Photosensitive resin composition, resist laminate and cured product 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 has excellent resolution and excellent adhesion to supports containing metal portions, and is useful in the production of MEMS parts, micromachine parts, microfluidic parts, μ-TAS (micro total analytical system) parts, inkjet print head parts, microreactor parts, insulating layers for electronic parts such as capacitors and inductors, LIGA parts, molds and stamps used in microinjection molding and hot embossing, screens and stencils for microprinting applications, MEMS sensors mounted on mobile terminals and IoT parts, packaging parts for semiconductor devices, frequency filter devices and the like, bioMEMS, biophotonic devices, and printed wiring boards. [Background technology]

[0002] Photolithographically processable resists are widely used in semiconductor, MEMS, and micromachine applications, etc. In such applications, lithographic processing with negative photoresists is achieved by subjecting a photoresist layer on a substrate to a patterned exposure to select the desired exposure area, followed by development with a developer. In recent years, as information terminal devices that require high-frequency communication become smaller, the electronic components and semiconductor package components used in these application fields are becoming smaller and thinner.

[0003] The substrates used in these applications are not limited to the conventionally commonly used silicon wafers, but various types of substrates may be used depending on the application, such as silicon nitride, lithium tantalate, lithium niobate, etc., and substrates provided with a supported body such as a metal circuit pattern may also be used. Therefore, the cured photoresist is required to have excellent adhesion to these substrates and supported bodies. Furthermore, in the case of semiconductor packages, when the manufacturing process includes a step of resin-sealing the cured photoresist together with other components, a high elastic modulus at high temperatures is required so that the shape of the cured product is maintained during resin sealing.

[0004] Patent Documents 1 to 3 relate to photosensitive compositions with excellent fine-line resolution that contain a specific epoxy compound and a specific cationic photopolymerization initiator, and state that the use of a specific adhesion promoter or adhesion aid improves the adhesion of the cured product to the substrate. However, compositions that contain an onium salt compound as the cationic photopolymerization initiator and a glycidoxysilane compound as the adhesion promoter have poor adhesion to metals (particularly copper, aluminum, tantalum, gold, platinum, chromium, etc.), and although pattern formation by lithography is possible, there is a problem in that the composition easily peels off from the point of contact with the metal.

[0005] Patent Document 4 describes a photosensitive dry film resist using a specific naphthalimide compound as a photoacid generator, but does not mention that the composition contains an epoxy resin and a specific silicon compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4691047 [Patent Document 2] Patent No. 5872470 [Patent Document 3] Patent No. 6205522 [Patent Document 4] Patent No. 6691203 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition that can form a fine pattern and that has excellent adhesion to a metal-containing support when cured, and a dry film resist using the composition. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that the above-mentioned 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 have thus completed the present invention. That is, the present invention [1] (A) the following general formula (1)

[0009] [ka]

[0010] (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-camphoryl 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, except for the case where all of R2 to R7 are hydrogen atoms), (B) the following general formula (2)

[0011] [ka]

[0012] (In formula (2), R 10 ~R 15 R 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.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; R 16 If there are multiple R 16 may be the same or different, and R 17 If there are multiple R 17 may be the same or different. X1 and X2 represent a sulfur atom. a and b each represent an integer of 0 or more satisfying the relationship 1≦a+b≦4. Silicon compounds represented by the formula: (C) Epoxy compound A photosensitive resin composition comprising: [2] The photosensitive resin composition according to the above item [1], wherein R1 is a fluoroalkyl group having 1 to 8 carbon atoms, 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]R 10 ~R 15 the photosensitive resin composition according to the above item [1] or [2], wherein each of the groups independently represents a methyl group or an ethyl group; [4]R 16 and R 17 the photosensitive resin composition according to any one of items [1] to [3] above, wherein each independently represents an alkylene group having 1 to 10 carbon atoms, and a is 1; [5]R 16 and R 17 the photosensitive resin composition according to any one of the above items [1] to [3], wherein at least one of the following 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 (C) the epoxy compound contains an epoxy compound having two or more epoxy groups in one molecule. [7] The photosensitive resin composition according to any one of [1] to [6] above, wherein (C) the epoxy compound contains an epoxy compound having a softening point of 40 to 120°C and an epoxy equivalent of 100 to 5000 g / eq.; [8] A resist laminate or a dry film resist obtained by sandwiching the photosensitive resin composition according to any one of the preceding items [1] to [7] between substrates; and [9] A photosensitive resin composition according to any one of the preceding items [1] to [7], or a cured product of the dry film resist according to the preceding item [8]. Regarding. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a photosensitive resin composition that can form a fine pattern, the cured product of which does not corrode a metal supported body provided on a substrate, and has good adhesion to a metal supported body, and a dry film resist using the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described. Note that the present embodiment is an example for explaining the present invention, and is not intended to limit the present invention.

