Photosensitive resin composition, resin film, and semiconductor device

Abstract

To provide a photosensitive resin composition capable of forming a resin film with good film thickness uniformity, a resin film with good film thickness uniformity, and a semiconductor device comprising such a resin film. [Solution] The photosensitive resin composition according to the present invention comprises one or more resins (A) selected from the group consisting of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and phenol resin, a photosensitive agent (B), a surfactant (C), and a solvent, wherein the surfactant (C) is composed of a non-fluorinated surfactant, and when 7.5 mL of the photosensitive resin composition is contained in a dispenser as a container, the tip of the dispenser is immersed in a mixed solution of 70% by mass of PGME and 30% by mass of PGMEA for 20 seconds, and then the container is removed and the viscosity is measured with an E-type viscometer, the measured viscosity is 68% or more and 80% or less of the viscosity of the photosensitive resin composition that has not been immersed.

Description

[Technical Field]

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

[0002] The resin film obtained by applying the photosensitive resin composition can be used, for example, as a redistribution layer or buffer coat layer in semiconductor devices.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing an alkaline aqueous solution-soluble resin, a crosslinking agent, a photopolymerization initiator, and an epoxy resin (thermosetting resin). By using this photosensitive resin composition, a cured product with excellent flexibility, adhesion, etc., can be obtained. Furthermore, it is disclosed that this cured product can be used as an interlayer insulating material for electronic components. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-80871 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] With the increasing sophistication of semiconductor devices, there is a growing demand for uniformity in the film thickness of resin films used as insulating films or protective films in these devices. However, depending on the environment in which the photosensitive resin composition is applied, the state of the photosensitive resin composition may change during storage. As a result, the uniformity of the film thickness of the formed resin film may decrease.

[0006] The object of the present invention is to provide a photosensitive resin composition capable of forming a resin film with good film thickness uniformity, a resin film with good film thickness uniformity, and a semiconductor device comprising such a resin film. [Means for solving the problem]

[0007] These objectives are achieved by the present invention as described in (1) to (8) below. (1) One or more resins (A) selected from the group consisting of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and phenol resin, Photosensitive material (B), Surfactant (C) and Solvent and, A photosensitive resin composition comprising, The surfactant (C) is composed of a non-fluorinated surfactant. When 7.5 mL of the photosensitive resin composition is contained in a dispenser, and the tip of the dispenser is immersed for 20 seconds in a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA), the contents are removed and the viscosity is measured using an E-type viscometer, A photosensitive resin composition characterized in that the measured viscosity is 68% or more and 80% or less of the viscosity of the photosensitive resin composition that has not been immersed.

[0008] (2) The nonfluorine-based surfactant (C) is a silicone-based surfactant, as described in (1) above, in the photosensitive resin composition.

[0009] (3) The photosensitive resin composition according to (2) above, wherein the silicone-based surfactant is a polyether-modified dimethylsiloxane or an aralkyl-modified dimethylsiloxane.

[0010] (4) With the photosensitive resin composition having a volume of 7.5 mL accommodated in a dispenser as the contained material, the tip of the dispenser is immersed in a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds, and then the contained material is taken out in three portions of 2.5 mL each, namely the first portion, the second portion, and the third portion. Thermogravimetric analysis is performed on each portion under a nitrogen atmosphere. When the weight loss rate at 146.6 °C of the first portion is taken as the first analysis value, the weight loss rate at 146.6 °C of the second portion is taken as the second analysis value, and the weight loss rate at 146.6 °C of the third portion is taken as the third analysis value, The photosensitive resin composition according to any one of (1) to (3) above, wherein each of the first analysis value, the second analysis value, and the third analysis value is 101% or more and 115% or less of the weight loss rate at 146.6 °C of the photosensitive resin composition that has not been immersed.

[0011] (5) The photosensitive resin composition according to any one of (1) to (4) above, wherein the resin (A) is a phenol resin.

[0012] (6) The photosensitive resin composition according to any one of (1) to (4) above, wherein the resin (A) is a polyimide precursor or a polybenzoxazole precursor.

[0013] (7) A resin film characterized by being composed of a cured product of the photosensitive resin composition according to any one of (1) to (6) above.

[0014] (8) A semiconductor device, comprising: the resin film according to (7) above provided on the surface of the semiconductor device; and.

Advantages of the Invention

[0015] According to the present invention, a photosensitive resin composition capable of forming a resin film with good film thickness uniformity can be obtained.

[0016] Moreover, according to the present invention, a resin film with good film thickness uniformity can be obtained. Furthermore, according to the present invention, a semiconductor device including the above resin film can be obtained.

Brief Description of the Drawings

[0017] [Figure 1] It is a cross-sectional view showing a semiconductor device (semiconductor device according to an embodiment) including a resin film according to an embodiment.

Modes for Carrying Out the Invention

[0018] Hereinafter, the photosensitive resin composition, resin film, and semiconductor device according to the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.

[0019] 1. Photosensitive Resin Composition The photosensitive resin composition according to the present embodiment is a resin material used to form a resin film included in a semiconductor device. This photosensitive resin composition contains a resin (A), a photosensitizer (B), a surfactant (C), and a solvent. The surfactant (C) is composed of a non-fluorine-based surfactant.

[0020] Moreover, the photosensitive resin composition according to the present embodiment has a property that the viscosity measured after being subjected to a solvent immersion test falls within 68% or more and 80% or less of the viscosity measured before being subjected to the solvent immersion test.

[0021] This solvent immersion test is a test in which, with a photosensitive resin composition having a volume of 7.5 mL accommodated in a dispenser, the tip of the dispenser is immersed in a test solution for 20 seconds. The test solution is a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA).

[0022] As a result of the inventors' investigations, it was found that a photosensitive resin composition satisfying the above-mentioned characteristics exhibits suppressed changes in state regardless of the storage environment. Furthermore, it was found that a resin film with good film thickness uniformity can be formed by using such a photosensitive resin composition, thus leading to the completion of the present invention.

[0023] 1.1. Resin (A) The resin (A) comprises one or more selected from the group consisting of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and phenol resin.

[0024] 1.1.1. Polyamides As the polyamide, for example, it is preferable to use an aromatic polyamide that contains an aromatic ring in its structural unit, and more preferably one that contains a structural unit represented by the following formula (PA1). This improves the physical properties of the resin film made of the photosensitive resin composition, such as its mechanical strength. As a result, the uniformity of the film thickness of the resin film is improved, and the occurrence of defects can be suppressed.

[0025] Examples of aromatic rings include benzene rings; condensed aromatic rings such as naphthalene, anthracene, and pyrene rings; and heteroaromatic rings such as pyridine and pyrrole rings. Of these, polyamides are preferably made to contain a benzene ring as an aromatic ring from the viewpoint of mechanical strength and other factors.

[0026] [ka]

[0027] 1.1.2. Polybenzoxazoles and their precursors Polyamides containing the structural unit represented by the above formula (PA1) are precursors of polybenzoxazoles. Polyamides containing the structural unit represented by the above formula (PA1) undergo dehydration and ring closure to form polybenzoxazoles by heat treatment, for example, at a temperature of 150°C to 380°C for 30 minutes to 10 hours. Polybenzoxazoles contain the structural unit shown by the following formula (PBO1).

[0028] If the resin (A) is a polyamide containing the structural unit represented by the above formula (PA1), for example, the photosensitive resin composition may be dehydrated and cyclized by the above heat treatment to obtain a polybenzoxazole.

[0029] Furthermore, if the resin (A) is a polyamide containing the structural unit represented by the above formula (PA1), the resin film described later may be prepared and then subjected to the above heat treatment to dehydrate and closure the ring, thereby obtaining a polybenzoxazole.

[0030] By dehydrating and opening the ring of polyamide to form polybenzoxazole, the mechanical and thermal properties can be improved. This also helps to suppress deformation of the resin film.

[0031] [ka]

[0032] 1.1.3. Polyimides and their precursors As the polyamide, for example, one containing the structural unit represented by the following general formula (PA2) may be used. A polyamide containing the structural unit represented by the following general formula (PA2) is a precursor of polyimide. A polyamide containing the structural unit represented by the following general formula (PA2) undergoes dehydration and ring closure to become polyimide by heat treatment, for example, at a temperature of 150°C to 380°C for 30 minutes to 10 hours. Polyimide contains the structural unit shown by the following general formula (PI1).

[0033] If the resin (A) is a polyamide containing structural units represented by the following general formula (PA2), the photosensitive resin composition may be dehydrated and ring-closed by the above heat treatment to obtain a polyimide.

[0034] Furthermore, if the resin (A) is a polyamide containing structural units represented by the following general formula (PA2), the resin film described later may be prepared and then subjected to the above heat treatment to dehydrate and closure the ring, thereby obtaining a polyimide.

[0035] [ka]

[0036] In general formula (PA2), R B and R C Each of these is an organic group with between 1 and 30 carbon atoms.

[0037] [ka]

[0038] In the general formula (PI1), R B and R C This is the same as the general formula (PA2) above. R in general formula (PA2) and general formula (PI1) B and R C Each of these is preferably an organic group having an aromatic ring.

