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

Abstract

This photosensitive resin composition comprises: a resin which is at least one among a cyclized resin and a precursor of the cyclized resin; a photosensitizer; and a solvent, wherein the photosensitizer contains a photosensitizer having photobleaching properties, and the solvent contains a solvent A and a solvent B having a higher vapor pressure at 25ºC than the solvent A.

Description

Photosensitive resin composition, method for manufacturing patterned cured products, cured products, and electronic components

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

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

[0003] Japanese Patent Publication No. 2021-85977

[0004] Cured products obtained using photosensitive resin compositions are sometimes required to have excellent elongation properties. This disclosure has been made in view of the above-mentioned conventional circumstances, and aims to provide a photosensitive resin composition that can produce cured products with excellent elongation properties, as well as a method for manufacturing cured products and patterned cured products using the photosensitive resin composition, and electronic components.

[0005] Specific means for solving the above problems include the following embodiments: <1> A photosensitive resin composition comprising a resin which is at least one of a cyclized resin and a precursor of the cyclized resin, a photosensitive agent, and a solvent, wherein the photosensitive agent comprises a photobleaching agent, and the solvent comprises solvent A and solvent B which has a higher vapor pressure at 25°C than solvent A. <2> The photosensitive resin composition according to <1>, wherein the reduction rate of i-line absorbance obtained by the measurement method A below is 10% or more. (Measurement method A) A pre-baking treatment is performed in which a film of the photosensitive resin composition is applied to a glass substrate such that the average thickness of the film after pre-baking is 13 μm, and the film is dried at 90°C for 4 minutes, followed by irradiation at a dose of 800 mJ / cm². ２Exposure is performed by irradiating with i-rays under the following conditions. The absorbance A1 of the i-rays transmitted through the film before irradiation and the absorbance A2 of the i-rays transmitted through the film after irradiation are measured, and the percentage decrease in i-ray absorbance is calculated using the following formula (A). (Percentage decrease in i-ray absorbance (%)) = {1 - (absorbance A2) / (absorbance A1)} × 100 ... (A) <3> The photosensitive resin composition according to <1> or <2>, wherein the photosensitive agent having photobleaching properties is a photopolymerization initiator. <4> The photosensitive resin composition according to <3>, wherein the photopolymerization initiator is an oxime ester-based photopolymerization initiator. <5> The photosensitive resin composition according to <4>, wherein the photopolymerization initiator contains a diphenyl sulfide skeleton. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the vapor pressure of solvent A at 25°C is less than 1.0 mmHg, and the vapor pressure of solvent B at 25°C is 1.0 mmHg or more. <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the content of solvent A is 40.0% by mass to 99.0% by mass relative to the total of solvent A and solvent B. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the resin which is at least one of the cyclized resin and the precursor of the cyclized resin is a resin which is at least one of polyimide and a polyimide precursor. <9> The photosensitive resin composition according to <8>, wherein the polyimide precursor contains a structural unit represented by the following formula (1).

[0006]

[0007] (In 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 or a monovalent organic group, R ６ and R ７At least one of the components has polymerizable unsaturated bonds, where * indicates the bonding position with other structures.) <10> A method for producing a patterned cured product, comprising the steps of: applying a photosensitive resin composition according to any one of <1> to <9> onto a substrate and drying it to form a resin film; pattern exposing the resin film to obtain a post-exposure resin film; developing the post-exposure resin film using a developer to obtain a patterned resin film; and heat-treating the patterned resin film. <11> A cured product of a photosensitive resin composition according to any one of <1> to <9>. <12> The cured product according to <11>, which is a patterned cured product. <13> The cured product according to <11> or <12>, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film. <14> An electronic component comprising the cured product according to any one of <11> to <13>.

[0008] According to this disclosure, a photosensitive resin composition that can produce a cured product with excellent elongation properties, a method for producing a cured product and a patterned cured product using the photosensitive resin composition, and an electronic component can be provided.

[0009] This is a manufacturing process diagram of an electronic component according to one embodiment of the present disclosure.

[0010] The embodiments of this disclosure are described below. However, this disclosure is not limited to the embodiments described below.

[0011] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that are not clearly distinguishable from other processes, provided that the purpose of the process is achieved. In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced by 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 observing the region in which the layer or film exists, it is formed not only over the entire region, but also on only a part of the region. In this disclosure, "(meth)acryloyl group" means at least one of an acryloyl group and a methacryloyl group, and "(meth)acryloyloxy group" means at least one of an acryloyloxy group and a methacryloyloxy group. 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, a scanning stylus, an optical interferometer, or the like. In this disclosure, if the thickness of a layer or film can be measured directly, it shall be measured using an optical interferometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing a cross-section of the object to be measured using an electron microscope.

[0012] [Photosensitive resin composition] The photosensitive resin composition of the present disclosure comprises a resin which is at least one of a cyclized resin and a precursor of the cyclized resin, a photosensitive agent, and a solvent, wherein the photosensitive agent comprises a photobleaching agent, and the solvent comprises solvent A and solvent B which has a higher vapor pressure at 25°C than solvent A.

[0013] The cured product of the photosensitive resin composition of this disclosure exhibits excellent elongation. The inventors attribute this to the following reasons, but this disclosure is not limited to these assumptions. The photosensitive resin composition of this disclosure contains a photobleaching photosensitive agent. The inclusion of a photobleaching photosensitive agent allows light to penetrate deeper into the photosensitive resin composition when the crosslinking reaction is promoted by light irradiation. This reduces the variation in crosslink density in the thickness direction after light irradiation, and also reduces the variation in film density after light irradiation. As a result, the film stretches uniformly in the evaluation of elongation, resulting in excellent elongation.

[0014] Furthermore, the photosensitive resin composition of this disclosure contains solvents A and B, which causes an azeotrope-like phenomenon during pre-baking, making the solvents more likely to volatilize. Therefore, it is possible to form a cured film with excellent film thickness uniformity after pre-baking. A cured film with suppressed film thickness variation exhibits stable elongation characteristics, resulting in excellent elongation.

[0015] Furthermore, when using a negative-type photosensitive resin composition (i.e., a resin composition that removes unexposed areas to form a pattern) as the photosensitive resin composition, the following effects tend to be easily obtained when using the photosensitive resin composition of this disclosure. First, when pattern exposure by light irradiation is performed using a photosensitive resin composition that does not contain a photobleaching photosensitive agent, the crosslinking reaction tends to proceed from the side irradiated with light, making it difficult for light to reach the bottom. In this case, the cured product of the resulting photosensitive resin composition may have an inverse taper shape. On the other hand, since the photosensitive resin composition of this disclosure contains a photobleaching photosensitive agent, the crosslinking reaction of the photosensitive resin composition proceeds at a constant rate, and light easily reaches the bottom. For this reason, when using the photosensitive resin composition of this disclosure, the cured product tends to have a forward taper shape. Comparing the cured products of the two types of photosensitive resin compositions described above, the forward taper shaped cured product obtained using the photosensitive resin composition of this disclosure is more effective at suppressing peeling between the substrate and other materials. Furthermore, the effect of light easily reaching the bottom is also advantageous for positive-type photosensitive resin compositions (i.e., resin compositions that remove the exposed area to form a pattern).

[0016] The components contained in the photosensitive resin composition of this disclosure will be described below. The photosensitive resin composition of this disclosure may be a positive-type photosensitive resin composition or a negative-type photosensitive resin composition, but it is preferable to be a negative-type photosensitive resin composition.

[0017] <Resin> The photosensitive resin composition of this disclosure includes a resin which is at least one of a cyclized resin and a precursor of a cyclized resin. The cyclized resin is not particularly limited as long as it is a resin which has a ring structure in its structure. A precursor of a cyclized resin is a resin which undergoes a change in chemical structure due to external stimuli such as heat or light to become a cyclized resin. Resins which undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins which undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. The photosensitive resin composition of this disclosure may contain only one of the cyclized resin and the precursor of a cyclized resin, or it may contain both the cyclized resin and the precursor of a cyclized resin.

[0018] The resin is preferably at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. In particular, the resin is more preferably a resin that is at least one of polyimide and / or a polyimide precursor, and even more preferably a resin that is a polyimide precursor.

[0019] (Polyimide) The polyimide is not particularly limited as long as it is a polymer compound having multiple structural units containing imide bonds, for example, it may be a polymer in which the polyimide precursor described later has been imidized. The polymer compound having multiple structural units containing imide bonds preferably includes a compound having a structural unit represented by the following general formula (X).

[0020]

[0021] In general formula (X), X represents a tetravalent organic group, Y represents a divalent organic group, and * represents a bonding position with other structures. 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 below. Polyimide may have multiple structural units represented by the above general formula (X), and X and Y in the multiple structural units may be the same or different. In this disclosure, "* represents a bonding position with other structures" can also be expressed as "* represents a bonding position with other atoms" or "* represents a bonding position with other structures or atoms."