[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-camphoryl 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, except for the case where all of R2 to R7 are hydrogen atoms.

[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 have been replaced with fluorine atoms, and the structure of the alkyl group is not limited to any of linear, branched, and cyclic. Examples of the fluoroalkyl group having 1 to 18 carbon atoms represented by R1 in formula (1) include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoroisobutyl group, a perfluoropentyl group, a perfluoroisopentyl group, a perfluorotert-pentyl group, a perfluorohexyl group, a perfluoro2-hexyl group, a perfluoro3-hexyl group, a perfluoroheptyl group, and a perfluoro2-heptyl group. , perfluoro-3-heptyl group, perfluoroisoheptyl group, perfluoro-tert-heptyl group, perfluorooctyl group, perfluoroisooctyl group, perfluoro-tert-octyl 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 aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, as long as it contains 1 to 18 carbon atoms and a hydrogen atom, and may be linear, branched, or cyclic, or may be a combination of linear, branched, and cyclic. Specific examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms include alkenyl groups such as allyl and 2-propenyl groups, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentyl ... propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, propyl, 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-mentioned substituents (for example, a 4-methylcyclohexyl group that combines a methyl group and a cyclohexyl group). Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R1 in formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isohept ... 2-heptyl group, a 3-heptyl group, a 3-pentyl group, a 2-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a 2-pentyl group, a Heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, 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 are preferred.

[0018] Specific examples of the aryl group having 6 to 20 carbon atoms represented by R1 in formula (1) include a phenyl group, a naphthyl group, a tolyl group, an orthoxyl group, an anthracenyl group, and a 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 a substituent. In this specification, for example, an "aryl group having 6 to 20 carbon atoms and having a substituent" means an aryl group having 6 to 20 carbon atoms and having a known substituent or an atom other than a hydrogen atom with a valence of 1 (in other words, an aryl group in which a hydrogen atom of an aryl group has been replaced with a known substituent or an atom other than a hydrogen atom with a valence of 1), and examples of this include a methylphenyl group and a chlorophenyl group. The substituent that may be possessed by 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) is not particularly limited as long as it is a known substituent or an atom other than a hydrogen atom and has a valence of 1. Examples of the substituent include an aliphatic hydrocarbon group (specific examples are the same as those described in the section "Aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R1 in formula (1)"), an aryl group (specific examples are the same as those described in the section "Aryl group having 6 to 20 carbon atoms represented by R1 in formula (1)"), an acyl group (specific examples are those having the above-mentioned alkyl groups), and arylcarbonyl groups having the above-mentioned aryl groups), halogen atoms (specific examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom), halogenated alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 18 carbon atoms (specific examples include the above-mentioned alkoxy groups in which an alkyl group and an oxygen atom are bonded), and alkylthio groups having 1 to 18 carbon atoms (specific examples include the above-mentioned alkylthio groups in which an alkyl group and a sulfur atom are bonded).

[0020] R1 in formula (1) is preferably a fluoroalkyl group having 1 to 18 carbon atoms, more preferably a fluoroalkyl group having 1 to 8 carbon atoms, still more preferably a straight-chain fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a straight-chain fluoroalkyl group having 1 to 4 carbon atoms.

[0021] The alkyl group having 1 to 10 carbon atoms represented by R2 to R7 in formula (1) may be any of linear, branched, and cyclic, or may be a combination of linear, branched, and cyclic. Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R2 to R7 in formula (1) include the alkyl groups and alicyclic hydrocarbon groups having 1 to 10 carbon atoms described as specific examples in the section on the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R1 in formula (1), and alkyl groups having 1 to 10 carbon atoms in combination with the above-mentioned substituents. The alkyl group having 1 to 10 carbon atoms represented by R2 to R7 in formula (1) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, an isooctyl group, a nonyl group, an isoninyl group, a decyl group, or an isodecyl group. The hydrogen atom of the alkyl group may be substituted with a known substituent or an atom other than a hydrogen atom having a valence of one.

[0022] The alkenyl group having 2 to 10 carbon atoms represented by R2 to R7 in formula (1) is an aliphatic hydrocarbon group having one carbon-carbon double bond and containing 2 to 10 carbon atoms, and may be linear, branched, or cyclic. Specific examples of the alkenyl group having 2 to 10 carbon atoms 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, isodecenyl, etc. The hydrogen atom of the alkenyl group may be substituted with a known substituent or an atom other than a hydrogen atom having a valence of one.

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

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

[0025] The aromatic group represented by R2 to R7 in formula (1) is a residue obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound, and examples thereof include a phenyl group, a biphenyl group, a trityl group, a styryl group, a diphenylvinyl group, a phenylethynyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group, etc. The hydrogen atom of the aromatic group may be substituted with a known substituent or an atom other than a hydrogen atom having a valence of one.