[0039] The organic group having an aromatic ring preferably includes a benzene ring, a naphthalene ring, or an anthracene ring, and more preferably includes a benzene ring.

[0040] 1.1.4. Polyimides having an imide ring structure The polyimide may include a polyimide having an imide ring structure. This polyimide has an azole structure.

[0041] The azole structure may be located on the side chain of the polyimide or at its terminus. Due to the availability of raw materials and ease of synthesis, it is preferable that the polyimide has an azole structure at least at one end. The polyimide may have azole structures at both ends, or at only one end.

[0042] Examples of azole structures include triazole and tetraazole structures. There are two types of triazole structures: the 1,2,3-triazole structure and the 1,2,4-triazole structure, which differ in the position of the nitrogen atom.

[0043] Examples of triazole structures include a monovalent group obtained by removing a hydrogen atom from a triazole compound. Examples of triazole compounds include triazole, benzotriazole, tolyltriazole (benzotriazole in which a methyl group is substituted on the benzene ring), carboxybenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, 4,5,6,7-tetrahydrotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'5'-di-tert-butylphenyl)benzotriazole, and 2-(2'-hydroxy-4-octoxyphenyl)benzotriazole.

[0044] Examples of tetrazole structures include monovalent groups obtained by removing hydrogen atoms from tetrazole compounds. Examples of tetrazole compounds include 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1H-tetrazole-5-acetic acid, and 1H-tetrazole-5-succinic acid.

[0045] More specifically, the azole structure may include the structure represented by the following general formula (AZ). The asterisk (*) represents a bond with polyimide.

[0046] [ka]

[0047] In the general formula (AZ), R is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms. Y is -CH= or -N=.

[0048] The alkyl group of R may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, and docosyl groups. Examples of branched alkyl groups include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0049] The cycloalkyl group of R may be monocyclic or polycyclic. Specifically, examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

[0050] Examples of aromatic hydrocarbon groups for R include phenyl groups, naphthyl groups, and anthranil groups.

[0051] Polyimides may contain polyimides that include fluorine atoms. Polyimides containing fluorine atoms tend to have better solubility in organic solvents than polyimides that do not contain fluorine atoms. Therefore, using polyimides containing fluorine atoms makes it easier to give the photosensitive resin composition a varnish-like appearance. The polyimide preferably contains structural units represented by the following general formula (a).

[0052] [ka]

[0053] In the above general formula (a), X is a divalent organic group, and Y is a tetravalent organic group. At least one of X and Y is a fluorine-containing group.

[0054] At least one of the divalent organic group of X and the tetravalent organic group of Y preferably contains an aromatic ring structure, and more preferably a benzene ring structure. This further enhances the heat resistance of the resin film. Furthermore, from the viewpoint of solubility in organic solvents, it is preferable that both X and Y are fluorine atom-containing groups.

[0055] At least one of the divalent organic group of X and the tetravalent organic group of Y preferably has a structure in which 2 to 6 benzene rings are linked by single bonds or divalent linking groups. Examples of divalent linking groups include alkylene groups, alkylene fluorides, and ether groups. The alkylene group and alkylene fluorides may be linear or branched.

[0056] The number of carbon atoms in the divalent organic group of X is preferably 6 to 30. The number of carbon atoms in the tetravalent organic group of Y is preferably 6 to 20. In the above general formula (a), it is preferable that the two imide rings are each five-membered rings. Polyimide is more preferably composed of structural units represented by the following general formula (aa).

[0057] [ka]

[0058] In the above general formula (aa), Y' is a single bond or an alkylene group. X is the same as X in general formula (a).

[0059] The alkylene group of Y' may be linear or branched. Preferably, some or all of the hydrogen atoms of the alkylene group of Y' are substituted with fluorine atoms. The number of carbon atoms in the alkylene group of Y' is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

[0060] 1.1.5. Phenolic resin Examples of phenolic resins include phenol novolac resins, naphthalene ring-containing phenolic resins, aralkyl-type phenolic resins, triphenolalkane-type phenolic resins, biphenyl-type phenolic resins, alicyclic phenolic resins, heterocyclic phenolic resins, naphthalene ring-containing phenolic resins, and bisphenol-type phenolic resins. One or more of these can be used.

[0061] Of these, biphenyl-type phenolic resin is preferably used as the phenolic resin. Biphenyl-type phenolic resin is a phenolic resin having a biphenyl structure. This improves the low-temperature curability of the photosensitive resin composition and the reliability of the resin film. Furthermore, the improvement in low-temperature curability makes it possible to improve, for example, the wiring density of the redistribution layer.

[0062] 1.2. Photosensitive material (B) The photosensitive agent (B) generates active species upon exposure to light, thereby curing the photosensitive resin composition.

[0063] Examples of photosensitive agents include photoacid generators and photoradical generators. Of these, photoacid generators generate acid in response to light and act as catalysts for cationic polymerization, crosslinking reactions, and the like.

[0064] Examples of photoacid generators 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-oxyimide sulfonates, aromatic sulfamides, and benzoquinone diazosulfonic acid esters. Among these, naphthoquinone diazide compounds are particularly preferred.

[0065] Examples of naphthoquinone diazide compounds that can be used include naphthoquinone diazide adducts of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and naphthoquinone diazide adducts of tetrahydroxybenzophenone. Here, the addition of naphthoquinone diazide can be carried out, for example, by reacting o-quinone diazide sulfonyl chlorides with hydroxyl compounds or amino compounds.

[0066] Furthermore, the photosensitive resin composition can be made positive or negative by selecting the appropriate photoacid generator. Specifically, when a photoacid generator that generates acid in the exposed area is used, the solubility of the exposed area in a developer solution such as an alkaline aqueous solution increases. As a result, a positive-type photosensitive resin composition is obtained. On the other hand, when a photoacid generator that causes insolubilization upon exposure is used, the solubility of the exposed area in a developer solution decreases. As a result, a negative-type photosensitive resin composition is obtained.

[0067] Furthermore, photoradical generators are particularly effective in polymerizing polyfunctional (meth)acrylic compounds.

[0068] Examples of photoradical generators include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and 2-methyl-1-(4 Alkylphenone compounds such as -methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4′-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl ether, benzo Benzoin compounds such as isopropyl ether and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6- Halomethylated triazine compounds such as bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbokynylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, and 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethano Examples include oxime ester compounds such as n,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. Among these, oxime ester compounds are particularly preferred.

[0069] The amount of photoradical generator is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylic compound.

[0070] The photosensitive agent (B) may be one or more of the above-mentioned photosensitive agents. From the viewpoint of improving curability, the content of photosensitive agent (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of resin (A). Furthermore, from the viewpoint of suppressing a decrease in reliability, the content of photosensitive agent (B) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, per 100 parts by mass of resin (A).

[0071] 1.3. Surfactants (C) Surfactant (C) improves the wettability of the photosensitive resin composition during coating, contributing to the acquisition of a uniform coating film and resin film. A non-fluorinated surfactant is used as surfactant (C). Non-fluorinated surfactants are surfactants that do not contain fluorine, and examples include silicone-based surfactants and hydrocarbon-based surfactants; silicone-based surfactants are preferred. By using such a non-fluorinated surfactant, it is possible to realize a photosensitive resin composition that suppresses changes in state regardless of the storage environment and can form a resin film with particularly good film thickness uniformity. Furthermore, it is possible to reduce the amount of so-called PFAS (fluorinated chemical substances) used.

[0072] Furthermore, non-fluorinated surfactants can suppress foaming compared to fluorinated surfactants. Therefore, they are useful from the perspective of suppressing changes in state due to foaming during storage.

[0073] 1.3.1. Silicone-based surfactants Examples of silicone-based surfactants include organically modified polysiloxanes such as polyether-modified polysiloxanes, aralkyl-modified polysiloxanes, and polyester-modified polysiloxanes. These are compounds obtained by performing various organic modifications on basic polydimethylsiloxane. As a result, highly polar moieties are added, improving compatibility with solvents and contributing to improved wettability to metal materials. This leads to the acquisition of a uniform coating film (improved coatability), improved developability, and improved adhesive strength.

[0074] The organically modified polysiloxane mentioned above is preferably a compound represented by the following formula (1). This compound contains an organically modified unit containing the modifying group X, and a dimethylsiloxane unit derived from dimethylsiloxane. Therefore, the above properties can be easily controlled according to the ratio of these structural units. As a result, the dissolved state (dispersed state) of the components is maintained and changes are suppressed regardless of the environment in which the photosensitive resin composition is stored. Consequently, variations in the film thickness of the resin film formed using the photosensitive resin composition are suppressed, and a resin film with particularly good film thickness uniformity can be obtained.

[0075] [ka]

[0076] In formula (1) above, X represents a polyether group containing a polyether (polyoxyalkylene) structure, an aralkyl group, or a polyester group containing a polyester structure. m and n each represent an integer between 1 and 100.

