Photosensitive resin composition, pattern cured product, method for producing pattern cured product, and electronic component

Abstract

The photosensitive resin composition contains a polyimide precursor having a polymerizable unsaturated bond and a trifunctional or higher polymerizable monomer, and when the photosensitive resin composition is heated at 100 DEG C for 120 seconds and then heated at 110 DEG C for 120 seconds, the photosensitive resin film having a thickness of 7 [mu] m has an i-ray transmittance of 30% or less.

Description

Technical Field

[0001] This disclosure relates to photosensitive resin compositions, patterned cured products, methods for manufacturing patterned cured products, and electronic components. Background Technology

[0002] Conventionally, polyimide, polybenzoxazole, and other materials with excellent heat resistance, electrical properties, and mechanical properties have been used in the surface protective film and interlayer insulating film of semiconductor devices. In recent years, photosensitive resin compositions that impart photosensitive properties to these resins themselves have been used. Using such photosensitive resin compositions can simplify the manufacturing process of patterned cured products and shorten complex manufacturing processes (for example, see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2009-265520 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] As semiconductor devices become more high-performance and rewiring becomes more miniaturized, high resolution is also required for the polyimide used to form the insulating film.

[0008] In view of the above-mentioned prior art, an object of one embodiment of the present disclosure is to provide a photosensitive resin composition capable of achieving high resolution, a patterned cured product using the photosensitive resin composition, a method for manufacturing the patterned cured product, and an electronic component.

[0009] Methods for solving problems

[0010] The specific methods for achieving the above objectives are as follows.

[0011] <1> A photosensitive resin composition comprising a polyimide precursor having polymerizable unsaturated bonds, a polymerizable monomer with three or more functions, and a photopolymerization initiator, wherein the i-ray transmittance of a 7 μm thick photosensitive resin film obtained by heating the above photosensitive resin composition at 100°C for 120 seconds and then at 110°C for 120 seconds is less than or equal to 30%.

[0012] <2> According to the photosensitive resin composition described in <1>, the polyimide precursor having polymerizable unsaturated bonds has the structural unit represented by the following general formula (1).

[0013] [Chemistry 1]

[0014]

[0015] (In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. R 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has polymerizable unsaturated bonds.

[0016] <3> The photosensitive resin composition according to <1> or <2> further contains at least one selected from the group consisting of a sensitizer and an ultraviolet absorber.

[0017] <4> According to the photosensitive resin composition described in <1> or <2>, the above-mentioned photopolymerization initiator contains an oxime compound.

[0018] <5> A method for manufacturing a patterned cured material, comprising:

[0019] The process of coating the photosensitive resin composition of any one of <1> to <4> onto a substrate and drying it to form a photosensitive resin film;

[0020] The process of obtaining a resin film by pattern exposure of the above-mentioned photosensitive resin film;

[0021] The process of developing the exposed resin film using a developer to obtain a patterned resin film; and

[0022] The process of heat-treating the above-mentioned patterned resin film.

[0023] <6> A patterned cured product, which is formed by curing the photosensitive resin composition described in any one of <1> to <4>.

[0024] <7> The patterned cured material according to <6> is used as an interlayer insulating film, a cover coating, or a surface protective film.

[0025] <8> An electronic component comprising the patterned cured material described in <6> or <7>.

[0026] Invention Effects

[0027] According to one embodiment of this disclosure, a photosensitive resin composition capable of achieving high resolution, a patterned cured product using the photosensitive resin composition, a method for manufacturing the patterned cured product, and an electronic component can be provided. Attached Figure Description

[0028] Figure 1 This is a manufacturing process diagram of an electronic component according to one embodiment of the present disclosure.

[0029] Figure 2(A) is a cross-sectional FIB-SEM image of a through-hole pattern formed using the photosensitive resin composition of Example 1, and (B) is a cross-sectional SEM image of a through-hole pattern formed using the photosensitive resin composition of Comparative Example 1. Detailed Implementation

[0030] The following describes in detail the methods for implementing this disclosure. However, this disclosure is not limited to the following embodiments. In the following embodiments, unless specifically stated otherwise, the constituent elements (including element steps, etc.) are not essential. Similarly, numerical values ​​and their ranges are not limiting to this disclosure.

[0031] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, as long as the purpose of the process can be achieved.

[0032] In this disclosure, within the numerical range represented by “~”, the numerical values ​​recorded before and after “~” are respectively the minimum and maximum values.

[0033] In the numerical ranges described in this disclosure, the upper or lower limit of one numerical range can be replaced by the upper or lower limit of another numerical range described in other stages. Furthermore, the upper or lower limit of a numerical range described in this disclosure can also be replaced by the values ​​shown in the embodiments.

[0034] In this disclosure, each component may contain multiple corresponding substances. When multiple substances equivalent to each component are present in the composition, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition.

[0035] In this disclosure, the term "layer" or "film" includes, in addition to the case where it is formed entirely in the region where the layer or film is observed, the case where it is formed only in a part of the region.

[0036] In this disclosure, "(meth)acryloyl" means at least one of acryloyl and methacryloyl, and "(meth)acryloyloxy" means at least one of acryloyloxy and methacryloyloxy.

[0037] In this disclosure, the average thickness of the layer or film is set as the value provided by measuring the thickness of 5 points of the layer or film to be targeted as their arithmetic mean.

[0038] The thickness of a layer or film can be measured using a micrometer, a scanning stylus probe, or an optical interferometric film thickness measuring device. In this disclosure, when the thickness of a layer or film can be directly measured, an optical interferometric film thickness measuring device is used. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it can be measured by observing the cross-section of the object being measured using an electron microscope.

[0039] <Photosensitive Resin Composition>

[0040] The photosensitive resin composition disclosed herein comprises a polyimide precursor having polymerizable unsaturated bonds and a polymerizable monomer with three or more functions. A 7 μm thick photosensitive resin film obtained by heating the above photosensitive resin composition at 100°C for 120 seconds and then at 110°C for 120 seconds exhibits an i-ray transmittance of less than or equal to 30%. Hereinafter, "polyimide precursor having polymerizable unsaturated bonds" will also be referred to as "unsaturated polyimide precursor," and "polymerizable monomer with three or more functions" will also be referred to as "specific polymerizable monomer."

[0041] The photosensitive resin composition described above enables high resolution. The reason for this is not yet clear, but it is speculated as follows.

[0042] In conventional photosensitive resin compositions, difunctional monomers are used as polymerizable monomers. When difunctional monomers polymerize, they form linear polymers, resulting in low crosslinking density in the cured film. Consequently, patterns obtained by developing such cured films swell due to the developing solution, making it difficult to obtain high-resolution patterns.

[0043] On the other hand, polymerizable monomers with three or more functions are highly reactive and polymerize by reacting with a small amount of free radicals generated by photopolymerization initiators using light reflected from the substrate to the unexposed area, thus resulting in a pattern shape different from what was intended. Especially when the lines are made finer, a cured material forms at the bottom of the pattern, or a bridging cured material (so-called microbridges) forms in the upper part in the thickness direction than the bottom, which can easily lead to significant defects in the pattern shape.

[0044] It can be inferred that by using monomers with three or more functions in the photosensitive resin composition disclosed herein, the crosslinking density is increased, the swelling of the developer is suppressed, and the amount of i-rays reaching the substrate is reduced. This suppresses the light reflected from the substrate to the unexposed area, suppresses the polymerization reaction in the unexposed area, and increases the resolution.

[0045] The i-ray transmittance of the 7 μm thick photosensitive resin film (hereinafter referred to as "photosensitive resin film") obtained by heating the photosensitive resin composition of this disclosure at 100°C for 120 seconds and then at 110°C for 120 seconds is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, and even more preferably less than or equal to 18%.

[0046] Furthermore, from the viewpoint of transmittance, the i-ray transmittance of the photosensitive resin film is preferably greater than or equal to 5%, more preferably greater than or equal to 10%.

[0047] The method for determining i-ray transmittance is as described in the examples.

[0048] The i-ray transmittance of photosensitive resin films can be adjusted by adding ultraviolet absorbers, sensitizers, compounds with i-ray absorption capabilities and adjusting their amounts, as well as by selecting the types and adjusting the amounts of photopolymerization initiators and unsaturated polyimide precursors. For example, if a rust inhibitor has i-ray absorption capabilities, then the rust inhibitor is equivalent to a compound with i-ray absorption capabilities.

[0049] The components contained in the photosensitive resin composition of this disclosure will be described below. It should be noted that the photosensitive resin composition of this disclosure is preferably a negative photosensitive resin composition.

[0050] (Unsaturated polyimide precursor)

[0051] The photosensitive resin composition disclosed herein contains a polyimide precursor having polymerizable unsaturated bonds (hereinafter, sometimes referred to as "unsaturated polyimide precursor").

[0052] Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

[0053] Unsaturated polyimide precursors can be synthesized using tetracarboxylic dianhydrides and diamine compounds. Alternatively, tetracarboxylic acids can be used instead of tetracarboxylic dianhydrides in the synthesis of unsaturated polyimide precursors.