[0026] The aromatic groups represented by R2 to R7 in formula (1) may have a substituent. The substituent that may be possessed by the aromatic group represented by R2 to R7 in formula (1) is not particularly limited as long as it is a known substituent or an atom other than a hydrogen atom having a valence of one, and examples thereof include the same substituents as those described in the section on the substituent that may be possessed by 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).

[0027] With respect to R2 to R7 in formula (1), it is preferable that R2 and R5 to R7 are hydrogen 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 hydrocarbon group.

[0028] The aromatic imide compound represented by formula (1) can be synthesized in accordance with known methods described in, for example, Japanese Patent No. 5990447, Japanese Patent No. 6211001, Japanese Patent No. 6274655, Japanese Patent No. 6591699, Japanese Patent No. 6505243, Japanese Patent No. 6545268, etc.

[0029] The content of the aromatic imide compound (A) in the photosensitive resin composition of the present invention is preferably 0.5 to 10.0 mass %, more preferably 1.0 to 7.0 mass %, and even more preferably 2.0 to 5.0 mass %, relative to the content of the epoxy compound (C) (described later), and these compounds may be used alone or in combination. When the aromatic imide compound (A) has a high molar absorption coefficient at a wavelength of 300 to 380 nm, the amount may be adjusted appropriately depending on the volume and thickness of the photosensitive resin composition when used. In the photosensitive resin composition of the present invention, the (A) aromatic imide compound functions as a photopolymerization initiator for copolymerizing the (B) silicon compound (described below) and the (C) 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 R 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. 16 and R 17each 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; R 16 If there are multiple R 16 may be the same or different, and R 17 If there are multiple R 17 may be the same or different. X1 and X2 represent a sulfur atom. a and b each represent an integer of 0 or more that satisfies 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 any of linear, branched, and cyclic, and may be a combination of linear, branched, and cyclic. R in Equation (2) 10 ~R 15 Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R include the alkyl groups and alicyclic hydrocarbon groups having 1 to 10 carbon atoms described as specific examples in the section on the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R in formula (1), and alkyl groups having 1 to 10 carbon atoms in combination with the above-mentioned substituents.

[0032] R in Equation (2) 10 ~R 15 Specific examples of the aryl group having 6 to 10 carbon atoms represented by the formula (I) include a phenyl group, a naphthyl group, a tolyl group, an orthoxyl group, an anthracenyl group, and a pyrenyl group.

[0033] R in Equation (2) 10 ~R 15 The alkenyl group having 2 to 10 carbon atoms represented by R2 to R7 in formula (1) means the same as the alkenyl group having 2 to 10 carbon atoms represented by R2 to R7 in formula (1), and specific examples and preferred examples thereof are also the same as the specific examples and preferred examples of the alkenyl group having 2 to 10 carbon atoms 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 the formula (I) may have a substituent. R in Equation (2) 10 ~R 15 The substituent that the 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 R1 in formula (1) may have is not particularly limited as long as it is a known substituent or an atom other than a hydrogen atom having a valence of one, and examples thereof include the same substituents as those described in the section on the substituent 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.

[0035] R in Equation (2) 10 ~R 15 are each independently preferably a methyl group or an ethyl group.

[0036] R in Equation (2) 16 and R 17 The alkylene group having 1 to 10 carbon atoms represented by the formula (I) is a divalent linking group formed by removing two hydrogen atoms from an alkane having 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 the formula (I) may be linear, branched, or cyclic, or may have a structure combining these (for example, a cycloalkane having an alkyl group), as long as it is a saturated hydrocarbon compound consisting of only 1 to 10 carbon atoms and hydrogen atoms, and the positions at which the two hydrogen atoms are removed from the alkane are not particularly limited.

[0037] R in Equation (2) 16 and R 17 The alkenylene group having 2 to 10 carbon atoms represented by the formula (I) is a divalent linking group formed by removing two hydrogen atoms from an alkene having 2 to 10 carbon atoms. R in Equation (2) 16 and R 17The alkene that can become the alkenylene group having 2 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, or may have a structure combining these (for example, a cycloalkene having an alkyl group) as long as it is a hydrocarbon compound consisting of only 2 to 10 carbon atoms and hydrogen atoms and having one carbon-carbon double bond, and the positions at 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 having 2 to 10 carbon atoms represented by the formula (I) is a divalent linking group formed by removing two hydrogen atoms from an alkyne having 2 to 10 carbon atoms. R in Equation (2) 16 and R 17 The alkyne that can become the alkynylene group having 2 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, or may have a structure combining these (for example, a cycloalkyne having an alkyl group) as long as it is a hydrocarbon compound consisting of only 2 to 10 carbon atoms and hydrogen atoms and having one carbon-carbon triple bond, and the positions at which the two hydrogen atoms are removed from the alkyne are not particularly limited.

[0039] R in Equation (2) 16 and R 17 are each independently preferably an alkylene group having 1 to 10 carbon atoms. As for a and b in formula (2), it is preferable that a is 1 and b is an integer of 0 to 3, or a is an integer of 1 to 4 and b is 0.

