JP2023039804A - Resin composition, method for manufacturing semiconductor device, cured product, and semiconductor device - Google Patents

Abstract

To provide a resin composition that can suppress diffusion of copper under a high-temperature and high-humidity condition.SOLUTION: A resin composition contains: at least one polymer (A) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor; and a nitrogen-containing organic silicon compound (B) having a nitrogen-containing skeleton and an organic silicon skeleton.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to a resin composition, a method for manufacturing a semiconductor device, a cured product, and a semiconductor device.

In recent years, three-dimensional mounting of semiconductor chips has been studied in order to improve the degree of integration of LSIs (Large Scale Integrated Circuits). Non-Patent Document 1 discloses an example of three-dimensional mounting of semiconductor chips.

When three-dimensional mounting of semiconductor chips is performed by C2W (Chip-to-Wafer) bonding, hybrid bonding technology used for W2W (Wafer-to-Wafer) bonding is used to perform fine bonding of wiring between devices. is being considered.

In C2W hybrid bonding, there is a possibility that positional deviation may occur due to thermal expansion of the base material, chip, etc. due to heating during bonding. In response to such a problem, Patent Literature 1 discloses an example of technology capable of lowering the bonding temperature by using a cyclic olefin resin.

JP 2019-204818 A

F.C. Chen et al., “System on Integrated Chips (SoIC TM) for 3D Heterogeneous Integration”,2019 IEEE 69th Electronic Components and Technology Conference (ECTC),p.594-599(2019)

When three-dimensional mounting of a semiconductor chip is performed by C2W (Chip-to-Wafer) bonding, W2W (Wafer-to-Wafer) bonding, etc., an insulation that is a cured product obtained by curing an electrode layer containing copper and a resin composition The substrates having the films or the substrate and the chip having the electrode layer and the insulating film are joined. The problem is that when the bonded structure is exposed to high temperature and high humidity conditions such as the HAST test after bonding substrates, chips, etc., copper from electrode layers, wiring, etc. tends to diffuse into the insulating film, resulting in a decrease in insulating properties. There is Therefore, a resin composition capable of suppressing the diffusion of copper under high temperature and high humidity conditions is desired.

The present disclosure has been made in view of the above, and provides a resin composition capable of suppressing diffusion of copper under high temperature and high humidity conditions, a method for manufacturing a semiconductor device using the above resin composition, and the above resin composition. and a semiconductor device comprising an organic insulating film obtained by curing the resin composition.

Specific means for achieving the above object are as follows.
<1> at least one polymer (A) selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors;
a nitrogen-containing organosilicon compound (B) having a nitrogen-containing skeleton and an organosilicon skeleton;
A resin composition comprising:
<2> The resin composition according to <1>, wherein the nitrogen-containing skeleton includes a heterocyclic structure containing a nitrogen atom.
<3> The polymer (A) contains a polyimide precursor, the polyimide precursor resin according to <1> or <2> containing a compound having a structural unit represented by the following general formula (1) Composition.

In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group.
<4> The resin composition according to <3>, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).

In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O —C(=O)—), silylene bond (—Si(R ^A ) ₂ —; two R ^A each independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (—O— (Si(R ^B ) ₂ —O—) _n ; each of the two R ^B independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more), or at least It represents a divalent group in which two are combined.
<5> The resin composition according to <3> or <4>, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H).

In formula (H), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer of 0-4. D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC (=O) -), a silylene bond (-Si(R ^A ) ₂ -; two R ^A each independently represent a hydrogen atom, an alkyl group or a phenyl group.), a siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; two R 2 ^B each independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more.) or a combination of at least two of these represents the group of
<6> In the general formula (1), the monovalent organic group for R ⁶ and R ⁷ is a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group. The resin composition according to any one of <3> to <5>.

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group.
<7> The resin composition according to any one of <1> to <6>, further comprising a solvent (C).
<8> The resin composition according to <7>, wherein the solvent (C) contains at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (7).

In formulas (3) to (7), R ¹ , R ² , R ⁸ and R ¹⁰ are each independently an alkyl group having 1 to 4 carbon atoms, and R ³ to R ⁷ and R ⁹ are each independently and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer of 0-8, t is an integer of 0-4, r is an integer of 0-4, and u is an integer of 0-3.
<9> The resin composition according to any one of <1> to <8>, further comprising (D) a photopolymerization initiator and (E) a polymerizable monomer.

<10> The resin composition according to any one of <1> to <9> is used to prepare at least one of the first organic insulating film and the second organic insulating film, and the following step (1 ) to step (5) to manufacture a semiconductor device.
Step (1) Prepare a first semiconductor substrate having a first substrate body, and the first organic insulating film and the first electrode provided on one surface of the first substrate body.
Step (2) Prepare a second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body.
Step (3) Individualizing the second semiconductor substrate to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one of the second electrodes. .
Step (4) Bonding the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other.
Step (5) Bonding the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.
<11> A cured product obtained by curing the resin composition according to any one of <1> to <9>.
<12> a first semiconductor substrate having a first substrate body, and the first organic insulating film and the first electrode provided on one surface of the first substrate body;
a semiconductor chip having a semiconductor chip substrate body, and an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body;
wherein the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together, and the first electrode of the first semiconductor substrate and the first electrode of the semiconductor chip are bonded together. 2 electrodes and are joined,
A semiconductor device, wherein at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film obtained by curing the resin composition according to any one of <1> to <9>.

According to the present disclosure, a resin composition capable of suppressing diffusion of copper under high temperature and high humidity conditions, a method for manufacturing a semiconductor device using the above resin composition, and a cured product obtained by curing the above resin composition and a semiconductor device comprising an organic insulating film formed by curing the resin composition described above.

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by a semiconductor device manufacturing method according to an embodiment of the present invention. 2A to 2D are diagrams sequentially showing a method for manufacturing the semiconductor device shown in FIG. FIG. 3 is a diagram showing in more detail the bonding method in the method of manufacturing the semiconductor device shown in FIG. FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and sequentially shows steps after the step shown in FIG. FIG. 5 is a diagram showing an example in which the semiconductor device manufacturing method according to one embodiment of the present invention is applied to Chip-to-Wafer (C2W). (A) is a top view showing a sample for a copper mass measurement test produced in each example and each comparative example, and (B) is a cross-sectional view taken along the line AA of (A).

Hereinafter, embodiments for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

In the present disclosure, “A or B” may include either A or B, or may include both.
In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
In the present disclosure, the term “layer” or “film” refers to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present, and only a part of the region. It also includes the case where it is formed.
In the present disclosure, the thickness of a layer or film is a value obtained by measuring the thickness of the target layer or film at five points and giving the arithmetic mean value.
The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, where the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of one layer or the total thickness of a plurality of layers, the thickness may be measured by observing the cross section of the object to be measured using an electron microscope.
In the present disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group".
In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms in the substituent.
When embodiments are described in the present disclosure with reference to drawings, the configurations of the embodiments are not limited to the configurations shown in the drawings. In addition, the sizes of the members in each drawing are conceptual, and the relative relationship between the sizes of the members is not limited to this.

<Resin composition>
The resin composition of the present disclosure contains at least one polymer (A) selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors, and a nitrogen-containing skeleton and an organic silicon skeleton. and a nitrogen organosilicon compound (B).

The resin composition of the present disclosure can suppress diffusion of copper under high temperature and high humidity conditions. The reason for this is presumed to be that the nitrogen-containing organosilicon compound (B) contained in the resin composition exerted an anticorrosive effect and suppressed corrosion of copper. A resin composition containing a nitrogen-containing organosilicon compound (B) can reduce the amount of rust inhibitor such as benzotriazole to be used. Furthermore, the resin composition containing the nitrogen-containing organosilicon compound (B) has excellent adhesion to substrates and the like, and can reduce the amount of silane coupling agent used.

The resin composition of the present disclosure is, for example, C2W (Chip-to-Wafer) bonding, W2W (Wafer-to-Wafer) bonding and other hybrid bonding applications, adhesive layers, insulating layers, rewiring insulating layers, etc. Forming applications can be used.

