Photosensitive resin compositions, resist laminates, and cured products thereof

Abstract

To provide a photosensitive resin composition that enables the formation of fine patterns, a cured product of which exhibits superior adhesion to a support including metal, and a dry film resist including the composition.SOLUTION: A photosensitive resin composition includes (A) an aromatic imide compound represented by general formula (1), (B) a silicon compound represented by general formula (2), and (C) an epoxy compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition that is useful in the manufacture of MEMS components, micromachine components, microfluidic components, μ-TAS (micro-total analysis system) components, inkjet printhead components, microreactor components, insulating layers for electronic components such as capacitors and inductors, LIGA components, molds and stamps used in micro-injection molding and thermal embossing, screens and stencils for micro-printing applications, MEMS sensors mounted on mobile terminals and IoT components, package components such as semiconductor devices and frequency filter devices, bio-MEMS, biophotonic devices, and printed circuit boards, and is useful in these applications, having excellent resolution and excellent adhesion to a support containing metal parts. [Background technology]

[0002] Photolithographic resists are widely used in semiconductor, MEMS, and micromachine applications. In such applications, lithography using negative photoresists is achieved by selecting a desired exposure area by patterning exposure of the photoresist layer on a substrate, and then developing it with a developer. In recent years, with the miniaturization of information terminal devices that require high-frequency communication, electronic components and semiconductor package components used in these application areas are also becoming smaller and lower profile.

[0003] In these applications, substrates may include not only silicon wafers, which have been commonly used in the past, but also various other types of substrates depending on the application, such as silicon nitride, lithium tantalate, and lithium niovate. In some cases, substrates with support structures such as metal circuit patterns may also be used. Therefore, photoresists are required to have excellent adhesion between their cured product and these substrates and support structures. In addition, in a semiconductor package, when the manufacturing process includes a step of resin-sealing a cured product of a photoresist together with other components, in order to maintain the shape of the cured product during resin-sealing, it is required to have a high elastic modulus at high temperatures.

[0004] Patent Documents 1 to 3 relate to a photosensitive composition excellent in fine line resolution containing a specific epoxy compound and a specific photo cationic polymerization initiator, and it is described that by using a specific adhesion promoter or adhesion assistant in combination, the adhesion of the cured product to the substrate is improved. However, a composition containing an onium salt compound as a photo cationic polymerization initiator and a glycidoxysilane compound as an adhesion-imparting agent has poor adhesion to metals (particularly, copper, aluminum, tantalum, gold, platinum, chromium, etc.), and even if pattern formation by lithography processing is possible, there was a problem that it would easily peel off from the contact points with metals.

[0005] Patent Document 4 describes a photosensitive dry film resist using a specific naphthalimide compound as a photoacid generator, but there is no description regarding the composition of the same document containing an epoxy resin and a specific silicon compound.

Prior Art Documents

Patent Documents

[0006] <000008i>

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition capable of forming a fine pattern and having a cured product excellent in adhesion to a support containing a metal, and a dry film resist using the composition. [Means for Solving the Problems]

[0008] As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by using a photosensitive resin composition containing an aromatic imide compound having a specific structure, a silicon compound having a specific structure, and an epoxy compound, and the present invention has been completed. That is, the present invention [1] (A) The following general formula (1)

[0009] [Chemical formula]

[0010] (In formula (1), R1 represents a fluoroalkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having C1 to C18, a substituted or unsubstituted aryl group having C6 to C20, or a 10-camphyl group. R2 to R7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylthio group having 2 to 10 carbon atoms, or a substituted or unsubstituted aromatic group 。) an aromatic imide compound represented by (B) The following general formula (2)

[0011] [Chemical formula]

[0012] (In formula (2), R 10 to R 15 each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms. R16 and R 17 each independently represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms, and R 16 when there are a plurality of R's, each R 16 may be the same as or different from each other, and when there are a plurality of R's, each R 17 may be the same as or different from each other. X1 and X2 represent sulfur atoms. a and b each represent an integer of 0 or more satisfying the relationship of 1 ≦ a + b ≦ 4.) 17 (The silicon compound represented by , and a photosensitive resin composition containing (C) an epoxy compound ) [2] The photosensitive resin composition according to [1] above, wherein R1 is a fluoroalkyl group having 1 to 8 carbon atoms, and at least one of R3 and R4 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a thioester group, or a substituted or unsubstituted aromatic group, and R2 and R5 to R7 are hydrogen atoms. [3] The photosensitive resin composition according to any one of [1] to [2] above, wherein R 10 to R 15 are each independently a methyl group or an ethyl group. [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein R 16 and R 17 are each independently an alkylene group having 1 to 10 carbon atoms, and a is 1. [5] The photosensitive resin composition according to any one of [1] to [3] above, wherein at least one of R 16 and R 17 is an alkylene group having 1 to 10 carbon atoms, and b is 0. [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein the (C) epoxy compound contains an epoxy compound having two or more epoxy groups in one molecule. [7](C)A photosensitive resin composition according to any one of the preceding paragraphs [1] to [6], wherein the epoxy compound has a softening point of 40 to 120°C and an epoxy equivalent of 100 to 5000 g / eq. [8] A resist laminate or dry film resist obtained by sandwiching a photosensitive resin composition described in any one of the preceding paragraphs [1] to [7] between substrates, and [9] A photosensitive resin composition according to any one of the preceding paragraphs [1] to [7], or a cured product of a dry film resist according to the preceding paragraph [8], Regarding. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a photosensitive resin composition that can form fine patterns, whose cured product does not corrode a metal support provided on a substrate, and which has good adhesion to the metal support, and a dry film resist using the photosensitive resin composition. [Modes for carrying out the invention]

[0014] The following describes embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit it.

[0015] The photosensitive resin composition of the present invention contains (A) an aromatic imide compound represented by the above general formula (1). In formula (1), R1 represents a fluoroalkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a 10-camphayl group. R2 to R7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a thioester group, or a substituted or unsubstituted aromatic group. 。

[0016] The fluoroalkyl group having 1 to 18 carbon atoms represented by R1 in formula (1) is a substituent in which all of the hydrogen atoms of an alkyl group having 1 to 18 carbon atoms are replaced with fluorine atoms, and the structure of the alkyl group is not limited to linear, branched, or cyclic. The fluoroalkyl group having 1 to 18 carbon atoms represented by R1 in formula (1) includes perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoro2-butyl, perfluoro3-butyl, perfluoroisobutyl, perfluoropentyl, perfluoroisopentyl, perfluoro3-pentyl, perfluorohexyl, perfluoro2-hexyl, perfluoro3-hexyl, perfluoroheptyl, and perfluoro2-heptyl groups. Perfluoro-3-heptyl group, perfluoroisoheptyl group, perfluoro-3heptyl group, perfluorooctyl group, perfluoroisooctyl group, perfluoro-3octyl group, perfluoro-2-ethylhexyl group, perfluorononyl group, perfluoroisononyl group, perfluorodecyl group, perfluorododecyl group, perfluorotridecyl group, perfluorotetradecyl group, perfluoropentadecyl group, perfluorohexadecyl group, perfluorohebrotadecyl group, and perfluorooctadecyl group are preferred.

