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

Abstract

A photosensitive resin composition comprising a polyimide precursor having polymerizable unsaturated bonds and a solvent, said solvent comprising: at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate and ethylene carbonate; and ethyl lactate.

Description

Technical Field

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

[0002] Polyimide resins, which possess excellent heat resistance, electrical properties, and mechanical properties, are widely used as materials for resin films used as surface protective films and interlayer insulating films for components in semiconductor devices. In recent years, it has been proposed to form resin films using photosensitive polyimide resins and through pattern exposure (for example, see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-85977 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] In recent years, considering the environmental and biological impacts, there has been a growing trend of replacing N-methyl-2-pyrrolidone (NMP), a representative solvent, with other solvents. For example, γ-butyrolactone has been widely used as an alternative solvent for NMP. However, there is room for improvement in the storage stability of resin compositions containing γ-butyrolactone as a solvent at room temperature. Furthermore, γ-butyrolactone is a restricted drug, and its continued use remains a concern.

[0008] Therefore, it is desirable to develop a new solvent composition that can replace the solvents used in existing photosensitive resin compositions.

[0009] In view of the above-mentioned prior art, an object of one embodiment of this disclosure is to provide a photosensitive resin composition having a novel solvent composition, a patterned cured product using the photosensitive resin composition, a method for manufacturing the patterned cured product, and an electronic component.

[0010] Solution for solving the problem

[0011] The specific solutions for achieving the above-mentioned goals are as follows.

[0012] <1> A photosensitive resin composition comprising a polyimide precursor having polymerizable unsaturated bonds and a solvent, said solvent comprising: at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate and ethylene carbonate; and ethyl lactate.

[0013] <2> according to <1> The photosensitive resin composition wherein the polyimide precursor having polymerizable unsaturated bonds has structural units represented by the following general formula (1).

[0014] [Chemistry 1]

[0015]

[0016] (In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. R 6 and R 7 Each can independently represent a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has a polymerizable unsaturated bond.

[0017] <3> according to <1> or <2> The photosensitive resin composition further contains a photopolymerization initiator.

[0018] <4> according to <1> ~ <3> The photosensitive resin composition described in any one of the following examples has an X / Y ratio of 0.2 to 5.0, calculated based on the amount X of at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate, and ethylene carbonate in the solvent and the amount Y of ethyl lactate.

[0019] <5> A method for manufacturing a patterned cured material, comprising: <1> ~ <4> The steps of coating the photosensitive resin composition of any one of the following onto a substrate and drying it to form a photosensitive resin film; the steps of patterning the photosensitive resin film to obtain a resin film; the steps of developing the patterned resin film with a developer to obtain a patterned resin film; and the steps of heat-treating the patterned resin film.

[0020] <6> A patterned curing material, which is to... <1> ~ <4> It is formed by curing the photosensitive resin composition described in any one of the above.

[0021] <7> according to <6> The patterned cured material is used as an interlayer insulating film, a covering coating, or a surface protective film.

[0022] <8> An electronic component comprising <6> or <7> The aforementioned patterned cured material.

[0023] Invention Effects

[0024] According to one embodiment of the present disclosure, a photosensitive resin composition having a novel solvent composition, 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

[0025] Figure 1 This is a manufacturing process diagram of an electronic component according to one embodiment of the present disclosure. Detailed Implementation

[0026] 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.

[0027] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that can be clearly distinguished from other processes, as long as the purpose of the process can be achieved.

[0028] In this disclosure, within the numerical range represented by "~", the values ​​recorded before and after "~" are respectively the minimum and maximum values.

[0029] 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, in the numerical ranges described in this disclosure, the upper or lower limit of that range can be replaced by the values ​​shown in the embodiments.

[0030] 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.

[0031] In this disclosure, the term "layer" or "membrane" is used not only to refer to the entirety of the region in which the layer or membrane is observed, but also to refer to the portion of the region in which it is formed.

[0032] In this disclosure, "(meth)acryloyl" means at least one of acryloyl and methacryloyl, and "(meth)acryloyloxy" means at least one of acryloyloxy and methacryloyloxy.

[0033] In this disclosure, the average thickness of a layer or film is set as the value given by measuring the thickness of five points of the layer or film being studied and using it as their arithmetic mean.

[0034] The thickness of a layer or film can be measured using a micrometer, a scanning probe meter, 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. When measuring the thickness of a single layer or the total thickness of multiple layers, the measurement can be performed by observing the cross-section of the object under test using an electron microscope.

[0035] <Photosensitive Resin Composition>

[0036] The photosensitive resin composition disclosed herein comprises a polyimide precursor having polymerizable unsaturated bonds and a solvent, said solvent comprising: at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate and ethylene carbonate; and ethyl lactate.

[0037] As shown in the examples described later, photosensitive resin compositions comprising at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate and ethylene carbonate, and ethyl lactate as a solvent exhibit good photosensitivity.

[0038] 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 (i.e., a resin composition that forms a pattern by removing unexposed areas).

[0039] (Unsaturated polyimide precursor)

[0040] The photosensitive resin composition disclosed herein contains a polyimide precursor having polymerizable unsaturated bonds (hereinafter, sometimes referred to as "unsaturated polyimide precursor").

[0041] Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

[0042] 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.

[0043] The unsaturated polyimide precursor preferably has the structural unit shown in the following general formula (1).

