Resin Composition, Method for Manufacturing Semiconductor Device

Abstract

A resin composition which contains: at least one resin that is selected from the group consisting of a polyamide, a polyamide-imide, a polyimide and a polyamide acid; at least one solvent A that has a lactone structure; and at least one glycol ester solvent B1 that is compatible with the solvent A. With respect to this resin composition, the (solvent A) / (solvent B1) mass ratio is from 90 / 10 to 75 / 25; and the resin contains a resin (A) which has a structural unit represented by formula (Ia) and a structural unit represented by formula (IIa), or a resin (B) which has a structural unit represented by formula (IIa) and a structural unit represented by formula (IVa).

Description

Technical Field

[0001] One embodiment of the present invention relates to a resin composition containing a resin such as polyamideimide and an organic solvent, and more particularly to a resin composition substantially free of 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 Art

[0002] Resins such as polyamideimide, polyamide, and polyimide are excellent in various properties such as heat resistance, chemical resistance, and mechanical properties. Therefore, for example, they are widely used in various applications as binder resins for paints. A polar solvent is used during the synthesis of resins such as polyamideimide, polyamide, and polyimide, and during the preparation of varnishes or paints. Among them, N-methyl-2-pyrrolidone (NMP) is widely used as a suitable organic solvent for polyamideimide resins (Patent Document 1).

[0003] However, in recent years, regulations regarding the use of organic solvents have become stricter from the viewpoints of environmental protection and safety and hygiene. Furthermore, there are concerns about the harmfulness of NMP to the human body, and safety and hygiene in the working environment during the use of NMP are regarded as problems in the industry. For example, in Europe, according to the REACH regulation, NMP is classified as a substance of very high concern (SVHC), and its use is regulated. Therefore, in applications using resins such as polyamideimide, polyamide, and polyimide, the need for alternative solvents to NMP is increasing.

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In the prior art, when using a solvent as an alternative to NMP, the properties tend to deteriorate compared to the resin composition using NMP, and the property level is not sufficiently satisfactory. Therefore, an embodiment of the present invention provides a resin composition that does not substantially contain NMP as a solvent and can achieve properties comparable to those of a conventional resin composition using NMP. In particular, one embodiment of the present invention provides a resin composition capable of suppressing the occurrence of whitening after coating and obtaining excellent coating film properties.

Means for Solving the Problems

[0007] In view of the above situation, the present inventor has conducted various studies on solvents as alternatives to NMP. As a result, it has been found that by a specific combination of organic solvents, the occurrence of whitening after coating can be suppressed and excellent coating film properties can be obtained, leading to the completion of 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.

[0008] One embodiment relates to a resin composition comprising at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, at least one solvent A having a lactone structure, and at least one solvent B compatible with the solvent A, wherein the solvent B has a water content of 2% by mass or less after being stored in an environment of 30°C and 60% RH for 3 hours.

[0009] One embodiment relates to a resin composition comprising at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, at least one solvent A having a lactone structure, At least one solvent B that is miscible with the above solvent A and The present invention relates to a resin composition comprising the above, wherein the solvent B is selected from the group consisting of glycol ester solvents and cyclic ketone solvents.

[0010] In the above embodiment, the mass ratio of the above solvent A / the above solvent B is preferably 90 / 10 to 10 / 90.

[0011] The boiling points of the above solvent A and the above solvent B are each preferably 100 to 250 °C.

[0012] The above resin preferably contains a polyamideimide resin having a structural unit represented by the following formula (1).

Chemical formula

[0013] In the above embodiment, the above resin is preferably a resin having a structural unit represented by the following formula (Ia).

Chemical formula

[0014] In the formula, R 1 ~R 4 each independently represents a hydrogen atom or one or more substituents 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. X is a single bond or a divalent organic group selected from the following.

Chemical formula

[0015] In the formula, R 5 and R 6is, independently of each other, a hydrogen atom, or one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group.

[0016] In the above embodiment, it is preferable that the resin is a resin having a structural unit represented by the following formula (IIa) or (VIa).

Chemical formula

[0017] In the formula, R 7 ~R 10 each independently represents a hydrogen atom or a substituent, and R 11 and R 12 each independently represents a divalent hydrocarbon group, and m is an integer of 1 or more.

[0018]

Chemical formula

[0019] In the formula, each R independently represents a hydrogen atom or at least one substituent 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, and n represents an integer of 1 to 6.

[0020] In the above embodiment, it is preferable that the resin is a resin having a structural unit represented by the following formula (IVa).

Chemical formula

[0021] In the formula, each X independently represents a hydrogen atom or at least one substituent selected from the group consisting of 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. The above resin preferably further contains at least one structural unit selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc).

Chemical formula

[0022] In the formulas, S each independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 3, and c represents an integer of 0 to 4.

[0023] Another embodiment relates to a method for manufacturing a semiconductor device, including forming a coating film using the resin composition of the above embodiment.

[0024] The formation of the above coating film is preferably performed before the sealing step.

[0025] The above coating film is preferably a primer layer or an insulating layer.

Advantages of the Invention

[0026] According to the embodiment of the present invention, a resin composition that does not substantially contain NMP as a solvent and can achieve characteristics comparable to those of a conventional resin composition using NMP can be provided. The resin composition according to the embodiment of the present invention is less likely to turn white after coating and can be suitably used for various applications such as paints and semiconductor device materials.

