Method for producing photosensitive resin compositions, cured products, and patterned cured products, and electronic components

Abstract

To provide a photosensitive resin composition that can simplify the formation process of a polyimide resin cured film.SOLUTION: A photosensitive resin composition includes a polyimide precursor with a radical polymerizable group, and a compound that is liquid at 25°C and is at least one selected from the group consisting of a monovalent methacrylate compound with a 5 to 6-membered heterocycle structure containing oxygen atoms, a monovalent vinyl compound with a 5 to 6-membered heterocycle structure containing oxygen atoms, a monovalent methacrylate compound with an ethylene oxide structure, and a monovalent vinyl compound with an ethylene oxide structure. The solvent content is 10 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive resin composition, a cured product, a method for producing a patterned cured product, and an electronic component. [Background technology]

[0002] In recent years, organic materials with high heat resistance, such as polyimide resins, have been widely used as protective film materials for semiconductor integrated circuits (LSIs) (see, for example, Patent Document 1). Such a protective film (cured film) using polyimide resin is obtained by coating and drying a resin composition containing a polyimide precursor onto a substrate, irradiating the resin film with active light, developing it to obtain a patterned resin film, and then curing it by heating. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2016-199662 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] To increase the density of semiconductor packages such as LSIs and simplify the assembly process, it is desirable to simplify the process of forming the polyimide resin cured film. One way to simplify the formation of the protective film (cured film) is to reduce the solvent content in the resin composition containing the polyimide precursor. By reducing the solvent content, it becomes possible to simplify the drying process of the resin composition when forming the polyimide resin cured film. However, polyimide precursors generally have low solubility in solvents, and resin compositions containing polyimide precursors contain a large amount of solvent. This disclosure is made in view of the above-mentioned conventional circumstances and aims to provide a photosensitive resin composition that can simplify the process of forming a polyimide resin cured film, a method for manufacturing cured products and patterned cured products using this photosensitive resin composition, and electronic components. [Means for solving the problem]

[0005] The specific means for achieving the aforementioned objectives are as follows: <1> A polyimide precursor having a radical polymerizable group, The compound comprises at least one compound that is liquid at 25°C, selected from the group consisting of a monovalent (meth)acrylate compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom, a monovalent vinyl compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom, a monovalent (meth)acrylate compound having an ethylene oxide structure, and a monovalent vinyl compound having an ethylene oxide structure. A photosensitive resin composition having a solvent content of 10% by mass or less. <2> The solvent content is 1% by mass or less. <1> The photosensitive resin composition described in [reference]. <3> The polyimide precursor having the radical polymerizable group includes a compound having a structural unit represented by the following general formula (1). <1> or <2> The photosensitive resin composition described in [reference].

[0006] [ka]

[0007] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R 6 and R 7 Each of these independently represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a radical polymerizable group, R 6 and R 7 At least one of them is a radical polymerizable group. <4> The tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E), and the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H). The photosensitive resin composition according to <3>.

[0008]

Chemical formula

[0009] In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R A )2-; two Rs A each independently represent a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; two Rs B each independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these.

[0010]

Chemical formula

[0011] In formula (H), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer of 0 to 4. D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R A )2-; two Rs A each independently represent a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; two RsB Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these. <5> In the group represented by formula (E), C is an ether bond, and in the group represented by formula (H), D is a single bond. <4> The photosensitive resin composition described in [reference]. <6> <1> ~ <5> The photosensitive resin composition described in any one of the items is applied to a substrate and dried to form a photosensitive resin film, The photosensitive resin film is subjected to pattern exposure to form a resin film, The resin film after pattern exposure is developed using a developer to form a patterned resin film. A method for producing a patterned cured product, comprising: heat-treating the patterned resin film to form a patterned cured product. <7> <1> ~ <5> A cured product obtained by curing a photosensitive resin composition described in any one of the items. <8> It is a patterned cured product. <7> The cured product described above. <9> Used as an interlayer insulating film, cover coat layer, or surface protective film. <7> or <8> The cured product described above. <10> <7> ~ <9> An electronic component containing a cured product as described in any one of the items. [Effects of the Invention]

[0012] According to this disclosure, it is possible to provide a photosensitive resin composition that can simplify the process of forming a polyimide resin cured film, a method for manufacturing cured products and patterned cured products using this photosensitive resin composition, and electronic components. [Modes for carrying out the invention]

[0013] The embodiments of this disclosure are described in detail below. However, this disclosure is not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit this disclosure.

[0014] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the terms “layer” or “film” include cases where, when the region in which the layer or film exists is observed, it is formed not only over the entire region but also over only a portion of the region. In this disclosure, the term "lamination" refers to stacking layers, and two or more layers may be bonded together or detachable. In this disclosure, "(meth)acryloyl" means at least one of acryloyl and methacryloyl, and "(meth)acrylate" means at least one of acrylate and methacrylate. In this disclosure, the average thickness of a layer or film is given as the arithmetic mean of measuring the thickness of five points on the layer or film in question. The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, if the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, the measurement may be performed by observing the cross-section of the object to be measured using an electron microscope.

[0015] <Photosensitive resin composition> The photosensitive resin composition of this disclosure comprises a polyimide precursor having a radical polymerizable group (hereinafter sometimes referred to as a specific polyimide precursor), and at least one compound that is liquid at 25°C (hereinafter sometimes referred to as a specific liquid compound) selected from the group consisting of a monovalent (meth)acrylate compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom, a monovalent vinyl compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom, a monovalent (meth)acrylate compound having an ethylene oxide structure, and a monovalent vinyl compound having an ethylene oxide structure, wherein the solvent content is 10% by mass or less. In this disclosure, "solvent" refers to components that may volatilize when the photosensitive resin composition is heated at 250°C for 30 minutes, and which do not contain functional groups that can be radically polymerized.