[0040] The silicon compound represented by formula (2) can be obtained, for example, by a method in which a trialkoxysilyl monothiol compound and a trialkoxysilanol compound are reacted under reflux with stirring in the presence of a catalyst, and the reaction mixture is allowed to cool and then washed; or by a method in which a trialkoxysilane compound and an alkylthiol compound are reacted in the presence of a catalyst, and then a trialkoxysilyl monothiol compound is added dropwise to cause further reaction.

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

[0042] The photosensitive resin composition of the present invention contains (C) an epoxy compound. The epoxy compound (C) 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. Examples of (C) epoxy compounds include novolak or non-novolak polyfunctional epoxy resins obtained by reacting novolaks obtained by reacting phenols (phenol, alkyl-substituted phenols, various bisphenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde in the presence of an acid catalyst with halohydrins such as epichlorohydrin and methylepichlorohydrin; 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] Specific examples of the epoxy compound (C) 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, and NC-3000H (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Marproof G-0105SA, G-0130SP, G-0150M, G-1005S, and G-2050M (all trade names, manufactured by NOF Corporation), Epikote 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), EHPE3150 (trade name, manufactured by Daicel Corporation), and EPON SU-8 (trade name, manufactured by Hexion), jER-4007p, jER-4004p, jER-1001, jER-1002, jER-1003, jER-1004, jER-1007, jER-1009 (all trade 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), 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 Co., Ltd.), 1,3,5-tris(4,5-epoxypentyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Nissan Chemical Industries, Ltd., TEPIC-VL), etc. (C) The epoxy compound may be a single epoxy compound or a mixture of two or more epoxy compounds.

[0044] The softening point of the epoxy compound (C) is preferably 50 to 120°C. The softening point of the epoxy compound in this specification means a measured value obtained in accordance with the ring and ball method described in JIS K 7234-1986, and when two or more epoxy compounds are used in combination, it means the softening point of the mixture. By setting the softening point of the (C) epoxy compound within the above preferred range, mask sticking during patterning is less likely to occur. Furthermore, when the photosensitive resin composition of the present invention is used as a dry film resist, softening at room temperature is prevented and the adhesiveness to the substrate is improved.

[0045] The epoxy equivalent of the (C) epoxy compound is preferably 100 to 5,000 g / eq. In this specification, the epoxy equivalent of an epoxy compound refers to a measured value obtained in accordance with JIS K 7236:2001, and when two or more epoxy compounds are used in combination, it refers to the epoxy equivalent of the mixture. For example, when 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. By setting the epoxy equivalent of the (C) epoxy compound within the above preferred range, the cure shrinkage rate of the photosensitive resin composition is reduced, making the cured product less likely to warp or crack, and the crosslink density of the photosensitive resin composition is increased, resulting in improved 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 a phenol resin, a phenoxy resin, an acrylic resin, a styrene resin, a styrene-butadiene resin, a polyethersulfone resin, a polycarbonate resin, or a caprolactone polyol resin. The amount of these optional resin components used is not particularly limited as long as it does not impair the effects of the present invention, and therefore cannot be generalized. As a rough guide, however, the amount is preferably 10% by mass or less, and more preferably 5% by mass or less, of 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 organic solvents that are commonly used in inks, paints, etc. and that can dissolve each component of the photosensitive resin composition are preferably used. Examples of 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 suitable solvents include esters such as butyl-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 solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These solvents can be used alone or in combination of two or more. The solvent is added for the purpose of adjusting the film thickness and coatability when applied to a substrate, and is preferably used in an amount of 95% by mass or less, more preferably 10 to 90% by mass, in the photosensitive resin composition, taking into consideration the solubility of the main components, the volatility of the components, the liquid viscosity of the composition, etc.

[0048] The photosensitive resin composition of the present invention may contain various additives such as colorants, thickeners, and leveling agents, if necessary. Examples of colorants include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of thickeners include orben, bentone, 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 is preferably used in an amount that is 30 mass % or less based on the solid content of the photosensitive resin composition excluding the solvent. The content of the thickener and leveling agent may more preferably be used so that it is 1 mass % or less based on 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, an inorganic filler such as barium sulfate, barium titanate, silicon oxide, 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 is within a range that does not impair the effects of the present invention, and is preferably used in an amount that is 60 mass % or less of 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 examples of sensitizers include thioxanthones and anthracene compounds having alkoxy groups at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives). Examples of the alkoxy groups include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy. The 9,10-dialkoxyanthracene derivatives may further contain a substituent. Examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl; sulfonic acid alkyl ester groups; and carboxylic acid alkyl ester groups. Examples of the alkyl in the sulfonic acid alkyl ester group and carboxylic acid alkyl ester group include alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

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

[0052] Examples of the 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-carboxylic acid methyl ester.

