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

Abstract

This photosensitive resin composition contains: a polyimide precursor having a polymerizable unsaturated bond; and at least one among a nitrogen-containing compound having a solubility parameter of 32 or greater and a hydroxyl group, and a nitrogen-containing compound having a solubility parameter of 39 or greater.

Description

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

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

[0002] Conventionally, surface protective films and interlayer insulating films for semiconductor elements have been made of polyimides, polybenzoxazoles, and the like, which have excellent heat resistance as well as electrical and mechanical properties. In recent years, photosensitive resin compositions in which these resins themselves are given photosensitivity have been used, and their use can simplify the manufacturing process of patterned cured products and shorten the complicated manufacturing process (see, for example, Patent Document 1).

[0003] JP 2009-265520 A

[0004] To prevent a decrease in production yield, it is desirable to cure photosensitive polyimide precursors at lower temperatures than conventionally used. However, when photosensitive polyimide precursors are cured at lower temperatures, the peel strength, which is an index of adhesion and bondability to copper substrates, decreases.

[0005] In view of the above-described conventional circumstances, an object of one embodiment of the present disclosure is to provide a photosensitive resin composition that can improve peel strength from a copper substrate even when cured at a lower temperature than conventionally, as well as a cured product using the photosensitive resin composition, a method for producing a patterned cured product, and an electronic component.

[0006] Specific means for achieving the above object are as follows. <1> A photosensitive resin composition containing a polyimide precursor having a polymerizable unsaturated bond and at least one selected from the group consisting of a nitrogen-containing compound having a hydroxyl group and a solubility parameter of 32 or more, and a nitrogen-containing compound having a solubility parameter of 39 or more. <2> The photosensitive resin composition according to <1>, in which the nitrogen-containing compound contains inosine. <3> The photosensitive resin composition according to <1> or <2>, in which the polyimide precursor having a polymerizable unsaturated bond has a structural unit represented by the following general formula (1): (In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７each independently represents a hydrogen atom or a monovalent organic group; R ６ and R ７ at least one of which has a polymerizable unsaturated bond.) <4> The photosensitive resin composition according to any one of <1> to <3>, further containing at least one selected from the group consisting of a polymerizable monomer, a photopolymerization initiator, a sensitizer, a coupling agent, and a solvent. <5> A method for producing a patterned cured product, comprising the steps of: applying the photosensitive resin composition according to any one of <1> to <4> onto a substrate and drying to form a photosensitive resin film; patternwise exposing the photosensitive resin film to obtain a resin film; developing the resin film after the patternwise exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film. <6> A cured product obtained by curing the photosensitive resin composition according to any one of <1> to <4>. <7> The cured product according to <6>, which is a patterned cured product. <8> The cured product according to <6> or <7>, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film. <9> An electronic component comprising the cured product according to any one of <6> to <8>.

[0007] According to one embodiment of the present disclosure, it is possible to provide a photosensitive resin composition that can improve peel strength against a copper substrate even when cured at a lower temperature than conventionally, as well as a cured product using the photosensitive resin composition, a method for producing a patterned cured product, and an electronic component.

[0008] 1A to 1C are diagrams illustrating a manufacturing process for an electronic component according to an embodiment of the present disclosure.

[0009] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0010] In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another staged numerical range. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in a composition, the content or amount of each component refers to the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire region when the region in which the layer or film is present is observed, as well as cases where the layer or film is formed only over a portion of the region. In the present disclosure, the term "(meth)acryloyl group" refers to at least one of an acryloyl group and a methacryloyl group, and the term "(meth)acryloyloxy group" refers to at least one of an acryloyloxy group and a methacryloyloxy group. In the present disclosure, the average thickness of a layer or film is a value obtained by measuring the thickness of five points on the target layer or film and calculating the arithmetic mean value. The thickness of a layer or film can be measured using a micrometer, a scanning stylus meter, an optical interference film thickness measuring device, or the like. In the present disclosure, when the thickness of a layer or film can be measured directly, it is measured using an optical interference film thickness measuring device. 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 the cross section of the target using an electron microscope. In the present disclosure, "curing at a lower temperature than conventional" refers to curing at, for example, 250°C.

[0011] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond, and at least one of a nitrogen-containing compound having a hydroxyl group and a solubility parameter of 32 or more, and a nitrogen-containing compound having a solubility parameter of 39 or more. Hereinafter, the "solubility parameter" may also be referred to as the SP value.

[0012] The photosensitive resin composition having the above-described configuration can improve the peel strength from a copper substrate even when cured at low temperatures. The reason for this is unclear, but is presumed to be as follows. It has been revealed that when the photosensitive resin composition is cured, the nitrogen-containing compound is likely to be present near the interface. It is believed that increasing the SP value of the nitrogen-containing compound present near the interface reduces the difference in surface free energy between the copper substrate and the nitrogen-containing compound layer, and between the nitrogen-containing compound layer and the resin layer, thereby improving the peel strength. It has been revealed that the above effect can be achieved by using a nitrogen-containing compound with an SP value of 39 or more, or by having a hydroxyl group in the case of a nitrogen-containing compound with an SP value of 32 or more.

[0013] Each component contained in the photosensitive resin composition of the present disclosure will be described below. The photosensitive resin composition of the present disclosure is preferably a negative photosensitive resin composition. The photosensitive resin composition of the present disclosure may further contain at least one selected from the group consisting of a polymerizable monomer, a photopolymerization initiator, a sensitizer, a coupling agent, and a solvent.

[0014] (Unsaturated Polyimide Precursor) The photosensitive resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond (hereinafter, may be referred to as an "unsaturated polyimide precursor"). Examples of the polymerizable unsaturated bond include a carbon-carbon double bond.

[0015] The unsaturated polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound, or may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0016] The unsaturated polyimide precursor preferably has a structural unit represented by the following general formula (1).

[0017]

[0018] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group; R ６ and R ７ At least one of them has a polymerizable unsaturated bond.

[0019] The unsaturated polyimide precursor may have a plurality of structural units represented by the general formula (1), and X, Y, R in the plurality of structural units may be ６ and R ７ may be the same or different. ６ and R ７ are each independently a hydrogen atom or a monovalent organic group, the combination of which is not particularly limited. For example, R ６ and R ７ At least one of R may be a hydrogen atom and the rest may be a monovalent organic group described later, or they may be the same or different monovalent organic groups. ６ and R ７ The combinations may be the same or different.