[0016] According to this disclosure, the process for forming a cured polyimide resin film can be simplified. The photosensitive resin composition of this disclosure contains a specific liquid compound together with a specific polyimide precursor. The specific liquid compound has a 5- to 6-membered heterocyclic structure or an ethylene oxide structure containing an oxygen atom in its molecule. The inventors have discovered that compounds having these specific molecular structures have the function of dissolving the specific polyimide precursor, and have completed the present invention. Because 5- to 6-membered heterocyclic structures containing oxygen atoms or ethylene oxide structures have a high affinity for polyimide precursors, it is presumed that compounds with these specific molecular structures function effectively as solvents for polyimide precursors. Furthermore, because (meth)acryloyl groups or vinyl groups have structures similar to the radical polymerizable groups contained in polyimide precursors and have a high affinity for each other, it is presumed that compounds with these specific molecular structures function effectively as solvents for polyimide precursors. Furthermore, the specific liquid compound is a monovalent (meth)acrylate compound or a monovalent vinyl compound, and has the property of curing upon irradiation with active light. The specific liquid compound contained in the resin film hardens when the resin film is irradiated with active light during the formation process of the polyimide resin cured film. Even if the drying process is simplified and the specific liquid compound remains in the resin film, the amount of the specific liquid compound remaining in the patterned resin film becomes negligible after irradiation with active light. Therefore, it is presumed that the formation process of the polyimide resin cured film can be simplified.

[0017] The photosensitive resin composition of this disclosure is preferably a negative-type photosensitive resin composition. The following describes each component contained in the photosensitive resin composition of this disclosure.

[0018] (Polyimide precursor) The photosensitive resin composition of this disclosure contains a specific polyimide precursor. Examples of radical polymerizable groups of the specific polyimide precursor include (meth)acryloyl groups, allyl groups, and groups containing these functional groups, with (meth)acryloyl groups or groups containing (meth)acryloyl groups that exhibit high radical polymerizability being preferred.

[0019] The specific polyimide precursor preferably contains a compound having a structural unit represented by the following general formula (1). This tends to result in electronic components having a cured film that exhibits high reliability.

[0020] [ka]

[0021] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. 6 and R 7 Each of these independently represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a radical polymerizable group, R 6 and R 7 At least one of them is a radical polymerizable group. The specific polyimide precursor may have multiple structural units represented by the above general formula (1), and X, Y, R in the multiple structural units 6 and R 7 These may be the same or different. When a specific polyimide precursor has multiple structural units represented by the above general formula (1), the R of each structural unit 6 and R 7 The combinations may be the same or different.

[0022] R 6 and R 7 Specific examples of saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, represented by , include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups, with ethyl, isobutyl, and t-butyl groups being preferred. R 6 and R 7 A specific example of a radical polymerizable group represented by the following general formula (2) is the group represented by the following general formula (2). By including the group represented by the following general formula (2), the transmittance of i-line is high, and a good cured film tends to be formed even when curing at low temperatures below 400°C.

[0023] [ka]

[0024] In general formula (2), R 8 ~R 10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x This represents a divalent linking group.

[0025] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. 8 ~R 10 Specific examples of the aliphatic hydrocarbon group represented by include the methyl group, ethyl group, n-propyl group, isopropyl group, etc., with the methyl group being preferred.

[0026] R in general formula (2) 8 ~R 10 As for combinations, R 8 and R 9 is a hydrogen atom, and R 10 A combination of hydrogen atoms or methyl groups is preferred.

[0027] R in general formula (2) x The linking group is a divalent linking group, 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. R x The number of carbon atoms in the compound is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0028] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0029] [ka]

[0030] In general formula (2'), R 8 ~R 10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer from 1 to 10.

[0031] In general formula (2'), q is an integer between 1 and 10, preferably between 2 and 5, and more preferably 2 or 3.

[0032] In general formula (1), R 6 and R 7 At least one of them is represented by the general formula (2) above. It is preferable that it be a group that is R 6 and R 7 It is more preferable that both are groups represented by the general formula (2).

[0033] If a specific polyimide precursor has a structural unit represented by the general formula (1) described above, the R of all structural units contained in the compound 6 and R 7 The group R, represented by the general formula (2) for the sum of 6 and R 7 The proportion 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 may be 100 mol%. Furthermore, the aforementioned percentage may be greater than 0 mol% and less than 60 mol%.

[0034] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, groups with 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, amino groups, and the like. When the tetravalent organic group represented by X contains a benzene ring, it is preferable that the tetravalent organic group represented by X contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), or a silylene bond (-Si(R)). A )2-; Two R AEach of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. The rings may be linked by linking groups such as , or by a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be linked at two locations by a single bond and at least one of a linking group, forming a five-membered or six-membered ring containing a linking group between the two benzene rings.

[0035] In general formula (1), -COOR 6 The group and the -CONH- group are preferably in the ortho position relative to each other, and -COOR 7 It is preferable that the group and the -CO- group are in the ortho position relative to each other.

[0036] Specific examples of the tetravalent organic group represented by X include the groups represented by formulas (A) to (F) below. Among these, the group represented by formula (E) below is preferred from the viewpoint of obtaining a cured film with excellent flexibility and suppression of void generation at the bonding interface, and more preferably the group represented by formula (E) below, in which C is a group containing an ether bond, and even more preferably an ether bond. Formula (F) below is a structure in which C in formula (E) below is a single bond. This disclosure is not limited to the specific examples listed below.

[0037] [ka]

[0038] In formula (D), A and B are independently single bonds or divalent groups not conjugated to a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups not conjugated to a benzene ring include methylene groups, halide methylene groups, halide methylmethylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), sulfide bonds (-S-), and silylene bonds (-Si(R)).A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group.) are some examples. Among these, A and B are preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, etc., and an ether bond is more preferred.

[0039] In formula (E), C is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably an ether bond. Furthermore, C may have a structure represented by the following formula (C1).

[0040] [ka]

[0041] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of alkylene groups represented by C in formula (E) include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; methylmethylene group, methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, and 1,1-dimethyl Examples include branched alkylene groups such as methylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group. Among these, methylene groups are preferred.

[0042] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom in the alkylene group represented by C in formula (E) above is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene groups, difluoromethylene groups, and hexafluorodimethylmethylene groups are preferred.

[0043] R included in the above silylene bond or siloxane bond A or R BThe alkyl group represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. I. R A or R B Specific examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0044] Specific examples of the tetravalent organic group represented by X may be the groups represented by the following formulas (J) to (O).

