Photosensitive resin composition, method for manufacturing patterned cured product, and cured product

Abstract

A photosensitive resin composition comprising (A) a polyimide precursor, (B) a polymerizable monomer not containing a cyclic skeleton, (C) a photopolymerization initiator, and (D) a compound containing an anthracene structure, the content of a polymerizable monomer containing a cyclic skeleton being less than or equal to 20% by mass relative to the total amount of the (A) polyimide precursor.

Description

Technical Field

[0001] This disclosure relates to a photosensitive resin composition, a method for manufacturing a patterned cured product, and the cured product. Background Technology

[0002] Conventionally, polyimide, polybenzoxazole, and other resins 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 (see, for example, Patent Document 1).

[0003] In recent years, the miniaturization of transistors, which has been supporting the high performance of computers, has reached the limit of the law of scale. In order to further increase performance and speed, the stacked device structure, in which semiconductor elements are stacked in three dimensions, has attracted attention.

[0004] In stacked device structures, multi-die fanout wafer level packaging is a type of packaging that seals multiple chips together in a single package. Compared to previously proposed fanout wafer level packaging (which seals a single chip in a single package), it is expected to offer lower costs and higher performance, and therefore has attracted much attention.

[0005] In the fabrication of multi-chip fan-out wafer-level packaging, from the perspectives of protecting high-performance chips, protecting sealing materials with low heat resistance, and improving yield, low-temperature curing capability is strongly required (for example, see Patent Document 2).

[0006] In addition, as a resin composition, a resin composition containing a polyimide precursor has been disclosed (for example, see Patent Document 3).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2009-265520

[0010] Patent Document 2: International Publication No. 2008 / 111470

[0011] Patent Document 3: Japanese Patent Application Publication No. 2016-199662 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] In photosensitive resin compositions containing polyimide precursors, there is a need to improve exposure-based reactivity, for example, to increase the residual film yield of the cured film. Furthermore, when a cured film of a photosensitive resin composition is formed on a substrate such as a silicon wafer, it is necessary to suppress warping after curing.

[0014] The purpose of this disclosure is to provide a photosensitive resin composition with excellent reactivity and the ability to suppress warping after curing, a method for manufacturing a patterned cured product using the photosensitive resin composition, and a cured product obtained by curing the photosensitive resin composition.

[0015] Methods for solving problems

[0016] The specific methods for achieving the above objectives are as follows.

[0017] <1> A photosensitive resin composition comprising:

[0018] (A) Polyimide precursor,

[0019] (B) Polymerizable monomers without a cyclic backbone

[0020] (C) Photopolymerization initiator, and

[0021] (D) Compounds containing anthracene structure

[0022] The content of polymerizable monomers containing a cyclic backbone is less than or equal to 20% by mass relative to the total amount of the polyimide precursor (A).

[0023] <2> The photosensitive resin composition according to <1> further comprises (E) solvent.

[0024] <3> According to the photosensitive resin composition described in <1> or <2>, the polymerizable monomer (B) above comprises a (meth)acrylic compound containing two (meth)acrylic groups.

[0025] <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymerizable monomer of the above (B) comprises a (meth)acrylic acid compound containing three or more (meth)acrylic acid groups.

[0026] <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the polyimide precursor comprises a compound having a structural unit represented by the following general formula (1).

[0027] [Chemistry 1]

[0028]

[0029] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R... 6and 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.

[0030] <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the above-mentioned (D) compound comprises a compound represented by the following general formula (D).

[0031] [Chemistry 2]

[0032]

[0033] In general formula (D), R x Each of the following is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 5 to 18 carbon atoms, or a halogen atom, where n is an integer from 0 to 10.

[0034] <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the above-mentioned (D) compound comprises at least one selected from the group consisting of dibutoxyanthracene, dimethoxyanthracene, diethoxyanthracene and diethoxyethylanthracene.

[0035] <8> The photosensitive resin composition according to any one of <1> to <7> further comprises (F) a thermal polymerization initiator.

[0036] <9> The photosensitive resin composition according to any one of <1> to <8> is used for panel-level encapsulation.

[0037] <10> A method for manufacturing a patterned cured material, comprising:

[0038] The process of coating the photosensitive resin composition described in any one of <1> to <9> onto a substrate and drying it to form a photosensitive resin film;

[0039] The process of obtaining a resin film by pattern exposure of the above-mentioned photosensitive resin film;

[0040] The process of developing the above-mentioned resin film after pattern exposure using an organic solvent to obtain a patterned resin film; and

[0041] The process of heat-treating the above-mentioned patterned resin film.

[0042] <11> A cured product, which is formed by curing the photosensitive resin composition described in any one of <1> to <9>.

[0043] Invention Effects

[0044] According to this disclosure, a photosensitive resin composition with excellent reactivity and the ability to suppress warping after curing, a method for manufacturing a patterned cured product using the photosensitive resin composition, and a cured product obtained by curing the photosensitive resin composition are provided. Attached Figure Description

[0045] Figure 1 This is a manufacturing process diagram of an electronic component according to one embodiment of the present disclosure. Detailed Implementation

[0046] The following describes in detail the methods for implementing this disclosure. However, this disclosure is not limited to the following embodiments.

[0047] In this disclosure, except where specifically stated otherwise, the constituent elements (including element steps, etc.) are not essential. Similarly, numerical values ​​and their ranges do not limit this disclosure.

[0048] 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.

