Negative photosensitive resin composition, negative photosensitive resin composition coating film, negative photosensitive resin composition film, cured film, and electronic component using same

Abstract

This negative photosensitive resin composition comprises cationically polymerizable compound as a component (A), and a photocationic polymerization initiator as a component (B), wherein the component (A) contains, as a component (A1), a polyfunctional aromatic glycidyl ether having an epoxy equivalent of 80-145 g / eq and having at least two epoxy groups in a molecule, with the content of the component (A1) in the entirety of the component (A) being 45%-100% by mass. Provided is a negative photosensitive resin composition which is preferably used for adhesion of a semiconductor element or electronic component and which achieves both excellent resolution and adhesiveness.

Description

Negative photosensitive resin composition, negative photosensitive resin composition coating, negative photosensitive resin composition film, cured film, and electronic components using these

[0001] The present invention relates to a negative photosensitive resin composition, a negative photosensitive resin composition coating, a negative photosensitive resin composition film, a cured film, and a semiconductor device using them. More specifically, the present invention relates to a resin composition, a resin composition coating, a resin composition film, a cured film, and a cured film that are suitable for use in surface protection films for semiconductor elements and electronic components, interlayer insulating films, and MEMS (microelectromechanical systems) structures and adhesive members, and a semiconductor device using them.

[0002] Photosensitive materials are used as interlayer insulating films, surface protection films, and structural components in electronic components such as semiconductor devices and MEMS (Micro Electro Mechanical Systems). Photosensitive materials are classified into positive-type photosensitive materials using diazonaphthoquinone compounds and negative-type photosensitive materials using photopolymerizable compounds. Major negative-type photosensitive materials include photoradical polymerization-based materials using a radically polymerizable compound such as an acrylic compound and a photoradical polymerization initiator, and photocationic polymerization-based materials using a cationic polymerizable compound such as an epoxy compound and a photocationic polymerization initiator. In particular, photocationic polymerization-based negative-type photosensitive materials have excellent resolution and low shrinkage during pattern formation, making them suitable for use as interlayer insulating films and structural components (see, for example, Patent Document 1).

[0003] In the manufacturing process of electronic components and the like, a technique has been proposed in which a pattern is formed on a substrate using a photosensitive material, and another substrate is placed facing the formed pattern and bonded to the substrate by thermocompression bonding. Examples of such a technique include a method for connecting electrode pads formed on an integrated circuit element (Patent Document 2), a method for bonding circuit boards (Patent Document 3), and a method for manufacturing a semiconductor package (Patent Document 4). In recent years, particularly in electronic components such as MEMS, there has been a demand for replacing the metal materials used to bond substrates with photosensitive materials to reduce costs and achieve smaller and thinner components. To meet such demands, there is a need for photosensitive materials that combine the resolution necessary to form fine patterns with good adhesion.

[0004] Japanese Patent No. 5247396, Japanese Patent No. 3050345, Japanese Patent No. 2660943, Japanese Patent Laid-Open No. 2003-347357

[0005] However, when using conventional photosensitive resin compositions for bonding semiconductor elements and electronic components, there has been a problem in achieving both resolution and adhesion. Positive-type photosensitive materials have excellent resolution, but there is a concern that voids will form at the adhesive interface due to gas generation from photosensitizers such as diazonaphthoquinone compounds during thermal curing, resulting in reduced adhesive strength. Negative-type photosensitive materials based on photoradical polymerization lack resolution and are subject to reduced adhesive strength due to the large internal stress caused by curing shrinkage. Furthermore, negative-type photosensitive materials based on photocationic polymerization, such as those described in Patent Document 1, have excellent resolution, but the high photoreactivity of the cationic polymerizable compound results in a high crosslink density after pattern formation, which leads to the problem of voids forming at the adhesive surface when substrates are thermocompressed.

[0006] In view of the above circumstances, an object of the present invention is to provide a negative photosensitive resin composition that is suitable for the above-mentioned adhesive applications and that has both excellent resolution and adhesiveness.

[0007] As a result of extensive research, the inventors have found that in a negative-tone photosensitive resin composition containing a cationically polymerizable compound and a cationic photopolymerization initiator, by intentionally suppressing the cationic photopolymerization reactivity to a certain level or less, it is possible to achieve both excellent resolution and adhesion. Specifically, by incorporating a polyfunctional aromatic glycidyl ether having an epoxy equivalent weight within a specific range or more into the negative-tone photosensitive resin composition, it is possible to suppress the cationic photopolymerization reactivity to a certain level or less, thereby providing a negative-tone photosensitive resin composition that is suitable for use in bonding semiconductor elements and electronic components and that achieves both excellent resolution and adhesion.

[0008] The present invention is as follows.

[0009] <1> A negative-type photosensitive resin composition containing a cationically polymerizable compound as component (A) and a cationic photopolymerization initiator as component (B), wherein the component (A) contains, as component (A1), a polyfunctional aromatic glycidyl ether having an epoxy equivalent of 80 to 145 g / eq and having at least two epoxy groups in the molecule, and the content of the component (A1) in the entire component (A) is 45 to 100 mass%.

[0010] <2> The negative photosensitive resin composition according to <1>, wherein the content of the component (A) in the entire negative photosensitive resin composition is 45 to 70 mass%.

[0011] <3> The negative photosensitive resin composition according to <1> or <2>, wherein the component (A1) contains a liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 to 150,000 mPa·s at 25°C.

[0012] <4> The negative photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) contains a cationically polymerizable compound selected from compounds represented by the following general formulas (1) and (2):

[0013]

[0014] In general formula (1), l, m, and n each independently represent an integer of 1 to 6; in general formula (2), R １ , R ２ are each independently a divalent organic group.

[0015] <5> The negative photosensitive resin composition according to any one of <1> to <4>, further comprising at least one polymer compound selected from polyamide, polyimide, and polyamideimide as a component (C).

[0016] <6> The negative photosensitive resin composition according to <5>, wherein the component (C) contains a diamine residue derived from a diamine represented by any one of the following general formulas (3) to (7):

[0017]

[0018] <7> A negative photosensitive resin composition film comprising the negative photosensitive resin composition according to any one of <1> to <6>.

[0019] <8> A negative photosensitive resin composition film having the negative photosensitive resin composition coating according to <7> and a support.

[0020] <9> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <6> or the negative photosensitive resin composition film according to <7>.

[0021] <10> An electronic component having the cured film according to <9>.

[0022] <11> An electronic component having a structure in which two substrates are bonded via the cured film according to <9>.

[0023] The present invention can provide a negative-type photosensitive resin composition, a negative-type photosensitive resin composition coating, a negative-type photosensitive resin composition film, a cured film, and an electronic component using any of these, which are suitable for use in bonding semiconductor elements and electronic components and which combine excellent resolution and adhesion.