[0045] [ka]

[0046] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bond positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, it is preferable that the divalent organic group represented by Y is a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (for example, groups with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0047] Specific examples of divalent aromatic groups represented by Y include the groups represented by formulas (G) to (I) below. Formula (I) is a structure in which D in formula (H) is a single bond. Among these, the group represented by formula (H) below is preferred from the viewpoint of obtaining a cured film with excellent flexibility and suppression of void generation at the bonding interface, more preferably represented by formula (H) below, where D is a group containing an ether bond or a single bond (i.e., the group represented by formula (I)), and even more preferably represented by the group represented by formula (I).

[0048] [ka]

[0049] In formulas (G) to (I), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. In formula (H), D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these. Furthermore, D may be the structure represented by formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of C in formula (E).

[0050] The alkyl group represented by R in formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of alkyl groups represented by R in formulas (G) to (I) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group.

[0051] The alkoxy group represented by R in formulas (G) to (I) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (I) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, etc.

[0052] The halogenated alkyl group represented by R in formulas (G) to (I) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (I) include alkyl groups in which at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (I) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups are preferred.

[0053] In equations (G) to (I), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0054] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, divalent groups having a polyalkylene oxide structure, and divalent groups having a polysiloxane structure.

[0055] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. 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.

[0056] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of cycloalkylene groups represented by Y include cyclopropylene and cyclohexylene.

[0057] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among these, polyethylene oxide structure or polypropylene oxide structure is preferred as the polyalkylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0058] Examples of divalent groups having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atoms in the polysiloxane structure are bonded to hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 18 carbon atoms. Specific examples of C1-C20 alkyl groups that bond to silicon atoms in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl groups. Among these, the methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents on the aryl group include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, the phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group, etc.

[0059] The group represented by formula (G) may also be the group represented by formula (G') below, the group represented by formula (H) may also be the group represented by formula (H') or formula (H") below, and the group represented by formula (I) may also be the group represented by formula (I') below.

[0060] [ka]

[0061] In formula (I'), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0062] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited. Examples of combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include the combination where X is the group represented by formula (E) and Y is the group represented by formula (G); and the combination where X is the group represented by formula (E) and Y is the group represented by formula (H). Among these, a combination in which X is a group represented by formula (E) and Y is a group represented by formula (H) is preferred, a combination in which C in the group represented by formula (E) is an ether bond and D in the group represented by formula (H) is a single bond (i.e., a group represented by formula (I)) is more preferred, and a combination in which C in the group represented by formula (E) is an ether bond and R in the group represented by formula (I') is a methyl group is even more preferred.

[0063] The content of the structural unit represented by general formula (1) in a compound having the structural unit represented by 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 the total structural units. The upper limit of the aforementioned content is not particularly limited and may be 100 mol%.

[0064] The specific polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The specific polyimide precursor may also be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0065] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, and 2,3,5,6-pyridine Tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) Examples include propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more types.

[0066] 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-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, and 2 ,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6- Diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, 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-A Minophenyl)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,Examples include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Diamine compounds may be used individually or in combination of two or more.

[0067] Compounds having a structural unit represented by general formula (1) can be obtained, for example, by the following methods (a) or (b). (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R-OH in an organic solvent to form a diester derivative, and then the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2. (b) A tetracarboxylic dianhydride is reacted with a diamine compound represented by H2N-Y-NH2 in an organic solvent to obtain a polyamic acid solution, and the compound represented by R-OH is converted to polyamic acid. In addition to the acidic solution, the reaction is carried out in an organic solvent to introduce ester groups. Here, Y in the diamine compound represented by H2N-Y-NH2 is the same as Y in general formula (1), and the specific examples and preferred examples are also the same. Also, R in the compound represented by R-OH is the same as R in general formula (1), excluding the hydrogen atom. 6 and R 7 The same applies to specific examples and preferred examples. The tetracarboxylic dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may each be used individually or in combination of two or more. Examples of the aforementioned organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide, with 3-methoxy-N,N-dimethylpropionamide being preferred. A polyimide precursor may be synthesized by reacting a dehydrating condensation agent with a compound represented by R-OH in a polyamic acid solution. The dehydrating condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0068] The specific polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, then reacting it with a chlorinating agent such as thionyl chloride to convert it to an acid chloride, and then reacting the acid chloride with a diamine compound represented by H2N-Y-NH2. A specific polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then reacting the diester derivative with a diamine compound represented by H2N-Y-NH2 in the presence of a carbodiimide compound. A specific polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H2N-Y-NH2 to produce a polyamic acid, then isoimidizing the polyamic acid in the presence of a dehydrating condensation agent such as trifluoroacetic anhydride, and then reacting it with a compound represented by R-OH. Alternatively, a portion of the tetracarboxylic dianhydride may be reacted with a compound represented by R-OH beforehand, and the partially esterified tetracarboxylic dianhydride may be reacted with a diamine compound represented by H2N-Y-NH2.

[0069] [ka]

[0070] 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.

[0071] Compounds represented by R-OH used in the synthesis of specific polyimide precursors include those with the R group represented by general formula (2). x The compound may be one in which a hydroxyl group is bonded to the group, or one in which a hydroxyl group is bonded to the terminal methylene group of the group represented by general formula (2'). 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 acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0072] There are no particular restrictions on the molecular weight of the specific polyimide precursor; for example, it is preferably 10,000 to 200,000 in weight-average molecular weight, and more preferably 10,000 to 100,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography and then converted using a standard polystyrene calibration curve.

[0073] The photosensitive resin composition of this disclosure may further contain a dicarboxylic acid, and the specific polyimide precursor contained in the photosensitive resin composition may have a structure in which some of the amino groups in the specific polyimide precursor react with the carboxyl groups of the dicarboxylic acid. For example, when synthesizing the specific polyimide precursor, some of the amino groups of the diamine compound may be reacted with the carboxyl groups of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acryloyl group, for example, a dicarboxylic acid represented by the following formula. In this case, when synthesizing the specific polyimide precursor, a methacrylic group derived from the dicarboxylic acid can be introduced into the specific polyimide precursor by reacting a portion of the amino group of the diamine compound with the carboxyl group of the dicarboxylic acid.

