Resin composition and method for producing semiconductor device

Abstract

At least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, and At least one type of solvent A having a lactone structure, and It comprises at least one glycol ester-based solvent B1 that is commercially compatible with the above solvent A, and The mass ratio of the above solvent A / the above solvent B1 is 90 / 10 to 75 / 25, and A resin composition comprising: a resin (A) having a structural unit represented by the following formula (Ia) and a structural unit represented by the following formula (IIa); or a resin (B) having a structural unit represented by the following formula (IIa) and a structural unit represented by the following formula (IVa).

Description

Technology Field

[0001] One embodiment of the present invention relates to a resin composition comprising a resin such as polyamideimide and an organic solvent, and more specifically, to a resin composition that substantially does not contain NMP. Another embodiment of the present invention relates to a method for manufacturing a semiconductor device using the resin composition of the above embodiment. Background Technology

[0002] Resins such as polyamideimide, polyamide, and polyimide are excellent in various properties, such as heat resistance, chemical resistance, and mechanical properties. For this reason, they are widely used for various applications, for example, as binder resins for paints. Polar solvents are used when synthesizing resins such as polyamideimide, polyamide, and polyimide, and when preparing varnishes or paints. Among these, N-methyl-2-pyrrolidone (NMP) is widely used as a preferred organic solvent for polyamideimide resins (Patent Document 1).

[0003] However, recently, regulations regarding the use of organic solvents have become stricter from the perspective of environmental conservation and safety and hygiene. Furthermore, due to concerns regarding the harmful effects of NMP on the human body, safety and hygiene in the work environment when NMP is used are becoming an issue in the industrial sector. For example, in Europe, under the REACH rule, NMP is classified as a Substance of Very High Concern (SVHC) and its use is regulated. Consequently, there is a growing demand for alternative solvents to NMP for applications using resins such as polyamideimide, polyamide, and polyimide.

[0004] For example, N-ethyl-2-pyrrolidone (NEP) is known as an alternative solvent to NMP. However, because NEP has a similar molecular structure to NMP, it is highly likely that its use will be regulated in the future, just like NMP. Prior art literature

[0005] Japanese Published Patent Application No. 2012-241082 The problem to be solved

[0006] In conventional technology, when a substitute solvent for NMP is used, the properties tend to deteriorate compared to a resin composition using NMP, and it has not reached a sufficiently satisfactory level of properties.

[0007] Therefore, embodiments of the present invention provide a resin composition that substantially does not contain NMP as a solvent and can achieve properties equivalent to those of a conventional resin composition using NMP. In particular, one embodiment of the present invention provides a resin composition that can suppress the occurrence of whitening after coating, thereby obtaining excellent coating film properties. means of solving the problem

[0008] Taking into account the circumstances described above, the inventors conducted various studies on alternative solvents for NMP. As a result, they discovered that by combining specific organic solvents, the occurrence of whitening after coating can be suppressed and excellent film properties obtained, thereby completing the present invention. That is, the embodiments of the present invention are as follows. However, the present invention is not limited to the following embodiments.

[0009] One embodiment comprises at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, and

[0010] At least one type of solvent A having a lactone structure, and

[0011] The present invention relates to a resin composition comprising at least one solvent B that is in use with the above solvent A, wherein the moisture content of the solvent B is 2 mass% or less after being stored for 3 hours in an environment of 30°C and 60% RH.

[0012] One embodiment comprises at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, and

[0013] At least one type of solvent A having a lactone structure, and

[0014] The present invention relates to a resin composition comprising at least one solvent B that is in use with the above solvent A, wherein the solvent B is selected from the group consisting of glycol ester-based solvents and cyclic ketone-based solvents.

[0015] In the above embodiment, the mass ratio of solvent A to solvent B is preferably 90 / 10 to 10 / 90.

[0016] Preferably, the boiling points of the above solvent A and the above solvent B are each 100 to 250°C.

[0017] The above resin preferably comprises a polyamideimide resin having a structural unit represented by the following formula (1).

[0018] [Chemical Formula 1]

[0019]

[0020] In the formula, R represents a residue from which an amino group has been removed from a diamine compound or a residue from which an isocyanate group has been removed from a diisocyanate compound, and n represents an integer greater than or equal to 1.

[0021] In the above embodiment, the resin is preferably a resin having a structural unit represented by the following formula (Ia).

[0022] [Chemical Formula 2]

[0023]

[0024] In the formula, R1 to R4 each independently represent one or more substituents selected from the group consisting of a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom.

[0025] X is a single bond, or a divalent organic group selected from the following.

[0026] [Chemical Formula 3]

[0027]

[0028] In the formula, R5 and R6 are each independently a hydrogen atom, or one or more substituents selected from the group consisting of alkyl groups having 1 to 9 carbon atoms, trifluoromethyl groups, trichloromethyl groups, and phenyl groups.

[0029] In the above embodiment, the resin is preferably a resin having a structural unit represented by the following formula (IIa) or (VIa).

[0030] [Chemical Formula 4]

[0031]

[0032] Among the foods, R7~R 10 Each independently represents a hydrogen atom or a substituent, and R 11 and R 12 Each independently represents a hydrocarbon group of 2, and m is an integer greater than or equal to 1.

[0033] [Chemical Formula 5]

[0034]

[0035] In the formula, R represents, each independently, at least one substituent selected from the group consisting of a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom, and n represents an integer from 1 to 6.

[0036] In the above embodiment, the resin is preferably a resin having a structural unit represented by the following formula (IVa).

[0037] [Chemical Formula 6]

[0038]

[0039] In the formula, X represents, each independently, at least one substituent selected from the group consisting of a hydrogen atom, or a halogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a hydroxyalkyl group.

[0040] It is preferable that the above resin further comprises at least one structural unit selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc).

[0041] [Chemical Formula 7]

[0042]

[0043] In the formula, S represents, each independently, an alkyl group having 1 to 3 carbon atoms, a represents an integer from 0 to 4, b represents an integer from 0 to 3, and c represents an integer from 0 to 4.

[0044] Another embodiment relates to a method for manufacturing a semiconductor device, comprising forming a film using the resin composition of the above embodiment.

[0045] It is preferable that the formation of the above film be carried out before the encapsulation process.

[0046] The above coating is preferably a primer layer or an insulating layer. Effects of the invention

[0047] According to an embodiment of the present invention, a resin composition can be provided that substantially does not contain NMP as a solvent and can achieve properties equivalent to those of a conventional resin composition using NMP. The resin composition according to an embodiment of the present invention is less prone to whitening after application and can be preferably used for various applications such as paints and semiconductor device materials. Specific details for implementing the invention

[0048] Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments and includes various embodiments.

[0049] <Resin Composition>

[0050] A resin composition of one embodiment of the present invention comprises an organic solvent other than NMP and at least one resin selected from the group consisting of polyamideimide, polyimide, polyamide, and polyamide acid. The term "resin composition" may be used interchangeably with "varnish" or "paint."

[0051] The above resin composition substantially does not contain NMP. In one embodiment, "substantially does not contain NMP" means that, based on the total mass of the resin composition, the content of NMP may preferably be less than 0.3 mass%. The content of NMP may preferably be less than 0.2 mass%, and more preferably less than 0.1 mass%. Therefore, it does not completely exclude NMP that is incorporated during a process such as the synthesis of the resin and remains in the resin composition.

[0052] (Organic solvent)

[0053] In the above resin composition, the organic solvent comprises solvent A and solvent B described below. In one embodiment, solvent A is at least one solvent having a lactone structure (cyclic ester structure). It is preferable that at least solvent A dissolves at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid.

[0054] The term "dissolution" above means that when the solution obtained by adding solvent A to the resin and stirring at room temperature is visually inspected, there are no precipitates, no turbidity, and the entire solution becomes transparent. Here, the "room temperature" may generally be in the range of 10 to 40°C, and the range of 20 to 30°C is preferred. In one embodiment, it is preferable that solvent A can dissolve up to 30 mg of resin powder per 100 mL of solvent A. The "stirring" above may be carried out at a condition of 40 to 50 rpm using a stirrer such as a mix rotor.