[0017] The aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R1 in formula (1) may be a saturated or unsaturated aliphatic hydrocarbon group, as long as it consists of 1 to 18 carbon atoms and hydrogen atoms, and may be linear, branched, or cyclic, or a combination of linear, branched, and cyclic. Specific examples of aliphatic hydrocarbon groups having 1 to 18 carbon atoms include alkenyl groups such as allyl and 2-propenyl groups, methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, 3-butyl, isobutyl, pentyl, isopentyl, 3-pentyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, 3-heptyl, octyl, isooctyl, 3-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, and pentyl groups. Examples include alkyl groups such as thadecyl, hexadecyl, hebrotadecyl, and octadecyl groups, alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, and adamantyl groups, and substituents that combine the above substituents (for example, 4-methylcyclohexyl group, which combines a methyl group and a cyclohexyl group). The aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R1 in formula (1) includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, 3-butyl group, isobutyl group, pentyl group, isopentyl group, 3-pentyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, and 3- Heptyl group, octyl group, isooctyl group, tertiary octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, bicyclo[2.1.1]hexyl group, bicyclo[2.2.1]heptyl group, bicyclo[3.2.1]octyl group, bicyclo[2.2.2]octyl group, and adamantyl group are preferred.

[0018] Specific examples of the aryl group having 6 to 20 carbon atoms represented by R1 in formula (1) include the phenyl group, naphthyl group, tolyl group, orthoxylyl group, anthracenyl group, and pyrenyl group.

[0019] The aliphatic hydrocarbon group having 1 to 18 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R1 in formula (1) may have substituents. In this specification, for example, "substituted aryl group having 6 to 20 carbon atoms" means an aryl group having 6 to 20 carbon atoms that has known substituents or atoms with a valence of 1 other than hydrogen atoms (in other words, an aryl group in which the hydrogen atoms of the aryl group are replaced with known substituents or atoms with a valence of 1 other than hydrogen atoms), such as the methylphenyl group and the chlorophenyl group. The substituents that the aliphatic hydrocarbon group having 1 to 18 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R1 in formula (1) may have are not particularly limited as long as they are known substituents or atoms with a valence of 1 other than hydrogen atoms, but for example, aliphatic hydrocarbon groups (specific examples are the same as those described in the section on "Aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R1 in formula (1)"), aryl groups (specific examples are the same as those described in the section on "Aryl group having 6 to 20 carbon atoms represented by R1 in formula (1)"), and acyl groups (specific examples include those having the alkyl group described above). Examples include alkylcarbonyl groups and arylcarbonyl groups having the aryl group described above), halogen atoms (specific examples include chlorine atoms, bromine atoms, iodine atoms, and fluorine atoms), C1 to C4 halogenated alkyl groups, C1 to C18 alkoxy groups (specific examples include alkoxy groups in which the alkyl group described above is bonded to an oxygen atom), and C1 to C18 alkylthio groups (specific examples include alkylthio groups in which the alkyl group described above is bonded to a sulfur atom).

[0020] In formula (1), R1 is preferably a fluoroalkyl group having 1 to 18 carbon atoms, more preferably a fluoroalkyl group having 1 to 8 carbon atoms, even more preferably a linear fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a linear fluoroalkyl group having 1 to 4 carbon atoms.

[0021] The alkyl groups having 1 to 10 carbon atoms represented by R2 to R7 in formula (1) may be linear, branched, or cyclic, or a combination of linear, branched, and cyclic. Specific examples of C1-C10 alkyl groups represented by R2 to R7 in formula (1) include C1-C1 to C10 alkyl groups and alicyclic hydrocarbon groups described as specific examples in the section on C1-C18 aliphatic hydrocarbon groups represented by R1 in formula (1), as well as C1-C1 to C10 alkyl groups, and C1-C1 to C10 alkyl groups formed by the aforementioned substituents. The alkyl groups of carbon atoms 1 to 10 represented by R2 to R7 in formula (1) are preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, isooctyl, nonyl, isoninyl, decyl, and isodecyl groups. The hydrogen atoms of the alkyl groups may be substituted with known substituents or atoms other than hydrogen atoms that have a valence of 1.

[0022] The alkenyl groups having 2 to 10 carbon atoms represented by R2 to R7 in formula (1) are aliphatic hydrocarbon groups having one carbon-carbon double bond and containing 2 to 10 carbon atoms, and may be linear, branched, or cyclic. Specific examples of the C2 to C10 alkenyl groups represented by R2 to R7 in formula (1) include ethenyl, propenyl, isopropenyl, butenyl, 2-butenyl, hexenyl, 2-hexenyl, heptenyl, isoheptenyl, octenyl, isooctenyl, nonenyl, isononenyl, decenyl, and isodecenyl groups. The hydrogen atoms of the alkenyl groups may be substituted with known substituents or atoms other than hydrogen atoms that have a valence of 1.

[0023] The alkynyl groups having 2 to 10 carbon atoms represented by R2 to R7 in formula (1) are aliphatic hydrocarbon groups having one carbon-carbon triple bond and containing 2 to 10 carbon atoms, and having at least one triple bond, and may be linear, branched, or cyclic. Specific examples of alkynyl groups having 2 to 10 carbon atoms represented by R2 to R7 in formula (1) include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, pentynyl, hexynyl, isohexynyl, heptynyl, isoheptynyl, octinyl, isooctynyl, noninyl, and desynyl groups. The hydrogen atoms of the alkynyl group may be substituted with known substituents or atoms other than hydrogen atoms with a valence of 1.

[0024] The alkylthio groups having 2 to 10 carbon atoms represented by R2 to R7 in formula (1) are monovalent substituents in which a sulfur atom is bonded to a linear, branched, or cyclic alkyl group having 2 to 10 carbon atoms. Specific examples of the alkyl groups of the alkylthio group include the alkyl groups having 1 to 10 carbon atoms and alicyclic hydrocarbon groups described as specific examples in the section on aliphatic hydrocarbon groups having 1 to 18 carbon atoms represented by R1 in formula (1), as well as alkyl groups having 1 to 10 carbon atoms combined with the aforementioned substituents. Alkylthio groups having linear or branched alkyl groups having 1 to 6 carbon atoms are preferred, and alkylthio groups having linear or branched alkyl groups having 1 to 4 carbon atoms are more preferred.