[0074] [ka]

[0075] The photosensitive resin composition of this disclosure may contain resin components other than the specific polyimide precursor. From the viewpoint of heat resistance, examples of resin components other than the specific polyimide precursor include polyimide resin, novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. Among these, it is preferable that the resin component other than the specific polyimide precursor contains a polyimide resin. Resin components other than the specific polyimide precursor may be used individually or in combination of two or more.

[0076] The polyimide resin is not particularly limited as long as it is a polymer compound having multiple structural units containing imide bonds. For example, it is preferable to include a compound having a structural unit represented by the following general formula (X). This tends to result in electronic components containing cured products that exhibit high reliability.

[0077] [ka]

[0078] 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 preferred examples of substituents X and Y in general formula (1) described above.

[0079] By combining a specific polyimide precursor with a polyimide resin, it is possible to suppress the generation of volatile substances due to dehydration cyclization during imide ring formation. This tends to suppress the generation of voids. The polyimide resin referred to here is a resin in which all or part of the resin skeleton has an imide skeleton. It is preferable that the polyimide resin is soluble in the photosensitive resin composition containing the specific polyimide precursor.

[0080] In the photosensitive resin composition of this disclosure, the content of the specific polyimide precursor relative to the total amount of resin components is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0081] When the photosensitive resin composition of this disclosure contains a resin component other than the specific polyimide precursor (preferably a polyimide resin), the ratio of the resin component other than the specific polyimide precursor (preferably a polyimide resin) to the total of the specific polyimide precursor and the resin component other than the specific polyimide precursor may be 15% to 50% by mass, or 10% to 20% by mass.

[0082] (Specific liquid compounds) The photosensitive resin composition of this disclosure contains a specific liquid compound. The specific liquid compound may be used alone or in combination of two or more types. In this disclosure, "monovalent (meth)acrylate compound" means a compound that contains one structure represented as "-CO-CR=CH2(R: hydrogen atom or methyl group)" in its molecule. In this disclosure, "monovalent vinyl compound" means a compound that contains one structure represented as "-CH=CH2" in its molecule and does not fall under the aforementioned "monovalent (meth)acrylate compound".

[0083] The heterocyclic rings in monovalent (meth)acrylate compounds having a 5- to 6-membered heterocyclic structure containing an oxygen atom, and monovalent vinyl compounds having a 5- to 6-membered heterocyclic structure containing an oxygen atom, may have substituents. Examples of substituents that the heterocyclic ring may have include alkyl groups having 1 to 3 carbon atoms. It is preferable that monovalent (meth)acrylate compounds having an ethylene oxide structure and monovalent vinyl compounds having an ethylene oxide structure do not contain aromatic rings in their molecules.

[0084] The specific liquid compound is preferably at least one compound selected from the group consisting of monovalent (meth)acrylate compounds having a 5- to 6-membered heterocyclic structure containing an oxygen atom and monovalent (meth)acrylate compounds having an ethylene oxide structure, and more preferably a monovalent (meth)acrylate compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom. Specific examples of monovalent (meth)acrylate compounds having a 5- to 6-membered heterocyclic structure containing an oxygen atom and monovalent (meth)acrylate compounds having an ethylene oxide structure include the following compounds. However, the specific liquid compounds used in this disclosure are not limited to the following examples.

[0085] [ka]

[0086] In the photosensitive resin composition of this disclosure, the content of the specific liquid compound is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and even more preferably 180 parts by mass or more, per 100 parts by mass of the specific polyimide precursor (if the photosensitive resin composition of this disclosure contains resin components other than the specific polyimide precursor, the total of the specific polyimide precursor and the resin components other than the specific polyimide precursor), from the viewpoint of solubility of the specific polyimide precursor. On the other hand, the content of the specific liquid compound is preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and even more preferably 220 parts by mass or less, per 100 parts by mass of the specific polyimide precursor (if the photosensitive resin composition of this disclosure contains resin components other than the specific polyimide precursor, the total of the specific polyimide precursor and the resin components other than the specific polyimide precursor), from the viewpoint of improving the heat resistance of the cured product. The content of the specific liquid compound is preferably 100 to 300 parts by mass per 100 parts by mass of the specific polyimide precursor (if the photosensitive resin composition of this disclosure contains resin components other than the specific polyimide precursor, the total of the specific polyimide precursor and the resin components other than the specific polyimide precursor).

[0087] (Cross-linkable monomer) The photosensitive resin composition of this disclosure may contain a crosslinkable monomer. The crosslinkable monomer has at least two groups containing polymerizable unsaturated double bonds, and preferably has at least two (meth)acryloyl groups from the viewpoint of being suitably polymerizable in combination with a photopolymerization initiator. From the viewpoint of improving crosslink density and photosensitivity, it is more preferable to have 2 to 6 groups containing polymerizable unsaturated double bonds, and even more preferable to have 2 to 4 groups. The crosslinkable monomer may be used alone or in combination of two or more types.

[0088] The crosslinkable monomer having a (meth)acryloyl group is not particularly limited, and includes, for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri( Examples include meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, isocyanurate tris(2-acryloyloxyethyl), 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO)-modified bisphenol A di(meth)acrylate, and the like.

[0089] In the photosensitive resin composition of this disclosure, the content of the crosslinkable monomer may be 30 parts by mass or less, 28 parts by mass or less, 25 parts by mass or less, 22 parts by mass or less, or 20 parts by mass or less per 100 parts by mass of the specific polyimide precursor, from the viewpoint of the insulation reliability of the cured film. By having a crosslinkable monomer content of 30 parts by mass or less per 100 parts by mass of the specific polyimide precursor, it is less likely that unreacted crosslinkable monomer will be generated after curing. As a result, it is presumed that metals (e.g., copper) contained in electrodes etc. will be less likely to diffuse into the cured film, and the decrease in insulation resistance will be suppressed, resulting in excellent insulation reliability. The lower limit of the crosslinkable monomer content may be 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more, per 100 parts by mass of the specific polyimide precursor.