Components contained in the resin composition of the present disclosure and components that may be contained are described below.

[Polymer (A)]
The resin composition of the present disclosure contains at least one polymer (A) selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors (hereinafter also referred to as "component (A)". )including.

Polymer (A) may be a single polymer or a combination of two or more polymers. For example, the polymer (A) may be a polyimide, a polyimide precursor, a polybenzoxazole, or a polybenzoxazole precursor, or a combination of a polyimide and a polyimide precursor, or a polybenzoxazole and a polybenzoxazole. It may also be a combination of oxazole precursors.

(polyimide)
The polyimide is not particularly limited as long as it is a polymer compound having a plurality of structural units containing an imide bond. For example, it preferably contains a compound having a structural unit represented by the following general formula (X). This tends to result in an insulating film exhibiting high reliability.

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 later.
Polyimide may have a plurality of structural units represented by the general formula (X), and X and Y in the plurality of structural units may be the same or different.

(polyimide precursor)
A polyimide precursor means a compound corresponding to either a polyamic acid or a compound in which hydrogen atoms of at least part of the carboxy groups in the polyamic acid are substituted with monovalent organic groups. The polyimide precursor preferably contains a polyimide precursor having a polymerizable unsaturated bond.

The polyimide precursor preferably contains a compound having a structural unit represented by the following general formula (1). This tends to result in an insulating film exhibiting high reliability.

In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. ^R6 and ^R7 each independently represent a hydrogen atom or a monovalent organic group.
The polyimide precursor may have a plurality of structural units represented by the general formula (1), and X, Y, R ⁶ and R ⁷ in the plurality of structural units may be the same or different. may be
The combination of R ⁶ and R ⁷ is not particularly limited as long as they are each independently a hydrogen atom or a monovalent organic group. For example, both R ⁶ and R ⁷ may be a hydrogen atom, or one may be a hydrogen atom and the other may be a monovalent organic group described later, and both may be the same or different monovalent organic groups may be As described above, when the polyimide precursor has a plurality of structural units represented by the general formula (1), the combination of R ⁶ and R ⁷ in each structural unit may be the same or different. .

In the general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. .
The tetravalent organic group represented by X may contain an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (eg, the number of carbon atoms constituting the aromatic ring is 6 to 20), aromatic heterocyclic groups (eg, the number of atoms constituting the heterocyclic ring is 5 to 20), and the like. be done. The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Aromatic hydrocarbon groups include benzene ring, naphthalene ring, phenanthrene ring and the like.
When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, amino groups and the like.
When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, and contains 1 to 3 benzene rings. is more preferred, and it is even more preferred to contain one or two benzene rings.
When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be connected by 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 silylene bond (--Si(R ^A ) ₂ --; each of two R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (—O—(Si(R ^B ) ₂ —O—) _n ; each of the two R ^B independently represents a hydrogen atom, an alkyl group or a phenyl group, and n is an integer of 1 or 2 or more ), or a composite linking group in which at least two of these linking groups are combined. In addition, two benzene rings may be bonded at two locations by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

In the general formula (1), when the tetravalent organic group represented by X contains a benzene ring, the -COOR ⁶ group and the -CONH- group are preferably ortho-positioned to each other, and the -COOR ⁷ group and - The CO-groups are preferably ortho-positioned to each other.

Specific examples of the tetravalent organic group represented by X include groups represented by the following formulas (A) to (F). Among them, from the viewpoint of obtaining an insulating film with excellent flexibility, a group represented by the following formula (E) is preferable, represented by the following formula (E), and C is more preferably a group containing an ether bond. It is preferably an ether bond, more preferably an ether bond. The following formula (F) is a structure in which C in the following formula (E) is a single bond.
Note that the present disclosure is not limited to the following specific examples.

In Formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups not conjugated to a benzene ring include a methylene group, a methylene halide group, a methylmethylene halide group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), and a silylene bond. (—Si(R ^A ) ₂ —; each of the two R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group) and the like. Among them, A and B are each independently preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O —C(=O)—), silylene bond (—Si(R ^A ) ₂ —; two R ^A each independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (—O— (Si(R ^B ) ₂ —O—) _n ; each of the two R ^B independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more), or at least It represents a divalent group in which two are combined. C preferably contains an ether bond, preferably an ether bond.
Moreover, C may have a structure represented by the following formula (C1).

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 1 carbon atom. or 2 alkylene groups are more preferred.
Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene; 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, 1,1-dimethyltrimethylene 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- branched chain alkylene groups such as a dimethyltetramethylene group, a 1,3-dimethyltetramethylene group, a 2,3-dimethyltetramethylene group and a 1,4-dimethyltetramethylene group; Among these, a methylene group is preferred.

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. More preferably, it is a halogenated alkylene group having 1 to 3 carbon atoms.
Specific examples of the halogenated alkylene group represented by C in formula (E) include at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) being a fluorine atom, a chlorine atom, or the like. An alkylene group substituted with a halogen atom is mentioned. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group and the like are preferable.

The alkyl group represented by R ^A or R ^B contained in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. is more preferred, and an alkyl group having 1 or 2 carbon atoms is even more preferred. Specific examples of the alkyl group represented by R ^A or R ^B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and the like. mentioned.

In the general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms. .
The 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. The divalent aromatic group includes a divalent aromatic hydrocarbon group (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), a divalent aromatic heterocyclic group (for example, a The number of atoms is 5 to 20), etc., and divalent aromatic hydrocarbon groups are preferred.

Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulas (G) to (I). Among them, from the viewpoint of obtaining an insulating film with excellent flexibility, a group represented by the following formula (H) is preferable, and more preferably represented by the following formula (H), and D is a group containing an ether bond. It is preferably an ether bond, more preferably an ether bond.

In formulas (G) to (I), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer of 0 to 4. show.
In formula (H), D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O —C(=O)—), silylene bond (—Si(R ^A ) ₂ —; two R ^A each independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (—O— (Si(R ^B ) ₂ —O—) _n ; each of the two R ^B independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more), or at least It represents a divalent group in which two are combined. D may also have a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as specific examples of C in formula (E).
D in formula (H) is preferably 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.

The alkyl group represented by R in formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. , more preferably an alkyl group having 1 or 2 carbon atoms.
Specific examples of the alkyl group represented by R in formulas (G) to (I) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, A t-butyl group and the like can be mentioned.

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

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

n in Formulas (G) to (I) is each independently preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.

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

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. More preferably, it is an alkylene group with a number of 1-10.
Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a 2-methylpentamethylene group. , 2-methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group and the like.

The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, 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.

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. 1 to 4 alkylene oxide structures are more preferred. Among them, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The number of unit structures in the polyalkylene oxide structure may be one, or two or more.

As the divalent group having a polysiloxane structure represented by Y, a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. A divalent group having a polysiloxane structure is included.
Specific examples of the alkyl group having 1 to 20 carbon atoms 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, n-dodecyl group and the like. Among these, a methyl group is preferred.
The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. When the aryl group has a substituent, specific examples of the substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include phenyl group, naphthyl group, benzyl group and the like. Among these, a phenyl group is preferred.
The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or two or more types.
A silicon atom constituting a divalent group having a polysiloxane structure represented by Y is an NH group in the general formula (1) via an alkylene group such as a methylene group, an ethylene group, an arylene group such as a phenylene group, or the like. may be combined with

The group represented by formula (I) is preferably a group represented by formula (I') below.

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

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. As a combination of a tetravalent organic group represented by X and a divalent organic group represented by Y, X is a group represented by formula (E) and Y is represented by formula (H). A combination of groups; X is a group represented by formula (E), Y is a combination of groups represented by formula (I); X is a group represented by formula (E), and Y is a formula A combination of a group represented by (G) and a group represented by formula (H) may be mentioned.

^R6 and ^R7 each independently represent 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, and a group represented by the following general formula (2), an ethyl group, It is more preferably either an isobutyl group or a t-butyl group, more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and the following general formula It is particularly preferred to contain a group represented by (2). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-line transmittance is high, and even when cured at a low temperature of 400 ° C. or less. It tends to form a good cured product.
Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group and the like, among which ethyl group, Isobutyl and t-butyl groups are preferred.