[0054] The unsaturated polyimide precursor preferably has the structural unit represented by the following general formula (1).

[0055] [Chemistry 2]

[0056]

[0057] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has polymerizable unsaturated bonds.

[0058] Unsaturated polyimide precursors can have multiple structural units represented by the above general formula (1), wherein X, Y, R in the multiple structural units 6 and R 7 They can be the same or different.

[0059] It should be noted that R 6 and R 7 The combination of these groups is not particularly limited as long as each atom is an independent hydrogen atom or a monovalent organic group. For example, R 6 and R 7 At least one of them can be a hydrogen atom, and the rest can be monovalent organic groups as described later, or they can all be the same or different monovalent organic groups. As mentioned above, when the unsaturated polyimide precursor has multiple structural units represented by the above general formula (1), the R of each structural unit 6 and R 7 The combinations can be the same or different.

[0060] In general formula (1), the number of carbon atoms in the tetravalent organic group represented by X is preferably 4 to 25, more preferably 5 to 13, and even more preferably 6 to 12.

[0061] The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (e.g., those constituting the aromatic ring with 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., those constituting the heterocycle with 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings.

[0062] When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have substituents or be unsubstituents. Examples of substituents for aromatic rings include alkyl groups, fluorine atoms, haloalkyl groups, hydroxyl groups, and amino groups.

[0063] When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, more preferably 1 to 3 benzene rings, and even more preferably 1 or 2 benzene rings.

[0064] When the tetravalent organic group represented by X contains more than two benzene rings, these benzene rings can be linked by single bonds, or by alkylene groups, haloalkylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), thioether bonds (-S-), or methylenesilane bonds (-Si(R)). A )2-;2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group; siloxane bond (-O-(Si(R)). B )2-O-) n; 2 R B Each of the following groups independently represents a hydrogen atom, an alkyl group, or a phenyl group, where n represents 1 or an integer greater than or equal to 2. The two benzene rings can be bonded together by single bonds and at least one of the linking groups at two different sites, thereby forming a 5-membered or 6-membered ring containing the linking group between the two benzene rings.

[0065] In general formula (1), -COOR 6 The -COOR group and the -CONH- group are preferably located adjacent to each other. 7 The -CO- group and the -CO- group are preferably located in adjacent positions.

[0066] Specific examples of the tetravalent organic group represented by X include groups represented by formulas (A) to (F) below. From the viewpoint of obtaining an insulating film with excellent flexibility and further suppressing the formation of voids at the bonding interface, groups represented by formula (E) below are preferred, more preferably groups represented by formula (E) below where C contains an ether bond, and even more preferably ether bonds. Formula (F) below is a structure where C in formula (E) below is a single bond.

[0067] It should be noted that this disclosure is not limited to the specific examples described below.

[0068] [Chemistry 3]

[0069]

[0070] In formula (D), A and B are each independently a single bond or a divalent group not conjugated with the benzene ring. However, A and B are not both single bonds. Examples of divalent groups not conjugated with the benzene ring include methylene, halomethylene, halomethylmethylene, carbonyl, sulfonyl, ether (-O-), thioether (-S-), and methylenesilane (-Si(R)). A )2-;2 R A Each of A and B independently represents a hydrogen atom, alkyl group, or phenyl group. Preferably, A and B are methylene, bis(trifluoromethyl)methylene, difluoromethylene, ether bond, thioether bond, etc., and more preferably ether bond.

[0071] In formula (E), C represents a single bond, alkylene group, haloalkylene group, carbonyl group, sulfonyl group, ether bond (-O-), thioether bond (-S-), phenylene group, ester bond (-OC(=O)-), methylenesilane bond (-Si(R)-). A )2-;2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group; siloxane bond (-O-(Si(R)). B )2-O-) n ; 2 R BEach of the following can independently represent a hydrogen atom, an alkyl group, or a phenyl group, where n represents 1 or an integer greater than or equal to 2. Alternatively, it can be a divalent group composed of at least two of these. C preferably contains an ether bond, and more particularly an ether bond.

[0072] In general formula (1), the number of carbon atoms in the divalent organic group represented by Y is preferably 4 to 25, more preferably 6 to 20, and even more preferably 12 to 18.

[0073] The skeleton of the divalent organic group represented by Y can also be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y can also be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y can be a structure in which two bonding positions of the tetravalent organic group represented by X are replaced by atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups).

[0074] The divalent organic group represented by Y can be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (e.g., those with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (e.g., those with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0075] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulas (G) and (H). From the viewpoint of obtaining an insulating film with excellent flexibility and further suppressing the formation of voids at the bonding interface, the group represented by the following formula (H) is preferred. More preferably, in the following formula (H), D is a single bond or a group containing an ether bond; even more preferably, a single bond or a group containing an ether bond; particularly preferably, a group containing an ether bond; and extremely preferably, an ether bond.

[0076] [Chemistry 4]

[0077]

[0078] In formulas (G) to (H), R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom, and n independently represents an integer from 0 to 4.

[0079] In formula (H), D represents a single bond, alkylene group, haloalkylene group, carbonyl group, sulfonyl group, ether bond (-O-), thioether bond (-S-), phenylene group, ester bond (-OC(=O)-), methylenesilane bond (-Si(R)-). A )2-;2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group; siloxane bond (-O-(Si(R)). B)2-O-) n ; 2 R B Each of these can independently represent a hydrogen atom, an alkyl group, or a phenyl group, where n represents 1 or an integer greater than or equal to 2. Alternatively, D can be the structure represented by formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of C in formula (E).

[0080] As for D in formula (H), it is preferred that each of them is independently a single bond, an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group.

[0081] The alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.

[0082] Specific examples of alkyl groups represented by R in formulas (G) to (H) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0083] The alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group with 1 to 10 carbon atoms, more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably an alkoxy group with 1 or 2 carbon atoms.

[0084] Specific examples of alkoxy groups represented by R in formulas (G) to (H) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

[0085] The alkyl halogroup represented by R in formulas (G) to (H) is preferably an alkyl halogroup having 1 to 5 carbon atoms, more preferably an alkyl halogroup having 1 to 3 carbon atoms, and even more preferably an alkyl halogroup having 1 or 2 carbon atoms.

[0086] As a specific example of a haloalkyl group represented by R in formulas (G) to (H), an alkyl group in which at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H) is replaced by a halogen atom such as a fluorine atom or a chlorine atom can be cited. Among them, fluoromethyl, difluoromethyl, trifluoromethyl and the like are preferred.

[0087] In formulas (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0088] Specific examples of the divalent aliphatic group represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups with polyoxyalkylene structures.

[0089] As represented by Y, the linear or branched alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.

[0090] Specific examples of alkylene groups represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonamethylene, and 2-methyldecamethylene.

[0091] The cycloalkyl group represented by Y is preferably a cycloalkyl group with 3 to 10 carbon atoms, and more preferably a cycloalkyl group with 3 to 6 carbon atoms.

[0092] Specific examples of cycloalkylene compounds represented by Y include cyclopropylene and cyclohexylene.

[0093] The unit structure contained in the divalent group representing the polyepoxide structure (Y) is preferably an epoxide structure with 1 to 10 carbon atoms, more preferably an epoxide structure with 1 to 8 carbon atoms, and even more preferably an epoxide structure with 1 to 4 carbon atoms. Among these, the polyepoxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the epoxide structure can be linear or branched. The unit structure in the polyepoxide structure can be one type or two or more types.

[0094] The divalent organic group represented by Y can be a divalent group with a polysiloxane structure. Examples of divalent groups with a polysiloxane structure represented by Y include those in which a silicon atom in a polysiloxane structure is bonded to a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 18 carbon atoms.

[0095] Specific examples of alkyl groups with 1 to 20 carbon atoms bonded to silicon atoms in a polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl. Among these, methyl is preferred.

[0096] In the polysiloxane structure, the aryl group with 6 to 18 carbon atoms bonded to silicon atoms can be unsubstituted or substituted. Specific examples of substituents when the aryl group has substituents include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups with 6 to 18 carbon atoms include phenyl, naphthyl, and benzyl groups. Among these, phenyl is preferred.

[0097] The polysiloxane structure may contain one or more alkyl groups with 1 to 20 carbon atoms or aryl groups with 6 to 18 carbon atoms.

[0098] The silicon atoms that constitute the divalent group with the polysiloxane structure represented by Y can be bonded to the NH group in general formula (1) via alkylene such as methylene and ethylene, arylene such as phenylene, etc.

[0099] The group represented by formula (G) is preferably the group represented by formula (G') below, and the group represented by formula (H) is preferably the group represented by formula (H'), formula (H”) or formula (H”') below. From the viewpoint of having a soft skeleton and excellent bonding properties, the group represented by formula (H') or formula (H”) below is more preferred.

[0100] [Chemistry 5]

[0101]

[0102] In formula (H”'), each R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0103] There is no particular limitation on the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1). For example, the following combinations can be cited as combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y.

[0104] X is a group represented by formula (E), and Y is a combination of groups represented by formula (H).