[0055] Meanwhile, solvent B is at least one solvent that is in use with solvent A, and is characterized by having a moisture content of 2 mass% or less after storing the dried solvent B for 3 hours in an environment of 30°C and 60% RH (relative humidity). The moisture content is a value measured for solvent B after placing 30 g of dried solvent B into a cylindrical container with a radius of 2 cm and storing it for 3 hours in an environment of 30°C and 60% RH. The moisture content is preferably 2 mass% or less, more preferably 1.5 mass% or less, and even more preferably 1 mass% or less. By having the moisture content of solvent B be 2 mass% or less, whitening (resin precipitation) of the resin composition can be easily suppressed, and a uniform coating film can be easily obtained.

[0056] The above moisture content refers to the ratio of the amount of moisture contained in solvent B based on the total mass of solvent B. In this specification, it is a value measured using a Karl Fischer moisture measuring device (moisture meter) according to the Karl Fischer total titration method at room temperature. For example, the moisture meter CA-21 manufactured by Nitto Seiko Analitech Co., Ltd. may be used.

[0057] The compatibility of solvent B and solvent A is determined as follows. First, 10 mL of solvent B is mixed with 10 mL of solvent A in a colorless, transparent glass container. Next, the solution obtained by stirring or dispersing them at 25°C is left to stand for 10 minutes. Afterward, the interface of the solution is observed visually from the side of the glass container. If an interface is observed in the solution, it is determined that they are "incompatible." On the other hand, if no interface is observed in the solution, it is determined that they are "compatible." The stirring or dispersing when preparing the above solution may be carried out under conditions such as holding the glass container in your hand and shaking it rapidly up and down about 10 times.

[0058] Specific examples of solvent A include lactones such as γ-butyrolactone (GBL), γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone. In one embodiment, solvent A preferably comprises at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, and γ-caprolactone, and more preferably comprises at least γ-butyrolactone.

[0059] Meanwhile, solvent B is at least one solvent that is in use with solvent A as described above, and has a moisture content of 2 mass% or less after being stored for 3 hours in an environment of 30°C and 60% RH (relative humidity), and is not particularly limited.

[0060] Specific examples of solvent B include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents (excluding cyclic ester solvents), ether solvents, and ketone solvents. One of these may be used alone, or two or more may be used in combination.

[0061] More specifically, the aromatic hydrocarbon solvent may be, for example, xylene, ethylbenzene, tetramethylbenzene, etc.

[0062] Aliphatic hydrocarbon solvents may be, for example, hexane, octane, decane, etc. Also, mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, etc. may be used.

[0063] The ester-based solvent (excluding cyclic ester-based solvents) may be an alkyl acetate such as ethyl acetate, propyl acetate, or butyl acetate. In addition, the ester-based solvent may be a glycol ester-based solvent. Specific examples include monoalkylene glycol monoalkyl ether monoacetates or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate (butyl cellosolve acetate), diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate.

[0064] In addition, the ester solvent may be a polycarboxylic acid alkyl ester such as dialkyl glutarate, dialkyl succinate, dialkyl adipicate, etc.

[0065] Among these, glycol ester-based solvents are preferred, monoalkylene glycol monoalkyl ether monoacetate is more preferred, and ethylene glycol monomethyl ether acetate is even more preferred.

[0066] The ether-based solvent may be an alkyl ether such as diethyl ether or ethyl butyl ether. In addition, it may be a glycol ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, or triethylene glycol diethyl ether. In addition, it may be a cyclic ether such as tetrahydrofuran.

[0067] Ketone-based solvents may be acyclic ketones such as acetone and methyl ethyl ketone, and cyclic ketones such as cyclopentanone, cyclohexanone, and isophorone. Among these, cyclic ketone-based solvents are preferred, and cyclopentanone or cyclohexanone is more preferred.

[0068] As solvent B, the solvent described above may be used alone or in combination of two or more types. In one embodiment, solvent B preferably comprises at least one selected from the group consisting of a glycol ester-based solvent (hereinafter also referred to as "solvent B1") and a cyclic ketone-based solvent (hereinafter also referred to as "solvent B2"). In one embodiment, solvent B is more preferably composed of one or more selected from the group consisting of ethylene glycol monomethyl ether acetate (butyl cellosolve acetate) (BuCA), cyclopentanone (CPN), and cyclohexanone (CHN).

[0069] Although not specifically limited, examples of desirable combinations of solvent A / solvent B include GBL / CPN, GBL / CHN, and GBL / BuCA.

[0070] Although not bound by theory, for example, GBL, which is an example of solvent A, is a polar solvent like NMP, but tends to have inferior solubility in resin compared to NMP. Consequently, it is thought that whitening is likely to occur after coating in resin compositions using GBL. On the other hand, solvent B is a solvent with low water absorption, for example, a solvent whose moisture content becomes 2 mass% or less after being stored for 3 hours in an environment of 30°C and 60% RH. Therefore, it is presumed that the water absorption of solvent A can be suppressed by using solvent A and solvent B with low water absorption in combination. Furthermore, it is presumed that the coating film properties can be improved by using solvent A and solvent B in combination.

[0071] The mass ratio of solvent A to solvent B can be appropriately adjusted from the perspective of the solubility and water absorption of the resin. In one embodiment, the mass ratio of solvent A to solvent B may be 90 / 10 to 10 / 90. Below, the case where the resin is the resin (A) or resin (B) described later will be explained in more detail.

[0072] In one embodiment, when solvent A / solvent B is a cyclic ketone-based solvent (B2) such as GBL / CPN or CHN, the mass ratio of solvent A / solvent B2 is preferably 90 / 10 to 10 / 90. The mass ratio is more preferably 70 / 30 to 30 / 70, and even more preferably 60 / 40 to 40 / 60. With such a combination, the surface roughness of the coating film after drying tends to be improved, and it becomes easier to prevent the nozzle from drying out when dispensing.

[0073] In another embodiment, when solvent A / solvent B is a glycol ester-based solvent (B1) such as GBL / BuCA, the mass ratio of solvent A / solvent B1 is preferably 90 / 10 to 60 / 40, and more preferably 90 / 10 to 70 / 30. The mass ratio is even more preferably 85 / 15 to 75 / 25. In addition, the mass ratio of solvent A / solvent B1 is also preferably 90 / 10 to 75 / 25. With such a combination, the absorption rate is reduced, and there is a tendency to suppress the precipitation of resin during film formation.

[0074] In one embodiment, the resin composition may additionally include a solvent different from solvent A and solvent B within a range that does not degrade the desired properties. Based on the total mass of the solvents, the total amount of solvent A and solvent B is preferably 90 mass% or more, more preferably 95 mass% or more, and even more preferably 99.7 mass% or more.

[0075] In one embodiment, from the perspective of drying properties during film formation, the boiling points of solvent A and solvent B are preferably 100 to 250 °C each. The boiling points are more preferably 130 to 220 °C, and even more preferably 150 to 210 °C. Among the solvents exemplified above, from the perspective of boiling point, solvent A is preferably γ-butyrolactone (GBL, boiling point 204 °C). Meanwhile, solvent B is preferably cyclopentanone (CPN, boiling point 131 °C), cyclohexanone (CHN, boiling point 156 °C), and butyl cellosolve acetate (BuCA, boiling point 192 °C).

[0076] When these solvents are used, since they have a boiling point equal to or lower than that of NMP, excellent drying properties can be easily obtained when forming a film, just as when using NMP.

[0077] (profit)

[0078] In the resin composition of the above embodiment, the resin may be a resin known in the art, but it is preferable to include at least one resin selected from the group consisting of polyamideimide, polyimide, polyamide, and polyamic acid. These resins have excellent heat resistance, are tough, and also have excellent flexibility. Therefore, a resin composition using these resins can easily form a film having desirable characteristics, for example, as an insulating layer or primer layer of a semiconductor device.

[0079] Polyamideimide, polyimide, polyamide, and polyamic acid can be synthesized according to methods known in the art. In the resin composition of the above embodiment, at least one resin selected from the group consisting of polyamideimide, polyimide, polyamide, and polyamic acid may include, for example, a structural unit represented by the following formula (Ia). In addition, it may include a structural unit represented by the following formula (IIa).

[0080] [Chemical Formula 8]

[0081]

[0082] In the formula, R1 to R4 each independently represent one or more substituents selected from the group consisting of a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom.