[0020] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent on the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.

[0021] When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, more preferably 1 to 3 benzene rings, and even more preferably 1 or 2 benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be connected by a single bond, or may be connected by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater.) or a composite linking group comprising at least two of these linking groups. Furthermore, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0022] In the general formula (1), -COOR ６ The —COOR group and the —CONH— group are preferably in the ortho position relative to each other. ７ The group and the —CO— group are preferably in the ortho position relative to each other.

[0023] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulas (A) to (F). Among them, from the viewpoint of obtaining an insulating film that is excellent in flexibility and further suppresses the occurrence of voids at the bonding interface, a group represented by the following formula (E) is preferred, and in the formula (E) below, C is more preferably a group containing an ether bond, and even more preferably an ether bond. Formula (F) below has a structure in which C in formula (E) below is a single bond. It should be noted that the present disclosure is not limited to the specific examples below.

[0024]

[0025] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups that are not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represent a hydrogen atom, an alkyl group, or a phenyl group. Among these, A and B each independently preferably represent a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

[0026] In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａeach independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each 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 combining at least two of these. C preferably contains an ether bond, and is preferably an ether bond. C may also contain a structure represented by the following formula (C1):

[0027]

[0028] 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 a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethylethylene group, a branched-chain alkylene groups such as 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene; and the like. Among these, a methylene group is preferred.

[0029] 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 contained in the alkylene group represented by C in formula (E) above has been substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0030] R contained in the silylene bond or siloxane bond Ａ or R Ｂ The alkyl group represented by R 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 the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0031] Specific examples of the tetravalent organic group represented by X may be groups represented by the following formulae (J) to (O).

[0032]

[0033] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, 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 bonding 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 the divalent aromatic group include a divalent aromatic hydrocarbon group (for example, an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (for example, a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.

[0034] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formula (G) and formula (H). Among these, from the viewpoint of obtaining an insulating film that is excellent in flexibility and in which the generation of voids at the bonding interface is further suppressed, the group represented by the following formula (H) is preferred, and among these, in the following formula (H), D is more preferably a group containing a single bond or an ether bond, even more preferably a group containing a single bond or an ether bond, particularly preferably a group containing an ether bond, and extremely preferably an ether bond.

[0035]

[0036] In formulas (G) to (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 0 to 4. In formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ ) ２-; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each 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 combining at least two of them. D may also be a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as the specific examples of C in formula (E). As D in formula (H), each independently is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, or the like.

[0037] The alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulas (G) to (H) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0038] The alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (H) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0039] The halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom contained 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, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0040] In formulae (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0041] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, and a divalent group having a polyalkylene oxide structure.

[0042] 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 a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0043] 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.

[0044] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Of these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene 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 of one type or two or more types.

[0045] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, and an n-dodecyl group. Among these, a methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent in the aryl group include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Of these, a phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0046] The group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H"), or formula (H'"), and from the viewpoint of having a flexible skeleton and excellent bonding properties, a group represented by the following formula (H') or formula (H") is more preferred.

[0047]

[0048] In formula (H'''), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0049] In general formula (1), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited. Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include the following: A combination where X is a group represented by formula (E) and Y is a group represented by formula (H) A combination where X is a group represented by formula (F) and Y is a group represented by formula (H) A combination where X is a group represented by formula (E) and Y is a group represented by formulas (G) and (H) A combination where X is a group represented by formulas (A) and (E) and Y is a group represented by formula (H) A combination where X is a group represented by formulas (E) and (F) and Y is a group represented by formula (H)

[0050] R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, provided that at least one of them has a polymerizable unsaturated bond. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably a group 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 above is a group represented by general formula (2). When the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-line transmittance is high, and a good cured product tends to be formed even when cured at a low temperature of 250°C or less. Furthermore, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond moiety is eliminated by the (C) compound.

[0051] Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group, and among these, an ethyl group, an isobutyl group, and a t-butyl group are preferred.

[0052]

[0053] In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group.

[0054] R in general formula (2) ８ ~R １０ The carbon number of the aliphatic hydrocarbon group represented by R is 1 to 3, and preferably 1 or 2. ８ ~R １０ Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0055] R in general formula (2) ８ ~R １０ As a combination of ８ and R ９ is a hydrogen atom, and R １０ is preferably a hydrogen atom or a methyl group.

[0056] R in general formula (2) ｘ is a divalent linking group, and is 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. ｘThe number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0057] In general formula (1), R ６ and R ７ At least one of R is preferably a group represented by the general formula (2), ６ and R ７ It is more preferable that both of the above are groups represented by the general formula (2).

[0058] When the unsaturated polyimide precursor contains a compound having a structural unit represented by the general formula (1), the R ６ and R ７ The ratio of the group R represented by general formula (2) to the total ６ and R ７ The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. The upper limit is not particularly limited and may be 100 mol%. The proportion may be 0 mol% or more and less than 60 mol%.

[0059] The group represented by formula (2) is preferably a group represented by the following formula (2').

[0060]

[0061] In general formula (2'), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0062] In formula (2'), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0063] The content of the structural unit represented by general formula (1) contained in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total structural units. The upper limit of the content is not particularly limited, and may be 100 mol%.

[0064] The unsaturated 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 unsaturated polyimide precursor may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0065] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-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 acid. dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornane tetracarboxylic acid dianhydride, 2,2-bis{4-(4'-phenoxy)phenyl}propane tetracarboxylic acid dianhydride, and the like.Among these, at least one 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 tetracarboxylic dianhydride is preferred, at least one selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride is more preferred, and from the viewpoint of bonding at lower temperatures, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride is even more preferred. The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[0066] Specific examples of the diamine compound 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, 2,4'-diaminodiphenyl ether, and 2,4'-diaminodiphenyl ether. , 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-amino (aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,Examples of the diamine compound 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 compound 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 from the viewpoint of having a flexible skeleton and excellent adhesiveness, at least one compound 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. The diamine compounds may be used alone or in combination of two or more.