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group.

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

As for the combination of R ⁸ to R ¹⁰ in general formula (2), a combination in which R ⁸ and R ⁹ are hydrogen atoms and R ¹⁰ is a hydrogen atom or a methyl group is preferred.

R ^x in general formula (2) 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.
The number of carbon atoms in R ^x is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

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

(A) When the component contains a compound having a structural unit represented by the above general formula (1), the total of R ⁶ and R ⁷ of all structural units contained in the compound represented by general formula (2) The ratio of R ⁶ and R ⁷ , which are groups to be combined, is preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more. The upper limit is not particularly limited, and may be 100 mol %.
In addition, the aforementioned ratio may be 0 mol % or more and less than 60 mol %.

The group represented by general formula (2) is preferably a group represented by general formula (2') below.

In general formula (2′), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1-3 carbon atoms, and q represents an integer of 1-10.

q in the general formula (2′) is an integer of 1 to 10, preferably an integer of 2 to 5, more preferably 2 or 3.

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

When the component (A) is a polyimide or a polyimide precursor, it may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (X) or general formula (1), X corresponds to a residue derived from tetracarboxylic dianhydride, and Y corresponds to a residue derived from a diamine compound. The component (A) may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3′,4,4′- Tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4′-(2,3-di Carboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis{4′-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4′-( 3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-di carboxyphenyl)fluorene dianhydride and the like.
Tetracarboxylic dianhydrides may be used alone or in combination of two or more.

2,2′-dimethylbiphenyl-4,4′-diamine Specific examples of diamine compounds include 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-difluoro-4 ,4'-diaminobiphenyl, 2,2'-dimethylbiphenyl-4,4'-diamine, 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-tolysine, o-tolysine 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-aminophenyl)propane, 9,9-bis(4 -aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl- 1,7-diaminoheptane, 2-methyl-1,8-diaminooc tane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane and the like. Preferred diamine compounds are m-phenylenediamine, 4,4'-diaminodiphenyl ether and 2,2'-dimethylbiphenyl-4,4'-diamine.
A diamine compound may be used individually by 1 type, or may use 2 or more types together.

A compound having a structural unit represented by the general formula (1) and in which at least one of R ⁶ and R ⁷ in the general formula (1) is a monovalent organic group is represented by the following general formula (8) A tetracarboxylic dianhydride represented by and a compound represented by R—OH are reacted in an organic solvent such as N-methyl-2-pyrrolidone to form a diester derivative, and then the diester derivative and H ₂ N -Y-NH ₂ is subjected to a condensation reaction, or a tetracarboxylic dianhydride and a diamine compound represented by H ₂ N--Y--NH ₂ are reacted in an organic solvent. It can be obtained by obtaining a polyamic acid, adding a compound represented by R—OH, and reacting it in an organic solvent to introduce an ester group.
Here, Y in the diamine compound represented by H ₂ N--Y--NH ₂ is the same as Y in general formula (1), and specific examples and preferred examples are also the same. Further, R in the compound represented by R--OH represents a monovalent organic group, and specific examples and preferable examples are the same as those of R ⁶ and R ⁷ in general formula (1).
Each of the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H ₂ N--Y--NH ₂ and the compound represented by R--OH may be used alone. Well, you may combine two or more types.
The above-mentioned compound contained in the component (A) is a diester derivative obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH, followed by thionyl chloride, etc. can be obtained by reacting a diamine compound represented by H ₂ N--Y--NH ₂ with the acid chloride.
The above-mentioned compound contained in component (A) is obtained by reacting a compound represented by R—OH with a tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, and then a carbodiimide compound. It can be obtained by reacting a diamine compound represented by H ₂ N--Y--NH ₂ with a diester derivative in the presence.
The aforementioned compound contained in the component (A) is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H ₂ N--Y--NH ₂ to form a polyamic acid. After that, the polyamic acid is isoimidated in the presence of trifluoroacetic anhydride, and then reacted with a compound represented by R--OH. Alternatively, a part of the tetracarboxylic dianhydride is reacted in advance with a compound represented by R—OH to form a partially esterified tetracarboxylic dianhydride and H ₂ N—Y—NH ₂ . may be reacted with the diamine compound to be used.

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

As the compound represented by R-OH used in the synthesis of the above-mentioned compound contained in component (A), a compound in which a hydroxy group is bonded to R ^x of the group represented by general formula (2), a compound represented by general formula ( A compound or the like in which a hydroxy group is bonded to the terminal methylene group of the group represented by 2') may also be used. 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, acrylic 2-hydroxypropyl acid, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like, and among them, methacrylic acid 2 -hydroxyethyl and 2-hydroxyethyl acrylate are preferred.

(polybenzoxazole)
Polybenzoxazole means a polymer containing a benzoxazole structure in its structural unit.
Polybenzoxazole preferably contains a compound having a structural unit represented by general formula (Z-1) below.

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

Polybenzoxazole is 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 examples include terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), and phthalic acid (benzene-1,2-dicarboxylic acid). , 4,4′-dicarboxydiphenylmethane, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxybiphenyl and 2,2-(4,4′-dicarboxydiphenyl)propane.
The diaminodihydroxy compound is 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.

(polybenzoxazole precursor)
The polybenzoxazole precursor is polyhydroxyamide, and preferably contains, for example, a compound having a structural unit represented by the following general formula (Z-2). This tends to result in an insulating film exhibiting high reliability.

In general formula (Z-2), U represents a single bond or a divalent linking group, and W represents a divalent linking group.
The polybenzoxazole precursor may have a plurality of structural units represented by the general formula (Z-2), and U and W in the plurality of structural units may be the same or different. good too.

A polybenzoxazole precursor is obtained, for example, by a condensation polymerization reaction between a dicarboxylic acid and a diaminodihydroxy compound. Examples of dicarboxylic acids and diaminodihydroxy compounds include the dicarboxylic acids and diaminodihydroxy compounds exemplified in the section on polybenzoxazole described above.

The molecular weight of component (A) is not particularly limited.
The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be obtained by conversion using a standard polystyrene calibration curve.

The resin composition of the present disclosure may contain resin components other than component (A). For example, from the viewpoint of heat resistance, the resin composition of the present disclosure includes novolak resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyvinyl chloride resins, and the like. It may contain other resins. Other resins may be used singly or in combination of two or more.

In the resin composition of the present disclosure, the content of component (A) with respect to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 90% by mass. % to 100 mass %.

(Nitrogen-containing organosilicon compound (B))
The resin composition of the present disclosure contains a nitrogen-containing organosilicon compound (B) having a nitrogen-containing skeleton and an organosilicon skeleton (hereinafter also referred to as "component (B)").

The nitrogen-containing skeleton is not particularly limited as long as it contains one or more nitrogen atoms, and for example, a heterocyclic structure containing nitrogen atoms is preferable. Heterocyclic structures containing nitrogen atoms include benzotriazole, triazole, pyrazole, tetrazole, benzimidazole, imidazole, and purine groups. Among them, a benzotriazole group is preferred. In heterocyclic structures containing nitrogen atoms, hydrogen atoms attached to the heterocyclic ring may be substituted with other atoms or functional groups.

Organosilicon skeletons include structures in which organic groups are attached to one or more silicon atoms. Examples of the organic group include an alkoxy group, an alkyl group, etc., which may have a substituent.

Examples of organosilicon skeletons include trialkylsilyl groups, trialkoxysilyl groups, alkyldialkoxysilyl groups, and dialkylalkoxysilyl groups.

Alkyl groups constituting trialkylsilyl groups, alkyldialkoxysilyl groups, dialkylalkoxysilyl groups and the like include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and s-butyl group. , t-butyl group and the like. The three alkyl groups constituting the trialkylsilyl group and the two alkyl groups constituting the dialkylalkoxysilyl group may independently be the same or different.

Examples of alkoxy groups constituting trialkoxysilyl groups, alkyldialkoxysilyl groups, dialkylalkoxysilyl groups and the like include methoxy, ethoxy, propoxy and butoxy groups. The three alkoxy groups constituting the trialkoxysilyl group and the two alkoxy groups constituting the alkyldialkoxysilyl group may independently be the same or different.