[0024] The negative-type photosensitive resin composition of the present invention is a negative-type photosensitive resin composition containing a cationically polymerizable compound as component (A) and a cationic photopolymerization initiator as component (B), wherein the component (A) contains, as component (A1), a polyfunctional aromatic glycidyl ether having an epoxy equivalent of 80 to 145 g / eq and having at least two epoxy groups in the molecule, and the content of the component (A1) in the entire component (A) is 45 to 100 mass%.

[0025] <Component (A)> The negative photosensitive resin composition of the present invention contains a cationically polymerizable compound as component (A) (hereinafter, may be referred to as "cationically polymerizable compound (A)"). By containing the cationically polymerizable compound (A), the negative photosensitive resin composition of the present invention undergoes photocationic polymerization and exhibits excellent negative pattern processability.

[0026] Preferred examples of the cationically polymerizable compound (A) include cyclic ether compounds (epoxy compounds, oxetane compounds, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters.

[0027] In the negative-tone photosensitive resin composition of the present invention, the component (A) contains, as component (A1), a polyfunctional aromatic glycidyl ether having an epoxy equivalent of 80 to 145 g / eq and at least two epoxy groups per molecule. The inclusion of component (A1) reduces the reaction rate of the cationically polymerizable groups throughout the component (A) during pattern processing, making the resin composition more flexible and improving adhesion. As a result, voids do not form on the bonding surface when the resin composition is bonded to a substrate, even under lower temperature and pressure conditions. The mechanism by which the inclusion of component (A1) reduces the reaction rate of the cationically polymerizable groups is unclear, but it is believed that the nucleophilicity and molecular mobility of the cationically polymerizable compound contribute to this. Cationic polymerization proceeds through an activation reaction of the cationically polymerizable compound with an acid, an initiation reaction, and a propagation reaction, with the nucleophilicity of the cationically polymerizable compound affecting the reactivity of the propagation reaction. Since the nucleophilicity of an epoxy compound is affected by the electron density of the oxygen atom, it is presumed that the use of alicyclic epoxy compounds, which are commonly used in conventional negative-type photosensitive materials based on cationic photopolymerization, increases the nucleophilicity due to the electron-donating properties of the alicyclic structure. On the other hand, the use of aromatic glycidyl ethers reduces the nucleophilicity due to the electron-withdrawing properties and the stabilizing effect of the aromatic ring due to resonance, which is presumed to result in a decrease in cationic polymerization reactivity. Furthermore, considering molecular mobility, it is presumed that epoxy compounds with low epoxy equivalents tend to have a low reactivity because the mobility of the system decreases significantly even with slight reaction progress. Therefore, the epoxy equivalent of component (A1) is 145 g / eq or less. Furthermore, since too low an epoxy equivalent results in an excessively low reactivity, the epoxy equivalent of component (A1) is 80 g / eq or more. For these reasons, it is presumed that the inclusion of component (A1) reduces the reactivity of the cationically polymerizable group.

[0028] Furthermore, in the negative-type photosensitive resin composition of the present invention, the content of the component (A1) relative to the entire component (A) is 45 to 100% by mass. When the content of the component (A1) is at least the lower limit, the cationic polymerization reaction rate of the entire component (A) is sufficiently reduced, the resin composition becomes flexible, and adhesion is improved, preventing voids from forming on the bonding surface when the composition is bonded to a substrate. Furthermore, the content of the component (A1) relative to the entire component (A) is preferably 45 to 80% by mass. The lower limit of the content is more preferably 50% by mass or more, and even more preferably 60% by mass or more. The upper limit of the content is more preferably 70% by mass or less. When the content of the component (A1) is at least the lower limit of the preferred range, adhesion is improved as described above, and when it is at most the upper limit of the preferred range, resolution during pattern processing is improved and internal stress after curing is reduced, which are preferable.

[0029] Examples of polyfunctional aromatic glycidyl ethers that can be used as the component (A1) include compounds represented by the following chemical formulas (A1-1), (A1-2), and (A1-3).

[0030]

[0031] In the negative-tone photosensitive resin composition of the present invention, the component (A1) preferably contains a liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 to 150,000 mPa·s at 25°C. The component (A1) preferably contains a liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 mPa·s or more at 25°C, which further reduces the cationic polymerization reaction rate of the entire component (A) during pattern processing, making the resin composition more flexible and further improving adhesion. The component (A1) preferably contains a liquid polyfunctional aromatic glycidyl ether having a viscosity of 150,000 mPa·s or less at 25°C, which improves the compatibility of the negative-tone photosensitive resin composition and improves resolution. Examples of the liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 to 150,000 mPa s at 25° C. that can be used include compounds represented by the chemical formulas (A1-2) and (A1-3). From the viewpoint of improving adhesiveness, the content of the liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 to 150,000 mPa s at 25° C. in the component (A1) is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, and even more preferably 80 to 100% by weight.

[0032] The negative-type photosensitive resin composition of the present invention may contain, as the component (A), a cationically polymerizable compound other than the component (A1). Preferred examples of such a component (A) include epoxy compounds, oxetane compounds, ethylenically unsaturated compounds (such as vinyl ethers and styrenes), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters, which are not included in the component (A1).

[0033] As the epoxy compound, known compounds can be used, and preferred examples include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0034] Preferred examples of the aromatic epoxy compound include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0035] Preferred examples of the alicyclic epoxy compound include compounds obtained by epoxidizing a compound having at least one cyclohexene ring or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0036] Preferred examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxy compounds of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0037] As the oxetane compound, known compounds can be used, and preferred examples thereof include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0038] As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, and preferred examples include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationically polymerizable nitrogen-containing monomers.

[0039] Preferred examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0040] Preferred examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0041] Preferred examples of the polyfunctional vinyl ether include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0042] Preferred examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0043] Preferred examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0044] Preferred examples of the bicyclo orthoester include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.

[0045] Preferred examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0046] Preferred examples of the spiro orthoester include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0047] Of these cationically polymerizable compounds, compounds selected from epoxy compounds, oxetane compounds and vinyl ethers are preferred, and compounds selected from epoxy compounds and oxetane compounds are more preferred.

[0048] By including an epoxy compound having an isocyanurate skeleton as the component (A), it is possible to maintain cationic polymerizability while keeping the dielectric constant and dielectric dissipation factor of the cured film obtained by curing the resin composition low, which is preferable. Although the epoxy compound having an isocyanurate skeleton itself is not soluble in an alkaline aqueous solution, when developing with an alkaline aqueous solution, it is possible to perform pattern processing with an alkaline aqueous solution without inhibiting the alkali solubility of the resin composition. Although the reason for this is unclear, it is thought to be due to its compatibility with the alkali-soluble component (C) described below.

[0049] The component (A) preferably contains a cationically polymerizable compound selected from the compounds represented by the following general formulas (1) and (2).

[0050] As the component (A), an epoxy compound represented by general formula (1) is particularly preferred from the viewpoint of alkali solubility and photoreactivity during pattern processing.

[0051]

[0052] In the general formula (1), l, m, and n each independently represent an integer of 1 to 6.

