Resin composition, cured product production method, cured product, and electronic component

Abstract

This resin composition contains an adhesive auxiliary agent and a resin that is at least one of a cyclized resin and a precursor of the cyclized resin. The adhesive auxiliary agent contains a compound represented by general formula (1). In general formula (1), R1 represents an alkyl group having 1-3 carbon atoms, R2 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms, R3 represents a group including a ring structure or a straight-chain structure having four or more atoms, and m represents an integer of 0-3.

Description

Resin composition, method for manufacturing cured product, cured product, and electronic component

[0001] This disclosure relates to resin compositions, methods for producing cured products, cured products, and electronic components.

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

[0003] Patent Document 1: Japanese Unexamined Patent Publication No. 2021-85977

[0004] When forming a resin film using a resin composition containing a resin such as polyimide resin and an adhesive aid, and then curing the resin film to form a cured product, there is a problem in that "white clumps," which are foreign substances such as condensates of the adhesive aid, tend to form. It is desirable to suppress the formation of such white clumps in the resin film or cured product.

[0005] In view of the above-mentioned conventional circumstances, one embodiment of the present disclosure aims to provide a resin composition capable of suppressing the occurrence of white clumps when formed into a resin film or cured product, as well as a method for producing a cured product using this resin composition, a cured product, and an electronic component.

[0006] The specific means for achieving the above objectives are as follows: <1> A resin composition comprising a cyclized resin and a resin which is at least one of a precursor of the cyclized resin, and an adhesive aid, wherein the adhesive aid comprises a compound represented by the following general formula (1). In general formula (1), R １ R is an alkyl group having 1 to 3 carbon atoms. ２ R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ R is a group having four or more atoms in a linear or cyclic structure, and m is an integer from 0 to 3. <2> In the compound represented by the general formula (1), R ３ The resin composition described in <1> has a structure that decomposes at 50°C to 300°C. <3> In the compound represented by the general formula (1), R ３The resin composition described in <1> or <2> is a structure represented by the following general formula (2). In general formula (2), R ４ represents a group that dissociates upon heating, and * represents the bond position. <4> The resin composition according to any one of <1> to <3>, wherein the resin is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. <5> The resin composition according to <4>, wherein the resin comprises the polyimide precursor, and the polyimide precursor 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 ７ (Each represents independently a hydrogen atom or a monovalent organic group.) <6> A resin composition according to any one of <1> to <5>, further containing a photopolymerization initiator or a photoacid generator. <7> A resin composition according to any one of <1> to <6>, further containing a crosslinking agent. <8> A resin composition according to any one of <1> to <7> used for making a redistribution layer. <9> A method for producing a cured product, comprising the steps of: applying the resin composition according to any one of <1> to <8> onto a substrate and drying it to form a resin film; and heat-treating the resin film. <10> A cured product obtained by curing the resin composition according to any one of <1> to <8>. <11> The cured product according to <10>, used as an interlayer insulating film, a redistribution layer, a cover coat layer, or a surface protective film. <12> An electronic component comprising the cured product according to <10> or <11>.

[0007] According to one embodiment of the present disclosure, a resin composition capable of suppressing the occurrence of white clumps when formed into a resin film or cured product, as well as a method for producing a cured product using this resin composition, a cured product, and an electronic component are provided.

[0008] This is a diagram illustrating the manufacturing process of an electronic component according to one embodiment of the present disclosure. This is a diagram showing the three-dimensional structures of adhesive aids 3 and 10 used in the examples and comparative examples.

[0009] The following describes in detail the forms for implementing this disclosure. However, this disclosure is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit this disclosure.

[0010] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that are not clearly distinguishable from other processes, provided that the purpose of the process is achieved. In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced by the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the terms "layer" or "film" include cases where, when observing the region in which the layer or film exists, it is formed not only over the entire region, but also on only a part of the region. In this disclosure, "(meth)acryloyl group" means at least one of an acryloyl group and a methacryloyl group, and "(meth)acryloyloxy group" means at least one of an acryloyloxy group and a methacryloyloxy group. In this disclosure, the average thickness of a layer or film is given as the arithmetic mean of measuring the thickness of five points on the layer or film in question. The thickness of a layer or film can be measured using a micrometer, a scanning stylus, an optical interferometer, or the like. In this disclosure, if the thickness of a layer or film can be measured directly, it shall be measured using an optical interferometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing a cross-section of the object to be measured using an electron microscope.

[0011] <Resin Composition> The resin composition of the present disclosure comprises a resin that is at least one of a cyclized resin and a precursor of the cyclized resin, and an adhesion assistant, wherein the adhesion assistant comprises a compound represented by the following general formula (1).

[0012]

[0013] In general formula (1), R １ is an alkyl group having 1 to 3 carbon atoms, R ２ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ３ is a group comprising a linear structure or a cyclic structure having 4 or more atoms, and m is an integer of 0 to 3.

[0014] In a case where a resin film is formed using a resin composition comprising a resin such as a polyimide resin and an adhesion assistant, and then the resin film is cured to form a cured product, white granules, which are foreign matters such as condensates of the adhesion assistant, are likely to occur. On the other hand, the resin composition of the present disclosure comprises an adhesion assistant containing the compound represented by general formula (1). R in the compound represented by general formula (1) ３ is a group comprising a linear structure having 4 or more atoms or a group comprising a cyclic structure. Such a compound represented by general formula (1) has a relatively bulky structure at the terminal on the propyl group side of the propylsilyl group, which makes condensation of the adhesion assistant less likely to occur. For this reason, it is presumed that white granules, which are foreign matters such as condensates of the adhesion assistant, are less likely to occur.

[0015] For example, in the examples described later, adhesion assistant 3 corresponding to the compound represented by general formula (1) wherein R ３ is a 3,5-dimethyl-1H-pyrazole-1-carboxamide group is used, and in the comparative example, adhesion assistant 10 (corresponding to other adhesion assistants) wherein R ３ is a urea bond is used. Adhesion assistant 3 has a steric structure as R ３ that is the portion circled in Figure 2, and this steric structure is bulkier than the urea bond that is the structure corresponding to R ３ in adhesion assistant 10. In the compound represented by general formula (1) including adhesion assistant 3 and the like, R ３It is presumed that the bulky structure makes it less likely for condensation of the adhesive aid to occur.