[0077] Of these, X is preferably a polyether group or an aralkyl group. In other words, the silicone-based surfactant is preferably a polyether-modified dimethylsiloxane or an aralkyl-modified dimethylsiloxane.

[0078] When X in formula (1) above is a polyether group, the polyether group represented by formula (2-1) below is preferably used as X.

[0079] [ka]

[0080] In the above equation (2-1), R 20 R represents an alkyl group with 1 to 6 carbon atoms. 21represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl ether group having 1 to 6 carbon atoms, or an unsaturated alkyl ether group having 1 to 6 carbon atoms. EO represents an ethylene oxide group. PO represents a propylene oxide group. o represents an integer of 1 or more, and p represents an integer of 0 or more. The order of EO and PO may be random.

[0081] When X in the above formula (1) contains a propylene oxide group, the lower limit of the molar ratio of the propylene oxide group to the total molar amount of the ethylene oxide group and the propylene oxide group is preferably 1% or more, more preferably 10% or more, and even more preferably 20% or more. On the other hand, the upper limit of the molar ratio of the propylene oxide group is preferably 99% or less, more preferably 90% or less, and even more preferably 80% or less. By setting the molar ratio of the propylene oxide group within the above range, the dissolution state (dispersion state) of the components contained in the photosensitive resin composition can be maintained particularly well regardless of the storage environment. Thereby, a resin film having particularly good film thickness uniformity can be obtained.

[0082] When X in the above formula (1) is a polyester group, as X, a polyester group represented by the following formula (2-2) is preferably used.

[0083] [Chemical formula]

[0084] In the above formula (2-2), R 22 , R 23 , R 24 and R 25 each independently represent an alkyl group having 1 to 20 carbon atoms, and r represents an integer of 1 or more.

[0085] When X in the above formula (1) is an aralkyl group, as X, an aralkyl group represented by the following formula (2-3) is preferably used.

[0086] [Chemical formula]

[0087] In the above equation (2-3), R 26 This represents an alkyl group having 1 to 30 carbon atoms. In formula (1) above, the lower limit of the ratio of m to the sum of m and n is preferably 0.5% or more, more preferably 1% or more, even more preferably 5% or more, and particularly preferably 10% or more. On the other hand, the upper limit of the ratio of m is preferably 60% or less, more preferably 50% or less, even more preferably 40% or less, and particularly preferably 30% or less. By setting the ratio of m within the above range, the dissolved state (dispersed state) of the components contained in the photosensitive resin composition can be maintained in particularly good condition regardless of the storage environment. As a result, a resin film with particularly good film thickness uniformity can be obtained.

[0088] 1.3.2. Hydrocarbon-based surfactants Examples of hydrocarbon-based surfactants include ether-type nonionic surfactants and ester-type nonionic surfactants. Of these, ether-type nonionic surfactants are preferred.

[0089] The ether-type nonionic surfactant is preferably a polyoxyalkylene alkyl ether represented by the following formula (3-1), or a polyoxyalkylene alkylphenyl ether represented by the following formula (3-2).

[0090] [ka]

[0091] In equations (3-1) and (3-2) above, R 1∫ represents an alkyl group or alkenyl group, preferably having 6 to 22 carbon atoms, more preferably 8 to 18, and particularly preferably 10 to 15 carbon atoms. The alkyl group may be a single alkyl group or a mixed alkyl group. A represents an alkylene group, and X represents a phenylene group. n is preferably an integer from 1 to 70, more preferably from 10 to 30. The oxyalkylene group represented by AO may be a single oxyalkylene group such as an ethylene oxide group or a propylene oxide group, or it may be composed of multiple types of oxyalkylene groups such as an ethylene oxide group and a propylene oxide group.

[0092] Examples of ether-type nonionic surfactants include NOF Corporation's "Nonion K-204" (polyoxyethylene lauryl ether), "Nonion K-220" (polyoxyethylene lauryl ether), "Nonion K-230", "Persoft NK-60", "Persoft NH-90C", "Persoft NK-100", "Nonion EAD-13" (all polyoxyethylene alkyl ethers), "Nonion P-208", and "Nonion P-210". "Nonion P-213" (all polyoxyethylene cetyl ether), "Nonion E-202", "Nonion E-202S", "Nonion E-205", "Nonion E-205S", "Nonion E-212", "Nonion E-215", "Nonion E-230" (all polyoxyethylene oleyl ether), "Nonion S-202", "Nonion S-207", "Nonion S-215", "Nonion S-220" (all polyoxyethylene stearyl ether) (Polyoxyethylene isodecyl ether), "Nonion ID-203", "Nonion ID-206", "Nonion ID-209" (all polyoxyethylene isodecyl ether), "Nonion EH-204" (polyoxyethylene 2-ethylhexyl ether), "Nonion EH-208" (polyoxyethylene 2-ethylhexyl ether), "Polyoxydispanol TOC", "Nonion ET-505", "Nonion ET-507", "Nonion ET-510", "Nonion ET-51 Examples include "2", "Nonion ET-515", "Nonion ET-518" (all polyoxyethylene-polyoxypropylene-alkyl ethers), "Unilube MS-70K" (polyoxypropylene stearyl ether), "Dispanol 16", "Dispanol 16A", "Dispanol LS-100", "Nonion MN-811", "Dispanol WI-106", "Dispanol WI-115", and "Dispanol WI-133".

[0093] Other examples include "LB-220", "LB-53B", "LB-720", "LB-820", "LB-54C", "LB-83", "LB-93", "LB-103", "LB-1220", and "LB-1520" (all polyoxyalkylene lauryl ethers), "LA-675B", "LA-775", "LA-875", "LA-975", and "LA-1275" (all polyoxyethylene lauryl ethers), "OA-7" (polyoxyethylene oleyl ether), "TN-40", "TN-80", "TN-100", "TO-120", "UA-70N", "UA-90N", "LO-3", and "LO-7" (all primary alcohol ethoxylates), and "SO-80", "SO-105", "SO-120", "SO-135", "SO-145", and "SO-160" (all secondary alcohol ethoxylates), all manufactured by ADEKA Corporation.

[0094] The content of surfactant (C) is preferably 0.001 parts by mass or more and 1 part by mass or less, more preferably 0.005 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.03 parts by mass or more and 0.3 parts by mass or less, per 100 parts by mass of resin (A). By keeping the content of surfactant (C) within the above range, the compatibility between resin (A) and other components can be particularly enhanced. As a result, the effect of suppressing changes in the state of the photosensitive resin composition regardless of the storage environment and forming a resin film with good film thickness uniformity becomes more pronounced. If surfactant (C) contains multiple components, the above content is the sum of the content of each component.

[0095] Furthermore, if the amount of surfactant (C) falls below the lower limit or exceeds the upper limit, depending on the storage environment, there is a risk that the state of the photosensitive resin composition, such as viscosity and weight loss rate, may change significantly.

[0096] 1.4. Adhesion enhancer The photosensitive resin composition may contain an adhesion promoter. Examples of adhesion promoters include triazole compounds, silane compounds, and imide compounds, with silane compounds being particularly preferred. By using these, the affinity between the photosensitive resin composition and the substrate can be improved.

[0097] Triazole compounds include, specifically, 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4-triazole-3-amine, 3,4-diamino-4H-1,2,4-triazole, and 3,5-diamino-4H- Examples of 1,2,4-triazoles include 1,2,4-triazole, 1,2,4-triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carboxamide, 3,5-diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, and 4-methyl-1,2,4-triazole-3-carboxamide. One or more of the above specific examples can be used as the triazole compound.

[0098] Silane compounds specifically include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; and 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxy Methacrylsilanes such as propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylicsilanes such as 3-acryloxypropyltrimethoxysilane; isocyanurate silanes; alkylsilanes; ureidosilanes such as 3-ureidopropyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatetopropyltriethoxysilane;Condensate of cyclohexene-1,2-dicarboxylic acid anhydride and 3-aminopropyltriethoxysilane, condensate of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride and 3-aminopropyltriethoxysilane, condensate of 4,4'-oxydiphthalic acid anhydride and 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[ Examples of aminosilane compounds include 3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-(3-triethoxysilylpropyl)ethylenediamine, N,N'-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(methyldiethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(dimethylmethoxysilyl)propyl]ethylenediamine, N-[3-(methyldimethoxysilyl)propyl]-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]diaminopropane, N,N'-bis[3-(trimethoxysilyl)propyl]diaminohexane, and N,N'-bis[3-(trimethoxysilyl)propyl]diethylenetriamine. One or more of the above specific examples of silane compounds can be used.

[0099] Silane compounds particularly improve the affinity between the photosensitive resin composition and the substrate. This results in a photosensitive resin composition capable of forming a more reliable resin film.

[0100] The lower limit of the adhesion aid content is preferably 0.1 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 2.0 parts by mass or more, and particularly preferably 3.0 parts by mass or more, per 100 parts by mass of resin (A). The upper limit of the adhesion aid content is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of resin (A).