[0083] The above alkyl group or alkoxy group may be any of a straight-chain structure, a branched structure, or a cyclic structure. The above alkyl group and the above alkoxy group are more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0084] The above halogen atom may be any of a fluorine atom, a chlorine atom, or a bromine atom.

[0085] X is a single bond or a divalent organic group selected from the following. In one embodiment, X is preferably -CR5R6-.

[0086] [Chemical Formula 9]

[0087]

[0088] In the formula, R5 and R6 are each independently a hydrogen atom, or one or more substituents selected from the group consisting of alkyl groups having 1 to 9 carbon atoms, trifluoromethyl groups, trichloromethyl groups, and phenyl groups.

[0089] The above alkyl group may be any of a straight-chain structure, a branched structure, and a cyclic structure. In one embodiment, in the formula, R5 and R6 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.

[0090] [Chemical Formula 10]

[0091]

[0092] Among the foods, R7~R 10 Each independently represents a hydrogen atom or a substituent, and R 11 and R 12 Each independently represents a hydrocarbon group of 2, and m is an integer greater than or equal to 1.

[0093] In one embodiment, the R7 to R 10 Preferably, each is independently a substituent. The substituent may be at least one selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom. The alkyl group and the alkoxy group may have a straight-chain structure, a branched structure, or a cyclic structure. R7 to R 10It is more preferable that the silver be an alkyl group having 1 to 6 carbon atoms or a phenyl group. The hydrogen atoms in the phenyl group may be substituted with an alkyl group having 1 to 6 carbon atoms. In one embodiment, R7 to R 10 Each is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0094] The above R 11 and R 12 Each may independently be an alkylene group having 1 to 9 carbon atoms or a phenylene group. A hydrogen atom in the phenylene group may be substituted with an alkyl group having 1 to 3 carbon atoms. The alkylene group may have a straight chain structure, a branched structure, or a cyclic structure. In one embodiment, R 11 and R 12 Each is preferably a straight-chain alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, and even more preferably an alkylene group having 3 or 4 carbon atoms.

[0095] In the above formula, m is preferably 1 to 100, more preferably 1 to 40, and even more preferably 1 to 10.

[0096] In one embodiment, the resin may be a polyamideimide resin comprising a structural unit represented by the following formula (IIIa).

[0097] [Chemical Formula 11]

[0098]

[0099] In one embodiment, at least one resin selected from the group consisting of polyamideimide, polyimide, polyamide, and polyamic acid may include, for example, a structural unit having a cardo-structured fluorene backbone represented by the following formula (IVa). In addition, it may include at least one selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc).

[0100] [Chemical Formula 12]

[0101]

[0102] [Chemical Formula 13]

[0103]

[0104] In the above formula (IVa), X represents, respectively, at least one substituent selected from the group consisting of a hydrogen atom, or a halogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a hydroxyalkyl group.

[0105] The above halogen atom may be a fluorine atom, a chlorine atom, or a bromine atom. The above alkyl group and the above alkoxy group may be any of a straight chain structure, a branched structure, and a cyclic structure.

[0106] In one embodiment, X is preferably independently a hydrogen atom, a C1 to C9 alkyl group, or a halogen atom. The alkyl group is more preferably an C1 to C6 alkyl group, and even more preferably an C1 to C3 alkyl group. In one embodiment, X is preferably a hydrogen atom.

[0107] In the above formulas (Va), (Vb), and (Vc), S independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer from 0 to 4, b represents an integer from 0 to 3, and c represents an integer from 0 to 4.

[0108] In one embodiment, the resin may additionally include a structural unit (VIa) represented by the following formula.

[0109] [Chemical Formula 14]

[0110]

[0111] In the formula, R represents, each independently, at least one substituent selected from the group consisting of a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom, and n represents an integer from 1 to 6.

[0112] The above halogen atom may be a fluorine atom, a chlorine atom, or a bromine atom. The above alkyl group and the above alkoxy group may be any of a straight chain structure, a branched structure, and a cyclic structure.

[0113] In one embodiment, R is preferably, independently, an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms.

[0114] n is preferably an integer from 2 to 4, and more preferably 3 or 4.

[0115] In the above embodiment, the resin is preferably a resin comprising a structural unit represented by formula (Ia) and a structural unit represented by formula (IIa) or (VIa). The resin is more preferably a polyamideimide resin comprising a structural unit represented by formula (Ia) and a structural unit represented by formula (IIa) or (VIa). The resin is even more preferably a polyamideimide resin comprising a structural unit represented by formula (Ia), a structural unit represented by formula (IIa) or (VIa), and a structural unit represented by the following formula (IIIa).

[0116] In the above embodiment, the resin is preferably a resin comprising a structural unit represented by formula (IVa) and a structural unit represented by any one of formulas (Va), (Vb), and (Vc). The resin is more preferably a resin comprising a structural unit represented by formula (IVa), a structural unit represented by any one of formulas (Va), (Vb), and (Vc), and a structural unit represented by formula (IIa) or (VIa). The resin is more preferably a polyamideimide resin comprising a structural unit represented by formula (IVa), a structural unit represented by any one of formulas (Va), (Vb), and (Vc), and a structural unit represented by (IIa) or (VIa) as needed, and is even more preferably a polyamideimide resin comprising a structural unit represented by the following formula (IIIa).

[0117] [Chemical Formula 15]

[0118]

[0119] As another embodiment of the polyamideimide resin (B) having the above cardo-structured fluorene backbone, instead of the structural unit represented by any one of the above formulas (Va), (Vb), and (Vc), the structural unit represented by the following formula (Vd) may be used.

[0120] [Chemical Formula 16]

[0121]

[0122] In the above formula, A represents a divalent group or a single bond. The divalent group is any one group selected from the group consisting of an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a dimethylmethylene group, a hexafluoroisopropylidene group, an amide group, an ester group, a diphenyl ketone group, a 1,4-phenyleneoxy group, a 1,4-biphenyleneoxy group, a sulfonylbis(1,4-phenyleneoxy) group, an isopropylidenebis(1,4-phenyleneoxy) group, and a hexafluoroisopropylidenebis(1,4-phenyleneoxy) group. In one embodiment, A is preferably an oxygen atom.

[0123] B represents, respectively, a hydrogen atom, or at least one substituent selected from the group consisting of a C1-9 alkyl group, a C1-9 alkoxy group, a trifluoromethyl group, a carboxylic acid group, a hydroxyl group, and a halogen atom. The halogen atom may be a fluorine atom, a chlorine atom, or a bromine atom.

[0124] In one embodiment, B is preferably, independently, a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. The alkyl group is more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms.

[0125] (Polyamideimide)

[0126] Below, polyamideimide is described in more detail as an example of a resin.

[0127] Polyamideimide is a resin obtained by reacting a diamine compound or a diisocyanate compound with an acid component including a tribasic acid anhydride or a tribasic acid halide. Here, each raw material compound may be used in combination of multiple types as desired.

[0128] The diamine compound or diisocyanate compound may be, for example, an aromatic diamine or aromatic diisocyanate, an aliphatic diamine or an aliphatic diisocyanate. An aromatic diamine or aromatic diisocyanate is preferred.

[0129] Examples of aromatic diamines (diisocyanates) include 2,7-diaminofluorene, 9,9-bis[4-(4-aminophenoxy)phenyl]-9H-fluorene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diamino-2,2'-biphenyldisulfonic acid, 3,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,6-diaminocarbazole, 4,4'-bis(4-aminophenoxy)biphenyl, 2-trifluoromethyl-1,4-diaminobenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl ether, 4-aminophenyl sulfide, 4,4'-diamino-3,3'-dimethylbiphenyl, Examples include naphthalene diamine and naphthalene diisocyanate.

[0130] Examples of aliphatic diamines (diisocyanates) include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-di(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 4,4'-methylenebis(cyclohexylamine), hexamethylenediamine, and hexamethylene diisocyanate.

[0131] In one embodiment, it is preferable to use a diamine compound or a diisocyanate compound capable of deriving structural units represented by the formulas (Ia), (IIa), (IVa), (Va) to (Vd), and (VIa) described above.

[0132] For example, a diamine compound or diisocyanate compound capable of deriving a structural unit represented by formula (IVa) is represented by the following formula (IV). In the formula, X is as previously described, and Y represents an amino group (-NH2) or an isocyanate group (-NCO).