[0016] The components contained in the resin composition of this disclosure are described below. The resin composition of this disclosure may be a photosensitive resin composition or a non-photosensitive resin composition. The photosensitive resin composition may be a positive-type photosensitive resin composition (i.e., a resin composition that removes the exposed areas to form a pattern) or a negative-type photosensitive resin composition (i.e., a resin composition that removes the unexposed areas to form a pattern). If the resin composition of this disclosure is a photosensitive resin composition, it is preferably a negative-type photosensitive resin composition.

[0017] The applications of the resin composition disclosed herein are not particularly limited. For example, it may be a composition used for producing a redistribution layer, or a composition used for producing an interlayer insulating film, a redistribution layer, a cover coat layer, or a surface protective film.

[0018] [Resin] The resin composition of this disclosure comprises a resin which is at least one of a cyclized resin and a precursor of a cyclized resin. The cyclized resin is not particularly limited as long as it is a resin which has a ring structure in its structure. A precursor of a cyclized resin is a resin which undergoes a change in chemical structure due to external stimuli such as heat or light to become a cyclized resin. Resins which undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins which undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. The resin composition of this disclosure may contain only one of the cyclized resin and the precursor of a cyclized resin, or it may contain both the cyclized resin and the precursor of a cyclized resin.

[0019] The resin is preferably at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. More preferably, the resin contains at least one selected from the group consisting of polyimide precursor and polybenzoxazole precursor, and even more preferably contains a polyimide precursor.

[0020] (Polyimide) The polyimide is not particularly limited as long as it is a polymer compound having multiple structural units containing imide bonds, and it is preferable to include, for example, a compound having a structural unit represented by the following general formula (X).

[0021]

[0022] In general formula (X), X represents a tetravalent organic group and Y represents a divalent organic group. Preferred examples of substituents X and Y in general formula (X) are the same as preferred examples of substituents X and Y in general formula (1) described below. Polyimide may have multiple structural units represented by the above general formula (X), and X and Y in the multiple structural units may be the same or different.

[0023] (Polyimide Precursor) A polyimide precursor refers to an intermediate in the synthesis of polyimide. A polyimide precursor may refer to a compound that is either a polyamic acid or a compound in which at least some of the hydrogen atoms of the carboxyl groups in a polyamic acid are replaced with a monovalent organic group. When the resin composition of this disclosure is a photosensitive resin composition, it is preferable that the polyimide precursor contained in the resin composition contains a polyimide precursor having polymerizable unsaturated bonds. Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

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

[0025]

[0026] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group. When the resin composition of this disclosure is a photosensitive resin composition, R ６ and R ７ Preferably, at least one of them has a polymerizable unsaturated bond.

[0027] The polyimide precursor may have multiple structural units represented by the above general formula (1), and X, Y, R in the multiple structural units６ and R ７ These may be the same or different. ６ and R ７ The combination of each is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups. For example, R ６ and R ７ At least one of them is a hydrogen atom, and the rest may be monovalent organic groups as described later, and they may all be the same or different monovalent organic groups. As mentioned above, when the polyimide precursor has multiple structural units represented by the general formula (1), the R of each structural unit ６ and R ７ The combinations may be the same or different.

[0028] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (for example, aromatic rings with 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, heterocyclic rings with 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings. When the tetravalent organic group represented by X includes an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of substituents on aromatic rings include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, and amino groups.

[0029] When the tetravalent organic group represented by X contains a benzene ring, it is preferable that the tetravalent organic group represented by X contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), or a silylene bond (-Si(R)).Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. The rings may be linked by linking groups such as ( ), or by a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be linked at two locations by a single bond and at least one of a linking group, forming a five-membered or six-membered ring containing a linking group between the two benzene rings.

[0030] In general formula (1), -COOR ６ The group and the -CONH- group are preferably in the ortho position relative to each other, and -COOR ７ It is preferable that the group and the -CO- group are in the ortho position relative to each other.

[0031] Specific examples of the tetravalent organic group represented by X include the groups represented by formulas (A) to (F) below. Among these, the group represented by formula (E) below is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, and more preferably the group represented by formula (E) below, in which C is a group containing an ether bond, and even more preferably an ether bond. Formula (F) below is a structure in which C in formula (E) below is a single bond. Note that this disclosure is not limited to the following specific examples.

[0032]

[0033] In formula (D), A and B are independently single bonds or divalent groups not conjugated to a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups not conjugated to a benzene ring include methylene groups, halide methylene groups, halide methylmethylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), sulfide bonds (-S-), and silylene bonds (-Si(R)). Ａ ) ２ -; Two R's ＡEach of these independently represents a hydrogen atom, an alkyl group, or a phenyl group.) are some examples. Among these, A and B are preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, etc., and an ether bond is more preferred.

[0034] In formula (E), C is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-O-C(=O)-), silylene bond (-Si(R) Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably is an ether bond. Furthermore, C may include a structure represented by the following formula (C1).

[0035]

[0036] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; methylmethylene group, methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, and 1,1-dimethyl Examples include branched alkylene groups such as methylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group. Among these, methylene groups are preferred.

[0037] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom in the alkylene group represented by C in formula (E) above is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene groups, difluoromethylene groups, and hexafluorodimethylmethylene groups are preferred.

[0038] R included in the above silylene bond or siloxane bond Ａ or R ＢThe alkyl group represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Ａ or R Ｂ Specific examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0039] Specific examples of the tetravalent organic group represented by X may be the groups represented by the following formulas (J) to (O).

[0040]

[0041] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bond positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (for example, groups with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

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

[0043]

[0044] In formulas (G) to (H), R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. 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)-), or a silylene bond (-Si(R) Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of the following independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. Furthermore, D may be the structure represented by formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of C in formula (E). Preferably, D in formula (H) independently represents a single bond, an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group.

[0045] 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0046] 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 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups.

[0047] 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 in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups are preferred.

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

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

[0050] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonameethylene, and 2-methyldecamethylene.

[0051] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.

