WO2024204181A1 - Resin composition, cured product, laminate, semiconductor device, and method for producing semiconductor device - Google Patents

Abstract

The present invention pertains to a resin composition containing a solvent and a resin (A) having a structural unit represented by formula (1) and/or a structural unit represented by formula (2). With respect to a total of 100 mol% of acid dianhydride residues (X1) and (X2) and diamine residues (Y1) and (Y2) contained in the resin (A), the resin (A) contains a total of 10-40 mol% of at least one of an acid dianhydride residue (A1) having a structure represented by formula (3) and a diamine residue (A2) having a structure represented by formula (4). The resin (A) contains 1.0-20 mol% of a diamine residue (A3) having a structure represented by formula (5). The proportion of all Si atoms included in the resin (A) is 0.5-5.0 parts by mass with respect to 100 parts by mass of the resin (A). (Formulae (1)-(5) are as defined in the description.)

Description

Resin composition, cured product, laminate, semiconductor device, and method for manufacturing semiconductor device

The present invention relates to a resin composition, a cured product, a laminate, a semiconductor device, and a method for manufacturing a semiconductor device. More specifically, the present invention relates to a resin composition that is suitable for thinning semiconductor devices, and a cured product, a laminate, a semiconductor device, and a method for manufacturing a semiconductor device that use the resin composition.

In recent years, semiconductor devices have been rapidly becoming smaller and thinner. For example, there is a demand for thinner devices in order to increase the processing speed and reduce costs of semiconductor devices. Display devices using μLEDs have also been proposed, and there is a demand for further miniaturization and thinning in order to increase the resolution of display devices and reduce the cost of μLED chips. When used for lighting, etc., there is a demand for further thinning in terms of design and cost reduction. In addition, these semiconductor devices are generally manufactured through heat treatment processes such as solder reflow and mechanical processes such as thinning processes. Therefore, the adhesives used in these devices and parts must not only be thin, but also not peel or produce voids during or after the heat treatment and mechanical processes of the above devices.

As adhesives for use in these semiconductor devices, for example, technology has been proposed in which the glass transition temperature of polyimide resin is designed to be 40°C or less to improve adhesion (Patent Document 1), and technology has been proposed in which crosslinkable groups are introduced into silicone-modified polyimide resin to impart heat resistance (Patent Document 2). Furthermore, technology has been proposed in which the glass transition temperature of polyimide resin is designed to be 300°C or more to improve heat resistance and dimensional stability (Patent Document 3).

International Publication No. 2014/050878 Japanese Patent Application Publication No. 2019-172894 Japanese Patent Application Publication No. 2014-61685

The resin compositions of the inventions described in Patent Documents 1 and 2 contain a large amount of silicone components, so they can bond devices at low temperatures. On the other hand, because they contain a large amount of flexible silicone components, they have the problem of low dimensional stability. As a result, warping occurs when the device substrate and the support substrate are bonded together, and when the device is made extremely thin, the adhesive layer twists, causing the device to be damaged without being thinned uniformly. In addition, there are problems such as the device being misaligned due to dimensional changes in the adhesive during heat treatment after the device is bonded together. The invention described in Patent Document 3 does not contain a component that imparts adhesiveness, so it has the problem that it cannot be applied to semiconductor devices that are laminated by bonding substrates together. In addition, the inventions described in Patent Documents 1 to 3 all have the problem that peeling is likely to occur when the adhesive layer is made thin, so the adhesive layer must be made thick, and as a result, the thickness of the adhesive layer affects the thickness of the device. Therefore, the technology of the present invention has been discovered that solves the problems of the conventional technology as described above and can achieve extremely thin devices.

In order to solve the above problems, the present invention has the following configuration.
[1]
A resin composition comprising a resin (A) having at least one structural unit selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), and a solvent,
With respect to 100 mol % in total of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A),
the resin (A) contains at least one of an acid dianhydride residue (A1) having a structure represented by formula (3) and a diamine residue (A2) having a structure represented by formula (4) in a total amount of 10 mol % or more and 40 mol % or less,
The resin (A) contains 1.0 mol % or more and 20 mol % or less of a diamine residue (A3) having a structure represented by formula (5),
A resin composition, wherein a ratio of all Si atoms contained in the resin (A) is 0.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the resin (A).

(In formula (1) and formula (2), ^X1 and ^X2 each independently represent a tetravalent acid dianhydride residue having 4 to 50 carbon atoms, ^Y1 and ^Y2 each independently represent a divalent diamine residue having 2 to 100 carbon atoms, and ^R1 and ^R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.)

(In formulas (3) to (5), R ³ to R ¹⁶ each independently represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom. R ¹⁷ to R ²⁰ each independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. R ²¹ and R ²² each independently represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. n represents an integer from 1 to 20. ^* 3a and ^* 3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or ^* 3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and ^* 3b represents a bonding site connected to a carbon atom of a carboxylic acid or a carboxylate ester in the structural unit represented by formula (2). ^* 4, and ^* 5 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).

[2]
The resin composition according to the above-mentioned [1], wherein the diamine residue (A2) is a diamine residue having a structure represented by formula (6).

(In formula (6), ^* 6 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).)

[3]
The resin composition according to the above [1], wherein in the diamine residue (A3), n in the formula (5) is 1.

[4]
The resin composition according to the above-mentioned [1], wherein the solvent contained in the resin composition has a viscosity of 1.8 mPa·s or more and 3.1 mPa·s or less.

[5]
The resin composition according to the above [1] or [2], further comprising a silane coupling agent.

[6]
The resin composition according to the above [5], wherein the silane coupling agent contains a compound represented by formula (7).

(In formula (7), R ²³ represents an alkylene group having 5 to 10 carbon atoms. R ²⁴ each independently represents an alkyl group having 1 to 5 carbon atoms. Z represents a hydrogen atom or a group represented by any one of the following formulas (8) to (14).)

(In formulas (8) to (14), R ²⁵ to R ³¹ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^* 8 to ^* 14 represent bonding sites with R ²³ in formula (7).)

[7]
The resin composition according to the above [1] or [2], further comprising inorganic particles.
[8]
A cured product obtained by curing any one of the resin compositions [1] to [4] above.
[9]
A laminate having the cured product according to the above item [8].
[10]
The laminate according to the above-mentioned [9], wherein the thickness of the cured product is 0.5 μm or more and 8.0 μm or less.
[11]
The laminate according to the above-mentioned [10], which has a plurality of layers made of the cured product.
[12]
The laminate according to the above-mentioned [10], which has a compound semiconductor layer.
[13]
A semiconductor device comprising the stack according to [10] above.
[14]
A method for manufacturing a semiconductor device, comprising at least one of a step of thinning the laminate described in [10] above and a step of singulating the laminate described in [10] above.

The resin composition of one embodiment of the present invention has excellent adhesion and can stably bond devices even when thin. In addition, since the resin composition of one embodiment of the present invention has a low linear expansion coefficient, warping is small when substrates are bonded together, and even when heat treatment is performed after bonding, the resin composition has excellent dimensional stability and can reduce misalignment and peeling of bonded devices. Therefore, a semiconductor device containing a cured product of the resin composition of one embodiment of the present invention has excellent reliability even when the cured product is thinned and laminated.

FIG. 1 is an enlarged cross-sectional view of a mounting portion of an LED element of a monolithic LED. FIG. 2 is an enlarged view of the monolithic LED element 1. As shown in FIG. FIG. 3A shows an example of step (3-a) in the manufacturing process of a monolithic LED display. FIG. 3B shows an example of step (3-b) in the manufacturing process of a monolithic LED display. FIG. 3C shows an example of step (3-c) in the manufacturing process of a monolithic LED display. FIG. 3D shows an example of step (3-d) in the manufacturing process of a monolithic LED display. FIG. 3E shows an example of step (3-e) in the manufacturing process of a monolithic LED display. FIG. 3F shows an example of step (3-f) in the manufacturing process of a monolithic LED display. FIG. 3G shows an example of step (3-g) in the manufacturing process of a monolithic LED display. FIG. 3H shows an example of step (3-h) in the manufacturing process of a monolithic LED display. FIG. 3I shows an example of step (3-i) in the manufacturing process of a monolithic LED display. FIG. 3J shows an example of step (3-j) in the manufacturing process of a monolithic LED display. FIG. 3K shows an example of step (3-k) in the manufacturing process of a monolithic LED display.