Component (B) is preferably a compound in which a nitrogen-containing skeleton and an organic silicon skeleton are bonded via a single bond or a divalent linking group, and the heterocyclic structure containing a nitrogen atom and the organic silicon skeleton are preferably It is more preferably a compound bonded via a single bond or a divalent linking group, and a single bond between a benzotriazole group and a trialkylsilyl group, trialkoxysilyl group, alkyldialkoxysilyl group or dialkylalkoxysilyl group. or a compound bonded via a divalent linking group.

In the resin composition of the present disclosure, the content of component (B) may be 0.1 parts by mass to 20 parts by mass, or 0.5 parts by mass to 15 parts by mass, relative to 100 parts by mass of component (A). It may be 1 part by mass or 1 part by mass to 10 parts by mass.

(Solvent (C))
The resin composition of the present disclosure may contain a solvent (C) (hereinafter also referred to as “component (C)”). Component (C) contains at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (7), for example, from the viewpoint of reducing the reproductive toxicity and environmental load of the resin composition. is preferred, and it is more preferred to contain at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (6).

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

In formula (3), s is preferably 0.
In formula (4), the alkyl group having 1 to 4 carbon atoms for R ² is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, more preferably 1.
In formula (5), the C 1-4 alkyl group for R ³ is preferably a methyl group, an ethyl group, a propyl group or a butyl group. The alkyl group having 1 to 4 carbon atoms for R ⁴ and R ⁵ is preferably a methyl group or an ethyl group.
In formula (6), the alkyl group having 1 to 4 carbon atoms for R ⁶ to R ⁸ is preferably a methyl group or an ethyl group. r is preferably 0 or 1, more preferably 0.
In formula (7), the alkyl group having 1 to 4 carbon atoms for R ⁹ and R ¹⁰ is preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0;

Component (C) may be, for example, at least one of the compounds represented by formulas (4), (5) and (6), the compound represented by formula (5) or the compound represented by formula (7) It may be a compound represented by.

Specific examples of the component (C) include the following compounds.

The component (C) contained in the resin composition of the present disclosure is not limited to the compounds described above, and may be other solvents. Component (C) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, or the like.

Ester solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates such as methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate and ethyl ethoxyacetate), 3-alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxypropionate acid ethyl), 2-alkoxypropionate alkyl esters such as methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, and propyl 2-alkoxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -ethyl 2-alkoxy-2-methylpropionate such as ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. is mentioned.

Ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene. Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of solvents for ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone and 3-heptanone.
Limonene etc. are mentioned as a solvent of hydrocarbons.
Solvents for aromatic hydrocarbons include toluene, xylene, anisole and the like.
Dimethyl sulfoxide etc. are mentioned as a solvent of sulfoxides.

Preferred examples of solvents for component (C) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

In the resin composition of the present disclosure, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of NMP may be 1% by mass or less with respect to the total amount of the resin composition, and the total amount of component (A) may be It may be 3% by mass or less.

In the resin composition of the present disclosure, the content of component (C) is preferably 50 parts by mass to 10000 parts by mass with respect to 100 parts by mass of component (A).

Component (C) is at least one solvent selected from the group consisting of compounds represented by formulas (3) to (6), solvent (1), ester solvents, ether solvents, and ketone solvents. , a hydrocarbon solvent, an aromatic hydrocarbon solvent, and a sulfoxide solvent (2).
Further, the content of the solvent (1) may be 5% by mass to 100% by mass, or 5% by mass to 50% by mass, with respect to the total of the solvent (1) and the solvent (2). good.
The content of the solvent (1) may be 10 parts by mass to 1000 parts by mass, or may be 10 parts by mass to 100 parts by mass, or 10 parts by mass to It may be 50 parts by mass.

The resin composition of the present disclosure preferably further contains a photopolymerization initiator (D) and a polymerizable monomer (E) (hereinafter also referred to as component (D) and component (E), respectively). In addition, the resin composition of the present disclosure may further contain a thermal polymerization initiator (F) (hereinafter also referred to as component (F)). Preferred forms of components (D) to (F) are described below.

(Photoinitiator (D))
The resin composition of the present disclosure preferably contains a photopolymerization initiator (D). This makes it possible to reduce the number of processes for manufacturing the electrodes in the process of manufacturing the semiconductor device, and reduce the cost of the entire process when manufacturing the semiconductor device.

Specific examples of component (D) include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- 4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, Benzophenone derivatives such as fluorenone; acetophenone, 2,2-diethoxyacetophenone, 3′-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone acetophenone derivatives such as; thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives; benzoin, benzoin Benzoin derivatives such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin, propylbenzoin; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1, 2-propanedione-2-(O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-( O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) and other oxime derivatives; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5- Diphenylimidazole dimer, 2-(o- or p-methoxyphenyl phenyl)-4,5-diphenylimidazole dimer and other aromatic biimidazoles; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and other acyl Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF) and the like, such as phosphine oxide derivatives.
(D) Component may be used individually by 1 type, and may combine 2 or more types.
Among these, oxime compound derivatives are preferable from the viewpoint of not containing a metal element, high reactivity and high sensitivity.

When the resin composition of the present disclosure contains the (D) component, the content of the (D) component is 0.00% per 100 parts by mass of the (A) component, from the viewpoint that the photocrosslinking is likely to be uniform in the film thickness direction. 1 part by mass to 20 parts by mass is preferable, 0.1 part by mass to 10 parts by mass is more preferable, and 0.1 part by mass to 6 parts by mass is even more preferable.

The resin composition of the present disclosure may contain an antireflection agent that suppresses reflected light from the direction of the substrate from the viewpoint of improving photosensitive properties.

(Polymerizable monomer (E))
The resin composition of the present disclosure preferably contains a polymerizable monomer (E). Component (E) preferably has at least one group containing a polymerizable unsaturated double bond, and from the viewpoint of being suitably polymerizable in combination with a photopolymerization initiator, at least a (meth)acrylic group It is more preferable to have one. From the viewpoint of improving crosslink density and improving photosensitivity, it preferably has 2 to 6 groups containing polymerizable unsaturated double bonds, more preferably 2 to 4 groups.
A polymerizable monomer may be used individually by 1 type, and may combine 2 or more types.

The (meth)polymerizable monomer having an acrylic group is not particularly limited, and examples thereof include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, methacrylates, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, Trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate , ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, 2-hydroxyethyl (meth)acrylate, 1,3-bis((meth)acryloyloxy)-2 - hydroxypropane, ethylene oxide (EO) modified bisphenol A diacrylate and ethylene oxide (EO) modified bisphenol A dimethacrylate.

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

The component (E) is not limited to a compound having a group containing a polymerizable unsaturated double bond, and may be a compound having a polymerizable group other than an unsaturated double bond group (for example, an oxirane ring). .

When the resin composition of the present disclosure contains component (E), the content of component (E) is not particularly limited, and may be 1 part by mass to 100 parts by mass with respect to 100 parts by mass of component (A). It is preferably from 1 part by mass to 75 parts by mass, and even more preferably from 1 part by mass to 50 parts by mass.

(Thermal polymerization initiator (F))
From the viewpoint of improving the physical properties of the cured product, the resin composition of the present disclosure preferably contains a thermal polymerization initiator (F).

Specific examples of component (F) include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy ) Cyclohexane, peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide Hydroperoxides such as dicumyl peroxide, dialkyl peroxide such as di-t-butyl peroxide, dilauroyl peroxide, diacyl peroxide such as dibenzoyl peroxide, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2- ethylhexyl) peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, 1,1,3,3- Peroxy esters such as tetramethylbutyl peroxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide and the like. The thermal polymerization initiator may be used singly or in combination of two or more.

When the resin composition of the present disclosure contains component (F), the content of component (F) may be 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of component (A). It may be 1 part by mass to 15 parts by mass, or may be 5 parts by mass to 10 parts by mass.

(Polymerization inhibitor (G))
The resin composition of the present disclosure may contain a polymerization inhibitor (G) (hereinafter also referred to as “(G) component”) from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.