[0067] Having a structural unit represented by general formula (1), and R in general formula (1) ６ and R ７ The compound in which at least one of the above is a monovalent organic group can be obtained, for example, by the following method (a) or (b): (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R—OH in an organic solvent to form a diester derivative, and then the diester derivative and H ２ N-Y-NH ２ (b) A condensation reaction is carried out between a tetracarboxylic acid dianhydride and a diamine compound represented by the formula: ２ N-Y-NH ２ In an organic solvent, a polyamic acid solution is obtained by reacting a diamine compound represented by the formula: R--OH with the polyamic acid solution, and the compound represented by R--OH is added to the polyamic acid solution and reacted in the organic solvent to introduce an ester group.

[0068] R in general formula (1) ６ and R ７ Since at least one of these has a polymerizable unsaturated bond, at least one of R—OH in which R has a polymerizable unsaturated bond is used.

[0069] Here, H ２ N-Y-NH ２ In the diamine compound represented by the formula (1), Y is the same as Y in the general formula (1), and specific examples and preferred examples are also the same. In addition, R in the compound represented by R—OH represents a monovalent organic group, and specific examples and preferred examples are the same as R in the general formula (1). ６ and R ７ The same applies to the case of the tetracarboxylic acid dianhydride represented by the general formula (8), H ２ N-Y-NH ２ The diamine compound represented by the formula (I) and the compound represented by R—OH may each be used alone or in combination of two or more.

[0070] Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropanamide, with 3-methoxy-N,N-dimethylpropanamide being preferred. An unsaturated polyimide precursor may be synthesized by allowing a dehydration condensation agent to act on a polyamic acid solution together with a compound represented by R—OH. The dehydration condensation agent preferably includes at least one selected from the group consisting of trifluoroacetic anhydride, N,N′-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0071] The above-mentioned compound contained in the unsaturated polyimide precursor is prepared by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, which is then converted into an acid chloride by reacting with a chlorinating agent such as thionyl chloride, and then reacting with a chlorinating agent such as thionyl chloride to form an acid chloride. ２ N-Y-NH ２ The compound contained in the unsaturated polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, and then reacting the diester derivative with a carbodiimide compound in the presence of H ２ N-Y-NH ２The compound can be obtained by reacting a diamine compound represented by the following formula with a diester derivative.

[0072] The unsaturated polyimide precursor is a compound represented by the following general formula (8) and a tetracarboxylic acid dianhydride represented by the following general formula (8). ２ N-Y-NH ２ The polyamic acid is then isoimidized in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then reacted with a compound represented by R—OH to obtain a polyamic acid. Alternatively, a compound represented by R—OH may be reacted in advance with a part of a tetracarboxylic dianhydride to obtain a partially esterified tetracarboxylic dianhydride and H ２ N-Y-NH ２ Alternatively, the compound may be reacted with a diamine compound represented by the following formula:

[0073]

[0074] In the general formula (8), X is the same as X in the general formula (1), and specific examples and preferred examples are also the same.

[0075] The compound represented by R—OH used in the synthesis of the above-mentioned compound contained in the unsaturated polyimide precursor is R ｘ The compound represented by R-OH may be a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'), or a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'). Specific examples of the compound represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, and among these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0076] The molecular weight of the unsaturated polyimide precursor is not particularly limited, and for example, the weight-average molecular weight is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0077] The photosensitive resin composition of the present disclosure may further contain a dicarboxylic acid, and the unsaturated polyimide precursor contained in the photosensitive resin composition may have a structure formed by reaction of some of the amino groups in the unsaturated polyimide precursor with carboxy groups in the dicarboxylic acid. For example, when synthesizing the unsaturated polyimide precursor, some of the amino groups of a diamine compound may be reacted with carboxy groups in the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula: In this case, when synthesizing the unsaturated polyimide precursor, by reacting some of the amino groups of the diamine compound with carboxy groups in the dicarboxylic acid, methacrylic groups derived from the dicarboxylic acid can be introduced into the unsaturated polyimide precursor.

[0078]

[0079] The photosensitive resin composition of the present disclosure may contain a polyimide resin in addition to the unsaturated polyimide precursor. By combining the unsaturated polyimide precursor and the polyimide resin, it is possible to suppress the generation of volatiles due to dehydration cyclodehydration during imide ring formation, which tends to suppress the generation of voids. The polyimide resin referred to here refers to a resin having an imide skeleton in all or part of the resin skeleton. It is preferable that the polyimide resin be soluble in a solvent in the photosensitive resin composition using the unsaturated polyimide precursor.

[0080] The polyimide resin is not particularly limited as long as it is a polymer compound having a plurality of structural units containing imide bonds, and preferably contains, for example, a compound having a structural unit represented by the following general formula (X): This tends to provide a semiconductor device having an insulating film that exhibits high reliability.

[0081]

[0082] In general formula (X), X represents a tetravalent organic group, and Y represents a divalent organic group. Preferred examples of the substituents X and Y in general formula (X) are the same as the preferred examples of the substituents X and Y in general formula (1).

[0083] When the photosensitive resin composition of the present disclosure contains a polyimide resin, the proportion of the polyimide resin relative to the total of the unsaturated polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or may be 10% by mass to 20% by mass.

[0084] The photosensitive resin composition of the present disclosure may contain a resin other than the unsaturated polyimide precursor and the polyimide resin. Examples of the other resin include, from the viewpoint of heat resistance, novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. The other resin may be used alone or in combination of two or more.

[0085] (Nitrogen-containing compound) The photosensitive resin composition of the present disclosure contains at least one of a nitrogen-containing compound having an SP value of 32 or more and a hydroxyl group and a nitrogen-containing compound having an SP value of 39 or more. The "nitrogen-containing compound having an SP value of 32 or more and a hydroxyl group" and the "nitrogen-containing compound having an SP value of 39 or more" are also referred to as "specific nitrogen-containing compounds." The specific nitrogen-containing compounds may be used alone or in combination of two or more.

[0086] When the nitrogen-containing compound has a hydroxyl group, the SP value of the nitrogen-containing compound is 32 or more, preferably 33 or more, more preferably 34 or more, and even more preferably 35 or more. When the nitrogen-containing compound does not have a hydroxyl group, the SP value of the nitrogen-containing compound is 39 or more, preferably 40 or more, more preferably 40 to 43, and even more preferably 40 to 42. Note that when the SP value is 39 or more, nitrogen-containing compounds without a hydroxyl group are also included.