[0105] X is a group represented by formula (F), and Y is a combination of groups represented by formula (H).

[0106] X is the group represented by formula (E), and Y is a combination of the groups represented by formulas (G) and (H).

[0107] X is a group represented by formulas (A) and (E), and Y is a combination of groups represented by formula (H).

[0108] X is a group represented by formulas (E) and (F), and Y is a combination of groups represented by formula (H).

[0109] In the above combination, it is preferable that X is a group represented by formula (E) and Y is a group represented by formula (H).

[0110] R 6 and R 7Each group independently represents a hydrogen atom or a monovalent organic group, at least one of which has a polymerizable unsaturated bond. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably any one of the groups represented by the following general formula (2), ethyl, isobutyl, or tert-butyl, and even more preferably an aliphatic hydrocarbon group containing 1 or 2 carbon atoms or a group represented by the following general formula (2). In this case, R 6 and R 7 At least one of them is a group represented by general formula (2).

[0111] In addition, when the monovalent organic group includes an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond portion is removed by the (C) compound.

[0112] Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc., among which ethyl, isobutyl, and tert-butyl are preferred.

[0113] [Chemistry 6]

[0114]

[0115] In general formula (2), R 8 ~R 10 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R x This indicates a divalent linker.

[0116] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented has 1 to 3 carbon atoms, preferably 1 or 2. As R 8 ~R 10 Specific examples of the aliphatic hydrocarbon groups represented include methyl, ethyl, n-propyl, isopropyl, etc., with methyl being preferred.

[0117] R in general formula (2) 8 ~R 10 The combination of R is preferred. 8 and R 9 It is a hydrogen atom, and R 10 It is a combination of hydrogen atoms or methyl groups.

[0118] R in general formula (2) x It is a divalent linker, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups.

[0119] R xThe number of carbon atoms in the sample is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0120] In general formula (1), R is preferred. 6 and R 7 At least one of them is a group represented by the above general formula (2), more preferably R 6 and R 7 Both are groups represented by the general formula (2) above.

[0121] When the unsaturated polyimide precursor comprises a compound having structural units represented by the above general formula (1), R relative to all structural units contained in the compound 6 and R 7 The sum of these is represented by R, which is the group represented by general formula (2). 6 and R 7 The proportion is preferably greater than or equal to 60 mol%, more preferably greater than or equal to 70 mol%, and even more preferably greater than or equal to 80 mol%. There is no particular upper limit, and it can be 100 mol%.

[0122] It should be noted that the above proportions can be greater than or equal to 0 mol% and less than 60 mol%.

[0123] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0124] [Chemistry 7]

[0125]

[0126] In general formula (2'), R 8 ~R 10 Each group independently represents an aliphatic hydrocarbon group with 1 to 3 hydrogen or carbon atoms, and q represents an integer from 1 to 10.

[0127] In general formula (2'), q is an integer from 1 to 10, preferably an integer from 2 to 5, and more preferably 2 or 3.

[0128] The percentage of the structural unit represented by general formula (1) in a compound having the structural unit represented by general formula (1) is preferably greater than or equal to 60 mol%, more preferably greater than or equal to 70 mol%, and even more preferably greater than or equal to 80 mol%. There is no particular upper limit to the above percentage, and it can be 100 mol%.

[0129] Unsaturated polyimide precursors can be synthesized using tetracarboxylic dianhydride and diamine compounds. In this case, in general formula (1), X corresponds to residues from tetracarboxylic dianhydride, and Y corresponds to residues from diamine compounds. It should be noted that unsaturated polyimide precursors can also be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0130] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 3,4,9,10... -Perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,4,4'-(4,4'-isopropyldiphenoxy)phthalic anhydride, 4,4'-oxodiphthalic anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis( 3,4-Dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxobisphthalic dianhydride, 4,4'-sulfonylbisphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone dispironnorbornene tetracarboxylic dianhydride, 2,2-bis{4-(4'-phenoxy)phenyl}propane tetracarboxylic dianhydride, etc.

[0131] Preferably, it is selected from at least one of the group consisting of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxobisphthalic anhydride and 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, more preferably at least one of the group consisting of pyromellitic dianhydride and 4,4'-oxobisphthalic anhydride, and from the viewpoint of bonding at lower temperatures, it is even more preferred to include 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride.

[0132] Tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0133] Specific examples of diamine compounds include: 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3 4'-Diaminodiphenyl sulfone, 3,3'-Diaminodiphenyl sulfone, 2,4'-Diaminodiphenyl sulfone, 2,2'-Diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfide, 2,4'-Diaminodiphenyl sulfide, 2,2'-Diaminodiphenyl sulfide, o-toluidine, o-toluidine sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminotrimethylbenzene, 1,5 -Diaminonaphthalene, 4,4'-benzophenone diamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6 Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc. As diamine compounds, 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene are preferred.

[0134] More preferably, it is at least one selected from the group consisting of 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, m-phenylenediamine and 1,3-bis(3-aminophenoxy)benzene. From the viewpoint of having a soft skeleton and excellent adhesion, it is even more preferably at least one selected from the group consisting of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane.

[0135] Diamine compounds can be used alone or in combination with two or more.

[0136] Having a structural unit represented by general formula (1), and R in general formula (1) 6 and R 7 Compounds in which at least one of the organic groups is a monovalent organic group can be obtained, for example, by the following methods (a) or (b).

[0137] (a) After reacting a tetracarboxylic dianhydride (preferably the tetracarboxylic dianhydride represented by the following general formula (8)) with a compound represented by R-OH in an organic solvent to prepare a diester derivative, the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2.

[0138] (b) A polyamic acid solution is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound represented by H2N-Y-NH2 in an organic solvent, and then adding a compound represented by R-OH to the polyamic acid solution and reacting it in an organic solvent to introduce ester groups.

[0139] Because R in general formula (1) 6 and R 7 At least one of them has a polymerizable unsaturated bond, therefore at least one of R-OH having a polymerizable unsaturated bond is used.

[0140] Here, the Y in the diamine compound represented by H2N-Y-NH2 is the same as the Y in general formula (1), and the specific examples and preferred examples are also the same. Furthermore, the R in the compound represented by R-OH represents a monovalent organic group, and the specific examples and preferred examples are the same as the R in general formula (1). 6 and R 7 The same applies to the case.

[0141] The tetracarboxylic acid dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH can each be used individually or in combination of two or more.

[0142] Examples of organic solvents mentioned above include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolinone, and 3-methoxy-N,N-dimethylpropionamide, among which 3-methoxy-N,N-dimethylpropionamide is preferred.

[0143] Alternatively, the dehydrating condensing agent can be reacted together with the compound represented by R-OH in a polyamic acid solution to synthesize an unsaturated polyimide precursor. The dehydrating condensing agent preferably comprises at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0144] The above-mentioned compounds contained in the unsaturated polyimide precursor can be obtained by reacting the compound represented by R-OH with the tetracarboxylic acid dianhydride represented by the following general formula (8) to form a diester derivative, then converting it into an acyl chloride by chlorinating agents such as thionyl chloride, and then reacting the diamine compound represented by H2N-Y-NH2 with the acyl chloride.

[0145] The above-mentioned compounds contained in the unsaturated polyimide precursor can be obtained by reacting the compound represented by R-OH with the tetracarboxylic acid dianhydride represented by the following general formula (8) to prepare a diester derivative, and then reacting the diamine compound represented by H2N-Y-NH2 with the diester derivative in the presence of the carbodiimide compound.

[0146] The above-mentioned compounds contained in the unsaturated polyimide precursor can be obtained by reacting the tetracarboxylic dianhydride represented by the following general formula (8) with the diamine compound represented by H2N-Y-NH2 to prepare polyamic acid, followed by isoimidization of the polyamic acid in the presence of a dehydrating condensing agent such as trifluoroacetic anhydride, and then allowing the compound represented by R-OH to take effect. Alternatively, the compound represented by R-OH can be applied to a portion of the tetracarboxylic dianhydride beforehand, and the partially esterified tetracarboxylic dianhydride can be reacted with the diamine compound represented by H2N-Y-NH2.

[0147] [Chemistry 8]

[0148]

[0149] In general formula (8), X is the same as X in general formula (1), and the specific example and preferred example are also the same.

[0150] The compound represented by R-OH used in the synthesis of the above-mentioned compounds contained in the unsaturated polyimide precursor can be the R-OH group represented by the group in general formula (2). xCompounds with a hydroxyl group bonded to the top, and compounds with a hydroxyl group bonded to the terminal methylene group represented by the general formula (2'), etc. Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, etc., among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0151] There is no particular limitation on the molecular weight of the unsaturated polyimide precursor, but it is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, based on weight-average molecular weight.

[0152] Weight-average molecular weight can be determined, for example, by gel permeation chromatography, or by conversion using a standard polystyrene standard curve.

[0153] The photosensitive resin composition disclosed herein may further comprise a dicarboxylic acid, and the unsaturated polyimide precursor contained in the photosensitive resin composition may have a structure formed by the reaction of a portion of the amino group in the unsaturated polyimide precursor with a carboxyl group in the dicarboxylic acid. For example, in the synthesis of the unsaturated polyimide precursor, a portion of the amino group of the diamine compound may be reacted with a carboxyl group of the dicarboxylic acid.