[0133] [Chemical Formula 17]

[0134]

[0135] Specific examples of the compound represented by the above formula (IV) include 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, 9,9-bis(4-amino-3-fluorophenyl)fluorene, etc. These can preferably be used as diamine compounds capable of deriving structural unit (IVa).

[0136] In addition, specific examples of compounds capable of deriving a structural unit represented by formula (VIa) include 1,3-bis(3-aminopropyl)1,1,3,3-tetramethyldisiloxane, 1,3-bis(2-aminoethyl)1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminomethyl)1,1,3,3-tetramethyldisiloxane, 1,3-bis(4-aminobutyl)1,1,3,3-tetramethyldisiloxane, 1,3-bis(5-aminopentyl)1,1,3,3-tetramethyldisiloxane, and 1,3-bis(6-aminohexyl)1,1,3,3-tetramethyldisiloxane.

[0137] In one embodiment, the polyamideimide resin (A) preferably has a structural unit represented by formula (Ia) and a structural unit represented by formula (IIa). In this polyamideimide resin (A), the total amount of the ratio of the structural unit represented by formula (Ia) and the ratio of the structural unit represented by formula (IIa) relative to the total amount of structural units derived from a diamine compound or a diisocyanate compound may be greater than 80 mol% and may be 100 mol%.

[0138] In addition, as another embodiment, the polyamideimide resin (B) may be a resin having a structural unit represented by formula (IIa) and a structural unit represented by formula (IVa), and additionally preferably has at least one structural unit selected from the group consisting of structural units represented by formulas (Va), (Vb), and (Vc). In this polyamideimide resin (B), the total amount of the ratio of the structural unit represented by formula (IIa), the ratio of the structural unit represented by formula (IVa), and the ratio of at least one structural unit selected from the group consisting of structural units represented by formulas (Va), (Vb), and (Vc), relative to the total amount of structural units derived from a diamine compound or a diisocyanate compound, may be greater than 80 mol% and may be 100 mol%. Here, with respect to the total amount of structural units derived from diamine compounds or diisocyanate compounds, the ratio of the structural unit represented by formula (IVa) may preferably be 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%. By adjusting the ratio of the structural unit represented by formula (IVa) to within the above range, it becomes easier to balance solubility while increasing the heat resistance of the resin.

[0139] In either of the polyamideimide resins (A) and (B) of the above embodiment, the ratio of the structural unit represented by formula (IIa) to the total amount of structural units derived from a diamine compound or a diisocyanate compound may preferably be 1 to 50 mol%, more preferably 3 to 30 mol%, and even more preferably 5 to 10 mol%.

[0140] In one embodiment, to produce a polyamideimide resin, other diamine compounds or diisocyanate compounds capable of deriving structural units other than those represented by formulas (Ia), (IIa), (IVa), (Va) to (Vd), and (VIa) may be used in combination. It is preferable that the proportion of structural units derived from other diamine compounds or diisocyanate compounds be 20 mol% or less relative to the total amount of structural units derived from diamine compounds or diisocyanate compounds. It is more preferable that the proportion of structural units derived from the other compounds be 10 mol% or less, and even more preferable that it be 5 mol% or less.

[0141] As for the tribasic acid anhydride, it is not particularly limited, but preferably an aromatic tribasic acid anhydride is used, and among these, trimellitic acid anhydride is preferred. As for the tribasic acid halide, it is not particularly limited, but a tribasic acid chloride is used, and furthermore, an aromatic tribasic acid chloride is preferably used. Examples include trimellitic acid anhydride chloride (anhydrous trimellitic acid chloride). From the perspective of reducing the burden on the environment, it is desirable to use trimellitic acid anhydride, etc.

[0142] In this regard, in one embodiment, the polyamideimide resins (A) and (B) preferably further comprise the formula (IIIa) derived from trimellitic anhydride as a structural unit derived from tribasic acid anhydride. Based on the total amount of structural units derived from acid components, the ratio of the structural unit represented by the formula (IIIa) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol%. In one embodiment, based on the total amount of structural units derived from acid components, the ratio of the structural unit represented by the formula (IIIa) may be 100 mol%.

[0143] As for the acid component, in addition to the above tribasic acid anhydride (or tribasic acid halide), saturated or unsaturated polybasic acids such as dicarboxylic acids and tetracarboxylic acid dihydrides may be used within a range that does not impair the properties of polyamideimide.

[0144] Examples of dicarboxylic acids include, but are not particularly limited, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, etc. Examples of tetracarboxylic acid dihydrides include, but are not particularly limited, pyromellitic acid dihydride, benzophenone tetracarboxylic acid dihydride, biphenyl tetracarboxylic acid dihydride, etc. These may be used individually or in any combination thereof.

[0145] The total amount of carboxylic acids other than tribasic acids (dicarboxylic acids and tetracarboxylic acids) is preferably used in the range of 0 to 50 mol% of the total carboxylic acids to maintain the properties of the polyamideimide, and is more preferably in the range of 0 to 30 mol%.

[0146] The ratio of the diamine compound (or diisocyanate compound) and the acid component (the total amount of tribasic acid anhydride or tribasic acid anhydride halide and, if necessary, dicarboxylic acid and tetracarboxylic acid dihydride) is preferably adjusted in terms of the molecular weight and degree of crosslinking of the resulting polyamideimide. For example, for a total amount of acid component of 1.0 mole, it is preferable to have the diamine compound (or diisocyanate compound) in an amount of 0.8 to 1.1 moles, more preferable to have an amount of 0.95 to 1.08 moles, and particularly more preferable to have an amount of 1.0 to 1.05 moles.

[0147] Polyamideimide is a resin having amide bonds and imide bonds within its molecular backbone, and is obtained, for example, by the reaction of a diamine compound or a diisocyanate compound with an acid component such as a tricarboxylic acid anhydride. In one embodiment, it is preferable that the polyamideimide has a structural unit represented by the following formula (1).

[0148] [Chemical Formula 18]

[0149]

[0150] In the formula, R represents a residue from which an amino group has been removed from a diamine compound, or a residue from which an isocyanate group has been removed from a diisocyanate compound, and n represents an integer greater than or equal to 1.

[0151] In one embodiment, R may be a structural unit represented by the previously described formula (Ia) and a structural unit represented by formula (IIa). A polyamideimide (A) having such a structure can be obtained, for example, by reacting 2,2-bis[4-(4-aminophenoxy)phenyl]propane with 1,3-bis(3-aminopropyl)1,1,3,3-tetramethyldisiloxane and trimellitic anhydride chloride.

[0152] In other embodiments, R may be a structural unit represented by the previously described formula (IVa), a structural unit represented by any one of formulas (Va), (Vb), and (Vc), and a structural unit represented by formula (VIa). A polyamideimide (B) having such a structure can be obtained, for example, by reacting 9,9-bis(4-aminophenyl)fluorene with 4,4'-methylenebis[2,6-bis(1-methylethyl)benzenamine] with trimellitic anhydride chloride.

[0153] (Method for manufacturing polyamideimide resin)

[0154] Polyamideimide resins can be manufactured according to known methods and are not particularly limited. Polyamideimide resins can be manufactured, for example, by reacting a diamine component and / or a diisocyanate component with an acid component. The diamine component, the diisocyanate component, and the acid component are as described above. The above reaction can be carried out in the presence of a solvent-free or organic solvent. The reaction temperature is preferably in the range of 25°C to 250°C. The reaction time can be appropriately adjusted depending on the batch size, the reaction conditions employed, etc.

[0155] The organic solvent (synthetic solvent) used in the manufacture of polyamideimide resin is not particularly limited. Examples of usable organic solvents include ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane; cyclic ester-based (lactone-based) solvents such as γ-butyrolactone; non-cyclic ester-based solvents such as cellosolve acetate; ketone-based solvents such as cyclohexanone and methyl ethyl ketone; nitrogen-containing solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; and aromatic hydrocarbon-based solvents such as toluene and xylene. One of these organic solvents may be used alone, or two or more may be used in combination.