[0049] In this disclosure, within the numerical range represented by “~”, the numerical values ​​recorded before and after “~” are respectively the minimum and maximum values.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] In this disclosure, the 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.

[0054] The thickness of a layer or film can be measured using a micrometer or similar tool. In this disclosure, when the thickness of a layer or film can be measured directly, a micrometer is used. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, the measurement can be performed by observing a cross-section of the object being measured using an electron microscope.

[0055] In this disclosure, "(meth)acrylate" refers to "acrylate" and "methacrylate", "(meth)acrylate" refers to "acrylate" and "methacrylate", and "(meth)acryloyl" refers to "acryloyl" and "methacryloyl".

[0056] In this disclosure, when the functional group has substituents, the number of carbon atoms in the functional group refers to the total number of carbon atoms, including the number of carbon atoms of the substituents.

[0057] In this disclosure, embodiments are described with reference to the accompanying drawings, but the configuration of these embodiments is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in the drawings are conceptual, and the relative sizes of the components are not limited thereto.

[0058] <Photosensitive Resin Composition>

[0059] The photosensitive resin composition disclosed herein comprises (A) a polyimide precursor, (B) a polymerizable monomer without a cyclic backbone, (C) a photopolymerization initiator and (D) a compound containing an anthracene structure, wherein the content of the polymerizable monomer containing a cyclic backbone is less than or equal to 20% by mass relative to the total amount of the polyimide precursor (A).

[0060] The photosensitive resin composition disclosed herein exhibits excellent reactivity and is able to suppress warping after curing. The reasons for this are speculated as follows. It should be noted that this disclosure is not limited to the following speculation.

[0061] The photosensitive resin composition exhibits excellent exposure-based reactivity by comprising (A) a polyimide precursor and (D) a compound containing an anthracene structure. For example, there is a tendency to produce cured products with excellent photosensitivity and high residual film yield upon h-ray exposure.

[0062] Furthermore, the photosensitive resin composition contains (B) polymeric monomers without a cyclic backbone, and the content of polymeric monomers containing a cyclic backbone is less than or equal to 20% by mass, preferably less than or equal to 10% by mass, and more preferably less than or equal to 5% by mass, relative to the total amount of the polyimide precursor (A). This enables the suppression of warping after curing.

[0063] There is no particular limit to the lower limit of the content of polymerizable monomers containing cyclic skeletons; it can be 0 by mass.

[0064] Furthermore, by using a polymerizable monomer containing a cyclic framework and (D) a compound containing an anthracene structure, peeling (undercutting) is likely to occur at the bottom of the opening side of the cured product during production. In this disclosure, by reducing the content of the polymerizable monomer containing the cyclic framework, undercutting as described above can be suppressed.

[0065] The photosensitive resin composition disclosed herein is preferably a negative photosensitive resin composition.

[0066] Furthermore, from the viewpoint of photosensitivity during h-ray exposure, the photosensitive resin composition of this disclosure is preferably used for panel-level packaging (e.g., packaging with a structure where there is no packaging substrate, but instead a rewiring layer that connects to external terminals by routing wires from the chip terminals). The photosensitive resin composition of this disclosure is preferably a material for panel-level packaging or a material for electronic components.

[0067] The following describes in detail the components contained in the photosensitive resin composition disclosed herein.

[0068] (A) Polyimide precursor)

[0069] The photosensitive resin composition disclosed herein comprises (A) a polyimide precursor (hereinafter also referred to as "(A) component").

[0070] (A) The preferred component is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Polyamic acid ester and polyamic acid amide are compounds in which at least a portion of the hydrogen atoms of the carboxyl groups in polyamic acid are replaced by monovalent organic groups, and polyamic acid salt is a compound in which at least a portion of the carboxyl groups in polyamic acid form a salt structure with a basic compound with a pH greater than 7.

[0071] (A) Components can have polymerizable unsaturated bonds.

[0072] (A) The components preferably include compounds having structural units represented by the following general formula (1). As a result, there is a tendency to obtain electronic components with cured products exhibiting high reliability.

[0073] [Chemistry 3]

[0074]

[0075] 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.

[0076] The polyimide precursor may 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.

[0077] 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 It can be at least one hydrogen atom and the rest monovalent organic groups described later, or it can be monovalent organic groups that are all the same or different from each other. As mentioned above, when the 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.

[0078] 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.

[0079] 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.

[0080] When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have substituents or no substituents. Examples of substituents for aromatic rings include alkyl groups, fluorine atoms, haloalkyl groups, hydroxyl groups, and amino groups.

[0081] 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.

[0082] 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 BEach 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 sites, forming a 5-membered or 6-membered ring containing the linking group between the two benzene rings.

[0083] 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.

[0084] Specific examples of the tetravalent organic group represented by X include groups represented by formulas (A) to (F) below. From the viewpoint of obtaining a cured product with excellent flexibility, 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.

[0085] It should be noted that this disclosure is not limited to the specific examples described below.

[0086] [Chemistry 4]

[0087]

[0088] 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.

[0089] 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 formed by combining at least two of these. C preferably contains an ether bond, and more particularly an ether bond.

[0090] In addition, C may contain the structure represented by the following formula (C1).

[0091] [Chemistry 5]

[0092]

[0093] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.

[0094] Specific examples of the alkylene group represented by C in formula (E) include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene, methyl ethylene, ethyl methylene, dimethylmethylene, 1,1-dimethyl ethylene, 1-methyl trimethylene, 2-methyl trimethylene, ethyl ethylene, 1-methyl tetramethylene, 2-methyl tetramethylene, 1-ethyl trimethylene, 2-ethyl trimethylene, 1,1 Branched alkylene groups, such as dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene, are preferred.