[0154] The dicarboxylic acid can be a dicarboxylic acid having a (meth)acryloyl group, for example, it can be a dicarboxylic acid represented by the following formula. In this case, when synthesizing the unsaturated polyimide precursor, a methacryloyl group from the dicarboxylic acid can be introduced into the unsaturated polyimide precursor by reacting a portion of the amino group of the diamine compound with the carboxyl group of the dicarboxylic acid.

[0155] [Chemistry 9]

[0156]

[0157] In addition to the unsaturated polyimide precursor, the photosensitive resin composition disclosed herein may also contain a polyimide resin. By combining the unsaturated polyimide precursor and the polyimide resin, the generation of volatiles caused by dehydration cyclization during imide ring formation can be suppressed, thus exhibiting a tendency to suppress void formation. The polyimide resin referred to herein is a resin whose entire or partial resin backbone has an imide backbone. The polyimide resin is preferably soluble in a solvent used in the photosensitive resin composition employing the unsaturated polyimide precursor.

[0158] As for polyimide resins, there are no particular limitations as long as they are polymeric compounds having multiple structural units containing imide bonds; for example, compounds having structural units represented by the following general formula (X) are preferred. Therefore, there is a tendency to obtain semiconductor devices with insulating films exhibiting high reliability.

[0159] [Chemistry 10]

[0160]

[0161] In general formula (X), X represents a tetravalent organic group and Y represents a divalent organic group. Preferred examples of substituents X and Y in general formula (X) are the same as those of substituents X and Y in general formula (1) above.

[0162] When the photosensitive resin composition disclosed herein contains a polyimide resin, the proportion of the polyimide resin to the total of the unsaturated polyimide precursor and the polyimide resin can be 15% to 50% by mass, or 10% to 20% by mass.

[0163] The photosensitive resin composition disclosed herein may comprise resins other than unsaturated polyimide precursors and polyimide resins. Examples of other resins, from the viewpoint of heat resistance, include phenolic varnish resins, acrylic resins, polyether nitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, and polyvinyl chloride resins. Other resins may be used alone or in combination of two or more.

[0164] In the photosensitive resin composition disclosed herein, the content of the unsaturated polyimide precursor is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass, relative to the total amount of solid components.

[0165] The term "solid component" refers to the residual components after the photosensitive resin composition is coated onto a substrate and heated at 100°C for 120 seconds, and then heated at 110°C for 120 seconds to remove solvents, etc.

[0166] (polymerizable monomers)

[0167] The photosensitive composition disclosed herein contains a polymerizable monomer with three or more functions (specific polymerizable monomer). In this disclosure, the functional group in the polymerizable monomer refers to a group capable of reacting with the polymerizable unsaturated bond of the unsaturated polyimide precursor. The specific polymerizable monomer has three or more such functional groups, and may have four or more. The number of functional groups in the specific polymerizable monomer is preferably less than or equal to eight, more preferably less than or equal to six, and even more preferably less than or equal to five. The number of functional groups in the specific polymerizable monomer is preferably three or four.

[0168] A specific polymerizable monomer can be used alone or in combination of two or more.

[0169] Examples of functional groups include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadicimide, and (meth)acryloyl. From the viewpoint of polymerization reactivity, (meth)acryloyl and vinyl are preferred, and (meth)acryloyl is more preferred.

[0170] As a specific polymerizable monomer, it is preferably a compound represented by the following general formula (6).

[0171] [Chemistry 11]

[0172]

[0173] R in equation (6) x and R 8 ~R 10 respectively with R in equation (2) x and R 8 ~R 10 Synonyms. R x Each of them is preferably -(CH2) independently. q -, q is synonymous with q in general formula (2').

[0174] In formula (6), n represents an integer from 3 to 6, preferably from 3 to 5, and more preferably 3 or 4.

[0175] In equation (6), each p independently represents an integer of 0 or greater than or equal to 1, preferably 0 to 30, more preferably 0 to 20, and even more preferably 0 to 5.

[0176] In formula (6), A is an n-valent organic group. A can be any of the following: linear, cyclic, or branched.

[0177] Examples of n-valent organic groups include n-valent hydrocarbon groups that may contain oxygen atoms, n-valent groups from bisphenols, n-valent groups from fluorene, n-valent groups from tricyclodecane, and n-valent groups from isocyanuric acid groups.

[0178] Examples of n-valent hydrocarbon groups that can contain oxygen atoms include n-valent aliphatic hydrocarbon groups that can contain oxygen atoms and n-valent aromatic hydrocarbon groups that can contain oxygen atoms, with n-valent aliphatic hydrocarbon groups that can contain oxygen atoms being the most preferred.

[0179] The following groups can be cited as n-valent aliphatic hydrocarbon groups that can contain oxygen atoms.

[0180] [Chemistry 12]

[0181]

[0182] In the above chemical formulas, * indicates the position connected to the structure enclosed in parentheses in formula (6). n independently represents 0 or an integer greater than or equal to 1, preferably 0 or 1.

[0183] [Chemistry 13]

[0184]

[0185] In the above chemical formulas, R independently represents a hydrogen atom or a (meth)acryloyl group (-O-CO-CH=CH2, -O-CO-CCH3=CH2).

[0186] n independently represents an integer that is 0 or greater than or equal to 1, preferably 0 or 1.

[0187] m represents an integer greater than or equal to 2.

[0188] * indicates the position connected to the structure enclosed in parentheses in formula (6), or a hydroxyl group.

[0189] Wherein, A in formula (6) is preferably an n-valent aliphatic hydrocarbon group that can contain an oxygen atom or an n-valent group from an isocyanuric acid group, and more preferably an n-valent aliphatic hydrocarbon group that can contain an oxygen atom and an n-valent group from an isocyanuric acid group.

[0190] Specific examples of monomers with particular polymerizability include tri-(2-acryloyloxyethyl)isocyanurate and ethoxylated pentaerythritol tetraacrylate.

[0191] Specific polymerizable monomers can be synthesized or commercially available products can be used. Examples of commercially available products include NK ESTER A-9300 (3-functional) and ATM-4E (4-functional) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0192] In addition to specific polymerizable monomers, difunctional polymerizable monomers may also be used as polymerizable monomers. Examples of functional groups in difunctional polymerizable monomers include those described in specific polymerizable monomers, preferably (meth)acryloyl and phenylethynyl, more preferably (meth)acryloyl.

[0193] Examples of difunctional polymerizable monomers include alicyclic polymerizable monomers and linear polymerizable monomers.

[0194] The alicyclic cyclic skeleton contained in the alicyclic polymerizable monomer is not particularly limited, and examples include tricyclic decane skeleton, cyclohexane skeleton, cyclopentane skeleton, 1,3-adamantane skeleton, hydrogenated bisphenol A skeleton, hydrogenated bisphenol F skeleton, hydrogenated bisphenol S skeleton, isobornyl skeleton, etc. Among them, the tricyclic decane skeleton is preferred.

[0195] As an alicyclic polymerizable monomer, the preferred option is a compound represented by the following general formula (3).

[0196] [Chemistry 14]

[0197]

[0198] In general formula (3), R 1 and R 2 Each group is an aliphatic hydrocarbon group with 1 to 4 carbon atoms or a group represented by the general formula (3-1) below. n1 represents 0 or 1, n2 represents an integer from 0 to 2, and n1+n2 is 1 or 2. n1 R 1 and n2 R 2 At least two of them are groups represented by the following general formula (3-1).

[0199] [Chemistry 15]

[0200]

[0201] In general formula (3-1), R 1A This represents a hydrogen atom or a methyl group, and m represents an integer from 1 to 10.

[0202] As R 1 and R 2 Specific examples of aliphatic hydrocarbon groups with 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and n-butyl.

[0203] The compound represented by general formula (3) can be a compound represented by formula (3A) or formula (3B) below.

[0204] [Chemistry 16]

[0205]

[0206] The compound represented by formula (3A) can be obtained, for example, as A-DCP (tricyclodecanediethanol diacrylate) of Shin-Nakamura Chemical Industry Co., Ltd., and the compound represented by formula (3B) can be obtained, for example, as DCP (tricyclodecanediethanol dimethacrylate) of Shin-Nakamura Chemical Industry Co., Ltd.

[0207] As a linear polymerizable monomer, it is preferably a compound represented by the following general formula (4) or the following general formula (5).

[0208] [Chemistry 17]

[0209]

[0210] In general formula (4) or general formula (5), R 3 Each can independently represent a hydrogen atom or a methyl group, R4 R represents a straight-chain alkylene group having 1 to 8 carbon atoms. 5 Represents a straight-chain alkylene group with 1 to 8 carbon atoms, where p represents an integer from 2 to 5. Multiple Rs 3 and R 5 They can be the same or different.

[0211] R in general formula (4) or general formula (5) 3 Preferably, it is methyl.