[0044] [Chemistry 2]

[0045]

[0046] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. 6 and R 7 Each can independently represent a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has a polymerizable unsaturated bond.

[0047] The unsaturated polyimide precursor may have multiple structural units as shown in the general formula (1) above, wherein X, Y, R in the multiple structural units 6 and R 7 They can be the same or different.

[0048] It should be noted that R 6 and R 7The combination of these groups is not particularly limited as long as each group 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 remainder can be monovalent organic groups 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 shown in the above general formula (1), the R of each structural unit 6 and R 7 The combinations can be the same or different.

[0049] 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.

[0050] The tetravalent organic group shown as X may contain an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (e.g., the number of carbon atoms constituting the aromatic ring is 6 to 20) and aromatic heterocyclic groups (e.g., the number of atoms constituting the heterocycle is 5 to 20). The tetravalent organic group shown as X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings.

[0051] When the tetravalent organic group shown 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.

[0052] When the tetravalent organic group shown in X contains a benzene ring, the tetravalent organic group shown in X preferably contains 1 to 4 benzene rings, more preferably 1 to 3 benzene rings, and even more preferably 1 or 2 benzene rings.

[0053] When the tetravalent organic group shown in X contains more than two benzene rings, the benzene rings can be connected by single bonds, or by alkylene groups, haloalkylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), thioether bonds (-S-), or methylene silane bonds (-Si(R)). A )2-, where 2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group. ), siloxane bond (-O-(Si(R) B )2-O-) n Two of them are R B Each of these groups independently represents a hydrogen atom, an alkyl group, or a phenyl group, where n represents an integer of 1 or 2 or more. The two benzene rings can be bonded together by connecting groups such as single bonds and at least one of the connecting groups at two sites, forming a 5-membered or 6-membered ring containing the connecting group between the two benzene rings.

[0054] 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.

[0055] 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.

[0056] It should be noted that this disclosure is not limited to the specific examples described below.

[0057] [Chemistry 3]

[0058]

[0059] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with the benzene ring. However, it is not possible for both A and B to be single bonds. Examples of divalent groups that are not conjugated with the benzene ring include methylene, halomethylene, halomethylmethylene, carbonyl, sulfonyl, ether (-O-), thioether (-S-), and methylenesilane (-Si(R)). A )2-, where 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.

[0060] 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-, where 2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group. ), siloxane bond (-O-(Si(R) B )2-O-) n Two of them are R B Each of the following can independently represent a hydrogen atom, an alkyl group, or a phenyl group, where n represents an integer of 1 or more. 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.

[0061] In addition, C may contain the structure shown in the following formula (C1).

[0062] [Chemistry 4]

[0063]

[0064] As for the alkylene group represented by C in formula (E), it 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.

[0065] Specific examples of alkylene groups represented by C in formula (E) include linear 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.

[0066] 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.

[0067] As a specific example of the alkyl halide represented by C in formula (E), an alkyl halide is formed in which at least one hydrogen atom contained in the alkyl halide represented by C in the above formula (E) is replaced by a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene, difluoromethylene, hexafluorodimethylmethylene, etc. are preferred.

[0068] As the R contained in the above-mentioned methylene silane bond or siloxane bond A Or R B The alkyl group shown 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 R B Specific examples of alkyl groups shown include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0069] Specific examples of the tetravalent organic groups represented by X can be the groups shown in the following formulas (J) to (O).

[0070] [Chemistry 5]

[0071]

[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 shown in Y can be the same as the skeleton of the tetravalent organic group shown in X, and the preferred skeleton of the divalent organic group shown in Y can be the same as the preferred skeleton of the tetravalent organic group shown in X. The skeleton of the divalent organic group shown in Y can be a structure in which two bonding positions of the tetravalent organic group shown in 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 either 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 formulas (G) and (H) 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 (H) below are preferred. In formula (H) below, it is more preferable that 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 6]

[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-, where 2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group. ), siloxane bond (-O-(Si(R) B )2-O-) n Two of them are R BEach of these can independently represent a hydrogen atom, an alkyl group, or a phenyl group, where n represents an integer of 1 or 2 or more. Alternatively, D can be a divalent group formed by combining at least two of these. Furthermore, D can be the structure shown in 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] As for the alkyl group represented by R in formulas (G) to (H), it is preferred to be an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 5 carbon atoms, and even more preferably an alkyl group with 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] As for the alkoxy group represented by R in formulas (G) to (H), it is preferred to be 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] As for the alkyl halogroup represented by R in formulas (G) to (H), it is preferred to be an alkyl halogroup with 1 to 5 carbon atoms, more preferably an alkyl halogroup with 1 to 3 carbon atoms, and even more preferably an alkyl halogroup with 1 or 2 carbon atoms.

[0086] Specific examples of alkyl halides represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom 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.

[0087] In equations (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 the linear or branched alkylene group represented by Y, it is preferred to be an alkylene group with 1 to 20 carbon atoms, more preferably an alkylene group with 1 to 15 carbon atoms, and even more preferably an alkylene group with 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] As the cycloalkyl group represented by Y, a cycloalkyl group having 3 to 10 carbon atoms is preferred, and a cycloalkyl group having 3 to 6 carbon atoms is more preferred.

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

[0093] The unit structure contained in the divalent group of the polyepoxide structure shown in 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, a polyepoxide structure or a polyepoxide-propylene structure is preferred as the polyepoxide 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 also 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.