[0095] The alkyl halide represented by C in formula (E) is preferably an alkyl halide with 1 to 10 carbon atoms, more preferably an alkyl halide with 1 to 5 carbon atoms, and even more preferably an alkyl halide with 1 to 3 carbon atoms.

[0096] As a specific example of a haloalkylene group represented by C in formula (E), an alkylene group in which at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) is replaced by a halogen atom such as a fluorine atom or a chlorine atom can be given. Among them, fluoromethylene, difluoromethylene, hexafluorodimethylmethylene, etc. are preferred.

[0097] As the R contained in the above-mentioned methylene silane bond or siloxane bond A Or R B The alkyl group represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. As R A Or RB Specific examples of the alkyl groups represented include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0098] 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.

[0099] The skeleton of the divalent organic group represented by Y can 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 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).

[0100] 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.

[0101] 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 a cured product with excellent flexibility, groups represented by the following formula (H) are preferred, wherein in the following formula (H), D is more preferably 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.

[0102] [Chemistry 6]

[0103]

[0104] 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.

[0105] 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 BEach 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).

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] As a specific example of the alkyl halide represented by R in formulas (G) to (H), one can refer to 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. Among these, fluoromethyl, difluoromethyl, trifluoromethyl, etc. are preferred.

[0113] In formulas (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0114] Specific examples of the divalent aliphatic group represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups with polyoxyalkylene structures.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] Specific examples of cycloalkylene compounds represented by Y include cyclopropylene and cyclohexylene.

[0119] 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.

[0120] 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 with a polysiloxane structure in which silicon atoms are bonded to hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, or aryl groups with 6 to 18 carbon atoms.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] The silicon atoms of the divalent groups that constitute the polysiloxane structure represented by Y can be bonded to the NH group in general formula (1) via alkylene groups such as methylene and ethylene, arylene groups such as phenylene, etc.

[0125] 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, the group represented by formula (H') or formula (H”) below is more preferred.

[0126] [Chemistry 7]

[0127]

[0128] 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.

[0129] 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). Examples of combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include combinations where X is a group represented by formula (E) and Y is a group represented by formula (H).

[0130] R 6 and R 7 Each 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 includes an aliphatic hydrocarbon group having 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).

[0131] In the case where 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 a base or the like.

[0132] 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.

[0133] [Chemistry 8]

[0134]

[0135] 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.

[0136] 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.

[0137] R in general formula (2) 8 ~R 10 The combination of R is preferred. 8 and R 9 For hydrogen atoms, R 10 It is a combination of hydrogen atoms or methyl groups.

[0138] 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.

[0139] R x The number of carbon atoms in the sample is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0140] 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.

[0141] When (A) the polyimide precursor comprises a compound having structural units represented by the general formula (1) above, 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%.

[0142] It should be noted that the above ratio can be greater than or equal to 0 mol% and less than 60 mol%.

[0143] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0144] [Chemistry 9]

[0145]

[0146] 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.

[0147] 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.

[0148] 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%, relative to all structural units. There is no particular upper limit to the above percentage, which can be 100 mol%.

[0149] (A) The polyimide precursor can be synthesized using tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. It should be noted that (A) the polyimide precursor can also be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0150] 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, 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'-isopropylidenediphenoxy)phthalic 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-dicarboxy) 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 dispirocyclic norbornene tetracarboxylic dianhydride, 2,2-bis{4-(4'-phenoxy)phenyl}propane tetracarboxylic dianhydride, etc. Preferably, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride are preferred.

[0151] Tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0152] 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. From the viewpoint of having a soft skeleton and excellent adhesion, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane are more preferred.

[0153] Diamine compounds can be used alone or in combination with two or more.

[0154] Having structural units 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).

[0155] (a) After preparing a diester derivative by reacting a tetracarboxylic dianhydride (preferably the tetracarboxylic dianhydride represented by the general formula (8) below) with a compound represented by R-OH in an organic solvent, the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2.

[0156] (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.

[0157] 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 situation is the same.

[0158] 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 alone or in combination of two or more.

[0159] 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.

[0160] Alternatively, a dehydrating condensing agent can be reacted together with the compound represented by R-OH in a polyamic acid solution to synthesize a 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).

[0161] (A) The above-mentioned compounds contained in the 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 reacting a chlorinating agent such as thionyl chloride, and then reacting the diamine compound represented by H2N-Y-NH2 with the acyl chloride.

[0162] (A) The above-mentioned compounds contained in the 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.

[0163] (A) The above-mentioned compounds contained in the 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.

[0164] [Chemistry 10]

[0165]

[0166] 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.

[0167] The compound represented by R-OH used in the synthesis of the above-mentioned compound contained in (A) polyimide precursor can be the R-OH group represented by the group in general formula (2). x Compounds 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.

[0168] (A) The molecular weight of the polyimide precursor is not particularly limited, but is preferably 10,000 to 200,000 by weight-average molecular weight, and more preferably 10,000 to 100,000.

[0169] Weight-average molecular weight can be determined, for example, by gel permeation chromatography, or by conversion using a standard polystyrene standard curve.

[0170] The photosensitive resin composition disclosed herein may comprise resins other than (A) the polyimide precursor. Examples of such other resins, from the viewpoint of heat resistance, include polyimide resins, 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.