[0212] R in general formula (4) 4 Specific examples of straight-chain alkylene groups with 1 to 8 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, etc.

[0213] As R in general formula (5) 5 Specific examples of straight-chain alkylene groups having 1 to 8 carbon atoms include methylene, ethylene, trimethylene, methyl ethylene, dimethyl methylene, tetramethylene, hexamethylene, octamethylene, etc., preferably methyl ethylene, ethylene, etc., and more preferably ethylene.

[0214] p in general formula (5) is preferably an integer from 3 to 4.

[0215] As linear polymerizable monomers, examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate.

[0216] Tetraethylene glycol dimethacrylate is preferred.

[0217] The proportion of a specific polymerizable monomer relative to the total content of polymerizable monomers is not particularly limited and can be appropriately adjusted based on factors such as the i-ray transmittance and film characteristics of the photosensitive resin film. For example, the proportion of a specific polymerizable monomer relative to the total content of polymerizable monomers can be greater than or equal to 5% by mass, greater than or equal to 15% by mass, or greater than or equal to 50% by mass. Conversely, the proportion of a specific polymerizable monomer relative to the total content of polymerizable monomers can be less than or equal to 100% by mass, less than or equal to 80% by mass, or less than or equal to 70% by mass.

[0218] From a high-resolution perspective, the total content of polymerizable monomers is preferably 1 to 50 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass.

[0219] (Photopolymerization initiator)

[0220] The photosensitive composition disclosed herein contains a photopolymerization initiator.

[0221] There are no particular restrictions on photopolymerization initiators, as long as they are compounds capable of generating free radicals upon exposure to active light. Examples of active light include ultraviolet rays (such as I-rays), visible light, and radiation. A single photopolymerization initiator can be used, or a combination of two or more can be employed.

[0222] Examples of photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, and acyldialkoxymethane compounds.

[0223] Examples of photopolymerization initiators include compounds represented by the following general formula (9A), compounds represented by the following general formula (9B), compounds represented by the following general formula (10A), and compounds represented by the following general formula (10B).

[0224] [Chemistry 18]

[0225]

[0226] In general formula (9A), R 11 It is an alkyl group with 1 to 12 carbon atoms, and a1 is an integer from 0 to 5. R 12 It is an alkyl group having 1 to 12 hydrogen atoms or carbon atoms. R 13 and R 14 Each can independently represent a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer greater than or equal to 2, R... 11 They can be the same or different.

[0227] R 11 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. a1 is preferably 1. R 12 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably an ethyl group. R 13 and R 14 Preferably, each alkyl group has 1 to 4 carbon atoms, and more preferably, it is a methyl group.

[0228] As a compound represented by the general formula (9A), for example, a compound represented by the following formula (9A-1) can be obtained as "IRGACURE OXE 02" manufactured by BASF Japan Co., Ltd.

[0229] [Chemistry 19]

[0230]

[0231] [Chemistry 20]

[0232]

[0233] In general formula (9B), R 15 For -OH, -COOH, -OCH2OH, -O(CH2)2OH, -COOCH2OH or -COO(CH2)2OH, R 16 and R 17 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. b1 is an integer from 0 to 5. When b1 is an integer greater than or equal to 2, R 15 They can be the same or different.

[0234] R 15 Preferably -O(CH2)2OH. b1 is preferably 0 or 1. R 16 Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably methyl or hexyl. 17 Preferably, it is an alkyl or phenyl group having 1 to 6 carbon atoms, more preferably methyl or phenyl.

[0235] As a compound represented by general formula (9B), for example, a compound represented by the following formula (9B-1) can be obtained as "IRGACURE OXE 01" manufactured by BASF Japan Co., Ltd. Additionally, a compound represented by the following formula (9B-2) can be obtained as "NCI-930" manufactured by ADEKA Co., Ltd.

[0236] [Chemistry 21]

[0237]

[0238] [Chemistry 22]

[0239]

[0240] In general formula (10A), R 21 R is an alkyl group having 1 to 12 carbon atoms. 22 and R 23 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, where c1 is an integer from 0 to 5. When c1 is an integer greater than or equal to 2, R 21They can be the same or different.

[0241] c1 is preferably 0. R 22 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. 23 Preferably, it is an alkoxy group with 1 to 12 carbon atoms, more preferably an alkoxy group with 1 to 4 carbon atoms, and even more preferably a methoxy or ethoxy group.

[0242] As a compound represented by the general formula (10A), for example, a compound represented by the following formula (10A-1) can be obtained as "G-1820(PDO)" manufactured by Lambson.

[0243] [Chemistry 23]

[0244]

[0245] [Chemistry 24]

[0246]

[0247] In general formula (10B), R 24 and R 25 Each is an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each an integer from 0 to 5, s and t are each an integer from 0 to 3, and the sum of s and t is 3. When d is an integer greater than or equal to 2, R... 24 They can be the same or different. When e is an integer greater than or equal to 2, R... 25 The groups within the parentheses can be the same or different. When s is an integer greater than or equal to 2, the groups within the parentheses can be the same or different. When t is an integer greater than or equal to 2, the groups within the parentheses can be the same or different.

[0248] d is preferably 0. R 25 Preferably, each alkyl group has 1 to 4 carbon atoms, and more preferably, a methyl group. e is preferably an integer from 2 to 4, and more preferably 3. The combination of s and t (s, t) is preferably (1, 2) or (2, 1).

[0249] As a compound represented by general formula (10B), the compound represented by the following formula (10B-1) can be obtained as "IRGACURE TPO" manufactured by BASF Japan Co., Ltd. Additionally, the compound represented by the following formula (10B-2) can be obtained as "IRGACURE 819" manufactured by BASF Japan Co., Ltd.

[0250] [Chemistry 25]

[0251]

[0252] As a photopolymerization initiator, from the viewpoint of resolution, it is preferable to use at least one selected from the group consisting of the compound represented by general formula (9A), the compound represented by general formula (9B), and the compound represented by general formula (10A), more preferably at least one selected from the group consisting of the compound represented by general formula (9A) and the compound represented by general formula (9B), even more preferably the compound represented by general formula (9B), and particularly preferably the compound represented by formula (9B-1).

[0253] The compound represented by formula (9B-1) decomposes upon exposure to i-rays, and the decomposed product exhibits higher i-ray transmittance compared to the compound represented by formula (9B-1) before decomposition. Therefore, when the coating of the photosensitive resin composition is exposed to i-rays, the i-ray transmittance is low in the initial stages of exposure, suppressing light reflection on the substrate. Then, as exposure continues, the i-ray transmittance increases, and the i-rays reach near the bottom of the substrate. As a result, the rectangularity of the cross-sectional pattern shape increases, resulting in an excellent pattern shape.

[0254] When using a compound represented by general formula (10A) as a photopolymerization initiator, from the viewpoint of adjusting the i-ray transmittance of the photosensitive resin film, it is preferable to use a sensitizer described later.

[0255] The content of photopolymerization initiator is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of unsaturated polyimide precursor, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 6 parts by mass.

[0256] (Sensitizers, UV absorbers)

[0257] The photosensitive resin composition may further contain at least one selected from the group consisting of a sensitizer and an ultraviolet absorber. By further containing at least one selected from the group consisting of a sensitizer and an ultraviolet absorber, the i-ray transmittance of the photosensitive resin film can be adjusted.

[0258] UV absorber

[0259] The absorbance of the ultraviolet absorber at a concentration of 10 mg / L and at 365 nm is preferably greater than or equal to 0.05, more preferably greater than or equal to 0.1.

[0260] Examples of UV absorbers include benzotriazole compounds, salicylate compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenyl cyanoacrylate compounds, benzothiazole compounds, azobenzene compounds, polyphenol compounds, and nickel complex salt compounds. A single UV absorber can be used, or two or more can be used in combination.

[0261] Examples of benzotriazole compounds include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2-H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, and 2-(2H-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimide-methyl). Phenol, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-p-cresol, etc.

[0262] Examples of salicylate compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0263] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0264] Examples of diphenyl acrylate compounds include ethyl 2-cyano-3,3-diphenyl acrylate.

[0265] Examples of diphenylcyanoacrylate compounds include 2-cyano-3,3-diphenylacrylate (2'-ethylhexyl ester).

[0266] Examples of azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0267] Examples of polyphenolic compounds include pyrogallol, fluoroglycine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, quercetin, geranium, anthocyanins, aurantinidin, luteolinidin, peonidin, rosinidin, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadien-3,5-dione (curcumin), and 1,7-bis(4-hydroxyphenyl)-1,6-heptadien-3,5-dione.

[0268] Examples of polyphenolic compounds include [2,2'-thiobis(4-tert-octylphenol ester)]-2-ethylhexylamine nickel(II).

[0269] In the above, as an ultraviolet absorber, at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, azobenzene compounds, and polyphenol compounds is preferred.

[0270] Furthermore, from the viewpoint of resolution, it is more preferable to use at least one selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadien-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadien-3,5-dione as the ultraviolet absorber.

