applying the above-mentioned resin composition to a substrate to form a coating film, and then drying the coating film. In the dry coating film forming step, it is also possible to form a dry coating film on the substrate by laminating a resin layer of a dry film on the substrate.

[0090] The method for applying the resin composition to a substrate is not particularly limited, and examples thereof include a method using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., a spray coating method using a spray coater, and an inkjet method. The thickness of the applied film is not particularly limited, and can be, for example, 10 μm or less, 5 μm or less, or 3 μm or less. By reducing the film thickness, finer L / S patterning becomes possible while maintaining the aspect ratio of the pattern.

[0091] The method for drying the coating film is not particularly limited, and examples thereof include air drying, heat drying in an oven or on a hot plate, vacuum drying, etc. Conditions for heat drying include a heating temperature of 70 to 140°C and a drying time of 1 to 30 minutes, for example.

[0092] The resin layer of the dry film is preferably laminated onto the substrate under pressure and heat using a vacuum laminator, etc. The heating temperature can be, for example, 60 to 100°C.

[0093] The substrate is not particularly limited, and may be, for example, a printed wiring board on which a circuit is formed, a flexible printed wiring board, or a wafer on which a semiconductor element is formed.

[0094] 4-2. Exposure process The exposure step is a step in which the dried coating film formed in the dried coating film formation step is irradiated with light such as ultraviolet light or visible light through a photomask capable of forming a desired pattern, thereby sensitizing the photoacid generator in the exposed area and generating active species. If patterning is not required, there is no need to use a photomask. Alternatively, a pattern may be directly written with a laser using a direct writing device.

[0095] The wavelength of light such as ultraviolet light or visible light is one that can activate the photoacid generator, and in order to perform fine patterning, a maximum wavelength of 410 nm or less is preferred. The irradiation energy can be adjusted depending on the thickness of the formed dried coating film, and is, for example, 10 to 1500 mJ / cm. 2 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, or the like can be used.

[0096] 4-3.PEB process The PEB process is, for example, a process of heat-treating a dried coating film made of a resin composition exposed in the exposure process, thereby imparting development resistance to the exposed portion of the dried coating film. In the PEB process, an acid generated from a photoacid generator in the exposed portion acts as an active species to promote a crosslinking reaction between the polyhydroxyamide compound, the phenolic resin, and the crosslinking agent, thereby making the exposed portion insoluble in a developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be performed using a known method such as a hot plate or a heating furnace.

[0097] 4-4.Developing process The development step is a step in which the dried coating film heated in the PEB step is treated with a developer to obtain a patterned coating film. More specifically, the unexposed areas of the dried coating film are dissolved and removed in the developer to obtain a patterned coating film. As the development method, a known method can be used, such as a rotary spray method, a paddle method, or an immersion method accompanied by ultrasonic treatment.

[0098] Known developers can be used, and examples of such developers include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, water-soluble organic solvents such as methanol, ethanol, and isopropyl alcohol, and surfactants can be added.

[0099] After the treatment with the developer, the coating film can be washed with a rinse solution as needed to obtain a patterned coating film. The rinse solution is not particularly limited, and examples thereof include pure water, methanol, ethanol, and isopropyl alcohol. These can be used alone or in combination in any ratio.

[0100] 4-5. Post-development heating process The post-development heating step is a step of heating the patterned coating film formed in the development step to complete curing of the patterned coating film and obtain a cured patterned coating film (cured product). The heating temperature can be 150 to 250°C, and the heating time can be 1 to 120 minutes. Heating can be performed using a known method such as a hot plate or an inert oven.

[0101] When the resin composition of the present embodiment is a positive-type photosensitive resin composition, a dissolution inhibitor is used as a photoacid generator, and the coating film is treated with a developer in the development step, whereby the exposed areas of the dried coating film are dissolved and removed in the developer, thereby obtaining a patterned coating film.

[0102] 5. Semiconductor Devices The semiconductor device of this embodiment has the above-described cured product. The semiconductor device of this embodiment has the above-described cured product as, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip-chip devices, etc.

[0103] 6. Uses of resin compositions The resin composition of the present embodiment can be suitably used as a forming material for electronic components, display devices, optical components, building materials, and the like, in addition to the semiconductor devices described above. [Example]

[0104] 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.

[0105] <Synthesis of Polyhydroxyamide Compounds> The polyhydroxyamide compound was synthesized as follows.