[Resin composition]
The resin composition according to one aspect of the present invention (hereinafter also referred to as "the present embodiment") comprises:
A resin composition comprising a resin (A) having at least one structural unit selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), and a solvent,
With respect to 100 mol % in total of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A),
the resin (A) contains at least one of an acid dianhydride residue (A1) having a structure represented by formula (3) and a diamine residue (A2) having a structure represented by formula (4) in a total amount of 10 mol % or more and 40 mol % or less;
The resin (A) contains 1.0 mol % or more and 20 mol % or less of a diamine residue (A3) having a structure represented by formula (5),
The resin composition has a ratio of all Si atoms contained in the resin (A) of 0.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the resin (A).

In formula (1) and formula (2), ^X1 and ^X2 each independently represent a tetravalent acid dianhydride residue having 4 to 50 carbon atoms, and ^Y1 and ^Y2 each independently represent a divalent diamine residue having 2 to 100 carbon atoms. ^R1 and ^R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.

In formulas (3) to (5), R ³ to R ¹⁶ each independently represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom. R ¹⁷ to R ²⁰ each independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. R ²¹ and R ²² each independently represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. n represents an integer of 1 to 20. ^* 3a and ^* 3b represent a bonding site connected to an imide group in the structural unit represented by formula (1) above, or ^* 3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2) above, and ^* 3b represents a bonding site connected to a carbon atom of a carboxylic acid or a carboxylate in the structural unit represented by formula (2) above. ^* 4 and ^* 5 represent bonding sites connecting to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).

(Resin (A))
The acid dianhydride residue (A1) having a structure represented by formula (3) (hereinafter also referred to as "acid dianhydride residue (A1)") and the diamine residue (A2) having a structure represented by formula (4) (hereinafter also referred to as "diamine residue (A2)") are residues of monomers having a biphenyl skeleton, and by containing at least one of them, a rigid structure can be introduced into the resin (A). The resin (A) contained in the resin composition contains at least one of the acid dianhydride residue (A1) and the diamine residue (A2) in a total amount of 10 mol % or more and 40 mol % or less with respect to the total of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A), which is 100 mol %.

The resin (A) contained in the resin composition contains at least one of the acid dianhydride residue (A1) and the diamine residue (A2) in a total amount of 10 mol% or more relative to the total 100 mol% of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A), and when the resin composition is cured by heat treatment, the cured product has a low linear expansion coefficient and is less susceptible to thermal deformation. Therefore, when a substrate or a device is bonded together, or when a device substrate is bonded together to thin it, warping of the device substrate and twisting of the film to damage the device substrate can be prevented. A more preferable range of the total amount of the acid dianhydride residue (A1) and the diamine residue (A2) is 15 mol% or more relative to the total 100 mol% of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A). This further reduces the linear expansion coefficient of the formed cured material, making it possible to suppress warping of the laminate even in configurations in which multiple cured materials are stacked.

In addition, by having the resin (A) contained in the resin composition contain at least one of the acid dianhydride residue (A1) and the diamine residue (A2) in a total amount of 40 mol % or less relative to the total of 100 mol % of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A), the glass transition temperature of the cured product obtained by curing the resin composition can be adjusted to an appropriate range. This allows the substrate to be thermally laminated at a temperature that does not affect the device. A more preferable range for the total amount of the acid dianhydride residues (A1) and the diamine residues (A2) is 30 mol % or less relative to 100 mol % of all monomer residues in the resin (A). This allows uniform lamination.

The acid dianhydride constituting the acid dianhydride residue (A1) may contain residues of known acid dianhydrides. Specific examples include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, and 5,5'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride is particularly preferred from the viewpoint of ease of availability.

Diamines constituting the diamine residue (A2) include 4,4'-biphenyldiamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diamino-3,3',5,5'-tetramethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 2,2'-benzidine disulfonic acid, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-3,3'-diethylbiphenyl dihydrochloride, octafluorobenzidine, and 4,4'-diamino-3,3'-dimethoxybiphenyl. Since this gives the resin (A) a more rigid structure, those having hydrogen or a methyl group as a substituent, such as 4,4'-biphenyldiamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diamino-3,3',5,5'-tetramethylbiphenyl, and 4,4'-diamino-3,3'-dimethylbiphenyl, are preferred.

Among these, it is particularly preferable that the diamine residue (A2) is a diamine residue having a structure represented by the following formula (6). The effect of the methyl group is that it is possible to improve the solubility in a solvent while maintaining the rigidity of the resin (A). This allows a smooth coating film to be obtained, and it is possible to further suppress poor lamination caused by poor in-plane uniformity of the coating film during the substrate lamination process.

In formula (6), ^* 6 represents a bonding site connecting to the nitrogen atom of the imide group in the structural unit represented by formula (1) above or the amide bond in the structural unit represented by formula (2) above.

An example of a diamine that constitutes a diamine residue having the structure represented by formula (6) is 2,2'-dimethylbiphenyl-4,4'-diamine.

The diamine residue (A3) having the structure represented by formula (5) (hereinafter also referred to as "diamine residue (A3)") is a flexible diamine residue having a siloxane bond.

In formula (5), R ¹⁷ to R ²⁰ each independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. R ²¹ and R ²² may be the same or different, and each represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. n is an integer of 1 to 20. When n is 1 or more, the diamine residue (A3) has a silicone structure, and the resin composition can obtain high adhesiveness. When n is 20 or less, compatibility with other monomers is improved when polymerizing the resin (A), and polymerization of the resin becomes easy. A more preferable range of n is 10 or less, and this allows the silicone structure-containing moiety to be dispersed and present in the resin (A), thereby obtaining uniform adhesiveness in the coating film.

In the diamine residue (A3), the repeating unit n in formula (5) is preferably n = 1. By setting n = 1, it is possible to impart adhesiveness without impairing the rigidity of the film, thereby significantly improving dimensional stability, which is difficult to achieve with conventional adhesives.

The resin (A) contained in the resin composition contains diamine residues (A3) in an amount of 1.0 mol % or more and 20 mol % or less relative to the total of 100 mol % of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A).

The resin (A) contained in the resin composition contains 1.0 mol% or more of diamine residue (A3) relative to the total of 100 mol% of the acid dianhydride residues (X1) and (X2) and diamine residues (Y1) and (Y2) contained in the resin (A), thereby imparting adhesiveness to the resin composition (A). A more preferred range of the content of diamine residue (A3) is 2.0 mol% or more relative to the total of 100 mol% of the acid dianhydride residues (X1) and (X2) and diamine residues (Y1) and (Y2) contained in the resin (A). This allows the diamine residue (A3), which is a component involved in adhesion, to be uniformly present in the resin (A). Therefore, in the process of bonding the substrates, uneven adhesion is less likely to occur, and adhesion failure can be reduced, particularly when bonding a thin film of the resin composition is performed.

In the resin (A) contained in the resin composition, the diamine residue (A3) is contained in an amount of 20 mol% or less relative to the total of 100 mol% of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A). This improves heat resistance when the substrates are heated after bonding, thereby suppressing clouding and peeling of the film caused by decomposition gas. A more preferred range of the diamine residue (A3) is 17 mol% or less relative to the total of 100 mol% of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A). This prevents excessive softening of the adhesive layer during heat treatment, and provides excellent dimensional stability during heat treatment.

Diamines constituting the diamine residue (A3) include tetramethyl-1,3-bis(3-aminopropyl)disiloxane as a diamine with n=1, and α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydipropylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, and α,ω-bis( Examples of such polydimethylsiloxanes include α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydiphenoxysiloxane, α,ω-bis(4-aminophenyl)polydimethylsiloxane, and α,ω-bis(4-aminophenyl)polydiphenoxysiloxane. n may be a single value or may be a mixture of multiple values of n, so n in formula (5) represents an average value. From the viewpoints of ease of availability and efficient imparting of adhesiveness without impairing the rigidity of the resin (A), the diamine constituting the diamine residue (A3) is preferably tetramethyl-1,3-bis(3-aminopropyl)disiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, or a combination thereof.

Preferred combinations of the acid dianhydride constituting the acid dianhydride residue (A1), the diamine constituting the diamine residue (A2), and the diamine constituting the diamine residue (A3) include a combination of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-dimethylbiphenyl-4,4'-diamine, and tetramethyl-1,3-bis(3-aminopropyl)disiloxane, and a combination of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diamino-3,3'-dimethylbiphenyl, and α,ω-bis(3-aminopropyl)polydimethylsiloxane.