[0025] The aromatic groups represented by R2 to R7 in formula (1) are residues obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound. Examples include phenyl, biphenyl, trityl, styryl, diphenylvinyl, phenylethynyl, naphthyl, fluorenyl, anthracenyl, and phenanthryl groups. The hydrogen atoms of the aromatic groups may be substituted with known substituents or atoms other than hydrogen with a valence of 1.

[0026] The aromatic groups represented by R2 to R7 in formula (1) may have substituents. The substituents that the aromatic group represented by R2 to R7 in formula (1) may have are not particularly limited as long as they are known substituents or atoms with a valence of 1 other than hydrogen atoms, but include, for example, the same ones described in the section on substituents that the aliphatic hydrocarbon group having 1 to 18 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R1 in formula (1) may have.

[0027] In formula (1), it is preferable that R2 and R5 to R7 are hydrogen atoms, and at least one of R3 and R4 is a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, a thioester group, or a substituted or unsubstituted aromatic hydrocarbon group.

[0028] Aromatic imide compounds represented by formula (1) can be synthesized, for example, by known methods described in Japanese Patent Publication No. 5990447, No. 6211001, No. 6274655, No. 6591699, No. 6505243, No. 6545268, etc.

[0029] The content of (A) aromatic imide compound in the photosensitive resin composition of the present invention is preferably 0.5 to 10.0% by mass, more preferably 1.0 to 7.0% by mass, and even more preferably 2.0 to 5.0% by mass, relative to the content of (C) epoxy compound (described later), and can be used alone or in a mixture of two or more. If the molar extinction coefficient of (A) aromatic imide compound at a wavelength of 300 to 380 nm is high, the amount may be adjusted to an appropriate level depending on the volume and thickness of the photosensitive resin composition used. Furthermore, in the photosensitive resin composition of the present invention, (A) the aromatic imide compound functions as a photopolymerization initiator for copolymerizing (B) the silicon compound (described later) and (C) the epoxy compound.

[0030] The photosensitive resin composition of the present invention contains (B) a silicon compound represented by the above general formula (2). In formula (2), R 10 ~R 15 Each of these independently represents a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, or a substituted or unsubstituted C2 to C10 alkenyl group. 16 and R 17Each of these independently represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms, and R 16 If there are multiple R 16 They may be the same or different from each other, R 17 If there are multiple R 17 X1 and X2 represent sulfur atoms. a and b represent non-negative integers satisfying the relationship 1 ≤ a + b ≤ 4.

[0031] R in equation (2) 10 ~R 15 The alkyl group having 1 to 10 carbon atoms represented by may be linear, branched, or cyclic, or a combination of linear, branched, and cyclic. R in equation (2) 10 ~R 15 Specific examples of the C1 to C10 alkyl group represented by include the C1 to C10 alkyl groups and alicyclic hydrocarbon groups described as specific examples in the section on the C1 to C18 aliphatic hydrocarbon group represented by R1 in formula (1), as well as C1 to C10 alkyl groups and alicyclic hydrocarbon groups, and C1 to C10 alkyl groups that combine the aforementioned substituents.

[0032] R in equation (2) 10 ~R 15 Specific examples of aryl groups having 6 to 10 carbon atoms represented by include phenyl, naphthyl, tolyl, orthoxylyl, anthracenyl, and pyrenyl groups.

[0033] R in equation (2) 10 ~R 15 The C2 to C10 alkenyl group represented by means is the same as the C2 to C10 alkenyl group represented by R2 to R7 in formula (1), and its specific examples and preferred examples are the same as the specific examples and preferred examples of the C2 to C10 alkenyl group represented by R2 to R7 in formula (1).

[0034] R in equation (2) 10 ~R 15The alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the alkenyl group having 2 to 10 carbon atoms represented by may have substituents. R in equation (2) 10 ~R 15 The substituents that the C1-C10 alkyl group, C6-C10 aryl group, and C2-C10 alkenyl group represented by may have are not particularly limited as long as they are known substituents or atoms with a valence of 1 other than hydrogen atoms, but include, for example, the same ones described in the section on substituents that the C1-C1 to C18 aliphatic hydrocarbon group and C6-C20 aryl group represented by R1 in formula (1) may have.

[0035] R in equation (2) 10 ~R 15 As for the group, a methyl group or an ethyl group is preferred, independently of each other.

[0036] R in equation (2) 16 and R 17 The alkylene group represented by is a divalent linking group obtained by removing two hydrogen atoms from an alkane with 1 to 10 carbon atoms. R in equation (2) 16 and R 17 The alkane that can become the alkylene group having 1 to 10 carbon atoms represented by can be linear, branched, or cyclic, as long as it is a saturated hydrocarbon compound consisting only of 1 to 10 carbon atoms and hydrogen atoms, and it can also be a combination of these structures (e.g., a cycloalkane having an alkyl group), and the positions of the two hydrogen atoms removed from the alkane are not particularly limited.

[0037] R in equation (2) 16 and R 17 The alkenylene group represented by is a divalent linking group obtained by removing two hydrogen atoms from an alkene with 2 to 10 carbon atoms. R in equation (2) 16 and R 17The alkenes that can become the C2-C10 alkenylene group represented by can be linear, branched, or cyclic hydrocarbon compounds consisting only of 2-C10 carbon atoms and hydrogen atoms, and having one carbon-carbon double bond. They can also be combinations of these structures (e.g., cycloalkenes with alkyl groups), and the positions from which the two hydrogen atoms are removed from the alkene are not particularly limited.

[0038] R in equation (2) 16 and R 17 The alkynylene group represented by is a divalent linking group obtained by removing two hydrogen atoms from an alkyne with 2 to 10 carbon atoms. R in equation (2) 16 and R 17 The alkynes that can become the alkyline group having 2 to 10 carbon atoms represented by can be linear, branched, or cyclic, as long as they are hydrocarbon compounds consisting only of 2 to 10 carbon atoms and hydrogen atoms and having one carbon-carbon triple bond, and can also have a structure that combines these (for example, a cycloalkyne having an alkyl group), and the positions from which the two hydrogen atoms are removed from the alkyne are not particularly limited.

[0039] R in equation (2) 16 and R 17 Preferably, each of these is an alkylene group having 1 to 10 carbon atoms. In formula (2), it is preferable that a is 1 and b is an integer from 0 to 3, or that a is an integer from 1 to 4 and b is 0.

[0040] The silicon compound represented by formula (2) can be obtained, for example, by reacting a trialkoxysilylmonothiol compound with a trialkoxysilanol compound under reflux stirring with a catalyst, followed by cooling and washing, or by reacting a trialkoxysilane compound with an alkylthiol compound under a catalyst, and then adding a trialkoxysilylmonothiol compound dropwise to further react the compounds.

[0041] In the photosensitive resin composition of the present invention, the content of (B) the silicon compound represented by general formula (2) is preferably 0.2 to 15.0% by mass, more preferably 0.2 to 10.0% by mass, and even more preferably 0.5 to 7.5% by mass, relative to the content of (C) the epoxy compound (described later), and can be used alone or in combination of two or more.