[0052] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among these, polyethylene oxide structure or polypropylene oxide structure is preferred as the polyalkylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0053] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of divalent groups 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, a C1-C20 alkyl group, or a C6-C18 aryl group. Specific examples of C1-C20 alkyl groups bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, and n-dodecyl group. Among these, the methyl group is preferred. The C6-C18 aryl group bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents when the aryl group has a substituent include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, phenyl groups are preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via methylene groups, alkylene groups such as ethylene groups, or arylene groups such as phenylene groups.

[0054] The group represented by formula (G) is preferably the group represented by formula (G') below (m-phenylene group) or p-phenylene group, and the group represented by formula (H) is preferably the group represented by formula (H'), formula (H''), or formula (H'''), and more preferably the group represented by formula (H') or formula (H'') below from the viewpoint of having a flexible skeleton and excellent bonding properties.

[0055]

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

[0057] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited. Examples of combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include: A combination where X is the group represented by formula (E) and Y is the group represented by formula (H) A combination where X is the group represented by formula (F) and Y is the group represented by formula (H) A combination where X is the group represented by formula (E) and Y is the group represented by formula (G) and / or formula (H) A combination where X is the group represented by formula (A) and / or (E) and Y is the group represented by formula (H) A combination where X is the group represented by formula (A) and Y is the group represented by formula (H)

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

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

[0060]

[0061] In general formula (2), R ８~R １０ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R ｘ This represents a divalent linking group.

[0062] R in general formula (2) ８ ~R １０ The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. ８ ~R １０ Specific examples of the aliphatic hydrocarbon group represented by include methyl group, ethyl group, n-propyl group, isopropyl group, etc., with methyl group being preferred.

[0063] R in general formula (2) ８ ~R １０ As for combinations, R ８ and R ９ is a hydrogen atom, R １０ A combination of hydrogen atoms or methyl groups is preferred.

[0064] R in general formula (2) ｘ R is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups. ｘ The number of carbon atoms in this compound is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

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

[0066] If the polyimide precursor contains a compound having a structural unit represented by the general formula (1) above, the R of all structural units contained in the compound ６ and R ７ The group R, represented by the general formula (2) for the sum of ６ and R ７The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. There is no particular upper limit, and it may be 100 mol%. The aforementioned proportion may be 0 mol% or more and less than 60 mol%.

[0067] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0068]

[0069] In general formula (2'), R ８ ~R １０ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer from 1 to 10.

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

[0071] The content of the structural unit represented by general formula (1) in a compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to the total structural units. The upper limit of the aforementioned content is not particularly limited and may be 100 mol%.

[0072] The polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The polyimide precursor may also be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0073] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride. Dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 1,1,4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) (L) 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 Examples include aqueous solutions, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornanetetracarboxylic acid dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propanetetracarboxylic acid dianhydride.Among these, it is preferable that at least one is selected from the group consisting of pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, more preferably at least one is selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, and even more preferably that 4,4'-oxydiphthalic anhydride (also called 3,3',4,4'-diphenyl ethertetracarboxylic acid dianhydride) is included from the viewpoint of bonding at lower temperatures. One tetracarboxylic acid dianhydride may be used alone or two or more may be used in combination.

[0074] Specific examples of diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2 ,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6- Diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-A Minophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane and the like. Preferable examples of the diamine compound include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether and 1,3-bis(3-aminophenoxy)benzene. Among these, at least one selected from the group consisting of 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, m-phenylenediamine and 1,3-bis(3-aminophenoxy)benzene is more preferable, and from the viewpoint of having a flexible skeleton and excellent adhesiveness, at least one selected from the group consisting of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane is still more preferable. One type of the diamine compound may be used alone, or two or more types thereof may be used in combination.,

[0075] A compound having a structural unit represented by general formula (1), wherein at least one of R in general formula (1) ６ and R ７ is a monovalent organic group can be obtained, for example, by the following method (a) or (b): (a) After reacting tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) with a compound represented by R-OH in an organic solvent to obtain a diester derivative, the diester derivative and H ２ N-Y-NH ２ is subjected to a condensation reaction with a diamine compound represented by. (b) After reacting tetracarboxylic dianhydride with a diamine compound represented by H ２ N-Y-NH ２ in an organic solvent to obtain a polyamic acid solution, a compound represented by R-OH is added to the polyamic acid solution, and the mixture is reacted in an organic solvent to introduce an ester group.

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

[0077] Here, H ２ N-Y-NH ２ Y in the diamine compound represented by is the same as Y in 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 those for R ６ and R ７ in general formula (1). The tetracarboxylic dianhydride represented by general formula (8), H ２ N-Y-NH ２ The diamine compound represented by and the compound represented by R-OH may each be used alone, or two or more thereof may be used in combination.

[0078] Examples of the aforementioned organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropanamide, etc. Among them, 3-methoxy-N,N-dimethylpropanamide is preferred. A dehydration condensation agent may be allowed to act on a polyamic acid solution together with the compound represented by R-OH to synthesize a polyimide precursor. It is preferable that the dehydration condensation agent includes at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC) and 1,3-diisopropylcarbodiimide (DIC).

[0079] The aforementioned compound contained in the polyimide precursor can be obtained by allowing a compound represented by R-OH to act on a tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, then allowing a chlorinating agent such as thionyl chloride to act thereon to convert it into an acid chloride, then allowing H ２ N-Y-NH ２ to react with the diamine compound represented by and the acid chloride. The aforementioned compound contained in the polyimide precursor can be obtained by allowing a compound represented by R-OH to act on a tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, then reacting with H ２N-Y-NH ２ It can be obtained by reacting a diamine compound represented by [formula] with a diester derivative.

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

[0081]

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

[0083] The compound represented by R-OH used in the synthesis of the aforementioned compound contained in the polyimide precursor is the R group represented by general formula (2). ｘ The compound may be one in which a hydroxyl group is bonded to the group, or one in which a hydroxyl group is bonded to the terminal methylene group of the group represented by general formula (2'). Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

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

[0085]

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

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

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

[0089]

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

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

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

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

[0094]

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

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

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

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

[0099] [Adhesion Aid] The resin composition of this disclosure includes an adhesion aid containing a compound represented by the following general formula (1) (hereinafter also referred to as a specific compound). By using an adhesion aid containing a specific compound, the occurrence of white spots in the resin film or cured product can be suppressed. The specific compound may be used alone or in combination of two or more types.