[0095] Specific examples of alkyl groups with 1 to 20 carbon atoms bonded to silicon atoms in the 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] The aryl group with 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted. Specific examples of substituents when the aryl group has substituents include halogen atoms, alkoxy groups, hydroxyl groups, etc. Specific examples of aryl groups with 6 to 18 carbon atoms include phenyl, naphthyl, benzyl, etc. 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 of the divalent groups that constitute the polysiloxane structure shown in 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.

[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 7]

[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 X and the divalent organic group Y in general formula (1). Examples of combinations of the tetravalent organic group X and the divalent organic group Y include:

[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 combination of the groups shown in formulas (A) and (E) and Y is a combination of the groups shown in formula (H);

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

[0109] 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. As a monovalent organic group, it 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 shown in general formula (2) below, ethyl, isobutyl, or tert-butyl, and even more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group shown in general formula (2) below. In this case, R 6 and R 7 At least one of them is a group represented by general formula (2).

[0110] By including an organic group having an unsaturated double bond in the monovalent organic group, preferably a group represented by the following general formula (2), the i-ray transmittance is high, and there is a tendency to form a well-cured product even when cured at low temperatures below 400°C. 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 is removed by imidization.

[0111] 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.

[0112] [Chemistry 8]

[0113]

[0114] In general formula (2), R 8 ~R 10 Each can independently represent a hydrogen atom or an aliphatic hydrocarbon group with 1 to 3 carbon atoms, R x It represents a divalent linker.

[0115] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group shown has 1 to 3 carbon atoms, preferably 1 or 2. As R 8 ~R 10 Specific examples of aliphatic hydrocarbon groups shown include methyl, ethyl, n-propyl, isopropyl, etc., with methyl being preferred.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] In general formula (1), R is preferred. 6 and R 7 At least one of them is a group represented by the general formula (2), more preferably R 6 and R 7Both are groups represented by the general formula (2).

[0120] When the unsaturated polyimide precursor comprises a compound having the structural unit shown in the above general formula (1), R, as the group shown in general formula (2), 6 and R 7 R relative to all structural units contained in this compound 6 and R 7 The total percentage is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. There is no particular upper limit, and it can be 100 mol%.

[0121] It should be noted that the above ratio can be above 0 mol% and less than 60 mol%.

[0122] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0123] [Chemistry 9]

[0124]

[0125] 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.

[0126] 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.

[0127] The content of the structural unit of general formula (1) in the compound having the structural unit of general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to all structural units. There is no particular upper limit to the above content, and it can be 100 mol%.

[0128] Unsaturated polyimide precursors can be synthesized using tetracarboxylic dianhydride and diamine compounds. In this case, in general formula (1), X corresponds to residues derived from tetracarboxylic dianhydride, and Y corresponds to residues derived from diamine compounds. It should be noted that unsaturated polyimide precursors can be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0129] 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 3,4,9,1 0-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, 4,4'-oxobisphthalic anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, (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-dicarboxyphenyl)propane dianhydride α-(3,4-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.

[0130] Among these, preferably at least one is selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxobisphthalic anhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride, more preferably at least one is selected from 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'-biphenyltetracarboxylic dianhydride.

[0131] Tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0132] 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, etc. 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.

[0133] More preferably, it is selected from at least one of 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 selected from at least one of the group consisting of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane.

[0134] Diamine compounds can be used alone or in combination with two or more.

[0135] Having the structural unit shown in general formula (1) and R in general formula (1) 6 and R 7 Compounds in which at least one of the components is a monovalent organic group can be obtained, for example, by the following methods (a) or (b).

[0136] (a) After reacting a tetracarboxylic dianhydride (preferably the tetracarboxylic dianhydride shown in general formula (8) below) with the compound shown in R-OH in an organic solvent to prepare a diester derivative, the diester derivative is subjected to a condensation reaction with the diamine compound shown in H2N-Y-NH2.

[0137] (b) A polyamic acid solution is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound shown in H2N-Y-NH2 in an organic solvent, and then adding a compound shown in R-OH to the polyamic acid solution and reacting it in an organic solvent to introduce ester groups.

[0138] To make R in general formula (1) 6 and R 7 At least one of them has a polymerizable unsaturated bond, and R uses at least one of R-OH with a polymerizable unsaturated bond.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] The dehydrating condensing agent can also be reacted with the compound shown in 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).

[0143] 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 reacting it with a chlorinating agent such as thionyl chloride to convert it into acyl chloride, and then reacting the diamine compound represented by H2N-Y-NH2 with the acyl chloride.

[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 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.

[0145] The aforementioned 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 reacting with the compound represented by R-OH. Alternatively, the compound represented by R-OH can be reacted on 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.

[0146] [Chemistry 10]

[0147]

[0148] In general formula (8), X is the same as X in general formula (1), and the specific examples and preferred examples are also the same.

[0149] The compound represented by R-OH used in the synthesis of the above-mentioned compounds contained in the unsaturated polyimide precursor can be an R-OH group with a hydroxyl group bonded to the group represented by general formula (2). xCompounds, compounds in which a hydroxyl group is bonded to a terminal methylene group of the group represented by 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.

[0150] 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, and even more preferably 10,000 to 50,000, based on weight-average molecular weight.

[0151] Weight-average molecular weight can be determined, for example, by gel permeation chromatography, or by conversion using a standard polystyrene standard curve.

[0152] 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.