Specific examples of component (G) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl- 2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, hindered phenol compounds and the like. A polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types. Combining two or more polymerization inhibitors tends to make it easier to adjust the photosensitive characteristics due to the difference in reactivity. The hindered phenol-based compound may have both the function of a polymerization inhibitor and the function of an antioxidant described later, or may have either one of the functions.

When the resin composition of the present disclosure contains component (G), the content of component (G) is 100 parts by mass of component (A) from the viewpoint of the storage stability of the resin composition and the heat resistance of the resulting cured product. For, it is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass .

The resin composition of the present disclosure may further contain antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors or nitrogen-containing compounds.

(Antioxidant)
The resin composition of the present disclosure may contain an antioxidant from the viewpoint of suppressing a decrease in adhesiveness by scavenging oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, and the like. By including an antioxidant in the resin composition of the present disclosure, it is possible to suppress oxidation of the electrode during an insulation reliability test.

Specific examples of antioxidants include 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,
2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate , 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3- methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate], N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), isooctyl-3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6 -t-butylphenol),
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-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,
pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate], 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-2,5-dimethylbenzyl)-1,3,5-triazine -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1 , 3,5-triazine-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)- trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-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.
An antioxidant may be used individually by 1 type, and may combine 2 or more types.

When the resin composition of the present disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of component (A). It is more preferably 1 part by mass to 10 parts by mass, and even more preferably 0.1 part by mass to 5 parts by mass.

(coupling agent)
The resin composition of the present disclosure may contain a coupling agent. In the heat treatment, the coupling agent reacts with the component (A) to be crosslinked, or the coupling agent itself is polymerized. This tends to further improve the adhesiveness between the obtained cured product and the substrate.

Specific examples of the coupling agent are not particularly limited. Coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl) Succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1 , 4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N Silane coupling agents such as '-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane; aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetate aluminum-based adhesion promoters such as aluminum acetate diisopropylate; and the like.
A coupling agent may be used individually by 1 type, and may combine 2 or more types.

When the resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass, preferably 0.3 parts by mass, relative to 100 parts by mass of component (A). ~10 parts by mass is more preferable, and 1 part by mass to 10 parts by mass is even more preferable.
In the resin composition of the present disclosure, the content of the coupling agent may be 0.5 parts by mass or less, or may be 0.3 parts by mass or less with respect to 100 parts by mass of component (A). , 0.1 parts by mass or less. In the resin composition of the present disclosure, since the nitrogen-containing organosilicon compound (B) is included, it is possible to improve the adhesion between the cured product and the substrate, so that the amount of the coupling agent can be reduced. be.
In the present disclosure, the nitrogen-containing organosilicon compound (B) shall not be classified as a coupling agent.

(Surfactant and leveling agent)
The resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent. By including at least one of a surfactant and a leveling agent in the resin composition, coatability (for example, suppression of striation (unevenness in film thickness)), improvement of adhesion, compatibility of compounds in the resin composition, etc. can be improved.

Surfactants or leveling agents include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like.

Surfactants and leveling agents may be used singly or in combination of two or more.

When 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 the leveling agent is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of component (A). It is preferably 0.05 to 5 parts by mass, even more preferably 0.05 to 3 parts by mass.

(anti-rust)
The resin composition of the present disclosure may contain a rust inhibitor from the viewpoint of suppressing corrosion of metals such as copper and copper alloys, and from the viewpoint of suppressing discoloration of the metals. Examples of rust preventives include azole compounds and purine derivatives.

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, 2-[2-hydroxy- 3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 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)benzo triazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.

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, 8-aminoadenine, 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 derivatives thereof. be done.

The rust preventives may be used singly or in combination of two or more.

When the resin composition of the present disclosure contains a rust preventive, the content of the rust preventive is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of component (A). It is more preferably from 1 part by mass to 5 parts by mass, and even more preferably from 0.5 part by mass to 3 parts by mass. In particular, when the content of the rust inhibitor is 0.1 parts by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the resin composition of the present disclosure is applied to the surface of copper or copper alloy. be done.
In the resin composition of the present disclosure, the content of the rust inhibitor may be 0.5 parts by mass or less, or 0.1 parts by mass or less, relative to 100 parts by mass of component (A). , 0.01 parts by mass or less.
In the resin composition of the present disclosure, it is possible to suppress corrosion of metals such as copper and copper alloys by including the nitrogen-containing organosilicon compound (B), so it is possible to reduce the amount of rust inhibitor. is.
In the present disclosure, the nitrogen-containing organosilicon compound (B) is not classified as a rust inhibitor.

The resin composition of the present disclosure may contain a nitrogen-containing compound from the viewpoint of promoting the imidization reaction of component (A) to obtain a highly reliable cured product.

Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N- phenylethanolamine, 4-phenylmorpholine, 2,2′-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide , 4-aminoacetophenone, among others, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2 '-(4-methylphenylimino)diethanol and the like are preferred. A nitrogen-containing compound may be used individually by 1 type, and may combine 2 or more types.

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

In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group. and at least one (preferably one) of R _31A to R _33A is a monovalent aromatic group. Adjacent groups of R _31A to R _33A may form a ring structure. The ring structure to be formed includes a 5-membered ring, a 6-membered ring, etc. which may have a substituent such as a methyl group and a phenyl group. A hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than a hydroxy group.

In formula (17), at least one (preferably one) of R _31A to R _33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic It is preferably a family group.

In formula (17), the monovalent aliphatic hydrocarbon groups of R _31A to R _33A preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. A monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, or the like.

In formula (17), the monovalent aliphatic hydrocarbon group having a hydroxy group of R _31A to R _33A is a monovalent aliphatic hydrocarbon group of R _31A to R _33A , and one or more hydroxy groups are bonded to it. A group having 1 to 3 hydroxy groups is more preferred. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group, a hydroxyethyl group, etc. Among them, a hydroxyethyl group is preferred.

The monovalent aromatic groups of R _31A to R _33A in formula (17) include monovalent aromatic hydrocarbon groups, monovalent aromatic heterocyclic groups and the like, and monovalent aromatic hydrocarbon groups are preferred. The monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
A phenyl group, a naphthyl group, etc. are mentioned as a monovalent aromatic hydrocarbon group.

The monovalent aromatic groups of R _31A to R _33A in formula (17) may have a substituent. The substituents include monovalent aliphatic hydrocarbon groups represented by R _31A to R _33A of formula (17), and monovalent aliphatic hydrocarbons having hydroxy groups represented by R _31A to R _33A of formula (17) above. and the same groups as above.

When the resin composition of the present disclosure contains a nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of component (A). From the viewpoint of properties, it is more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass.

<Cured product>
The cured product of the present disclosure is obtained by curing the resin composition of the present disclosure. The cured product is used for, for example, insulating layers, adhesive layers, and rewiring insulating layers.

<Semiconductor device>
A semiconductor device of the present disclosure includes: a first semiconductor substrate having a first substrate body; the first organic insulating film and the first electrode provided on one surface of the first substrate body; a semiconductor chip substrate body; a semiconductor chip having an organic insulating film portion and a second electrode provided on one surface of a semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate and the organic insulating film of the semiconductor chip. the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are bonded together, and at least one of the first organic insulating film and the organic insulating film portion A semiconductor device is an insulating film obtained by curing the disclosed resin composition.
In the semiconductor device of the present disclosure, since at least one of the first organic insulating film and the organic insulating film portion is an insulating film formed by curing the resin composition of the present disclosure, diffusion of copper is suppressed under high temperature and high humidity conditions. It is possible. Also, the semiconductor device of the present disclosure can be manufactured through steps (1) to (5) described below.

<Method for manufacturing a semiconductor device>
In the method for manufacturing a semiconductor device of the present disclosure, a semiconductor device is manufactured using the resin composition of the present disclosure. Specifically, a semiconductor device can be manufactured through steps (1) to (5) using the resin composition of the present disclosure.
Step (1) Prepare a first semiconductor substrate having a first substrate body, and the first organic insulating film and the first electrode provided on one surface of the first substrate body.
Step (2) Prepare a second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body.
Step (3) Individualizing the second semiconductor substrate to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one of the second electrodes. .
Step (4) Bonding the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other.
Step (5) Bonding the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.