[0022] (Polyimide Precursor) The polyimide precursor may be a polyamic acid, or a compound in which at least some of the hydrogen atoms of the carboxyl groups in the polyamic acid are replaced with monovalent organic groups. The polyimide precursor preferably contains a polyimide precursor having polymerizable unsaturated bonds. Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

[0023] In the present disclosure, a polyimide precursor means an intermediate in the synthesis of polyimide. The polyimide precursor can typically be a compound polymer capable of forming a polyimide by an imidization reaction. The polyimide precursor may be a polymer that has not been imidized (i.e., a polymer having no imide bond), a polymer in which a part of the molecule has been imidized (i.e., a polymer having an imide bond; a partially imidized polymer), or a mixture thereof. More specifically, the polyimide precursor can be a polymer having a cyclizable amide group and a carboxylic acid group in the molecule (such as polyamic acid, polyamic acid ester, etc.). The polyimide precursor may be a polymer in which all of the cyclizable amide groups and carboxylic acid groups in the molecule are uncyclized, a polymer in which a part of the cyclizable amide groups and carboxylic acid groups in the molecule are cyclized and a part are uncyclized, or a mixture thereof.

[0024] The polyimide precursor preferably has a structural unit represented by the following general formula (1).

[0025]

[0026] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７ each independently represent a hydrogen atom or a monovalent organic group. At least one of R ６ and R ７ preferably has a polymerizable unsaturated bond. * represents the bonding position with another structure or atom.

[0027] The polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, R ６ and R ７ in the plurality of structural units may be the same or different from each other. Note that R ６ and R ７ each independently represent a hydrogen atom or a monovalent organic group, and the combination thereof is not particularly limited. For example, R ６ and R ７At least one of them is a hydrogen atom, and the rest may be monovalent organic groups as described later, and they may all be the same or different monovalent organic groups. As mentioned above, when the polyimide precursor has multiple structural units represented by the general formula (1), the R of each structural unit ６ and R ７ The combinations may be the same or different.

[0028] 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, aromatic rings with 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, heterocyclic rings 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 includes an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of substituents on aromatic rings include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, and amino groups.

[0029] 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'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 ＢEach 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.

[0030] 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.

[0031] 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 an insulating 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. Note that this disclosure is not limited to the following specific examples. Also, in formulas (A) to (F) below, * indicates the bonding position with other structures.

[0032]

[0033] 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's ＡEach 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.

[0034] 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 (-O-C(=O)-), 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 2 or more. ) or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably is an ether bond. Furthermore, C may include a structure represented by the following formula (C1). In the following formula (C1), * represents the bond position with other structures.

[0035]

[0036] 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 the alkylene group 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.

[0037] 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.

[0038] 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. 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.

[0039] Specific examples of the tetravalent organic group represented by X may be the groups represented by formulas (J) to (O) below. In formulas (J) to (O) below, * indicates the bond position with other structures.

[0040]

[0041] 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, the divalent organic group represented by Y is preferably 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 heterocyclic ring), with divalent aromatic hydrocarbon groups being preferred.

[0042] Specific examples of divalent aromatic groups represented by Y include the groups represented by formulas (G) and (H) below. Among these, the group represented by formula (H) below is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, and in formula (H) below, it is more preferable that D is a group containing a single bond or an ether bond, even more preferable that D is a group containing a single bond or an ether bond, particularly preferable that D is a group containing an ether bond, and extremely preferable that D is an ether bond. In formulas (G) and (H) below, * indicates the bond position with other structures.

[0043]

[0044] In equation (G), R ８ R represents an alkyl group, alkoxy group, halogenated alkyl group, phenyl group, or halogen atom, and n1 represents an integer from 0 to 4. In formula (H), R ９ and R １０ Each of the following independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and each of the following independently represents an integer from 0 to 4. In formula (H), 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)-), or a silylene bond (-Si(R Ｑ ) ２ -; Two R's Ｑ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｓ ) ２ -O-) ｓ ; Two R's ＳEach of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and s represents an integer of 1 or 2 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). Preferably, D in formula (H) independently represents a single bond, an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group.

[0045] R in equations (G) to (H) ８ , R ９ , or R １０ The alkyl group represented by 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 the alkyl group represented by R in formulas (G) to (H) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0046] R in equations (G) to (H) ８ , R ９ , or R １０ The alkoxy group represented by 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. R in formulas (G) to (H) ８ , R ９ , or R １０ Specific examples of alkoxy groups represented by include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, and the like.

[0047] R in equations (G) to (H) ８ , R ９ , or R １０The halogenated alkyl group represented by 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. R in formulas (G) to (H) ８ , R ９ , or R １０ Specific examples of halogenated alkyl groups represented by formulas (G) to (H) include alkyl groups in which at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl groups, difluoromethyl groups, trifluoromethyl groups, etc., are preferred.

[0048] In formulas (G) to (H), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0049] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups containing polyalkylene oxide structures.

[0050] 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 the alkylene group represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonameethylene, and 2-methyldecamethylene.

[0051] 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 the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.

[0052] The unit structure contained in the divalent group including the 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.

[0053] The divalent organic group represented by Y may be a divalent group containing a polysiloxane structure. Examples of divalent groups containing a polysiloxane structure represented by Y include divalent groups containing a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, a C1-C20 alkyl group, or a C6-C18 aryl group. Specific examples of C1-C20 alkyl groups bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, and n-dodecyl group. Among these, the methyl group is preferred. The C6-C18 aryl group bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents when the aryl group contains a substituent 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, phenyl groups are 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 containing the polysiloxane structure represented by Y may be bonded to the NH group in formula (1) via methylene groups, alkylene groups such as ethylene groups, or arylene groups such as phenylene groups.

[0054] The group represented by formula (G) is preferably the group represented by formula (G') below, and the group represented by formula (H) is preferably the group represented by formula (H'), formula (H''), or formula (H''') below, and more preferably the group represented by formula (H') or formula (H'') below from the viewpoint of including a flexible skeleton and having excellent bonding properties. In formulas (G') to (H''') below, * indicates the bonding position with other structures.

[0055]

[0056] In the formula (H'''), R １１ and R １２ Each of these independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom. １１ and R １２ The group is preferably an alkyl group, and more preferably a methyl group.

[0057] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in 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 following: A combination where X is the group represented by formula (E) and Y is the group represented by formula (H) A combination where X is the group represented by formula (F) and Y is the group represented by formula (H) A combination where X is the group represented by formula (E) and Y is the groups represented by formulas (G) and (H) A combination where X is the group represented by formulas (A) and (E) and Y is the group represented by formula (H) A combination where X is the group represented by formula (A) and Y is the group represented by formula (H)

[0058] R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably one of the groups represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). In this case, R ６ and R ７At least one of the groups is represented by general formula (2). When the monovalent organic group contains an organic group with an unsaturated double bond, preferably the group represented by general formula (2) below, the transmittance of i-line is high, and good cured products tend to be formed even when curing at low temperatures of 400°C or below. Furthermore, when the monovalent organic group contains an organic group with an unsaturated double bond, preferably the group represented by formula (2) below, at least a part of the unsaturated double bond portion is eliminated by imidization. In general formula (2) below, * represents the bond position with other structures.

[0059] Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups, with ethyl, isobutyl, and t-butyl groups being preferred.

[0060]

[0061] In general formula (2), R １３ ~R １５ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R Ｘ This represents a divalent linking group.

[0062] R in general formula (2) １３ ~R １５ The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. １３ ~R １５ Specific examples of the aliphatic hydrocarbon group represented by include methyl group, ethyl group, n-propyl group, isopropyl group, etc., with methyl group being preferred.

[0063] R in general formula (2) １３ ~R １５ As for combinations, R １３ and R １４ is a hydrogen atom, R １５ A combination of hydrogen atoms or methyl groups is preferred.

[0064] R in general formula (2) Ｘis a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups. R Ｘ preferably has 1 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 or 3 carbon atoms.

[0065] In general formula (1), at least one of R ６ and R ７ is preferably a group represented by the above general formula (2), and more preferably both R ６ and R ７ are groups represented by the above general formula (2).

[0066] When the polyimide precursor contains a compound containing a structural unit represented by the above general formula (1), the total of R ６ and R ７ in all the structural units contained in the compound, the proportion of R １３ and R １４ which are groups represented by the general formula (2) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. The upper limit is not particularly limited and may be 100 mol%. Note that the above proportion may also be 0 mol% or more and less than 60 mol%.