[0106] In a 200 mL vial equipped with a stirrer and thermometer (at room temperature), 75.82 g (293.5 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) and 9.93 g (91.0 mmol) of 3-aminophenol (3-AP) were dissolved in 411 g of N-methylpyrrolidone (NMP) with stirring. 90.47 g (306.5 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was then added. After stirring at room temperature for 16 hours, the precipitate was collected using water and methanol as a poor solvent. The resulting solid was dried under reduced pressure and then dissolved in 447 g of tetrahydrofuran. 88 g of anion exchange resin (Organo Corporation, Amberlyst B-20) was added and vigorously stirred for 1 hour. The precipitate was collected from the stirred solution using water and methanol as a poor solvent. The collected solid was then dried under reduced pressure to obtain a polyhydroxyamide compound. The polyhydroxyamide compound obtained had an Mw of 9,300, an Mn of 4,600, and a PDI of 2.0. [ka]

[0107] <Phenol resin> Resitop ELP83H {manufactured by Gun-ei Chemical Industry Co., Ltd., a phenolic resin having a repeating unit structure represented by formula (2)} VPS-2515 {Polyhydroxystyrene resin manufactured by Nippon Soda Co., Ltd.}

[0108] <Crosslinking agent> MW-390 {Hexamethoxymethylmelamine compound manufactured by Nippon Carbide Industries Co., Ltd.} [ka]

[0109] <Photoacid generator> Irgacure PAG103 {BASF Japan Ltd., oxime sulfonate compound} [ka]

[0110] <Basic compounds> Triethanolamine (TEA) [ka]

[0111] <Solvent> Cyclopentanone {Tokyo Chemical Industry Co., Ltd.}

[0112] <Preparation of Resin Composition> Varnishes of the resin compositions of the Examples and Comparative Examples were obtained by blending the components in the amounts (parts by mass) shown in Table 1 below and dissolving and adjusting the non-volatile component concentration in the varnish to 30% with a solvent. Note that the blending amounts of the components in Table 1, except for the blending amount of the solvent, are shown in parts by mass of the solid content.

[0113] <Evaluation> The resin compositions obtained in each of the Examples and Comparative Examples were evaluated as follows. The results of the evaluations are shown in Table 1.

[0114] (Evaluation of Adhesion) The varnish was applied to a silicon wafer using a spin coater and then dried on a hot plate at 90°C for 3 minutes to obtain a dry film of the resin composition (approximately 5 μm thick). The resulting dry film was exposed to UV light (365 nm) at an exposure dose of 1,000 mJ / cm, heated at 120°C for 1 minute, and then heated in an inert gas oven (KOYO THERMO SYSTEMS CO., LTD., CLH-21CD-S) under a nitrogen atmosphere at 220°C for 60 minutes to obtain a cured film on the silicon wafer.

[0115] The cured film thus obtained was cut into a grid of 100 squares of 1 mm each using a single-edged blade, and the film was peeled off using Scotch tape (registered trademark), and the number of squares that peeled off out of the 100 was counted and evaluated according to the following criteria. Evaluation criteria A: Number of peeled pieces is 0 to 10 B: Number of peeled pieces: 11 to 60 C: Number of peeled pieces: 61-90 D: 91 or more peeled pieces or complete peeling

[0116] (Evaluation of compatibility) The varnish was applied to a silicon wafer using a spin coater and then dried at 90°C for 3 minutes using a hot plate to obtain a dry film (approximately 5 µm thick) of the resin composition. The dry film was visually observed and evaluated according to the following criteria. The fewer whitened areas in the dry film, the better the compatibility of the resin composition. Evaluation criteria A: No bleaching was observed B: No bleaching was observed in more than half of the area. C: Whitening was observed in more than half of the area.

[0117] [Table 1] [Industrial Applicability]

[0118] The resin composition of the present invention can give a cured product that has excellent adhesion to silicon substrates, and can therefore be suitably used as a forming material for semiconductor devices, electronic components, display devices, optical components, building materials, etc.

Claims

1. a polyhydroxyamide compound containing a repeating structure represented by the following formula (1); a phenolic resin containing a repeating structure represented by the following formula (2); Including, The resin composition has a phenol resin content of 12 to 90% by mass, with the total amount of the polyhydroxyamide compound and the phenol resin being 100% by mass. 【Chemistry 1】 {In formula (1), R １ is a divalent organic group, R ２ is a tetravalent organic group. 【Chemistry 2】 {In formula (2), R ３ represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms which may have an unsaturated double bond.}

2. The resin composition according to claim 1, wherein the polyhydroxyamide compound contains a repeating structure represented by the following formula (1-1): 【Transformation 3】

3. The resin composition according to claim 1 , wherein the phenolic resin has a structure having a phenolic skeleton derived from cashew nut shell liquid.

4. The resin composition according to claim 1 , further comprising a photoacid generator and / or a crosslinking agent.

5. A cured product obtained by curing the resin composition according to claim 1.

6. A semiconductor device comprising the cured product according to claim 5.

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