[0101] By keeping the content of the adhesion aid within the above range, the adhesion aid can be suitably dispersed in the photosensitive resin composition, improving the adhesion of the photosensitive resin composition to the substrate, and a photosensitive resin composition that can form a resin film with excellent adhesion to the substrate even in high temperature and high humidity environments can be obtained. In addition, it is possible to suppress the decrease in the solubility of the coating film formed using the photosensitive resin composition in the developer solution due to the adhesion aid.

[0102] The adhesion enhancer may include titanium coupling agents, aluminum coupling agents, zirconium coupling agents, etc.

[0103] 1.5. Solvents and modifiers The photosensitive resin composition may contain a dissolution modifier. Examples of dissolution modifiers include low molecular weight compounds having one or more alkali-soluble groups. The molecular weight of such low molecular weight compounds is preferably 50 to 1000, more preferably 150 to 750, and even more preferably 200 to 500. By including such low molecular weight compounds in the dissolution modifier, the solubility of the coating film formed using the photosensitive resin composition in the developer can be further enhanced. Furthermore, by using these dissolution modifiers in combination with the surfactants mentioned above, changes in viscosity can be suppressed regardless of the environment in which the photosensitive resin composition is stored.

[0104] Examples of alkali-soluble groups in a dissolution modifier include carboxyl groups and phenolic hydroxyl groups. Of these, from the viewpoint of affinity with alkaline developers, for example, phenolic hydroxyl groups are preferred as the alkali-soluble group. In other words, it is preferable that the dissolution modifier contains a low-molecular-weight compound having one or more phenolic hydroxyl groups. By including such a low-molecular-weight compound in the dissolution modifier, the generation of development residue (scum) can be suppressed even when the development speed of the coating film formed using the photosensitive resin composition is increased. From the viewpoint of ensuring good coatability, the number of alkali-soluble groups in one molecule of the dissolution modifier is preferably 1 to 6.

[0105] Specific examples of dissolving agents include 4-ethyl resorcinol, 2-propyl resorcinol, 4-butyl resorcinol, 4-hexyl resorcinol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dihydroxydiphenyl disulfide, 4,4'-dihydroxydiphenyl sulfone, 2,2'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, biphenol, 2,2 Examples include '-methylenebisphenol, 4,4'-(1,3-dimethylbutylidene)diphenol, 4,4'-(2-ethylhexylidene)diphenol, 4,4'-ethylidenebisphenol, 2,2'-ethylenedioxydiphenol, 3,3'-ethylenedioxydiphenol, biphenyl-2,3',4,5',6-pentaol (phloroglucid), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,5-bis(o-hydroxyphenoxy)-3-oxapentane, bisphenol A, bisphenol F, etc. Note that the solvent modifier may use only one of the above compounds, or two or more may be used in combination.

[0106] The lower limit of the content of the dissolution modifier is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, and particularly preferably 2.0 parts by mass or more, per 100 parts by mass of resin (A). By having the content of the dissolution modifier within this range, the development speed of the coating film can be further improved.

[0107] The upper limit of the content of the dissolution modifier is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of resin (A). By keeping the content of the dissolution modifier within this range, the curability of the photosensitive resin composition can be further improved.

[0108] 1.6. Crosslinking Agents The photosensitive resin composition may contain a crosslinking agent that reacts with resin (A) to improve crosslinkability. This improves the mechanical properties, such as tensile elongation at break, of the cured product obtained by post-baking the photosensitive resin composition. It also improves the sensitivity of the coating film formed by the photosensitive resin composition. Furthermore, the crosslinking agent helps suppress the generation of development residue (scum) even when the development speed of the coating film formed using the photosensitive resin composition is increased.

[0109] Specifically, crosslinking agents include compounds having a methylol group such as 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (paraxylene glycol), 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis(hydroxymethyl)-p-cresol, and 4,4'-methylenebis(2,6-dialkoxymethylphenol); compounds having an alkoxymethyl group such as 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, 2,6-naphthalenedicarboxylate methyl, and 4,4'-methylenebis(2,6-dimethoxymethylphenol); and methylolmelamine compounds represented by hexamethylmelamine and hexabutanolmelamine. Examples of crosslinking agents include: alkoxymelamine compounds such as hexamethoxymelamine; alkoxymethyl glycoluryl compounds such as tetramethoxymethyl glycoluryl; methylolurea compounds such as methylolbenzoguanamine compounds and dimethylolethyleneurea; cyano compounds such as dicyanoaniline, dicyanophenol, and cyanophenylsulfonic acid; isocyanate compounds such as 1,4-phenylenediisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; epoxy group-containing compounds such as ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, isocyanurate triglycidyl, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene-based epoxy resin, biphenyl type epoxy resin, and phenol novolac resin type epoxy resin; and maleimide compounds such as N,N'-1,3-phenylenedimaleimide and N,N'-methylenedimaleimide. One or more of the above specific examples can be used as crosslinking agents.

[0110] Furthermore, the above-mentioned crosslinking agent is particularly preferred when the resin (A) contains polybenzoxazole or its precursor.

[0111] Furthermore, when resin (A) contains a phenolic resin, examples of crosslinking agents include urea compounds, epoxy compounds, melamine compounds, cyano compounds, isocyanate compounds, maleimide compounds, benzoguanamine compounds, and metal chelating agents, and one or more of these can be used. It is also preferable to include both urea compounds and epoxy compounds as crosslinking agents. This particularly enhances the deformation resistance of the resin film formed by the photosensitive resin composition. Additionally, by using these crosslinking agents in combination with the aforementioned surfactants, changes in viscosity can be suppressed regardless of the environment in which the photosensitive resin composition is stored.

[0112] Urea compounds are urea compounds that have an average of two or more functional groups contributing to crosslinking in a single molecule. Urea compounds are compounds containing a urea structure (-NC(=O)N-). Examples of functional groups include methylol groups and alkoxyalkyl groups.

[0113] Specific examples of urea compounds include difunctional urea compounds having an average of two functional groups, and polyfunctional urea compounds having an average of three or more functional groups.

[0114] Examples of bifunctional urea compounds include glycoluryl compounds such as dihydroxymethylated glycoluryl, dimethoxymethylated glycoluryl, diethoxymethylated glycoluryl, dipropoxymethylated glycoluryl, and dibutoxymethylated glycoluryl; urea compounds such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; dihydroxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, and dipropoxy Examples include ethyleneurea compounds such as dimethylated ethyleneurea and dibutoxymethylated ethyleneurea, propyleneurea compounds such as dihydroxymethylated propyleneurea, dimethoxymethylated propyleneurea, diethoxymethylated propyleneurea, dipropoxymethylated propyleneurea, and dibutoxymethylated propyleneurea, and imidazolidinone compounds such as 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0115] Examples of polyfunctional urea compounds include trifunctional urea compounds such as trihydroxymethylated glycoluryl, trimethoxymethylated glycoluryl, triethoxymethylated glycoluryl, trippropoxymethylated glycoluryl, and tripbutoxymethylated glycoluryl, and tetrafunctional urea compounds such as tetrahydroxymethylated glycoluryl, tetramethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, and tetrabutoxymethylated glycoluryl.

[0116] Epoxy compounds are epoxy compounds (epoxy resins) that have an average of two or more epoxy groups in one molecule that contribute to crosslinking.

[0117] Specific examples of epoxy compounds include bifunctional epoxy compounds having an average of two epoxy groups, and polyfunctional epoxy compounds having an average of three or more epoxy groups.

[0118] While the bifunctional epoxy compound is not particularly limited as long as it is a bifunctional epoxy compound, it is preferable to use a bifunctional phenoxy-type epoxy resin. This makes it easier to create longer molecular chains, which imparts high flexibility to the resin film. As a result, a resin film with particularly high elongation can be obtained. In addition, because it contains aromatic rings, the mechanical properties (such as tensile strength) of the resin film can be enhanced.

[0119] Examples of bifunctional phenoxy epoxy resins include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol S type phenoxy resin, bisphenolacetophenone type phenoxy resin, novolac type phenoxy resin, biphenyl type phenoxy resin, fluorene type phenoxy resin, dicyclopentadiene type phenoxy resin, norbornene type phenoxy resin, naphthalene type phenoxy resin, anthracene type phenoxy resin, adamantane type phenoxy resin, terpene type phenoxy resin, and trimethylcyclohexane type phenoxy resin.

[0120] Specific examples of bifunctional epoxy compounds include EXA-4850-150, EXA-4816, EXA-4822 from DIC Corporation; EP-4000S, EP-4000SS, EP-4003S, EP-4010S, EP-4011S from ADEKA Corporation; BEO-60E, BPO-20E from Shin Nippon Rika Co., Ltd.; YX-7105, YX-7110, YX-7400, YX-7180 ​​from Mitsubishi Chemical Corporation; and LX-01 from Osaka Soda Co., Ltd.

[0121] The polyfunctional epoxy compound is not particularly limited as long as it is a polyfunctional epoxy compound (having three or more functional groups).