Resin (A) contains Si atoms in an amount of 0.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of resin (A). When resin (A) contains Si atoms in an amount of 0.5 parts by mass or more, it is possible to bond the entire surface of the substrate and the device substrate. A more preferable content of Si atoms is 2.0 parts by mass or more per 100 parts by mass of resin (A). When resin (A) contains Si atoms in this range, the adhesiveness is further improved, so that it is possible to suppress the bonding of the substrate in a thin film and the peeling after the device is singulated. In addition, when resin (A) contains 5.0 parts by mass or less of Si atoms per 100 parts by mass of resin (A), it is possible to maintain high heat resistance of resin (A), so that it is possible to reduce the peeling of the substrate and the generation of voids due to degassing when the bonded substrate is heat-treated. A more preferable range of the content of Si atoms is 4.0 parts by mass or less per 100 parts by mass of resin (A). This allows both adhesion and dimensional stability to be achieved, allowing substrates to be bonded together without peeling or warping. The proportion of Si atoms in resin (A) can be determined by elemental analysis of resin (A).

The Si atoms contained in the resin (A) may be derived from a diamine residue (A3) or from a monomer having a silsesquioxane structure. When the resin (A) contains a diamine residue (A3), it is possible to impart uniform adhesiveness to the resin composition.

Furthermore, the resin (A) may have a monomer residue other than the acid dianhydride residue (A1), the diamine residue (A2), and the diamine residue (A3). Examples of such monomer residues include residues of monomers having a silsesquioxane structure.

The acid dianhydride residue other than the acid dianhydride residue (A1) may contain residues of known acid dianhydrides, and preferably contains residues of aromatic tetracarboxylic acid dianhydrides. Specific examples of the residue of aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfoxide tetracarboxylic dianhydride, 3,3',4 ,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethylene tetracarboxylic dianhydride, 4,4'-isopropylidenediphthalic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1 , 2,5,6-naphthalenetetracarboxylic dianhydride, 3,3",4,4"-para-terphenyltetracarboxylic dianhydride, 3,3",4,4"-meta-terphenyltetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride residues, etc. may be included. The above aromatic tetracarboxylic dianhydride residues may contain only one type, or may contain two or more types.

In addition, resin (A) may contain a residue of a tetracarboxylic dianhydride having an aliphatic ring as an acid dianhydride residue other than the acid dianhydride residue (A1), to the extent that the heat resistance of resin (A) is not impaired. Specific examples of the residue of a tetracarboxylic dianhydride having an aliphatic ring include 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,5-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione residue, and double-decker silsesquioxane alicyclic acid dianhydride. Resin (A) may contain only one type of the above tetracarboxylic dianhydride residue, or may contain two or more types.

In addition, resin (A) may contain residues of known diamines as diamine residues other than diamine residues (A2) and diamine residues (A3). Specific examples of diamines include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2-methoxy-1,4-phenylenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 3,3'-dimethyl-4,4'-diaminobenzanilide, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(3-aminophenyl)fluorene, 9,9-bis(3-methyl-4-aminophenyl)fluorene, 9,9-bis(3,5-dimethyl-4-aminophenyl)fluorene, 9,9-bis(3-methoxy-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis (4-aminophenyl)fluorene-4-methyl, 9,9-bis(4-aminophenyl)fluorene-4-methoxy, 9,9-bis(4-aminophenyl)fluorene-4-ethyl, 9,9-bis(4-aminophenyl)fluorene-4-sulfone, 9,9-bis(4-aminophenyl)fluorene-3-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-3-methyl, 1,3-diaminocyclohexane, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, p-aminobenzylamine, m-aminobenzylamine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminodiphenyl methane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, bis [4-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 3,3'-methylenebis(cyclohexylamine), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 2,2-bis(3-amino-4 hydroxyphenyl)hexafluoropropane, and the like. Resin (A) may contain the above diamine residue alone or two or more kinds.

The molecular weight of resin (A) can be adjusted by using equimolar amounts of the acid dianhydride component and the diamine component used in the synthesis, or by using an excess of either one. Either the acid dianhydride component or the diamine component can be used in excess, and the polymer chain ends can be blocked with an end-capping agent such as an acid component or an amine component. Dicarboxylic acids or their anhydrides are preferably used as end-capping agents for the acid component, and monoamines are preferably used as end-capping agents for the amine component. In this case, it is preferable to use equimolar amounts of the acid equivalent of the tetracarboxylic acid component, including the end-capping agent for the acid component or amine component, and the amine equivalent of the diamine component.

　The monoamines that can be used as the terminal blocking agent for the amine component can be any known monoamine, of which aniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine, 3-aminophenol, 4-aminophenol, etc. are preferred. Two or more of these may be used as the terminal blocking agent for the amine component.

Furthermore, as the terminal blocking agent for the acid component, compounds such as monocarboxylic acid, monoacid chloride compound, monoactive ester compound, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, monocarboxylic acids such as 3-carboxyphenol, 1-hydroxy-6-carboxynaphthalene, and monoacid chloride compounds in which the carboxyl group of these is acid chloride, monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, and the like is acid chloride, and active ester compounds obtained by reacting monoacid chloride compounds with N-hydroxybenzotriazole, imidazole, or N-hydroxy-5-norbornene-2,3-dicarboximide are preferred. Two or more of these may be used as the terminal blocking agent for the acid component.

The weight average molecular weight of the resin (A) is preferably 5000 or more and 50000 or less. The weight average molecular weight of the resin (A) is preferably 5000 or more from the viewpoint of heat resistance, more preferably 8000 or more from the viewpoint of reliability when used permanently as an adhesive in a device, preferably 50000 or less from the viewpoint of viscosity of the resin composition when handling film formation and varnish, and more preferably 30000 or less from the viewpoint of ease of production of the resin (A).
Here, the weight average molecular weight of resin (A) can be calculated as a polystyrene equivalent value by performing gel permeation chromatography (GPC) analysis on a solution in which resin (A) is dissolved in N-methyl-2-pyrrolidone to give a resin concentration of 0.1% by weight.

In addition, the proportion of F atoms contained in resin (A) is preferably small from the viewpoint of adhesion, and is preferably 2.0 parts by mass or less per 100 parts by mass of resin (A). This allows for high adhesion to the substrate. More preferably, the content of F atoms is 0.2 parts by mass or less per 100 parts by mass of resin (A). This allows for high adhesion when the resin layer is made thin.

The molar ratio of the dianhydride component/diamine component of resin (A) can be adjusted as appropriate so that the resin composition containing resin (A) is in a range that is easy to use in coating, etc. It is common to adjust the molar ratio of the dianhydride component/diamine component to a range of 100/100 to 100/95, or 100/100 to 95/100. If the molar ratio of the dianhydride component/diamine component of resin (A) is outside the above range, the molecular weight of resin (A) will decrease, and the mechanical strength of the formed film will decrease. This may result in uneven adhesion, so it is preferable to adjust the molar ratio within a range in which the adhesion is stable.

The resin (A) may be a polyimide precursor that undergoes ring closure upon heating to become a polyimide, a polyimide that has undergone ring closure upon heating, or a polyimide precursor in which part of the resin has undergone ring closure upon heating.

There are no particular limitations on the method for polymerizing resin (A). For example, when polymerizing polyamic acid, which is a polyimide precursor, tetracarboxylic dianhydride and diamine are stirred in an organic solvent at 0 to 100°C for 1 to 100 hours to obtain a polyamic acid resin solution. If resin (A) is soluble in an organic solvent, after polymerization of polyamic acid, the temperature is raised to 120 to 300°C and stirred for 1 to 100 hours to convert it to polyimide, and a solution of resin (A) is obtained. At this time, toluene, o-xylene, m-xylene, p-xylene, etc. may be added to the reaction solution, and the water produced by the imidization reaction may be removed by azeotroping with these solvents.