[0171] In the photosensitive resin composition disclosed herein, the content of (A) polyimide precursor relative to the total amount of polymer components is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0172] (B) Polymerizable monomers without a cyclic backbone)

[0173] The photosensitive resin composition disclosed herein comprises (B) a polymerizable monomer without a cyclic backbone (hereinafter also referred to as "(B) component"). Component (B) preferably comprises at least one group containing a polymerizable unsaturated double bond, and more preferably comprises at least one (meth)acrylate group, from the viewpoint that it can be suitably polymerized by use in conjunction with a photopolymerization initiator (C). From the viewpoint of increasing crosslinking density and photosensitivity, it preferably comprises 2 to 6 groups containing polymerizable unsaturated double bonds, and more preferably 2 to 4 groups.

[0174] Polymerizable monomers can be used alone or in combination of two or more.

[0175] (B) The polymerizable monomer may include (meth)acrylic compounds containing two (meth)acrylic groups (difunctional (meth)acrylic compounds), or (meth)acrylic compounds containing three or more (meth)acrylic groups (polyfunctional (meth)acrylic compounds), or the above-mentioned difunctional (meth)acrylic compounds and polyfunctional (meth)acrylic compounds.

[0176] As a polymerizable monomer containing (meth)acrylic acid groups, there are no particular limitations; examples include:

[0177] (Meth)acrylic acid compounds such as 2-hydroxyethyl methacrylate containing one (meth)acrylic acid group;

[0178] 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, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, and other (meth)acrylic acid compounds containing two (meth)acrylate groups; and

[0179] Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, and other (meth)acrylic acid compounds containing three or more (meth)acrylic acid groups.

[0180] (B) The component may also be tetraethylene glycol dimethacrylate, ethoxylated pentaerythritol tetraacrylate or a mixture thereof.

[0181] (B) The component may be a polymeric monomer containing (meth)acrylic acid groups, or a polymeric monomer other than a polymeric monomer containing (meth)acrylic acid groups, or a combination thereof.

[0182] There are no particular limitations on polymerizable monomers other than those containing (meth)acrylic acid groups, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide.

[0183] (B) The component is not limited to a compound having a group containing a polymeric unsaturated double bond, but may also be a compound having a polymeric group other than an unsaturated double bond group (e.g., an ethylene oxide ring).

[0184] When the photosensitive resin composition disclosed herein contains component (B), the content of component (B) is not particularly limited, but is preferably 1 to 100 parts by mass relative to 100 parts by mass of component (A), more preferably 5 to 75 parts by mass, even more preferably 10 to 50 parts by mass, and particularly preferably 25 to 45 parts by mass.

[0185] When component (B) is a mixture of tetraethylene glycol dimethacrylate (B1) and ethoxylated pentaerythritol tetraacrylate (B2), the mass ratio of B2 to B1 (B2 / B1) can be 30 / 100 to 100 / 100 or 40 / 100 to 70 / 100.

[0186] (C) Photopolymerization initiator)

[0187] The photosensitive resin composition disclosed herein may contain (C) a photopolymerization initiator (hereinafter also referred to as "(C) component").

[0188] As a component (C), there are no particular limitations; for example, the following can be cited:

[0189] 1-Phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenyltriketone-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxytriketone Oxime compounds such as ketone-2-(O-benzoyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyl oxime), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 1-[4-(4-hydroxyethoxyphenylthio)phenyl]-1,2-propanedione-2-(O-acetyl oxime);

[0190] Acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylacetophenone, 4'-(methylthio)-α-morpholino-α-methylacetophenone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives;

[0191] Thioxanone, 2-methylthioxanone, 2-isopropylthioxanone, 2-chlorothioxanone, diethylthioxanone and other thioxanone derivatives;

[0192] Benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal, and benzoyl-β-methoxyethyl acetal;

[0193] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin and other benzoin derivatives;

[0194] N-phenylglycine and other N-arylglycine derivatives;

[0195] Benzoyl peroxide and other peroxides;

[0196] Aromatic biimidazolium derivatives such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazolium dimer;

[0197] Acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, Irgacure OXE03 (manufactured by BASF), and Irgacure OXE04 (manufactured by BASF).

[0198] From the viewpoint of excellent exposure sensitivity, component (C) preferably contains oxime compounds.

[0199] (C) Components can be used alone or in combination of two or more.

[0200] The content of oxime compounds relative to the total amount of component (C) is preferably greater than or equal to 60% by mass, more preferably greater than or equal to 80% by mass, further preferably greater than or equal to 90% by mass, and particularly preferably greater than or equal to 95% by mass.

[0201] The content of component (C) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 20 parts by mass, even more preferably 2 to 10 parts by mass, and particularly preferably 3 to 6 parts by mass.

[0202] ((D) Compounds containing anthracene structures)

[0203] The photosensitive resin composition disclosed herein preferably further comprises (D) a compound containing an anthracene structure (hereinafter also referred to as "(D) component").

[0204] From the perspective of balancing sensitivity and resolution, component (D) preferably contains compounds represented by general formula (D).

[0205] [Chemistry 11]

[0206]

[0207] In general formula (D), R x Each of the following is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 5 to 18 carbon atoms, or a halogen atom, where n is an integer from 0 to 10.

[0208] The alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 2 to 5 carbon atoms.

[0209] Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, tert-butyl, and n-butyl.

[0210] The alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 2 to 5 carbon atoms.

[0211] Specific examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, and butoxy (e.g., n-butoxy).

[0212] The aryl group having 6 to 18 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.