[0122] Specific examples of polyfunctional epoxy compounds include Epicote 180 and Epicote 157 from Mitsubishi Chemical Corporation; UVR-6610, UVR-6620, and UVR-6650 from Union Carbide Corporation; TACT1X742 from Dow Chemical Corporation; and Techmore VG3101L from Printec Corporation.

[0123] Epoxy compounds preferably contain aromatic rings. With such a configuration, a rigid structure with stable properties derived from the aromatic rings is formed in the resin film, while a flexible structure is easily formed between the aromatic rings and the epoxy groups. As a result, a resin film that achieves both good mechanical properties and high elongation can be obtained.

[0124] The lower limit of the crosslinking agent content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more, per 100 parts by mass of resin (A). The upper limit of the crosslinking agent content is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and even more preferably 100 parts by mass or less, per 100 parts by mass of resin (A).

[0125] 1.7. Polyfunctional (meth)acrylic compounds The photosensitive resin composition may contain a polyfunctional (meth)acrylic compound.

[0126] A polyfunctional (meth)acrylic compound refers to a compound having two or more (meth)acryloyl groups in a single molecule. It is believed that polyfunctional (meth)acrylic compounds, through polymerization, form a network structure that encloses the resin's backbone. This complex, interwoven structure is thought to improve the performance of the resin film. Furthermore, by using these polyfunctional (meth)acrylic compounds in combination with the aforementioned surfactants, changes in viscosity can be suppressed regardless of the storage environment of the photosensitive resin composition.

[0127] Specific examples of polyfunctional (meth)acrylic compounds include, for example, polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy acrylates such as bisphenol A diglycidyl ether di(meth)acrylate and hexanediol diglycidyl ether di(meth)acrylate; and urethane (meth)acrylates obtained by the reaction of polyisocyanates with hydroxyl group-containing (meth)acrylates such as hydroxyethyl (meth)acrylate.

[0128] Furthermore, commercially available polyfunctional (meth)acrylic compounds include Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10, NK Ester A-GLY-9E, NK Ester A-9550, NK Ester A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and others.

[0129] The content of the polyfunctional (meth)acrylic compound is preferably 1 to 150 parts by mass, more preferably 20 to 120 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of resin (A).

[0130] 1.8. Thermal Radical Initiators The photosensitive resin composition may contain a thermal radical initiator.

[0131] When a photosensitive resin composition contains a polyfunctional (meth)acrylic compound, using a thermal radical initiator can accelerate the polymerization reaction of the polyfunctional (meth)acrylic compound, thereby improving the heat resistance of the resin film. Furthermore, it can improve the chemical resistance (resistance to organic solvents, etc.) of the resin film.

[0132] The thermal radical initiator preferably includes an organic peroxide. Examples of organic peroxides include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy 2-ethylhexanoate, t-hexyl peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, parachlorobenzoyl peroxide, and cyclohexanone peroxide.

[0133] The content of the thermal radical initiator is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylic compound.

[0134] 1.9. Epoxy Compounds The photosensitive resin composition may contain an epoxy compound. The epoxy compound is thought to form chemical bonds through reactions with resin (A), reactions with other epoxy compounds, etc. These bonds can enhance the mechanical properties of the resin film. The epoxy compound is not particularly limited as long as it is a compound having an epoxy group in its molecule.

[0135] Specific examples of epoxy compounds include epoxy resins. Specific examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin), and tetramethylbisphenol F type epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, and novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure; and bif Phenyl epoxy resins; xylylene epoxy resins, biphenylaralkyl epoxy resins, and other aralkyl epoxy resins; epoxy resins having a naphthalene skeleton, such as naphthylene ether epoxy resins, naphthol epoxy resins, naphthalene epoxy resins, naphthalenediol epoxy resins, 2-4 functional epoxy naphthalene resins, binaphthyl epoxy resins, and naphthalenearalkyl epoxy resins; anthracene epoxy resins; phenoxy epoxy resins; dicyclopentadiene epoxy resins; norbornene epoxy resins; adamantane epoxy resins; fluorene epoxy resins, phosphorus-containing epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, bisphenol A novolac epoxy resins, bixylenol epoxy resins, trihydroxyphenylmethane epoxy resins, stilbene epoxy resins, tetraphenyloleethane epoxy resins, triglycidyl isocyanurate, and other heterocyclic epoxy resins;Examples include glycidylamines such as N,N,N',N'-tetraglycidylmetoxylendiamine, N,N,N',N'-tetraglycidylbisaminomethylcyclohexane, and N,N-diglycidylaniline; copolymers of glycidyl (meth)acrylates with compounds having ethylenically unsaturated double bonds; epoxy resins having a butadiene structure; diglycidyl ethers of bisphenols; diglycidyl ethers of naphthalenediols; and glycidyl ethers of phenols.

[0136] Furthermore, as the epoxy resin, a polyfunctional epoxy resin with three or more functions, that is, one molecule containing three or more epoxy groups, is preferably used. More preferably, the polyfunctional epoxy resin has three to twenty functions.

[0137] Furthermore, epoxy compounds can also be those having one or more epoxy-containing groups and one or more (meth)acryloyl groups in a single molecule. Preferably, these compounds have one epoxy-containing group at one end of the molecule and one (meth)acryloyl group at the other end. Specific examples include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate.

[0138] The epoxy compound content is preferably 0.5 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, and even more preferably 3 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of resin (A).

[0139] These epoxy compounds are particularly preferred when the resin (A) contains polyimide or its precursor.

[0140] 1.10.Curing catalyst The photosensitive resin composition may contain a curing catalyst. When the photosensitive resin composition contains an epoxy compound, using a curing catalyst can accelerate the polymerization reaction of the epoxy compound, for example, further improving the tensile elongation of the resin film.

[0141] Examples of curing catalysts include diazabicycloalkenes and their derivatives such as 1,8-diazabicyclo[5,4,0]undecene-7; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organophosphines such as triphenylphosphine and methyldiphenylphosphine; tetrasubstituted phosphonium salts such as tetraphenylphosphonium·tetraphenylborate, tetraphenylphosphonium·tetrabenzoic acid borate, tetraphenylphosphonium·tetranaphthoyloxyborate, tetraphenylphosphonium·tetranaphthyloxyborate, and tetraphenylphosphonium·4,4'-sulfonyldiphenolate; and triphenylphosphine adducted with benzoquinone.

[0142] The content of the curing catalyst is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.3 parts by mass to 5 parts by mass, and even more preferably 0.5 parts by mass to 3 parts by mass, per 100 parts by mass of the epoxy compound.

[0143] 1.11. solvent The photosensitive resin composition contains a solvent. As a result, the photosensitive resin composition has a varnish-like consistency and good coatability.

[0144] The solvent is used such that the concentration of total solids (non-volatile components) in the photosensitive resin composition is preferably 10% to 60% by mass, more preferably 20% to 50% by mass, and even more preferably 25% to 48% by mass. This range allows for sufficient dissolution or dispersion of each component and ensures good coatability.

[0145] Examples of organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone (GBL), methyl lactate, ethyl lactate, butyl lactate, 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), N-vinyl-2-pyrrolidone (NVP), etc., and one or more of these can be used.

[0146] 1.12. Other Ingredients In addition to the above-mentioned components, the photosensitive resin composition may also contain additives such as fillers, sensitizers, antioxidants, film-forming agents, and stabilizers.

[0147] The filler is appropriately selected according to the mechanical and thermal properties required for the resin film formed by the photosensitive resin composition.

[0148] Examples of fillers include inorganic fillers and organic fillers.

[0149] Examples of inorganic fillers include silica such as molten crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, and fine silica; metal compounds such as alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; and glass fibers. One or more of the above specific examples can be used as inorganic fillers.

[0150] Examples of organic fillers include organosilicone powder and polyethylene powder. One or more of the above examples can be used as the organic filler.

[0151] 1.13. Physical Properties Next, the physical properties of the photosensitive resin composition according to this embodiment will be described.

[0152] 1.13.1. Ratio of viscosity after solvent immersion test to initial viscosity The photosensitive resin composition according to this embodiment has a viscosity measured after a solvent immersion test (solvent immersion test) that is 68% or more and 80% or less of the viscosity measured before the solvent immersion test (initial viscosity).

[0153] As mentioned above, the solvent immersion test involves immersing the tip of a dispenser in the test solution for 20 seconds, with a volume of 7.5 mL of the photosensitive resin composition contained within the dispenser. The test solution is a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA).

[0154] The dispenser comprises a metal needle with an inner diameter of 500 μm and a length of 13 mm, and a cylinder with a volume of more than 7.5 mL. It functions to supply a varnish-like photosensitive resin composition stored in the cylinder through the tip of the needle. In the solvent immersion test, 50% of the length of the needle, from the tip, is immersed in the test solution. The temperature of both the photosensitive resin composition and the test solution is set to 25°C.