[0087] The SP value is the solubility parameter calculated by the Fedors method [unit: (J / cm ３ ) １／２ SP value [cal / cm ３ ) １／２ ] = (ΔH / V) １／２ SP value [J / cm ３ ) １／２ ] = (ΔH / V) １／２ × 2.04598 where ΔH represents the molar heat of vaporization [cal] and V represents the molar volume [cm ３ As ΔH and V, the sum of the molar heats of vaporization (Δei) of the atomic groups, ΣΔei (=ΔH), and the sum of the molar volumes (Δvi), ΣΔvi(V), can be used, as described in "POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 151-153)", where (ΣΔei / ΣΔvi) １／２ is required from.

[0088] When the specific nitrogen-containing compound has a hydroxyl group, the number of hydroxyl groups may be 1, 2, 3, or 4 or more. Furthermore, when the specific nitrogen-containing compound has a hydroxyl group, it may be a sugar.

[0089] The specific nitrogen-containing compounds include orotic acid (SP value: 39.1), 6-azahypoxanthine (SP value: 39.1), 6-hydrazinouracil (SP value: 39.3), pyromellitic diimide (SP value: 39.5), 5-hydroxymethyluracil (SP value: 39.7), 5-formyluracil (SP value: 39.7), 1,2,4-triazole-3-carboxamide (SP value: 39.8), 4-amino-6-hydroxypyrazolo[3,4-d]pyrimidine (SP value: 39.9), 5-methyluridine (SP value: 40.1), 8-oxoadenosine (SP value: 40.5), inosine (SP value: 40.6), and 5-hydroxymethyluracil (SP value: 39.7). P value: 40.6), 6-azauracil (SP value: 40.9), oxypurinol (SP value: 41.3), xanthine (SP value: 41.3), 5-aminoorotic acid (SP value: 41.4), luminol (SP value: 41.5), guanosine (SP value: 41.9), uracil 1-β-D-arabinofuranoside (SP value: 42.3), uridine (SP value: 42.3), 5-hydroxyuracil (SP value: 42.9), urazole (SP value: 44.0), xanthosine (SP value: 44.1), 6-azauridine (SP value: 45.0), xanthopterin (SP value: 45.2), and the like. Among the above-mentioned specific nitrogen-containing compounds, from the viewpoint of suppressing the formation of a residual film in the unexposed area, compounds containing inosine, uridine, etc. are preferred, and compounds containing inosine are more preferred.

[0090] The photosensitive resin composition of the present disclosure may contain, in addition to the specific nitrogen-containing compound, another nitrogen-containing compound. The other nitrogen-containing compound is not particularly limited as long as it is a nitrogen-containing compound having a solubility parameter of less than 32 and a hydroxyl group, or a nitrogen-containing compound having a solubility parameter of less than 39 and no hydroxyl group, and examples thereof include azole compounds and purine derivatives. The other nitrogen-containing compounds may be used alone or in combination of two or more.

[0091] From the viewpoint of improving the adhesion between the cured product and the copper substrate, the proportion of the total amount of the specific nitrogen-containing compounds relative to the total amount of nitrogen-containing compounds is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, extremely preferably 99% by mass or more, and may be 100% by mass.

[0092] The content of the nitrogen-containing compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 2.0 to 5 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0093] (Solvent) Examples of the solvent include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, etc. The solvents may be used alone or in combination of two or more.

[0094] Examples of ester solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates such as methyl alkoxyacetate, ethyl alkoxyacetate, and butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), and alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate). 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate; methyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate; ethyl 2-alkoxy-2-methylpropionates such as ethyl 2-ethoxy-2-methylpropionate; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

[0095] Examples of ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP). Examples of hydrocarbon solvents include limonene. Examples of aromatic hydrocarbon solvents include toluene, xylene, and anisole. Examples of sulfoxide solvents include dimethyl sulfoxide.

[0096] Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred from the viewpoints of excellent solubility of each component and excellent coatability during photosensitive resin film formation.

[0097] Furthermore, as the solvent, a compound represented by the following general formula (11) may be used.

[0098]

[0099] In general formula (11), R ４１ ~R ４３ are each independently an alkyl group having 1 to 10 carbon atoms.

[0100] R in general formula (11) ４１ ~R ４３ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 3, and more preferably 1 or 3. ４１ ~R ４３Specific examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (11) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The compound represented by the formula (11) is preferably 3-methoxy-N,N-dimethylpropanamide (for example, the trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).

[0101] The content of the solvent is not particularly limited, but is generally 50 to 1,000 parts by mass per 100 parts by mass of the unsaturated polyimide precursor.

[0102] (Polymerizable Monomer) The resin composition of the present disclosure may further contain a polymerizable monomer from the viewpoint of improving the physical properties of the cured film. The polymerizable monomer may be used alone or in combination of two or more types.

[0103] The polymerizable monomer preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being polymerizable by a coupling agent, etc. From the viewpoint of improving crosslink density and improving photosensitivity, it preferably has two to four groups containing a polymerizable unsaturated double bond.

[0104] The polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof 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, trimethylolpropane triacrylate, trimethylolpropane diacrylate,

[0033] Examples of the polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate.

[0034] Examples of the polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate.

[0035] Examples of the polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate.

[0105] When the resin composition of the present disclosure contains a polymerizable monomer, the proportion of the polymerizable monomer having a (meth)acrylic group in the total amount of polymerizable monomers is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, from the viewpoint of the physical properties of the cured film.

[0106] The polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.

[0107] When the resin composition of the present disclosure contains a polymerizable monomer, the content of the polymerizable monomer is not particularly limited, and is preferably 1 part by mass to 50 parts by mass relative to 100 parts by mass of the polyimide precursor. From the viewpoint of the thermal properties of the cured film, the content is more preferably 5 parts by mass to 50 parts by mass, and even more preferably 5 parts by mass to 40 parts by mass.

[0108] (Photopolymerization initiator) The photosensitive resin composition of the present disclosure may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals when irradiated with actinic rays. Examples of actinic rays include ultraviolet rays such as i-rays, visible light, and radioactive rays.