The resin composition of the present disclosure may be a negative photosensitive resin composition or a positive photosensitive resin composition. In addition, the negative photosensitive resin composition or the positive photosensitive resin composition arranges a plurality of terminal electrodes on the first organic insulating film provided on one surface of the first substrate body in the step (1). and providing a plurality of through holes for arranging a plurality of terminal electrodes in the second organic insulating film provided on one surface of the second substrate body in the step (2). It may be used for at least one of providing.

Hereinafter, one embodiment of the semiconductor device of the present disclosure and one embodiment of the method for manufacturing the semiconductor device of the present disclosure will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and overlapping descriptions are omitted. In addition, unless otherwise specified, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Furthermore, the dimensional ratios of the drawings are not limited to the illustrated ratios.

(Example of semiconductor device)
FIG. 1 is a cross-sectional view schematically showing an example of the semiconductor device of the present disclosure. As shown in FIG. 1, a semiconductor device 1 is an example of a semiconductor package, and includes a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar portion 30, and a rewiring layer 40. , a substrate 50 and a circuit board 60 .

The first semiconductor chip 10 is a semiconductor chip such as an LSI (Large Scale Integrated Circuit) chip or a CMOS (Complementary Metal Oxide Semiconductor) sensor, and has a three-dimensional mounting structure in which the second semiconductor chip 20 is mounted downward. there is The second semiconductor chip 20 is a semiconductor chip such as an LSI or a memory, and is a chip component having a smaller area in plan view than the first semiconductor chip 10 . The second semiconductor chip 20 is chip-to-chip (C2C) bonded to the rear surface of the first semiconductor chip 10 . The terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 and the insulating films surrounding them are micro-joined firmly without misalignment by hybrid bonding, the details of which will be described later.

The pillar portion 30 is a connection portion in which a plurality of pillars 31 made of metal such as copper (Cu) are sealed with a resin 32 . The plurality of pillars 31 are conductive members extending from the upper surface of the pillar section 30 toward the lower surface. The plurality of pillars 31 may have, for example, a cylindrical shape with a diameter of 3 μm or more and 20 μm or less (in one example, a diameter of 5 μm), and may be arranged so that the center-to-center distance of each pillar 31 is 15 μm or less. The plurality of pillars 31 flip-chip connect the terminal electrodes on the lower side of the first semiconductor chip 10 and the terminal electrodes on the upper side of the rewiring layer 40 . By using the pillar portion 30, in the semiconductor device 1, connection electrodes can be formed without using a technique of making holes in a mold called TMV (Through mold via) for solder connection. The pillar part 30 has, for example, the same thickness as the second semiconductor chip 20, and is arranged laterally of the second semiconductor chip 20 in the horizontal direction. A plurality of solder balls may be arranged instead of the pillar portion 30, and the terminal electrodes on the lower side of the first semiconductor chip 10 and the terminal electrodes on the upper side of the rewiring layer 40 are electrically connected by the solder balls. You may

The rewiring layer 40 is a wiring layer having a terminal pitch conversion function, which is a function of the package substrate. This is the layer on which the rewiring pattern is formed. The rewiring layer 40 is formed with the first semiconductor chip 10, the second semiconductor chip 20, etc. turned upside down (see FIG. 4D).

The rewiring layer 40 electrically connects the terminal electrodes on the lower surface of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via the pillar portions 30 to the terminal electrodes of the substrate 50 . The terminal pitch of the substrate 50 is wider than the terminal pitch of the pillars 31 and the terminal pitch of the second semiconductor chip 20 . Various electronic components 51 may be mounted on the substrate 50 . In addition, when there is a large difference in terminal pitch between the rewiring layer 40 and the substrate 50, an inorganic interposer or the like is used between the rewiring layer 40 and the substrate 50 to electrically connect the rewiring layer 40 and the substrate 50. You can make a connection.

The circuit board 60 mounts the first semiconductor chip 10 and the second semiconductor chip 20 thereon, and is electrically connected to the board 50 connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic components 51, and the like. and a substrate having therein a plurality of through electrodes. In the circuit board 60 , terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 are electrically connected to terminal electrodes 61 provided on the back surface of the circuit board 60 by a plurality of through electrodes.

(An example of a method for manufacturing a semiconductor device)
Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to FIGS. 2 to 4. FIG. 2A to 2D are diagrams sequentially showing a method for manufacturing the semiconductor device shown in FIG. FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method of manufacturing the semiconductor device shown in FIG. FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and sequentially shows steps after the step shown in FIG.

The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
(a) a step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10;
(b) a step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20;
(c) Polish one surface 101a, which is the surface of the first semiconductor substrate 100, by using the CMP method so that each surface 103a of the terminal electrode 103 is at the same position as or protrudes from the surface 102a of the insulating film 102; (see (a) of FIG. 3).
(d) The one surface 201a side of the second semiconductor substrate 200 is subjected to the CMP method so that each surface 203a of the terminal electrode 203 is at the same position or protrudes from the surface 202a of the insulating film 202. A step of polishing (see (a) of FIG. 3).
(e) As shown in (b) of FIG. 2, a step of dividing the second semiconductor substrate 200 into individual pieces to obtain a plurality of semiconductor chips 205 .
(f) As shown in (c) of FIG. 2, a step of aligning the terminal electrodes 203 of the plurality of semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100 .
(g) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and the insulating film portions 202b of the plurality of semiconductor chips 205 to each other (see (d) of FIG. 2 and (b) of FIG. 3). At this time, heat H, pressure or both may be applied.
(h) A step of joining the terminal electrodes 103 of the first semiconductor substrate 100 and the terminal electrodes 203 of the plurality of semiconductor chips 205 (see (c) of FIG. 3).
(i) A step of forming a plurality of pillars 300 (corresponding to the pillars 31) between a plurality of semiconductor chips 205 on the connecting surface of the first semiconductor substrate 100 (see FIG. 4A).
(j) A step of molding a resin 301 on the connecting surface of the first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillars 300 to obtain a semi-finished product M1 (see (b) of FIG. 4).
(k) A step of grinding and thinning the resin 301 side of the semi-finished product M1 molded in step (j) to obtain a semi-finished product M2 (see (c) in FIG. 4).
(l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 in the semifinished product M2 thinned in step (k) (see (d) of FIG. 4).
(m) A step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in the step (l) along the cutting line A so as to form each semiconductor device 1 (see FIG. 4(d)).
(n) A step of reversing the semiconductor device 1a singulated in the step (m) and placing it on the substrate 50 and the circuit substrate 60 (see FIG. 1).

For example, in the resin composition of the present disclosure, step (1) corresponds to the above steps (a) and (c), step (2) corresponds to the above steps (b) and (d), Step (3) corresponds to step (e), step (4) corresponds to step (g), and step (5) corresponds to step (h). Furthermore, the resin composition of the present disclosure provides a first organic insulating film and a second organic insulating film in a method for manufacturing a semiconductor device including at least one step corresponding to step (f) and steps (i) to (n). It may be a resin composition for use in producing at least one of the insulating films.

Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate on which integrated circuits are formed, which correspond to a plurality of first semiconductor chips 10 and are composed of semiconductor elements and wires connecting them. In step (a), as shown in FIG. 2(a), a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum or the like are formed on one surface 101a of a first substrate body 101 made of silicon or the like. An insulating film 102 (first insulating film) is provided at intervals and is a cured product obtained by curing the resin composition of the present disclosure. The plurality of terminal electrodes 103 may be provided after the insulating film 102 is provided on the surface 101a of the first substrate body 101, or the plurality of terminal electrodes 103 may be provided on the surface 101a of the first substrate body 101 before the insulating film is formed. 102 may be provided.