[0153] The dicarboxylic acid can be a dicarboxylic acid having a (meth)acryloyl group, for example, it can be a dicarboxylic acid as shown below. 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.

[0154] [Chemistry 11]

[0155]

[0156] (Polyimide resin)

[0157] The photosensitive resin composition disclosed herein may include a polyimide resin in addition to an unsaturated polyimide precursor. By combining the unsaturated polyimide precursor and the polyimide resin, the generation of volatiles due to 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 a polyimide resin, there is no particular limitation as long as it is a polymeric compound having multiple structural units containing imide bonds; for example, compounds having structural units having the following general formula (X) are preferred. This leads to a tendency to obtain semiconductor devices with insulating films exhibiting high reliability.

[0159] [Chemistry 12]

[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 individually or in combination of two or more.

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

[0165] Solid components refer to the components remaining after drying the photosensitive resin composition at 200~400℃.

[0166] (solvent)

[0167] The photosensitive resin composition disclosed herein comprises at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate and ethylene carbonate, and ethyl lactate as a solvent.

[0168] Dihydro-L-glucanone, propylene carbonate, ethylene carbonate, and ethyl lactate exhibit low toxicity in organic solvents. Therefore, the photosensitive resin composition disclosed herein demonstrates excellent environmental and human affinity.

[0169] Dihydro-L-glucanone is a biomass-derived organic solvent synthesized by hydrogenating L-glucanone obtained from the thermal decomposition of cellulose. Commercially available dihydro-L-glucanone products include, for example, Cyrene (a registered trademark) manufactured by Sigma-Aldrich.

[0170] The value of X / Y, calculated based on the amount X of at least one selected from the group consisting of dihydrol-L-glucanone, propylene carbonate, and ethylene carbonate, and the amount Y of ethyl lactate in the solvent, is not particularly limited, and can be selected from the range of 0.2 to 5.0.

[0171] From the perspective of balancing the properties of the photosensitive resin composition, the value of X / Y can be 0.2 or more, 0.5 or more, 0.6 or more, 0.7 or more, or 0.8 or more.

[0172] From the perspective of balancing the properties of the photosensitive resin composition, the value of X / Y can be 3.0 or less, 2.0 or less, 1.8 or less, 1.5 or less, or 1.2 or less.

[0173] From the viewpoint of environmental and human affinity, the total proportion of dihydro-L-glucanone, propylene carbonate, ethylene carbonate and ethyl lactate in the solvent contained in the photosensitive resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, extremely preferably 99% by mass or more, and may also be 100% by mass.

[0174] The photosensitive resin composition disclosed herein may contain solvents other than dihydro-L-glucanone, propylene carbonate, ethylene carbonate and ethyl lactate (other solvents).

[0175] Other solvents can be used alone or in combination with two or more.

[0176] Other solvents that can be listed include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, carbonate solvents other than propylene carbonate or ethylene carbonate, and urea solvents.

[0177] Examples of ester solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate, and other alkyl alkoxyacetic acid esters (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 3-methoxypropionate, ethyl 3-ethoxypropionate, etc.). Alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc.), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), 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.

[0178] Examples of ether solvents 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.

[0179] Examples of ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP).

[0180] Examples of hydrocarbon solvents include limonene.

[0181] Examples of aromatic hydrocarbon solvents include toluene, xylene, and anisole.

[0182] Examples of sulfoxide solvents include dimethyl sulfoxide.

[0183] Examples of carbonate solvents include dimethyl carbonate.

[0184] Examples of urea solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0185] (Cross-linking agent)

[0186] The photosensitive resin composition may contain a crosslinking agent that can be crosslinked or polymerized by heating.

[0187] In the process of coating, exposing, developing, and then heat-treating the photosensitive resin composition, the compound serving as a crosslinking agent reacts with the unsaturated polyimide precursor to crosslink, or the compound serving as a crosslinking agent polymerizes itself. As a result, even at lower curing temperatures, such as below 200°C, the strength of the cured film is improved, and mechanical properties, chemical resistance, flux resistance, etc., are enhanced.

[0188] Crosslinking agents can be used alone or in combination of two or more.

[0189] As crosslinking agents, compounds having two or more groups containing polymerizable unsaturated bonds (hereinafter also referred to as functional groups) can be listed. From the viewpoint of polymerization reactivity, (meth)acryloyl and vinyl groups are preferred as functional groups, and (meth)acryloyl is more preferred.

[0190] Crosslinking agents can undergo alkoxylation treatments such as ethoxylation and propoxylation.

[0191] Examples of difunctional crosslinking agents 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, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, tricyclodecanediethanol diacrylate, and tricyclodecanediethanol dimethacrylate.

[0192] Examples of trifunctional crosslinking agents include trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and tris(2-methacryloyloxyethyl)isocyanurate.

[0193] Examples of crosslinking agents with four or more functions include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and tetramethylolmethane tetra(methyleneoxyethyl) acrylate.

[0194] When the photosensitive resin composition disclosed herein contains a crosslinking agent, the content of the crosslinking agent is preferably 1 to 50 parts by weight relative to 100 parts by weight of the unsaturated polyimide precursor, more preferably 3 to 50 parts by weight, and even more preferably 5 to 40 parts by weight.

[0195] (Photopolymerization initiator)

[0196] The photosensitive resin composition disclosed herein may contain a photopolymerization initiator.

[0197] 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.

[0198] Examples of photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, and acyldialkoxymethane compounds.