[0213] Specific examples of aryl groups with 6 to 18 carbon atoms include phenyl and naphthyl groups.

[0214] The heteroaryl group having 5 to 18 atoms is preferably a heteroaryl group having 5 to 12 atoms, and more preferably a heteroaryl group having 5 to 10 atoms.

[0215] Specific examples of heteroaryl groups with 5 to 18 atoms include pyridyl, quinolinyl, and carbazolyl.

[0216] From the viewpoint of balancing solubility and photosensitivity in the photosensitive resin composition, component (D) preferably includes dialkoxyanthracene (e.g., 9,10-dialkoxyanthracene) which may have substituents, and more preferably includes at least one selected from the group consisting of dibutoxyanthracene (e.g., 9,10-dibutoxyanthracene), dimethoxyanthracene (e.g., 9,10-dimethoxyanthracene), diethoxyanthracene (e.g., 9,10-diethoxyanthracene) and diethoxyethylanthracene (e.g., 9,10-diethoxy-2-ethylanthracene).

[0217] Examples of substituents include methyl, ethyl, tert-butyl, and n-butyl.

[0218] (D) Components can be used alone or in combination of two or more.

[0219] From the viewpoint of improving solubility and photosensitivity in the photosensitive resin composition, the content of component (D) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 0.2 to 10 parts by mass, even more preferably 0.3 to 5 parts by mass, and particularly preferably 0.4 to 2 parts by mass.

[0220] ((E) solvent)

[0221] The photosensitive resin composition disclosed herein preferably further comprises (E) solvent (hereinafter also referred to as "(E) component").

[0222] As for component (E), there are no particular limitations, and examples include ester solvents, ketone solvents, carbonate solvents, heterocyclic compound solvents, amide solvents, etc.

[0223] Ester solvents, ketone solvents, carbonate solvents, and amide solvents may or may not have a cyclic structure.

[0224] (E) Components can be used alone or in combination of two or more.

[0225] (E) The component may include, for example, at least one of the groups of compounds represented by formulas (3) to (10) below.

[0226] (E) Components can be used alone or in combination of two or more.

[0227] [Chemistry 12]

[0228]

[0229] [Chemistry 13]

[0230]

[0231] In equations (3) to (10), R 1 R 2 R 8 R 10 R 11 R 13 and R 14 Each is an alkyl group having 1 to 4 carbon atoms, R 3 ~R 7 R 9 and R 12 Each is independently an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, u is an integer from 0 to 3, v is an integer from 0 to 3, w is an integer from 0 to 4, and x is an integer from 0 to 5.

[0232] In equation (3), s is preferably 0.

[0233] In equation (4), R is used as 2 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. t is preferably 0, 1 or 2, more preferably 1.

[0234] In equation (5), R is used as 3 An alkyl group having 1 to 4 carbon atoms, preferably methyl, ethyl, propyl, or butyl. As R 4 and R 5 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl.

[0235] In equation (6), R is used as 6 ~R 8 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. r is preferably 0 or 1, more preferably 0.

[0236] In equation (7), R is used as 9 and R 10 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. u is preferably 0 or 1, more preferably 0.

[0237] In equation (8), R is used as 11 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. u is preferably 0 or 1, more preferably 0.

[0238] In equation (9), R is used as 12 An alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. As R 13 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. w is preferably 0 or 1, more preferably 0.

[0239] In equation (10), R is used as 14 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. x is preferably 0 or 1, more preferably 0.

[0240] Specific examples of component (E) include the following compounds.

[0241] [Chemistry 14]

[0242]

[0243] [Chemistry 15]

[0244]

[0245] In the photosensitive resin composition disclosed herein, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of N-methyl-2-pyrrolidone (NMP) may be less than or equal to 1% by mass relative to the total amount of the photosensitive resin composition, or less than or equal to 3% by mass relative to the total amount of component (A).

[0246] In the photosensitive resin composition disclosed herein, the content of component (E) is preferably 1 part to 10,000 parts by mass relative to 100 parts by mass of component (A), and more preferably 50 parts to 10,000 parts by mass.

[0247] The photosensitive resin composition disclosed herein may also contain, as needed, at least one of the following: (F) sensitizer (excluding component (D)); (G) coupling agent; thermal polymerization initiator; polymerization inhibitor; antioxidant; surfactant; leveling agent; rust inhibitor; nitrogen-containing compound; dicarboxylic acid; filler material; etc.

[0248] (F) Sensitizer)

[0249] The photosensitive resin composition disclosed herein may contain a (F) sensitizer (hereinafter also referred to as the "(F) component"). Examples of (F) 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, benzoyl dimethyl ketal, benzoyl diethyl Ketals, 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, N-phenyldiethanolamine, and 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and compounds represented by the following formulas, etc.

[0250] (F) Components can be used alone or in combination of two or more.

[0251] [Chemistry 16]

[0252]

[0253] When the photosensitive resin composition disclosed herein contains component (F), the content of component (F) is not particularly limited, but is preferably 0.1 to 3 parts by mass relative to 100 parts by mass of component (A), more preferably 0.1 to 2 parts by mass.

[0254] (G) Coupling agent)

[0255] The photosensitive resin composition disclosed herein may contain a (G) coupling agent (hereinafter also referred to as the "(G) component").