[0100]

[0101] In general formula (1), R １ R is an alkyl group having 1 to 3 carbon atoms. ２ R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ R is a group containing a linear or cyclic structure with four or more atoms, and m is an integer from 0 to 3. In general formula (1), R １ or R ２ If multiple R １ The Rs may be the same or different, and there may be multiple Rs. ２ They may be the same or they may be different.

[0102] R in specific compounds ３This refers to a group containing a linear structure with four or more atoms, or a group containing a ring structure. A group containing a linear structure with four or more atoms, or a group containing a ring structure, may also contain a urethane bond or a urea bond.

[0103] Groups containing a linear structure with four or more atoms may include groups containing urethane bonds, ester bonds, (meth)acryloyloxy groups, urea bonds, thiourea bonds, or amino groups in the linear structure. In this disclosure, "linear structure with four or more atoms" means a structure in which four or more atoms (these atoms may be the same or different) are linked in a linear chain, and branched structures may exist. Note that branched structures are not counted in the number of atoms of the linear structure.

[0104] The ring structure is not particularly limited and includes cyclic hydrocarbons, heterocycles, etc. Examples of cyclic hydrocarbons include alicyclic hydrocarbons and aromatic hydrocarbons. Examples of heterocycles include cyclic ether structures, lactam structures, cyclic carbonate structures, pyrazole structures, imidazole structures, pyridine structures, triazole structures, imidazoline structures, and piperidine structures. The ring structure may or may not have substituents.

[0105] In a compound represented by general formula (1), R ３ It is preferable that the material has a structure that decomposes at 50°C to 300°C, and more preferably that it has a structure that decomposes at 50°C to 300°C to generate an isocyanate group.

[0106] In a compound represented by general formula (1), R ３ It is preferable that the structure is represented by the following general formula (2).

[0107]

[0108] In general formula (2), R ４ The symbol (*) represents a group that dissociates upon heating, and the asterisk (*) represents the bond position. ４ When heated, it dissociates, R ３ It is converted to an isocyanate group (*-N=C=O). From the viewpoint of adhesion of the cured product after development, R ４It is preferably a pyrazole structure, and more preferably a 3,5-dimethylpyrazole structure.

[0109] In the resin composition of this disclosure, the content of the adhesive aid is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of resin.

[0110] The adhesive aid in the resin composition of this disclosure may consist of a compound represented by the general formula (1) described above (a specific compound), or it may consist of a specific compound and other adhesive aids.

[0111] The content of the specific compound may be 50 to 100 parts by mass, 70 to 100 parts by mass, or 90 to 100 parts by mass, per 100 parts by mass of the adhesive aid.

[0112] The resin compositions of this disclosure may contain other adhesion aids. These other adhesion aids are not particularly limited and include silane coupling agents such as 3-aminopropyltrimethoxysilane, triethoxysilylpropylurea, and 3-mercaptopropylmethyldimethoxysilane; and aluminum-based adhesion aids such as aluminum tris(ethylacetate), aluminum tris(acetylacetonate), and ethylacetate aluminum diisopropylate. These other adhesion aids may be used individually or in combination of two or more.

[0113] [Solvent] The resin composition of this disclosure may contain a solvent. The solvent may be used alone or in combination of two or more types.

[0114] The solvent may be at least one selected from the group consisting of, for example, amide compounds, lactone compounds, urea compounds, sulfoxide compounds, alcohol compounds, ether compounds, and ester compounds. Preferably, the solvent contains at least one selected from the group consisting of amide compounds, lactone compounds, urea compounds, and sulfoxide compounds.

[0115] Examples of solvents include N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, γ-valerolactone, N,N-dimethylpropionamide (DMPr), 1,3-dimethyl-2-imidazolidinone (DMI), propylene carbonate, ethylene carbonate, dimethyl sulfoxide, ethyl lactate, methanol, ethanol, 2-propanol, tetrahydrofuran, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-acetoxy-1-methoxypropane, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

[0116] The solvent content may be 60.0% by mass or less, 55.0% by mass or less, or 50.0% by mass or less, based on the total amount of the resin composition. The solvent content may be 40.0% by mass or more, 45.0% by mass or more, or 50.0% by mass or more, based on the total amount of the resin composition.

[0117] [Crosslinking Agent] The resin composition may contain a crosslinking agent. In the process of exposing or heat-treating the resin composition, the crosslinking agent compound reacts with the resin (for example, a polyimide precursor having polymerizable unsaturated bonds or a polybenzoxazole precursor having polymerizable unsaturated bonds) with the crosslinking agent, or with other crosslinking agents, to form crosslinks, or the crosslinking agent compound itself polymerizes. As a result, even at relatively low curing temperatures, for example, below 200°C, the strength of the resulting cured film is increased, and mechanical properties, chemical resistance, flux resistance, etc., can be improved. The crosslinking agent may be used alone or in combination of two or more types.

[0118] Examples of crosslinking agents include compounds having two or more polymerizable unsaturated bonded groups (hereinafter also referred to as functional groups). From the viewpoint of polymerization reactivity, (meth)acryloyl groups and vinyl groups are preferred as functional groups, with (meth)acryloyl groups being more preferred. Crosslinking agents may be subjected to alkoxylation treatments such as ethoxylation or propoxylation.

[0119] Examples of bifunctional crosslinking agents include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, tricyclodecanedimethanol diacrylate, and tricyclodecanedimethanol dimethacrylate.

[0120] Examples of trifunctional crosslinking agents include trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and tris-(2-methacryloxyethyl) isocyanurate.

[0121] Examples of crosslinking agents with four or more functions include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and tetrakisacrylate methanetetrayltetrakis (methyleneoxyethylene).

[0122] If the resin composition of this disclosure contains a crosslinking agent, the amount of the crosslinking agent is preferably 1 to 50 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass, per 100 parts by mass of the resin.

[0123] [Photopolymerization initiator or photoacid generator] The resin composition of this disclosure may contain a photopolymerization initiator or a photoacid generator. The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals upon irradiation with active light. Examples of active light include ultraviolet rays such as i-rays, visible light, and radiation. The photoacid generator is not particularly limited as long as it is a compound that can generate acid upon irradiation with the active light described above.

[0124] Examples of photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, and acyldialkoxymethane compounds.