[0053] These can be used alone or in combination, but 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene are most preferred. Because the sensitizer component is effective in small amounts, its use ratio is preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the (A) aromatic imide compound component.

[0054] The photosensitive resin composition of the present invention can be obtained by blending preferably 0.5 to 10 parts by mass of (A) an aromatic imide compound, 0.2 to 15 parts by mass of (B) a silicon compound, 100 parts by mass of (C) an epoxy compound, and 5.0 to 2500 parts by mass of a solvent, and optionally the adhesion promoter, sensitizer, ion catcher, thermoplastic resin, colorant, thickener, antifoaming agent, leveling agent, or inorganic filler, and then stirring and dissolving the blend by a known method. If necessary, the blend may be dispersed and mixed using a dispersing machine such as a dissolver, homogenizer, or three-roll mill, or the blend 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 a metal oxide film of copper, aluminum, platinum, gold, titanium, chromium, tantalum, or the like, a ceramic substrate of lithium tantalate, lithium niobate, glass, silicon oxide, silicon nitride, alumina, sapphire, or a substrate of polyimide or polyethylene terephthalate, using a spin coater, to a thickness of 0.1 to 1000 μm, 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. Heat treatment (post-exposure bake) is performed at 50 to 130°C for about 1 to 50 minutes. Thereafter, 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. Finally, heat treatment is performed at 130 to 200°C, thereby obtaining a permanent protective film that satisfies various properties.

[0056] As the developer, for example, an organic solvent such as γ-butyrolactone, triethylene glycol dimethyl ether, or propylene glycol monomethyl ether acetate, or a mixture of the above organic solvents, can be used. A developing device such as a paddle type, spray type, or shower type may be used for development, and ultrasonic irradiation may be performed as necessary. Preferred metal substrates for use with the photosensitive resin composition of the present invention 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 appropriately as necessary.

[0057] The photosensitive resin composition of the present invention can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, or the like, and then a predetermined amount of solvent is evaporated and dried in a drying oven set at 45 to 100° C., and a cover film or the like is further laminated, if necessary, to form a dry film resist. In this case, the thickness of the dry film resist is preferably adjusted to 2 to 200 μm. The base film and cover film may be made of, for example, polyester, polypropylene, polyethylene, TAC, polyimide, etc. These films may be treated with a release agent such as a silicone-based release agent or a non-silicone-based release agent, if necessary. To use the dry film resist obtained in this manner, for example, the cover film is peeled off, and the dry film resist is transferred to a substrate using a hand roll, a laminator, or the like, preferably at a temperature of 40 to 100°C and a pressure of 0.05 to 2 MPa, and then exposed, post-exposure baked, developed, and heat-treated 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 mentioned above, and can be adjusted appropriately as needed.

[0058] As described above, if the photosensitive resin composition is supplied as a dry film resist, the steps of coating on a support and drying can be omitted, and pattern formation using the photosensitive resin composition of the present invention can be more easily performed.

[0059] When used as MEMS packages and semiconductor packages, the photosensitive resin composition of the present invention can be used by coating or forming a hollow structure. Substrates for MEMS and semiconductor packages include substrates in which a thin metal film of aluminum, copper, platinum, gold, titanium, chromium, tantalum, or the like is formed to a thickness of 10 to 5,000 Å on a silicon wafer of various shapes by sputtering, vapor deposition, or CVD, and then the metal is microfabricated by etching or other methods. In some cases, an inorganic protective film of silicon oxide or silicon nitride may be further formed to a thickness of 10 to 10,000 Å on the substrate. A MEMS or semiconductor device is then fabricated or installed on the substrate, and a coating or hollow structure must be created to isolate the device from the outside air. Coating with the photosensitive resin composition of the present invention can be performed using the method described above. Alternatively, a hollow package structure can be fabricated by forming a partition wall on the substrate using the method described above, and then laminating a dry film on top of the partition wall and patterning it to form a lid, using the method described above. After production, if necessary, a heat treatment can be carried out at 130 to 250° C. for 10 to 120 minutes, thereby making it possible to obtain MEMS package components and semiconductor package components that satisfy various characteristics.

[0060] The term "packaging" refers to a sealing method used to block the intrusion of external gases and liquids in order to maintain the stability of substrates, wiring, elements, etc. The packaging described in this invention refers to hollow packages for protecting devices with driving parts such as MEMS, or resonators such as SAW devices and BAW devices, as well as surface protection and resin airtight sealing performed to prevent deterioration of semiconductor substrates, printed wiring boards, wiring, etc. Furthermore, "wafer-level packaging" refers to a packaging method in which a protective film, terminals, wiring processing, and packaging are performed on a wafer, and then the wafer is cut into chips.