[0042] The photosensitive resin composition of the present invention contains (C) an epoxy compound. (C) The epoxy compound is not particularly limited as long as it is a compound having an epoxy group, but a compound having two or more epoxy groups in one molecule is preferred. (C) Examples of epoxy compounds include novolacs obtained by reacting novolacs, which are produced by reacting phenols (phenol, alkyl-substituted phenols, various bisphenol types, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde under an acidic catalyst, with halohydrins such as epichlorohydrin and methylepichlorohydrin, as well as novolac-type or non-novolac polyfunctional epoxy resins, epoxy compounds obtained by oxidation reactions of olefin-containing compounds, copolymers of glycidyl (meth)acrylate and styrene, and aliphatic glycidyl ethers obtained by reacting aliphatic alcohols with halohydrins.

[0043] (C)Specific examples of epoxy compounds include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-4400H, EPPN-201, EPPN-501, EPPN-502, XD-1000, BREN-S, NER-7604, NER-7403, NER-1302, NER-7516, NC-3000H (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Marproof G-0105SA, G-0130SP, G-0150M, G-1005S, G-2050M (all trade names, manufactured by NOF Corporation), Epicote 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), EHPE3150 (trade name, manufactured by Daicel Corporation), EPON SU-8 (product name, manufactured by Hexion), jER-4007p, jER-4004p, jER-1001, jER-1002, jER-1003, jER-1004, jER-1007, jER-1009 (all product names, manufactured by Mitsubishi Chemical Corporation), diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (manufactured by ADEKA Corporation, ED506), trimethylolpropane triglycidyl ether (manufactured by ADEKA Corporation, ED50 5) Examples include dicyclopentadienyl diglycidyl ether (low chlorine type, manufactured by ADEKA Corporation, EP-4088L), trimethylolpropane triglycidyl ether (low chlorine type, manufactured by Nagase ChemteX Corporation, EX321L), pentaerythritol tetraglycidyl ether, bisphenol F type bifunctional glycidyl ether (manufactured by Nippon Steel Chemical & Material Corporation), and 1,3,5-tris(4,5-epoxypentyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Nissan Chemical Corporation, TEPIC-VL). (C) The epoxy compound may be an epoxy compound alone or a mixture of two or more epoxy compounds.

[0044] (C) The softening point of the epoxy compound is preferably 50 to 120°C. In this specification, the softening point of an epoxy compound refers to a measurement obtained in accordance with the ring-sphere method described in JIS K 7234-1986, and when two or more epoxy compounds are used in mixture, it refers to the softening point of the mixture. (C) By setting the softening point of the epoxy compound to the above preferred range, mask sticking during patterning becomes less likely to occur. Furthermore, when the photosensitive resin composition of the present invention is used as a dry film resist, it is possible to prevent softening at room temperature and improve adhesion to the substrate.

[0045] (C) The epoxy equivalent of the epoxy compound is preferably 100 to 5,000 g / eq. In this specification, the epoxy equivalent of an epoxy compound refers to the measured value obtained in accordance with JIS K 7236:2001. When two or more epoxy compounds are used in mixture, it refers to the epoxy equivalent of the mixture. For example, if a mixture contains 10 parts by mass of an epoxy compound with an epoxy equivalent of 200 g / eq. and 50 parts by mass of an epoxy compound with an epoxy equivalent of 1000 g / eq., the epoxy equivalent of the mixture is (10 parts by mass + 50 parts by mass) / (10 parts by mass ÷ 200 + 50 parts by mass ÷ 1000) = 600 g / eq. (C) By setting the epoxy equivalent of the epoxy compound to the above preferred range, the curing shrinkage rate of the photosensitive resin composition is reduced, making it less likely for the cured product to warp or crack, and the crosslinking density of the photosensitive resin composition is increased, improving the strength, chemical resistance, heat resistance, crack resistance, etc. of the cured film.

[0046] The photosensitive resin composition of the present invention may contain any resin component such as phenolic resin, phenoxy resin, acrylic resin, styrene resin, styrene-butadiene resin, polyethersulfone resin, polycarbonate resin, and caprolactone polyol resin. The amount of any resin component used is not particularly limited as long as it does not impair the effects of the present invention, and therefore cannot be stated in general terms, but a general guideline is preferably 10% by mass or less, more preferably 5% by mass or less, in the solid content of the photosensitive resin composition excluding the solvent.

[0047] The photosensitive resin composition of the present invention may be used in combination with a solvent. The solvent that can be used in combination is not particularly limited, but an organic solvent commonly used in inks and paints that can dissolve each component of the photosensitive resin composition is preferably used. Such organic solvents include ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone; aromatic hydrocarbons such as toluene, xylene, methoxybenzene and tetramethylbenzene; glycol ethers such as diglyme, dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; ethyl lactate, butyl lactate, propyl lactate, ethyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl Examples of solvents include esters such as 3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and propylene glycol monomethyl ether acetate; lactones such as α-acetolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; alcohols such as methanol, ethanol, cellosolve, and methyl cellosolve; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These solvents can be used individually or in combination of two or more. The solvent is added to adjust the film thickness and coatability when applying to the substrate. Considering the solubility of the main component, the volatility of the components, and the viscosity of the composition, the solvent is preferably used in an amount of 95% by mass or less, and more preferably 10 to 90% by mass, in the photosensitive resin composition.

[0048] The photosensitive resin composition of the present invention may optionally contain various additives such as colorants, thickeners, and leveling agents. Examples of colorants include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium dioxide, carbon black, and naphthalene black. Examples of thickeners include olbene, bentonite, and montmorillonite. Examples of leveling agents include silicone-based, fluorine-based, and polymer-based agents. The content of these various additives in the photosensitive resin composition of the present invention is not particularly limited as long as it does not impair the effects of the present invention, and preferably an amount of 30% by mass or less is used in the solid content of the photosensitive resin composition excluding the solvent. The content of the thickener and leveling agent may more preferably be 1% by mass or less in the solid content of the photosensitive resin composition excluding the solvent.

[0049] The photosensitive resin composition of the present invention may further contain, if necessary, inorganic fillers such as barium sulfate, barium titanate, silicon dioxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, or mica powder. The content of these inorganic fillers in the photosensitive resin composition of the present invention is not particularly limited as long as it does not impair the effects of the present invention, and preferably an amount of 60% by mass or less is used in the solid content of the photosensitive resin composition excluding the solvent.

[0050] The photosensitive resin composition of the present invention may further contain a sensitizer to absorb ultraviolet light and provide the absorbed light energy to the photocationic polymerization initiator. Preferred sensitizers include, for example, thioxanthones and anthracene compounds having alkoxy groups at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives). Examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy groups. The 9,10-dialkoxyanthracene derivative may further have substituents. Examples of substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and propyl groups, alkyl sulfonate ester groups, and alkyl carboxylate ester groups. Examples of alkyl groups in alkyl sulfonate ester groups and alkyl carboxylate esters include alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably at the 2nd position.