[0053] Preferred examples of the epoxy compound represented by general formula (1) include triglycidyl isocyanurates such as TEPIC (registered trademark)-S, TEPIC (registered trademark)-L, TEPIC (registered trademark)-VL, TEPIC (registered trademark)-PASB26L, TEPIC (registered trademark)-PASB22, TEPIC (registered trademark)-FL, and TEPIC (registered trademark)-UC (trade names, all manufactured by Nissan Chemical Industries, Ltd.). Preferred examples of the epoxy compound represented by general formula (1) include TEPIC (registered trademark)-S, TEPIC (registered trademark)-L, TEPIC (registered trademark)-VL, and TEPIC (registered trademark)-FL (trade names, all manufactured by Nissan Chemical Industries, Ltd.).

[0054] From the viewpoint of resolution during pattern processing and photoreactivity, it is preferable that the component (A) contains an epoxy compound represented by general formula (2).

[0055]

[0056] In general formula (2), R １ , R ２ are each independently a divalent organic group.

[0057] Preferred examples of the epoxy compound represented by general formula (2) include OGSOL (registered trademark) PG-100, OGSOL (registered trademark) CG-500, OGSOL (registered trademark) EG-200, and OGSOL (registered trademark) EG-280 (trade names, all manufactured by Osaka Gas Chemicals Co., Ltd.), and from the viewpoint of compatibility, OGSOL (registered trademark) EG-200 and OGSOL (registered trademark) EG-280 (trade names, all manufactured by Osaka Gas Chemicals Co., Ltd.) are particularly preferred.

[0058] The cationically polymerizable compound (A) may be used alone or in combination of two or more kinds.

[0059] Furthermore, in the negative photosensitive resin composition of the present invention, the content of the component (A) relative to the entire negative photosensitive resin composition is preferably 45 to 70% by mass. The lower limit of the content is more preferably 50% by mass or more. The upper limit of the content is more preferably 60% by mass or less. Having the content of the component (A) equal to or greater than the lower limit of the preferred range is preferable in that the contrast in dissolution rate between exposed and unexposed areas in a developer during pattern formation is increased, thereby improving resolution. Having the content of the component (A) equal to or less than the upper limit of the preferred range is preferable in that, when the negative photosensitive resin composition is formed into a film, i.e., a resin composition film, the surface of the resin composition film is free of tack and easy to handle, and in that the solubility in a developer is increased, thereby improving resolution.

[0060] In the present invention, the content of the component (A) in the entire negative photosensitive resin composition refers to the content ratio of the component (A) when the total of all components excluding the solvent is taken as 100 mass %. The same applies to the contents of other components.

[0061] <Component (B)> The negative-type photosensitive resin composition of the present invention contains a cationic photopolymerization initiator as component (B) (hereinafter, sometimes referred to as cationic photopolymerization initiator (B)). The component (B) generates an acid when exposed to light, causing cationic polymerization.

[0062] Although known compounds can be used as component (B), it is preferred that component (B) contains a sulfonium salt and that the counter anion forming the sulfonium salt contains at least one selected from the group consisting of borate ions, phosphate ions, and gallate ions. The inclusion of such a compound in component (B) is preferred because it allows the cationic polymerization of component (A) to proceed sufficiently during pattern processing, resulting in the production of a good pattern.

[0063] Examples of the cations that form the sulfonium salt include triphenylsulfonium, tri-p-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio) phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenyl) 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolyls ...10-Dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoyl)phenylthio]phenyldiphenylsulfonium triarylsulfoniums such as 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenenium; diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium, Preferred examples include diarylsulfonium such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium; and preferred examples include, but are not limited to, dimethylphenacylsulfonium, phenacylterahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

[0064] When the cationic photopolymerization initiator as component (B) contains a sulfonium salt, preferred examples of the counter anion that forms the sulfonium salt include a borate ion, a phosphate ion, a gallate ion, etc. Here, a borate ion is a complex ion having boron as the central atom, a phosphate ion is a complex ion having phosphorus as the central atom, and a gallate ion is a complex ion having gallium as the central atom.

[0065] Preferred examples of borate ions include pentafluorophenylborate, trifluorophenylborate, tetrafluorophenylborate, trifluoromethylphenylborate, bis(trifluoromethyl)phenylborate, pentafluoroethylphenylborate, bis(pentafluoroethyl)phenylborate, fluoro-bis(trifluoromethyl)phenylborate, fluoro-pentafluoroethylphenylborate, and fluoro-bis(pentafluoroethyl)phenylborate, but are not limited to these.

[0066] Preferred examples of the phosphate ion include, but are not limited to, hexafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, and the like.

[0067] Preferred examples of the gallate ion include, but are not limited to, tetrakis(pentafluorophenyl)gallate and tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate.

[0068] The content of the (B) component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the entire resin composition. This allows the cationically polymerizable compound to exhibit sufficient curability and improve pattern processability. On the other hand, in order to improve the storage stability of the resin composition, the content of the (B) component is preferably 10% by mass or less, more preferably 8% by mass or less.

[0069] <Component (C)> The negative-type photosensitive resin composition of the present invention preferably contains, as component (C), at least one polymer compound selected from polyamide, polyimide, and polyamideimide. In the present invention, the polyimide precursor and the polybenzoxazole precursor correspond to the above-mentioned polyamide, respectively.

[0070] The resin composition of the present invention is preferable in that it contains the component (C), which provides excellent film-forming properties when the resin composition is made into a film-like resin composition coating, and also provides excellent tensile strength and tensile elongation when cured. Furthermore, the inclusion of the component (C) is preferable in that the reactivity of the cationically polymerizable compound (A) is appropriately suppressed by the functional group such as an imide group or an amide group, thereby improving adhesion when adhering to a substrate. The component (C) may be used alone or in combination of two or more.

[0071] The weight average molecular weight of the component (C) is not particularly limited, but is preferably from 1,000 to 200,000. The weight average molecular weight of the component (C) in the present invention is determined by measuring it by gel permeation chromatography (GPC) and calculating it in terms of polystyrene.

[0072] The component (C) is preferably alkali-soluble. This is because the component (C) can be developed with an aqueous alkali solution without using an organic solvent, which is a factor in environmental load, during pattern processing. The term "alkali-soluble" as used herein refers to a component that dissolves at 25°C in an amount of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0073] In order to exhibit alkali solubility, it is desirable that the component (C) has an alkali-soluble functional group. The alkali-soluble functional group is a functional group having acidity, and specific examples thereof include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group. Among the alkali-soluble functional groups, the alkali-soluble functional group is preferably a phenolic hydroxyl group in view of problems such as the storage stability of the resin composition and corrosion of copper wiring as a conductor. In other words, the component (C) is preferably a compound having a phenolic hydroxyl group in the molecular chain.

[0074] Furthermore, in the resin composition of the present invention, the molecular chain terminal of the component (C) preferably has a structure derived from a carboxylic acid residue, but it is also possible to include a polymer compound whose molecular chain terminal does not have a structure derived from a carboxylic acid residue.