[0125] The photoacid generator may be an ionic photoacid generator or a nonionic photoacid generator. Examples of ionic photoacid generators include onium salt compounds and quaternary ammonium salt compounds. Examples of nonionic photoacid generators include trichloromethyl-s-triazine compounds, diazomethane compounds, and sulfonate compounds.

[0126] Examples of photopolymerization initiators include compounds represented by the following general formula (9A), compounds represented by the following general formula (9B), compounds represented by the following general formula (10A), and compounds represented by the following general formula (10B).

[0127]

[0128] In general formula (9A), R １１ R is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer from 0 to 5. １２ R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. １３ and R １４ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer of 2 or more, R １１ These may be the same or different.

[0129] R １１ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. R １２R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. １３ and R １４ Preferably, each is independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0130] Examples of compounds represented by general formula (9A) include the compound represented by the following formula (9A-1), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

[0131]

[0132]

[0133] In general formula (9B), R １５ -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 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group. b1 is an integer from 0 to 5. If b1 is an integer of 2 or more, R １５ These may be the same or different. １５ Preferably, -O(CH ２ ) ２ It is OH. b1 is preferably 0 or 1. R １６ R is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or a hexyl group. １７ The group is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.

[0134] Examples of compounds represented by general formula (9B) include the compound represented by the following formula (9B-1), which is available as "IRGACURE OXE 01" from BASF Japan Ltd. Also, examples include the compound represented by the following formula (9B-2), which is available as "NCI-930" from ADEKA Corporation.

[0135]

[0136]

[0137] In general formula (10A), R ２１ R is an alkyl group having 1 to 12 carbon atoms. ２２ and R ２３ Each of these is independently a hydrogen atom, a C1-C12 (preferably C1-C4) alkyl group, a C1-C12 (preferably C1-C4) alkoxy group, a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group, and c1 is an integer from 0 to 5. When c1 is an integer of 2 or more, R ２１ These may be the same or different. c1 is preferably 0. R ２２ R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. ２３ The group is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group or an ethoxy group. Examples of compounds represented by general formula (10A) include the compound represented by the following formula (10A-1) (1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime). This compound is available as "G-1820 (PDO)" from Lambson.

[0138]

[0139]

[0140] In general formula (10B), R ２４ and R ２５Each of these is an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each independent integers from 0 to 5, s and t are each independent integers from 0 to 3, and the sum of s and t is 3. When d is an integer of 2 or more, R ２４ These may be the same or different. If e is an integer greater than or equal to 2, R ２５ These may be the same or different. If s is an integer greater than or equal to 2, the bases in the parentheses may be the same or different. If t is an integer greater than or equal to 2, the bases in the parentheses may be the same or different. d is preferably 0. R ２５ Preferably, each is an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. e is preferably an integer from 2 to 4, and more preferably 3. The combination of s and t (s, t) is preferably (1, 2) or (2, 1). Examples of compounds represented by general formula (10B) include the compound represented by the following formula (10B-1), which is available as "IRGACURE TPO" manufactured by BASF Japan Ltd. Also, examples of compounds represented by the following formula (10B-2) include the compound available as "IRGACURE 819" manufactured by BASF Japan Ltd.

[0141]

[0142] The content of the photopolymerization initiator or photoacid generator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 6 parts by mass, per 100 parts by mass of resin.

[0143] [Thermal polymerization initiator] The resin composition of this disclosure may further contain a thermal polymerization initiator from the viewpoint of promoting the polymerization reaction. Preferred thermal polymerization initiators are compounds that do not decompose when heated (dried) to remove the solvent during film formation, but decompose when heated during curing to generate radicals, thereby promoting the polymerization reaction between crosslinking agents or between the resin and the crosslinking agent. Preferred thermal polymerization initiators are compounds with a decomposition point of 110°C to 200°C, and from the viewpoint of promoting the polymerization reaction at a lower temperature, compounds with a decomposition point of 110°C to 175°C are more preferred.

[0144] Specific examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, and di- Examples include diacyl peroxides such as uroyl peroxide and dibenzoyl peroxide, peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and bis(1-phenyl-1-methylethyl)peroxide. Commercially available products include those with the trade names "Parkmil D," "Parkmil P," and "Parkmil H" (all manufactured by NOF Corporation).

[0145] If the resin composition of this disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 to 20 parts by mass per 100 parts by mass of resin, more preferably 0.2 to 20 parts by mass to ensure good flux resistance, and even more preferably 0.3 to 10 parts by mass from the viewpoint of suppressing the decrease in solubility due to decomposition during drying.

[0146] [Imidification accelerator] If the resin composition of this disclosure contains a polyimide precursor, a nitrogen-containing compound may be included as an imidization accelerator from the viewpoint of promoting the imidation reaction.

[0147] Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenyldiethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc. Among these, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenyldiethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. Nitrogen-containing compounds may be used individually or in combination of two or more.

[0148] If the resin composition of this disclosure contains an imidation accelerator, the content of the imidation accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyimide precursor.

[0149] [Sensitizer] The resin composition of this disclosure may contain a sensitizer. By containing a sensitizer in the resin composition, it is possible to achieve both maintenance of residual film ratio and good resolution over a wide range of exposure levels. One type of sensitizer may be used alone, or two or more types may be used in combination.

[0150] Sensitizers include Michlar's ketone, ethyl methyl ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, and benzyl Examples include dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrene quinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrene quinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.

[0151] When the resin composition of this disclosure contains a sensitizer, the amount of sensitizer is not particularly limited, but is preferably 0.1 to 1.0 parts by mass, and more preferably 0.2 to 0.8 parts by mass, per 100 parts by mass of resin.

[0152] [Stabilizer] The resin composition of this disclosure may contain a stabilizer. The inclusion of a stabilizer in the resin composition can improve its stability when stored.

[0153] Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenol compounds.

[0154] The stabilizer may be used alone or in combination of two or more types. Combining two or more stabilizers tends to make it easier to adjust the photosensitive properties due to differences in reactivity. The hindered phenol compound may have both the function of a stabilizer and the function of an antioxidant (described later), or it may have only one of the functions.

[0155] Examples of stabilizers include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), and triethylene glycol-bis [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (Nol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy Roxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxyl Examples include C-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, N,N'-hexane-1,6-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide.