[0199] Compounds represented by the following general formula (9A), the following general formula (9B), the following general formula (10A), and the following general formula (10B) can be listed as photopolymerization initiators.

[0200] [Chemistry 13]

[0201]

[0202] 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 of 2 or more, R... 11 They can be the same or different.

[0203] 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. 13 and R 14 Preferably, each alkyl group has 1 to 4 carbon atoms, and more preferably, it is a methyl group.

[0204] 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.

[0205] [Chemistry 14]

[0206]

[0207] [Chemistry 15]

[0208]

[0209] In general formula (9B), R15 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 with 1 to 12 carbon atoms, a cycloalkyl group with 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 2, R 15 They can be the same or different.

[0210] 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.

[0211] As a compound represented by general formula (9B), for example, the compound shown in formula (9B-1) below can be obtained as "IRGACURE OXE 01" manufactured by BASF Japan Co., Ltd. Additionally, the compound shown in formula (9B-2) below can be obtained as "NCI-930" manufactured by ADEKA Co., Ltd.

[0212] [Chemistry 16]

[0213]

[0214] [Chemistry 17]

[0215]

[0216] 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, and c1 is an integer from 0 to 5. When c1 is an integer of 2 or more, R 21 They can be the same or different.

[0217] 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.

[0218] As a compound represented by general formula (10A), for example, a compound represented by the following formula (10A-1) (1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime) can be listed. This compound can be obtained as "G-1820(PDO)" manufactured by Lambson.

[0219] [Chemistry 18]

[0220]

[0221] [Chemistry 19]

[0222]

[0223] 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 of 2 or more, R 24 They can be the same or different. When e is an integer greater than 2, R... 25 The groups within the parentheses can be the same or different. When s is an integer greater than 2, the groups within the parentheses can be the same or different. When t is an integer greater than 2, the groups within the parentheses can be the same or different.

[0224] 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).

[0225] As a compound represented by the 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.

[0226] [Chemistry 20]

[0227]

[0228] 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.

[0229] (Thermal polymerization initiator)

[0230] From the viewpoint of promoting polymerization reactions, the photosensitive resin compositions disclosed herein may further include a thermal polymerization initiator.

[0231] As a thermal polymerization initiator, the following compounds are preferred: they do not decompose during heating (drying) to remove solvents during film formation, but decompose during heating during curing and generate free radicals, thereby promoting the polymerization reaction of polymerizable monomers with each other, or unsaturated polyimide precursors and polymerizable monomers.

[0232] 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.

[0233] Specific examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, ketal peroxides such as 1,1-di(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxide)cyclohexane, and 1,1-di(tert-butylperoxide)cyclohexane, hydrogen peroxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, as well as dialkyl peroxides such as dicumyl peroxide and ditert-butyl peroxide. Diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di(4-tert-butylcyclohexyl) peroxide, di(2-ethylhexyl) peroxide, tert-butyl peroxide-2-ethylhexanoate, tert-hexyl isopropyl peroxide monocarbonate, tert-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, and bis(1-phenyl-1-methylethyl) peroxide, etc.

[0234] As commercially available products, examples include "PERCUMYL D", "PERCUMYL P", and "PERCUMYL H" (all manufactured by Nippon Oil Co., Ltd.).

[0235] 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 weight relative to 100 parts by weight of the unsaturated polyimide precursor, more preferably 0.2 to 20 parts by weight to ensure good flux resistance, and even more preferably 0.3 to 10 parts by weight from the viewpoint of suppressing the decrease in solubility caused by decomposition during drying.

[0236] (Imidification accelerator)

[0237] From the viewpoint of promoting imidization reactions, the resin compositions disclosed herein may contain nitrogen-containing compounds as imidization promoters.

[0238] Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)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 can be used alone, or in combination of two or more.

[0239] When the photosensitive 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 preservation stability, and even more preferably 0.5 to 10 parts by weight.

[0240] (Sensitizer)

[0241] The photosensitive resin composition disclosed herein may contain a sensitizer. By including 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. A single sensitizer may be used alone, or two or more may be used in combination.

[0242] 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, and benzoin dimethyl Ketals, benzoyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, dicoumarin compounds, N-phenylglycine, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, etc.

[0243] 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.

[0244] (Stabilizer)

[0245] The photosensitive resin composition disclosed herein may contain a stabilizer. By including a stabilizer in the photosensitive resin composition, good storage stability can be achieved.

[0246] 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, copper ether, 2,5-p-benzoquinone, tannic acid, p-benzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenolic compounds.

[0247] Stabilizers can be used alone or in combination of two or more. Combining two or more stabilizers, due to their different reactivity, tends to easily adjust photosensitivity properties. Hindered phenolic compounds can possess both the functions of stabilizers and antioxidants (described later), or only one of these functions.

[0248] 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-thiodiethyleneethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. [Butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol tetratetra[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-dimethylbenzyl)trione, 1,3,5-tris(3-hydroxy-2,6-dimethylbenzyl)trione (-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-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,6-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-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], 2,2,6,6-tetramethylpiperidine-1-oxo radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo radical, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.

[0249] 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.

[0250] (Antioxidants)

[0251] From the viewpoint that the decrease in adhesion can be suppressed by capturing oxygen free radicals and peroxide free radicals generated during high-temperature storage, reflow soldering, 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.

[0252] 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), propionyl hexamethylenediamine, 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.