[0109] Examples of the photopolymerization initiator include an oxime compound, an acylphosphine oxide compound, and an acyldialkoxymethane compound.

[0110] Examples of the photopolymerization initiator include a compound represented by the following general formula (9A), a compound represented by the following general formula (9B), a compound represented by the following general formula (10A), and a compound represented by the following general formula (10B).

[0111]

[0112] In general formula (9A), R １１ is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. １２ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. １３ and R １４ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. １１ may be the same or different.

[0113] R １１is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. a1 is preferably 1. R １２ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. １３ and R １４ are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

[0114] An example of the compound represented by general formula (9A) is a compound represented by the following formula (9A-1), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

[0115]

[0116]

[0117] In general formula (9B), R １５ is -OH, -COOH, -OCH ２ OH, —O(CH ２ ) ２ OH, -COOCH ２ OH or -COO(CH ２ ) ２ OH and R １６ and R １７ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R １５ may be the same or different. １５ is preferably —O(CH ２ ) ２ OH. b1 is preferably 0 or 1. R １６ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or a hexyl group. １７ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.

[0118] Examples of the compound represented by general formula (9B) include a compound represented by the following formula (9B-1), which is available as "IRGACURE OXE 01" manufactured by BASF Japan Ltd., and a compound represented by the following formula (9B-2), which is available as "NCI-930" manufactured by ADEKA Corporation.

[0119]

[0120]

[0121] In general formula (10A), R ２１ is an alkyl group having 1 to 12 carbon atoms, and R ２２ and R ２３ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R ２１ may be the same or different. c1 is preferably 0. R ２２ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. ２３ 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 the compound represented by general formula (10A) is a compound represented by the following formula (10A-1), which is available as "G-1820 (PDO)" manufactured by Lambson.

[0122]

[0123]

[0124] In general formula (10B), R ２４ and R ２５ are each independently an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each independently an integer of 0 to 5, s and t are each independently an integer of 0 to 3, and the sum of s and t is 3. When d is an integer of 2 or more, R ２４may be the same or different. When e is an integer of 2 or more, R ２５ may be the same or different. When s is an integer of 2 or more, the groups in the parentheses may be the same or different. When t is an integer of 2 or more, the groups in the parentheses may be the same or different. d is preferably 0. R ２５ are preferably each independently an alkyl group having 1 to 4 carbon atoms, and are preferably a methyl group. e is preferably an integer of 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 general formula (10B) include compounds represented by the following formula (10B-1), which is available as "IRGACURE TPO" manufactured by BASF Japan Ltd. Examples of compounds represented by formula (10B-2) include compounds represented by the following formula (10B-3), which is available as "IRGACURE 819" manufactured by BASF Japan Ltd.

[0125]

[0126] The content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0127] (Sensitizer) The photosensitive resin composition of the present disclosure may contain a sensitizer. By containing a sensitizer in the photosensitive resin composition, it is possible to maintain both the remaining film rate and good resolution over a wide range of exposure doses. The sensitizer may be used alone or in combination of two or more.

[0128] Examples of sensitizers include Michler'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-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, benzyl dimethyl ketone, and the like. tar, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutylate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and the like.

[0129] When the photosensitive resin composition of the present disclosure contains a sensitizer, the amount of the sensitizer is not particularly limited, but is preferably 0.1 parts by mass to 2.0 parts by mass, and more preferably 0.2 parts by mass to 1.0 part by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0130] (Coupling Agent) The photosensitive resin composition of the present disclosure may contain a coupling agent. By containing a coupling agent, the adhesion between the obtained cured product and the substrate can be further improved.

[0131] The coupling agent is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)methylsilane ... Examples of suitable coupling agents include silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane; and aluminum compounds such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate. These coupling agents may be used alone or in combination of two or more.

[0132] When the photosensitive resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, and even more preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0133] (Stabilizer) The photosensitive resin composition of the present disclosure may contain a stabilizer. When the photosensitive resin composition contains a stabilizer, the storage stability can be improved.

[0134] Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenol compounds.

[0135] The stabilizer may be used alone or in combination of two or more. By combining two or more stabilizers, photosensitive characteristics tend to be easily adjusted due to differences in reactivity. The hindered phenol compound may have both a stabilizer function and an antioxidant function described below, or may have only one of these functions.

[0136] 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'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 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-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) alcohol), 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-hydroxybenzyl) 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-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-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.

[0137] When the photosensitive resin composition of the present disclosure contains a stabilizer, the content of the stabilizer is preferably 0.05 parts by mass to 1.0 parts by mass, and more preferably 0.1 parts by mass to 0.8 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0138] The photosensitive resin composition of the present disclosure may further contain a thermal polymerization initiator, an imidization accelerator, an antioxidant, an ultraviolet absorber, a surfactant, a leveling agent, or the like.

[0139] (Thermal Polymerization Initiator) From the viewpoint of accelerating the polymerization reaction, the photosensitive resin composition of the present disclosure may further contain a thermal polymerization initiator. As the thermal polymerization initiator, a compound that does not decompose when heated (dried) to remove the solvent during film formation, but decomposes when heated during curing to generate radicals and promotes the polymerization reaction between polymerizable monomers, or between an unsaturated polyimide precursor and a polymerizable monomer, is preferred. As the thermal polymerization initiator, a compound having a decomposition point of 110°C to 200°C is preferred, and from the viewpoint of promoting the polymerization reaction at a lower temperature, a compound having a decomposition point of 110°C to 175°C is more preferred.

[0140] Specific examples of the thermal polymerization initiator 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 dialkyl peroxides such as dicyclohexane. Examples of suitable peroxyesters include diacyl peroxides such as dibenzoyl peroxide and 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 peroxyesters include those sold under the trade names "Percumyl D," "Percumyl P," and "Percumyl H" (all manufactured by NOF Corporation).

[0141] When the photosensitive resin composition of the present disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 0.2 parts by mass to 20 parts by mass in order to ensure good flux resistance, and even more preferably 0.3 parts by mass to 10 parts by mass in order to suppress a decrease in solubility due to decomposition during drying.

[0142] (Imidization Accelerator) The resin composition of the present disclosure may contain an imidization accelerator from the viewpoint of accelerating the imidization reaction.