[0067] The group represented by the above general formula (2) is preferably a group represented by the following general formula (2'). In the following general formula (2'), * represents the bonding position with other structures.

[0068]

[0069] In general formula (2'), R １３ ' to R １５ ' each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and n4 represents an integer of 1 to 10.

[0070] In general formula (2'), n4 is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0071] The content of the structural unit represented by general formula (1) in a compound containing 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%.

[0072] The 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 polyimide precursor may also be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0073] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. 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, 1,1,4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl Examples include 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, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornanetetracarboxylic acid dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propanetetracarboxylic acid dianhydride.Among these, it is preferable that at least one is selected from the group consisting of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, more preferably at least one is selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, and even more preferably that 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride is included from the viewpoint of bonding at lower temperatures. Tetracarboxylic dianhydrides may be used individually or in combination of two or more.

[0074] 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, 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. Preferred diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. Among these, at least one selected from the group consisting of 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, m-phenylenediamine, and 1,3-bis(3-aminophenoxy)benzene is more preferred, and at least one selected from the group consisting of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane is even more preferred from the viewpoint of containing a flexible skeleton and having excellent adhesive properties. The diamine compound may be used alone or in combination of two or more types.

[0075] It includes a structural unit represented by general formula (1), and R in general formula (1). ６ and R ７ Compounds in which at least one of the groups is a monovalent organic group 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)) and R １６ A compound represented by -OH is reacted in an organic solvent to form a diester derivative, and then the diester derivative and H ２ N-Y-NH ２ (b) A condensation reaction is carried out with a diamine compound represented by . ２ N-Y-NH ２ A diamine compound represented by is reacted with an organic solvent to obtain a polyamic acid solution, R １６ A compound represented by -OH is added to a polyamic acid solution and reacted in an organic solvent to introduce an ester group.

[0076] R in general formula (1) ６ and R ７Since at least one of them contains a polymerizable unsaturated bond, R is used as at least one R-OH containing a polymerizable unsaturated bond.

[0077] Here, H ２ N-Y-NH ２ In the diamine compound represented by , Y is the same as Y in general formula (1), and the specific examples and preferred examples are also the same. Also, R １６ R in compounds represented by -OH １６ R represents a monovalent organic group, and specific and preferred examples are shown in general formula (1) R ６ and R ７ The same applies as in the case of tetracarboxylic dianhydride represented by general formula (8), H ２ N-Y-NH ２ Diamine compounds represented by and R １６ Each compound represented by -OH may be used individually or in combination of two or more.

[0078] Examples of the aforementioned organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropanamide, among which 3-methoxy-N,N-dimethylpropanamide is preferred. １６ A polyimide precursor may be synthesized by reacting a dehydrating condensation agent with a compound represented by -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).

[0079] The aforementioned compound contained in the polyimide precursor is a tetracarboxylic dianhydride represented by the following general formula (8) and R １６ After reacting with a compound represented by -OH to form a diester derivative, a chlorinating agent such as thionyl chloride is reacted to convert it to an acid chloride, and then H ２ N-Y-NH ２ It can be obtained by reacting a diamine compound represented by the formula with an acid chloride. The aforementioned compound contained in the polyimide precursor is a tetracarboxylic dianhydride represented by the following general formula (8) with R１６ After reacting with a compound represented by -OH to form a diester derivative, H is added in the presence of a carbodiimide compound. ２ N-Y-NH ２ It can be obtained by reacting a diamine compound represented by [formula] with a diester derivative.

[0080] The aforementioned compound contained in the polyimide precursor is a tetracarboxylic dianhydride represented by the following general formula (8) and H ２ N-Y-NH ２ After reacting with a diamine compound represented by to obtain a polyamic acid, the polyamic acid is isoimide is formed in the presence of a dehydrating condensation agent such as trifluoroacetic anhydride, and then R １６ It can be obtained by reacting a compound represented by -OH. Alternatively, a portion of the tetracarboxylic dianhydride may be pre-treated with R １６ By reacting with a compound represented by -OH, a partially esterified tetracarboxylic dianhydride and H ２ N-Y-NH ２ It may also be reacted with a diamine compound represented by .

[0081]

[0082] In general formula (8), X is the same as X in formula (1) above, and the specific examples and preferred examples are also the same.

[0083] R used in the synthesis of the aforementioned compounds contained in polyimide precursors １６ Compounds represented by -OH include the group R represented by general formula (2). ｘ This could be a compound in which a hydroxyl group is bonded, or a compound in which a hydroxyl group is bonded to the terminal methylene group of a group represented by general formula (2'), etc. １６Specific examples of compounds represented by -OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 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.

[0084] (Polybenzoxazole) Polybenzoxazole refers to a polymer that contains a benzoxazole structure as a structural unit. Polybenzoxazole preferably includes compounds having a structural unit represented by the following general formula (Z-1).

[0085]

[0086] In the general formula (Z-1), U represents a single bond or a divalent linking group, W represents a divalent linking group, and * represents the position of bond with other structures. Polybenzoxazole may have multiple structural units represented by the above general formula (Z-1), and U and W in the multiple structural units may be the same or different.

[0087] Polybenzoxazoles can be obtained, for example, by a cyclization reaction (condensation polymerization reaction) between a dicarboxylic acid and a diaminodihydroxy compound. The dicarboxylic acid is not particularly limited and includes, for example, terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), phthalic acid (benzene-1,2-dicarboxylic acid), 4,4'-dicarboxybiphenylmethane, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxybiphenyl, and 2,2-(4,4'-dicarboxybiphenyl)propane. The diaminodihydroxy compounds are not particularly limited, and examples include 1,3-diamino-4,6-dihydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, and 2,2-(3,3'-diamino-4,4'-dihydroxydiphenyl)propane.

[0088] (Polybenzoxazole precursor) The polybenzoxazole precursor is a polyhydroxyamide, and preferably includes a compound having a structural unit represented by the following general formula (Z-2).

[0089]

[0090] In general formula (Z-2), U represents a single bond or a divalent linking group, W represents a divalent linking group, and X represents a hydrogen atom or a monovalent organic group. A polybenzoxazole precursor may have multiple structural units represented by the above general formula (Z-2), and U, W, and X in the multiple structural units may be the same or different. X is R in general formula (1). ６ and R ７ Similar to the preferred range, it is preferable that at least one of X in general formula (Z-2) has a polymerizable unsaturated bond.

[0091] Polybenzoxazole precursors can be obtained, for example, by a condensation polymerization reaction between a dicarboxylic acid and a diaminodihydroxy compound. Examples of dicarboxylic acids and diaminodihydroxy compounds include those exemplified in the section on polybenzoxazoles above.

[0092] There are no particular restrictions on the molecular weight of the resin; for example, it is preferably 10,000 to 200,000 in weight-average molecular weight, more preferably 10,000 to 100,000, and even more preferably 10,000 to 50,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography and can be determined by conversion using a standard polystyrene calibration curve.

[0093] The photosensitive resin composition of this disclosure may further contain a dicarboxylic acid, and the polyimide precursor or polybenzoxazole precursor that may be included in the photosensitive resin composition may have a structure in which some of the amino groups in the polyimide precursor react with the carboxyl groups in the dicarboxylic acid. For example, when synthesizing the 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)acrylic group, and may be, for example, a dicarboxylic acid represented by the following formula. In this case, when synthesizing the polyimide precursor, a methacrylic group derived from the dicarboxylic acid can be introduced into the polyimide precursor by reacting some of the amino groups of the diamine compound with the carboxyl groups of the dicarboxylic acid.

[0094]

[0095] The photosensitive resin composition of this disclosure may contain polyimide in addition to the polyimide precursor, and may contain polybenzoxazole in addition to the polybenzoxazole precursor. By combining the polyimide precursor and polyimide, or by combining the polybenzoxazole precursor and polybenzoxazole, it is possible to suppress the generation of volatile substances due to dehydration cyclization during ring formation. This tends to suppress the generation of voids.

[0096] The photosensitive resin composition of this disclosure may contain other resins other than polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor. Examples of other resins, from the viewpoint of heat resistance, include novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. The other resins may be used individually or in combination of two or more.

[0097] In the photosensitive resin composition of this disclosure, the resin content relative to the total amount of solids is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, and even more preferably 70% to 90% by mass. The solids refer to the residue after drying the photosensitive resin composition at 200°C to 400°C.

[0098] The photosensitive resin composition of this disclosure may not contain other resins. In the photosensitive resin composition of this disclosure, the content of other resins relative to the total amount of solids may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more. In the photosensitive resin composition of this disclosure, the content of other resins relative to the total amount of solids may be 50% by mass or less, 30% by mass or less, 10% by mass or less, or 5% by mass or less.