[0156] In one embodiment, it is preferable to select and use an organic solvent capable of dissolving the resin produced, and it is preferable to use a polar solvent. Although not particularly limited, specific examples of polar solvents include nitrogen-containing solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, γ-butyrolactone, and N,N'-dimethylpropylene urea [1,3-dimethyl-3,4,5,6-tetrahydropyridimin-2(1H)-one], dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, sulfolane, etc. Among these, nitrogen-containing solvents are preferred.

[0157] The amount of synthetic solvent used is not particularly limited, but it is preferably 300 to 3,500 parts by mass and more preferably 400 to 2,000 parts by mass per 100 parts by mass of the total amount of the acid component and the diamine compound or diisocyanate compound.

[0158] Generally, the synthesis solvent is removed according to known techniques after the synthesis of the resin, and the resin is recovered. For example, water is added to a reaction solution containing the resin to precipitate the resin, and the resin is obtained by separating and recovering the precipitate. If necessary, a process for heating and drying the recovered resin may be provided. Heating and drying may be carried out in two or more stages, or by heating to a temperature within a range that does not cause phase transition or decomposition of the resin.

[0159] In one embodiment, the polyamideimide resin can be produced by a method in which a precursor of the polyamideimide resin is first prepared by reacting an acid component with a diamine component, and then the precursor is dehydrated and closed to obtain the polyamideimide resin. However, the method of closing the precursor is not particularly limited, and methods known in the art may be used. For example, a thermal closing method in which dehydrated and closed the precursor by heating under atmospheric pressure or reduced pressure, or a chemical closing method using a dehydrating agent such as acetic anhydride in the presence or absence of a catalyst may be used.

[0160] In the case of the thermal closed-loop method, it is preferable to carry out the process while removing the water generated by the dehydration reaction out of the system. During the dehydration reaction, the reaction solution may be heated to 80°C to 400°C, preferably 100°C to 250°C. In addition, water may be removed by azeotropy by using an organic solvent capable of azeotropy with water, such as benzene, toluene, or xylene.

[0161] In the case of the chemical ring-closing method, the reaction may be carried out at 0°C to 120°C, preferably 10°C to 80°C, in the presence of a chemical dehydrating agent. As the chemical dehydrating agent, it is preferable to use, for example, acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride, or carbodiimide compounds such as dicyclohexylcarbodiimide. During the reaction, it is preferable to use a substance that promotes the cyclization reaction, such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine, and imidazole.

[0162] Chemical dehydrating agents may be used in a ratio of 90 to 600 mol% relative to the total amount of diamine components, and substances that promote cyclization reactions may be used in a ratio of 40 to 300 mol% relative to the total amount of diamine components. In addition, dehydrating catalysts such as triphenylphosphite, tricyclohexylphosphite, triphenylphosphate, phosphoric acid, phosphorus pentaoxide, and other phosphorus compounds, and boron compounds such as boric acid and boric anhydride may be used.

[0163] In one embodiment, the weight average molecular weight (Mw) of the polyamideimide is preferably 30,000 or more, more preferably 35,000 or more, and even more preferably 38,000 or more, from the perspective of ensuring strength of the coating film. Meanwhile, from the perspective of ensuring solubility in organic solvents, the weight average molecular weight of the polyamideimide is preferably 150,000 or less, more preferably 130,000 or less, and even more preferably 120,000 or less. The “Mw” described in this specification is a value measured by standard polystyrene conversion using gel permeation chromatography.

[0164] In one embodiment, the Mw of the polyamideimide is preferably in the range of 30,000 to 150,000. The Mw is more preferably in the range of 35,000 to 130,000, and even more preferably in the range of 38,000 to 120,000. When a polyamideimide having an Mw within the above range is used, changes in the viscosity of the resin composition can be suppressed, and good storage stability can be easily obtained.

[0165] The Mw of polyamideimide can be measured by sampling during resin synthesis and using a calibration curve of standard polystyrene by gel permeation chromatography (GPC). By continuing the synthesis of polyamideimide until the desired number-average molecular weight is achieved, it can be managed within the above-mentioned desirable range. The measurement conditions for GPC will be described later in the examples.

[0166] In one embodiment, the glass transition temperature (Tg) of the polyamideimide is preferably 120°C or higher, more preferably 150°C or higher, and even more preferably 200°C or higher. Meanwhile, from the perspective of solubility, Tg is preferably 400°C or lower, more preferably 380°C or lower, and even more preferably 350°C or lower.

[0167] Here, Tg is a value obtained by performing a dynamic viscoelasticity test using a film obtained by applying and drying a resin (varnish) dissolved in a solvent. Tg is preferably 120 to 400 ℃, more preferably 150 to 380 ℃, and even more preferably 200 to 350 ℃.

[0168] Since the polyamideimide has a Tg of 150°C or higher, it is possible to obtain excellent reliability, for example, even in a heat cycle test. In addition, when the above resin composition is applied to form a primer layer of a power semiconductor device, it is easy to suppress the softening of the coating film due to heat generation during operation, which reduces adhesion.

[0169] By designing the resin with a framework in which the Tg of the polyamideimide is 350°C or lower, solubility in solvents can be ensured, thereby improving film-forming processability.

[0170] The resin content in the resin composition can be appropriately set according to the application. Although not particularly limited, in one embodiment, the resin content is preferably 5 to 30 mass% based on the total mass of the resin composition, and more preferably 10 to 25 mass%, from the perspective of balance with other components.

[0171] By making the resin content in the resin composition 5 mass% or more, the amount of coating required to achieve the target film thickness after coating and drying the resin composition is reduced, so processability can be easily improved. On the other hand, by making the resin content in the resin composition 25 mass% or less, viscosity stability when the resin composition is stored for a long period can be easily improved.

[0172] In one embodiment, the viscosity of the resin composition is not particularly limited, but may be in the range of, for example, 10 to 400 mPa·s. The viscosity of the resin composition can be adjusted according to the application method. In this regard, in one embodiment, the viscosity of the resin composition may preferably be 10 to 200 mPa·s, more preferably 10 to 150 mPa·s, and even more preferably 10 to 100 mPa·s. In another embodiment, the viscosity of the resin composition may preferably be 100 to 400 mPa·s, more preferably 150 to 350 mPa·s, and even more preferably 200 to 300 mPa·s.

[0173] Here, the viscosity is a value obtained by measuring a varnish dissolved in a solvent such that the non-volatile component (solid component) is 1 to 20% using an E-type viscometer at 10 rpm under conditions of 25 ℃.

[0174] If the viscosity measured at 10 rpm is 10 mPa·s or higher, it is easy to secure a sufficient film thickness during application. Also, if the viscosity is 400 mPa·s or lower, it tends to be easier to secure a uniform film thickness during application. In addition, the viscosity can be measured using, for example, a viscometer (RE type) manufactured by Toki Industry Co., Ltd. For the measurement, the measurement temperature is set to 25 ℃ ± 0.5 ℃, and then 1 mL to 1.5 mL of the resin composition solution is added to the viscometer, and the viscosity is recorded 10 minutes after the start of the measurement.

[0175] (Other ingredients)

[0176] In one embodiment, the resin composition may include any component in addition to the resin and organic solvent, depending on the intended use. For example, the resin composition may preferably be used as a paint. When the resin composition is used as a paint, any component such as pigments, fillers, defoaming agents, preservatives, and surfactants may be added as needed. Additionally, it may include a resin other than the above resin.

[0177] The resin composition above can be used for film formation. A method for manufacturing the film includes, for example, applying the resin composition of the above embodiment to a substrate, and drying the resin composition on the substrate by heating to obtain a coating film. In one embodiment, the resin composition is preferably a resin composition comprising polyamide, polyamideimide, or polyimide. When such a resin composition is used, the drying is preferably carried out in two stages by heating at 30 to 120°C and then heating at 150 to 300°C. Since the resin composition of the above embodiment does not require a reaction such as imidization in the process of forming the coating film, a coating film can be obtained at a lower heating temperature compared to the case where a polyamide acid is applied and imidized.

[0178] In one embodiment, the resin composition may be a varnish or a paint used as a semiconductor device material. For example, the paint may include polyamideimide, an organic solvent comprising solvent A and solvent B, and a silane coupling agent. Such a paint (resin composition) can preferably be used as a coating material for manufacturing a semiconductor device. In this regard, one embodiment of the present invention relates to a semiconductor device having a coating formed using the paint of the above embodiment.