[0061] The photosensitive resin composition of the present invention is useful in the production of MEMS parts, micromachine parts, microfluidic parts, μ-TAS (micro total analytical system) parts, inkjet print head parts, microreactor parts, insulating layers for electronic parts such as capacitors and inductors, LIGA parts, molds and stamps for microinjection molding and hot embossing, screens or stencils for microprinting applications, packaging parts such as MEMS sensors, semiconductor devices, and frequency filter devices mounted on mobile terminals and IoT parts, bioMEMS and biophotonic devices, and printed wiring boards. In the examples, "parts" means parts by mass, and "%" means % by mass. [Example]

[0062] The present invention will be described in more detail below with reference to examples. These examples are merely illustrative examples for suitably explaining the present invention, and are not intended to limit the present invention in any way.

[0063] Synthesis Example 1 (Synthesis of aromatic imide compound represented by the following formula (A-1)) A flask was charged with 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, and the mixture was stirred at 100°C for 15 hours. The reaction solution obtained above was poured into 1N hydrochloric acid, and the precipitated reaction product was collected by filtration, washed with water, and then recrystallized using ethanol to obtain 4.36 parts of N-hydroxy-1,8-naphthalimide (yield 81.2%). 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 charged to the flask and the mixture was 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 the toluene, and then recrystallized from 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 aromatic imide compound represented by the following formula (A-2)) 0.05 parts of trifluoromethanesulfonic acid-1,8-naphthalimide represented by the following formula (A-2) was obtained in the same manner as in Synthesis Example 1, except that 1.0 parts of nonafluorobutanesulfonic anhydride was changed to 0.7 parts (2.5 mmol) of trifluoromethanesulfonic anhydride.

[0066] [ka]

[0067] Synthesis Example 3 (Synthesis of aromatic imide compound represented by the following formula (A-3)) A flask was charged with 26.3 parts (94.9 mmol) of 4-bromo-1,8-naphthalic anhydride, 1.99 parts (7.59 mmol) of PPh3, 20.17 parts (0.199 mmol) of triethylamine, and 200 mL of THF. The mixture was stirred for 1 hour, and then 0.542 parts (2.85 mmol) of CuI and 0.666 parts (0.9492 mmol) of bis(diphenylphosphino)palladium dichloride were added under a nitrogen atmosphere and refluxed. A solution of 10.0 parts (0.1 mol) of 1-hexyne dissolved in 0.5 L of THF was added dropwise. The mixture was refluxed for 14.5 hours, cooled to room temperature, and 2 mL of water was added. The precipitated yellow solid was collected by filtration and dissolved in 100 mL of methylene chloride. This solution was washed with 150 mL of water, and then the separated organic layer was evaporated to remove a crude product. This crude product was then 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 HNOH·HCl, and 37 parts (0.47 mol) of pyridine were placed in a flask and heated under reflux for 4 hours. The mixture was then cooled to -13°C, and 31.0 parts (80 mmol) of nonafluorobutanoic anhydride was added dropwise while maintaining the temperature below 10°C, and the mixture was allowed to react for 4 hours. 2 L of water was added to the reaction mixture obtained above, and the mixture was stirred at room temperature for 1 hour. After that, 13.9 parts of the crude product were removed by filtration and purified by recrystallization to obtain 11.5 parts of an aromatic imide compound represented by formula (A-3):

[0068] [ka]

[0069] Synthesis Example 4 (Synthesis of aromatic imide compound represented by the following formula (A-4)) 10.0 parts of an aromatic imide compound represented by the following formula (A-4) was obtained in the same manner as in Synthesis Example 3, except that 10.0 parts of 1-hexyne was changed to 13.4 parts of 1-octyne and 31.0 parts of nonafluorobutanoic anhydride was changed to 15.0 parts of trifluoromethane anhydride.

[0070] [ka]

[0071] Synthesis Example 5 (Synthesis of aromatic imide compound represented by the following formula (A-5)) 12.0 parts of an aromatic imide compound represented by the following formula (A-5) was obtained in the same manner as in Synthesis Example 3, except that 10.0 parts of 1-hexyne was changed to 9.3 parts of isopropylthiol.

[0072] [ka]

[0073] Synthesis Example 6 (Synthesis of aromatic imide compound represented by the following formula (A-6)) 11.8 parts of an aromatic imide compound represented by the following formula (A-6) were obtained in the same manner as in Synthesis Example 4, except that 10.0 parts of 1-octyne was changed to 12.4 parts of phenylacetylene.