[0099] <Photosensitive Agent> The photosensitive resin composition of this disclosure contains a photosensitive agent. The photosensitive agent may be used alone or in combination of two or more types. Examples of photosensitive agents include substances that absorb light and trigger a chemical reaction, such as photopolymerization initiators and photoacid generators. The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals upon irradiation with active light. Examples of active light include ultraviolet light such as i-rays, visible light, and radiation. In this disclosure, i-rays refer to the spectral lines of mercury having a wavelength of 365 nm. Examples of light sources that can irradiate with i-rays include ultra-high pressure mercury lamps. The photoacid generator is not particularly limited as long as it is a compound that can generate acid upon irradiation with the above-mentioned active light.

[0100] Examples of photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, and acyldialkoxymethane compounds. Among these, oxime compounds are preferred.

[0101] The photoacid generator may be an ionic photoacid generator or a nonionic photoacid generator. Examples of ionic photoacid generators include onium salt compounds and quaternary ammonium salt compounds. Examples of nonionic photoacid generators include diazomethane compounds and sulfonate compounds.

[0102] Examples of photopolymerization initiators include compounds represented by the following formula (20A), compounds represented by formula (20B) described later, compounds represented by formula (30A) described later, and compounds represented by formula (30B) described later.

[0103]

[0104] In formula (20A), R ２１ R is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer from 0 to 5. ２２ R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. ２３ and R ２４ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer of 2 or more, R ２１ These may be the same or different.

[0105] R ２１ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. R ２２ R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. ２３ and R ２４ Preferably, each is independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0106] Examples of compounds represented by formula (20A) include the compound represented by formula (20A-1) below, which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

[0107]

[0108]

[0109] In formula (20B), R ２５ -OH, -COOH, -OCH ２ OH, -O(CH ２ ) ２ OH, -COOCH ２ OH or -COO (CH ２ ) ２ OH and R ２６ and R ２７ Each of these is independently a hydrogen atom, a C1-C12 alkyl group, a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group. b1 is an integer from 0 to 5. If b1 is an integer of 2 or more, R ２５ These may be the same or different. ２５ Preferably, -O(CH ２ ) ２ It is OH. b1 is preferably 0 or 1. R ２６ R is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or a hexyl group. ２７ The group is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.

[0110] Examples of compounds represented by formula (20B) include the compound represented by formula (20B-1) below, which is available as "IRGACURE OXE 01" from BASF Japan Ltd. Another example is the compound represented by formula (20B-2) below, which is available as "NCI-930" from ADEKA Corporation.

[0111]

[0112]

[0113] In formula (30A), R ３１ R is an alkyl group having 1 to 12 carbon atoms. ３２ and R ３３ Each of these is independently a hydrogen atom, a C1-C12 (preferably C1-C4) alkyl group, a C1-C12 (preferably C1-C4) alkoxy group, a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group, and c1 is an integer from 0 to 5. When c1 is an integer of 2 or more, R ３１ These may be the same or different. c1 is preferably 0. R ３２ R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. ３３ The group is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group or an ethoxy group. An example of a compound represented by formula (30A) is the compound represented by the following formula (30A-1) (1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime). This compound is available from Lambson as "G-1820 (PDO)".

[0114]

[0115]

[0116] In formula (30B), R ３４ and R ３５Each of these is an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each independent integers from 0 to 5, s and t are each independent integers from 0 to 3, and the sum of s and t is 3. When d is an integer of 2 or more, R ３４ These may be the same or different. If e is an integer greater than or equal to 2, R ３５ These may be the same or different. If s is an integer greater than or equal to 2, the bases in the parentheses may be the same or different. If t is an integer greater than or equal to 2, the bases in the parentheses may be the same or different. d is preferably 0. R ３５ Preferably, each is an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. e is preferably an integer from 2 to 4, and more preferably 3. The combination of s and t (s, t) is preferably (1, 2) or (2, 1). Examples of compounds represented by formula (30B) include the compound represented by formula (30B-1) below, which is available as "IRGACURE TPO" manufactured by BASF Japan Ltd. Also, examples of compounds represented by formula (30B-2) below include the compound available as "IRGACURE 819" manufactured by BASF Japan Ltd.

[0117]

[0118] The amount of photosensitive agent 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 6 parts by mass, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0119] (Photosensitive agent having photobleaching properties) The photosensitive agent contained in the photosensitive resin composition of this disclosure includes a photosensitive agent having photobleaching properties. By using the photosensitive agent having photobleaching properties, a cured product of the photosensitive resin composition with excellent elongation properties can be obtained. One type of photosensitive agent may be used alone, or two or more types may be used in combination. The photosensitive agent may be, for example, a photopolymerization initiator, a photoacid generator, etc., and is preferably a photopolymerization initiator.

[0120] Whether a photosensitive agent has photobleaching properties can be determined, for example, by the following method. First, the percentage decrease in i-line absorbance obtained by measurement method B below is measured using any resin composition, and it is confirmed that the percentage decrease is 0% when a predetermined resin composition X is used. Next, a resin composition Y is prepared by adding the photosensitive agent to be judged to the formulation of resin composition X so that the photosensitive agent content is 1 part by mass per 100 parts by mass of resin component, and the percentage decrease in i-line absorbance obtained by measurement method B below is measured using resin composition Y. If the percentage decrease is greater than 0% (>0%), it can be determined that the photosensitive agent to be judged has photobleaching properties. (Measurement method B) A film of a photosensitive resin composition is applied to a glass substrate so that the average thickness of the film after pre-baking is 13 μm, and after pre-baking by drying at 90°C for 4 minutes, an irradiation dose of 800 mJ / cm is applied. ２ Exposure is performed by irradiating with i-rays under the following conditions. The absorbance B1 of the i-rays transmitted through the film before irradiation and the absorbance B2 of the i-rays transmitted through the film after irradiation are measured, and the percentage decrease in i-ray absorbance is calculated using the following formula (B). (Percentage decrease in i-ray absorbance (%)) = {1 - (absorbance B2) / (absorbance B1)} × 100 ... (B) The above percentage decrease should be greater than 0%, preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more. There is no particular upper limit to the percentage decrease, and it may be 100% or less, 70% or less, or 50% or less.

[0121] The photosensitive agent having photobleaching properties is preferably a photopolymerization initiator. Examples of photopolymerization initiators include oxime ester-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are preferred from the viewpoint of being able to further improve elongation.

[0122] From the viewpoint of improving elongation, oxime ester-based photopolymerization initiators are preferably compounds containing a diphenyl sulfide skeleton.

[0123] From the viewpoint of easily improving the elongation properties, the compound containing the diphenyl sulfide skeleton is preferably a compound represented by the following formula (10).

[0124]

[0125] From the viewpoint of easily improving the spreadability, the content of the photosensitive agent having photobleaching properties is preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, even more preferably 90 to 100 parts by mass, particularly preferably 95 to 100 parts by mass, and may also be 100 parts by mass, per 100 parts by mass of the photosensitive agent.

[0126] From the viewpoint of further improving the elongation properties, the amount of photosensitive agent 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 6 parts by mass, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0127] <Solvents> The photosensitive resin composition of this disclosure contains solvent A and solvent B as solvents. Solvents A and B may be used independently, individually or in combination of two or more.

[0128] The combination of solvent A and solvent B is not particularly limited, as long as the vapor pressure of solvent B at 25°C is higher than that of solvent A.

[0129] The vapor pressure of solvent A at 25°C is preferably less than 1.0 mmHg, and the vapor pressure of solvent B at 25°C is more preferably 1.0 mmHg or more.

[0130] The ratio of the vapor pressure of solvent B at 25°C to the vapor pressure of solvent A at 25°C (hereinafter also referred to as the "vapor pressure ratio") is not particularly limited as long as it is greater than 1.

[0131] In this disclosure, the vapor pressure at 25°C can be estimated from the Antoine equation using, for example, the Hansen Solubility Parameter in Practice (HSPiP) software.

[0132] The ratio of vapor pressures may be 2 or more, 3 or more, 5 or more, 10 or more, or 50 or more. There is no particular upper limit to the ratio of vapor pressures; it may be 5000 or less, 3000 or less, or 1000 or less.

[0133] The vapor pressure of solvent A at 25°C may be, for example, 0.010 mmHg to 0.9 mmHg, 0.020 mmHg to 0.8 mmHg, or 0.030 mmHg to 0.7 mmHg. If solvent A is a combination of two or more solvents, the vapor pressure of solvent A at 25°C represents the sum of the products of the saturated vapor pressure of each solvent and the mole fraction of each solvent.

[0134] Solvent A may be at least one selected from the group consisting of, for example, amide compounds, lactone compounds, urea compounds, and sulfoxide compounds.