[0051] Specific examples of thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diisopropylthioxanthone, with 2,4-diethylthioxanthone (trade name Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) and 2-isopropylthioxanthone being preferred.

[0052] Examples of 9,10-dialkoxyanthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester, 9,10-diethoxyanthracene-2-sulfonic acid methyl ester, and 9,10-dimethoxyanthracene-2-carboxylate methyl ester.

[0053] These can be used individually or in combination of two or more, but the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene is most preferred. Since the sensitizer component is effective even in small amounts, its usage ratio is preferably 30% by mass or less, and particularly preferably 20% by mass or less, relative to the (A) aromatic imide compound component.

[0054] The photosensitive resin composition of the present invention is preferably obtained by mixing and dissolving (A) 0.5 to 10 parts by mass of an aromatic imide compound, (B) 0.2 to 15 parts by mass of a silicon compound, (C) 100 parts by mass of an epoxy compound and 5.0 to 2500 parts by mass of a solvent, and optionally adding the adhesion imparter, sensitizer, ion catcher, thermoplastic resin, colorant, thickener, defoamer, leveling agent, or inorganic filler, by stirring in a known manner. If necessary, dispersion and mixing may be carried out using a disperser such as a dissolver, homogenizer, or three-roll mill, and after mixing, the mixture may be further filtered using a mesh, membrane filter, or the like.

[0055] Next, a method for forming a permanent protective film on a substrate using the photosensitive resin composition of the present invention will be described. First, a photosensitive resin composition containing a solvent is applied to a substrate such as a silicon substrate, a substrate with a metal film or metal oxide film such as copper, aluminum, platinum, gold, titanium, chromium, or tantalum, a ceramic substrate such as lithium tantalate, lithium niobate, glass, silicon oxide, silicon nitride, alumina, or sapphire, or a substrate such as polyimide or polyethylene terephthalate, to a thickness of 0.1 to 1000 μm using a spin coater, and the solvent is removed by heat treatment at 60 to 130°C for about 5 to 60 minutes to form a photosensitive resin composition layer. Next, a mask having a predetermined pattern is placed on the photosensitive resin composition layer obtained above, and ultraviolet light is irradiated. After heat treatment (post-exposure baking) is performed at 50 to 130°C for about 1 to 50 minutes, the unexposed areas are developed using a developer at room temperature (e.g., 15°C or higher) to 50°C for about 1 to 180 minutes to form a pattern, and finally, a permanent protective film satisfying various properties can be obtained by heat treatment at 130 to 200°C.

[0056] As the developing solution, for example, organic solvents such as γ-butyrolactone, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a mixture of the above organic solvents can be used. For development, developing devices such as paddle type, spray type, or shower type may be used, and ultrasonic irradiation may be performed as needed. When using the photosensitive resin composition of the present invention, preferred metal substrates include copper and aluminum. The conditions for forming a permanent protective film using the photosensitive resin composition of the present invention are not limited to those described above and can be adjusted as needed.

[0057] The photosensitive resin composition of the present invention can be made into a dry film resist by applying the composition onto a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then removing a predetermined amount of solvent by volatilizing and drying it in a drying oven set at 45 to 100°C, and further laminating a cover film or the like as needed. At this time, the thickness of the dry film resist is preferably adjusted to 2 to 200 μm. For the base film and cover film, films such as polyester, polypropylene, polyethylene, TAC, and polyimide can be used. These films may also be treated with silicone-based or non-silicone-based release agents as needed. To use the dry film resist obtained in this way, for example, the cover film is peeled off, and the dry film resist is transferred to the substrate using a hand roll, laminator, etc., preferably at a temperature of 40 to 100°C and a pressure of 0.05 to 2 MPa. Then, exposure, post-exposure baking, development, and heat treatment are performed in the same manner as in the formation of the permanent protective film. The conditions for forming and using a dry film resist using the photosensitive resin composition of the present invention are not limited to those described above and can be adjusted as needed.

[0058] As described above, by supplying the photosensitive resin composition as a dry film resist, the steps of coating and drying on a support can be omitted, making it possible to more easily form patterns using the photosensitive resin composition of the present invention.

[0059] When used as a MEMS package or semiconductor package, the photosensitive resin composition of the present invention can be used by coating it with the composition or by creating a hollow structure with it. As substrates for MEMS and semiconductor packages, substrates are used in which thin metal films of aluminum, copper, platinum, gold, titanium, chromium, tantalum, etc. are deposited on silicon wafers of various shapes to a thickness of 10 to 5,000 Å by sputtering, vapor deposition, or CVD, and the metal is micro-processed by etching or the like. In some cases, silicon oxide or silicon nitride may also be deposited as an inorganic protective film to a thickness of 10 to 10,000 Å. Next, a MEMS or semiconductor device is fabricated or installed on the substrate, and it is necessary to create a coating or hollow structure to isolate the device from the outside air. When coating with the photosensitive resin composition of the present invention, this can be done by the method described above. When creating a hollow structure, a partition wall is formed on the substrate by the method described above, and then a dry film is laminated on top of it by the method described above and patterned to form a lid on the partition wall, thereby creating a hollow package structure. Furthermore, after fabrication, MEMS package components and semiconductor package components that satisfy various properties can be obtained by heat treatment at 130 to 250°C for 10 to 120 minutes as needed.

[0060] Furthermore, "packaging" refers to a sealing method used to prevent the ingress of gases and liquids from the outside air in order to maintain the stability of substrates, wiring, elements, etc. The packaging described in this invention refers to hollow packages for protecting moving parts such as MEMS, oscillators such as SAW devices and BAW devices, surface protection and resin hermetically sealed packaging performed to prevent deterioration of semiconductor substrates, printed circuit boards, wiring, etc. Furthermore, "wafer-level packaging" refers to a packaging method in which protective film, terminals, wiring processing, and packaging are performed on the wafer before cutting it into chips.

[0061] The photosensitive resin composition of the present invention is useful in the manufacture of MEMS components, micromachine components, microfluidic components, μ-TAS (micro-total analysis system) components, inkjet printhead components, microreactor components, insulating layers for electronic components such as capacitors and inductors, LIGA components, molds and stamps for micro-injection molding and thermal embossing, screens or stencils for micro-printing applications, MEMS sensors mounted in mobile terminals and IoT components, semiconductor devices, frequency filter devices and other package components, bio-MEMS and biophotonic devices, and printed circuit boards. In the examples, "parts" refers to parts by mass, and "%" refers to mass percent. [Examples]

[0062] The present invention will be described in detail below with reference to examples. These examples are merely illustrative to illustrate the present invention and do not limit it in any way.