[0090] (solvent) The photosensitive resin composition of this disclosure may or may not contain a solvent. If the photosensitive resin composition of this disclosure contains a solvent, the solvent content is 10% by mass or less. When the solvent content is 10% by mass or less, it tends to reduce the amount of degassing when producing a cured film using the photosensitive resin composition of this disclosure. If the photosensitive resin composition of this disclosure contains a solvent, the solvent content is preferably 1% by mass or less, and more preferably 0.1% by mass or less. The solvent content can be measured by the following method. The photosensitive resin composition is heated at 250°C for 30 minutes to determine the proportion of volatile matter in the photosensitive resin composition. Separately, GC-MS (Gas Chromatography Mass Spectrometry) analysis is performed on the volatile matter to identify the compounds contained in it. The proportion of the compounds contained in the volatile matter that do not contain radically polymerizable functional groups is calculated. The value obtained by multiplying the proportion of volatile matter in the photosensitive resin composition by the proportion of the compounds contained in the volatile matter that do not contain radically polymerizable functional groups is expressed as a percentage, and this value is taken as the solvent content. If the composition of the photosensitive resin composition is known, the proportion of the solvent in the photosensitive resin composition shall be defined as the solvent content.

[0091] If the photosensitive resin composition of this disclosure contains a solvent, the solvent preferably contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7). If the photosensitive resin composition of this disclosure contains a solvent, the solvent may be used alone or in combination of two or more types.

[0092] [ka]

[0093] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10is, independently of each other, an alkyl group having 1 to 4 carbon atoms, R 3 ~R 7 and R 9 are, independently of each other, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer of 0 to 8, t is an integer of 0 to 4, r is an integer of 0 to 4, and u is an integer of 0 to 3.

[0094] In formula (3), s is preferably 0. In formula (4), the alkyl group having 1 to 4 carbon atoms of R 2 is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, and more preferably 1. In formula (5), the alkyl group having 1 to 4 carbon atoms of R 3 is preferably a methyl group, an ethyl group, a propyl group or a butyl group. The alkyl groups having 1 to 4 carbon atoms of R 4 and R 5 are preferably a methyl group or an ethyl group. In formula (6), the alkyl groups having 1 to 4 carbon atoms of R 6 ~R 8 are preferably a methyl group or an ethyl group. r is preferably 0 or 1, and more preferably 0. In formula (7), the alkyl groups having 1 to 4 carbon atoms of R 9 and R 10 are preferably a methyl group or an ethyl group. u is preferably 0 or 1, and more preferably 0.

[0095] The solvent may be, for example, at least one of the compounds represented by formulas (4), (5), (6) and (7), or may be the compound represented by formula (5) or the compound represented by formula (7). From the viewpoint of reducing the reproductive toxicity and environmental load of the photosensitive resin composition, it may be the compound represented by formula (5).

[0096] Specific examples of the solvent include the following compounds.

[0097]

Chemical formula

[0098] The solvents that may be included in the photosensitive resin composition of this disclosure are not limited to the compounds described above, but may include other solvents. The solvents may include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, and the like.

[0099] If the photosensitive resin composition of this disclosure contains a solvent, preferred solvents include 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, cyclopentanone, ethyl lactate, and the like.

[0100] If the photosensitive resin composition of this disclosure contains a solvent, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of N-methyl-2-pyrrolidone may be 1% by mass or less of the total amount of the photosensitive resin composition, or 3% by mass or less of the total amount of the solvent.

[0101] The photosensitive resin composition of this disclosure preferably further contains a photopolymerization initiator. Furthermore, the photosensitive resin composition of this disclosure may further contain a thermal polymerization initiator. Preferred forms of the photopolymerization initiator and thermal polymerization initiator will be described below.

[0102] (Photopolymerization initiator) The photosensitive resin composition of this disclosure preferably contains a photopolymerization initiator. This reduces the number of steps required to manufacture electronic components and lowers the overall cost of the manufacturing process for electronic components.

[0103] Specific examples of photopolymerization initiators include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, o-methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives; acetophenone, 2 Acetophenone derivatives such as 2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethylketal, and benzyl-β-methoxyethylacetal; benzo Benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1, Oxime derivatives such as 3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), and ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime); N-arylglycines such as N-phenylglycine; Peroxides such as benzoyl peroxide;Examples include aromatic biimidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and Irgacure OXE02 (BASF), Irgacure OXE03 (BASF), and Irgacure OXE04 (BASF). The photopolymerization initiator may be used alone or in combination of two or more types. Among these, oxime compound derivatives are preferred because they do not contain metal elements, are highly reactive, and offer high sensitivity.

[0104] If the photosensitive resin composition of this disclosure contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.8 to 5 parts by mass, per 100 parts by mass of the specific polyimide precursor, from the viewpoint of ensuring that photocrosslinking is uniform in the film thickness direction.

[0105] The photosensitive resin composition of this disclosure may include an anti-reflective agent that suppresses reflected light from the substrate direction, from the viewpoint of improving photosensitive properties.

[0106] (Thermal polymerization initiator) The photosensitive resin composition of this disclosure preferably contains a thermal polymerization initiator from the viewpoint of improving the physical properties of the cured product.

[0107] Specific examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, dilauroyl peroxide, and diben Examples include diacyl peroxides such as zoyl peroxide, peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl)peroxide, dicumyl peroxide, di-t-butyl peroxide, and di(2-t-butylperoxyisopropyl)benzene. The thermal polymerization initiator may be used alone or in combination of two or more.

[0108] If the photosensitive resin composition of this disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator may be 0.1 to 20 parts by mass, 1 to 15 parts by mass, or 5 to 10 parts by mass per 100 parts by mass of the specific polyimide precursor.

[0109] (Polymerization inhibitor) The photosensitive resin composition of this disclosure may contain a polymerization inhibitor from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization suppressants.

[0110] Specific examples of polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-thulquinone, tannic acid, parabenzylaminophenol, nitrosamines, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide, and hindered phenol compounds. Polymerization inhibitors may be used individually or in combination of two or more. Combining two or more polymerization inhibitors tends to make it easier to adjust the photosensitive properties due to differences in reactivity. Hindered phenol compounds may have both the function of a polymerization inhibitor and the function of an antioxidant described later, or they may have only one of the functions.