[0156] If the resin composition of this disclosure contains a stabilizer, the amount of 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, per 100 parts by mass of resin.

[0157] [Antioxidant] The resin composition of this disclosure may contain an antioxidant, from the viewpoint of suppressing a decrease in adhesion by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow processing, etc. The inclusion of an antioxidant in the resin composition of this disclosure can suppress oxidation of electrodes during insulation reliability testing.

[0158] Specific examples of antioxidants include the compounds exemplified above as hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl),propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants may be used individually or in combination of two or more.

[0159] If the resin composition of this disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin.

[0160] [Rust Inhibitor] The resin composition of this disclosure may contain a rust inhibitor. By containing a rust inhibitor in the resin composition, corrosion and discoloration of copper and copper alloys can be suppressed. Examples of rust inhibitors include azole compounds and purine derivatives. The rust inhibitor may be used alone or in combination of two or more types.

[0161] Specific examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0162] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, and 8-amino Examples include adenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives.

[0163] If the resin composition of this disclosure contains a rust inhibitor, the amount of rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of resin.

[0164] [UV Absorbers] The resin compositions of this disclosure may contain UV absorbers. When a resin composition contains UV absorbers, crosslinking of unexposed areas due to diffuse reflection during exposure tends to be suppressed. Examples of UV absorbers include benzotriazole compounds, salicylate ester compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenylcyanoacrylate compounds, benzothiazole compounds, azobenzene compounds, polyphenol compounds, nickel complex salt compounds, etc. UV absorbers may be used alone or in combination of two or more.

[0165] Examples of benzotriazole compounds include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-( Examples include 2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazole-2-yl)-p-cresol.

[0166] Examples of salicylic acid ester compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0167] 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.

[0168] Examples of diphenyl acrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.

[0169] Examples of diphenylcyanoacrylate compounds include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).

[0170] Examples of azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0171] Examples of polyphenol compounds include pyrogallol, phloroglysine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagine, quercetagene, goshipetin, pelargonidine, cyanidin, aurantinidin, luteolinidin, peonidin, rosinidine, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.

[0172] Examples of polyphenol compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).

[0173] Among the above, it is preferable to use at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, azobenzene compounds, and polyphenol compounds as the ultraviolet absorber.

[0174] Furthermore, from the viewpoint of resolution, it is more preferable to use at least one selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-p-cresol), 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione as the ultraviolet absorber.

[0175] If the resin composition of this disclosure contains an ultraviolet absorber, the amount of ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, per 100 parts by mass of resin, from the viewpoint of resolution. Furthermore, from the viewpoint of suppressing insufficient photocuring inside the coating film, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0176] [Surfactants and Leveling Agents] The resin compositions of this disclosure may contain at least one of a surfactant and a leveling agent. By containing at least one of a surfactant and a leveling agent, the coating properties (e.g., suppression of striations (unevenness in film thickness)) and developability of the resin composition can be improved.

[0177] Examples of surfactants or leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include the trade names "Megafac® F171", "F173", and "R-08" (all manufactured by DIC Corporation), "Florard FC430" and "FC431" (both manufactured by Sumitomo 3M Limited), and "Organosiloxane Polymer KP341", "KBM303", and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0178] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0179] If the resin composition of the present disclosure contains at least one of a surfactant and a leveling agent, the total content of the surfactant and leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, per 100 parts by mass of resin.

[0180] [Other Components] The resin compositions of this disclosure may further contain other components and unavoidable impurities. The total amount of resin, crosslinking agent, photopolymerization initiator and solvent in the resin compositions of this disclosure may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. Furthermore, the total amount of resin, crosslinking agent, photopolymerization initiator, solvent, stabilizer, sensitizer, ultraviolet absorber, rust inhibitor, antioxidant and coupling agent in the resin compositions of this disclosure may be 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or 99% by mass or more.

[0181] <Cured Products> The cured products of this disclosure can be obtained by curing the resin composition of this disclosure. The cured products of this disclosure may be used as patterned cured products or as cured products without patterns. The average thickness of the cured products is preferably 5 μm to 30 μm.

[0182] The elongation at break of the cured product is preferably 25% or more, more preferably 35% or more, and even more preferably 50% or more. There is no particular upper limit on the elongation at break of the cured product.

[0183] <Method for manufacturing a cured product, and electronic components> The method for manufacturing a cured product according to the present disclosure includes the steps of: applying the resin composition according to the present disclosure onto a substrate and drying it to form a resin film; and heat-treating the resin film.

[0184] The method disclosed herein may be a method for manufacturing a patterned cured product (hereinafter also referred to as a patterned cured product), or it may be a method for manufacturing a cured product without a pattern. In the method for manufacturing a patterned cured product, a photosensitive resin composition may be used as the resin composition of the disclosure. The method for manufacturing a patterned cured product includes, for example, the steps of: applying a photosensitive resin composition onto a substrate and drying it to form a photosensitive resin film; pattern exposing the photosensitive resin film to light to obtain a resin film; developing the resin film after pattern exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film.

[0185] The substrates include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), and TiO2. ２ Substrate, SiO ２Examples include metal oxide insulating substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0186] There are no particular restrictions on the method of applying the resin composition disclosed herein, and it can be done using a spinner or the like.

[0187] Drying can be carried out using a hot plate, oven, or the like. The drying temperature is preferably 90°C to 150°C, and more preferably 90°C to 120°C from the viewpoint of ensuring dissolution contrast. The drying time is preferably 30 seconds to 5 minutes. Drying may be carried out two or more times. This makes it possible to obtain a resin film in which the resin composition of this disclosure is formed into a film.

[0188] The average thickness of the photosensitive resin film is preferably 1 μm to 100 μm, more preferably 2 μm to 75 μm, and even more preferably 3 μm to 50 μm.

[0189] Pattern exposure involves exposing a predetermined pattern, for example, through a photomask. The active light used for irradiation can be ultraviolet light such as i-rays, visible light, or radiation, but i-rays are preferred. Exposure devices such as parallel exposure machines, aligners, projection exposure machines, steppers, and scanner exposure machines can be used.