[0075] When the resin composition of the present invention contains a polymer compound whose molecular chain terminals do not have a structure derived from a carboxylic acid residue, the smaller the content thereof, the better. Specifically, the content of the component (C) whose molecular chain terminals do not have a structure derived from a carboxylic acid residue is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass or more and 5 parts by mass or less, and particularly preferably 0 parts by mass or more and 2 parts by mass or less, relative to a total of 100 parts by mass of the component (C) whose molecular chain terminals have a structure derived from a carboxylic acid residue.

[0076] The content of the (C) component is not particularly limited, but is preferably 20% by mass or more and 95% by mass or less, where the entire resin composition is taken as 100% by mass. The lower limit of the content is more preferably 30% by mass or more. The upper limit of the content is more preferably 85% by mass or less, and particularly preferably 70% by mass or less. By including 20% ​​by mass or more of the (C) component in the resin composition, the film strength when the resin composition is formed into a cured film is improved. On the other hand, by setting the content of the (C) component in the resin composition to 95% by mass or less, the cationic polymerization reaction is more likely to proceed, and the chemical resistance of the cured film is improved.

[0077] By having the molecular chain terminal of the component (C) be a structure derived from a carboxylic acid residue, the molecular chain terminal can be made to have a molecular structure that does not have an amine terminal structure that can serve as a functional group that inhibits cationic polymerization, and as a result, even when polyamide, polyimide, or polyamideimide is used, it is preferable in that sufficient cationic polymerizability can be exhibited.

[0078] Here, the structure derived from a carboxylic acid residue at the molecular chain terminal of the component (C) is an organic group derived from a carboxylic acid residue that can constitute a polyamide, polyimide, or polyamideimide, and refers to a structure derived from a monocarboxylic acid, dicarboxylic acid, monoacid chloride compound, diacid chloride compound, tetracarboxylic acid, acid anhydride, acid dianhydride, etc. Among the above, it is particularly preferable that the structure derived from a carboxylic acid residue at the molecular chain terminal of the component (C) is a structure derived from a tetracarboxylic acid dianhydride.

[0079] The structure at the molecular chain terminal is derived from a tetracarboxylic dianhydride, which is preferable in that the storage stability of the resin composition before heat curing is improved, and further, when the resin composition is formed into a cured film, the terminal carboxylic anhydride group becomes a reactive functional group, which is preferable in that the heat resistance and chemical resistance after heat curing are improved.

[0080] Examples of the structure derived from a carboxylic acid residue at the molecular chain terminal of component (C) include, but are not limited to, structures derived from aromatic dicarboxylic acids, aromatic acid dianhydrides, alicyclic dicarboxylic acids, alicyclic acid dianhydrides, aliphatic dicarboxylic acids, aliphatic acid dianhydrides, etc. These may be used alone or in combination of two or more.

[0081] Among these, an organic group derived from an alicyclic dicarboxylic acid residue is preferred, since it allows the design of a resin that is transparent to the wavelength used during patterning, and as a result, enables the development of fine pattern processability in a thick film.

[0082] In the present invention, the component (C) is preferably at least one polymer compound selected from polyamide, polyimide, and polyamideimide, and more preferably a compound having at least one structure selected from the structures represented by the following general formula (8) and general formula (9).

[0083]

[0084] In the general formulas (8) and (9), X １ represents a divalent to octavalent organic group, and X ２ represents a tetravalent to octavalent organic group, and Y １ and Y ２ each independently represents a divalent to hexavalent organic group, R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, q represents an integer of 0 to 2, and r, s, t, and u each independently represent an integer of 0 to 4.

[0085] Y in the general formulas (8) and (9) １ and Y ２ is a diamine residue, and preferably contains a diamine residue having a phenolic hydroxyl group or a carboxyl group. By containing a diamine residue having a phenolic hydroxyl group or a carboxyl group, appropriate solubility of component (C) in an alkaline developer is obtained, thereby achieving high contrast between exposed and unexposed areas and enabling the formation of a desired pattern.

[0086] Specific examples of diamines having a phenolic hydroxyl group include, but are not limited to, aromatic diamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine; compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like; and diamines having the structures shown below. The other diamine to be copolymerized may be used as it is, or in the form of a corresponding diisocyanate compound or trimethylsilylated diamine. Two or more of these diamine components may also be used in combination.

[0087]

[0088]

[0089] Furthermore, from the viewpoints of pattern processability and adhesiveness, the component (C) preferably contains a diamine residue derived from any of the diamines represented by general formulas (3) to (7). Among these, the component (C) preferably contains a diamine residue derived from the diamine represented by general formula (5), which is particularly preferred because it appropriately suppresses the photoreactivity of the component (A) and improves adhesiveness.

[0090]

[0091] Y in general formulas (8) and (9) １ and Y ２may contain a diamine residue having an aromatic group other than those mentioned above. Copolymerization of these can improve heat resistance. Specific examples of diamines having an aromatic group other than those mentioned above include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-amino Examples of aromatic diamines include, but are not limited to, aromatic diamines such as {(phenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. The other diamine to be copolymerized can be used as is or as the corresponding diisocyanate compound or trimethylsilylated diamine. Two or more of these diamine components may also be used in combination.

[0092] In the above general formula (8) and general formula (9) of the present invention, X １ and X ２ is a carboxylic acid residue.

[0093] The carboxylic acid residue preferably has a structure derived from an alicyclic tetracarboxylic dianhydride, i.e., the component (C) is preferably at least one compound selected from the group consisting of polyamides, polyimides, and polyamideimides, and further has a structure derived from an alicyclic tetracarboxylic dianhydride.

[0094] When the carboxylic acid residue has a structure derived from an alicyclic tetracarboxylic dianhydride, the resin composition has a high light transmittance at the exposure wavelength, making it easy to process into a thick film of 20 μm or more. Furthermore, although the reason is not clear, when the component (C) has a structure derived from an alicyclic tetracarboxylic dianhydride, the reactivity of cationic polymerization is higher than that of aromatic acid dianhydrides, which is preferable in that the chemical resistance of the film when the resin composition is cured is improved.

[0095] Among the alicyclic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides having a polycyclic structure are preferred because they improve the chemical resistance and ion migration resistance of the cured product. As the alicyclic tetracarboxylic dianhydride having a polycyclic structure, a compound represented by at least one of the following general formulas (10) and (11) is preferred:

[0096]

[0097] In the formula, R １ , R ２ , R ３ each independently represents a hydrogen atom or a methyl group.

[0098] When the component (C) has a structure derived from the compound represented by the general formula (10) or (11), the resin skeleton has flexibility, and therefore the solubility of the resin composition before curing in an organic solvent is increased, and precipitation of the resin in the resin composition is unlikely to occur, which is preferable in terms of excellent storage stability.

[0099] Specific examples of the alicyclic tetracarboxylic acid dianhydride having a polycyclic structure include 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, and norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride.