[0155] The viscosity of the photosensitive resin composition is measured as follows: First, the raw materials of the photosensitive resin composition are stirred at room temperature until completely dissolved to obtain a solution. Next, the obtained solution is filtered through a polypropylene filter with a pore size of 0.2 μm. Then, the viscosity of the filtered solution is measured using an E-type viscometer. This obtains the initial viscosity (viscosity of the photosensitive resin composition before the solvent immersion test). Next, the solution is placed in a dispenser and the solvent immersion test described above is performed. Next, the contents are removed from the dispenser. Then, the viscosity of the removed contents is measured using an E-type viscometer. This obtains the viscosity after the test.

[0156] Furthermore, the ratio of the post-test viscosity to the initial viscosity is 68% to 80%, but preferably 70% to 78%.

[0157] If the ratio of the post-test viscosity obtained in this manner to the initial viscosity is within the aforementioned range, a photosensitive resin composition can be realized that suppresses changes in state regardless of the storage environment. In other words, even in environments where organic solvents such as the test solution are present in high concentrations, the decrease in viscosity due to the absorption of organic solvents is moderately suppressed, and as a result, a photosensitive resin composition with excellent weather resistance that can fully exhibit its original performance can be realized. By using such a photosensitive resin composition, a resin film with good film thickness uniformity can be formed. In addition, since the generation of foreign matter due to changes in state is suppressed, a resin film with a good appearance can be formed.

[0158] Furthermore, if the ratio of the post-test viscosity to the initial viscosity falls below the lower limit, the coatability of the photosensitive resin composition is more likely to change due to absorption of organic solvents, for example, in environments where organic solvents are present at high concentrations, and the uniformity of the film thickness of the formed resin film decreases. In addition, foreign matter may be generated in the photosensitive resin composition, potentially causing defects in the appearance of the formed resin film. On the other hand, if the ratio of the post-test viscosity to the initial viscosity exceeds the upper limit, while the storage stability of the photosensitive resin composition improves, it becomes more susceptible to the surface condition of the substrate to which it is coated (the coatability becomes more sensitive to the surface condition of the substrate), and from that perspective, the coatability decreases, resulting in a decrease in the uniformity of the film thickness of the formed resin film.

[0159] The ratio of the post-test viscosity to the initial viscosity can be controlled, for example, by the type and blending ratio of the surfactant, the combination of the surfactant and adhesion promoter, the combination of the surfactant and dissolution modifier, or the combination of the surfactant and crosslinking agent. Furthermore, since the post-test viscosity tends to be affected by the water content of the photosensitive resin composition, it is also possible to control the above ratio based on this. In addition, if the surfactant content is too high, or if a surfactant that strongly reduces surface tension is used, the post-test viscosity tends to decrease, so the above ratio may be adjusted based on this.

[0160] 1.13.2. Distribution of weight loss rate after solvent immersion test When the photosensitive resin composition is subjected to a solvent immersion test and then divided into three parts, and the weight loss rate of each part is measured, the weight loss rate of each of the three parts is preferably 101% or more and 115% or less of the weight loss rate measured before the solvent immersion test.

[0161] The process of dividing the photosensitive resin composition into three parts is carried out as follows: First, the raw materials of the photosensitive resin composition are stirred at room temperature until completely dissolved to obtain a solution. Next, the obtained solution is filtered through a polypropylene filter with a pore size of 0.2 μm. Next, the filtered solution is placed in a dispenser and the solvent immersion test described above is performed. Then, the contents of the dispenser (the photosensitive resin composition after the solvent immersion test) are taken out in three separate portions of 2.5 mL each: the first, second, and third parts. These three parts were distributed in the order of the first, second, and third parts from the tip to the base of the dispenser. Therefore, by measuring the weight loss rate of each of the extracted first, second, and third parts, the distribution of the weight loss rates of the three parts can be evaluated. In other words, within the dispenser, the area from the tip of the needle away from the test solution is less affected by the test solution as it moves away from the test solution towards the cylinder. From this perspective, evaluating the weight loss rate of the three parts leads to an evaluation of the storage stability of the photosensitive resin composition.

[0162] The weight loss rate of the photosensitive resin composition is measured as follows: First, the weight loss rate of the photosensitive resin composition at 146.6°C (weight loss rate with increasing temperature from 30°C to 146°C) is measured before the solvent immersion test (when the dispenser is not immersed in the test solution), and the measurement result is taken as the initial analysis value. The weight loss rate is measured using a thermogravimetric analyzer (TGA). The temperature range during measurement is from 30°C to 250°C, the heating rate during measurement is 10°C / min, and the measurement atmosphere is a nitrogen atmosphere. Next, the weight loss rate of the first portion taken out at 146.6°C is measured, and the measurement result is taken as the first analysis value. Next, the weight loss rate of the second portion taken out at 146.6°C is measured, and the measurement result is taken as the second analysis value. Next, the weight loss rate of the third portion taken out at 146.6°C is measured, and the measurement result is taken as the third analysis value.

[0163] If the first, second, and third analytical values ​​obtained in this manner all satisfy the aforementioned ratios to the initial analytical values, then even in environments where organic solvents such as the test solution are present in high concentrations, the change in the weight loss rate due to the absorption of organic solvents is appropriately suppressed. This results in less variation in the state and enables the realization of a weather-resistant photosensitive resin composition that can fully exhibit its original performance. By using such a photosensitive resin composition, a resin film with particularly good film thickness uniformity can be formed. Furthermore, because the generation of foreign matter due to changes in the state is suppressed, a resin film with a particularly good appearance can be formed.

[0164] Furthermore, the first, second, and third analytical values ​​are preferably 101% to 114% of the initial analytical value, and more preferably 102% to 112% of the initial analytical value.

[0165] Furthermore, if the ratio of at least one of the first, second, and third analytical values ​​to the initial analytical value falls below the lower limit, the storage stability of the photosensitive resin composition improves, but it also becomes more susceptible to the surface condition of the substrate to which it is coated (the coating properties become more sensitive to the surface condition of the substrate), and from that perspective, the coating properties decrease, which may reduce the uniformity of the film thickness of the formed resin film. On the other hand, if the ratio of at least one of the first, second, and third analytical values ​​to the initial analytical value exceeds the upper limit, for example, in an environment where organic solvents are present at high concentrations, the coating properties of the photosensitive resin composition may change due to absorption of organic solvents, which may reduce the uniformity of the film thickness of the formed resin film. In addition, foreign matter may be generated in the photosensitive resin composition, which may increase the likelihood of appearance defects in the formed resin film.

[0166] The ratios of the first, second, and third analytical values ​​to the initial analytical values ​​can be controlled, for example, by the type and blending ratio of surfactants, the combination of surfactants and adhesion aids, the combination of surfactants and dissolving modifiers, and the combination of surfactants and crosslinking agents. Furthermore, since the first, second, and third analytical values ​​tend to be affected by the water content of the photosensitive resin composition, it is also possible to control the above ratios based on this. In addition, if the surfactant content is too high, or if a surfactant with a strong effect of lowering surface tension is used, the first, second, and third analytical values ​​tend to decrease, so the above ratios may be adjusted based on this.

[0167] 1.13.3.Moisture content The moisture content of the photosensitive resin composition is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 8% by mass or less, and even more preferably 0.3% by mass or more and 5% by mass or less. With such a moisture content, the storage stability of the photosensitive resin composition is improved. This makes it possible to suppress large changes in the state of the photosensitive resin composition due to the influence of the storage environment.

[0168] The moisture content of the photosensitive resin composition is measured as follows: First, the raw materials of the photosensitive resin composition are stirred at room temperature until completely dissolved to obtain a solution. Next, the obtained solution is filtered through a polypropylene filter with a pore size of 0.2 μm. Then, the moisture content of the filtered solution is measured using a Karl Fischer moisture meter CA-31 (manufactured by Nitto Seikou Analytech Co., Ltd.) and a moisture vaporizer VA-230 (manufactured by Nitto Seikou Analytech Co., Ltd.). The titration reagent used is Karl Fischer reagent "Aquamicron Water Standard Solution," and the measurement is performed in accordance with the volumetric titration method specified in JIS K 0113:2005.

[0169] Furthermore, if the moisture content falls below the lower limit, the hygroscopicity may increase in humid environments, potentially leading to large fluctuations in moisture content. This could result in significant changes in the state of the photosensitive resin composition. On the other hand, if the moisture content exceeds the upper limit, the moisture content becomes excessive, potentially preventing the photosensitive resin composition from exhibiting its intended properties.

[0170] 2. Resin film Next, the resin film according to the embodiment will be described.

[0171] A cured product is obtained by curing the photosensitive resin composition according to this embodiment. The resin film according to this embodiment is composed of this cured product. Such a resin film is used as a resin film in a semiconductor device. The resin film is used, for example, as a permanent film or a resist. Of these, it is preferably used as a permanent film from the viewpoint of having high uniformity of film thickness and good appearance. Examples of permanent films include protective films such as buffer coat films, interlayer films such as redistribution insulating films, and dam materials.

[0172] 3. Semiconductor equipment Next, a semiconductor device according to an embodiment will be described.

[0173] Figure 1 is a cross-sectional view showing a semiconductor device (semiconductor device according to the embodiment) equipped with a resin film according to the embodiment.