Step (b) is a step of preparing a second semiconductor substrate 200 which is a silicon substrate on which integrated circuits corresponding to the plurality of second semiconductor chips 20 and having semiconductor elements and wirings connecting them are formed. In step (b), as shown in FIG. 2A, a plurality of terminal electrodes 203 (plurality of second electrodes) made of copper, aluminum or the like are formed on one surface 201a of a second substrate body 201 made of silicon or the like. are continuously provided, and an insulating film 202 (second insulating film), which is a cured product obtained by curing the resin composition of the present disclosure, is provided. The plurality of terminal electrodes 203 may be provided after the insulating film 202 is provided on the first surface 201a of the second substrate body 201, or the plurality of terminal electrodes 203 may be provided on the first surface 201a of the second substrate body 201 before the insulating film 202 is formed. may be provided.

The insulating films 102 and 202 used in steps (a) and (b) are not limited to the configuration in which both the resin compositions of the present disclosure are cured, and at least one of the insulating films 102 and 202 is the present It may be configured as a cured product obtained by curing the disclosed resin composition.

Also, although FIG. 1 shows an example of C2C bonding, the present invention may be applied to Chip-to-Wafer (C2W) bonding shown in FIG. In C2W, a semiconductor wafer 410 (first electrode) having a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes). A substrate main body 421 (second substrate main body), an insulating film portion 422 (second insulating film) provided on one surface of the substrate main body 421, and a plurality of terminal electrodes 423 (second electrodes) are prepared. A semiconductor substrate (second semiconductor substrate) before singulation of a plurality of semiconductor chips 420 having . Then, the one surface side of the semiconductor wafer 410 and the one surface side of the second semiconductor substrate before being singulated into semiconductor chips 420 are polished by the CMP method or the like in the same manner as in the above steps (c) and (d). . After that, the second semiconductor substrate is subjected to a singulation process similar to step (e) to obtain a plurality of semiconductor chips 420 .

Subsequently, as shown in FIG. 5A, the terminal electrodes 423 of the semiconductor chip 420 are aligned with the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 are bonded together (step (g)), and the terminal electrode 413 of the semiconductor wafer 410 and the terminal electrode 423 of the semiconductor chip 420 are bonded together. (step (h)) to obtain the semi-finished product shown in FIG. 5(b). As a result, the insulating film portion 412 and the insulating film portion 422 are joined together to form an insulating joint portion S3, and the semiconductor chip 420 is attached to the semiconductor wafer 410 mechanically firmly and with high accuracy. Moreover, the terminal electrode 413 and the corresponding terminal electrode 423 are joined to form an electrode joint portion S4, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly joined.

Thereafter, as shown in (c) and (d) of FIG. 5, a semiconductor device 401 is obtained by bonding a plurality of semiconductor chips 420 to a semiconductor wafer 410, which is a semiconductor wafer, in a similar manner. The plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or may be collectively bonded to the semiconductor wafer 410 by hybrid bonding.

In the method of manufacturing the semiconductor device 401 as described above, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 is made of the resin composition of the present disclosure, as in the method of manufacturing the semiconductor device 1 described above. It is an insulating film that is a cured product obtained by curing a material. Therefore, even if a foreign matter generated by dicing when singulating into the semiconductor chips 420 adheres to the insulating film, the insulating film around the foreign matter is easily deformed, and the foreign matter can be removed without forming a large gap in the insulating film. It can be contained within an insulating film. That is, the insulating film can suppress the influence of foreign matter. Therefore, in the C2W manufacturing method described above, similarly to the C2C, fine bonding between the semiconductor wafer 410 and the semiconductor chip 420 can be performed while reducing defective bonding.

Hereinafter, the present disclosure will be described more specifically based on examples and comparative examples. It should be noted that the present disclosure is not limited to the following examples.

[Synthesis Example 1]
3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) 62 g, 4,4′-diaminodiphenyl ether 23 g and m-phenylenediamine 5 g were combined with 3-methoxy-N,N-dimethylpropanamide 915 g. was dissolved in The resulting solution was stirred at 30° C. for 4 hours and then at room temperature overnight to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature and stirred at 45° C. for 10 hours. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A1.
A gel permeation chromatography (GPC) method was used to determine the weight average molecular weight of A1 by standard polystyrene conversion. A1 had a weight average molecular weight of 22,000. Specifically, a solution prepared by dissolving 0.5 mg of A1 in 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF) = 1/1 (volume ratio)] was used for measurement under the following conditions.
(Measurement condition)
Measuring device: Shimadzu Corporation SPD-M20A
Pump: Shimadzu Corporation LC-20AD
Column oven: Shimadzu Corporation: CTO-20A
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF/DMF = 1/1 (volume ratio)
LiBr (0.03 mol/L), _H3PO4 ( _0.06 mol/L)
Flow rate: 1.0 mL/min, detector: UV270 nm, column temperature: 40°C
Standard polystyrene: Create a calibration curve with TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, A-2500 manufactured by Tosoh

<Esterification rate>
By performing NMR measurement under the following conditions, the esterification rate of A1 (percentage of ester groups reacted with HEMA to the total of ester groups reacted with HEMA and carboxyl groups unreacted with HEMA) was calculated. . The esterification rate was 78 mol % and the proportion of unreacted carboxy groups was 22 mol %.
(Measurement condition)
Measuring instrument: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

[Synthesis Example 2]
The same procedure as in Synthesis Example 1 except that 36 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was used instead of 4,4'-diaminodiphenyl ether and m-phenylenediamine used in Synthesis Example 1. was performed to obtain a polyimide precursor A2.
The weight average molecular weight of A2 was determined under the conditions described above. A2 had a weight average molecular weight of 24,000.

The esterification rate of A2 was calculated by performing NMR measurement under the conditions described above. The esterification rate was 79 mol % and the proportion of unreacted carboxy groups was 21 mol %.

[Synthesis Example 3]
Into a 0.2-liter flask equipped with a stirrer and thermometer, 60 g of N-methylpyrrolidone was charged, and 13.92 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added. and dissolved by stirring. Subsequently, 10.69 g (40 mmol) of diphenyl ether dicarboxylic acid dichloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5° C., and the solution in the flask was stirred for 60 minutes. The above solution was poured into 3 liters of water, the precipitate was recovered, washed with pure water three times, and then depressurized to obtain polyhydroxyamide (polybenzoxazole precursor) A3.
The weight average molecular weight of A3 was determined under the conditions described above. A3 had a weight average molecular weight of 33,100.

Resin compositions of each example and each comparative example were prepared by mixing the components shown below in the ratios shown in Table 2. In addition, the numerical value of each component in Table 2 means the mass part of each component used when preparing a resin composition.
・Polymer (A)
A1, A2 and A3 above
・ Nitrogen-containing organosilicon compound (B)
B1: A compound represented by the following general formula (R represents a divalent linking group).
・Antirust agent B'1: benzotriazole ・Adhesion aid B'2: 50% methanol solution of 3-ureidopropyltriethoxysilane

・溶剤（Ｃ）
Ｃ１：３－メトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド
Ｃ２：Ｎ－メチル－２－ピロリドン
Ｃ３：γ－ブチロラクトン
Ｃ４：プロピレングリコールモノメチルエーテルアセテート
・光重合開始剤（Ｄ）
Ｄ１：２－［［（エトキシカルボニル）オキシ］イミノ］－１－フェニルプロパン－１－オン
Ｄ２：６－ジアゾ－５－オキソ－５，６－ジヒドロナフタレン－１－スルホン酸と４，４’－｛１－｛４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル｝エチリデン｝ジフェノールの反応生成物（モノ、ジ及びトリエステルの混合物）
・重合性モノマー（Ｅ）
Ｅ１：テトラエチレングリコールジメタクリレート
Ｅ２：２，２－ビス［３，５－ビス（ヒドロキシメチル）－４－ヒドロキフェニル］－１，１，１，３，３，３－ヘキサフルオロプロパン