(solvent)
The resin composition of the present embodiment contains a solvent. By including a solvent, the viscosity of the resin composition can be adjusted, and the thickness of the cured product described later can be adjusted. The content of the solvent is preferably 100 parts by mass or more and 2000 parts by mass or less per 100 parts by mass of the resin (A), and can be selected according to the desired film thickness. As the solvent used in the resin composition of the present embodiment, the solvent used in the polymerization may be used as it is, or another solvent may be added thereto to form a mixed solvent. In addition, the polymerization solvent may be removed from the polymerization liquid of the polymerized resin (A), and another solvent and the resin (A) may be mixed to form a resin composition. Specific examples of the solvent include polar aprotic solvents such as gamma-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol ethers such as ethylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and diacetone alcohol; Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methylpropionate, Examples of the solvent include esters such as methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-diethylacetamide. Among these, N-methylpyrrolidone, N-dimethylacetamide, N-diethylacetamide, cyclohexanone, and ethyl lactate are preferably used. The solvent may be used alone or in combination with two or more kinds, and is not limited to the above-mentioned solvents as long as it is compatible with the resin (A).

Furthermore, it is preferable that the viscosity of the solvent is 1.8 mPa·s or more and 3.1 mPa·s or less. By having a solvent viscosity of 1.8 mPa·s or more, it is possible to suppress shrinkage of the coating film at the edges of the substrate and wrap around to the back surface of the substrate when the resin composition is applied to the substrate, and by making the film thickness at the edges uniform, it is possible to improve adhesion at the edges and also suppress transportation errors when passing through the process. Furthermore, by having a solvent viscosity of 3.1 mPa or less, it is possible to increase the in-plane uniformity of the coating film. Examples of solvents with a viscosity of 1.8 mPa·s or more and 3.1 mPa·s or less include diacetone alcohol (viscosity: 2.90 mPa·s), cyclohexanone (viscosity: 1.97 mPa·s), ethyl lactate (2.44 mPa·s), dimethylimidazolidinone (viscosity: 2.63 mPa·s), and 3-methoxy-N,N-dimethylpropanamide (viscosity: 2.04 mPa·s).

(Silane coupling agent)
The resin composition of the present embodiment preferably contains a silane coupling agent. The silane coupling agent is preferably added at a temperature of room temperature to 50° C. after polymerization of the resin (A). By containing the silane coupling agent in the resin composition, the adhesiveness of the resin composition to the substrate can be improved. The preferred content of the silane coupling agent in the resin composition is preferably 1.0 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin (A). By containing 1.0 part by mass or more of the silane coupling agent in the resin composition, the adhesiveness to the substrate can be improved. It is more preferred that the resin composition contains 3.0 parts by mass or more of the silane coupling agent with respect to 100 parts by mass of the resin (A). This makes it possible to suppress peeling of the device substrate or the singulated substrate even when the process of thinning or dicing the device is performed after the substrates are bonded together. In addition, by containing 10 parts by mass or less of the silane coupling agent in the resin composition with respect to 100 parts by mass of the resin (A), it is possible to suppress degassing caused by the silane coupling agent during heat treatment. A more preferred content of the silane coupling agent in the resin composition is 7.0 parts by mass or less relative to 100 parts by mass of the resin (A). By containing the silane coupling agent in this range, the storage stability of the varnish is improved. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 7-octenyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and N-2-(aminoethyl)-8-aminooctyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. The silane coupling agent more preferably contains a compound represented by formula (7).

In formula (7), R ²³ represents an alkylene group having 5 to 10 carbon atoms. R ²⁴ each independently represents an alkyl group having 1 to 5 carbon atoms. Z represents a hydrogen atom or a group represented by any one of the following formulas (8) to (14).

In formulas (8) to (14), R ²⁵ to R ³¹ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^* 8 to ^* 14 represent bonding sites with R ²³ in formula (7).

Silane coupling agents having a structure represented by formula (8) include 8-glycidoxyoctyltrimethoxysilane, 6-glycidoxyhexyltrimethoxysilane, etc. Silane coupling agents having a structure represented by formula (9) include 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, etc. Silane coupling agents having a structure represented by formula (10) include 8-methacryloxyoctyltrimethoxysilane. Silane coupling agents having a structure represented by formula (11) include N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, N-2-(aminoethyl)-6-aminohexyltrimethoxysilane, etc. Silane coupling agents having a structure represented by formula (12) include 1-(6-(trimethoxysilyl)hexyl)urea), etc. Silane coupling agents having a structure represented by formula (13) include 1-(6-(trimethoxysilyl)hexyl)thiourea), etc. An example of a silane coupling agent having a structure represented by formula (14) is 8-phenyloctyltrimethoxysilane.

The silane coupling agent containing the compound represented by formula (7) has good compatibility with resin (A) and has a higher adhesion improving effect, so that peeling can be prevented even when the substrate after bonding is subjected to a heat treatment of 250°C or more. The preferred amount of the silane coupling agent containing the compound represented by formula (7) to be added is the same as the preferred amount of the silane coupling agent described above.

(Inorganic particles)
The resin composition of the present embodiment may contain inorganic particles from the viewpoint of improving dimensional stability and heat resistance. The content of the inorganic particles in the resin composition is preferably 2.0 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin (A). When the content of the inorganic particles in the resin composition is 2.0 parts by mass or more with respect to 100 parts by mass of the resin (A), an effect of improving dimensional stability is obtained. When the content of the inorganic particles in the resin composition is 10 parts by mass or less with respect to 100 parts by mass of the resin (A), the adhesiveness of the resin composition is maintained. Examples of inorganic particles include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, talc, etc. In particular, silica particles are preferable from the viewpoint of heat resistance.

(Crosslinking Agent)
The resin composition of the present embodiment may contain a crosslinking agent. By containing a crosslinking agent, the chemical resistance and heat resistance are improved after the resin composition is cured, and the processability and reliability of the device are improved. As the crosslinking agent, a known crosslinking agent can be used, and an epoxy-based crosslinking agent, an acrylic-based crosslinking agent, a methylol-based crosslinking agent, or the like can be selected.

(Resins other than resin (A))
The resin composition of the present embodiment may contain a resin other than the resin (A) within a range that does not impair the effects of the present invention. In addition, a surfactant may be added for the purpose of improving properties such as adhesion, heat resistance, coatability, and storage stability. In addition, the other resins and surfactants may be added during or after polymerization of the resin (A).

Examples of other resins include acrylic resins, epoxy resins, polystyrene resins, novolac resins, polybenzoxazole resins, silicone resins, etc. Examples of surfactants include silane-based surfactants, acrylic-based surfactants, and fluorine-based surfactants.
[Cured product]
Next, the cured product of this embodiment will be described.
The cured product of the resin composition is obtained by curing the resin composition, and it is preferable to cure the resin composition by heat treatment. When the resin (A) is a polyamic acid resin, it can be converted to polyimide by heat treatment. For the heat treatment, an oven, a hot plate, infrared rays, etc. can be used. The curing temperature and curing time are the temperature and time required to volatilize the solvent contained in the resin composition and to make the resin (A) into a film that does not flow at room temperature. Specifically, the temperature is 100°C to 300°C, and the time is several minutes to several hours.

The cured product may be a film-like cured product made by forming a coating film from the resin composition. By forming the cured product into a film, the thickness of the cured product can be made constant, and unevenness can be eliminated in the subsequent formation of a laminate and in the subsequent bonding to a device substrate. A method for forming the cured product into a film can be exemplified by a method in which the resin composition is applied to a substrate or the like, followed by the above-mentioned heat treatment. A known method can be selected as a method for applying the resin composition, and examples of such methods include rotary application using a spinner, spray application, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, and slit die coater.

The glass transition temperature of the cured product is preferably 150°C or higher from the viewpoint of dimensional stability during heat treatment, and is preferably 260°C or lower from the viewpoint of ease of lamination. The glass transition temperature can be measured using a differential scanning calorimeter (DSC) or thermomechanical analysis (TMA). A more detailed method for measuring the glass transition temperature is described in the examples below.

The coefficient of linear thermal expansion (CTE) of the cured product is preferably 30 ppm/K or more from the viewpoint of adhesion, and is preferably 100 ppm/K or less from the viewpoint of reducing warping when bonding a device or a substrate and peeling caused by warping. The coefficient of linear thermal expansion can be calculated, for example, according to the following formula (X), as the ratio of the change in sample length from a temperature 80° C. lower to a temperature 30° C. lower than the glass transition temperature of each cured product.
CTE (1/K) = ((sample length (m) at Tg-30 ° C)) - (sample length (m) at Tg-80 ° C)) / (sample length (m) before measurement × 50 (K)) ... formula (X)

The change in sample length due to temperature can be measured using thermomechanical analysis (TMA). A more detailed method for measuring the linear thermal expansion coefficient is described in the Examples section below.