[0063] Synthesis Example 1 (Synthesis of an aromatic imide compound represented by the following formula (A-1)) 5.0 parts (25.2 mmol) of 1,8-naphthalic anhydride, 24.5 parts (35.3 mmol) of hydroxylammonium chloride, and 50 mL of pyridine were placed in a flask and stirred at 100°C for 15 hours. The reaction solution obtained above was added to 1N hydrochloric acid, the precipitated reaction product was filtered off and washed with water, and then recrystallized with ethanol to obtain 4.36 parts (81.2% yield) of N-hydroxy-1,8-naphthalimide. Next, 0.6 parts (2.5 mmol) of N-hydroxy-1,8-naphthalimide, 1.0 part (2.5 mmol) of nonafluorobutanesulfonic anhydride, and toluene (10 mL) were placed in a flask and stirred at 100°C for 1 hour. The mixture obtained above was washed with a 15% aqueous sodium carbonate solution to separate the aqueous layer from the organic layer. The organic layer was dried over anhydrous magnesium sulfate to remove toluene, and then recrystallized with chloroform to obtain 0.07 parts of nonafluorobutanesulfonic acid-1,8-naphthalimide represented by the following formula (A-1).

[0064] [ka]

[0065] Synthesis Example 2 (Synthesis of an aromatic imide compound represented by the following formula (A-2)) Except for replacing 1.0 part of nonafluorobutanesulfonic acid anhydride with 0.7 parts (2.5 mmol) of trifluoromethanesulfonic acid anhydride, 0.05 parts of difluoromethanesulfonic acid-1,8-naphthalimide, represented by the following formula (A-2), were obtained using the same method as in Synthesis Example 1.

[0066] [ka]

[0067] Synthesis Example 3 (Synthesis of an aromatic imide compound represented by the following formula (A-3)) In a flask, 26.3 parts (94.9 mmol) of 4-bromo-1,8-naphthalic anhydride, 31.99 parts (7.59 mmol) of PPh, 20.17 parts (0.199 mmol) of triethylamine, and 200 mL of THF were added and stirred for 1 hour. Then, under a nitrogen atmosphere, 0.542 parts (2.85 mmol) of CuI and 0.666 parts (0.9492 mmol) of bis(diphenylphosphino)palladium dichloride were added and refluxed. A solution of 10.0 parts (0.1 mol) of 1-hexine dissolved in 0.5 L of THF was then added dropwise. After refluxing the mixture for 14.5 hours, it was cooled to room temperature, 2 mL of water was added, and the precipitated yellow solid was filtered and dissolved in 100 mL of methylene chloride. After washing this solution with 150 mL of water, the crude product was removed from the separated organic layer by evaporation and purified by recrystallization to obtain 20 parts of an intermediate (yield: 70%). Next, 10 parts (35.93 mol) of the intermediate obtained above, 2.55 parts (35.93 mmol) of H2NOH·HCl and 37 parts (0.47 mol) of pyridine were placed in a flask and heated under reflux for 4 hours. After cooling to -13°C and maintaining the temperature below 10°C, 31.0 parts (80 mmol) of nonafluorobutanoic acid anhydride were added dropwise and reacted for 4 hours. 2 L of water was added to the reaction solution obtained above and stirred at room temperature for 1 hour. Then, 13.9 parts of the crude product was removed by filtration and purified by recrystallization to obtain 11.5 parts of an aromatic imide compound represented by the following formula (A-3).

[0068] [ka]

[0069] Synthesis Example 4 (Synthesis of an aromatic imide compound represented by the following formula (A-4)) Except for replacing 10.0 parts of 1-hexine with 13.4 parts of 1-octyne and 31.0 parts of nonafluorobutanoic anhydride with 15.0 parts of trifluoromethaneic anhydride, 10.0 parts of an aromatic imide compound represented by the following formula (A-4) was obtained using the same method as in Synthesis Example 3.

[0070] [ka]

[0071] Synthesis Example 5 (Synthesis of an aromatic imide compound represented by the following formula (A-5)) Except for replacing 10.0 parts of 1-hexine with 9.3 parts of isopropylthiol, the same method as in Synthesis Example 3 was used to obtain 12.0 parts of an aromatic imide compound represented by the following formula (A-5).

[0072] [ka]

[0073] Synthesis Example 6 (Synthesis of an aromatic imide compound represented by the following formula (A-6)) Except for replacing 10.0 parts of 1-octyne with 12.4 parts of phenylacetylene, the same method as in Synthesis Example 4 was used to obtain 11.8 parts of an aromatic imide compound represented by the following formula (A-6).

[0074] [ka]

[0075] Synthesis Example 7 (Synthesis of an aromatic imide compound represented by the following formula (A-7)) In a flask, 500 mL of THF and 4.8 parts (74.3 mmol) of 1-butyllithium were placed, and while stirring, a suspension of 169 parts (750 mmol) of zinc bromide and 600 mL of THF was added dropwise, and the mixture was stirred for 1 hour to prepare the butylzinc reagent. To a mixture of 83.1 parts (300 mmol) of 3-bromonaphthalic anhydride, 3.5 parts (6.00 mmol) of bis(diphenylphosphino)palladium dichloride and 500 mL of THF, 1100 mL of the above butylzinc reagent was added dropwise, and the mixture was stirred at room temperature for 1 hour. 1 L of water was added to this mixture, and the separated organic layer was concentrated. To the resulting solid phase, 500 mL of toluene and 90.0 parts of silica gel were added and stirred, and the solid phase was filtered off to obtain the filtrate. The filtrate was concentrated to obtain a solid phase, to which 350 mL of methanol was added and heated. The solid phase was then filtered off, and the resulting filtrate was cooled to obtain 26.5 parts of crystallized 3-butylnaphthalic anhydride. 5.1 parts (20.0 mmol) of the obtained 3-butylnaphthalic anhydride was suspended in 30 parts of DMF, 1.3 parts (24.0 mmol) of ammonium chloride was added, and 2.00 parts of 48% sodium hydroxide aqueous solution were added dropwise. The mixture was stirred for 3 hours, and then 20.0 parts of dilute hydrochloric acid was added and the mixture was stirred for 1 hour. The solid sample filtered from the reaction solution obtained above was washed with isopropanol and dried to obtain 5.06 parts of hydroxyimide. A mixture of 5.0 parts (10.0 mmol) of this hydroxyimide and 18.9 parts of chloroform was mixed with 1.3 parts (15.9 mmol) of pyridine and cooled to below 2°C. Then, 3.7 parts (13.2 mmol) of trifluoromethanesulfonic anhydride were added and the mixture was stirred for 1 hour. After adding 20 parts of water to the reaction solution obtained above, the separated oil phase was removed, thoroughly washed with water, and concentrated. The precipitated crystals were filtered and dried to obtain 3.06 parts of an aromatic imide compound represented by the following formula (A-7).