[0179] A semiconductor device of one embodiment of the present invention can be obtained by a manufacturing method comprising forming a coating film using the paint (resin composition) of the above embodiment. For example, the coating film can be formed by applying the paint over a component of the semiconductor device and then heating and drying it. Conditions such as the heating temperature and heating time during coating film formation (heating and drying) can be appropriately adjusted.

[0180] In one embodiment, it is preferable that the heating and drying be carried out in two stages. In this embodiment, the heating and drying temperature of the first stage may preferably be in the range of 30 to 120°C, and more preferably in the range of 50 to 100°C. The heating and drying temperature of the second stage may be in the range of 150 to 300°C, more preferably in the range of 180 to 260°C, and even more preferably in the range of 200 to 230°C.

[0181] One embodiment of the present invention relates to a method for manufacturing a semiconductor device, comprising forming a coating film on the surface of a substrate mounted with at least a semiconductor device using the paint (resin composition) of the above embodiment. The paint may be used to form a coating film, for example, a protective layer of the semiconductor device, a primer layer that improves the adhesion between the encapsulant and the substrate, and an insulating layer of the semiconductor device. The method for manufacturing the semiconductor device may include a process for forming the coating film and a process for encapsulation. The process for forming the coating film is as described above and may be performed, for example, before the encapsulation process. Since the paint substantially does not contain NMP, not only is the work safety excellent, but the degradation of properties is suppressed compared to paints using NMP by a specific combination of solvents, making it possible to easily obtain desired properties. In addition, it is also easy to lower the drying temperature during coating film formation.

[0182] In one embodiment, a method for manufacturing a semiconductor device comprises, at least, applying a paint (resin composition) of the above embodiment to the surface of a substrate on which a semiconductor element is mounted and drying it to form an insulating film (insulating layer), and forming a resin encapsulation layer on the insulating layer.

[0183] In the above manufacturing method, from the perspective of workability, it is preferable that the resin composition includes a polyamideimide resin as a resin component. The formation of the insulating layer can be carried out by applying the resin composition to a predetermined point and drying the coating film. The application of the resin composition can be carried out by applying various coating methods. The method of application is not particularly limited, but examples include spray application, potting, dipping, and dispensing methods. Considering workability, potting or dispensing application is preferred.

[0184] In one embodiment, the film thickness of the coating obtained by forming a resin composition is not particularly limited, but may be in the range of 0.5 to 10 μm. By having a film thickness within the above range, it tends to be easier to secure sufficient adhesion to, for example, a substrate. In this regard, the film thickness is preferably in the range of 1 to 10 μm, and more preferably in the range of 3 to 10 μm.

[0185] The material of the substrate is not particularly limited and can be selected from materials well known in the art. From the perspective of manufacturing a power semiconductor device, it is preferable that the die pad material be at least one selected from the group consisting of Ni, Cu, and Ag plating formed thereon. It is preferable that the lead material of the lead frame be selected from the group consisting of Ni and Cu.

[0186] The material of the semiconductor device is not particularly limited and may be, for example, a silicon wafer, a silicon carbide wafer, etc.

[0187] The resin encapsulation layer may be composed of a cured product of a resin that is well known in the art as an encapsulation material. As the encapsulation material, for example, a liquid or solid epoxy resin composition may be used. The resin encapsulation layer may be formed, for example, by performing transfer molding using the encapsulation material.

[0188] In another embodiment, a method for manufacturing a semiconductor device comprises, for example, forming a resin layer by applying and drying a resin composition of the above embodiment on a semiconductor substrate having a plurality of wirings of the same structure formed thereon, and, if necessary, forming a redistribution wire on the resin layer that is electrically conductive with an electrode on the semiconductor substrate. In addition to these processes, if necessary, a protective layer (resin layer) may be formed on the redistribution wire or on the resin layer using the resin composition. In addition, in addition to the above processes, if necessary, an external electrode terminal may be formed on the resin layer, and then, if necessary, dicing may be included.

[0189] In the above semiconductor device, the semiconductor element is not particularly limited, but may be, for example, a silicon wafer, a silicon carbide wafer, etc. The method of applying the resin layer is not particularly limited, but is preferably spin coating, spray coating, or dispensing coating. The method of drying the resin layer can be carried out by a method known in the art. Since the resin composition of the above embodiment has excellent properties such as sputter resistance, plating resistance, and alkali resistance required in the process of forming redistribution, it is not limited to the configuration of the semiconductor device described above and can be preferably used as a constituent material for all kinds of semiconductor devices.

[0190] Exemplary embodiments of the present invention are summarized below.

[0191] [1] At least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, and

[0192] At least one type of solvent A having a lactone structure, and

[0193] It comprises at least one glycol ester-based solvent B1 that is commercially compatible with the above solvent A, and

[0194] The mass ratio of the above solvent A / the above solvent B1 is 90 / 10 to 75 / 25, and

[0195] A resin composition comprising: a resin (A) having a structural unit represented by the following formula (Ia) and a structural unit represented by the following formula (IIa); or a resin (B) having a structural unit represented by the following formula (IIa) and a structural unit represented by the following formula (IVa).

[0196] [Chemical Formula 19]

[0197]

[0198] (In the formula, R1 to R4 each independently represent one or more substituents selected from the group consisting of a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom, and

[0199] X is a single bond, or a divalent organic group selected from the following, and

[0200] [Chemical Formula 20]

[0201]

[0202] In the formula, R5 and R6 are each independently a hydrogen atom, or one or more substituents selected from the group consisting of C1 to C9 alkyl groups, trifluoromethyl groups, trichloromethyl groups, and phenyl groups.

[0203] [Chemical Formula 21]

[0204]

[0205] (In food, R7~ R 10 Each independently represents a hydrogen atom or a substituent, and R 11 and R 12 Each independently represents a 2-valent hydrocarbon group, and m is an integer greater than or equal to 1.

[0206] [Chemical Formula 22]

[0207]

[0208] (In the formula, X represents, respectively, at least one substituent selected from the group consisting of a hydrogen atom, or a halogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a hydroxyalkyl group.)

[0209] [2] At least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, and

[0210] At least one type of solvent A having a lactone structure, and

[0211] It comprises at least one cyclic ketone-based solvent B2 that is commercially compatible with the above solvent A, and

[0212] The mass ratio of the above solvent A / the above solvent B2 is 70 / 30 to 30 / 70, and

[0213] A resin composition comprising: a resin (A) having a structural unit represented by the following formula (Ia) and a structural unit represented by the following formula (IIa); or a resin (B) having a structural unit represented by the following formula (IIa) and a structural unit represented by the following formula (IVa).

[0214] [Chemical Formula 23]

[0215]

[0216] (In the formula, R1 to R4 each independently represent one or more substituents selected from the group consisting of a hydrogen atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom, and

[0217] X is a single bond, or a divalent organic group selected from the following, and

[0218] [Chemical Formula 24]

[0219]

[0220] In the formula, R5 and R6 are each independently a hydrogen atom, or one or more substituents selected from the group consisting of C1 to C9 alkyl groups, trifluoromethyl groups, trichloromethyl groups, and phenyl groups.

[0221] [Chemical Formula 25]

[0222]

[0223] (In food, R7~ R 10 Each independently represents a hydrogen atom or a substituent, and R 11 and R 12 Each independently represents a 2-valent hydrocarbon group, and m is an integer greater than or equal to 1.

[0224] [Chemical Formula 26]

[0225]

[0226] (In the formula, X represents, respectively, at least one substituent selected from the group consisting of a hydrogen atom, or a halogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a hydroxyalkyl group.)

[0227] [3] A resin composition described in [1] or [2], wherein the boiling point of the solvent A is 100 to 250°C.

[0228] [4] A resin composition described in any one of [1] to [3], wherein the boiling point of the solvent B1 or solvent B2 is 100 to 250°C.

[0229] [5] A resin composition described in [1], wherein solvent A comprises γ-butyrolactone and solvent B1 comprises ethylene glycol monomethyl ether acetate.

[0230] [6] A resin composition described in [2] above, wherein solvent A comprises γ-butyrolactone and solvent B2 comprises cyclopentanone or cyclohexanone.