The 1% weight loss temperature of the cured product is preferably 300° C. or higher and 600° C. or lower, from the viewpoint of heat resistance required in processes using the cured product.
The 1% weight loss temperature is measured using a thermogravimetric analyzer by holding the sample at 120° C. for 30 minutes and then increasing the temperature to 500° C. at a rate of 5° C./min.

[Laminate]
Next, a laminate having the cured product will be described. The laminate of this embodiment is preferably one in which the cured product is laminated on a substrate. Specific examples of the substrate include inorganic substrates, organic substrates, and organic films such as films. More specifically, substrates such as silicon, alkali glass, non-alkali glass, borosilicate glass, sapphire, quartz, and ceramics, II-VI group compound semiconductors such as ZnS and ZnCe, III-V group compound semiconductors such as GaN, InP, GaAs, AlN, and GaAlAs, IV-IV group compound semiconductors such as SiC, substrates containing oxide semiconductors such as LT, LN, and IGZO, organic substrates and films such as PET, aramid, polyester, polypropylene, cycloolefin, and polyimide, and combinations of these, as well as those in which circuits, patterns, and elements are formed. As a method for forming a cured product on a substrate, a method for forming a film-like cured product can be used.

Since the cured product of this embodiment can be used as a temporary adhesive or a permanent adhesive, the laminate may be configured by bonding the above-mentioned substrates together with the cured product, or by bonding individualized elements to the above-mentioned laminate. The substrates bonded together with the cured product may be the same or different, and depending on the application, device substrates may be bonded together, or a device substrate may be bonded to a support substrate that protects it. A laminate in which substrates are bonded together can be created by bonding another substrate to the exposed surface of the cured product of the laminate in which the cured product is laminated on the substrate. Examples of bonding methods include a method of bonding using a press, a roll laminator, etc., and when laminating individualized elements, a flip chip bonder can also be used. When bonding, the substrates may be heated and bonded as necessary. The temperature at this time is preferably 50°C or higher and 250°C or lower, and the more preferable bonding temperature is the glass transition temperature of the resin (A) or higher. By setting the bonding temperature to the glass transition temperature of the resin (A) or higher, the adhesiveness of the resin (A) is improved, so that the substrates can be bonded together evenly. In addition, the pressure bonding temperature is preferably 200°C or less. This can suppress damage to the device substrate. In addition, the pressure during compression is preferably 0.1 MPa or more and 5.0 MPa or less, and more preferably 0.2 MPa or more and 3.0 MPa or less. Compression bonding may be performed in air or nitrogen. It is preferable to perform the compression bonding under reduced pressure conditions or in a vacuum, as this can reduce the entrapment of air during compression bonding.

The laminate may further have multiple layers made of a cured product. A laminate having multiple layers made of a cured product can be produced by repeating a process of forming a further cured product on one side of the laminate in which the above-mentioned substrates are bonded together, or the laminate in which the substrate and the singulated element are bonded together, and then pressing the surface on which the cured product is exposed to another substrate or singulated element. It can also be produced by repeatedly pressing one side of a laminate in which substrates are bonded together, or the laminate in which the substrate and the singulated element are bonded together, to the surface on which the cured product is exposed of a laminate in which a cured film is formed on another substrate or singulated element.

The thickness of the cured product in the laminate is preferably 0.5 μm or more and 8.0 μm or less. The thickness of the cured product in the laminate is preferably 0.5 μm or more, which allows the substrates to be stably bonded together. More preferably, the thickness of the cured product is 1.0 μm or more, which allows the device to go through the thinning heat treatment process after bonding without damage or peeling. In addition, the thickness of the cured product is preferably 8.0 μm or less, which reduces the effect of the adhesive thickness on thin devices. More preferably, the thickness is 5.0 μm or less, which reduces warping of the laminate. The thickness of the cured film can be measured using a scanning electron microscope, optical film thickness gauge, step gauge, laser microscope, etc.

The laminate preferably has a compound semiconductor layer, and such a laminate can be applied to various semiconductor devices such as high-frequency devices, high-output devices, laser diodes, lighting using light-emitting diodes, and displays. The compound semiconductor layer is a layer made of a compound semiconductor. Examples of compound semiconductors include, but are not limited to, those exemplified in the description of the laminate above.

[Semiconductor device]
This embodiment is a semiconductor device having the laminate. As an application example of the laminate of this embodiment, a semiconductor device having a semiconductor element will be described with reference to the drawings, taking a display using a monolithic LED element as an example. Fig. 1 is an enlarged cross-sectional view of the mounting portion of the LED element of a monolithic LED. Fig. 1 shows a state in which a monolithic LED element 1 is mounted on a circuit board 2 so as to be conductive with the circuit board 2.

2 shows an enlarged view of the monolithic LED element 1. A first LED layer 10, in which a first n-type GaN layer 111, a first light-emitting layer 112, a first p-type GaN layer 113, and a first transparent electrode 114 are formed in this order on a first sapphire substrate 110, is laminated with a second LED layer 20, in which a second n-type GaN layer 121, a second light-emitting layer 122, a second p-type GaN layer 123, and a second transparent electrode 124 are formed in this order, via a second adhesive layer 220 made of the cured product of this embodiment at the interface between the first transparent electrode 114 and the second transparent electrode 124. ITO or the like can be used for the transparent electrode. Furthermore, the second LED layer is laminated with a third LED layer 30 in which a third n-type GaN layer 131, a third light-emitting layer 132, a third p-type GaN layer 133, and a third transparent electrode 134 are formed in this order, and a third adhesive layer 230 made of the cured product of this embodiment is laminated at the interface between the second n-type GaN layer 121 and the third transparent electrode 134. Furthermore, each layer is electrically connected by an electrode 320, and the parts other than the connected layers are insulated by a passivation layer 310. The laminate using the cured product of this embodiment has excellent dimensional stability, so that even when a laminate having such a large number of layers is formed, it does not warp or peel off, and a highly reliable device can be created.

The present embodiment is a method for manufacturing a semiconductor device using the laminate of the present embodiment, characterized in that it includes at least one of a step of thinning the laminate and a step of singulating the laminate. The method for manufacturing a semiconductor device may also include a step of thinning the device.

As for the manufacturing method of a semiconductor device, the method of creating a monolithic LED element will be explained using drawings as an example. Figures 3A to 3K show an example of the manufacturing process for the monolithic LED display shown in Figure 1.

First, as shown in FIG. 3A, a first n-type GaN layer 111, a first light-emitting layer 112, and a first p-type GaN layer 113 are epitaxially grown in this order on a first sapphire substrate 110 using a known method. Then, ITO is formed by deposition on the surface of the first p-type GaN layer 113 as a first transparent electrode 114, and a laminate is prepared in which the first LED layer 10 is laminated on the first sapphire substrate 110. Then, an electrode via is formed from the first transparent electrode 114 side to the first n-type GaN layer 111. A known method can be used to form the via, and a dry etching method can be applied. This is step (3-a).

Next, as shown in FIG. 3B, the second LED layer 20 is formed on the second sapphire substrate 120 in the same manner as described above, and the second adhesive layer 220 made of the cured product of this embodiment is formed on the surface of the second transparent electrode 124. Next, the surface of the first transparent electrode 114 of the first LED layer 10 and the surface of the second adhesive layer 220 are brought face to face, and the two laminates are bonded together. A known bonding device can be used for bonding, and it is particularly preferable to use a wafer bonder and perform the bonding while heating under reduced pressure conditions. This is step (3-b).

Next, as shown in FIG. 3C, the second sapphire substrate 120 is removed. Removal methods include mechanical peeling by polishing and peeling by laser, with peeling by laser being preferred in terms of processing speed and reuse of the sapphire substrate. When peeling the sapphire substrate with a laser, a laser with a wavelength that penetrates the sapphire substrate is irradiated from the surface of the sapphire substrate opposite the surface in contact with the n-type GaN layer, and the n-type GaN layer is ablated at the interface between the sapphire substrate and the n-type GaN layer, thereby peeling it off. Examples of laser wavelengths for peeling the sapphire substrate include 248 nm and 266 nm. This is step (3-c).

Next, as shown in FIG. 3D, vias are created from the second n-type GaN layer 121 side. The vias are created so as to reach the vias formed in step (3-a), the first transparent electrode 114, and the second transparent electrode 124, respectively. This is referred to as step (3-d).