[0256] As a (G) coupling agent, there are no particular limitations, 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, N-[3-(triethoxysilyl)propyl]phthalic acid, and benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4 Silane coupling agents such as '-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, ureomethyltrimethoxysilane, ureomethyltriethoxysilane, 2-ureoethyltrimethoxysilane, 2-ureoethyltriethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 4-ureobutyltrimethoxysilane, 4-ureobutyltriethoxysilane, etc.; aluminum-based adhesive additives such as tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethylaluminum diisopropyl acetoacetate, etc.

[0257] (G) Components can be used alone or in combination of two or more.

[0258] When the photosensitive resin composition disclosed herein contains a coupling agent (G), the content of the coupling agent is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass.

[0259] (Thermal polymerization initiator)

[0260] The photosensitive resin compositions disclosed herein may contain a thermal polymerization initiator.

[0261] As a thermal polymerization initiator, there are no particular limitations, but it is preferred to be a compound that does not decompose during heating (drying) to remove solvent during film formation, generates free radicals by heating during curing, and promotes the polymerization reaction of component (B) with each other or component (A) and component (B).

[0262] The thermal polymerization initiator is preferably a compound whose decomposition point is greater than or equal to 110°C and less than or equal to 200°C. From the viewpoint of promoting polymerization at lower temperatures, a compound with a decomposition point greater than or equal to 110°C and less than or equal to 175°C is more preferred.

[0263] As a thermal polymerization initiator, there are no particular limitations, but examples 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, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dicumene peroxide, and di-tert-butyl peroxide, etc. Peroxides, dilauroyl peroxide, benzoyl peroxide and other diacyl peroxides, di(4-tert-butylcyclohexyl) peroxide dicarbonate, di(2-ethylhexyl) peroxide dicarbonate and other peroxide dicarbonates, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate and other peroxide esters, bis(1-phenyl-1-methylethyl) peroxide, etc. Commercially available products include those under the trade names "PERCUMYL D", "PERCUMYL P", and "PERCUMYL H" (all manufactured by Nippon Oil Co., Ltd.).

[0264] 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 component (A), 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.

[0265] The preparation method of the photosensitive resin composition disclosed herein is not particularly limited; it is sufficient to simply mix the above-mentioned components.

[0266] <Cured product>

[0267] The cured product disclosed herein can be obtained by curing the above-described photosensitive resin composition.

[0268] The cured product disclosed herein can be used as a patterned cured product or as a non-patterned cured product.

[0269] The preferred film thickness of the cured material disclosed herein is 5 μm to 20 μm.

[0270] <Method for manufacturing patterned cured products>

[0271] The method for manufacturing patterned cured material disclosed herein includes: a step of coating the above-mentioned photosensitive resin composition 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 an organic solvent to obtain a patterned resin film; and a step of heat-treating the patterned resin film.

[0272] This allows us to obtain a patterned cured product.

[0273] A method for manufacturing a patternless cured material may include, for example, a step of forming the aforementioned photosensitive resin film and a step of performing a heat treatment. Furthermore, an exposure step may also be included.

[0274] Examples of substrates include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), metal oxide insulator substrates such as TiO2 substrates and SiO2 substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0275] There are no particular restrictions on the coating method; for example, a spin coater can be used.

[0276] Drying can be done using hot plates, ovens, etc.

[0277] 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.

[0278] The drying time is preferably 30 seconds to 5 minutes.

[0279] The drying process can be repeated more than twice.

[0280] Thus, a photosensitive resin film formed from the above-mentioned photosensitive resin composition can be obtained.

[0281] The thickness of the photosensitive resin film is preferably 5μm to 100μm, more preferably 6μm to 50μm, and even more preferably 7μm to 30μm.

[0282] Pattern exposure, for example, exposing a predetermined pattern through a light mask.

[0283] The active light source for irradiation can include i-rays, h-rays, ultraviolet light, visible light, and radiation, with h-rays being the preferred option.

[0284] As an exposure device, parallel exposure machines, projection exposure machines, step exposure machines, scanning exposure machines, etc. can be used.

[0285] By developing, a patterned resin film (patterned resin film) can be obtained. Typically, when using a negative photosensitive resin composition, the unexposed areas are removed with a developing solution.

[0286] Regarding the organic solvents used as developing solutions, a good solvent for photosensitive resin films can be used alone, or a good solvent and a bad solvent can be appropriately mixed.

[0287] 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.

[0288] Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0289] 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.

[0290] The development time can be set, for example, to twice the time required to immerse the photosensitive resin film until it is completely dissolved.

[0291] The development time varies depending on the (A) component 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.

[0292] After development, it can be cleaned using a rinsing solution.

[0293] 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. In addition, they can also be used in combination in stages.

[0294] By heating the patterned resin film, a cured pattern can be obtained.

[0295] (A) The polyimide precursor of component A undergoes a dehydration and ring-closing reaction through a heat treatment process to become the corresponding polyimide.

[0296] 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 less than or equal to 200°C or 160°C to 200°C.

[0297] Within the aforementioned range, damage to substrates, devices, etc., can be minimized, resulting in high-yield device production and energy-efficient processes.

[0298] The heat treatment time is preferably less than or equal to 5 hours, and more preferably 30 minutes to 3 hours.

[0299] Within the above-mentioned range, cross-linking or dehydration ring-closing reactions can be carried out sufficiently.

[0300] The heating atmosphere can be atmospheric or an inactive atmosphere such as nitrogen. From the viewpoint of preventing oxidation of the patterned resin film, a nitrogen atmosphere is preferred.

[0301] 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.

[0302] The cured product disclosed herein can be used as a passivation film, buffer coating, interlayer insulating film, cover coating, surface protective film, etc.