[0111] If the photosensitive resin composition of this disclosure contains a polymerization inhibitor, the amount of polymerization inhibitor is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the specific polyimide precursor, from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the resulting cured product.

[0112] The photosensitive resin composition of this disclosure may further contain antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, or nitrogen-containing compounds.

[0113] (Antioxidant) The photosensitive resin composition of this disclosure may contain an antioxidant, from the viewpoint of suppressing a decrease in adhesion by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow processing, etc. The inclusion of an antioxidant in the photosensitive resin composition of this disclosure can suppress oxidation of electrodes during insulation reliability testing.

[0114] Specific examples of antioxidants include hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-t-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-t-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants may be used individually or in combination of two or more types.

[0115] If the photosensitive resin composition of this disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific polyimide precursor.

[0116] (Coupling agent) The photosensitive resin composition of this disclosure may contain a coupling agent. The coupling agent reacts with a specific polyimide precursor to crosslink during heat treatment, or the coupling agent itself polymerizes. This tends to improve the adhesion between the resulting cured product and the substrate.

[0117] Specific examples of coupling agents are not particularly limited. Examples of coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidoic acid, and benzophenone-3,3'-bis(N-[3-triethoxy Examples include silane coupling agents such as sisilyl)propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane; and aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate. The coupling agent may be used alone or in combination of two or more types.

[0118] If the photosensitive resin composition of this disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the specific polyimide precursor.

[0119] (Surfactants and leveling agents) The photosensitive resin composition of this disclosure may contain at least one of a surfactant and a leveling agent. By including at least one of a surfactant and a leveling agent in the photosensitive resin composition, it is possible to improve the coatability (e.g., suppression of striations (unevenness of film thickness)), adhesion, and compatibility of compounds in the photosensitive resin composition.

[0120] Examples of surfactants or leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether.

[0121] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0122] If the photosensitive resin composition of this disclosure 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 mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the specific polyimide precursor.

[0123] (Rust inhibitor) The photosensitive resin composition of this disclosure may contain a rust inhibitor from the viewpoint of suppressing the corrosion of metals such as copper and copper alloys, and from the viewpoint of suppressing discoloration of said metals. Examples of rust inhibitors include azole compounds and purine derivatives.

[0124] 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-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, and 1-methyl-1H-tetrazol.

[0125] 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-amino Examples include adenine, 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.

[0126] Rust inhibitors may be used individually or in combination of two or more types.

[0127] When the photosensitive resin composition of this disclosure contains a rust inhibitor, the amount of rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the specific polyimide precursor. In particular, when the amount of rust inhibitor is 0.1 parts by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the photosensitive resin composition of this disclosure is applied to the surface of copper or copper alloy.

[0128] (nitrogen-containing compounds) The photosensitive resin composition of this disclosure may contain a nitrogen-containing compound, from the viewpoint of promoting the imidation reaction of a specific polyimide precursor to obtain a highly reliable cured product.

[0129] Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, 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-aminoacetanilide, 4-aminoacetophenone and the like can be mentioned. Among them, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol and the like are preferable. The nitrogen-containing compound may be used alone or in combination of two or more.

[0130] The nitrogen-containing compound preferably contains a compound represented by the following formula (17).

[0131]

Chemical formula

[0132] In formula (17), R 31A ~R 33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group, and at least one (preferably one) of R 31A ~R 33A is a monovalent aromatic group. R 31A ~R 33A may form a ring structure with adjacent groups. Examples of the formed ring structure include a 5-membered ring, a 6-membered ring, etc. which may have substituents such as a methyl group, a phenyl group. The hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than a hydroxy group.

[0133] In formula (17), at least one (preferably one) of R 31A ~R 33A is preferably a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.

[0134] In formula (17), R 31A ~R 33A The monovalent aliphatic hydrocarbon group has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. The monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, etc.

[0135] In formula (17), R 31A ~R 33A A monovalent aliphatic hydrocarbon group having a hydroxyl group is R 31A ~R 33A Preferably, the group is a monovalent aliphatic hydrocarbon group to which one or more hydroxyl groups are bonded, and more preferably, a group to which one to three hydroxyl groups are bonded. Specific examples of monovalent aliphatic hydrocarbon groups having hydroxyl groups include methylol group and hydroxyethyl group, with the hydroxyethyl group being preferred.

[0136] R in equation (17) 31A ~R 33A Examples of monovalent aromatic groups include monovalent aromatic hydrocarbon groups and monovalent aromatic heterocyclic groups, with monovalent aromatic hydrocarbon groups being preferred. For monovalent aromatic hydrocarbon groups, those with 6 to 12 carbon atoms are preferred, and those with 6 to 10 carbon atoms are more preferred. Examples of monovalent aromatic hydrocarbon groups include phenyl groups and naphthyl groups.

[0137] R in equation (17) 31A ~R 33A The monovalent aromatic group may have substituents. The substituent may be R of formula (17). 31A ~R 33A The monovalent aliphatic hydrocarbon group and the R of formula (17) described above. 31A ~R 33A Examples include monovalent aliphatic hydrocarbon groups having a hydroxyl group.

[0138] If the photosensitive resin composition of this disclosure contains a nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the specific polyimide precursor.

[0139] The photosensitive resin composition of this disclosure contains a specific polyimide precursor, a specific liquid compound, and optional components such as a crosslinkable monomer, a photopolymerization initiator, a solvent, a thermal polymerization initiator, a sensitizer, a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, and a nitrogen-containing compound, and may also contain other components and unavoidable impurities to the extent that they do not impair the effects of this disclosure. For example, 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass of the photosensitive resin composition of this disclosure Specific polyimide precursors and specific liquid compounds, Specific polyimide precursors, specific liquid compounds, crosslinkable monomers and photopolymerization initiators, Specific polyimide precursors, specific liquid compounds, crosslinkable monomers, photopolymerization initiators and solvents, or The material may consist of a specific polyimide precursor, a specific liquid compound, a crosslinkable monomer, a photopolymerization initiator and a solvent, and optionally a thermal polymerization initiator, a sensitizer, a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor and a nitrogen-containing compound.