[0076] [ka]

[0077] Synthesis Example 8 (Synthesis of an aromatic imide compound represented by the following formula (A-8)) A dispersion of 4.0 parts 3-propylthioacenaphthenequinone in 60 parts methanol was placed in a flask, and under a nitrogen atmosphere, 20 parts potassium peroxymonosulfate (double salt) was added. The mixture was refluxed for one day with stirring, then cooled to room temperature and added to a large amount of water. The resulting solid was filtered and dried under reduced pressure to obtain 3.0 parts of the precursor 2-propylthio-1,8-naphthalic anhydride. A dispersion consisting of 3.0 parts of this precursor 2-propylthio-1,8-naphthalic anhydride, 1.0 part of pyridine, and 47 parts of dichloromethane was cooled on ice, and 3.0 parts of nonafluorobutanesulfonate chloride was added dropwise and the mixture was reacted for 3 hours. The reaction solution obtained above was added to ice-cooled dilute hydrochloric acid and washed three times with water. The extract was concentrated to obtain a light brown solid, which was washed with propanol and dried to obtain 5.1 parts of an aromatic imide compound represented by the following formula (A-8).

[0078] [ka]

[0079] Synthesis Example 9 (Synthesis of silicon compounds represented by the following formula (B-1)) 252 parts of 4-(triethoxysilyl)-1-butanethiol and 138 parts of trimethoxysilanol were placed in a flask, and under stirring, a mixed solution of pure water and concentrated hydrochloric acid as an acid catalyst was added dropwise at 25°C. After refluxing for 1 hour, the mixture was cooled to room temperature. The reaction solution obtained was neutralized with alkali and repeatedly washed with water, then the water was removed by distillation and drying to obtain 350 parts of a silicon compound represented by the following formula (B-1).

[0080] [ka]

[0081] Synthesis Example 10 (Synthesis of silicon compounds represented by the following formula (B-2)) Except for changing the amount of 4-(trimethoxysilyl)-1-butanethiol used from 252 parts to 210 parts and replacing 138 parts of trimethoxysilanol with 180 parts of triethoxysilanol, the same method as in Synthesis Example 9 was used to obtain 380 parts of the silicon compound represented by the following formula (B-2).

[0082] [ka]

[0083] Synthesis Example 11 (Synthesis of a silicon compound represented by the following formula (B-3)) Except for replacing 252 parts of 4-(triethoxysilyl)-1-butanethiol with 200 parts of 4-(diethoxymonomethoxysilyl)-1-butanethiol, the same method as in Synthesis Example 9 was used to obtain 350 parts of the silicon compound represented by the following formula (B-3).

[0084] [ka]

[0085] Synthesis Example 12 (Synthesis of silicon compounds represented by the following formula (B-4)) In a flask, 164 parts of triethoxysilane and 116 parts of 1-hexanethiol were added and stirred at 110°C for 4 hours using a rhodium complex as a catalyst. Then, 154 parts of thiosilicic acid O,O,O-trimethyl ester were added and stirred for another hour. The reaction solution obtained above was repeatedly washed with water, and the water was removed by distillation and drying to obtain 430 parts of a silicon compound represented by the following formula (B-4).

[0086] [ka]

[0087] Synthesis Example 13 (Synthesis of silicon compounds represented by the following formula (B-5)) In a flask, 122 parts of trimethoxysilane and 116 parts of 1-hexanethiol were added and stirred at 110°C for 4 hours using a rhodium complex as a catalyst. Then, 196 parts of thiosilicic acid O,O,O-triethyl ester were added and stirred for a further 1 hour. The reaction solution obtained above was repeatedly washed with water, and the water was removed by distillation and drying to obtain 430 parts of a silicon compound represented by the following formula (B-5).

[0088] [ka]

[0089] Examples 1 to 17, Comparative Examples 1 to 5 (Preparation of photosensitive resin compositions and fabrication of laminates using them) According to the proportions listed in Tables 1 to 4, (A) an aromatic imide compound (or photopolymerization initiator), (B) a silicon compound, (C) an epoxy resin, and other components were stirred, mixed, and dissolved in a flask with a stirrer at 80°C for 1 hour. After cooling, the mixture was filtered through a 0.6 μm pore size filter to obtain the photosensitive resin composition solutions of the present invention and comparative examples. These photosensitive resin composition solutions were uniformly applied to a 30 μm thick polyethylene terephthalate (PET) film (base film, manufactured by Fujimori Kogyo Co., Ltd.) using a coater, dried in a hot air convection dryer at 80°C for 5 minutes and 100°C for 5 minutes, and then the release-treated side of a cover film (release-treated 38 micron thick PET film, manufactured by Mitsubishi Chemical Polyester Films Corporation) was laminated onto the dried coating surface to obtain laminates (dry films) with a photosensitive resin composition layer thickness of 20 μm.

[0090] (Patterning of laminates) The cover films of each laminate obtained in Examples 1 to 17 and Comparative Examples 1 to 5 were peeled off, and using a dry film laminator, the laminates were bonded to the copper-deposited surface of a copper-deposited silicon wafer, an aluminum substrate, and a lithium tantalate substrate at a lamination roll temperature of 40°C, a stage temperature of 40°C, an air pressure of 0.2 MPa, and a roll speed of 0.5 m / min. After the base film was peeled off, a resin layer made of a photosensitive resin composition was provided on the substrate. These resin layers on the substrates were then subjected to a photoresistance of 90 to 1,000 mJ / cm² using a mask aligner (MA-20, manufactured by Mikasa Corporation) via a predetermined resolution shape evaluation pattern photomask. 2 Exposure was performed with the specified irradiation dose (soft contact, ultra-high pressure mercury lamp). The exposed resin layer on the substrate obtained above was subjected to a stepwise post-exposure bake (PEB) using a hot plate at 45°C for 1 minute, then at 65°C for 3 minutes, and then at 100°C for 10 minutes. Subsequently, immersion development was performed using SU-8 Developer (trade name, manufactured by Kayaku Advanced Material Co., Ltd., mainly composed of propylene glycol monomethyl ether acetate) at 23°C for 3 minutes. After rinsing with the same developer and drying, hardened resin patterns were obtained on the substrate.

[0091] (Sensitivity, minimum resolution linewidth, and crack evaluation of photosensitive resin compositions) For the cured resin pattern on the substrate obtained in the "Laminate Patterning" described above, the smallest line-and-space resolution line width (μm) that resolves the pattern of the resolution shape evaluation pattern photomask without peeling, collapse, or bridging is defined as the "minimum resolution," and the exposure dose (mJ / cm²) at that time is defined as follows: 2 ) was defined as "sensitivity". Note that 1,000 mJ / cm 2 Samples that did not form a pattern after irradiation were marked with "×". The results are shown in Tables 1 to 4. Furthermore, the minimum resolution linewidth patterns described above were observed under a microscope, and the cracks were evaluated according to the following evaluation criteria. The results are shown in Tables 1 to 4. (Crack evaluation criteria) ○; No cracks were found at all. △; Cracks had formed on the surface.