[0303] 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 highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, stacked devices (multi-chip fan-out wafer-level packages, etc.) and other electronic components.

[0304] 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.

[0305] Figure 1 This is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure, which is an electronic component according to one embodiment of this disclosure.

[0306] 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.

[0307] 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.

[0308] Selective etching is performed on the interlayer insulating film 4 that exposes window 6A to create window 6B.

[0309] Next, the photosensitive resin layer 5 is completely removed using an etching solution that does not corrode the first conductor layer 3 exposed from window 6B but only corrodes the photosensitive resin layer 5.

[0310] Then, using known photolithography techniques, a second conductor layer 7 is formed to make an electrical connection with the first conductor layer 3.

[0311] 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.

[0312] Next, using the aforementioned photosensitive resin composition, 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.

[0313] It should be noted that, in the above examples, the photosensitive resin composition of this disclosure can also be used to form an interlayer insulating film.

[0314] Example

[0315] The present disclosure will now be described in more detail based on embodiments and comparative examples. It should be noted that the present disclosure is not limited to the embodiments described below.

[0316] (Synthesis Example 1 (Synthesis of polyimide precursor A1))

[0317] 7.07 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30 g of N-methyl-2-pyrrolidone (NMP). The mixture was stirred at 30 °C for 4 hours, and then stirred overnight at room temperature to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added under water cooling, and the mixture was stirred at 45 °C for 3 hours. Then, 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. The reaction mixture was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain polyimide precursor A1.

[0318] The weight-average molecular weight of polyimide precursor A1 was determined using gel permeation chromatography (GPC) and converted to standard polystyrene. The weight-average molecular weight of polyimide precursor A1 was 40,000. Specifically, the determination was performed using a solution prepared by dissolving 0.5 mg of polyimide precursor A1 in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] under the following conditions.

[0319] (Measurement conditions)

[0320] Measurement apparatus: Hitachi, Ltd. L4000 UV detector

[0321] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0322] Shimadzu Corporation C-R4A Chromatopac

[0323] Measurement conditions: Column Gelpack GL-S300 MDT-5 × 2 columns

[0324] Eluent: THF / DMF = 1 / 1 (volume ratio)

[0325] LiBr(0.03mol / L), H3PO4(0.06mol / L)

[0326] Flow rate: 1.0 mL / min, Detector: UV 270 nm

[0327] In addition, NMR measurements were performed under the following conditions to calculate the esterification rate of polyimide precursor A1 (the reaction rate of the carboxyl groups of ODPA with HEMA). The esterification rate was 80 mol% relative to all carboxyl groups of polyamic acid (the remaining 20 mol% were carboxyl groups).

[0328] Measurement instrument: Bruker BioSpin AV400M

[0329] Magnetic field strength: 400 MHz

[0330] Reference material: Tetramethylsilane (TMS)

[0331] Solvent: Dimethyl sulfoxide (DMSO)

[0332] (Preparation of photosensitive resin composition)

[0333] The photosensitive resin compositions of Examples 1-5 and Comparative Examples 1 and 2 were prepared using the components and proportions shown in Tables 1 and 2. The proportions of each component in Tables 1 and 2 are in parts by mass, and blank columns in Tables 1 and 2 indicate unproduced components. The components used are described below.

[0334] ·(A)Ingredients

[0335] A1: Polyimide precursor synthesized in Example 1

[0336] • (B) Components (polymerizable monomers without cyclic backbones)

[0337] B1: Tetraethylene glycol dimethacrylate (TEGDMA)

[0338] B2: Ethoxylated pentaerythritol tetraacrylate (ATM-4E, total number of ethoxy groups: 4)

[0339] (B)' Components (polymerizable monomers containing a cyclic backbone)

[0340] B'1: A-DCP (Tricyclodecanedimethyl diacrylate)

[0341] (C) Components

[0342] C1: PDO (1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime)

[0343] C2: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime)

[0344] ·(D) component

[0345] D1: 9,10-Diethoxyanthracene

[0346] D2: 9,10-Dibutoxyanthracene

[0347] ·(E) component

[0348] E1: N-methyl-2-pyrrolidone

[0349] E2: 3-Methoxy-N,N-Dimethylpropionamide

[0350] ·(F)Component

[0351] F1: 4,4'-Bis(diethylamino)benzophenone

[0352] • (G) Component thermal polymerization initiator

[0353] G1: Bis(1-phenyl-1-methylethyl)peroxide

[0354] ·(H) component

[0355] H1: 3-Urea-propyltriethoxysilane

[0356] H2: Benzotriazole

[0357] H3: 5-Amino-1H-tetrazole

[0358] [Table 1]

[0359]

[0360] [Table 2]

[0361]

[0362] (Determination of residual film rate after development 1)

[0363] Using the Act8 coating apparatus (manufactured by Tokyo Electron Co., Ltd.), the obtained photosensitive resin composition was spin-coated onto a silicon wafer, dried at 110°C for 2 minutes, and then dried at 120°C for 2 minutes to form a photosensitive resin film with a dry film thickness of approximately 13 μm.

[0364] The development time is set as twice the time it takes for the obtained photosensitive resin film to be immersed in cyclopentanone until it is completely dissolved.

[0365] In addition, the photosensitive resin film was prepared in the same manner as described above. The resulting photosensitive resin film was then irradiated with h-rays (wavelength 405 nm, irradiation intensity 2.3 mW / cm²) using an h-ray bandpass filter on a mask aligner MA-8 (manufactured by SUSS MicroTec). 2 Exposure was then performed. It should be noted that in Example 1 and Comparative Example 2, the curing reaction was carried out with a relatively low cumulative irradiation dose, at 100, 150, 200, or 300 mJ / cm². 2 h-rays.