[0100] The carboxylic acid residue may include a residue of an acid dianhydride other than the alicyclic tetracarboxylic dianhydride having a polycyclic structure. Specific examples of such an acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride. 1,1-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl) aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride; Examples of the dianhydride include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, and 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0101] The molar ratio of each structure constituting the compounds represented by general formulas (8) and (9) can be confirmed by a method of calculation from the molar ratio of the monomers used in polymerization, or by a method of detecting peaks of the polyamide structure, imide precursor structure, and imide structure in the obtained resin, resin composition, and cured film using a nuclear magnetic resonance (NMR) spectrometer.

[0102] The component (C) having a structure derived from a carboxylic acid residue at the molecular chain terminal can be obtained, for example, in the case of a polyimide having a carboxylic acid residue at the molecular chain terminal, by increasing the content of acid anhydride relative to the diamine used during polymerization.

[0103] In this case, when the total amount of carboxylic acid residues in the component (C) is taken as 100 mol%, the total amount of amine residues is preferably 60 mol% to 98 mol%. That is, when the total amount of carboxylic acid residues is taken as 100 mol%, the component (C) is preferably a compound obtained by polymerization such that the total amount of amine residues is 60 mol% to 98 mol%. When the total amount of amine residues is 60 mol% or more, the weight-average molecular weight of the polymer compound tends to be 1,000 or more, and the film-forming properties when the resin composition is formed into a film are excellent. When the total amount of amine residues is 98 mol% or less, the proportion of polymer compounds terminated with amine residues is small, which facilitates the cationic polymerization reaction and improves resolution.

[0104] Another method for obtaining the component (C) in which the molecular chain terminals are derived from a carboxylic acid residue is to use a specific compound from among the compounds generally used as an end-capping agent, specifically, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.

[0105] Furthermore, by capping the molecular chain ends of the component (C) with a terminal capping agent of a carboxylic acid or acid anhydride having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the dissolution rate of the component (C) in an alkaline aqueous solution and the mechanical properties of the resulting cured film can be easily adjusted within preferred ranges. Furthermore, multiple terminal capping agents may be reacted to introduce multiple different terminal groups.

[0106] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds as end-capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxy Preferred examples include monocarboxylic acids such as benzenesulfonic acid and 4-carboxybenzenesulfonic acid, and monoacid chloride compounds in which the carboxyl group of these compounds is converted to an acid chloride; monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is converted to an acid chloride; and active ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole, imidazole, or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these may be used.

[0107] The polymer compound into which these terminal blocking agents have been introduced becomes the component (C) in which the molecular chain terminals have a structure derived from carboxylic acid residues. The structure derived from the terminal blocking agent in the component (C) can be easily detected by the following method. For example, the component (C) into which the terminal blocking agent has been introduced is dissolved in an acidic solution and decomposed into the structural units, amine components and acid anhydride components, and the type of terminal blocking agent used can be easily detected by gas chromatography (GC) or NMR. Separately, the resin component into which the terminal blocking agent has been introduced can be directly analyzed by pyrolysis gas chromatography (PGC), infrared spectroscopy, and １３ It can also be easily detected by measuring the C-NMR spectrum.

[0108] In the present invention, the component (C) is synthesized, for example, by the following method, but is not limited thereto.

[0109] Polyimides are synthesized by known methods by replacing a portion of the diamine with a primary monoamine, which serves as an end-capping agent, or by replacing the tetracarboxylic dianhydride with a dicarboxylic anhydride, which serves as an end-capping agent. For example, a polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound and a monoamine at low temperature, by reacting a tetracarboxylic dianhydride with a dicarboxylic anhydride and a diamine compound at low temperature, or by reacting a tetracarboxylic dianhydride with an alcohol to obtain a diester, which is then reacted with a diamine and a monoamine in the presence of a condensing agent. Then, a polyimide can be synthesized by known imidization reaction methods.

[0110] In the present invention, the component (C) is preferably prepared by polymerizing the component (C) by the above-described method, then pouring the reaction mixture into a large amount of water or a mixture of methanol and water, etc., to precipitate the component (C), and then filtering, drying, and isolating the precipitate. The drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. This operation removes unreacted monomers and oligomer components such as dimers and trimers, thereby improving the film properties after thermal curing.

[0111] In the present invention, the imidization rate can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured, and the absorption peak of the imide structure due to polyimide (1780 cm －１ Near and 1377 cm －１ Next, the polymer was heat-treated at 350°C for 1 hour to obtain a sample with an imidization rate of 100%, and the infrared absorption spectrum was measured. －１ The imidization rate is determined by comparing the peak intensities around 50%. An imidization rate of 50% or more is preferable, and 80% or more is more preferable, because this suppresses changes in the ring closure rate during thermal curing and provides the effect of reducing stress.

[0112] <Other Components> The negative photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer is a compound that absorbs light, donates the absorbed light energy to the component (B), and generates an acid to cause cationic polymerization. Furthermore, the sensitizer absorbs light of the irradiation wavelength during pattern processing, and can therefore reduce the transmittance of a negative photosensitive resin composition film formed from the negative photosensitive resin composition. Therefore, by controlling the content of the sensitizer in the negative photosensitive resin composition, it becomes possible to arbitrarily control the transmittance of a negative photosensitive resin composition film obtained from the composition.

[0113] Although the sensitizer is not particularly limited, an anthracene compound is preferred, and for example, an anthracene compound having alkoxy groups at the 9th and 10th positions (9,10-dialkoxy-anthracene derivative) is more preferred. Preferred examples of the alkoxy group include C1 to C4 alkoxy groups such as methoxy, ethoxy, and propoxy. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Preferred examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine; C1 to C4 alkyl groups such as methyl, ethyl, and propyl; sulfonate alkyl ester groups; and carboxylate alkyl ester groups. Preferred examples of the alkyl in the sulfonate alkyl ester group and carboxylate alkyl ester group include C1 to C4 alkyls such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

[0114] The content of the sensitizer is not particularly limited, but is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, when the entire negative photosensitive resin composition is taken as 100% by mass. This makes it possible to reduce the transmittance of the negative photosensitive resin composition film, and even on substrates with rough surfaces such as ceramics, it is possible to suppress reflected light from the substrate surface and facilitate the processing of fine patterns. On the other hand, from the viewpoint of suppressing deterioration in the mechanical properties and thermal properties of the cured film of the negative photosensitive resin composition film formed from the negative photosensitive resin composition, when the entire negative photosensitive resin composition is taken as 100% by mass, the content of the sensitizer is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0115] The negative photosensitive resin composition of the present invention may contain a thermal crosslinking agent, preferably a compound having an alkoxymethyl group or a methylol group.

[0116] Examples of compounds having an alkoxymethyl group or a methylol group include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DM OM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC Preferred examples include MX-280, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0117] The negative-type photosensitive resin composition of the present invention may further contain a silane compound. By containing a silane compound, the adhesion of the negative-type photosensitive resin composition coating, which will be described later, is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0118] Furthermore, the negative photosensitive resin composition of the present invention may contain, as necessary, surfactants for the purpose of improving wettability with the support, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Furthermore, for the purpose of suppressing the thermal expansion coefficient or increasing or decreasing the dielectric constant, the composition may contain inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder.