[0143] Specific examples of the imidization accelerator include N-phenyldiethanolamine, 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, and 4-aminoacetophenone, and among these, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. The nitrogen-containing compounds may be used alone or in combination of two or more.

[0144] When the resin composition of the present disclosure contains an imidization accelerator, the content of the imidization accelerator is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, and from the viewpoint of storage stability, is more preferably 0.3 parts by mass to 15 parts by mass, and even more preferably 0.5 parts by mass to 10 parts by mass.

[0145] (Antioxidant) The photosensitive resin composition of the present disclosure may contain an antioxidant from the viewpoint of suppressing a decrease in adhesiveness by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, etc. When the photosensitive resin composition of the present disclosure contains an antioxidant, oxidation of an electrode during an insulation reliability test can be suppressed.

[0146] Specific examples of the antioxidant include the compounds exemplified above as the hindered phenol compound, 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, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, etc. The antioxidant may be used alone or in combination of two or more.

[0147] When the photosensitive resin composition of the present disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0148] (UV absorber) The photosensitive resin composition of the present disclosure may contain an UV absorber. When the photosensitive resin composition contains an UV absorber, crosslinking of unexposed areas due to diffuse reflection during exposure tends to be suppressed. Examples of UV absorbers include benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, diphenylacrylate-based compounds, cyanoacrylate-based compounds, diphenylcyanoacrylate-based compounds, benzothiazole-based compounds, azobenzene-based compounds, polyphenol-based compounds, and nickel complex salt-based compounds. The UV absorbers may be used alone or in combination of two or more.

[0149] 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-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-( 2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol), and the like.

[0150] Examples of salicylic acid ester compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0151] 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.

[0152] Examples of diphenylacrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.

[0153] Examples of diphenyl cyanoacrylate compounds include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).

[0154] Examples of the azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0155] Examples of polyphenol compounds include pyrogallol, phloroglycine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, gossypetin, pelargonidin, cyanidin, aurantidin, luteolinidin, peonidin, rosinidin, (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.

[0156] Examples of polyphenol compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).

[0157] Among the above, it is preferable to use at least one ultraviolet absorber selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds.

[0158] Furthermore, as the ultraviolet absorber, from the viewpoint of resolution, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -p- cresol), 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4- [ethyl (2-hydroxyethyl) amino] -4'-nitroazobenzene, (1E, 6E) -1,7-bis (4-hydroxy-3-methoxyphenyl) -1,6-heptadiene-3,5-dione, 1,7-bis (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione It is more preferable to use at least one selected from the group consisting of (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione.

[0159] When the photosensitive resin composition of the present disclosure contains an ultraviolet absorber, the content of the 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, relative to 100 parts by mass of the unsaturated polyimide precursor, from the viewpoint of resolution. Furthermore, from the viewpoint of preventing insufficient photocuring inside the coating film, the content 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.

[0160] (Surfactant and Leveling Agent) The photosensitive resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent. When the photosensitive resin composition contains at least one of a surfactant and a leveling agent, it is possible to improve coatability (for example, suppression of striations (uneven film thickness)) and developability.

[0161] Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Commercially available products include those sold under the trade names "Megafac (registered trademark) F171," "F173," and "R-08" (all manufactured by DIC Corporation), those sold under the trade names "Fluorad FC430" and "FC431" (all manufactured by Sumitomo 3M Limited), and those sold under the trade names "Organosiloxane Polymer KP341," "KBM303," and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0162] The surfactants and leveling agents may be used alone or in combination of two or more.

[0163] When 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 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, and even more preferably 0.05 parts by mass to 3 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0164] The photosensitive resin composition of the present disclosure may further contain inevitable impurities. The photosensitive resin composition of the present disclosure may have a total amount of the unsaturated polyimide precursor, the nitrogen-containing compound, the polymerizable monomer, the photopolymerization initiator, the sensitizer, the coupling agent, and the solvent of 80% by mass or more, 90% by mass or more, or 95% by mass or more.

[0165] <Cured Product> The cured product of the present disclosure 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 non-patterned cured product. The average thickness of the cured product is preferably 5 μm to 20 μm.

[0166] <Method for Producing Cured Product, and Electronic Component> The method for producing a patterned cured product of the present disclosure includes the steps of applying the photosensitive resin composition of the present disclosure onto a substrate and drying to form a photosensitive resin film, patternwise exposing the photosensitive resin film to light to obtain a resin film, developing the patterned exposed resin film with a developer to obtain a patterned resin film, and heat-treating the patterned resin film. This allows a patterned cured product to be obtained.

[0167] A method for producing a patternless cured product includes, for example, a step of forming a photosensitive resin film according to the present disclosure and a step of heat treatment. It may further include a step of exposing the film to light.

[0168] The substrate may be a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), or a TiO ２ Substrate, SiO ２ Examples of the substrate include a metal oxide insulator substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0169] The method for applying the photosensitive resin composition of the present disclosure is not particularly limited, and can be carried out using a spinner or the like.

[0170] Drying can be carried out using a hot plate, an oven, or the like. The drying temperature is preferably 90°C to 150°C, and from the viewpoint of ensuring dissolution contrast, more preferably 90°C to 120°C. 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 photosensitive resin film in which the photosensitive resin composition of the present disclosure is formed into a film shape.

[0171] The average thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, and even more preferably 7 μm to 30 μm.

[0172] The pattern exposure is performed by exposing the film to a predetermined pattern through a photomask, for example. The actinic ray to be irradiated may be ultraviolet light such as i-ray, visible light, or radiation, but i-ray is preferred. The exposure device may be a parallel exposure device, an aligner, a projection exposure device, a stepper, a scanner exposure device, or the like.

[0173] By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed areas are removed with a developer. As the developer, a good solvent for the photosensitive resin film can be used alone, or an appropriate mixture of a good solvent and a poor solvent can be used. 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.

[0174] A surfactant may be added to the developer in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.

[0175] The developing time can be, for example, twice the time required for the photosensitive resin film to be immersed and completely dissolved. The developing time varies depending on the unsaturated polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, even more preferably 20 seconds to 5 minutes.

[0176] After development, the resist may be washed with a rinse solution, such as distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, or propylene glycol monomethyl ether, which may be used alone or in appropriate mixtures, or in stepwise combinations.