[0271] When the photosensitive resin composition disclosed herein contains an ultraviolet absorber, from the viewpoint of resolution, the content of the ultraviolet absorber is preferably greater than or equal to 0.05 parts by mass, more preferably greater than or equal to 0.1 parts by mass, and even more preferably greater than or equal to 0.2 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0272] Furthermore, from the viewpoint of preventing insufficient photocuring inside the coating film, it is preferable to have less than or equal to 5 parts by mass, more preferably less than or equal to 3 parts by mass, and even more preferably less than or equal to 2 parts by mass.

[0273] [Sensitizer]

[0274] The photosensitive resin composition disclosed herein may contain a sensitizer. By containing a sensitizer in the photosensitive resin composition, it is possible to maintain both residual film yield and good resolution over a wide range of exposures.

[0275] Examples of sensitizers include milchone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzoin, benzoin dimethyl condensate Ketones, benzoyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzyl)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzyl)cyclopentanone, 2,6-bis(p-diethylaminobenzyl)-4-phenylcyclohexanone, aminostyryl ketone, 3-coumarinone compounds, dicoumarin compounds, N-phenylglycine, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, etc.

[0276] A single sensitizer can be used alone, or two or more can be used in combination.

[0277] When the photosensitive resin composition disclosed herein contains a sensitizer, the amount of sensitizer is not particularly limited, but is preferably 0.1 to 1.0 parts by weight, more preferably 0.2 to 0.8 parts by weight, relative to 100 parts by weight of the unsaturated polyimide precursor.

[0278] (Other ingredients)

[0279] The photosensitive resin composition preferably further contains at least one selected from the group consisting of stabilizers and solvents. Additionally, the photosensitive resin composition may contain rust inhibitors, antioxidants, imidization accelerators, coupling agents, thermal polymerization initiators, surfactants, leveling agents, unavoidable components, etc.

[0280] [solvent]

[0281] Examples of solvents include esters, ethers, ketones, hydrocarbons, aromatic hydrocarbons, and sulfoxides. A single solvent can be used, or a combination of two or more can be used.

[0282] Examples of solvents for esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate, and other alkyl alkoxyacetic acids (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, and other alkyl 3-alkoxypropionate esters (e.g., methyl 3-methoxypropionate, ethyl ... Alkyl 2-alkoxypropionates (e.g., methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-alkoxypropionate, etc.), methyl 2-alkoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, methyl 2-alkoxy-2-methylpropionate, methyl 2-alkoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl 2-alkoxy-2-methylpropionate, methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

[0283] Examples of solvents that can be used to treat ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0284] Examples of solvents for ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP).

[0285] Examples of solvents for hydrocarbons include limonene.

[0286] Examples of solvents for aromatic hydrocarbons include toluene, xylene, and anisole.

[0287] Examples of sulfoxide solvents include dimethyl sulfoxide.

[0288] From the viewpoint of excellent solubility of each component and excellent coatability during the formation of the photosensitive resin film, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc. are preferred.

[0289] Alternatively, compounds represented by the following general formula (11) can be used as solvents.

[0290] [Chemistry 26]

[0291]

[0292] In general formula (11), R 41 ~R 43 Each is an alkyl group having 1 to 10 carbon atoms.

[0293] R in general formula (11) 41 ~R 43 The alkyl group represented preferably has 1 to 3 carbon atoms, more preferably 1 or 3.

[0294] As R 41 ~R 43 Specific examples of alkyl groups with 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, etc.

[0295] The compound represented by general formula (11) is preferably 3-methoxy-N,N-dimethylpropionamide (e.g., trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).

[0296] The solvent content can be adjusted appropriately according to the viscosity of the photosensitive resin composition, for example, relative to 100 parts by weight of the unsaturated polyimide precursor, it can be greater than or equal to 100 parts by weight, greater than or equal to 200 parts by weight, or greater than or equal to 400 parts by weight. From the viewpoint of reducing the drying energy when forming the coating film, the solvent may be omitted if necessary. For example, relative to 100 parts by weight of the unsaturated polyimide precursor, the solvent content can be less than 100 parts by weight, less than or equal to 75 parts by weight, or less than or equal to 50 parts by weight.

[0297] From the viewpoint of reducing environmental impact, the proportion of N-methyl-2-pyrrolidone in the total amount of solvent is preferably less than or equal to 10% by mass, more preferably less than or equal to 5% by mass, even more preferably less than or equal to 1% by mass, and particularly preferably free of (0% by mass) N-methyl-2-pyrrolidone.

[0298] [Stabilizer]

[0299] The photosensitive resin composition disclosed herein may contain a stabilizer. By containing a stabilizer in the photosensitive resin composition, good storage stability can be achieved.

[0300] Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluenequinone, tannic acid, p-benzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenolic compounds.

[0301] Stabilizers can be used alone or in combination of two or more. Combining two or more stabilizers, due to their varying reactivity, tends to allow for easier adjustment of photosensitivity properties. Hindered phenolic compounds can possess both the functions of a stabilizer and an antioxidant (described later), or either one of these functions.

[0302] Examples of stabilizers include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. [3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxycinnamoamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, N,N′-hexane-1,6-dimethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.

[0303] When the photosensitive resin composition disclosed herein contains a stabilizer, the stabilizer content is preferably 0.05 to 1.0 parts by weight, more preferably 0.1 to 0.8 parts by weight, relative to 100 parts by weight of the unsaturated polyimide precursor.

[0304] [Antioxidants]

[0305] From the viewpoint of suppressing adhesion degradation by capturing oxygen free radicals and peroxide free radicals generated during high-temperature storage, reflow treatment, etc., the photosensitive resin composition of this disclosure may contain an antioxidant. By including an antioxidant in the photosensitive resin composition of this disclosure, electrode oxidation during insulation reliability testing can be suppressed.

[0306] Specific examples of antioxidants include compounds exemplified as hindered phenolic compounds, such as N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxalamide, N,N'-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhexanediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid.

[0307] Antioxidants can be used alone or in combination of two or more.

[0308] When the photosensitive resin composition disclosed herein contains an antioxidant, the antioxidant content is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the unsaturated polyimide precursor.

[0309] Hindered phenolic compounds that act as antioxidants include: 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3- [Hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione )-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2,6-dimethylbenzyl)-trione 1,3,5-Triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc.

[0310] [Imidination Accelerator]

[0311] From the viewpoint of promoting imidization reactions, the resin compositions disclosed herein may contain imidization accelerators.

[0312] Specific examples of imidization promoters include N-phenyldiethanolamine, 2-(methylphenylamino)ethanol, 2-(ethylaniline)ethanol, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetaniline, and 4-aminoacetophenone, among which N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. A single nitrogen-containing compound may be used alone, or in combination of two or more.

[0313] When the resin composition disclosed herein contains an imidization accelerator, the content of the imidization accelerator is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the unsaturated polyimide precursor, more preferably 0.3 to 15 parts by weight from the viewpoint of storage stability, and even more preferably 0.5 to 10 parts by weight.

[0314] [Coupled agent]

[0315] The coupling agent is not particularly limited, but examples include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl]phthalyl Silane coupling agents such as dicarboxylic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, phenyl-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureopropyltriethoxysilane; aluminum-based adhesives such as tri(ethylacetoacetic acid)aluminum, tri(acetylacetone)aluminum, and ethylaluminum diisopropylacetoacetate.

[0316] Coupling agents can be used alone or in combination of two or more.

[0317] When the photosensitive resin composition disclosed herein contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 1 to 10 parts by mass, and even more preferably 2 to 10 parts by mass.

[0318] Rust Inhibitor

[0319] From the viewpoint of inhibiting corrosion of copper and copper alloys and preventing discoloration, the resin composition disclosed herein may contain a rust inhibitor.

[0320] There are no particular limitations on rust inhibitors; examples include azole compounds and purine derivatives.

[0321] Rust inhibitors can be used alone or in combination of two or more.

[0322] Specific examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)] [3,5-di-tert-butyl-2-hydroxyphenyl]benzotriazole, 2-(3,5-di-tert-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

[0323] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, and 8-aminoadenine. Acids, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives, etc.

[0324] When the photosensitive resin composition disclosed herein contains a rust inhibitor, the content of the rust inhibitor is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the unsaturated polyimide precursor, more preferably 0.1 to 5 parts by weight, and even more preferably 0.5 to 3 parts by weight.

[0325] [Surfactants and leveling agents]

[0326] Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, and polyoxyethylene octylphenol ether. Examples of commercially available products include those with trade names such as "MEGAFAC (registered trademark) F171", "F173", and "R-08" (manufactured by DIC Corporation), "FLUORAD FC430" and "FC431" (manufactured by Sumitomo 3M Corporation), and "Organosiloxane Polymer" KP 341, "KBM 303", and "KBM 803" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0327] Surfactants and leveling agents can be used alone or in combination of two or more.

[0328] When the photosensitive resin composition disclosed herein contains at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.05 to 3 parts by weight, relative to 100 parts by weight of the unsaturated polyimide precursor.

[0329] [Thermal polymerization initiator]

[0330] From the viewpoint of promoting polymerization reactions, the photosensitive resin compositions disclosed herein may further include a thermal polymerization initiator.