[0119] <Negative Photosensitive Resin Composition Coating, Negative Photosensitive Resin Composition Film> The form of the negative photosensitive resin composition of the present invention before curing is not limited, and may be, for example, a varnish or a film. When the negative photosensitive resin composition of the present invention is in the form of a varnish, it is called a negative photosensitive resin composition varnish. When the negative photosensitive resin composition of the present invention is in the form of a film, it is called a negative photosensitive resin composition coating. When the negative photosensitive resin composition of the present invention is in the form of a varnish, it may further contain an organic solvent in addition to the components (A) to (C) and other components added as needed.

[0120] The negative photosensitive resin composition film of the present invention has a negative photosensitive resin composition coating of the present invention and a support. The negative photosensitive resin composition film of the present invention can be obtained by laminating the negative photosensitive resin composition of the present invention in the form of a film on a support. When the negative photosensitive resin composition of the present invention is in the form of a varnish, the negative photosensitive resin composition of the present invention can be applied to a support and then dried as necessary to obtain the negative photosensitive resin composition film of the present invention.

[0121] The thickness of the negative photosensitive resin composition film of the present invention is preferably 5 μm or more from the viewpoint of ease of handling. Furthermore, in terms of suppressing variation in film thickness, the thickness of the negative photosensitive resin composition film is preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 60 μm or less.

[0122] Next, a method for producing a negative photosensitive resin composition film using the negative photosensitive resin composition of the present invention will be described. The negative photosensitive resin composition film of the present invention can be obtained by applying a varnish-like negative photosensitive resin composition to a support and then drying it as necessary. The negative photosensitive resin composition varnish can be obtained by adding an organic solvent to the negative photosensitive resin composition. The organic solvent used here may be any solvent that can dissolve the negative photosensitive resin composition.

[0123] Specific examples of organic solvents include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate. ketones such as acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone; alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and other preferred solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone.

[0124] The negative photosensitive resin composition varnish may be filtered using filter paper or a filter. Although the filtration method is not particularly limited, a method of filtering by pressure filtration using a filter with a retention particle size of 0.4 μm to 10 μm is preferred.

[0125] The negative photosensitive resin composition film of the present invention is used by forming a negative photosensitive resin composition coating on a support. The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the negative photosensitive resin composition coating may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and releasability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

[0126] The negative photosensitive resin composition film of the present invention may further have a protective film on the film surface to protect the surface. This can protect the surface of the negative photosensitive resin composition film from pollutants such as dust and dirt in the atmosphere. Examples of the protective film include polyolefin films and polyester films. It is preferable that the protective film has low adhesive strength with the negative photosensitive resin composition film.

[0127] Methods for applying the negative photosensitive resin composition varnish to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and coating using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The coating film thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less.

[0128] For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and drying time may be within a range that allows the organic solvent to volatilize, and are preferably set appropriately within a range that leaves the negative photosensitive resin composition film in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 40°C to 120°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 70°C, 80°C, and 90°C for 1 minute each.

[0129] <Pattern Formation> Next, examples of a method for patterning a negative photosensitive resin composition varnish or a negative photosensitive resin composition film using the same, a method for thermocompression bonding to another member, and a method for joining another substrate via a pattern formed on a substrate will be described.

[0130] First, a method for forming a negative photosensitive resin composition film on a substrate using the negative photosensitive resin composition of the present invention or a negative photosensitive resin composition film using the same will be described.

[0131] When using a negative-type photosensitive resin composition varnish, the varnish is first applied to a substrate. Examples of application methods include spin coating using a spinner, spray coating, roll coating, and screen printing. The coating thickness varies depending on the application technique, the solids concentration, and viscosity of the negative-type photosensitive resin composition, but it is generally preferable to apply the varnish so that the film thickness after drying is 0.5 μm to 100 μm. Next, the substrate coated with the negative-type photosensitive resin composition varnish is dried to obtain a negative-type photosensitive resin composition film laminated on the substrate. Drying can be performed using an oven, a hot plate, infrared rays, or the like. The drying temperature and drying time should be within a range that allows the organic solvent to volatilize, and are preferably set appropriately so that the negative-type photosensitive resin composition film is in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature between 50 and 150°C for one minute to several hours.

[0132] When a negative photosensitive resin composition film is used, a protective film, if any, is peeled off, and the negative photosensitive resin composition film is placed opposite a substrate and bonded by thermocompression to obtain a negative photosensitive resin composition film laminated on the substrate. Thermocompression bonding can be performed by a heat press treatment, a heat lamination treatment, a heat vacuum lamination treatment, or the like. The lamination temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, the lamination temperature is preferably 150°C or lower to prevent the negative photosensitive resin composition film from curing during lamination, which would deteriorate the resolution of pattern formation in the exposure and development steps.

[0133] In either case, the substrates used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and circuit components arranged on these substrates. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates; composite copper-clad laminates such as glass nonwoven cloth / epoxy copper-clad laminates; heat-resistant / thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polysulfone resin substrates; and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates; and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit components include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low-dielectric materials containing glass-based materials and / or resins; high-dielectric materials containing resins and high-dielectric-constant inorganic particles; and insulators containing glass-based materials.

[0134] Next, the negative photosensitive resin composition film formed by the above method is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. In the case of a negative photosensitive resin composition film, if the support is made of a material that is transparent to these rays, exposure may be performed without peeling the support from the negative photosensitive resin composition film.

[0135] To form a pattern, after exposure, unexposed areas of the negative photosensitive resin composition coating are removed using a developer. Examples of the developer include aqueous solutions of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, these alkaline aqueous solutions may contain, alone or in combination, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone.

[0136] Development can be carried out by spraying the developer onto the coating surface, puddling the developer onto the coating surface, immersing the coating in the developer, or immersing the coating in the developer and applying ultrasonic waves, etc. The development conditions, such as the development time and the temperature of the developer in the development step, may be any conditions that allow the unexposed areas to be removed and a pattern to be formed.

[0137] After development, it is preferable to carry out a rinsing treatment with water. Here, too, the rinsing treatment may be carried out by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0138] If necessary, a baking treatment may be carried out before development. This may improve the resolution of the developed pattern and increase the tolerance for development conditions. The baking temperature is preferably in the range of 50 to 180°C, more preferably in the range of 60 to 120°C. The baking time is preferably from 5 seconds to several hours.

[0139] After pattern formation, unreacted cationically polymerizable compounds and photocationic polymerization initiators remain in the negative photosensitive resin composition film. Therefore, these may thermally decompose and generate gas during thermocompression bonding or curing. To avoid this, it is preferable to irradiate the entire surface of the negative photosensitive resin composition film after pattern formation with the above-described exposure light to generate acid from the photocationic polymerization initiator. By doing so, the reaction of the unreacted cationically polymerizable compounds proceeds during thermocompression bonding or curing, and the generation of gas due to thermal decomposition can be suppressed.