Furthermore, as shown in FIG. 3E, a laminate produced in the same manner as in step (3-b), in which a third sapphire substrate 130, a third LED layer 30, and a third adhesive layer 230 made of the cured product of this embodiment are laminated in that order, is bonded to the surface of the second n-type GaN layer 121 of the laminate produced in step (3-d) at the surface of the third adhesive layer 230, to obtain a laminate in which the first LED layer 10 to the third LED layer 30 are laminated. This is step (3-e).

Next, as shown in FIG. 3F, the first sapphire substrate 110 of the laminate is thinned by polishing, and then the third sapphire substrate 130 is peeled off and removed. This is step (3-f).

Next, as shown in FIG. 3G, vias are formed from the surface of the third n-type GaN layer 131. The vias are formed so as to reach the already formed vias, the second n-type GaN layer 121, and the third transparent electrode 134. This is step (3-g).

Next, as shown in Fig. 3H, a passivation layer 310 is formed on the surface of the third n-type GaN layer 131 and on the side surfaces of each via. The passivation layer can be formed by a known method, and can be formed by sputtering an inorganic material such as _SiO2 using a resist or a metal mask. This is referred to as step (3-h).

As shown in FIG. 3I, the inside of the via and the conductive portion with the circuit board 2 are filled with a metal to be used as an electrode by plating or the like to create the electrode 320. It is preferable to use Au or an alloy thereof as the electrode material. This is step (3-i).

As shown in Figure 3J, the completed LED device is then singulated to the size of the element. It is preferable to singulate using a mask, such as dry etching. This is referred to as step (3-j).

Finally, as shown in FIG. 3K, the obtained LED element is mounted on the circuit board 2. Known devices can be used for mounting, including a method of individually mounting the LED elements at the desired positions on the circuit board using a flip chip bonder, a method of mounting multiple LED elements at once using a stamp method, and a laser transfer method in which the LED element is temporarily attached to the exposed surface of a laser-transparent substrate on which another transfer material has been laminated, and then a laser is irradiated from the laser-transparent substrate side to mount it at the desired position. This is process (3-k).

As described above, this specification discloses the following:
＜1＞
A resin composition comprising a resin (A) having at least one structural unit selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), and a solvent,
With respect to 100 mol % in total of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A),
the resin (A) contains at least one of an acid dianhydride residue (A1) having a structure represented by formula (3) and a diamine residue (A2) having a structure represented by formula (4) in a total amount of 10 mol % or more and 40 mol % or less,
The resin (A) contains 1.0 mol % or more and 20 mol % or less of a diamine residue (A3) having a structure represented by formula (5),
A resin composition, wherein a ratio of all Si atoms contained in the resin (A) is 0.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the resin (A).

(In formula (1) and formula (2), ^X1 and ^X2 each independently represent a tetravalent acid dianhydride residue having 4 to 50 carbon atoms, ^Y1 and ^Y2 each independently represent a divalent diamine residue having 2 to 100 carbon atoms, and ^R1 and ^R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.)

(In formulas (3) to (5), R ³ to R ¹⁶ each independently represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom. R ¹⁷ to R ²⁰ each independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. R ²¹ and R ²² each independently represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. n represents an integer from 1 to 20. ^* 3a and ^* 3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or ^* 3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and ^* 3b represents a bonding site connected to a carbon atom of a carboxylic acid or a carboxylate ester in the structural unit represented by formula (2). ^* 4, and ^* 5 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).

＜2＞
The resin composition according to the above <1>, wherein the diamine residue (A2) is a diamine residue having a structure represented by formula (6).

(In formula (6), ^* 6 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).)

＜3＞
The resin composition according to <1> above, wherein in the diamine residue (A3), n in the formula (5) is 1.

＜4＞
The resin composition according to <1> above, wherein the solvent contained in the resin composition has a viscosity of 1.8 mPa·s or more and 3.1 mPa·s or less.

＜5＞
The resin composition according to the above item <1> or <2>, further comprising a silane coupling agent.

＜6＞
The resin composition according to <5> above, wherein the silane coupling agent contains a compound represented by formula (7):

(In formula (7), R ²³ represents an alkylene group having 5 to 10 carbon atoms. R ²⁴ each independently represents an alkyl group having 1 to 5 carbon atoms. Z represents a hydrogen atom or a group represented by any one of the following formulas (8) to (14).)

（式（８）～式（１４）中、Ｒ^２５～Ｒ^３１は、それぞれ独立に、水素原子、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基、水酸基またはハロゲン原子のいずれかを示す。^＊８～^＊１４は式（７）におけるＲ^２３との結合部位を表す。）

(In formulas (8) to (14), R ²⁵ to R ³¹ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^* 8 to ^* 14 represent bonding sites with R ²³ in formula (7).)

＜７＞
The resin composition according to any one of the above <1> to <6>, further comprising inorganic particles.
＜8＞
A cured product obtained by curing the resin composition according to any one of <1> to <7> above.
＜9＞
A laminate having the cured product according to the above item <8>.
＜10＞
The laminate according to the above item <9>, wherein the thickness of the cured product is 0.5 μm or more and 8.0 μm or less.
<11>
The laminate according to the above item <9> or <10>, wherein the laminate has a plurality of layers made of the cured product.
＜12＞
The laminate according to any one of <7> to <9> above, wherein the laminate has a compound semiconductor layer.
＜13＞
A semiconductor device comprising the laminate according to any one of items <9> to <11> above.
＜14＞
A method for manufacturing a semiconductor device, comprising at least one of a step of thinning the laminate described in any one of <9> to <11> above and a step of singulating the laminate described in any one of <9> to <11> above.

The present invention will be explained below with reference to examples, but the present invention is not limited to these examples.

<Evaluation method>
(1) Measurement of glass transition temperature and linear thermal expansion coefficient Resin compositions 1 to 43 obtained in the following production examples were applied to the glossy surface of an 18 μm-thick electrolytic copper foil with a bar coater so that the thickness after curing would be 10 μm, then dried at 80° C. for 10 minutes, and further heat-treated at 250° C. for 30 minutes in a nitrogen atmosphere to cure the resin, thereby obtaining a resin-laminated copper foil. Next, the copper foil of the obtained resin-laminated copper foil was entirely etched with a ferric chloride solution to obtain a cured single film of the resin composition.
The obtained cured single film was cut into a length of 1.5 cm x 3 cm, and the film was rolled up to prepare a cylindrical sample with a diameter of 2 mm and a length of 1.5 cm. This sample was measured in indentation mode using a thermal analyzer TMA/SS6600 (manufactured by Hitachi High-Tech Science Co., Ltd.). The glass transition temperature was calculated from the inflection point of the obtained TMA curve. In addition, the coefficient of linear thermal expansion (CTE) was calculated as the ratio of the change in sample length from a temperature 80°C lower to a temperature 30°C lower than the glass transition temperature of each cured product according to the following formula (X).
CTE (1/K) = ((sample length (m) at Tg-30 ° C)) - (sample length (m) at Tg-80 ° C)) / (sample length (m) before measurement × 50 (K)) ... formula (X)

(2) Measurement of thermal decomposition temperature Approximately 15 mg of the single film of the cured film used in the measurement of glass transition temperature and linear thermal expansion coefficient was packed into a standard aluminum container and measured using a thermogravimetric analyzer (TGA-50, manufactured by Shimadzu Corporation). The measurement conditions were as follows: after holding at 120°C for 30 minutes, the temperature was raised to 500°C at a heating rate of 5°C/min. The temperature at which the weight was reduced by 1% was read from the obtained weight loss curve, and this temperature was defined as the 1% weight loss temperature.