[0177] A patterned cured product can be obtained by heat-treating the patterned resin film, where the unsaturated polyimide precursor undergoes a dehydration ring-closing reaction to form the corresponding polyimide resin.

[0178] The temperature of the heat treatment is preferably 250° C. or less, more preferably 120° C. to 250° C., and even more preferably 160° C. to 200° C. By keeping the heat treatment temperature within the above range, damage to the substrate or device can be minimized, devices can be produced with a high yield, and energy savings can be achieved in the process.

[0179] The heat treatment time is preferably 5 hours or less, 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 be sufficiently progressed. The heat treatment atmosphere may be air or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the patterned resin film.

[0180] Examples of equipment used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0181] The cured product of the present disclosure can be used as an interlayer insulating film, a cover coat layer, or a surface protective film. Furthermore, the cured product of the present disclosure can be used as a passivation film, a buffer coat film, etc. Highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (such as multi-die fan-out wafer-level packages) can be manufactured using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, and surface protective film.

[0182] An example of a manufacturing process for a semiconductor device, which is an electronic component according to the present disclosure, will be described with reference to the drawings. Figure 1 is a diagram illustrating a manufacturing process for a semiconductor device with a multilayer wiring structure, which is an electronic component according to an 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. An interlayer insulating film 4 is then formed on the semiconductor substrate 1.

[0183] Next, a photosensitive resin layer 5 such as a chlorinated rubber or phenol novolac resin is formed on the interlayer insulating film 4, and windows 6A are formed by known photoetching techniques so that predetermined portions of the interlayer insulating film 4 are exposed.

[0184] The interlayer insulating film 4 where the window 6A is exposed is selectively etched to provide a window 6B. Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed through the window 6B.

[0185] Furthermore, a second conductor layer 7 is formed using a known photolithography technique, and electrically connected to the first conductor layer 3. When forming a multilayer wiring structure having three or more layers, the above steps can be repeated to form each layer.

[0186] Next, the photosensitive resin composition of the present disclosure is used to open windows 6C by pattern exposure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductor 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 the present disclosure.

[0187] The present disclosure will be described in more detail below based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0188] [Examples 1A to 3A and Comparative Example 1A] Each component shown in Table 1 was mixed in the amount shown in Table 1 to prepare a uniform solution. The obtained solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 1 μm to obtain photosensitive resin compositions of Examples 1A to 3A and Comparative Example 1A. The amount of each component in Table 1 is based on parts by mass. In Table 1, "-" means that the corresponding component is not contained. Details of each component shown in Table 1 are as follows.

[0189] Unsaturated Polyimide Precursor (Synthesis of Polymer I) 380 g of N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical Corporation) was placed in a 2 L separable flask, and 47.08 g (152 mmol) of 4,4'-oxydiphthalic anhydride (ODPA, Manac Corporation) was added and dissolved with stirring. 0.24 g (2.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane, Fujifilm Wako Pure Chemical Industries, Ltd.) was then added and dissolved, followed by the addition of 5.54 g (42.6 mmol) of 2-hydroxyethyl methacrylate (HEMA, Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at 30°C for 1 hour to obtain a reaction solution. Separately, 27.4 g (129 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP, Wakayama Seika Kogyo Co., Ltd.) was dissolved in 145 g of NMP to prepare a DMAP solution. 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, Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added dropwise at 30°C. After stirring at 45°C for 2 hours, 0.08 g (0.74 mmol) of BQ (benzoquinone, Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added, and 40.4 g (310 mmol) of HEMA was added dropwise. After stirring for 15 hours, the mixture was cooled to room temperature. The reaction solution was poured into purified water, and the precipitate was collected, washed with purified water, and then dried under reduced pressure to obtain Polymer I as an unsaturated polyimide precursor. The weight average molecular weight (Mw) of Polymer I was 22,100.

[0190] The measurement conditions for the weight-average molecular weight of the polymer determined by GPC in terms of standard polystyrene were as follows: 1 mL of a solution of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] was used per 0.5 mg of polymer. Measurement equipment: Detector, Hitachi, Ltd. L4000UV; Pump: Hitachi, Ltd. L6000; Shimadzu Corporation C-R4A Chromatopac; Measurement conditions: Column Gelpack GL-S300MDT-5 x 2; Eluent: THF / DMF = 1 / 1 (volume ratio); LiBr (0.03 mol / L), H ３ P.O. ４(0.06 mol / L) Flow rate: 1.0 mL / min, Detector: UV 270 nm

[0191] Solvent: I: N-methyl-2-pyrrolidone II: 3-methoxy-N,N-dimethylpropanamide Polymerizable monomer: tetraethylene glycol dimethacrylate (TEGDMA, manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerization initiator: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime) (G-1820 (PDO), manufactured by Lambson) Sensitizer: 4,4'-bis(diethylamino)benzophenone (EMK, manufactured by Merck) Coupling agent: 3-ureidopropyltriethoxysilane ("UCT-801" manufactured by United Chemical Technology) Nitrogen-containing compound I: inosine (SP value: 40.6) II: 6-azauracil (SP value: 40.9) III: Uridine (SP value: 42.3) IV: 1H-benzotriazole (SP value: 28.0)

[0192] (Preparation of Cured Film) The above-described resin composition was spin-coated onto a Cu-plated wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 90°C for 100 seconds, and then dried at 100°C for 100 seconds to form a resin film. The obtained resin film was exposed to 400 mJ / cm using a proximity exposure device MA8 (Mask Aligner manufactured by SUSS MicroTec, broadband light: wavelength 350 to 450 nm). ２ The resin film was then developed with cyclopentanone using a developing device Act8. The developed resin film was heated at 250°C for 2 hours in a nitrogen atmosphere using an inert gas oven INL-60N1-S (manufactured by JTEKT Thermo Systems Corporation) to obtain a cured film (film thickness after curing: 6 μm).