[0190] By developing the film, a patterned resin film (patterned resin film) can be obtained. Generally, when using a negative-type photosensitive resin composition, unexposed areas are removed with a developer. As the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be used in appropriate mixtures. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0191] A surfactant may be added to the developer. The amount added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0192] The development time can be, for example, twice the time it takes for the photosensitive resin film to be immersed and completely dissolved. The development time varies depending on the resin used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0193] After development, the film may be washed with a rinsing solution. The rinsing solution may be distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., either individually or in appropriate mixtures, or in a stepwise combination.

[0194] A patterned resin film can be heat-treated to obtain a patterned cured product. For example, a polyimide precursor or a polybenzoxazole precursor undergoes a dehydration and ring-closing reaction during the heat treatment process to become the corresponding polyimide or polybenzoxazole.

[0195] The temperature of the heat treatment is not particularly limited and may be, for example, 160°C to 400°C or 350°C to 400°C.

[0196] The heat treatment time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heat treatment time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can proceed sufficiently. The heat treatment atmosphere may be air or an inert atmosphere such as nitrogen, but from the viewpoint of preventing oxidation of the pattern resin film, a nitrogen atmosphere is preferred.

[0197] Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0198] The cured product of this disclosure can be used as an interlayer insulating film, a redistribution layer, a cover coat layer, or a surface protective film. Furthermore, the cured product of this disclosure can be used as a passivation film, a buffer coat film, a stress buffer film, etc. Using one or more selected from the group consisting of the above-mentioned passivation film, buffer coat film, interlayer insulating film, redistribution layer, cover coat layer, and surface protective film, highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, stacked devices (multi-die fan-out wafer-level packages, etc.), and other electronic components can be manufactured. The electronic components of this disclosure may include the aforementioned cured product of this disclosure, or they may include a patterned cured product.

[0199] An example of the manufacturing process for a semiconductor device, which is an electronic component of the present disclosure, will be described with reference to the drawings. Figure 1 is a manufacturing process diagram for a multilayer wiring structure semiconductor device, which is an electronic component according to one embodiment of the present disclosure. In Figure 1, a semiconductor substrate 1, such as a Si substrate having circuit elements, is covered with a protective film 2, such as a silicon oxide film, except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0200] Next, a photosensitive resin layer 5, such as a chlorinated rubber-based or phenol novolac-based resin, is formed on the interlayer insulating film 4, and a window 6A is provided so that a predetermined portion of the interlayer insulating film 4 is exposed by known photographic etching techniques.

[0201] The interlayer insulating film 4 with window 6A exposed is selectively etched to create 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 window 6B.

[0202] Furthermore, a second conductor layer 7 is formed using a known photoetching technique, and an electrical connection is made with the first conductor layer 3. When forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

[0203] Next, the window 6C is opened by pattern exposure using the resin composition of this disclosure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductive layer 7 from external stress, alpha rays, etc., and the resulting semiconductor device has excellent reliability. In addition, in the above example, the interlayer insulating film 4 can also be formed using the resin composition of this disclosure.

[0204] The present disclosure will be described in more detail below based on examples and comparative examples. However, the present disclosure is not limited to the examples described below.

[0205] As shown below, polyimide precursor 1 and polyimide precursor 2 were prepared as resins. In polyimide precursor 1, in the general formula (1) described above, X is represented by formula (E), C is a tetravalent organic group that is an ether bond, Y is represented by formula (H'''), R is a divalent organic group that is a methyl group, and R ６ and R ７ At least one of the polymers is a polymer having a structural unit with polymerizable unsaturated bonds. In the general formula (1) described above, polyimide precursor 2 is a tetravalent organic group represented by formula (F), Y is a p-phenylene group, and R ６ and R ７ These are polymers, each having a hydrogen atom as a structural unit.

[0206] <Synthesis of Polyimide Precursor 1> 380 g of N-methyl-2-pyrrolidone (NMP) was placed in a 2 L separable flask, and 47.08 g (152 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) was added while stirring to dissolve it. Then, 0.24 g (2.1 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO) was added and dissolved, and 5.54 g (42.6 mmol) of 2-hydroxyethyl methacrylate (HEMA) was added, followed by stirring at 30°C for 1 hour to obtain the reaction solution. Separately, 27.4 g (129 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was dissolved in 145 g of NMP to prepare a DMAP solution. The DMAP solution was added dropwise while stirring the reaction solution at 35°C, and then stirred at 30°C for 3 hours. Next, 59.7 g (284 mmol) of anhydrous trifluoroacetic acid (TFAA) was added dropwise to the reaction solution at 30°C, and the mixture was stirred at 45°C for 2 hours. Then, 0.08 g (0.74 mmol) of benzoquinone (BQ) was added to the reaction solution, and 40.4 g (310 mmol) of HEMA was added dropwise. The reaction solution was stirred for 15 hours and then cooled to room temperature. The reaction solution was added to purified water, and the precipitate was collected. The precipitate was washed with purified water and dried under reduced pressure to obtain unsaturated polyimide precursor 1 (PI precursor 1). The weight-average molecular weight (Mw) of polyimide precursor 1 was 25,000.

[0207] <Synthesis of Polyimide Precursor 2> 700 g of NMP and 0.43 g of purified water were placed in a 2 L separable flask, and 32.44 g (300 mmol) of p-phenylenediamine (PPD) was added while stirring to dissolve it. Furthermore, 88.27 g (300 mmol) of 3,3',4,4',4'-biphenyltetracarboxylic dianhydride (BPDA) was added in small increments, and the mixture was stirred for 48 hours to obtain the reaction solution. The reaction solution was added to purified water, and the precipitate was collected. The precipitate was washed with purified water and dried under reduced pressure to obtain unsaturated polyimide precursor 2 (PI precursor 2). The weight-average molecular weight (Mw) of polyimide precursor 2 was 57,000.

[0208] The weight-average molecular weight of the polyimide precursor was calculated using gel permeation chromatography (GPC) and a calibration curve using TSKgel standard polystyrene (Tosoh Corporation). The apparatus and conditions are shown below. The measurement sample was prepared by dissolving 2 mg of the sample in 1 mL of eluent (tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (v / v)), and then filtering it through a PTFE membrane filter with a pore size of 1 μm.