[0092] (Evaluation of adhesion of cured photosensitive resin compositions to various substrates) For the cured 100 μm square rectangular prism patterns on the substrate obtained in the "Laminate Patterning" procedure described above, the peel strength (MPa) using a ball shear tool was measured with a shear strength tester (Bonding Tester manufactured by Lesca Corporation), and the adhesion to copper, aluminum, and LT was evaluated according to the following evaluation criteria. The results are shown in Tables 1 to 4. (Evaluation criteria for adhesion) ◎; Those with a shear strength exceeding 25 MPa ○; Share strength was between 15 and 25 MPa ×; Those with a shear strength of less than 15 MPa

[0093] [Table 1]

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] The components used in Examples 1 to 17 and Comparative Examples 1 to 5 are as follows. (A-1) to (A-8): Aromatic imide compounds represented by formulas (A-1) to (A-8) obtained in Synthesis Examples 1 to 8. (a-1): Irgacure290 (product name, manufactured by BASF) (a-2): UVI-6976 (trade name, manufactured by Dow Chemical, a 50% concentration propylene carbonate solution; the amounts in Table 2 are listed on a solid content basis) (a-3): CPI-210S (product name, manufactured by Sunapro Co., Ltd.) (B-1) to (B-5): Silicon compounds represented by formulas (B-1) to (B-5) obtained in synthesis examples 9 to 13. (b-1): KBM-403 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) (C-1): SU-8 Resin (product name, manufactured by Hexion) (C-2):NER-7604 (product name, manufactured by Nippon Kayaku Co., Ltd.) (C-3):NC-3000H (product name, manufactured by Nippon Kayaku Co., Ltd.) (C-4):NC-6300H (product name, manufactured by Nippon Kayaku Co., Ltd.) (C-5):NC-7000L (product name, manufactured by Nippon Kayaku Co., Ltd.) (C-6): EOCN-103S (product name, manufactured by Nippon Kayaku Co., Ltd.) (C-7):XD-1000 (Product name, manufactured by Nippon Kayaku Co., Ltd.) (C-8):LCE-2615 (Product name, manufactured by Nippon Kayaku Co., Ltd.) (C-9): jER-4007p (product name, manufactured by Mitsubishi Chemical Corporation) (C-10): EHPE-3150 (Product name, manufactured by Daicel Corporation) (C-11): EP-4088L (Product name, manufactured by ADEKA) (C-12): TEPIC-VL (product name, manufactured by Nissan Chemical Corporation) (C-13): YDF-8170C (Product name, manufactured by Nippon Steel Chemical & Material Co., Ltd.) (C-14):RE-305S (product name, manufactured by Nippon Kayaku Co., Ltd.) (C-15): EX-321L (product name, manufactured by Nagase ChemteX Corporation) (L-1): Futergent 222F (product name, leveling agent, manufactured by Neos Co., Ltd.) (S-1): Methyl ethyl ketone (general product, solvent) [Industrial applicability]

[0098] According to the present invention, it is possible to provide a photosensitive resin composition that can form fine patterns, whose cured product does not corrode a metal support provided on a substrate, and which has good adhesion to the metal support, and a dry film resist using the photosensitive resin composition.

Claims

1. (A) The following general formula (1) 【Chemistry 1】 (In formula (1), R １ R is a fluoroalkyl group having 1 to 8 carbon atoms. ３ and R ４ Each is independently a hydrogen atom, a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, a C2 to C10 alkylthio group, or a substituted or unsubstituted aromatic group, R ３ and R ４ At least one of them is a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, a C2 to C10 alkylthio group, or a substituted or unsubstituted aromatic group, and R ２ and R ５ ~R ７ (This represents a hydrogen atom.) Aromatic imide compounds represented by (B) General formula (2) 【Chemistry 2】 (In formula (2), R １０ to R １５ each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms. R １６ and R １７ each independently represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms. When there are a plurality of R １６ , each R １６ may be the same as or different from each other. When there are a plurality of R １７ , each R １７ may be the same as or different from each other. X １ and X ２ represent sulfur atoms. a and b each represent an integer of 0 or more that satisfies the relationship 1 ≦ a + b ≦ 4.) Silicon compounds represented by, and (C) Epoxy compound A photosensitive resin composition containing [a specific substance].

2. R １０ ~R １５ The photosensitive resin composition according to claim 1, wherein each of them is independently a methyl group or an ethyl group.

3. R １６ and R １７ The photosensitive resin composition according to claim 1, wherein each of them is an alkylene group having 1 to 10 carbon atoms, and a is 1.

4. R １６ and R １７ The photosensitive resin composition according to any one of claims 1 to 3, wherein at least one of is an alkylene group having 1 to 10 carbon atoms, and b is 0.

5. (C) The photosensitive resin composition according to any one of claims 1 to 3, wherein the epoxy compound comprises an epoxy compound having two or more epoxy groups in one molecule.

6. (C) The photosensitive resin composition according to any one of claims 1 to 3, wherein the epoxy compound comprises an epoxy compound having a softening point of 40 to 120°C and an epoxy equivalent of 100 to 5000 g / eq.

7. (A) The following general formula (1) 【Chemistry 1】 (In formula (1), R １ R represents a fluoroalkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a 10-camphayl group. ２ ~R ７ Each of these independently represents a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C2-C10 alkylthio group, or a substituted or unsubstituted aromatic group. Aromatic imide compounds represented by (B) General formula (2) 【Chemistry 2】 (In formula (2), R １０ ~R １５ Each of these independently represents a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, or a substituted or unsubstituted C2 to C10 alkenyl group. １６ and R １７ Each of these independently represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms, and R １６ If there are multiple R １６ R can be the same or different from each other. １７ If there are multiple R １７ They may be the same or different from each other. X １ and X ２ (where represents a sulfur atom; a and b represent non-negative integers satisfying the relationship 1 ≤ a + b ≤ 4.) Silicon compounds represented by, and (C) Epoxy compound A photosensitive resin composition for MEMS or semiconductor packaging containing the following.

8. R ２ ~R ７ The photosensitive resin composition according to claim 7, wherein all of them are hydrogen atoms.

9. The photosensitive resin composition according to claim 7, wherein the aromatic imide compound is (A-1) or (A-2) as described below. 【Transformation 3】

10. A resist laminate or dry film resist obtained by sandwiching the photosensitive resin composition according to claim 1 or 7 between substrates.

11. A cured product of the photosensitive resin composition according to any one of claims 1 or 7.

12. A cured product of a dry film resist according to claim 10.

Images