[0174] The semiconductor device 100 shown in Figure 1 comprises a semiconductor element (not shown), a multilayer wiring layer including an interlayer insulating film 30 and an uppermost wiring layer 34 provided on the surface of the semiconductor element, a passivation film 32, a rewiring layer 40, a UBM layer 50, and bumps 52.

[0175] The interlayer insulating film 30 and the uppermost wiring layer 34 are located at the top of the multilayer wiring layer. The uppermost wiring layer 34 is made of a metallic material, such as aluminum or copper.

[0176] The passivation film 32 is provided on the multilayer wiring layer. An opening is provided in a part of the passivation film 32, exposing the uppermost layer wiring 34.

[0177] A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. The insulating layer 42 has an opening formed therein to connect the rewiring 46 to the uppermost wiring layer 34. The insulating layer 44 has an opening formed therein to connect the UBM layer 50 to the rewiring 46.

[0178] The bump 52 is electrically connected to the rewiring 46 via the UBM layer 50 (Under Bump Metallurgy). The semiconductor device 100 is connected to a wiring board (not shown) or the like via the bump 52.

[0179] Such a semiconductor device 100 includes the above-mentioned resin film. Specifically, in the semiconductor device 100, one or more of the above-mentioned resin films selected from the group consisting of a passivation film 32, an insulating layer 42, and an insulating layer 44 are used. Because the resin film has high uniformity of film thickness, it is possible to realize a semiconductor device 100 in which a high-density laminated structure is constructed.

[0180] 4. Effects achieved by the above embodiment As described above, the photosensitive resin composition according to the embodiment is a photosensitive resin composition comprising one or more resins (A) selected from the group consisting of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and phenol resin, a photosensitive agent (B), a surfactant (C), and a solvent. The surfactant (C) is composed of a non-fluorinated surfactant. Furthermore, when a 7.5 mL volume of the photosensitive resin composition is contained in a dispenser as a container, and the tip of the dispenser is immersed for 20 seconds in a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA), the container is removed and the viscosity is measured with an E-type viscometer, the measured viscosity is 68% to 80% of the viscosity of the photosensitive resin composition that has not been immersed.

[0181] This configuration makes it possible to realize a photosensitive resin composition that suppresses changes in state regardless of the storage environment. By using such a photosensitive resin composition, a resin film with good film thickness uniformity can be formed. In addition, since the generation of foreign matter due to changes in state is suppressed, a resin film with a good appearance can be formed.

[0182] In the photosensitive resin composition according to the above embodiment, the non-fluorinated surfactant (C) is preferably a silicone-based surfactant.

[0183] This configuration makes it possible to realize a photosensitive resin composition that can form a resin film with particularly good uniformity of film thickness and suppresses changes in state regardless of the storage environment. Furthermore, it is possible to reduce the amount of so-called PFAS used.

[0184] In the photosensitive resin composition according to the above embodiment, the silicone-based surfactant is preferably a polyether-modified dimethylsiloxane or an aralkyl-modified dimethylsiloxane.

[0185] This configuration yields a silicone-based surfactant that exhibits high compatibility with solvents and contributes to improved wettability of metal materials. This results in a photosensitive resin composition that provides a uniform coating film (improved coatability), improved developability, and enhanced adhesive strength.

[0186] In the above embodiment, with a volume of 7.5 mL of the photosensitive resin composition contained in a dispenser, the tip of the dispenser is immersed for 20 seconds in a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA). Then, the contents are removed in three separate portions of 2.5 mL each, and thermogravimetric analysis is performed on each portion under a nitrogen atmosphere. The weight loss rate at 146.6°C for the first portion is taken as the first analytical value, the weight loss rate at 146.6°C for the second portion is taken as the second analytical value, and the weight loss rate at 146.6°C for the third portion is taken as the third analytical value. Preferably, all of the first, second, and third analytical values ​​are 101% or more and 115% or less of the weight loss rate at 146.6°C of the photosensitive resin composition that has not been immersed.

[0187] With this configuration, even in environments where organic solvents such as test solutions are present at high concentrations, the change in weight loss rate due to the absorption of organic solvents is moderately suppressed. As a result, variations in the state are minimal, and a weather-resistant photosensitive resin composition with excellent performance can be realized that fully exhibits its original capabilities. By using such a photosensitive resin composition, a resin film with particularly good film thickness uniformity can be formed. Furthermore, because the generation of foreign matter due to changes in the state is suppressed, a resin film with a particularly good appearance can be formed.

[0188] In the photosensitive resin composition according to the above embodiment, the resin (A) may be a phenolic resin.

[0189] With this configuration, a photosensitive resin composition can be realized that contains a phenolic resin and can form a resin film with good film thickness uniformity.

[0190] In the photosensitive resin composition according to the above embodiment, the resin (A) may be a polyimide precursor or a polybenzoxazole precursor.

[0191] With this configuration, it is possible to realize a photosensitive resin composition that contains polyimide or polybenzoxazole and can form a resin film with good film thickness uniformity.

[0192] The resin film according to the above embodiment is composed of a cured product of the photosensitive resin composition according to the above embodiment.

[0193] With this configuration, a resin film with high film thickness uniformity can be obtained.

[0194] The semiconductor device 100 according to the above embodiment comprises a semiconductor element and a resin film (the resin film according to the above embodiment) provided on the surface of the semiconductor element.

[0195] With this configuration, a semiconductor device 100 can be obtained that has a resin film with high film thickness uniformity and a high-density laminated structure.

[0196] Although the photosensitive resin composition, resin film, and semiconductor device according to the present invention have been described above based on the embodiments, the present invention is not limited to the embodiments. For example, the photosensitive resin composition, resin film, and semiconductor device according to the present invention may be in which each part of the embodiments is replaced with any configuration having a similar function, or any configuration may be added to the embodiments. [Examples]

[0197] Next, specific embodiments of the present invention will be described. 5. Preparation of photosensitive resin composition Each of the raw materials shown in Tables 1 to 3 was blended and stirred at room temperature to obtain a solution. The obtained solution was filtered through a polypropylene filter with a pore size of 0.2 μm to prepare a varnish-like photosensitive resin composition.

[0198] The raw materials shown in Tables 1 to 3 are as follows. In Tables 1 to 3, those corresponding to the present invention are labeled as "Examples," and those not corresponding to the present invention are labeled as "Comparative Examples."

[0199] • Resin a1: A compound having repeating units represented by the following formula (A-1) (a precursor of polybenzoxazole)

[0200] [ka]

[0201] The weight-average molecular weight (Mw) of the above compound was 14,600, and the number-average molecular weight (Mn) was 9,250.

[0202] • Resin a2: Polyimide synthesized by the following method In a 5 L separable flask equipped with a stirrer and condenser, 272.2 g (0.85 mol) of 2,2'-bis(trifluoromethyl)benzidine, 355.4 g (0.80 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 62.0 g (0.20 mol) of 4,4'-oxydiphthalic dianhydride, and 2299 g of GBL were added and reacted under a nitrogen atmosphere at room temperature for 16 hours to carry out the polymerization reaction. Subsequently, the reaction mixture temperature was raised to 180°C in an oil bath and the reaction was carried out for 3 hours, after which it was cooled to room temperature to prepare a polyimide resin solution.

[0203] Next, the reaction mixture was added dropwise to a 4 / 7 mixture of isopropanol / water while stirring, and a resin solid was precipitated. The obtained solid was roughly filtered and then washed with isopropanol / 4 / 7 to obtain a white polyimide solid. The obtained white solid was vacuum-dried at 200°C to obtain a polyimide having an imide ring structure.

[0204] The weight-average molecular weight (Mw) of the obtained polyimide, as determined by GPC measurement, was 38,000.

[0205] • Resin a3: Biphenyl-type phenolic resin having the structure represented by the following formula (a1), manufactured by Sumitomo Bakelite Co., Ltd., PR-X21024, Mw=45,000, m:n=6:4

[0206] [ka]

[0207] • Method for producing biphenyl-type phenolic resin In a four-necked glass round-bottom flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, 186.2 g (1.00 mol) of 4,4'-biphenol, 86.5 g (0.8 mol) of p-cresol, 28.5 g (0.94 mol) of formaldehyde, 15.5 g (0.09 mol) of p-toluenesulfonic acid, and 308 g of γ-butyrolactone were charged. A polycondensation reaction was then carried out at 100°C for 5.5 hours while flowing nitrogen and refluxing the reaction mixture in an oil bath. Next, the resulting reaction mixture was cooled to room temperature, and 411 g of acetone was added and stirred until homogeneous. Subsequently, the resin component was precipitated by adding the reaction mixture in the round-bottom flask dropwise to 10 L of water and mixing. Next, the precipitated resin components were filtered and recovered, and then vacuum-dried at 60°C to obtain a biphenyl-type phenolic resin having the structure represented by formula (a1) above.