(3) Evaluation of adhesion of laminates Resin compositions 1 to 43 were applied onto a 4-inch silicon substrate with a thickness of 500 μm by adjusting the rotation speed of a spin coater so that the thickness after curing was 8 μm, and the resin was cured by heat treatment at 120° C. for 3 minutes and drying, and then heat treatment at 250° C. for 30 minutes. Next, a 4-inch glass substrate (manufactured by Corning Japan Co., Ltd., product name: EX-G) was placed on top of the substrate, and the upper and lower plates were pressure-bonded at a pressure of 1.0 MPa for 5 minutes using a vacuum bonder (manufactured by Mikado Technos Co., Ltd.) set at 200° C., respectively, to obtain a laminate in which a cured product was formed between the glass substrate and the silicon substrate.
Furthermore, Resin Compositions 1 to 43 were diluted with a solvent as necessary and applied to a 4-inch silicon substrate by a spin coater so that the film thickness after curing would be 2.0 μm, and a laminate having a cured film thickness of 2.0 μm was prepared in the same manner as in the preparation of the laminate having a cured film thickness of 8.0 μm described above.
These laminates were checked from the glass substrate side, and the adhesion areas were visually confirmed. Those in which 90% or more of the substrate area was bonded were rated A, those in which 80% or more but less than 90% was bonded were rated B, those in which 70% or more but less than 80% was bonded were rated C, those in which 50% or more but less than 70% was bonded were rated D, and those in which less than 50% was bonded were rated E.

(4) Evaluation of heat resistance of laminate The laminate with a cured film thickness of 2.0 μm prepared in the evaluation of the adhesiveness of the laminate was placed on a hot plate heated to 300° C. with the silicon substrate surface in contact with the hot plate and heated for 3 minutes. Thereafter, the laminate was transferred to a tray and cooled to room temperature, and then the bonding area was evaluated using the same evaluation method as in (3).

The names of the abbreviations for the acid dianhydrides, diamines, additives and solvents used in the following preparations are as follows.
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride. An acid dianhydride that gives the structure of an acid dianhydride residue (A1) after polymerization. (Mitsubishi Chemical Corporation)
PMDA: Pyromellitic dianhydride (manufactured by Daicel Corporation)
BSAA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (manufactured by SHPP Japan LLC)
6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (Merck Ltd.).
ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (manufactured by Toho Chemical Industry Co., Ltd.)
Benzidine: 4,4'-diaminobiphenyl. A diamine that gives the structure of diamine residue (A2) after polymerization. (Manufactured by Tokyo Chemical Industry Co., Ltd.)
m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl. A diamine that, after polymerization, gives a diamine residue (A2) having a structure represented by formula (6). (Manufactured by Wakayama Seika Kogyo Co., Ltd.)
LP-7100: Tetramethyl-1,3-bis(3-aminopropyl)disiloxane. A diamine having a silicon atom that gives the structure of diamine residue (A3) after polymerization. n in formula (5) is 1. (Product name: manufactured by Shin-Etsu Chemical Co., Ltd.)
APPS2: α,ω-bis(3-aminopropyl)polydimethylsiloxane. A diamine having a Si atom and giving the structure of diamine residue (A3) after polymerization. The number average molecular weight is 860, and the average of n in formula (5) is 9.
DDS: 3,3'-diaminodiphenyl sulfone (manufactured by Konishi Chemical Industry Co., Ltd.)
BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Merck Electronics Co., Ltd.)
NMP: N-methylpyrrolidone. Solvent used in polymerization and compounding. (Mitsubishi Chemical Corporation, viscosity: 1.70 mPa·s)
CHN: Cyclohexanone. Solvent used in polymerization and blending. (Manufactured by Toyo Gosei Co., Ltd., viscosity: 1.97 mPa.s)
DMI: Dimethylimidazolidinone. Solvent used in polymerization and preparation. (Manufactured by Fujifilm Wako Co., Ltd., viscosity: 2.63 mP·s).
DAA: Diacetone alcohol. Solvent used in polymerization and preparation. (Tokyo Chemical Industry Co., Ltd., viscosity: 2.90 mPa s)
DPM: Dipropylene glycol monomethyl ether. Solvent used in polymerization and blending. (Tokyo Chemical Industry Co., Ltd., viscosity: 3.47 mP·s)
KBM-403: 3-glycidoxypropyltrimethoxysilane. Silane coupling agent. (Product name: manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-1083: 7-octenyltrimethoxysilane. A silane coupling agent having a structure represented by formula (9). (Product name: manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-4803: 8-glycidoxyoctyltrimethoxysilane. A silane coupling agent represented by formula (8). (Product name: manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-5803: 8-methacryloxyoctyltrimethoxysilane. A silane coupling agent having a structure represented by formula (10). (Product name: manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-6803: N-2-(aminoethyl)-8-aminooctyltrimethoxysilane. A silane coupling agent having a structure represented by formula (11). (Product name: manufactured by Shin-Etsu Chemical Co., Ltd.)
MEK-EC-2030Y: Organosilica sol dispersed in methyl ethyl ketone ( _SiO2 concentration 30 wt%) (product name; manufactured by Nissan Chemical Industries, Ltd.)

<Production Example 1>
In a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating/cooling device using hot water/cooling water, and a stirrer, 18.5 g of LP-7100, 80.7 g of DDS, and 36.6 g of BAHF, which are diamine components, were dissolved together with 562.7 g of NMP. Then, 22.7 g of BPDA and 131.8 g of ODPA, which are acid dianhydride components, were added, and the mixture was stirred at 60° C. for 4 hours, and then reacted at 130° C. for 2 hours. After the polymerization was completed, NMP was added to adjust the concentration to 30% by weight of solids, and PI-1, which is a polymerization solution of polyimide/polyamic acid copolymer, was prepared.

<Production Examples 2 to 27>
Polymerization solutions of polyimide/polyamic acid copolymers PI-2 to PI-27 were prepared in the same manner as in Example 1, except that the acid anhydride, diamine, and solvent were changed to the compositions and amounts added shown in Tables 1 to 3.

<Examples 1 to 37 and Comparative Examples 1 to 6>
The polyimide/polyamic acid copolymer polymerization solutions obtained in Production Examples 1 to 27 were mixed and stirred with a silane coupling agent, inorganic particles, and a solvent according to the contents of Tables 4 to 6 to prepare resin compositions 1 to 43. The resin compositions were filtered through a PTFE filter with a pore size of 0.5 μm. Using these resin compositions, evaluation samples were prepared by the above-mentioned method, and various evaluations were performed. The evaluation results are shown in Tables 7 to 9.

[Comparative Example 1, Examples 1 and 7]
In Example 1, the resin (A) contains at least one of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) in a total amount of 100 mol % relative to the total amount of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A), and therefore the linear thermal expansion coefficient could be made lower than that of Comparative Example 1. As a result, the warping of the substrate due to heat treatment could be reduced, and peeling of the laminate after heat treatment could be reduced.
In addition, since Example 7 contains at least one of the acid dianhydride residue (A1) and the diamine residue (A2) in a total amount of 15 mol % or more, the coefficient of linear thermal expansion is further reduced, and peeling of the laminate after heat treatment can be further improved.

[Comparative Example 2, Examples 2 and 8]
In Example 2, the resin (A) contains at least one of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) in a total amount of 40 mol % or less relative to 100 mol % of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A), and therefore the glass transition temperature could be made to be an appropriate value compared to Comparative Example 2. As a result, the initial adhesiveness of the laminate could be improved.
In Example 8, the total content of at least one of the acid dianhydride residue (A1) and the diamine residue (A2) was set to 30 mol % or less, thereby further improving the initial adhesion of the laminate, and in particular significantly improving the adhesion of the thin film.

[Comparative Example 3, Examples 3 and 9]
In Example 3, the ratio of all Si atoms contained in the resin (A) was 0.5 parts by mass or more per 100 parts by mass of the resin (A), so that the laminate was easier to attach to the entire surface of the substrate compared to Comparative Example 3.
In addition, in Example 9, the ratio of all Si atoms contained in the resin (A) was 2.0 parts by mass or more per 100 parts by mass of the resin (A), and therefore the initial adhesion of the laminate was further improved.

[Comparative Example 4, Examples 4 and 10]
In Example 4, the ratio of all Si atoms contained in the resin (A) was 5.0 parts by mass or less relative to 100 parts by mass of the resin (A), and therefore the thermal stability was excellent and the 1% weight loss temperature was improved compared to Comparative Example 4. As a result, when the laminate was heat-treated, clouding and peeling due to decomposition of the Si component could be suppressed.
In Example 10, the ratio of all Si atoms contained in the resin (A) was 4.0 parts by mass or less per 100 parts by mass of the resin (A), and therefore the coefficient of linear thermal expansion was further reduced, thereby improving the adhesion of the laminate after heat treatment.