[0140] After development, a temperature of 150°C to 500°C is applied to promote a thermal crosslinking reaction. Crosslinking can improve heat resistance and chemical resistance. This heat treatment method can be selected by either selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. An example of the former is a method in which heat treatment is performed at 130°C and 200°C for 30 minutes each. An example of the latter is a method in which the temperature is linearly increased from room temperature to 400°C over 2 hours.

[0141] After forming a resin composition pattern on a substrate as described above, another substrate is placed facing the resin composition pattern and thermocompression bonded to the two substrates. Thermocompression bonding can be performed by a heat press treatment, a heat lamination treatment, a thermal vacuum lamination treatment, or the like. The temperature during compression bonding is preferably 60°C or higher in terms of adhesion to the substrate. Furthermore, the temperature during compression bonding is preferably 180°C or lower in order to reduce warping of the substrate after compression bonding.

[0142] If necessary, a temperature of 150°C to 500°C can be applied to the substrates bonded by thermocompression bonding to promote a thermal crosslinking reaction. Crosslinking can improve heat resistance and chemical resistance. This heat treatment method can be the same as the heat treatment after development described above.

[0143] <Cured Film, Semiconductor Device> The cured film of the present invention is obtained by curing the negative photosensitive resin composition of the present invention or the negative photosensitive resin composition film of the present invention. In the present invention, "curing" refers to applying a temperature of 150°C to 500°C to the negative photosensitive resin composition of the present invention or the negative photosensitive resin composition film of the present invention to cause a thermal crosslinking reaction. The cured film of the present invention can be used in electronic components such as semiconductor devices.

[0144] One embodiment of the electronic component of the present invention is an electronic component having the cured film of the present invention. Here, electronic components refer to devices in general that can function by utilizing the properties of semiconductor elements and the like. Electronic components include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these. Electronic components also include multilayer wiring boards for connecting semiconductor elements. The cured film of the present invention is suitable for use in a variety of electronic components. Specifically, the cured film of the present invention is suitable for use in applications such as interlayer insulating films for inductors, passivation films for semiconductors, surface protective films for semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between multiple semiconductor elements, interlayer insulating films between wiring layers in multilayer wiring for high-density packaging, insulating layers for organic electroluminescent elements, interlayer insulating films for probe cards, interlayer insulating films for magnetic sensors, structural components for wavelength-selective filters, and adhesive components for wavelength-selective filters, but is not limited thereto and can be used for a variety of applications.

[0145] Furthermore, the negative photosensitive resin composition of the present invention can bond two substrates by thermocompression bonding another substrate via a resin composition pattern formed on one substrate. That is, one embodiment of the electronic component of the present invention is an electronic component having a structure in which two substrates are bonded via the negative photosensitive resin composition of the present invention. As described above, the negative photosensitive resin composition of the present invention has good resolution and adhesion, so that metals conventionally used as bonding members can be replaced with the negative photosensitive resin composition of the present invention, making it possible to produce small, low-profile electronic components at low cost. After bonding, curing the negative photosensitive resin composition of the present invention yields an electronic component having a structure in which two substrates are bonded via the cured film of the present invention. Examples of electronic components having a structure in which two substrates are bonded include, but are not limited to, semiconductor packages, multilayer wiring boards for high-density mounting, and wavelength-selective filters.

[0146] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0147] <Evaluation of Pattern Processability> A 5 ​​cm square silicon substrate was prepared as a substrate. The protective film of the negative photosensitive resin composition film produced in each of the Examples and Comparative Examples described below was peeled off, and the resin composition film was placed on the substrate so that the peeled surface faced the substrate. Using a vacuum diaphragm laminator (MVLP-500 / 600 manufactured by Meiki Seisakusho Co., Ltd.), lamination was performed under the following conditions: upper and lower heating platen temperature 80°C, evacuation time 20 seconds, vacuum press time 30 seconds, and application pressure 0.5 MPa, to form a resin composition coating with a thickness of 10 μm on the silicon substrate. Subsequently, after peeling the support from the resin composition coating of the resin composition film, a mask having a line and space (L / S) pattern of 5 μm / 5 μm, 10 μm / 10 μm, 15 μm / 15 μm, 20 μm / 20 μm, 25 μm / 25 μm, 30 μm / 30 μm, 40 μm / 40 μm, and 50 μm / 50 μm was set in the exposure device, and exposure was performed using an ultra-high pressure mercury lamp and an i-line bandpass filter under the condition of an exposure gap of 100 μm between the mask and the resin composition coating. After exposure, post-exposure heating was performed on a hot plate at 90 ° C. for 10 minutes. Thereafter, the unexposed portions of the resin composition coating were removed by dip development using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and then rinsed with water. The development time was twice the time until the unexposed portions were completely dissolved.

[0148] The resin composition patterns thus obtained were observed under an optical microscope, and the minimum L / S size when there were no abnormalities such as distortion, clogging, or peeling in the pattern was taken as the resolution. For resin compositions in which abnormalities occurred in all patterns, a value of 0 was recorded in the resolution column.

[0149] <Adhesion Evaluation> Using the same method as in the pattern processability evaluation, the silicon substrate was replaced with a glass substrate, and a resin composition film with a film thickness of 10 μm was formed on the glass substrate. Subsequently, the entire surface of the resin composition film was exposed to light using an ultra-high pressure mercury lamp and an i-line bandpass filter. After exposure, the film was post-exposure baked on a hot plate at 90°C for 10 minutes, and then subjected to dip development using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The exposure dose and development time were the same as those conditions that resulted in the minimum resolution in the above-mentioned pattern processability evaluation.

[0150] A 5 cm square silicon substrate was placed on the developed resin composition film so as to face it, and the substrate was thermocompression bonded using a vacuum diaphragm laminator (MVLP-500 / 600, manufactured by Meiki Seisakusho Co., Ltd.) under the conditions of a vacuuming time of 20 seconds, a vacuum pressing time of 120 seconds, and an application pressure of 0.3 MPa. The temperatures of the upper and lower heating platens were varied to 120°C, 150°C, and 180°C.

[0151] After thermocompression bonding, the bonding surfaces of the resin composition coating and silicon substrate were observed with an optical microscope from the glass substrate side to confirm whether the entire surface was bonded without voids. The heating plate temperature during thermocompression bonding at which bonding without voids was achieved was recorded as the bonding temperature. For resin compositions that generated voids on the bonding surface under all conditions, a "-" was recorded in the bonding temperature column.

[0152] The compounds used in the examples and comparative examples are shown below.