[0208] • Photosensitive agent b1: Naphthoquinone-based photosensitive agent (manufactured by Toyo Gosei Kogyo Co., Ltd., product name: Tek-300) • Photosensitive agent b2: Oxime ester type photoradical generator (BASF, Irugacure OXE01) • Photosensitive agent b3: A naphthoquinone-based photosensitive agent having the structure represented by the following formula NQD-5 (manufactured by Daito Chemix Co., Ltd., product name: GPA-250)

[0209] [ka]

[0210] • Surfactant c1: Polyether-modified polydimethylsiloxane (a liquid silicone compound containing a polyether group, manufactured by BYK-Chemie Japan, BYK-333) • Surfactant c2: Aalkyl-modified polydimethylsiloxane (manufactured by BIC Chemie Japan, BYK-323) • Surfactant c3: Polyoxyethylene 2-ethylhexyl ether (manufactured by NOF Corporation, nonionic EH-204) • Surfactant c4: Polyether-modified polydimethylsiloxane (a liquid silicone compound containing a polyether group, manufactured by BYK-342, BIC Chemie Japan) • Surfactant c5: Fluorine-based surfactant (manufactured by 3M Japan, FC-4432) • Adhesion aid d1: Aminosilane compound having the structure represented by the following formula (3)

[0211] [ka]

[0212] • Manufacturing method of adhesion enhancer d1 In a reaction vessel of appropriate size equipped with a stirrer and condenser, cyclohexene-1,2-dicarboxylic acid anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g), and the temperature was adjusted to 30°C in a constant temperature bath. Next, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into a dropping funnel and added dropwise to the solution over 60 minutes. After the addition was complete, the mixture was stirred at 30°C for 18 hours to obtain an aminosilane compound having the structure represented by formula (3).

[0213] • Adhesion aid d2: Manufactured by Shin-Etsu Chemical Co., Ltd., amino group-containing silane coupling agent, X-12-5263HP • Adhesion enhancer d3: γ-glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E)

[0214] • Dissolving modifier e1: Phloroglucid • Crosslinking agent f1: 1,4-benzenedimethanol (paraxylene glycol: PXG) • Crosslinking agent f2: Urea-based compound (Daito Chemix Co., Ltd., Crolin-318) • Crosslinking agent f3: Epoxy compound (manufactured by Mitsubishi Chemical Corporation, YX-7105)

[0215] • Polyfunctional (meth)acrylate g1: NK ester A-9550 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dipentaerythritol polyacrylate) • Epoxy compound h1:4HBAGE (manufactured by Shinryo Co., Ltd., 4-hydroxybutyl acrylate glycidyl ether) • Thermal radical initiator i1: Percadox BC (manufactured by Nuurion Pharmaceuticals, dicumyl peroxide) • Curing catalyst j1: Phosphonium salt

[0216] • Solvent k1: NMP (N-methyl-2-pyrrolidone) • Solvent k2: EL (ethyl lactate) • Solvent k3: GBL (γ-butyrolactone)

[0217] 6. Characteristics of the photosensitive resin composition The following properties were obtained for the photosensitive resin composition.

[0218] 6.1. Moisture content measured by the Karl Fischer method The water content of the photosensitive resin compositions in each example and comparative example was measured using the method described above (Karl Fischer method). The measurement results are shown in Tables 1 to 3.

[0219] 6.2. Ratio of viscosity after solvent immersion test to initial viscosity For each example and comparative example of the photosensitive resin composition, the ratio of the viscosity after solvent immersion testing (post-test viscosity) to the initial viscosity was calculated using the method described above. The calculation results are shown in Tables 1 to 3.

[0220] 6.3. Distribution of weight loss rate after solvent immersion test For each example and comparative example of the photosensitive resin composition, the distribution of weight loss rates after solvent immersion testing was calculated using the method described above. Specifically, the weight loss rates for Part 1, Part 2, and Part 3 were measured, and the initial analysis value, first analysis value, second analysis value, and third analysis value were obtained. Next, the ratio of the first analysis value to the initial analysis value, the ratio of the second analysis value to the initial analysis value, and the ratio of the third analysis value to the initial analysis value were calculated, respectively. For each example and comparative example of the photosensitive resin composition, all three calculation results fell within the range of 101% to 115%. Therefore, the maximum value among the three calculation results (the calculation result with the largest deviation from the initial analysis value) was used as the evaluation index for the "distribution of weight loss rates," and this is shown in Tables 1 to 3.

[0221] 7. Evaluation of the resin film The photosensitive resin composition was placed in a dispenser and left for 24 hours. Then, the photosensitive resin composition was applied to an 8-inch silicon wafer using a spin coater to obtain a coating film. Next, the obtained coating film was cured at 220°C for 240 minutes to obtain a circular resin film. The obtained resin film was evaluated as follows.

[0222] 7.1. Uniformity of film thickness First, the resin film was cut along a line passing through its center. Next, the cut surface was observed, and the film thickness was measured at three locations: the center and both ends. Then, the variation in film thickness was measured, and the uniformity of the film thickness was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 3.

[0223] A: Film thickness variation is particularly small (film thickness range is less than 5 μm) B: Film thickness variation is relatively small (film thickness range is between 5 μm and less than 10 μm) C: Film thickness variation is somewhat large (film thickness range is between 10 μm and less than 15 μm) D: Film thickness variation is particularly large (film thickness range of 15 μm or more)

[0224] 7.2. Exterior First, the resin film was observed using an optical microscope. Next, the presence and degree of color unevenness in the resin film were checked. Then, the appearance was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 1 to 3.

[0225] A: The appearance is particularly good (very little color unevenness). B: The appearance is fairly good (slightly less color unevenness). C: The appearance is slightly poor (there are quite a few color inconsistencies). D: The appearance is particularly poor (there are many color inconsistencies).

[0226] [Table 1]

[0227] [Table 2]

[0228] [Table 3]

[0229] Based on the evaluation results shown in Tables 1 to 3, the following can be observed. It was found that by using a non-fluorinated surfactant as the surfactant and keeping the ratio of the viscosity after solvent immersion testing to the initial viscosity within a predetermined range, the uniformity of the film thickness of the resin film formed using the photosensitive resin composition can be improved, and appearance defects can be suppressed. • It was observed that the ratio of viscosity after the solvent immersion test to the initial viscosity, whether deviating from the lower or upper limit of a predetermined range, reduced the uniformity of the resin film thickness. It was observed that the ratio of viscosity after solvent immersion testing to the initial viscosity changed depending on the type and content of the surfactant. For example, surfactant c5 is a fluorine-based surfactant, and in the photosensitive resin composition using it, the above ratio fell outside the specified range. Also, surfactant c4 has a stronger effect of lowering surface tension compared to surfactant c1, and from a comparison between Example 1 and Comparative Example 1, for example, it is thought that this effect is influencing the above ratio. [Explanation of symbols]

[0230] 30 Interlayer insulating film 32 Passivation membrane 34 Top layer wiring 40 Redistribution layer 42 Insulating layer 44 Insulating layer 46 Rewiring 50 UBM layers 52 Bump 100 Semiconductor Devices

Claims

1. One or more resins (A) selected from the group consisting of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and phenolic resin, Photosensitive material (B), Surfactants (C) and Solvent and, A photosensitive resin composition comprising, The surfactant (C) is composed of a non-fluorinated surfactant. When 7.5 mL of the photosensitive resin composition is contained in a dispenser as a container, and the tip of the dispenser is immersed for 20 seconds in a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA), the container is removed and its viscosity is measured with an E-type viscometer, A photosensitive resin composition characterized in that the measured viscosity is 68% or more and 80% or less of the viscosity of the photosensitive resin composition that has not been immersed.

2. The photosensitive resin composition according to claim 1, wherein the non-fluorinated surfactant (C) is a silicone-based surfactant.

3. The photosensitive resin composition according to claim 2, wherein the silicone-based surfactant is a polyether-modified dimethylsiloxane or an aralkyl-modified dimethylsiloxane.

4. With 7.5 mL of the photosensitive resin composition contained in a dispenser, the tip of the dispenser is immersed for 20 seconds in a mixed solution of 70% by mass of propylene glycol monomethyl ether (PGME) and 30% by mass of propylene glycol monomethyl ether acetate (PGMEA). Then, the contents are removed in three separate portions of 2.5 mL each, and thermogravimetric analysis is performed on each portion under a nitrogen atmosphere. The weight loss rate at 146.6°C for the first portion is taken as the first analytical value, the weight loss rate at 146.6°C for the second portion is taken as the second analytical value, and the weight loss rate at 146.6°C for the third portion is taken as the third analytical value. The photosensitive resin composition according to any one of claims 1 to 3, wherein the first analytical value, the second analytical value, and the third analytical value are all 101% or more and 115% or less of the weight loss rate of the photosensitive resin composition at 146.6°C that has not been immersed.

5. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) is a phenolic resin.

6. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) is a polyimide precursor or a polybenzoxazole precursor.

7. A resin film characterized by being composed of a cured product of the photosensitive resin composition described in claim 1 or 2.

8. Semiconductor elements and The resin film according to claim 7 is provided on the surface of the semiconductor element, A semiconductor device characterized by comprising the following features.

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