[0135] Examples of solvent A include N-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone (NEP), 1-butyl-2-pyrrolidone (NBP), 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, γ-valerolactone, N,N-dimethylpropionamide (DMPr), 1,3-dimethyl-2-imidazolidinone (DMI), propylene carbonate, and ethylene carbonate.

[0136] The vapor pressure of solvent B at 25°C may be, for example, 1.0 mmHg to 200 mmHg, 1.0 mmHg to 100 mmHg, or 1.1 mmHg to 90 mmHg. If solvent B is a combination of two or more solvents, the vapor pressure of solvent B at 25°C represents the sum of the products of the saturated vapor pressure of each solvent and the mole fraction of each solvent.

[0137] Solvent B may be at least one selected from the group consisting of, for example, alcohol compounds, ether compounds, and ester compounds.

[0138] Solvent B can be any solvent with a higher vapor pressure at 25°C than solvent A. Specifically, examples include methanol, ethanol, 2-propanol, tetrahydrofuran, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-acetoxy-1-methoxypropane, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, dimethyl sulfoxide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc.

[0139] The content of solvent A may be 55.0% by mass or less, 53.0% by mass or less, or 50.0% by mass or less, based on the total amount of the photosensitive resin composition. The content of solvent A may be 35.0% by mass or more, 38.0% by mass or more, or 40.0% by mass or more, based on the total amount of the photosensitive resin composition.

[0140] The content of solvent B may be 1.00% by mass or more, 1.03% by mass or more, or 1.10% by mass or more, based on the total amount of the photosensitive resin composition. The content of solvent B may be 30.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, based on the total amount of the photosensitive resin composition.

[0141] The content of solvent A may be 40.0% to 99.0% by mass, 50.0% to 98.5% by mass, or 80.0% to 98.0% by mass, relative to the total of solvent A and solvent B.

[0142] When the solubility of the photosensitive agent in a solvent is improved, precipitation of the photosensitive agent is more likely to occur as the solvent evaporates. From the viewpoint of suppressing a decrease in the elongation of the cured product of the photosensitive resin composition, it is preferable to reduce the precipitation of the photosensitive agent. From the above viewpoint, the amount of photosensitive agent dissolved in solvent A is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, per 100 parts by mass of solvent. The upper limit of this content may be 100 parts by mass or less, 80 parts by mass or less, 60 parts by mass or less, or 100 parts by mass or less. This amount may also be adopted as the amount of photosensitive agent dissolved in N,N-dimethylpropionamide (DMPr), which can be used as an example of solvent A. For example, the amount of the compound represented by formula (10) above that dissolves in DMPr is 20 parts by mass or more per 100 parts by mass of solvent.

[0143] <Crosslinking Agent> The photosensitive resin composition may contain a crosslinking agent that can be crosslinked or polymerized by heating. In the process of coating, exposing, developing, and then heat-treating the photosensitive resin composition, the crosslinking agent compound reacts with the resin (for example, a polyimide precursor having polymerizable unsaturated bonds or a polybenzoxazole precursor having polymerizable unsaturated bonds) to form crosslinks, or the crosslinking agent compound itself polymerizes. As a result, even at relatively low crosslinking temperatures, for example, below 200°C, the strength of the crosslinked film can be increased, improving mechanical properties, chemical resistance, flux resistance, etc. The crosslinking agent may be used alone or in combination of two or more types.

[0144] Examples of crosslinking agents include compounds having two or more polymerizable unsaturated bonded groups (hereinafter also referred to as functional groups). From the viewpoint of polymerization reactivity, (meth)acryloyl groups and vinyl groups are preferred as functional groups, with (meth)acryloyl groups being more preferred. Crosslinking agents may be subjected to alkoxylation treatments such as ethoxylation or propoxylation.

[0145] Examples of bifunctional crosslinking agents include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, tricyclodecanedimethanol diacrylate, and tricyclodecanedimethanol dimethacrylate.

[0146] Examples of trifunctional crosslinking agents include trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and tris-(2-methacryloxyethyl) isocyanurate.

[0147] Examples of crosslinking agents with four or more functions include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and tetrakisacrylate methanetetrayltetrakis (methyleneoxyethylene).

[0148] If the photosensitive resin composition of the present disclosure contains a crosslinking agent, the amount of the crosslinking agent is preferably 1 to 50 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0149] <Thermal Polymerization Initiator> The photosensitive resin composition of this disclosure may further contain a thermal polymerization initiator from the viewpoint of promoting the polymerization reaction. Preferred thermal polymerization initiators are compounds that do not decompose when heated (dried) to remove the solvent during film formation, but decompose when heated during curing to generate radicals, thereby promoting the polymerization reaction between crosslinking agents or between the resin and the crosslinking agent. Preferred thermal polymerization initiators are compounds with a decomposition point of 110°C to 200°C, and from the viewpoint of promoting the polymerization reaction at a lower temperature, compounds with a decomposition point of 110°C to 175°C are more preferred.

[0150] 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, and p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, and di- Examples include diacyl peroxides such as uroyl peroxide and dibenzoyl 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, and bis(1-phenyl-1-methylethyl)peroxide. Commercially available products include those with the trade names "Parkmil D," "Parkmil P," and "Parkmil H" (all manufactured by NOF Corporation).

[0151] If the photosensitive resin composition of this disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass, with respect to 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin, and even more preferably 0.3 to 10 parts by mass, with respect to suppressing the decrease in solubility due to decomposition during drying.

[0152] [Imidification accelerator] If the resin composition of this disclosure contains a polyimide precursor, a nitrogen-containing compound may be included as an imidization accelerator from the viewpoint of promoting the imidation reaction.

[0153] Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc. Among these, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. Nitrogen-containing compounds may be used individually or in combination of two or more.

[0154] If the photosensitive resin composition of this disclosure contains an imidation accelerator, the content of the imidation accelerator 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, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0155] <Sensitizer> The photosensitive resin composition of this disclosure may contain a sensitizer. By containing a sensitizer in the photosensitive resin composition, it is possible to achieve both maintenance of residual film ratio and good resolution over a wide range of exposure levels. One type of sensitizer may be used alone, or two or more types may be used in combination.

[0156] Sensitizers include ethyl methyl ketone, Michlar's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, and benzyl Examples include dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrene quinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrene quinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.

[0157] When the photosensitive resin composition of this disclosure contains a sensitizer, the amount of sensitizer is not particularly limited, but is preferably 0.1 to 1.0 parts by mass, and more preferably 0.2 to 0.8 parts by mass, per 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0158] <Stabilizer> The photosensitive resin composition of this disclosure may contain a stabilizer. By containing a stabilizer, the photosensitive resin composition can have good storage stability.

[0159] Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenol compounds.

[0160] The stabilizer may be used alone or in combination of two or more types. Combining two or more stabilizers tends to make it easier to adjust the photosensitive properties due to differences in reactivity. The hindered phenol compound may have both the function of a stabilizer and the function of an antioxidant (described later), or it may have only one of the functions.

[0161] Examples of stabilizers include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), and triethylene glycol-bis [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (Nol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy Roxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxyl Examples include C-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, N,N'-hexane-1,6-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide.

[0162] If the photosensitive resin composition of the present disclosure contains a stabilizer, the amount of the stabilizer is preferably 0.05 to 1.0 parts by mass, and more preferably 0.1 to 0.8 parts by mass, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0163] <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.

[0164] Specific examples of antioxidants include the compounds exemplified above as hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl),propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants may be used individually or in combination of two or more.

[0165] If the photosensitive resin composition of the present 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, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0166] <Coupling Agent> The photosensitive resin composition of this disclosure may contain a coupling agent. Including a coupling agent can further improve the adhesion between the resulting cured product and the substrate.

[0167] The coupling agent is not particularly limited and includes 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, benzophenone-3,3'-bis(N-[3- Examples include silane coupling agents such as riethoxysilyl)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 agents may be used individually or in combination of two or more.

[0168] If the photosensitive resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0169] <Rust Inhibitor> The photosensitive resin composition of this disclosure may contain a rust inhibitor. By containing a rust inhibitor in the photosensitive resin composition, corrosion and discoloration of copper and copper alloys can be suppressed. Examples of rust inhibitors include azole compounds and purine derivatives. The rust inhibitor may be used alone or in combination of two or more types.

[0170] 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-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0171] 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.

[0172] If 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, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0173] <Ultraviolet Absorbers> The photosensitive resin composition of this disclosure may contain ultraviolet absorbers. When the photosensitive resin composition contains ultraviolet absorbers, crosslinking of unexposed areas due to diffuse reflection during exposure tends to be suppressed. Examples of ultraviolet absorbers include benzotriazole compounds, salicylate ester compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenylcyanoacrylate compounds, benzothiazole compounds, azobenzene compounds, polyphenol compounds, nickel complex salt compounds, etc. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

[0174] Examples of benzotriazole compounds include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-( Examples include 2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazole-2-yl)-p-cresol.