[0074] [ka]

[0075] Synthesis Example 7 (Synthesis of aromatic imide compound represented by the following formula (A-7)) A flask was charged with 500 mL of THF and 4.8 parts (74.3 mmol) of 1-butyllithium. A suspension of 169 parts (750 mmol) of zinc bromide in 600 mL of THF was added dropwise with stirring and stirred for 1 hour to prepare the butylzinc reagent. 1100 mL of the above butylzinc reagent was added dropwise 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 and stirred at room temperature for 1 hour. 1 L of water was added to the mixture, and the separated organic layer was concentrated. 500 mL of toluene and 90.0 parts of silica gel were added to the resulting solid phase and stirred. The solid phase was then filtered to obtain a filtrate. The filtrate was concentrated, and 350 mL of methanol was added to the resulting solid phase. The mixture was then heated. The solid phase was 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 resulting 3-butylnaphthalic anhydride was suspended in 30 parts of DMF, to which 1.3 parts (24.0 mmol) of ammonium chloride was added. 2.00 parts of 48% aqueous sodium hydroxide solution was added dropwise and stirred for 3 hours. 20.0 parts of dilute hydrochloric acid was then added, and the mixture was stirred for 1 hour. The solid collected by filtration from the reaction solution obtained above was washed with isopropanol and dried to obtain 5.06 parts of a hydroxyimide compound. To a mixture of 5.0 parts (10.0 mmol) of this hydroxyimide and 18.9 parts of chloroform, 1.3 parts (15.9 mmol) of pyridine was added and the mixture was cooled to below 2°C, after which 3.7 parts (13.2 mmol) of trifluoromethanesulfonic anhydride was added and stirred for 1 hour. 20 parts of water was added to the reaction mixture obtained above, and 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 aromatic imide compound represented by the following formula (A-8)) A flask was charged with a dispersion of 4.0 parts of 3-propylthioacenaphthenequinone in 60 parts of methanol. Under a nitrogen atmosphere, 20 parts of potassium peroxymonosulfate (double salt) was added. The mixture was refluxed with stirring for one day, then cooled to room temperature and poured into a large amount of water. The resulting solid was collected by filtration 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 parts of pyridine, and 47 parts of dichloromethane was ice-cooled, and 3.0 parts of nonafluorobutanesulfonic acid chloride was added dropwise and reacted for 3 hours. The resulting reaction solution was poured into ice-cooled dilute hydrochloric acid and washed three times with water. The extract was concentrated to obtain a light brown solid. This solid was then 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 compound represented by the following formula (B-1)) A flask was charged with 252 parts of 4-(triethoxysilyl)-1-butanethiol and 138 parts of trimethoxysilanol, and a mixed solution of pure water and concentrated hydrochloric acid as an acid catalyst was added dropwise at 25°C under stirring. The mixture was refluxed for 1 hour and then cooled to room temperature. The reaction solution obtained above was neutralized with an alkali and repeatedly washed with water. The water was then distilled off and the mixture was dried to obtain 350 parts of a silicon compound represented by the following formula (B-1).

[0080] [ka]

[0081] Synthesis Example 10 (Synthesis of silicon compound represented by the following formula (B-2)) 380 parts of a silicon compound represented by the following formula (B-2) was obtained in the same manner as in Synthesis Example 9, except that the amount of 4-(trimethoxysilyl)-1-butanethiol used was changed from 252 parts to 210 parts, and 138 parts of trimethoxysilanol was changed to 180 parts of triethoxysilanol.

[0082] [ka]

[0083] Synthesis Example 11 (Synthesis of silicon compound represented by the following formula (B-3)) 350 parts of a silicon compound represented by the following formula (B-3) was obtained in the same manner as in Synthesis Example 9, except that 252 parts of 4-(triethoxysilyl)-1-butanethiol was changed to 200 parts of 4-(diethoxymonomethoxysilyl)-1-butanethiol.

[0084] [ka]

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

[0086] [ka]

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

[0088] [ka]

[0089] Examples 1 to 17 and Comparative Examples 1 to 5 (Preparation of Photosensitive Resin Compositions and Fabrication of Laminates Using the Compositions) According to the blending amounts listed in Tables 1 to 4, (A) aromatic imide compound (or photopolymerization initiator), (B) silicon compound, (C) epoxy resin, and other components were dissolved by stirring in a flask equipped with a stirrer at 80°C for 1 hour. After cooling, the solution was filtered through a 0.6 μm pore size filter to obtain photosensitive resin composition solutions of the present invention and comparative examples. These photosensitive resin composition solutions were uniformly coated on a 30 μm thick polyethylene terephthalate (PET) film (base film, manufactured by Fujimori Kogyo Co., Ltd.) using a coater and dried in a hot air convection dryer at 80°C for 5 minutes and then at 100°C for 5 minutes. The release-treated surface of a cover film (38 μm thick PET film with a release treatment, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was then laminated onto the dried coating surface to obtain laminates (dry films) with a 20 μm thick photosensitive resin composition layer.