・Solvent (C)
C1: 3-methoxy-N,N-dimethylpropionamide C2: N-methyl-2-pyrrolidone C3: γ-butyrolactone C4: propylene glycol monomethyl ether acetate/photopolymerization initiator (D)
D1: 2-[[(ethoxycarbonyl)oxy]imino]-1-phenylpropan-1-one D2: 6-diazo-5-oxo-5,6-dihydronaphthalene-1-sulfonic acid and 4,4′- Reaction products of {1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene}diphenol (mixture of mono-, di- and triesters)
・Polymerizable monomer (E)
E1: Tetraethylene glycol dimethacrylate
E2: 2,2-bis[3,5-bis(hydroxymethyl)-4-hydroxyphenyl]-1,1,1,3,3,3-hexafluoropropane

[Adhesion test]
A cured film was produced using the resin composition of each example and each comparative example, and the adhesiveness of the produced cured film was evaluated by a cross-cut test (JIS K5400-8.5). The resin composition was spin-coated on a silicon wafer using a coating device spin coater, and a drying process was performed to form a resin film. The resulting resin film was exposed to light of 400 mJ/cm ² using a proximity exposure machine "Mask Aligner MA8" (manufactured by Suss Microtech Co., Ltd.). After that, the resin film was heated at 300° C. or 350° C. for a predetermined time in a nitrogen atmosphere using a clean oven to prepare a cured film. Furthermore, the obtained cured film was treated at 150° C. under HTS (High Temperature Storage) conditions in an air atmosphere for 300 hours. A cross-cut test was performed using the cured film after HTS.
Using a crosscut guide (manufactured by Cortec), a razor was used to make 10×10 grid cuts on the cured film to form 100 small pieces of 1 mm square. After affixing an adhesive tape (manufactured by Nichiban Co., Ltd.) there, it was peeled off. The adhesion of the cured product was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: 100 squares remain after peeling with the adhesive tape, and there is no peeling around the base mesh.
B: After peeling with the adhesive tape, peeling of one or more squares occurred.

[Copper mass measurement test]
The copper mass of the cured film was measured by SEM-EDX (scanning electron microscope-energy dispersive X-ray analysis). Titanium and copper are sputtered on one side of a silicon wafer (Si substrate having a _SiO2 film) and polyimide as shown in FIG. and the unnecessary sputtered layer was removed. A cured film obtained by curing the resin composition of each example and each comparative example was prepared between the electrodes in the same manner as in the [Adhesion test] described above. Furthermore, a HAST (Highly Accelerated Temperature and Humidity Stress Test) at 130° C. and 85% RH was performed on the cured film (a cured film prepared at a curing temperature of 300° C. and a cured film prepared at a curing temperature of 350° C.) provided between the electrodes. ) for 300 hours. SEM-EDX measurement was performed using the cured film after HAST.
Table 1 below shows the measurement conditions of SEM-EDX.

In this measurement, the mass % of each element was calculated from the EDX spectrum.
In this measurement, a quantification method called a standardless method, which does not use a standard sample for each measurement, was used to convert the mass % of each element from the EDX spectrum. In this method, a theoretical correction calculation was performed from the X-ray intensity of each element, and a quantitative analysis value was calculated so that the total concentration would be 100%. In this measurement, attention is paid to the copper mass % in order to observe whether copper diffusion occurs between the electrodes. This copper mass % is the mass % value of the copper element when calculated so that the sum of the mass % of each element is 100%. The evaluation criteria for copper mass (%) are as follows.
-Evaluation criteria-
A: Copper mass (%) was less than 0.5%.
B: Copper mass (%) was 0.5% to 1.25%.
C: Copper mass (%) exceeded 1.25% and was 1.9% or less.
D: Copper mass (%) exceeded 1.9%.

As shown in Table 2, in Examples 1 to 6, the evaluation of adhesion of the cured film was good, and it was possible to suppress the diffusion of copper under high temperature and high humidity conditions.
Furthermore, in Examples 1 to 6, by using the nitrogen-containing organosilicon compound (B), both the improvement of the adhesiveness of the cured film and the suppression of copper diffusion can be achieved without using an antirust agent and an adhesion aid. was possible. Even if the amount of the nitrogen-containing organosilicon compound (B) is less than or equal to the total amount of the antirust agent and the adhesion promoter, it is possible to achieve both improvement in adhesion of the cured film and suppression of copper diffusion. It turns out there is.

DESCRIPTION OF SYMBOLS 1, 1a, 401... Semiconductor device 10... First semiconductor chip 20... Second semiconductor chip 30... Pillar part 40... Rewiring layer 50... Substrate 60... Circuit board 61... Terminal electrode 100... First semiconductor substrate 101 First substrate body 101a One surface 102 Insulating film (first insulating film) 103 Terminal electrode (first electrode) 103a Surface 200 Second semiconductor substrate 201 Second substrate body 201a... One surface 202... Insulating film (second insulating film) 203... Terminal electrode (second electrode) 203a... Surface 205... Semiconductor chip 300... Pillar 301... Resin 410... Semiconductor Wafer (first semiconductor substrate) 411 Substrate body (first substrate body) 412 Insulating film (first insulating film) 413 Terminal electrode (first electrode) 420 Semiconductor chip (second semiconductor substrate) , 421... Substrate body (second substrate body), 422... Insulating film portion (second insulating film), 423... Terminal electrode (second electrode), A... Cutting line, H... Heat, M1 to M3... Semi-finished product, S1... Insulated joint portion, S2... Electrode joined portion, S3... Insulated joint portion, S4... Electrode joined portion.

Claims (12)

At least one polymer (A) selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors;
a nitrogen-containing organosilicon compound (B) having a nitrogen-containing skeleton and an organosilicon skeleton;
A resin composition comprising: The resin composition according to claim 1, wherein the nitrogen-containing skeleton contains a heterocyclic structure containing a nitrogen atom. The resin composition according to claim 1 or 2, wherein the polymer (A) contains a polyimide precursor, and the polyimide precursor contains a compound having a structural unit represented by the following general formula (1).

In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group. 4. The resin composition according to claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).

In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O —C(=O)—), silylene bond (—Si(R ^A ) ₂ —; two R ^A each independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (—O— (Si(R ^B ) ₂ —O—) _n ; each of the two R ^B independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more), or at least It represents a divalent group in which two are combined. 5. The resin composition according to claim 3, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H).

In formula (H), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer of 0-4. D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC (=O) -), a silylene bond (-Si(R ^A ) ₂ -; two R ^A each independently represent a hydrogen atom, an alkyl group or a phenyl group.), a siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; two R 2 ^B each independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more.) or a combination of at least two of these represents the group of In the general formula (1), the monovalent organic group for R ⁶ and R ⁷ is any of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group. The resin composition according to any one of claims 3 to 5.

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group. 7. The resin composition according to any one of claims 1 to 6, further comprising a solvent (C). 8. The resin composition according to claim 7, wherein the solvent (C) contains at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (7).

In formulas (3) to (7), R ¹ , R ² , R ⁸ and R ¹⁰ are each independently an alkyl group having 1 to 4 carbon atoms, and R ³ to R ⁷ and R ⁹ are each independently and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer of 0-8, t is an integer of 0-4, r is an integer of 0-4, and u is an integer of 0-3. 9. The resin composition according to any one of claims 1 to 8, further comprising (D) a photopolymerization initiator and (E) a polymerizable monomer. The resin composition according to any one of claims 1 to 9 is used to prepare at least one of the first organic insulating film and the second organic insulating film, and the following steps (1) to A semiconductor device manufacturing method for manufacturing a semiconductor device through (5).
Step (1) Prepare a first semiconductor substrate having a first substrate body, and the first organic insulating film and the first electrode provided on one surface of the first substrate body.
Step (2) Prepare a second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body.
Step (3) Individualizing the second semiconductor substrate to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one of the second electrodes. .
Step (4) Bonding the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other.
Step (5) Bonding the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip. A cured product obtained by curing the resin composition according to any one of claims 1 to 9. a first semiconductor substrate having a first substrate body, and the first organic insulating film and the first electrode provided on one surface of the first substrate body;
a semiconductor chip having a semiconductor chip substrate body, and an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body;
wherein the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together, and the first electrode of the first semiconductor substrate and the first electrode of the semiconductor chip are bonded together. 2 electrodes and are joined,
A semiconductor device, wherein at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film obtained by curing the resin composition according to any one of claims 1 to 9.

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