[0253] Antioxidants can be used alone or in combination of two or more.

[0254] When the photosensitive resin composition disclosed herein contains an antioxidant, the content of the antioxidant 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.

[0255] (Coupled agent)

[0256] The photosensitive resin composition disclosed herein may contain a coupling agent. If a coupling agent is contained, the adhesion between the resulting cured product and the substrate can be further improved.

[0257] As a 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, and N-[3-(triethoxysilyl)propyl] Phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-ureopropyltriethoxysilane, and other silane coupling agents; aluminum-based adhesives such as tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethylaluminum diisopropyl acetoacetate, etc.

[0258] Coupling agents can be used alone or in combination of two or more.

[0259] 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 weight relative to 100 parts by weight of the unsaturated polyimide precursor, more preferably 1 to 10 parts by weight, and even more preferably 2 to 10 parts by weight.

[0260] (Rust inhibitor)

[0261] The photosensitive resin composition disclosed herein may contain a rust inhibitor. By containing a rust inhibitor in the photosensitive resin composition, corrosion of copper and copper alloys can be inhibited and discoloration can be prevented.

[0262] Examples of rust inhibitors include azole compounds and purine derivatives.

[0263] Rust inhibitors can be used alone or in combination of two or more.

[0264] 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, 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.

[0265] 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. Purines, 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.

[0266] 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.

[0267] (UV absorber)

[0268] The photosensitive resin composition disclosed herein may contain an ultraviolet absorber. By containing an ultraviolet absorber in the photosensitive resin composition, it tends to suppress cross-linking of unexposed areas caused by diffuse reflection during exposure.

[0269] 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.

[0270] Examples of benzotriazole compounds include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-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.

[0271] Examples of salicylate compounds include phenyl salicylate and 4-tert-butyl phenyl salicylate.

[0272] 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.

[0273] Examples of diphenyl acrylate compounds include ethyl 2-cyano-3,3-diphenyl acrylate.

[0274] Examples of diphenylcyanoacrylate compounds include 2-cyano-3,3-diphenylacrylate (2'-ethylhexyl) ester.

[0275] Examples of azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0276] Examples of polyphenolic compounds include pyrogallol, phlorogallol, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin gallate, rutin, quercetin, quercetagin, quercetagetin, quercetin, pelargonidin, cyanidin, arantinidin, luteolinidin, peonidin, rosinidin, (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.

[0277] Examples of polyphenolic compounds include [2,2'-thiobis(4-tert-octylphenol ester)]-2-ethylhexylamine nickel(II).

[0278] 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.

[0279] 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.

[0280] When the photosensitive resin composition disclosed herein contains an ultraviolet absorber, from the viewpoint of resolution, the content of the ultraviolet absorber is preferably 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0281] Furthermore, from the viewpoint of preventing insufficient photocuring inside the coating film, it is preferable to use 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0282] (surfactants and leveling agents)

[0283] The photosensitive resin composition disclosed herein may contain at least one of a surfactant and a leveling agent. By containing at least one of a surfactant and a leveling agent in the photosensitive resin composition, it is possible to improve coatability (e.g., suppress streaks (film thickness unevenness)) and developability.

[0284] 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 KP341", "KBM303", and "KBM 803" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0285] Surfactants and leveling agents can be used alone or in combination of two or more.

[0286] 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.

[0287] (Other ingredients)

[0288] The photosensitive resin compositions disclosed herein may further contain other components and unavoidable impurities.

[0289] In the photosensitive resin composition disclosed herein, the total amount of unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, and solvent can be 80% or more by mass, 90% or more by mass, or 95% or more by mass.

[0290] In addition, in the photosensitive resin composition disclosed herein, the total amount of unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, solvent, stabilizer, sensitizer, ultraviolet absorber, rust inhibitor, antioxidant and coupling agent can be 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 98% or more by mass or 99% or more by mass.

[0291] <Cured product>

[0292] The cured product of this disclosure can be obtained by curing the photosensitive resin composition of this disclosure.

[0293] The cured product disclosed herein can be used as a patterned cured product or as a non-patterned cured product.

[0294] The average thickness of the cured material is preferably 5μm to 20μm.

[0295] The elongation at break of the cured material is preferably 25% or more, more preferably 35% or more, and even more preferably 50% or more. There is no particular limitation on the upper limit of the elongation at break of the cured material.

[0296] <Manufacturing methods for solidified materials and electronic components>

[0297] 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.

[0298] This allows us to obtain a patterned cured product.

[0299] Methods for manufacturing patternless cured materials may include steps such as forming the photosensitive resin film of this disclosure and performing a heat treatment. Furthermore, an exposure step may also be included.

[0300] 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.

[0301] The coating method of the photosensitive resin composition disclosed herein is not particularly limited, and can be performed using a rotator or the like.

[0302] Drying can be done using hot plates, ovens, etc.

[0303] 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.

[0304] The drying time is preferably 30 seconds to 5 minutes.

[0305] The drying process can be repeated more than twice.

[0306] 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.

[0307] The average thickness of the photosensitive resin film is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and even more preferably 3 μm to 30 μm.

[0308] Pattern exposure, for example, exposing a specified pattern through a light mask.

[0309] 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.

[0310] As an exposure device, parallel exposure machines, aligners, projection exposure machines, stepper exposure machines, scanner exposure machines, etc. can be used.

[0311] 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 developer.

[0312] 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.

[0313] 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.