[0140] <Cured products, methods for manufacturing the same, and electronic components> The cured product of this disclosure can be obtained by curing the photosensitive resin composition of this disclosure. The cured product of this disclosure may be used as a patterned cured product or as a cured product without a pattern. The average thickness of the cured product of this disclosure is preferably 5 μm to 20 μm.

[0141] The method for manufacturing a patterned cured product according to the present disclosure includes: applying the photosensitive resin composition according to the present disclosure onto a substrate and drying it to form a photosensitive resin film; pattern exposing the photosensitive resin film to light to form a resin film; developing the resin film after pattern exposure using a developer to form a patterned resin film; and heat-treating the patterned resin film to form a patterned cured product. This makes it possible to obtain a patterned cured product.

[0142] A method for producing a patternless cured product includes, for example, applying the photosensitive resin composition of this disclosure onto a substrate, drying it to form a photosensitive resin film, and heat-treating the photosensitive resin film. It may also include exposure.

[0143] Examples of substrates include semiconductor substrates such as glass substrates and Si substrates (silicon wafers), metal oxide insulating substrates such as TiO2 substrates and SiO2 substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0144] There are no particular restrictions on the method of applying the photosensitive resin composition of this disclosure, and it can be done using a spinner or the like.

[0145] Drying can be done using a hot plate, oven, etc. The drying temperature is preferably 90°C to 150°C, and more preferably 90°C to 120°C from the viewpoint of ensuring dissolution contrast. The drying time is preferably 30 seconds to 5 minutes. Drying can be done more than once. This makes it possible to obtain a photosensitive resin film formed in the form of a film using the photosensitive resin composition of this disclosure.

[0146] The average thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, and even more preferably 7 μm to 30 μm.

[0147] Pattern exposure involves exposing a predetermined pattern to light, for example, through a photomask. Examples of active light to be irradiated include ultraviolet light such as i-rays, visible light, and radiation, but i-rays are preferred. Exposure equipment can include parallel exposure machines, aligners, projection exposure machines, steppers, scanner exposure machines, and the like.

[0148] By developing the film, a patterned resin film (patterned resin film) can be obtained. Generally, when using a negative-type photosensitive resin composition, the unexposed areas are removed with a developer. As a developer, a good solvent for photosensitive resin films can be used alone, or a good solvent and a poor solvent can be used in appropriate combinations. 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. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0149] A surfactant may be added to the developer. The amount added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0150] The development time can be, for example, twice the time it takes for the photosensitive resin film to completely dissolve after being immersed in the developer. The development time varies depending on the specific polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0151] After developing, the film may be washed with a rinsing solution. As a rinsing solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., may be used individually or in appropriate mixtures.

[0152] A patterned cured product can be obtained by heat-treating the patterned resin film. A specific polyimide precursor undergoes a dehydration and ring-closing reaction through a heat treatment process, resulting in the corresponding polyimide resin.

[0153] The heat treatment temperature is preferably 250°C or lower, more preferably 120°C to 250°C, and even more preferably 160°C to 200°C. By keeping the heat treatment temperature within the above range, damage to the substrate or device can be minimized, enabling high-yield device production and energy savings in the process.

[0154] The heat treatment time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heat treatment time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can proceed sufficiently. The heat treatment can be performed in the atmosphere of air or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the pattern resin film.

[0155] Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0156] The cured product of this disclosure can be used as an interlayer insulating film, a cover coat layer, or a surface protective film. Furthermore, the cured product of this disclosure can be used as a passivation film, a buffer coat film, and the like. Using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, and surface protective film, highly reliable electronic components including the cured product of this disclosure, such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (multi-die fan-out wafer-level packages, etc.), can be manufactured. [Examples]

[0157] The present disclosure will be described in more detail below based on examples and comparative examples. However, the present disclosure is not limited to the examples described below.

[0158] (Synthesis of polyimide precursors) 7.07 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30 g of N-methyl-2-pyrrolidone (NMP). The resulting solution was stirred at 30°C for 4 hours, and then overnight at room temperature (25°C) to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added at room temperature (25°C), followed by 7.08 g of 2-hydroxyethyl methacrylate (HEMA), and the mixture was stirred at 45°C for 10 hours. This reaction mixture was added dropwise to distilled water, the precipitate was filtered off and collected, and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as Polymer A). The weight-average molecular weight of Polymer A, calculated using the GPC method on a standard polystyrene basis, was 20,000.

[0159] [Example 1] 100 parts by mass of polymer A and 160 parts by mass of tetrahydrofurfuryl acrylate (THFA, see compound below) were placed in a 100 mL plastic bottle and stirred for 24 hours using a mixing rotor at 25°C. Visual observation afterward revealed that polymer A had dissolved in THFA. This result suggests that THFA can be used as a solvent for photosensitive resin compositions.

[0160] [ka]

[0161] [Example 2] When observed in the same manner as in Example 1, except that THFA was replaced with 2-hydroxyethyl methacrylate (HEMA, the compound below), polymer A was almost completely dissolved in HEMA, although there were some undissolved particles. This result suggests that HEMA can be used as a solvent for photosensitive resin compositions.

[0162] [ka]

[0163] [Example 3] When observed in the same manner as in Example 1, except that THFA was replaced with ethoxyethoxyethyl acrylate (EEEA, the compound described below), polymer A was almost completely dissolved in EEEA, although there were some undissolved particles. This result suggests that EEEA can be used as a solvent for photosensitive resin compositions.

[0164] [ka]

[0165] [Example 4] When observed in the same manner as in Example 1, except that THFA was replaced with tetrahydrofurfuryl methacrylate (THFMA, the compound described below), polymer A was found to be soluble in THFMA. This result suggests that THFMA can be used as a solvent for photosensitive resin compositions.

[0166] [ka]

[0167] [Comparative Example 1] When observed in the same manner as in Example 1, except that THFA was replaced with dimethylaminopropyl methacrylate (MDAP, the compound below), polymer A did not dissolve in MDAP.

[0168] [Chemical formula]

[0169] [Comparative Example 2] When observed in the same manner as in Example 1 except that THFA was changed to n-dodecyl acrylate (DDA, the following compound), Polymer A did not dissolve in DDA.