[Comparative Example 5, Examples 5, 11, 30, and 32]
In Example 5, the resin (A) contains 1.0 mol % or more of the diamine residue (A3) relative to the total of 100 mol % of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A). Therefore, the Si component involved in adhesion is distributed throughout the cured product. As a result, the initial adhesion of the laminate was improved compared to Comparative Example 5.
Furthermore, in Examples 11, 30, and 32, the resin (A) contains 2.0 mol % or more of the diamine residue (A3) relative to the total of 100 mol % of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A). Therefore, the Si component is more uniformly distributed, and the adhesion of the laminate near the outer periphery of the substrate can be further improved.

[Comparative Example 6, Examples 6, 12, and 13]
In Example 6, the resin (A) contains 20 mol % or less of the diamine residue (A3) relative to the total of 100 mol % of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A). Therefore, the heat resistance was improved, and unlike Comparative Example 6, clouding of the film caused by decomposition gases during heat treatment of the laminate could be suppressed.
In addition, in Examples 12 and 13, the resin (A) contains 17 mol% or less of the diamine residue (A3) relative to the total of 100 mol% of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A), so that the linear thermal expansion coefficient and the glass transition temperature were optimized and excessive softening of the film during heat treatment could be suppressed. As a result, the adhesion of the laminate after heat treatment could be greatly improved.

[Example 29]
Example 29 has m-TB represented by formula (6) as the diamine residue (A2), and therefore the stability of the polymer in the varnish can be improved and the thickness uniformity of the coating film can be improved compared to Example 11. As a result, the adhesiveness, particularly in thin films, can be improved.

[Example 31]
In Example 31, the solvent constituting the resin element was CHN having a viscosity of 1.8 mPa·s or more, and the edge coating property when forming a coating film was improved. As a result, the adhesion of the laminate, especially in the thin film, was improved compared to Examples 11 and 30.

[Examples 33 and 34]
In Examples 33 and 34, the use of DAA or DMI, which has a viscosity of 3.1 mPa·s or less, as the solvent constituting the resin component improved the applicability when forming a coating film. As a result, the adhesion of the laminate was improved compared to Examples 11 and 30.

[Example 35]
Example 35 has m-TB represented by formula (6) as the diamine residue (A2), and therefore the stability of the polymer in the varnish can be improved and the thickness uniformity of the coating film can be improved compared to Examples 11 and 34. As a result, the adhesiveness, particularly in thin films, can be improved.

[Example 36]
Example 36 had LP-7100, which has a repeating unit number n=1 as the diamine residue (A3), and thus had improved heat resistance compared to Examples 33 and 34. As a result, the adhesiveness of the laminate after heat treatment was greatly improved.

[Example 37]
Example 37 had m-TB represented by formula (6) as the diamine residue (A2) and further had LP-7100 with a repeating unit number n=1 as the diamine residue (A3), and thus was able to improve the in-plane uniformity and heat resistance of the coating film compared to Examples 35 and 36. As a result, the adhesion of the laminate and the adhesion of the laminate after heat treatment were improved.
In addition, by using DMI, which has a viscosity of 1.8 mPa·s or more, as the solvent constituting the resin element, the film thickness uniformity at the end of the coating film could be improved compared to Example 13. As a result, the adhesiveness, especially in thin films, could be improved.

[Example 13]
In Example 13, the diamine residue (A2) contained 2,2'-dimethyl-4,4'-diaminobiphenyl, which has the structure of formula (6), and thus both the initial adhesion of the laminate and the adhesion after heat treatment were improved compared to Example 12.
In addition, since the number of repeating units n of the diamine residue (A3) was 1, both the heat resistance and the adhesiveness were improved compared to Example 29.

[Examples 14 to 18 and 23]
In Examples 14 to 18, the resin composition contained a silane coupling agent, and thus the initial adhesion of the laminate was improved compared to Example 12. Similarly, in Example 23, the initial adhesion of the laminate was improved compared to Example 13, particularly in the case of a thin film.

[Examples 19 to 22 and 24]
In Examples 19 to 22 and 24, the resin composition contained a silane coupling agent represented by formula (7), and the initial adhesion of the laminate and the adhesion after heat treatment were further improved compared to Example 17.

[Examples 25 to 27]
In Examples 25 to 27, the resin composition contained inorganic particles, and thus the coefficient of linear thermal expansion was lower than in Examples 12 and 13, and the decrease in adhesion due to heat treatment of the laminate was significantly reduced.

[Example 28]
In Example 28, the resin composition contains both the silane coupling agent represented by formula (7) and inorganic particles, so that peeling due to insufficient adhesion and peeling during heat treatment due to warping of the substrate can be efficiently suppressed. As a result, compared with Example 24, peeling of the laminate after heat treatment can be further reduced.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-054038) filed on March 29, 2023, and is incorporated by reference in its entirety. In addition, all references cited herein are incorporated in their entirety.

1 Monolithic LED element 2 Circuit board 10 First LED layer 20 Second LED layer 30 Third LED layer 110 First sapphire substrate 111 First n-type GaN layer 112 First light-emitting layer 113 First p-type GaN layer 114 First Transparent electrode 120 Second sapphire substrate 121 Second n-type GaN layer 122 Second light-emitting layer 123 Second p-type GaN layer 124 Second transparent electrode 130 Third sapphire substrate 131 Third n-type GaN layer 132 Third light-emitting layer 133 Three p-type GaN layer 134 Third transparent electrode 220 Second adhesive layer 230 Third adhesive layer 310 Passivation layer 320 Electrode

Claims (14)

A resin composition comprising a resin (A) having at least one structural unit selected from a structural unit represented by formula (1) and a structural unit represented by formula (2), and a solvent,
With respect to 100 mol % in total of the acid dianhydride residues (X1) and (X2) and the diamine residues (Y1) and (Y2) contained in the resin (A),
the resin (A) contains at least one of an acid dianhydride residue (A1) having a structure represented by formula (3) and a diamine residue (A2) having a structure represented by formula (4) in a total amount of 10 mol % or more and 40 mol % or less,
The resin (A) contains 1.0 mol % or more and 20 mol % or less of a diamine residue (A3) having a structure represented by formula (5),
A resin composition, wherein a ratio of all Si atoms contained in the resin (A) is 0.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the resin (A).

(In formula (1) and formula (2), ^X1 and ^X2 each independently represent a tetravalent acid dianhydride residue having 4 to 50 carbon atoms, ^Y1 and ^Y2 each independently represent a divalent diamine residue having 2 to 100 carbon atoms, and ^R1 and ^R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.)

(In formulas (3) to (5), R ³ to R ¹⁶ each independently represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom. R ¹⁷ to R ²⁰ each independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. R ²¹ and R ²² each independently represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. n represents an integer from 1 to 20. ^* 3a and ^* 3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or ^* 3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and ^* 3b represents a bonding site connected to a carbon atom of a carboxylic acid or a carboxylate ester in the structural unit represented by formula (2). ^* 4, and ^* 5 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2). The resin composition according to claim 1 , wherein the diamine residue (A2) is a diamine residue having a structure represented by formula (6).

(In formula (6), ^* 6 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).) The resin composition according to claim 1, wherein in the diamine residue (A3), n in formula (5) is 1. The resin composition according to claim 1, wherein the solvent contained in the resin composition has a viscosity of 1.8 mPa·s or more and 3.1 mPa·s or less. The resin composition according to claim 1 or 2, further comprising a silane coupling agent. The resin composition according to claim 5 , wherein the silane coupling agent contains a compound represented by formula (7).

(In formula (7), R ²³ represents an alkylene group having 5 to 10 carbon atoms. R ²⁴ each independently represents an alkyl group having 1 to 5 carbon atoms. Z represents a hydrogen atom or a group represented by any one of the following formulas (8) to (14).)

(In formulas (8) to (14), R ²⁵ to R ³¹ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^* 8 to ^* 14 represent bonding sites with R ²³ in formula (7).) The resin composition according to claim 1 or 2, further comprising inorganic particles. A cured product obtained by curing the resin composition according to any one of claims 1 to 4. A laminate having the cured product according to claim 8. The laminate according to claim 9, wherein the thickness of the cured product is 0.5 μm or more and 8.0 μm or less. The laminate according to claim 10, wherein the laminate has multiple layers made of the cured product. The laminate according to claim 10, wherein the laminate has a compound semiconductor layer. A semiconductor device having the laminate according to claim 10. A method for manufacturing a semiconductor device, comprising at least one of a process for thinning the laminate described in claim 10 and a process for singulating the laminate described in claim 10.

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