[0231] [7] The resin composition described in any one of [1] to [6], wherein the resin (A) and the resin (B) each comprise a polyamideimide having a structural unit represented by the following formula (1).

[0232] [Chemical Formula 27]

[0233]

[0234] (In the formula, R represents a residue obtained by removing an amino group from a diamine compound or a residue obtained by removing an isocyanate group from a diisocyanate compound, and n represents an integer greater than or equal to 1.)

[0235] [8] The resin (B) described in any one of [1] to [7] is a resin that further comprises at least one structural unit selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc).

[0236] [Chemical Formula 28]

[0237]

[0238] (In the formula, S independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer from 0 to 4, b represents an integer from 0 to 3, and c represents an integer from 0 to 4.)

[0239] [9] A semiconductor device having a film formed using a resin composition described in any one of [1] to [8] above.

[0240]

[10] A method for manufacturing a semiconductor device comprising forming a film using a resin composition described in any one of [1] to [8] above.

[0241]

[11] The formation of the above film is carried out before the encapsulation process, in the method of manufacturing a semiconductor device described in

[10] .

[0242]

[12] A method for manufacturing a semiconductor device as described in

[11] or

[12] , wherein the above film is a primer layer or an insulating layer.

[0243] Examples

[0244] Next, various embodiments are described, but it goes without saying that preferred embodiments of the present invention are not limited to these embodiments and include many other embodiments based on the well-known knowledge of the invention.

[0245] 1. Synthesis of Polyamideimide

[0246] (Synthesized Example 1)

[0247] In a 1-liter 4-neck flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil-water separator, 45.4 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 3.1 g of 1,3-bis(3-aminopropyl)1,1,3,3-tetramethyldisiloxane were added under a nitrogen stream, and 310.1 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and dissolved to obtain a solution.

[0248] Next, 26.1 g of trimellitic anhydride chloride (hereinafter referred to as TAC) was added to the above solution while cooling to not exceed 20 ℃. After stirring at room temperature for 2 hours, 15.0 g of triethylamine (hereinafter referred to as TEA) was added and reacted at room temperature for at least 15 hours to obtain a polyamic acid solution.

[0249] The obtained polyamic acid solution was further processed at 180°C for 6 hours to obtain a polyamideimide resin solution. The polyamideimide resin solution was diluted with water, and the resulting precipitate was separated, ground, and heated to dry to obtain a powdered polyamideimide (A).

[0250] Regarding the weight average molecular weight (Mw) of the obtained polyamideimide (A), the result was measured by standard polystyrene conversion using gel permeation chromatography (hereinafter referred to as GPC), and the Mw was 98,000. Also, the glass transition temperature (Tg) was 220 °C.

[0251] (Synthesized Example 2)

[0252] In a 1-liter 4-neck flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil-water separator, 15.7 g of 9,9-bis(4-aminophenyl)fluorene, 16.5 g of 4,4'-methylenebis[2,6-bis(1-methylethyl)benzenamine], and 2.5 g of 1,3-bis(3-aminopropyl)1,1,3,3-tetramethyldisiloxane were added under a nitrogen stream, and 298 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and dissolved to obtain a solution.

[0253] Next, 21.1 g of trimellitic acid chloride (hereinafter referred to as TAC) was added to the above solution while cooling to not exceed 20 ℃. After stirring at room temperature for 2 hours, 12.1 g of triethylamine (hereinafter referred to as TEA) was added and reacted at room temperature for at least 15 hours to obtain a polyamic acid solution.

[0254] The obtained polyamic acid solution was further processed at 180°C for 6 hours to obtain a polyamideimide resin solution. The polyamideimide resin solution was diluted with water, and the resulting precipitate was separated, ground, and heated to dry to obtain a powder of polyamideimide (B).

[0255] Regarding the weight average molecular weight (Mw) of the obtained polyamideimide (B), the result was measured by standard polystyrene conversion using gel permeation chromatography (hereinafter referred to as GPC), and the Mw was 67,000. Also, the glass transition temperature (Tg) was 330 °C.

[0256] In addition, the GPC measurement conditions for the polyamideimide obtained in Synthesis Examples 1 and 2 are as follows.

[0257] Liquid Transfer Pump: LC-20AD

[0258] UV-Vis Detector: SPD-20A

[0259] Flow rate: 1 mL / min

[0260] Column temperature: 40 ℃

[0261] Molecular weight standard material: Standard polystyrene

[0262] Eluent: NMP

[0263] In addition, the method for measuring the glass transition temperature (Tg) of the polyamideimide obtained in Synthesis Examples 1 and 2 is as follows.

[0264] The polyamideimides obtained in Synthesis Example 1 and Synthesis Example 2 were each dissolved in a mixed solvent of GBL / BuCA = 8 / 2 to prepare a varnish. The prepared varnish was applied onto a substrate using a bar coater and heat-dried to obtain a dry film with a thickness of 10 μm. The heat drying to form the dry film was carried out under conditions of heating at 100°C for 10 minutes followed by drying at 200°C for 1 hour.

[0265] The dried film obtained as described above was used as a sample for measurement, and the following measurements were performed.

[0266] A sample for measurement was installed in a dynamic viscoelasticity measuring device (Rheogel-E4000) manufactured by UBM Co., Ltd., and the glass transition temperature of the polyamideimide resin was measured. The measurement was performed under conditions of a clamping distance of 20 mm and a heating rate of 3 ℃ / min, and the glass transition temperature (Tg) was obtained from the peak position of tan δ.

[0267] 2. Preparation of a polyamideimide resin composition

[0268] (Example 1)

[0269] In a 0.5-liter four-necked flask equipped with an anchor wing with a diameter of 100 mm, 11.8 g of polyamideimide resin powder (A) obtained in Synthesis Example 1, 78.3 g of solvent A (GBL), 8.7 g of solvent B (BuCA), and 1.2 g of silane coupling agent (product name "KBM-403 (3-glycidoxypropylmethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.) were added under a nitrogen stream, and stirred at 100 rpm for 12 hours to obtain a yellow solution.

[0270] The obtained yellow solution was filled into a filter KST-47 (manufactured by Advantech Co., Ltd.) and filtered under pressure of 0.3 MPa to obtain a resin composition (1) (solid content 12.4 mass%).

[0271] (Examples 2 to 8)

[0272] In preparing the resin composition described in Example 1, resin compositions (2) to (8) were prepared in the same manner as in Example 1, except that the resin, solvent A, solvent B, and silane coupling agent were each changed to the formulations shown in Table 1. Various characteristics of the obtained resin compositions (2) to (8) are shown in Table 1.

[0273] (Comparative Example 1)

[0274] A resin composition (C1) was prepared in the same manner as in Example 1, except that solvent A was not used and the formulation was changed to that of Table 1. Various characteristics of the obtained resin composition (C1) are shown in Table 1.

[0275] (Comparative Example 2)

[0276] A resin composition (C2) was prepared in the same manner as in Example 1, except that solvent B was not used and the formulation was changed to that of Table 1. Various characteristics of the obtained resin composition (C2) are shown in Table 1.

[0277] (Comparative Example 3)

[0278] A resin composition (C2) was prepared in the same manner as in Example 1, except that BuCA was used instead of CPN in the preparation of the resin composition described in Comparative Example 1. The resin was insoluble in BuCA.

[0279] (Reference Example)

[0280] In preparing the resin composition described in Example 1, the resin composition was prepared in the same manner as in Example 1, except that NMP was used instead of solvent A and the formulation was changed to that of Table 1. Various characteristics of the obtained resin composition are shown in Table 1.

[0281] 3. Various evaluation results

[0282] Various properties of solvent A and solvent B used in the preparation of the resin composition were evaluated according to the method described below.

[0283] <Compatibility of Solvent A and Solvent B>

[0284] First, 10 ml of solvent B is mixed with 10 ml of solvent A in a colorless, transparent glass container. Next, the solution obtained by stirring (dispersing) these at 25°C is left to stand for 10 minutes. Afterward, the interface of the solution is observed from the side of the glass container. If an interface is observed in the solution, it is determined that it is not suitable for use. On the other hand, if no interface is observed in the solution, it is determined that it is suitable for use. The results of the determination for the solvents used in each example are shown in Table 1.