[0170] [Chemical formula]

[0171] [Comparative Example 3] When observed in the same manner as in Example 1 except that THFA was changed to 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (the following compound), Polymer A did not dissolve in 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate.

[0172] [Chemical formula]

[0173] [Comparative Example 4] When observed in the same manner as in Example 1 except that THFA was changed to N-acryloyloxyethylhexahydrophthalimide (the following compound), Polymer A did not dissolve in N-acryloyloxyethylhexahydrophthalimide.

[0174] [Chemical formula]

[0175] [Example 5] (Preparation of photosensitive resin composition) 200 parts by mass of THFA, 100 parts by mass of polymer A, 10 parts by mass of tricyclodecanedimethanol diacrylate (A-DCP), 10 parts by mass of ethoxylated pentaerythritol tetraacrylate (ATM-4E), and 1 part by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), Irgacure OXE02) were mixed to form a mixture. This mixture was kneaded overnight at 25°C in a general solvent-resistant container, and then pressure filtered using a 0.2 μm pore filter to obtain the photosensitive resin composition of Example 4. The solvent content of the photosensitive resin composition of Example 4 is 0% by mass.

[0176] (Resolution evaluation) The obtained photosensitive resin composition was spin-coated onto a silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Limited), dried at 105°C for 2 minutes, and then dried at 115°C for 2 minutes to form a photosensitive resin film with a dry thickness of 7 to 10 μm. The development time was set to twice the time it took for the resulting photosensitive resin film to completely dissolve when immersed in cyclopentanone. Furthermore, a photosensitive resin film was formed in the same manner as described above, and the resulting photosensitive resin film was exposed to an i-line stepper FPA-3000iW (manufactured by Canon Inc.) at an exposure dose of 500 mJ / cm². 2 Exposure was performed under the following conditions. Using Act8, exposure and subsequent heating were performed at 120°C for 3 minutes under atmospheric conditions. After exposure and heating, the resin film was paddle-developed with cyclopentanone using Act8 for the development time described above, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film. The obtained patterned resin film was heated in a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere at 175°C for 1 hour to obtain a patterned cured product (cured film thickness 5 μm). The resulting patterned cured material was observed using an optical microscope, and the resolution was defined as the smallest diameter in which an opening was formed that exposed 55% or more of the substrate surface area relative to the mask dimensions of the via. The resolution was 7 μm.

[0177] (Percentage of residual film after development) Similar to the resolution evaluation, a photosensitive resin film with a dry thickness of 7-10 μm was formed. The thickness of this photosensitive resin film was accurately measured using an optical interference film thickness analyzer (SCREEN Semiconductor Solutions Co., Ltd., VM-2210). Next, the resulting photosensitive resin film was exposed to an i-line stepper FPA-3000iW (manufactured by Canon Inc.) at an exposure dose of 500 mJ / cm². 2 Full-surface exposure was performed under the following conditions. Using Act8, exposure and subsequent heating were performed at 120°C for 3 minutes under atmospheric conditions. After exposure and heating, the resin film was paddle-developed with cyclopentanone using Act8 for the same development time as in the resolution evaluation. Then, it was rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a post-developed resin film. The thickness of this post-developed resin film was accurately measured using an optical interference film thickness analyzer (SCREEN Semiconductor Solutions Co., Ltd., VM-2210). Using the film thickness of the photosensitive resin film and the film thickness of the resin film after development, the residual film rate after development (%) was calculated based on the following formula, and the residual film rate after development was 68.8%. Developing residue percentage (%) = 100 × (Developing resin film thickness / Photosensitive resin film thickness)

[0178] [Reference example] The resolution and residual film percentage after development were evaluated in the same manner as in Example 4, except that 3-methoxy-N,N-dimethylpropanamide was used instead of THFA. The resolution was 7 μm and the residual film percentage after development was 69.9%. The solvent content of the photosensitive resin composition in the reference example is 62% by mass. A comparison of Example 5 with the Reference Example shows that the photosensitive resin composition of Example 5, which uses THFA, a type of specific liquid compound, exhibits photosensitive properties equivalent to those of the photosensitive resin composition of the Reference Example. Furthermore, since the photosensitive resin composition of Example 5 does not contain solvents, the process required for solvent removal (drying process) can be simplified compared to the photosensitive resin composition of the Reference Example.

Claims

1. A polyimide precursor having a radical polymerizable group, The compound comprises at least one compound that is liquid at 25°C, selected from the group consisting of a monovalent (meth)acrylate compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom, a monovalent vinyl compound having a 5- to 6-membered heterocyclic structure containing an oxygen atom, a monovalent (meth)acrylate compound having an ethylene oxide structure, and a monovalent vinyl compound having an ethylene oxide structure. A photosensitive resin composition having a solvent content of 10% by mass or less.

2. The photosensitive resin composition according to claim 1, wherein the content of the solvent is 1% by mass or less.

3. The photosensitive resin composition according to claim 1, wherein the polyimide precursor having the radical polymerizable group comprises a compound having a structural unit represented by the following general formula (1). 【Chemistry 1】 In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ６ and R ７ Each of these independently represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a radical polymerizable group, R ６ and R ７ At least one of them is a radical polymerizable group.

4. The photosensitive resin composition according to claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E), and the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H). 【Chemistry 2】 In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ )) ２ —; two R Ａ each independently represent a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (—O—(Si(R Ｂ )) ２ —O—) ｎ ; two R Ｂ each independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. 【Transformation 3】 In formula (H), R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), or a silylene bond (-Si(R) Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these.

5. The photosensitive resin composition according to claim 4, wherein C in the group represented by formula (E) is an ether bond, and D in the group represented by formula (H) is a single bond.

6. The photosensitive resin composition according to any one of claims 1 to 5 is applied to a substrate and dried to form a photosensitive resin film, The photosensitive resin film is subjected to pattern exposure to form a resin film, The resin film after pattern exposure is developed using a developer to form a patterned resin film. A method for producing a patterned cured product, comprising: heat-treating the patterned resin film to form a patterned cured product.

7. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5.

8. The cured product according to claim 7, which is a patterned cured product.

9. The cured product according to claim 7, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film.

10. An electronic component comprising the cured product described in claim 7.

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