[0153] (A) Cationic Polymerizable Compounds (A1-1) (liquid polyfunctional aromatic glycidyl ether having an epoxy equivalent of 111 g / eq and a viscosity of 400 mPa·s at 25°C) (A1-2) (liquid polyfunctional aromatic glycidyl ether having an epoxy equivalent of 113 g / eq and a viscosity of 112,000 mPa·s at 25°C) (A-1) (polyfunctional aliphatic epoxy compound having an epoxy equivalent of 127 g / eq, corresponding to general formula (1)) (A-2) (polyfunctional aromatic glycidyl ether having an epoxy equivalent of 170 g / eq) (A-3) (polyfunctional aromatic glycidyl amine having an epoxy equivalent of 115 g / eq) (A-4) OGSOL (registered trademark) EG-280 (manufactured by Osaka Gas Chemicals Co., Ltd.) (polyfunctional aromatic glycidyl ether having an epoxy equivalent of 460 g / eq, corresponding to general formula (2))

[0154]

[0155] (B) Photocationic polymerization initiator CPI-310FG (manufactured by San-Apro Co., Ltd.) Silane coupling agent X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0156] Synthesis Example 1 Synthesis of Polyimide (C-1) Under a dry nitrogen stream, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (29.30 g, 0.08 mol) was added to 80 g of γ-butyrolactone (hereinafter referred to as GBL) and dissolved with stirring at 120°C. Next, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, and the white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours to obtain polyimide (C-1).

[0157] Synthesis Example 2 Synthesis of Polyimide (C-2) Polyimide (C-2) was obtained in the same manner as in Synthesis Example 1, except that bis(3-amino-4-hydroxyphenyl)fluorene (hereinafter referred to as FHDA) (26.63 g, 0.07 mol) was used instead of BAHF (29.30 g, 0.08 mol).

[0158] Synthesis Example 3 Synthesis of Polyimide (C-3) Polyimide (C-3) was obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter referred to as BAP) (20.67 g, 0.08 mol) was used instead of BAHF (29.30 g, 0.08 mol).

[0159] Synthesis Example 4 Synthesis of Polyimide (C-4) Polyimide (C-4) was obtained in the same manner as in Synthesis Example 1, except that bis(3-amino-4-hydroxyphenyl)sulfone (hereinafter referred to as ABPS) (22.43 g, 0.08 mol) was used instead of BAHF (29.30 g, 0.08 mol).

[0160] Synthesis Example 5 Synthesis of Polyimide (C-5) Polyimide (C-5) was obtained in the same manner as in Synthesis Example 1, except that 1,3-bis(4-amino-3-hydroxyphenoxy)benzene (hereinafter referred to as AHPB) (22.70 g, 0.07 mol) was used instead of BAHF (29.30 g, 0.08 mol).

[0161] Synthesis Example 6 Synthesis of Polyimide (C-6) Polyimide (C-6) was obtained in the same manner as in Synthesis Example 1, except that 3,5-diaminobenzoic acid (hereinafter referred to as DABA) (7.61 g, 0.05 mol) and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (hereinafter referred to as SiDA) (9.94 g, 0.04 mol) were used instead of BAHF (29.30 g, 0.08 mol).

[0162] Example 1 6 g of epoxy compound (A1-1) as component (A), 0.3 g of CPI-310FG (trade name, manufactured by San-Apro Co., Ltd.) as component (B), 3.5 g of polyimide (C-1) as component (C), and 0.2 g of X-12-967C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent were dissolved in GBL. The amount of solvent added was adjusted so that the solids concentration was 60 mass%, with additives other than the solvent considered to be the solids content. The resulting solution was pressure-filtered using a filter with a retention particle size of 1 μm, to obtain a negative photosensitive resin composition varnish.

[0163] The resulting negative-type photosensitive resin composition varnish was applied to a 50 μm-thick PET film using a comma roll coater and dried at 120°C for 8 minutes. A 30 μm-thick polypropylene (PP) film was then laminated onto the film as a protective film to obtain a negative-type photosensitive resin composition film. The film thickness of the negative-type photosensitive resin composition film was adjusted to 10 μm. The resulting negative-type photosensitive resin composition film was used to evaluate pattern processability, adhesion, and the reaction rate of the cationically polymerizable group, as described above. The results are shown in Table 2.

[0164] Examples 2 to 10 Negative-type photosensitive resin composition films were prepared in the same manner as in Example 1, except that components (A) to (C) and other components were changed to the compounds shown in Table 1. As described above, evaluation of pattern processability, adhesion, and reaction rate of cationically polymerizable groups were performed. The results are shown in Table 2.

[0165] Comparative Examples 1 to 4 Resin composition films were prepared in the same manner as in Example 1, except that components (A) to (C) and other components were changed to compounds having the structures shown in Table 1. As described above, evaluation of pattern processability, adhesion, and reaction rate of cationically polymerizable groups were performed. The results are shown in Table 2.

[0166]

[0167]

[0168]

[0169]

[0170] As is clear from Tables 1 and 2, in Comparative Examples 1 to 4, voids were generated on the adhesive surface under all conditions in the adhesive property evaluation.

[0171] In contrast, the negative photosensitive resin composition of this example was shown to have both excellent resolution and adhesiveness.

[0172] Furthermore, a comparison between Example 1 and Example 2 shows that by including a liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 to 150,000 mPa s at 25°C as component (A1), the adhesiveness is further improved and bonding is possible even under lower temperatures under thermocompression bonding conditions.

[0173] Furthermore, a comparison of Example 5 with Examples 7 and 8 shows that better resolution and adhesion can be obtained by setting the content of the component (A) in the entire negative-type photosensitive resin composition to 45 to 70 mass%.

Claims

1. A negative-type photosensitive resin composition containing a cationic polymerizable compound as component (A) and a cationic photopolymerization initiator as component (B), wherein the component (A) contains a polyfunctional aromatic glycidyl ether as component (A1) having an epoxy equivalent of 80 to 145 g / eq and having at least two epoxy groups in the molecule, and the content of the component (A1) in the entire component (A) is 45 to 100 mass%.

2. A negative type photosensitive resin composition according to claim 1, wherein the content of said component (A) in the entire negative type photosensitive resin composition is 45 to 70 mass %.

3. The negative photosensitive resin composition according to claim 1, wherein the component (A1) contains a liquid polyfunctional aromatic glycidyl ether having a viscosity of 10,000 to 150,000 mPa·s at 25°C.

4. The negative type photosensitive resin composition according to claim 1, wherein the component (A) contains a cationic polymerizable compound selected from the compounds represented by the following general formulas (1) and (2): In the general formula (1), l, m, and n each independently represent an integer of 1 to 6; １ , R ２ each independently represents a divalent organic group.

5. The negative photosensitive resin composition according to claim 1, further comprising at least one polymeric compound selected from the group consisting of polyamides, polyimides and polyamideimides as component (C).

6. The negative type photosensitive resin composition according to claim 5, wherein the component (C) contains a diamine residue derived from a diamine represented by any one of the following general formulas (3) to (7):

7. A negative type photosensitive resin composition coating comprising the negative type photosensitive resin composition according to claim 1.

8. A negative type photosensitive resin composition film comprising the negative type photosensitive resin composition coating according to claim 7 and a support.

9. A cured film obtained by curing the negative type photosensitive resin composition according to claim 1 or the negative type photosensitive resin composition coating according to claim 7.

10. An electronic component having the cured film according to claim 9.

11. An electronic component having a structure in which two substrates are bonded via the cured film according to claim 9.

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