[0209] Equipment: Shimadzu Corporation, Prominence Column: Resonaq Corporation, Gelpak GL S300MDT-5 Eluent: THF / DMF = 1 / 1 (v / v), Lithium bromide 0.03 mol / L, Phosphate 0.06 mol / L Flow rate: 1.0 mL / min Measurement wavelength: 270 nm Injection volume: 10 μL

[0210] <Preparation of Resin Composition> Each component listed in Table 1 was mixed in the amounts listed in Table 1 to obtain a homogeneous solution. The obtained solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 1 μm to obtain the resin composition.

[0211] Details of each component listed in Table 1 are as follows. The amounts of each component in Table 1 are based on parts by mass. <Solvents> Solvent 1: 3-Methoxy-N,N-dimethylpropanamide Solvent 2: Methanol Solvent 3: Ethanol <Photosensitive agent> Photosensitive agent: 1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime <Crosslinking agent> Crosslinking agent: Tetraethylene glycol dimethacrylate <Specific adhesive aids> Adhesion aid 1: 3-Glycidoxypropyltriethoxysilane Adhesion aid 2: 3-Methacryloxypropyltriethoxysilane Adhesion aid 3: Blocked isocyanate represented by the following chemical formula (1) Adhesion aid 4: Blocked isocyanate represented by the following chemical formula (2) Adhesion aid 5: Blocked isocyanate represented by the following chemical formula (3) Adhesion aid 6: 3-Trimethoxysilylpropyl succinic anhydride Adhesion aid 7: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane Adhesion aid 8: Compound represented by the following chemical formula (4) Adhesion aid 9: Compound represented by the following chemical formula (5)

[0212]

[0213]

[0214] <Other Adhesion Aids> Adhesion Aid 10: Triethoxysilylpropylurea <Rust Inhibitors> Rust Inhibitor 1: Benzotriazole Rust Inhibitor 2: 5-Amino-1H-Tetrazole

[0215] The following evaluations were performed using the obtained resin compositions. The results are shown in Table 1.

[0216] <Evaluation of White Spot Formation 1> (Manufacturing of Patterned Resin Film) The resin composition obtained using polyimide precursor 1 was spin-coated onto a silicon wafer using a coating apparatus ACT8 (manufactured by Tokyo Electron Limited), and pre-baking (PB) was performed at 100°C for 6 minutes, followed by 110°C for 6 minutes to form a photosensitive resin film with a dry film thickness of 30 μm to 50 μm after PB. The development time was set to twice the time it took for the obtained photosensitive resin film to completely dissolve when immersed in cyclopentanone. A photosensitive resin film was also prepared in the same manner as above, and the obtained photosensitive resin film was exposed to an exposure dose of 500 mJ / cm using an i-line stepper FNES2W-i06 (manufactured by Nikon Engineering Co., Ltd.). ２ The resin film was then exposed by irradiating a photomask for via formation with a diameter of 1 μm to 100 μm. After exposure, it was heated in air at 100°C for 1 minute using Act8. The resin film after exposure and heating was paddle developed with cyclopentanone using Act8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate to obtain a patterned resin film.

[0217] The obtained patterned resin film was heated at 375°C for 1 hour under a nitrogen atmosphere using a high-temperature inert gas oven INH-9N1-S (manufactured by JTEKT Thermo Systems Co., Ltd.) to obtain a patterned cured product. The surface of a 20 μm square patterned cured product was observed using a scanning electron microscope (SEM), and the occurrence of white spots was evaluated according to the following evaluation criteria. If the evaluation is A or B, it can be determined that the occurrence of white spots is suppressed.

[0218] -Evaluation Criteria- A: No white balls were found. B: One or more white balls with a diameter of less than 50 nm were found. C: One or more white balls with a diameter of 50 nm to 100 nm were found. D: One or more white balls with a diameter exceeding 100 nm were found.

[0219] <Evaluation of White Spot Formation 2> The resin composition obtained using polyimide precursor 2 was spin-coated onto a silicon wafer using a coating apparatus ACT8 (manufactured by Tokyo Electron Limited), and pre-baking (PB) was performed at 100°C for 3 minutes, followed by 160°C for 3 minutes to form a resin film with a dry film thickness of 10 μm to 20 μm after PB. The obtained resin film was heated in a high-temperature inert gas oven INH-9N1-S under a nitrogen atmosphere at 250°C for 2 hours to obtain a cured product. White spot formation on the surface of the cured product was evaluated using a scanning electron microscope (SEM) according to the same criteria as in <Evaluation of White Spot Formation 1>.

[0220]

[0221] As shown in Table 1, the occurrence of white clumps was suppressed in Examples 1 to 10 using the resin composition of this disclosure.

[0222] The disclosure of Japanese Patent Application No. 2025-050672 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A resin composition comprising: a resin that is at least one of a cyclized resin and a precursor of the cyclized resin; and an adhesion assistant, wherein the adhesion assistant includes a compound represented by the following general formula (1). In general formula (1), R １ is an alkyl group having 1 to 3 carbon atoms, R ２ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ３ is a group including a linear structure or a cyclic structure having 4 or more atoms, and m is an integer of 0 to 3.

2. In the compound represented by the general formula (1) above, R ３ The resin composition according to claim 1, having a structure that decomposes at 50°C to 300°C.

3. In the compound represented by the general formula (1), R ３ The resin composition according to claim 1, wherein the structure is represented by the following general formula (2). In general formula (2), R ４ The symbol (*) represents a group that dissociates upon heating, and the asterisk (*) represents the bond position.

4. The resin composition according to claim 1, wherein the resin is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.

5. The resin composition according to claim 4, wherein the resin comprises the polyimide precursor, and the polyimide precursor 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 ７ Each of these independently represents either a hydrogen atom or a monovalent organic group.

6. The resin composition according to claim 1, further comprising a photopolymerization initiator or a photoacid generator.

7. The resin composition according to claim 1, further comprising a crosslinking agent.

8. The resin composition according to claim 1, used for producing a redistribution layer.

9. A method for producing a cured product, comprising the steps of: applying a resin composition according to any one of claims 1 to 8 onto a substrate and drying it to form a resin film; and heat-treating the resin film.

10. A cured product obtained by curing the resin composition according to any one of claims 1 to 8.

11. The cured product according to claim 10, which is used as an interlayer insulating film, a redistribution layer, a cover coat layer, or a surface protective film.

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

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