[0285] <Water content in Solvent B>

[0286] 30 g of dried solvent B was placed in a cylindrical container with a radius of 2 cm, and the moisture content of solvent B was measured after storing it for 3 hours under conditions of 30 ℃ and 60 % RH. The measurement was performed at room temperature using a moisture meter CA-21 manufactured by Nitto Seiko Analyticech Co., Ltd. The results are shown in Table 1.

[0287] <Viscosity of Resin Composition>

[0288] A viscometer (RE type) manufactured by Toki Industry Co., Ltd. was used, the measurement temperature was set to 25 ℃ ± 0.5 ℃, and then 1 mL to 1.5 mL of resin composition was added to the viscometer, and the viscosity was measured 10 minutes after the start of measurement.

[0289] For the resin compositions prepared in the examples and comparative examples, various properties were evaluated according to the method described below.

[0290] <Evaluation of Efflorescence (Resin Precipitation)>

[0291] 20 mg of a resin composition was applied onto a glass plate. Afterward, the glass plate having an undried coating was placed on a grid installed in a constant temperature bath at 30°C and 50% RH, and the top was covered to prevent direct contact with wind. After standing in this state for 5 minutes, the appearance of the coating was evaluated visually. The evaluation results are shown in Table 1.

[0292] (metewand)

[0293] A: There is no change in appearance after 5 minutes.

[0294] B: A white shadow was visible, but it remains transparent.

[0295] C: It became opaque due to the formation of a white precipitate.

[0296] <Surface Roughness>

[0297] For the resin compositions obtained in the examples and comparative examples, the surface roughness after the spray coating process was measured. Specifically, first, the resin compositions described in the examples and comparative examples were applied to the entire wafer at equal intervals using a spray coating device manufactured by San-Ei Tech Co., Ltd. on a silicon mirror wafer.

[0298] The spray application conditions are as follows.

[0299] · Nozzle Model Number: SV-91

[0300] · Resin composition supply pressure: 0.1 MPa

[0301] · Atomization pressure: 0.35 MPa

[0302] · Nozzle travel speed: 300 mm / s

[0303] · Pre-application interval 10 mm

[0304] · Discharge rate: 1.2 g / 5 s

[0305] Afterward, the silicon mirror wafer coated with the resin composition was placed on an 80°C hot plate and dried for 30 minutes, and the average surface roughness Ra was measured using a surface roughness meter from Tokyo Precision Manufacturing Co., Ltd. The measurement conditions for surface roughness are as follows.

[0306] · Device: Surfcom NEX100

[0307] · Measurement range: 10 mm

[0308] · Measurement speed 1.5 mm / s

[0309] From the values ​​obtained from the above measurements, the surface roughness (roughness) was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0310] (metewand)

[0311] Good: Ra is less than 0.5 µm.

[0312] Defect: Ra is 0.5 μm or greater.

[0313]

[0314] As can be seen from Table 1, the polyamideimide resin compositions obtained in the embodiments of the present invention that satisfy the requirements for a specific combination of solvent A and solvent B—that is, in each example—can provide excellent coating film characteristics with low surface roughness by suppressing resin precipitation. On the other hand, the polyamideimide resin compositions obtained in comparative examples that do not satisfy the requirements for the specific combination of solvent A and solvent B resulted in resin precipitation (Comparative Example 2) or the resin not dissolving in the solvent from the beginning (Comparative Example 3). In addition, even when resin precipitation was suppressed, the coating film characteristics were inferior due to high surface roughness (Comparative Example 1). This is thought to be because although CPN has excellent resin solubility, CPN alone has excessively high volatility, causing the coating film to dry rapidly after spray application.

[0315] As shown above, it can be seen that a resin composition using a specific solvent in combination as an alternative solvent to NMP can provide a resin composition capable of realizing at least the same degree of characteristics as when NMP is used, as shown in the reference example.

Claims

Claim 1 A resin composition comprising a resin containing polyamideimide, at least one solvent A having a lactone structure, and at least one glycol ester-based solvent B1 compatible with solvent A, wherein the mass ratio of solvent A to solvent B1 is 90 / 10 to 75 / 25, and wherein the resin comprises a polyamideimide (A) having a structural unit represented by the following formula (Ia), a structural unit represented by the following formula (IIa), and a structural unit represented by the following formula (1), or a polyamideimide (B) having a structural unit represented by the following formula (IIa), a structural unit represented by the following formula (IVa), and a structural unit represented by the following formula (1). (wherein, R1 to R4 each independently represent a hydrogen atom, or one or more substituents selected from the group consisting of a C1 to C9 alkyl group, a C1 to C9 alkoxy group, and a halogen atom, and X is a single bond or a divalent organic group selected from the following, In the formula, R5 and R6 are each independently a hydrogen atom, or one or more substituents selected from the group consisting of C1 to C9 alkyl groups, trifluoromethyl groups, trichloromethyl groups, and phenyl groups. (In food, R7~ R 10 Each independently represents a hydrogen atom or a substituent, and R 11 and R 12 Each independently represents a 2-valent hydrocarbon group, and m is an integer greater than or equal to 1. (In the formula, X represents, respectively, at least one substituent selected from the group consisting of a hydrogen atom, or a halogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a hydroxyalkyl group.) (In the formula, R represents a residue obtained by removing an amino group from a diamine compound or a residue obtained by removing an isocyanate group from a diisocyanate compound, and n represents an integer greater than or equal to 1.) Claim 2 A resin composition comprising a resin containing polyamideimide, at least one solvent A having a lactone structure, and at least one cyclic ketone-based solvent B2 that is compatible with said solvent A, wherein the mass ratio of said solvent A to said solvent B2 is 70 / 30 to 30 / 70, and said resin comprises a polyamideimide (A) having a structural unit represented by the following formula (Ia), a structural unit represented by the following formula (IIa), and a structural unit represented by the following formula (1), or a polyamideimide (B) having a structural unit represented by the following formula (IIa), a structural unit represented by the following formula (IVa), and a structural unit represented by the following formula (1). (wherein, R1 to R4 each independently represent a hydrogen atom, or one or more substituents selected from the group consisting of a C1 to C9 alkyl group, a C1 to C9 alkoxy group, and a halogen atom, and X is a single bond or a divalent organic group selected from the following, In the formula, R5 and R6 are each independently a hydrogen atom, or one or more substituents selected from the group consisting of C1 to C9 alkyl groups, trifluoromethyl groups, trichloromethyl groups, and phenyl groups. (In food, R7~ R 10 Each independently represents a hydrogen atom or a substituent, and R 11 and R 12 Each independently represents a 2-valent hydrocarbon group, and m is an integer greater than or equal to 1. (In the formula, X represents, respectively, at least one substituent selected from the group consisting of a hydrogen atom, or a halogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a hydroxyalkyl group.) (In the formula, R represents a residue obtained by removing an amino group from a diamine compound or a residue obtained by removing an isocyanate group from a diisocyanate compound, and n represents an integer greater than or equal to 1.) Claim 3 A resin composition according to claim 1 or 2, wherein the boiling point of solvent A is 100 to 250°C. Claim 4 A resin composition according to claim 1 or 2, wherein the boiling point of solvent B1 or solvent B2 is 100 to 250°C. Claim 5 A resin composition according to claim 1, wherein solvent A comprises γ-butyrolactone and solvent B1 comprises ethylene glycol monomethyl ether acetate. Claim 6 A resin composition according to claim 2, wherein solvent A comprises γ-butyrolactone and solvent B2 comprises cyclopentanone or cyclohexanone. Claim 7 A resin composition according to claim 1 or 2, additionally comprising a silane coupling agent. Claim 8 A resin composition according to claim 1 or 2, wherein the polyamideimide (B) is a resin further comprising at least one structural unit selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc). (In the formula, S independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer from 0 to 4, b represents an integer from 0 to 3, and c represents an integer from 0 to 4.) Claim 9 A semiconductor device having a coating film formed using the resin composition described in claim 1 or 2. Claim 10 A method for manufacturing a semiconductor device, comprising forming a coating film using a resin composition described in claim 1 or 2. Claim 11 A method for manufacturing a semiconductor device according to claim 10, wherein the formation of the coating film is performed prior to the encapsulation process. Claim 12 A method for manufacturing a semiconductor device according to claim 10, wherein the coating is a primer layer or an insulating layer.

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