[0366] After exposure, the resin film was immersed in cyclopentanone for the above-mentioned development time using Act8, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain the resin film.

[0367] For the film thickness after heating on a hot plate at 120°C for 2 minutes and the film thickness after development, a portion of the film was cut to expose the silicon wafer, and the height from the exposed silicon wafer surface to the film surface was measured using a Dektak 150 pin profiler (manufactured by Bruker) (the film thickness was measured in the same way below).

[0368] Divide the developed film thickness of 10 μm by the film thickness after heating on a hot plate at 120°C for 2 minutes, and calculate the percentage to obtain the residual film rate after development.

[0369] The results are shown in Tables 3 and 4.

[0370] (Undercut evaluation)

[0371] The above-mentioned photosensitive resin composition was spin-coated onto a silicon wafer using a coating apparatus Act8. After drying at 110°C for 2 minutes, it was dried at 120°C for 2 minutes to form a photosensitive resin film with a dry film thickness of about 13 μm.

[0372] The development time is set as twice the time it takes for the obtained photosensitive resin film to be immersed in cyclopentanone until it is completely dissolved.

[0373] In addition, the photosensitive resin film was prepared in the same manner as described above. The resulting photosensitive resin film was then irradiated with h-rays (wavelength 405 nm, irradiation intensity 2.3 mW / cm²) using an h-ray bandpass filter on a mask aligner MA-8 (manufactured by SUSS MicroTec). 2 Exposure was then performed. It should be noted that in Example 1 and Comparative Example 2, the curing reaction was carried out with a relatively low cumulative irradiation dose, at 100, 150, 200, or 300 mJ / cm². 2 h-rays.

[0374] After exposure, the resin film was immersed in cyclopentanone for the above-mentioned development time using Act8, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain the resin film.

[0375] The 20μm through-hole openings in the obtained patterned resin film were observed cross-sectionally using optical microscopy and SEM. Case A without undercut was designated as A, and case B with confirmed undercut was designated as B. The results are shown in Tables 3 and 4.

[0376] (Evaluation of warpage)

[0377] The above-described photosensitive resin composition was spin-coated onto a 6-inch silicon wafer using an Act8 coating apparatus. After drying at 110°C for 2 minutes, it was dried at 120°C for 2 minutes to form a photosensitive resin film with a dry film thickness of approximately 13 μm. Then, it was irradiated with 400 mJ / cm² using a mask aligner MA-8 (manufactured by SUSS MicroTech). 2 The UV light was applied and the mixture was heated in a nitrogen atmosphere at 200°C for 2 hours.

[0378] The warpage of a 6-inch silicon wafer with a photosensitive resin film after curing was measured using a laser displacement meter LK-G 5000 (manufactured by KEYENCE).

[0379] Cases with warpage less than 20 μm are designated as A, and cases with warpage greater than 20 μm are designated as B. The results are shown in Tables 3 and 4.

[0380] [Table 3]

[0381]

[0382] [Table 4]

[0383]

[0384] As shown in Tables 3 and 4, in Examples 1 to 5, the residual film rate after development was better than that in Comparative Examples 1 and 2, and the warpage was also suppressed.

[0385] Furthermore, in Examples 1 to 5, the residual film rate after development was the same as that in Comparative Example 2, and the undercutting was suppressed compared to Comparative Example 1.

[0386] The disclosure of Japanese Patent Application 2023-188829, filed on November 2, 2023, is incorporated herein by reference in its entirety.

[0387] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as the specific documents, patent applications and technical standards described therein.

Claims

1. A photosensitive resin composition comprising: (A) Polyimide precursor, (B) Polymerizable monomers without a cyclic backbone (C) Photopolymerization initiator, and (D) Compounds containing anthracene structure The content of polymerizable monomers containing a cyclic backbone is less than or equal to 20% by mass relative to the total amount of the polyimide precursor (A).

2. The photosensitive resin composition according to claim 1, further comprising (E) a solvent.

3. The photosensitive resin composition according to claim 1, wherein the (B) polymerizable monomer comprises a (meth)acrylic compound containing two (meth)acrylate groups.

4. The photosensitive resin composition according to claim 3, wherein the (B) polymerizable monomer comprises a (meth)acrylic acid compound containing three or more (meth)acrylic acid groups.

5. The photosensitive resin composition according to claim 1, wherein the polyimide precursor comprises a compound having 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.

6. The photosensitive resin composition according to claim 1, wherein the (D) compound comprises a compound represented by the following general formula (D), [Chemistry 2] In general formula (D), R x Each of the following is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 5 to 18 carbon atoms, or a halogen atom, where n is an integer from 0 to 10.

7. The photosensitive resin composition according to claim 1, wherein the (D) compound comprises at least one selected from the group consisting of dibutoxyanthracene, dimethoxyanthracene, diethoxyanthracene, and diethoxyethylanthracene.

8. The photosensitive resin composition according to claim 1, further comprising (F) a thermal polymerization initiator.

9. The photosensitive resin composition according to claim 1, used for panel-level encapsulation.

10. 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 9 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 an organic solvent to obtain a patterned resin film; and The process of heat-treating the patterned resin film.

11. A cured product formed by curing the photosensitive resin composition according to any one of claims 1 to 9.

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