[0314] Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0315] Surfactants can 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.

[0316] The development time can be set, for example, to twice the time required to immerse the photosensitive resin film until it is completely dissolved.

[0317] 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.

[0318] After development, it can be cleaned using a rinsing solution.

[0319] 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.

[0320] By heating the patterned resin film, a cured pattern can be obtained.

[0321] The unsaturated polyimide precursor undergoes a dehydration and ring-closure reaction through a heat treatment process to become the corresponding polyimide resin.

[0322] The heat treatment temperature is preferably below 250°C, more preferably 120°C to 250°C, and even more preferably 160°C to 200°C.

[0323] By keeping the heat treatment temperature within the above range, damage to the substrate or device can be minimized, devices can be produced with good yield, and energy-saving processes can be achieved.

[0324] The heat treatment time is preferably less than 5 hours, and more preferably 30 minutes to 3 hours.

[0325] By keeping the heat treatment time within the above range, the cross-linking reaction or the dehydration and ring-closing reaction can be carried out sufficiently.

[0326] 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.

[0327] Examples of devices used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing furnaces, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0328] The cured product of this disclosure can be used as an interlayer insulating film, a cover coating, or a surface protective film. Furthermore, the cured product of this disclosure can be used as a passivation film, a buffer coating, etc.

[0329] By using one or more of the above-mentioned passivation films, buffer coatings, interlayer insulating films, cover coatings and surface protective films, it is possible to manufacture electronic components such as highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (multi-chip fan-out wafer-level packages, etc.).

[0330] An example of a manufacturing process for a semiconductor device, which is an electronic component of this disclosure, will be described with reference to the accompanying drawings.

[0331] 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 the present disclosure.

[0332] exist Figure 1In 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.

[0333] 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, and a window 6A is set by means of exposing a predetermined portion of the interlayer insulating film 4 using a known photographic etching technique.

[0334] The interlayer insulating film 4 of window 6A was selectively etched to expose window 6B.

[0335] Next, the photosensitive resin layer 5 is removed using an etching solution that does not corrode the first conductor layer 3 exposed from window 6B but corrodes the photosensitive resin layer 5.

[0336] Then, using a known photographic etching technique, a second conductor layer 7 is formed to make an electrical connection with the first conductor layer 3.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] Example

[0341] 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.

[0342] Synthesis of Unsaturated Polyimide Precursors

[0343] In a 2L detachable flask, 380g of N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical Corporation) was placed, and 47.08g (152mmol) of 4,4'-oxophthalic anhydride (ODPA, MANAC Corporation) was added while stirring until dissolved. Then, 0.24g (2.1mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane, Fujifilm and Hikari Pure Chemicals Co., Ltd.) was added and dissolved, followed by 5.54g (42.6mmol) 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.

[0344] Separately, 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.

[0345] DMAP solution was added dropwise to the reaction solution while stirring 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 to the reaction solution at 30°C, and the mixture was stirred at 45°C for 2 hours. Then, 0.08 g (0.74 mmol) of BQ (benzoquinone, Fujifilm and Hikari Pure Chemicals Co., Ltd.) was added to the reaction solution, followed by 40.4 g (310 mmol) of HEMA. The reaction solution was stirred for 15 hours and then cooled to room temperature. The reaction solution was added to purified water, and the precipitate was recovered. The precipitate was washed with purified water and dried under reduced pressure to obtain the unsaturated polyimide precursor (unsaturated PI precursor).

[0346] The weight-average molecular weight (Mw) of the unsaturated polyimide precursor is 25,000.

[0347] The weight-average molecular weight of the unsaturated polyimide precursor was calculated by gel permeation chromatography (GPC) using a calibration curve based on 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.

[0348] Installation: Shimadzu Corporation, Prominence

[0349] Column: Lisenok Co., Ltd., Gelpak GL S300MDT-5

[0350] Eluent: THF / DMF = 1 / 1 (v / v), lithium bromide 0.03 mol / L, phosphoric acid 0.06 mol / L

[0351] Flow rate: 1.0 mL / min

[0352] Measurement wavelength: 270nm

[0353] Injection volume: 10 μL

[0354] <Preparation of Photosensitive Resin Composition>

[0355] The components listed in Table 1 were combined in the amounts specified in Table 1 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 a photosensitive resin composition.

[0356] The details of each component listed in Table 1 are as follows. The proportions of each component in Table 1 are based on parts by mass.

[0357] Solvent 1: γ-Butyrolactone (boiling point: 204℃)

[0358] Solvent 2: Dihydro-L-glucanone (boiling point: 227℃)

[0359] Solvent 3: Propylene carbonate (boiling point: 242℃)

[0360] Solvent 4: Ethyl lactate (boiling point: 154℃)

[0361] Stabilizer: 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide

[0362] Crosslinking agent: Tetraethylene glycol dimethacrylate

[0363] Photopolymerization initiator: 1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime

[0364] • Coupling agent: 3-Uretopropyltriethoxysilane

[0365] Rust inhibitor: 5-amino-1H-tetrazole

[0366] <Appearance of the pre-baked film>

[0367] A photosensitive resin composition was coated onto a Si wafer by spin coating to form a film. The film was then pre-baked (PB) at 100°C for 2 minutes followed by 110°C for 2 minutes to obtain a PB film with a thickness of 13.5 ± 0.5 μm. The appearance of the PB film was evaluated according to the following criteria. The results are shown in Table 1.