[0175] Examples of salicylic acid ester compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0176] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0177] Examples of diphenyl acrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.

[0178] Examples of diphenylcyanoacrylate compounds include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).

[0179] Examples of azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0180] Examples of polyphenol compounds include pyrogallol, phloroglysine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagine, quercetagene, goshipetin, pelargonidine, cyanidin, aurantinidin, luteolinidin, peonidin, rosinidine, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.

[0181] Examples of polyphenol compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).

[0182] Among the above, it is preferable to use at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, azobenzene compounds, and polyphenol compounds as the material absorbent.

[0183] Furthermore, from the viewpoint of resolution, it is more preferable to use at least one selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-p-cresol), 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione as the ultraviolet absorber.

[0184] If the photosensitive resin composition of this disclosure contains an ultraviolet absorber, the amount of ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin, from the viewpoint of resolution. Furthermore, from the viewpoint of suppressing insufficient photocuring inside the coating film, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0185] <Surfactants and Leveling Agents> The photosensitive resin compositions of this disclosure may contain at least one of a surfactant and a leveling agent. By containing at least one of a surfactant and a leveling agent, the photosensitive resin composition can improve coatability (e.g., suppression of striations (unevenness in film thickness)) and developability.

[0186] Examples of surfactants or leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include the trade names "Megafac® F171", "F173", and "R-08" (all manufactured by DIC Corporation), "Florard FC430" and "FC431" (both manufactured by Sumitomo 3M Limited), and "Organosiloxane Polymer KP341", "KBM303", and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0187] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0188] If the photosensitive resin composition of the present 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, based on 100 parts by mass of the total of the cyclized resin and the precursor of the cyclized resin.

[0189] <Other Components> The photosensitive resin composition of this disclosure may further contain other components and unavoidable impurities. The total amount of the cyclized resin and its precursor, photosensitive agent, and solvent in the photosensitive resin composition of this disclosure may be 80% by mass or more, 90% by mass or more, or 95% by mass or more, based on the total amount of the photosensitive resin composition. Furthermore, the total amount of the cyclized resin and its precursor, photosensitive agent, solvent, crosslinking agent, stabilizer, sensitizer, ultraviolet absorber, rust inhibitor, antioxidant, and coupling agent in the photosensitive resin composition of this disclosure may be 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or 99% by mass or more, based on the total amount of the photosensitive resin composition.

[0190] <Characteristics of the Photosensitive Resin Composition> <<Preparation of Cured Film>> The photosensitive resin composition of this disclosure is applied to a substrate and dried at 90°C for 4 minutes (pre-baking treatment) to form a resin film with a dry thickness of 20 μm. The obtained resin film is immersed in a solvent capable of dissolving the above resin film (hereinafter also referred to as "developer"), and the development time is set to twice the time it takes for the resin film to completely dissolve. For the obtained resin film, a photomask having a line pattern with a width of 5 mm and a length of 150 mm is used, and the exposure amount is 200 mJ / cm². ２ A post-exposure resin film with a line pattern is formed on the substrate by exposure under the specified conditions. The post-exposure resin film is paddle-developed with a developer for the above-mentioned development time to obtain a predetermined patterned resin film. Next, it is heated at 375°C for 1 hour under a nitrogen atmosphere to obtain a patterned cured product.

[0191] <<Elongation at Break>> The elongation at break of the cured product of the photosensitive resin composition of this disclosure is preferably 60% or more. The above elongation at break can be measured by the following method. The silicon wafer with the cured film obtained in the above-mentioned <<Preparation of Cured Film>> is immersed in a 4.9% hydrofluoric acid aqueous solution for 30 minutes, and the cured film is peeled off from the silicon wafer to obtain a strip-shaped cured film with a width of 5 mm and a length of 150 mm. The film is tested using a tensile testing apparatus at a speed of 5 mm / min at 25°C, and the elongation (%) is calculated from the S-S curve.

[0192] <<Reduction Rate of i-Line Absorbance>> The reduction rate of i-line absorbance obtained by the measurement method A below is preferably 1% or more, more preferably 5% or more, even more preferably 10% or more, particularly preferably 15% or more, and most preferably 20% or more, from the viewpoint of making it easier to improve the elongation. The upper limit of the reduction rate is not particularly limited and may be 100% or less, 70% or less, or 50% or less. (Measurement Method A) A film of the photosensitive resin composition is applied to a glass substrate so that the average thickness of the film after pre-baking is 13 μm, and after pre-baking, which is performed by drying at 90°C for 4 minutes, the irradiation dose is 800 mJ / cm ２ Exposure is performed by irradiating with i-rays under the specified conditions. The absorbance A1 of the i-rays transmitted through the film before irradiation and the absorbance A2 of the i-rays transmitted through the film after irradiation are measured, and the percentage decrease in i-ray absorbance is calculated using the following formula (A): (Percentage decrease in i-ray absorbance (%)) = {1 - (absorbance A2) / (absorbance A1)} × 100 ... (A)

[0193] <Method for producing the photosensitive resin composition> The method for producing the above-described photosensitive resin composition is not particularly limited and can be obtained by mixing the components contained in the photosensitive resin composition. The method for mixing each component is not particularly limited and can be carried out by known methods.

[0194] [Cured product] The cured product of the present disclosure is a cured product of the photosensitive resin composition of the present disclosure, and can be obtained by curing the photosensitive resin composition of the present disclosure. The cured product of the present disclosure may be used as a patterned cured product or as a cured product without a pattern. The average thickness of the cured product is preferably 5 μm to 30 μm.

[0195] The elongation at break of the cured product is preferably 50% or more, and more preferably 60% or more. There is no particular upper limit on the elongation at break of the cured product.

[0196] [Method for manufacturing a cured product, and electronic components] The method for manufacturing a patterned cured product according to the present disclosure includes the steps of: applying the resin composition according to the present disclosure onto a substrate and drying (pre-baking) it to form a resin film; pattern exposing the resin film to light to obtain a post-exposure resin film; developing the post-exposure resin film using a developer to obtain a patterned resin film; and heat-treating the patterned resin film. A patterned cured product can be obtained by this process.

[0197] A method for producing a cured product without a pattern comprises, for example, the steps of forming a resin film according to the present disclosure and heat treatment. It may further include an exposure step.

[0198] The substrates include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), and TiO2. ２ Substrate, SiO ２ Examples include metal oxide insulating substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0199] There are no particular limitations on the method of applying the resin composition of this disclosure (e.g., coating method), and it can be done using a spinner or the like.

[0200] Drying can be carried out using a hot plate, oven, or the like. 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 may be carried out two or more times. This makes it possible to obtain a resin film in which the photosensitive resin composition of this disclosure is formed into a film.

[0201] The average thickness of the resin film is preferably 1 μm to 100 μm, more preferably 2 μm to 75 μm, and even more preferably 3 μm to 50 μm.

[0202] Pattern exposure involves exposing a predetermined pattern, for example, through a photomask. The active light used for irradiation can be ultraviolet light such as i-rays, visible light, or radiation, but i-rays are preferred. Exposure devices such as parallel exposure machines, aligners, projection exposure machines, steppers, and scanner exposure machines can be used.

[0203] 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 the developer, a good solvent of the resin film after exposure can be used alone, or a good solvent and a poor solvent can be used in appropriate mixtures. 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.

[0204] 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.

[0205] The development time can be, for example, twice the time it takes for the resin film to be immersed after exposure and completely dissolved. The development time varies depending on the resin 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.

[0206] After development, the film may be washed with a rinsing solution. The rinsing solution may be distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., either individually or in appropriate mixtures, or in a stepwise combination.

[0207] A patterned resin film can be heat-treated to obtain a patterned cured product. For example, a polyimide precursor or a polybenzoxazole precursor undergoes a dehydration and ring-closing reaction during the heat treatment process to become the corresponding polyimide or polybenzoxazole.

[0208] The temperature of the heat treatment is not particularly limited and may be, for example, 160°C to 400°C or 350°C to 400°C.

[0209] 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 atmosphere may be air or an inert atmosphere such as nitrogen, but from the viewpoint of preventing oxidation of the pattern resin film, a nitrogen atmosphere is preferred.

[0210] 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.

[0211] The cured product of this disclosure can be used as an interlayer insulating film, an insulating film for a redistribution layer, 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, a stress buffer film, etc. Using one or more selected from the group consisting of the above-mentioned passivation film, buffer coat film, interlayer insulating film, insulating film for a redistribution layer, cover coat layer, and surface protective film, highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, stacked devices (multi-die fan-out wafer-level packages, etc.), and other electronic components can be manufactured. The electronic components of this disclosure may include the aforementioned cured product of this disclosure, or they may include a patterned cured product.