[0331] As a thermal polymerization initiator, it is preferably a compound that does not decompose during heating (drying) to remove solvent during film formation, but decomposes during heating during curing to generate free radicals, thereby promoting the polymerization reaction of polymerizable monomers with each other, or unsaturated polyimide precursors and polymerizable monomers.

[0332] The thermal polymerization initiator is preferably a compound with a decomposition point of 110°C to 200°C. From the viewpoint of promoting the polymerization reaction at lower temperatures, a compound with a decomposition point of 110°C to 175°C is more preferred.

[0333] Specific examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, peroxide ketals such as 1,1-di(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxide)cyclohexane, and 1,1-di(tert-butylperoxide)cyclohexane, peroxide hydrogen peroxide such as 1,1,3,3-tetramethylbutyl hydroperoxide, hydroperoxide such as cumene, hydroperoxide such as p-menthenane, diisopropylbenzene peroxide, and di-tert-butyl peroxide. Oxides, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di(4-tert-butylcyclohexyl) peroxide, di(2-ethylhexyl) peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide, etc.

[0334] As commercially available products, examples include "PERCUMYL D", "PERCUMYL P", and "PERCUMYL H" (all manufactured by Nippon Oil Co., Ltd.).

[0335] When the photosensitive resin composition disclosed herein contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 0.2 to 20 parts by mass to ensure good solderability, and even more preferably 0.3 to 10 parts by mass from the viewpoint of suppressing the decrease in solubility caused by decomposition during drying.

[0336] [Content of principal component]

[0337] In the photosensitive resin composition disclosed herein, the total amount of unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, sensitizer, ultraviolet absorber and solvent may be greater than or equal to 80% by mass, greater than or equal to 90% by mass or greater than or equal to 95% by mass.

[0338] In addition, in the photosensitive resin composition disclosed herein, the total amount of unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, sensitizer, ultraviolet absorber, solvent, stabilizer, imidization accelerator, rust inhibitor, antioxidant and coupling agent may be greater than or equal to 80% by mass, greater than or equal to 90% by mass, greater than or equal to 95% by mass, greater than or equal to 97% by mass, greater than or equal to 98% by mass or greater than or equal to 99% by mass.

[0339] <Cured product>

[0340] The cured product of this disclosure can be obtained by curing the photosensitive resin composition of this disclosure.

[0341] The cured product disclosed herein can be used as a patterned cured product.

[0342] The average thickness of the cured material is preferably 5 μm to 20 μm.

[0343] <Manufacturing Method of Cured Materials and Electronic Components>

[0344] The method for manufacturing a patterned cured product disclosed herein includes: a step of coating a photosensitive resin composition disclosed herein onto a substrate and drying it to form a photosensitive resin film; a step of pattern-exposing the photosensitive resin film to obtain a resin film; a step of developing the pattern-exposed resin film with a developer to obtain a patterned resin film; and a step of heat-treating the patterned resin film.

[0345] This allows us to obtain a patterned cured product.

[0346] Examples of substrates include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), metal oxide insulating substrates such as TiO2 substrates and SiO2 substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0347] The coating method of the photosensitive resin composition disclosed herein is not particularly limited, and can be carried out using a spin coater or the like.

[0348] Drying can be done using hot plates, ovens, etc.

[0349] The drying temperature is preferably 90°C to 150°C, and more preferably 90°C to 120°C from the viewpoint of ensuring solubility contrast.

[0350] The drying time is preferably 30 seconds to 5 minutes.

[0351] The drying process can be repeated more than twice.

[0352] Thus, it is possible to obtain a photosensitive resin film in which the photosensitive resin composition of the present disclosure is formed into a film.

[0353] The average thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, and even more preferably 7 μm to 30 μm.

[0354] Pattern exposure, for example, exposing a predetermined pattern through a light mask.

[0355] The active light source used for irradiation can include ultraviolet rays such as i-rays, visible light, and radiation, with i-rays being the preferred option.

[0356] As an exposure device, parallel exposure machines, aligners, projection exposure machines, step exposure machines, scanning exposure machines, etc. can be used.

[0357] By developing the resin, a patterned resin film (patterned resin film) can be obtained. Typically, when using a negative photosensitive resin composition, the unexposed areas are removed using a developer.

[0358] As a developer, a good solvent for photosensitive resin films can be used alone, or a good solvent and a bad solvent can be used in appropriate mixtures.

[0359] Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone.

[0360] Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0361] Surfactants may also be added to the developer. The amount added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the developer.

[0362] The development time can be set, for example, twice the time required to immerse the photosensitive resin film until it is completely dissolved.

[0363] The development time varies depending on the unsaturated polyimide precursor used, and is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, is even more preferably 20 seconds to 5 minutes.

[0364] After development, it can be cleaned using a rinsing solution.

[0365] As a rinsing solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., can be used alone or in appropriate combinations. They can also be used in stages.

[0366] By heating the patterned resin film, a cured pattern can be obtained.

[0367] The unsaturated polyimide precursor undergoes a dehydration and ring-closure reaction through a heat treatment process to become the corresponding polyimide resin.

[0368] The temperature of the heat treatment is preferably less than or equal to 250°C, more preferably 120°C to 250°C, and even more preferably 160°C to 200°C.

[0369] By heating the device to a temperature within the above range, damage to the substrate or device can be minimized, resulting in high-yield device production and energy-saving processes.

[0370] The heat treatment time is preferably less than or equal to 5 hours, and more preferably 30 minutes to 3 hours.

[0371] By heating the product for a period of time within the above-mentioned range, the cross-linking reaction or the dehydration and ring-closing reaction can be fully carried out.

[0372] The atmosphere for heat treatment can be atmospheric or an inactive atmosphere such as nitrogen, but from the viewpoint of preventing oxidation of the patterned resin film, a nitrogen atmosphere is preferred.

[0373] Examples of devices used for heat treatment include quartz tube furnaces, hot plates, rapid heat annealing furnaces, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0374] The cured products of this disclosure can be used as interlayer insulating films, overlay coatings, or surface protective films. Furthermore, the cured products of this disclosure can be used as passivation films, buffer coatings, etc.

[0375] One or more of the following can be selected from the group consisting of passivation film, buffer coating, interlayer insulating film, cover coating and surface protective film to manufacture high-reliability semiconductor devices, multilayer wiring boards, various electronic devices, stacked devices (multi-chip fan-out wafer-level packages, etc.) and other electronic components.

[0376] Referring to the accompanying drawings, an example of the manufacturing process of a semiconductor device, which is an electronic component of this disclosure, will be described.

[0377] Figure 1 This is a manufacturing process diagram of a semiconductor device with a multilayer wiring structure, which is an electronic component according to one embodiment of this disclosure.

[0378] exist Figure 1 In this process, a semiconductor substrate 1, such as a Si substrate, containing circuit elements, is covered with a protective film 2, such as a silicon oxide film, except for a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Then, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0379] Next, a photosensitive resin layer 5, such as a chlorinated rubber-based or phenolic varnish-based resin, is formed on the interlayer insulating film 4. A window 6A is then provided by using known photolithography techniques to expose a predetermined portion of the interlayer insulating film 4.

[0380] Selective etching is performed on the interlayer insulating film 4 that exposes window 6A to create window 6B.

[0381] Next, the photosensitive resin layer 5 is removed by using an etching solution that does not corrode the first conductor layer 3 exposed from window 6B but corrodes the photosensitive resin layer 5.

[0382] Then, using known photolithography techniques, a second conductor layer 7 is formed to make an electrical connection with the first conductor layer 3.

[0383] In the case of forming a multi-layer wiring structure with three or more layers, the above process can be repeated to form each layer.

[0384] Next, using the photosensitive resin composition disclosed herein, windows 6C are opened by pattern exposure to form a surface protective film 8. The surface protective film 8 protects the second conductor layer 7 from external stress, alpha rays, etc., resulting in a semiconductor device with excellent reliability.

[0385] It should be noted that, in the above examples, the photosensitive resin composition of this disclosure can also be used to form the interlayer insulating film 4.

[0386] Example

[0387] The present disclosure will be further described in detail below based on embodiments and comparative examples. It should be noted that the present disclosure is not limited to the following embodiments.

[0388] [Examples 1-9 and Comparative Examples 1-7]

[0389] The components listed in Table 1 or Table 2 were combined in the amounts specified in Table 1 or Table 2 to prepare a homogeneous solution. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 1 μm to obtain the photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-7.

[0390] It should be noted that the proportions of each component in Tables 1 and 2 are based on parts by mass. Additionally, in Tables 1 and 2, "-" indicates that the corresponding component is not present.

[0391] The details of each component recorded in Tables 1 and 2 are as follows.