[0368] A: No roughness was observed on the surface of the PB film.

[0369] B: Roughness was observed on the surface of the PB film.

[0370] C: The unsaturated polyimide precursor and rust inhibitor were not completely dissolved in the solvent, so a PB film could not be formed.

[0371] [Table 1]

[0372]

[0373] The X / Y values ​​in Table 1 are calculated based on the amount of dihydro-L-glucosamine or propylene carbonate X and the amount of ethyl lactate Y.

[0374] As shown in Table 1, the photosensitive resin compositions of Examples 1-7, which contain dihydro-L-glucanone or propylene carbonate and ethyl lactate as solvents, and the photosensitive resin compositions of the reference examples, which contain γ-butyrolactone as solvents, also did not show a rough appearance of the PB film.

[0375] The photosensitive resin compositions of Comparative Examples 1 and 2, which contained only dihydro-L-glucanone or propylene carbonate as solvents, were not evaluated for appearance of PB films because the unsaturated polyimide precursor and rust inhibitor were not completely dissolved.

[0376] The photosensitive resin composition of Comparative Example 3, which contained only ethyl lactate as a solvent, exhibited a rough surface on the PB film. This is believed to be due to the low boiling point of ethyl lactate, resulting in rapid drying of the coating.

[0377] <Evaluation of Storage Stability>

[0378] Cured films were prepared using the initial (freshly prepared) photosensitive resin composition and the photosensitive resin composition after being stored at room temperature (25°C) for 1 or 2 weeks.

[0379] Specifically, a photosensitive resin composition is coated onto a Si wafer by spin coating to form a coating film. The coating film is then pre-baked at 100°C for 2 minutes, followed by baking at 110°C for 2 minutes (PB) to obtain a PB film with a thickness of 13.5 ± 0.5 μm.

[0380] For PB films, exposure was performed using an i-ray stepper (exposure dose: 400 mJ / cm). 2 The film was developed using cyclopentanone (10 seconds x 2 times) to obtain a post-developed film with a pattern consisting of lines (exposed areas) 7 μm wide and intervals (unexposed areas) 7 μm wide.

[0381] <Evaluation of photosensitivity>

[0382] The surface of the developed film, which has a pattern consisting of 7 μm wide lines (exposed areas) and 7 μm wide intervals (unexposed areas), was observed using an electron microscope with the initial photosensitive resin composition, and the patterning performance was evaluated according to the following criteria. The results are shown in Table 2.

[0383] A: No poor pattern formation or film peeling after development was observed.

[0384] B: Poor pattern formation or film peeling observed after development.

[0385] The film thickness change rate was calculated using the following formula based on the film thickness of the PB film made using the initial photosensitive resin composition and the film thickness of the PB film made using the stored photosensitive resin composition, and evaluated according to the following criteria. The results are shown in Table 2.

[0386] Film thickness change rate (%) = {(film thickness after storage / initial film thickness) × 100} - 100

[0387] A: The film thickness variation rate is within ±2%.

[0388] B: Film thickness variation rate exceeds ±2%.

[0389] The residual film rate of the developed film made using the initial photosensitive resin composition and the residual film rate of the developed film made using the stored photosensitive resin composition are calculated using the following formulas.

[0390] Residual film yield (%) = (film thickness of the exposed section after development / film thickness after PB) × 100

[0391] Next, the rate of change in residual film rate was calculated using the following formula from the residual film rate of the developed film made using the initial photosensitive resin composition and the residual film rate of the developed film made using the stored photosensitive resin composition, and evaluated according to the following criteria. The results are shown in Table 2.

[0392] Residual film rate change rate (%) = {(Residual film rate after storage / Initial residual film rate) × 100} - 100

[0393] A: The rate of change in residual film rate is within ±2%.

[0394] B: The rate of change in residual film ratio exceeds ±2%.

[0395] [Table 2]

[0396]

[0397] As shown in Table 2, the photosensitive resin compositions of Examples 1-7, containing dihydroglucosamine or propylene carbonate and ethyl lactate as solvents, exhibited excellent patterning properties. Furthermore, compared to the photosensitive resin compositions of the reference examples containing γ-butyrolactone as solvents, the photosensitive resin compositions of Examples 1-7 showed superior results in terms of film thickness change rate and residual film rate change rate after 1 week and 2 weeks.

[0398] In Examples 1-7, Examples 1, 3, 5, 6, and 7, with an X / Y value of 1.0, showed superior evaluation results for the film thickness change rate or residual film rate change rate after 2 weeks compared to Examples 2 and 4, with an X / Y value of 2.0.

Claims

1. A photosensitive resin composition comprising a polyimide precursor having polymerizable unsaturated bonds and a solvent, The solvent comprises: at least one selected from the group consisting of dihydro-L-glucanone, propylene carbonate and ethylene carbonate; and ethyl lactate.

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 represents a tetravalent organic group. 6 and R 7 Each can independently represent a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has a polymerizable unsaturated bond.

3. The photosensitive resin composition according to claim 1, further comprising a photopolymerization initiator.

4. The photosensitive resin composition according to claim 1, wherein the ratio X / Y, calculated based on the amount X of at least one selected from the group consisting of dihydrol-L-glucanone, propylene carbonate, and ethylene carbonate in the solvent and the amount Y of ethyl lactate, is 0.2 to 5.

0.

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 cover coating, or a surface protective film.

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

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