[0212] An example of the manufacturing process for a semiconductor device, which is an electronic component of the present disclosure, will be described with reference to the drawings. Figure 1 is a manufacturing process diagram for a multilayer wiring structure semiconductor device, which is an electronic component according to one embodiment of the present disclosure. In Figure 1, a semiconductor substrate 1, such as a Si substrate having circuit elements, is covered with a protective film 2, such as a silicon oxide film, except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0213] Next, a resin layer 5 such as a chlorinated rubber-based or phenol novolac-based resin (preferably a photosensitive resin layer) is formed on the interlayer insulating film 4, and a window 6A is provided so that a predetermined portion of the interlayer insulating film 4 is exposed by known photographic etching techniques.

[0214] The interlayer insulating film 4 with window 6A exposed is selectively etched to create window 6B. Next, the resin layer 5 is removed using an etching solution that corrodes the resin layer 5 without corroding the first conductor layer 3 exposed through window 6B.

[0215] Furthermore, a second conductor layer 7 is formed using a known photoetching technique, and an electrical connection is made with the first conductor layer 3. When forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

[0216] Next, the window 6C is opened by pattern exposure using the photosensitive resin composition of this disclosure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductive layer 7 from external stress, alpha rays, etc., and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film 4 can also be formed using the photosensitive resin composition of this disclosure.

[0217] 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.

[0218] As shown below, unsaturated polyimide precursors 1 and 2, and unsaturated polyimide 1 were prepared as resins.

[0219] [Synthesis of Unsaturated Polyimide Precursors or Unsaturated Polyimides] <Unsaturated Polyimide Precursor 1> 380 g of N-methyl-2-pyrrolidone (NMP) was placed in a 2 L separable flask, and 47.08 g (152 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) was added while stirring to dissolve it. Then, 0.24 g (2.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane) was added and dissolved, and 5.54 g (42.6 mmol) of 2-hydroxyethyl methacrylate (HEMA) was added, followed by stirring at 30°C for 1 hour to obtain the reaction solution. Separately, 27.4 g (129 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was dissolved in 145 g of NMP to prepare a DMAP solution. The DMAP solution was added dropwise while stirring the reaction solution at 35°C, followed by stirring at 30°C for 3 hours. Next, 59.7 g (284 mmol) of TFAA (trifluoroacetic anhydride) was added dropwise to the reaction solution at 30°C, and the mixture was stirred at 45°C for 2 hours. Then, 0.08 g (0.74 mmol) of BQ (benzoquinone) was added to the reaction solution, and 40.4 g (310 mmol) of HEMA was added dropwise. The reaction solution was stirred for 15 hours and then cooled to room temperature. The reaction solution was added to purified water, and the precipitate was collected. The precipitate was washed with purified water and dried under reduced pressure to obtain unsaturated polyimide precursor (unsaturated PI precursor) 1. The weight-average molecular weight (Mw) of unsaturated polyimide precursor 1 was 25,000.

[0220] The weight-average molecular weight of unsaturated polyimide precursor 1 was calculated using gel permeation chromatography (GPC) and a calibration curve using TSKgel standard polystyrene (Tosoh Corporation). The apparatus and conditions are shown below. The measurement sample was prepared by dissolving 2 mg of the sample in 1 mL of eluent (tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (v / v)), and then filtering it through a PTFE membrane filter with a pore size of 1 μm. The method for calculating the weight-average molecular weight of unsaturated polyimide precursor 2 and unsaturated polyimide 1 described below is the same.

[0221] Equipment: Shimadzu Corporation, Prominence Column: Resonaq Corporation, Gelpak GL S300MDT-5 Eluent: THF / DMF = 1 / 1 (v / v), Lithium bromide 0.03 mol / L, Phosphate 0.06 mol / L Flow rate: 1.0 mL / min Measurement wavelength: 270 nm Injection volume: 10 μL

[0222] <Unsaturated Polyimide Precursor 2> 7.07 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA) and 3.88 g of 4,4'-diaminodiphenyl ether (ODA) were dissolved in 30 g of N,N-dimethylpropionamide (DMPr). The resulting solution was stirred at 30°C for 4 hours to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added at 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 unsaturated polyimide precursor 2. The weight-average molecular weight was determined using the GPC method, in the same manner as for unsaturated polyimide precursor 1, on a standard polystyrene basis. The weight-average molecular weight of unsaturated polyimide precursor 2 was 23,000.

[0223] <Unsaturated Polyimide 1> The unsaturated polyimide precursor 2 was dissolved in DMPr and heated at 80°C for 3 hours. １ The ring closure was confirmed by H NMP, and the reaction solution was cooled to room temperature. The reaction solution was added to purified water, and the precipitate was collected. The precipitate was washed with purified water and dried under reduced pressure to obtain unsaturated polyimide 1. The weight-average molecular weight was determined using the GPC method, in the same manner as for unsaturated polyimide precursor 1, on a standard polystyrene basis. The weight-average molecular weight of unsaturated polyimide 1 was 23,000.

[0224] [Preparation of Photosensitive Resin Composition] Each component was mixed according to the formulations shown in Table 1 to obtain a homogeneous solution. The obtained solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 1 μm to obtain a photosensitive resin composition.

[0225] Details of each component listed in Table 1 are as follows. The amounts of each component in Tables 2 to 4 are based on parts by mass. Furthermore, photosensitive agent A is a photosensitive agent with photobleaching properties, and photosensitive agent B is a photosensitive agent without photobleaching properties. <Solvent A> ・Solvent A1: N,N-dimethylpropionamide (DMPr, vapor pressure 0.513 mmHg at 25°C) ・Solvent A2: 3-methoxy-N,N-dimethylpropanamide (vapor pressure 0.031 mmHg at 25°C) <Solvent B> ・Solvent B1: Ethyl lactate (EL, vapor pressure 1.1 mmHg at 25°C) <Photosensitive agent A> ・Photosensitive agent A1: Compound represented by formula (10) above <Photosensitive agent B> ・Photosensitive agent B1: 2-[[(ethoxycarbonyl)oxy]imino]-1-phenylpropan-1-one ・Photosensitive agent B2: Compound represented by formula (20A-1) above <Sensitizer> ・Sensitizer 1: Ethyl methyl ketone <Crosslinking agent> ・Crosslinking agent 1: Triethylene glycol dimethacrylate <Adhesion aid> ・Adhesion aid 1: 3-ureidopropyltriethoxysilane

[0226] The vapor pressures of solvents A and B at 25°C were calculated using the Antoine formula with the Hansen Solubility Parameter in Practice (HSPiP) software.

[0227] Resin composition X was prepared in the same manner as in Example 1, except that it did not contain a photosensitive agent. Using resin composition X, the rate of decrease in i-line absorbance, which can be measured by the measurement method B shown below, was calculated. The rate of decrease in i-line absorbance was 0%. Next, resin composition Y was prepared in the same manner as in Example 1, except that the amount of photosensitive agent per 100 parts by mass of unsaturated polyimide precursor was changed to 1 part by mass. Using resin composition Y, the rate of decrease in i-line absorbance (%), which can be measured by the measurement method B shown below, was calculated. (Measurement method B) A film of the resin composition was applied to a glass substrate so that the average thickness of the film after pre-baking was 13 μm, and after pre-baking, which involved drying at 90°C for 4 minutes, an irradiation dose of 800 mJ / cm was applied. ２Exposure was performed by irradiating with i-rays under the specified conditions. The absorbance B1 of the i-rays transmitted through the film before irradiation and the absorbance B2 of the i-rays transmitted through the film after irradiation were measured, and the percentage decrease in i-ray absorbance was calculated using the following formula (B): (Percentage decrease in i-ray absorbance (%)) = {1 - (absorbance B2) / (absorbance B1)} × 100 ... (B) The percentage decrease in i-ray absorbance was 11.4%. Furthermore, Example 1 was changed to Comparative Example 1 and Comparative Example 2, and the percentage decrease in i-ray absorbance was calculated in the same manner. As a result, the percentage decrease in i-ray absorbance when changed to Comparative Example 1 was 0%, and the percentage decrease in i-ray absorbance when changed to Comparative Example 2 was also 0%. From the above, it was confirmed that the photosensitive agent A1 has photobleaching properties.

[0228] [Characterization] The following evaluations were performed using the obtained photosensitive resin composition. The results are shown in Table 1.