[0392] Polyimide precursor

[0393] Synthesis of Polymer I

[0394] 380 g of N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical Corporation) was placed in a 2 L detachable flask, and 47.08 g (152 mmol) of 4,4'-oxophthalic anhydride (ODPA, Manac Corporation) was added while stirring until dissolved. Then, 0.24 g (2.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane, Fujifilm and Hikari Pure Chemicals Co., Ltd.) was added and dissolved, followed by 5.54 g (42.6 mmol) of 2-hydroxyethyl methacrylate (HEMA, Fujifilm and Hikari Pure Chemicals Co., Ltd.). The mixture was stirred at 30 °C for 1 hour to obtain the reaction solution.

[0395] In addition, 27.4 g (129 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP, Wakayama Seika Kogyo Co., Ltd.) was dissolved in 145 g of NMP to prepare a DMAP solution.

[0396] DMAP solution was added dropwise while stirring the reaction solution at 35°C, and the mixture was stirred at 30°C for 3 hours. Next, 59.7 g (284 mmol) of TFAA (trifluoroacetic anhydride, Fujifilm and Hikari Pure Chemicals Co., Ltd.) was added dropwise at 30°C. After stirring at 45°C for 2 hours, 0.08 g (0.74 mmol) of BQ (benzoquinone, Fujifilm and Hikari Pure Chemicals Co., Ltd.) was added, followed by 40.4 g (310 mmol) of HEMA. After stirring for 15 hours, the mixture was cooled to room temperature. The reaction solution was added to purified water, the precipitate was recovered, washed with purified water, and dried under reduced pressure to obtain polymer I as a precursor to unsaturated polyimide.

[0397] The weight-average molecular weight (Mw) of polymer I is 22,100.

[0398] The weight-average molecular weight of the polymer was calculated by gel permeation chromatography (GPC) using a calibration curve based on the TSKgel standard polystyrene (Tosoh Corporation). The apparatus and conditions are shown below. It should be noted that the sample was prepared by dissolving 2 mg of the sample in 1 mL of eluent (tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (v / v)) and filtering it through a 1 μm PTFE membrane filter.

[0399] ·Device: Shimadzu Corporation, Prominence

[0400] ·Column: Lisenok Co., Ltd., Gelpak GL S300MDT-5

[0401] • Eluent: THF / DMF = 1 / 1 (v / v), lithium bromide 0.03 mol / L, phosphoric acid 0.06 mol / L

[0402] • Flow rate: 1.0 mL / min

[0403] • Measurement wavelength: 270nm

[0404] Injection volume: 10μL

[0405] Solvent:

[0406] I: γ-Butyrolactone

[0407] II: N-methyl-2-pyrrolidone

[0408] Polymerizable monomers

[0409] I: Triethylene glycol dimethacrylate (2-functional)

[0410] II: Tricyclodecanediethanol diacrylate (2-functional)

[0411] III: Polyethoxylated pentaerythritol tetraacrylate (4 functionalities)

[0412] IV: Tri-(2-Acryloyloxyethyl)isocyanurate (3-functional)

[0413] Photopolymerization initiator

[0414] I: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime)

[0415] II: 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone

[0416] III: 1-Phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]

[0417] Sensitizer: 4,4'-bis(diethylamino)benzophenone (EMK, Merck)

[0418] • UV absorber: curcumin

[0419] (Determination of I-ray transmittance of photosensitive resin film)

[0420] The obtained photosensitive resin composition was spin-coated onto quartz glass using an MS-B150 spin coater (manufactured by MIKASA Corporation). The glass was then pre-baked at 100°C for 120 seconds and then at 110°C for 120 seconds to produce a photosensitive resin film with a thickness of 7 μm.

[0421] The transmittance of i-rays (wavelength 365nm) was measured using a U-3900H series spectrophotometer (manufactured by Hitachi High Technology Co., Ltd.).

[0422] (Resolution evaluation)

[0423] A photosensitive resin film with a thickness of 7 μm was obtained using the same method as the i-ray transmittance determination described above. The development time was set as 1.2 times the time it took for the photosensitive resin film to be immersed in cyclopentanone until it was completely dissolved.

[0424] In addition, a photosensitive resin film was prepared using the same method as described above. The resulting photosensitive resin film was then exposed using an i-ray stepper FPA-3000iW (manufactured by Canon Corporation) at an exposure dose of 900 mJ·cm⁻¹. 2 The through-hole is formed by irradiating a photomask for exposure.

[0425] After exposure, the resin film is subjected to immersion development with cyclopentanone for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain the patterned resin film.

[0426] The patterned resin film was heated at 170°C for 3 hours in a vertical diffusion furnace μ-TF (manufactured by Koyo Thermal Systems Co., Ltd.) under a nitrogen atmosphere to obtain a cured patterned material (5 μm thick after curing).

[0427] The resulting patterned cured material was observed using an optical microscope, and the minimum diameter of the opening that exposed more than 55% of the substrate surface relative to the mask size of the through-hole was taken as the resolution. The results are shown in Table 2.

[0428] (Evaluation of residual film rate (FR) after development)

[0429] A photosensitive resin film was obtained using the same method as the i-ray transmittance measurement described above. Furthermore, a patterned resin film was obtained using the same method as the resolution evaluation.

[0430] The thickness of the obtained photosensitive resin film (before development) and patterned resin film (after development) was measured using a probe profilometer Dektak 150 (manufactured by Bruker), and the residual film rate after development was calculated using the following formula.

[0431] Residual film yield (FR)% after development = (thickness of patterned resin film (after development) / thickness of photosensitive resin film (before development)) × 100

[0432] [Table 1]

[0433]

[0434] [Table 2]

[0435]

[0436] As shown in Table 1, if the photosensitive resin compositions of Examples 1 to 5, which contain a polyimide precursor having polymerizable unsaturated bonds and a polymerizable monomer with more than 3 functions, and whose i-ray transmittance of the photosensitive resin film is less than or equal to 30%, are used, it is possible to form a through-hole pattern with a diameter of less than 6 μm.

[0437] On the other hand, in the photosensitive resin compositions of Comparative Examples 3 to 7 that do not contain polymerizable monomers with more than three functions, it is impossible to form through-hole patterns with a diameter of less than 6 μm.

[0438] Furthermore, in the photosensitive resin compositions of Comparative Examples 1 and 2, which contained polymerizable monomers with three or more functions but had an i-ray transmittance of more than 30%, it was also impossible to form a through-hole pattern with a diameter of less than 6 μm.

[0439] It should be noted that solvent I was used in the examples and solvent II was used in the comparative examples. However, the solvents were removed by heating before the i-ray transmittance measurement and before exposure, so the influence of the solvents was minimal in the measurement and evaluation.

[0440] As an example of the formed through-hole pattern Figure 2 (A) shows a cross-sectional SEM image of a through-hole pattern formed using the photosensitive resin composition of Example 1. Figure 2 (B) shows a cross-sectional SEM image of the through-hole pattern formed using the photosensitive resin composition of Comparative Example 1. It should be noted that this cross-sectional SEM image was taken after ion beam (FIB) excavation in a manner that allows observation of the cross-section of the through-hole pattern.

[0441] like Figure 2 As shown in (A), it can be seen that in Example 1, the pattern is formed with good rectangularity up to the bottom. In contrast, as shown in... Figure 2 As shown in (B), microbridges were generated in Comparative Example 1. Comparative Example 1 contained polymerizable monomers with more than three functions, and the i-ray transmittance when the product was cured was greater than 30%. Therefore, it was believed that the polymerization reaction was excessively carried out through i-rays reflected from the substrate.

[0442] Explanation of reference numerals in the attached figures

[0443] 1. Semiconductor substrate

[0444] 2. Protective film

[0445] 3 First Conductor Layer

[0446] 4-layer insulating film

[0447] 5. Photosensitive resin layer

[0448] Windows 6A, 6B, and 6C

[0449] 7 Second conductor layer

[0450] 8. Surface protective film.

Claims

1. A photosensitive resin composition comprising a polyimide precursor having polymerizable unsaturated bonds, a polymerizable monomer with three or more functions, and a photopolymerization initiator. The i-ray transmittance of a 7 μm thick photosensitive resin film obtained by heating the photosensitive resin composition at 100°C for 120 seconds and then at 110°C for 120 seconds is less than or equal to 30%.

2. The photosensitive resin composition according to claim 1, wherein the polyimide precursor having polymerizable unsaturated bonds has a structural unit represented by the following general formula (1), [Chemistry 1] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R... 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has polymerizable unsaturated bonds.

3. The photosensitive resin composition according to claim 1 or 2, further comprising at least one selected from the group consisting of a sensitizer and an ultraviolet absorber.

4. The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator comprises an oxime compound.

5. A method for manufacturing a patterned cured material, comprising: The process of coating the photosensitive resin composition according to any one of claims 1 to 4 onto a substrate and drying it to form a photosensitive resin film; The process of obtaining a resin film by pattern exposure of the photosensitive resin film; The process of developing the patterned resin film using a developer to obtain a patterned resin film; and The process of heat-treating the patterned resin film.

6. A patterned cured product, which is formed by curing the photosensitive resin composition according to any one of claims 1 to 4.

7. The patterned cured material according to claim 6, which is used as an interlayer insulating film, a covering coating, or a surface protective film.

8. An electronic component comprising the patterned cured material of claim 6 or 7.

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