[0090] (Laminate patterning) The cover film of each laminate obtained in Examples 1 to 17 and Comparative Examples 1 to 5 was peeled off, and the laminate was laminated to the copper-deposited surface of a copper-deposited silicon wafer, an aluminum substrate, or a lithium tantalate substrate using a dry film laminator 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. The base film was then peeled off, and a resin layer made of a photosensitive resin composition was formed on the substrate. A mask aligner (MA-20, manufactured by Mikasa Co., Ltd.) was used to apply 90 to 1,000 mJ / cm to the resin layer on the substrate through a predetermined pattern photomask for evaluating the resolution profile. 2 The resulting exposed resin layer on the substrate was then subjected to post-exposure baking (PEB) in stages using a hot plate at 45°C for 1 minute, then at 65°C for 3 minutes, and finally at 100°C for 10 minutes. The resulting layer was then subjected to immersion development in SU-8 Developer (product name, manufactured by Kayaku Advanced Materials, primarily propylene glycol monomethyl ether acetate) at 23°C for 3 minutes, followed by rinsing with the same developer and drying, yielding cured resin patterns on the substrate.

[0091] (sensitivity of photosensitive resin composition, minimum resolution line width, crack evaluation) Regarding the cured resin pattern on the substrate obtained by the above "Patterning of the laminate," the minimum line-and-space resolution line width (μm) that resolves the pattern of the pattern photomask for resolution shape evaluation without peeling, collapsing, or bridging is defined as the "minimum resolution," and the exposure dose (mJ / cm) at that time is defined as the "minimum resolution." 2 ) was defined as "sensitivity." 2 Those in which no pattern was formed even after irradiation were marked with "x." The results are shown in Tables 1 to 4. The pattern having the minimum resolvable line width was observed under a microscope and evaluated for cracks according to the following criteria. The results are shown in Tables 1 to 4. (Crack evaluation criteria) ○: No cracks occurred △: Cracks on the surface

[0092] (Evaluation of Adhesion of Cured Photosensitive Resin Composition to Various Substrates) The cured 100 μm square pillar patterns on the substrate obtained in the "Laminate Patterning" section above were measured for peel strength (MPa) using a ball shear tool with a shear strength tester (Rhesca Bonding Tester), and the adhesion to copper, aluminum, and LT was evaluated according to the following criteria. The results are shown in Tables 1 to 4. (Adhesion evaluation criteria) ◎: Shear strength was over 25 MPa ○: Shear strength was 15 to 25 MPa ×: Shear strength was 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): Irgacure 290 (product name, manufactured by BASF) (a-2): UVI-6976 (trade name, manufactured by Dow Chemical Company, a 50% concentration propylene carbonate solution; the blending amounts in Table 2 are listed in terms of solid content) (a-3): CPI-210S (product name, manufactured by San-Apro 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 (trade name, manufactured by Nissan Chemical Industries, Ltd.) (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 (trade name, leveling agent, manufactured by Neos Corporation) (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 a fine pattern, the cured product of which does not corrode a metal supported body provided on a substrate, and has good adhesion to a metal supported body, and a dry film resist using the photosensitive resin composition.

Claims

1. A) a compound represented by the following general formula (1): [Formula 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-camphoryl group. ２ ~R ７ each independently represents 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 the formula: (B) a compound represented by the following general formula (2): [Case 2] (In formula (2), R １０ ~R １５ R 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. 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; R １６ When there are multiple R １６ may be the same or different, R １７ When there are multiple R １７ may be the same or different. X １ and X ２ represents a sulfur atom; and a and b each represent an integer of 0 or more satisfying the relationship 1≦a+b≦4. Silicon compounds represented by the formula: (C) Epoxy compound A photosensitive resin composition comprising:

2. R １ is a fluoroalkyl group having 1 to 8 carbon atoms; R ３ and R ４ at least one of R 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 R ２ and R ５ ~R ７ The photosensitive resin composition according to claim 1, wherein is a hydrogen atom.

3. The photosensitive resin composition according to claim 1, wherein all of R 2 to R 7 are hydrogen atoms.

4. R １０ ~R １５ The photosensitive resin composition according to claim 1 , wherein each of the groups independently represents a methyl group or an ethyl group.

5. R １６ and R １７ 4. The photosensitive resin composition according to claim 1, wherein each independently represents an alkylene group having 1 to 10 carbon atoms, and a is 1.

6. R １６ and R １７ 4. The photosensitive resin composition according to claim 1, wherein at least one of the following is an alkylene group having 1 to 10 carbon atoms; and b is 0.

7. 4. The photosensitive resin composition according to claim 1, wherein the epoxy compound (C) comprises an epoxy compound having two or more epoxy groups in one molecule.

8. 4. The photosensitive resin composition according to claim 1, wherein the epoxy compound (C) comprises an epoxy compound having a softening point of 40 to 120° C. and an epoxy equivalent of 100 to 5,000 g / eq.

9. The photosensitive resin composition according to claim 1 or 3, wherein the aromatic imide compound is the following (A-1) or (A-2). [C3]

10. A resist laminate or a dry film resist obtained by sandwiching the photosensitive resin composition according to any one of claims 1 to 3 between substrates.

11. A cured product of the photosensitive resin composition according to claim 1 .

12. A hardened product of the dry film resist described in claim 10.

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