[0229] <Preparation of Cured Film> The obtained photosensitive resin composition was spin-coated onto a 6-inch silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), and dried (pre-baked) at 90°C for 4 minutes to form a resin film with a dry thickness of 20 μm. The spin-coating rotation conditions were fixed at a rotation time of 30 seconds, and the rotation speed was adjusted to achieve a dry thickness of 20 μm. In this evaluation, the range was 1000 rpm to 3000 rpm. The resin film obtained by the same method was immersed in cyclopentanone as a developer, and the development time was set to twice the time it took for the resin film to completely dissolve. For the obtained resin film, a photomask with a line pattern of width = 5 mm and length = 150 mm was used, and the exposure dose was 200 mJ / cm². ２ A post-exposure resin film with a line pattern was formed on a silicon wafer by exposure under the specified conditions. The post-exposure resin film was paddle-developed with cyclopentanone using Act8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a predetermined patterned resin film. Next, the obtained patterned resin film was heated at 375°C for 1 hour under a nitrogen atmosphere using an inert gas oven INL-60N1-S (manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a patterned cured product.

[0230] <Elongation at Break> The silicon wafer with the cured film obtained in the <Preparation of Cured Film> described above was immersed in a 4.9% hydrofluoric acid aqueous solution for 30 minutes, and the cured film was peeled off from the silicon wafer to obtain a strip-shaped cured film with a width of 5 mm, a length of 150 mm, and an average film thickness of 10 μm. The strip-shaped cured film was tested using a Shimadzu AGS-X 100N tensile testing device at 25°C and a speed of 5 mm / min, and the elongation (%) was calculated from the S-S curve. The evaluation criteria for elongation at break are as follows, with A being the best rank. -Evaluation Criteria- A: Average elongation at break is 60% or more. B: Average elongation at break is 50% or more and less than 60%. C: Average elongation at break is 40% or more and less than 50%. D: Average elongation at break is less than 40%.

[0231] <Decrease in i-line absorbance> The decrease in i-line absorbance (%) obtained by the following measurement method A was measured. (Measurement method A) A film of photosensitive resin composition was applied to a glass substrate so that the average thickness of the film after pre-baking was 13 μm, and after pre-baking by drying at 90°C for 4 minutes, an irradiation dose of 800 mJ / cm² was applied. ２ Exposure is performed by irradiating with i-rays under the specified conditions. The absorbance A1 of the i-rays transmitted through the film before irradiation and the absorbance A2 of the i-rays transmitted through the film after irradiation are measured, and the percentage decrease in i-ray absorbance is calculated using the following formula (A): (Percentage decrease in i-ray absorbance (%)) = {1 - (absorbance A2) / (absorbance A1)} × 100 ... (A)

[0232] <Openness in Thin Films> The photosensitive resin composition was prepared under the conditions described in <Preparation of Cured Films> above, but with a dry film thickness of 13 μm, and the photomask was changed to a photomask for forming circular holes with diameters of 1 μm to 100 μm and L / S patterns to obtain a patterned cured film. For the obtained patterned cured products, the circular hole patterns were observed using an optical microscope, and the openness was evaluated using the resolution of the smallest diameter in which an opening was formed in which 55% or more of the substrate surface was exposed relative to the area of ​​the mask dimensions. In addition, the pattern cross-section was cut out using a focused ion beam (FIB), and the cross-sectional shape of the pattern was evaluated. For L / S patterns, the pattern was observed using an optical microscope to evaluate whether or not there was delamination. The evaluation criteria for openness are as follows, with A being the best rank. -Evaluation Criteria- A: All of the following conditions were met: circular hole patterns of 6 μm or less were open, the taper was a forward taper, and no delamination was observed in the L / S pattern. B: All conditions were met: circular hole patterns between 6 μm and 10 μm were open, the taper was a forward taper, and no peeling was observed in the L / S pattern. C: One of the following conditions was met: circular hole patterns smaller than 10 μm were not open, the taper was a reverse taper, and peeling was observed in the L / S pattern.

[0233] <Opening properties in thick films> The photosensitive resin composition was prepared under the conditions described in <Preparation of cured films> above, with a dry film thickness of 40 μm, and the photomask was a photomask for forming circular holes with a diameter of 1 μm to 100 μm and an L / S pattern, with an exposure dose of 500 mJ / cm². ２The pattern was modified to obtain a patterned cured film. For the obtained patterned cured product, the circular hole patterns were observed using an optical microscope, and the aperture performance was evaluated using the resolution of the smallest diameter in which an opening was formed in which 55% or more of the substrate surface was exposed relative to the area of ​​the mask dimensions. In addition, the pattern cross-section was cut out using a focused ion beam (FIB), and the cross-sectional shape of the pattern was evaluated. For L / S patterns, the pattern was observed using an optical microscope to evaluate whether or not there was delamination. The evaluation criteria for aperture performance are as follows, with A being the best rank. -Evaluation Criteria- A: All of the following conditions are met: circular hole patterns of 20 μm or less are open, the taper is a forward taper, and no delamination is observed in the L / S pattern. B: All of the following conditions are met: circular hole patterns of more than 20 μm and less than or equal to 50 μm are open, the taper is a forward taper, and no delamination is observed in the L / S pattern. C: One of the following conditions is met: no circular holes smaller than 50 μm are open, the taper is a reverse taper, or delamination is observed in the L / S pattern.

[0234]

[0235] The photosensitive resin compositions of Examples 1 to 5, which contain a photosensitive agent having photobleaching properties and a solvent containing solvent A and solvent B having a higher vapor pressure at 25°C than solvent A, exhibited a reduction rate of 10% or more in i-line absorbance and excellent elongation at break, opening properties in thin films, and opening properties in thick films.

[0236] The disclosure of the international application PCT / JP2025 / 001952, filed on 22 January 2025, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated herein by reference.

[0237] 1. Semiconductor substrate 2. Protective film 3. First conductive layer 4. Interlayer insulating film 5. Resin layer 6A, 6B, 6C windows 7. Second conductive layer 8. Surface protective film

Claims

1. A photosensitive resin composition comprising a resin which is at least one of a cyclized resin and a precursor of the cyclized resin, a photosensitive agent, and a solvent, wherein the photosensitive agent comprises a photobleaching agent, and the solvent comprises solvent A and solvent B which has a higher vapor pressure at 25°C than solvent A.

2. The photosensitive resin composition according to claim 1, wherein the reduction rate of i-line absorbance obtained by the measurement method A below is 10% or more. (Measurement method A) A film of the photosensitive resin composition is applied to a glass substrate so that the average thickness of the film after pre-baking is 13 μm, and after performing a pre-baking treatment in which the film is dried at 90°C for 4 minutes, an irradiation dose of 800 mJ / cm² is applied. ２ Exposure is performed by irradiating with i-rays under the specified conditions. The absorbance A1 of the i-rays transmitted through the film before irradiation and the absorbance A2 of the i-rays transmitted through the film after irradiation are measured, and the percentage decrease in i-ray absorbance is calculated using the following formula (A): (Percentage decrease in i-ray absorbance (%)) = {1 - (absorbance A2) / (absorbance A1)} × 100 ... (A) 3. The photosensitive resin composition according to claim 1, wherein the photosensitive agent having photobleaching properties is a photopolymerization initiator.

4. The photosensitive resin composition according to claim 3, wherein the photopolymerization initiator is an oxime ester-based photopolymerization initiator.

5. The photosensitive resin composition according to claim 4, wherein the photopolymerization initiator comprises a diphenyl sulfide skeleton.

6. The photosensitive resin composition according to claim 1, wherein the vapor pressure of solvent A at 25°C is less than 1.0 mmHg, and the vapor pressure of solvent B at 25°C is 1.0 mmHg or more.

7. The photosensitive resin composition according to claim 1, wherein the content of solvent A is 40.0% by mass to 99.0% by mass relative to the total of solvent A and solvent B.

8. The photosensitive resin composition according to claim 1, wherein the resin which is at least one of the cyclized resin and the precursor of the cyclized resin is a resin which is at least one of polyimide and a polyimide precursor.

9. The photosensitive resin composition according to claim 8, wherein the polyimide precursor comprises a structural unit represented by the following formula (1). (In 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 or a monovalent organic group, R ６ and R ７ At least one of the structures has a polymerizable unsaturated bond, and * indicates the bond position with other structures.

10. A method for producing a patterned cured product, comprising the steps of: applying a photosensitive resin composition according to any one of claims 1 to 9 onto a substrate and drying it to form a resin film; pattern exposing the resin film to light to obtain a post-exposure resin film; developing the post-exposure resin film using a developer to obtain a patterned resin film; and heat-treating the patterned resin film.

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

12. The cured product according to claim 11, which is a patterned cured product.

13. The cured product according to claim 11, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film.

14. An electronic component comprising the cured product described in claim 11.

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