[0193] (Measurement of Peel Strength) Using SAICAS EN (manufactured by Daipla Wintes Co., Ltd.), the cured film was cut at a horizontal speed of 3.0 μm / sec and a vertical speed of 0.5 μm / sec. When the cutting blade reached the interface between the cured film and the substrate, it was advanced only horizontally, and the average peel strength was measured from 180 seconds to 270 seconds. The results are shown in Table 1. "A": Peel strength of 0.26 kN / m or more "B": Peel strength of 0.15 kN / m or more but less than 0.26 kN / m "C": Peel strength less than 0.15 kN / m

[0194]

[0195] As shown in Table 1, the cured films obtained from the compositions of Examples 1A to 3A, each containing a specific nitrogen-containing compound, had higher peel strengths than those obtained from Comparative Example 1A, which contained nitrogen-containing compound IV (1H-benzotriazole, SP value: 28.0), which was not a specific nitrogen-containing compound.

[0196] [Examples 4 to 6A] Cured films of Examples 4A to 6A were prepared and evaluated in the same manner as in Example 1, except that the blending amount of nitrogen-containing compound I (inosine) was changed as shown in Table 2. The results are shown in Table 2.

[0197]

[0198] As shown in Table 2, even when the blending amount of the specific nitrogen-containing compound was changed, the cured films obtained from the compositions of Examples 1A and 4A to 6A had superior peel strength compared to the cured film obtained from the composition of Comparative Example 1A.

[0199] [Examples 1B to 3B, Comparative Example 1B] Cured films of Examples 1B to 3B and Comparative Example 1B were prepared and evaluated in the same manner as in Example 1A, etc., except that Polymer I was changed to Polymer II as the unsaturated polyimide precursor and each component shown in Table 3 was blended in the amount shown in Table 3. The results are shown in Table 3. In Table 3, "-" means that the corresponding component was not contained.

[0200] (Synthesis of Polymer II) In a 0.5 liter plastic bottle, 43.624 g (200 mmol) of pyromellitic dianhydride (PMDA) dried for 24 hours in a dryer at 160°C, 54.919 g (401 mmol) of 2-hydroxyethyl methacrylate, and 0.220 g of hydroquinone were dissolved in 394 g of N-methyl-2-pyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, thereby obtaining a pyromellitic acid-hydroxyethyl methacrylate diester solution. This solution was designated as a PMDA (HEMA) solution.

[0201] Separately, in a 0.5 liter plastic bottle, 15.5 g of 4,4'-oxydiphthalic anhydride (ODPA) that had been dried for 24 hours in a drier at 160°C, 14.1 g of 2-hydroxyethyl methacrylate, and 0.1 g of hydroquinone were dissolved in 118 g of N-methyl-2-pyrrolidone, and a catalytic amount of 1,8-diazabicycloundecene was added to prepare a mixed solution. The mixed solution was stirred at room temperature (25°C) for 48 hours to carry out esterification, yielding a 4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester solution. This solution was designated as the ODPA (HEMA) solution.

[0202] A 0.5-liter flask equipped with a stirrer and thermometer was charged with 493.2 g of PMDA (HEMA) solution and 148.1 g of ODPA (HEMA) solution. Then, under ice cooling, 124.9 g of thionyl chloride was added dropwise using a dropping funnel so as to maintain the reaction solution temperature at 10°C or below. The molar ratio of PMDA (HEMA) to ODPA (HEMA) was 3:1. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice cooling for 2 hours to obtain a solution of acid chlorides of PMDA (HEMA) and ODPA (HEMA). Next, using the dropping funnel, a solution prepared by dissolving 80 g of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 83 g of pyridine, and 0.2 g of hydroquinone in 227 g of N-methyl-2-pyrrolidone was added dropwise, taking care not to allow the reaction solution temperature to exceed 10°C. The reaction mixture was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain Polymer II as an unsaturated polyimide precursor. The weight-average molecular weight (Mw) of Polymer II was 34,000.

[0203]

[0204] As shown in Table 3, the cured films obtained from the compositions of Examples 1B to 3B had superior peel strength compared to the cured film obtained from the composition of Comparative Example 1B.

[0205] From the results in Table 3, it is presumed that similar effects can be obtained even if the unsaturated polyimide precursor is changed to any of the following polymers III to V, since the cured films obtained from the compositions containing the specific nitrogen-containing compounds have excellent peel strength even when the type of unsaturated polyimide precursor is changed.

[0206] Polymer III: Acid component: ODPA; Amine component: 4,4'-diaminodiphenyl ether (ODA) and m-phenylenediamine (MPD)

[0207] Polymer IV Acid component: ODPA Amine component: ODA

[0208] Polymer V Acid component: 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) Amine component: ODA

[0209] [Examples 1C to 2C, Comparative Example 1C] Cured films of Examples 1C and 2C and Comparative Example 1C were prepared and evaluated in the same manner as in Example 1A, etc., except that solvent I was changed to solvent II and the components shown in Table 4 were blended in the amounts shown in Table 4. The results are shown in Table 4. In Table 3, "-" means that the corresponding component was not contained.

[0210]

[0211] As shown in Table 4, even when the type of solvent was changed, the cured films obtained from the compositions of Examples 1C to 2C had superior peel strength compared to the cured film obtained from the composition of Comparative Example 1C, indicating that similar effects can be obtained with other solvents.

[0212] REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductor layer 4 interlayer insulating film 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductor layer 8 surface protective film

Claims

1. A photosensitive resin composition comprising: a polyimide precursor having a polymerizable unsaturated bond; and at least one compound selected from the group consisting of a nitrogen-containing compound having a hydroxyl group and a solubility parameter of 32 or more, and a nitrogen-containing compound having a solubility parameter of 39 or more.

2. The photosensitive resin composition according to claim 1 , wherein the nitrogen-containing compound comprises inosine.

3. 3. The photosensitive resin composition according to claim 1, wherein the polyimide precursor having a polymerizable unsaturated bond has a structural unit represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group; R ６ and R ７ At least one of the groups has a polymerizable unsaturated bond.

4. 3. The photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of a polymerizable monomer, a photopolymerization initiator, a sensitizer, a coupling agent, and a solvent.

5. A step of applying the photosensitive resin composition according to claim 1 or 2 onto a substrate and drying it to form a photosensitive resin film; a step of pattern-exposing the photosensitive resin film to obtain a resin film; developing the resin film after the pattern exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film.

6. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

7. The cured product according to claim 6, which is a patterned cured product.

8. The cured product according to claim 6, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film.

9. An electronic component comprising the cured product according to claim 6 .

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