Modes for Carrying Out the Invention

[0027] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments and includes various embodiments.

[0028] <Resin Composition> The resin composition, which is one embodiment of the present invention, includes an organic solvent other than NMP and at least one resin selected from the group consisting of polyamide-imide, polyimide, polyamide, and polyamic acid. "Resin composition" may be used in a meaning equivalent to "varnish" or "paint".

[0029] 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, preferably the content of NMP may be less than 0.3% by mass. The content of the above NMP may preferably be less than 0.2% by mass, and more preferably less than 0.1% by mass. Therefore, for example, it does not completely exclude NMP remaining in the resin composition due to mixing in the process such as the synthesis of the resin.

[0030] (Organic solvent) In the above resin composition, the organic solvent includes solvent A and solvent B described later. In one embodiment, solvent A is at least one solvent having a lactone structure (cyclic ester structure). At least solvent A preferably dissolves at least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid. The above "dissolve" means that when the solution obtained by adding solvent A to the resin and stirring at room temperature is visually confirmed, there is no precipitate, no turbidity, and the whole solution is in a transparent state. Here, the above "room temperature" may generally be in the range of 10 to 40 °C, and preferably in the range of 20 to 30 °C. In one embodiment, it is preferable that solvent A can dissolve up to 30 mg of the resin powder with respect to 100 mL of solvent A. The above "stirring" may be carried out under the condition of 40 to 50 rpm using a stirrer such as a mix rotor.

[0031] On the one hand, Solvent B is at least one solvent that is miscible with the above Solvent A, and is characterized in that the water content after storing the dried Solvent B in an environment of 30 °C and 60% RH (relative humidity) for 3 hours is 2% by mass or less. The above water content is a value measured for Solvent B after putting 30 g of the dried Solvent B into a cylindrical container with a radius of 2 cm and storing it in an environment of 30 °C and 60% RH for 3 hours. The water content is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less. When the water content of Solvent B is 2% by mass or less, whitening (resin precipitation) of the resin composition can be easily suppressed, and a uniform coating film can be easily obtained. The above water content means the ratio of the amount of water contained in Solvent B based on the total mass of Solvent B. In this specification, it is a value measured using a Karl Fischer coulometric titration apparatus (moisture meter) in accordance with the Karl Fischer coulometric titration method at room temperature. For example, a moisture meter CA-21 manufactured by Nitto Seiko Analytic Co., Ltd. can be used.

[0032] The miscibility between Solvent B and Solvent A is determined as follows. First, 10 mL of Solvent B is mixed into 10 mL of Solvent A in a colorless and transparent glass container. Next, the solution obtained by stirring or dispersing these at 25 °C is allowed to stand for 10 minutes. Then, the interface of the solution is visually observed from the side of the glass container. If an interface is observed in the solution, it is determined as "immiscible". On the other hand, if no interface is observed in the solution, it is determined as "miscible". The stirring or dispersion when preparing the above solution may be carried out under conditions such as holding the glass container by hand and quickly reciprocating up and down about 10 times.

[0033] 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 contains at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, and γ-caprolactone, and more preferably contains at least γ-butyrolactone.

[0034] On the other hand, the solvent B is at least one solvent that is miscible with the solvent A as described above, and it suffices that the water content after storage for 3 hours in an environment of 30°C and 60% RH (relative humidity) is 2% by mass or less, and it is not particularly limited. Specific examples of the solvent B include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents (excluding cyclic ester solvents), ether solvents, and ketone solvents. These may be used alone or in combination of two or more.

[0035] More specifically, the aromatic hydrocarbon solvent may be, for example, xylene, ethylbenzene, tetramethylbenzene, etc. The aliphatic hydrocarbon solvent may be, for example, hexane, octane, decane, etc. Further, petroleum ether, white gasoline, solvent naphtha, etc., which are mixtures thereof, may also be used.

[0036] The ester solvent (excluding cyclic ester solvents) may be an alkyl acetate such as ethyl acetate, propyl acetate, butyl acetate, etc. Further, the ester solvent may be a glycol ester 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, butylene glycol monomethyl ether acetate, etc. Furthermore, the ester solvent may be a polycarboxylic acid alkyl ester such as dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Among them, glycol ester solvents are preferred, monoalkylene glycol monoalkyl ether monoacetates are more preferred, and ethylene glycol monomethyl ether acetate is even more preferred.

[0037] The ether solvents may be alkyl ethers such as diethyl ether and ethyl butyl ether. Further, they may be glycol ethers 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, and triethylene glycol diethyl ether. Furthermore, they may be cyclic ethers such as tetrahydrofuran.

[0038] The ketone solvents may be acyclic ketones such as acetone and methyl ethyl ketone, and cyclic ketones such as cyclopentanone, cyclohexanone, and isophorone. Among them, cyclic ketone solvents are preferred, and cyclopentanone or cyclohexanone is more preferred.

[0039] As the solvent B, the above-mentioned solvents may be used alone or in combination of two or more. In one embodiment, the solvent B preferably contains at least one selected from the group consisting of glycol ester solvents (hereinafter also referred to as "solvent B1") and cyclic ketone solvents (hereinafter also referred to as "solvent B2"). In one embodiment, the solvent B more preferably contains one or more selected from the group consisting of ethylene glycol monomethyl ether acetate (butyl cellosolve acetate) (BuCA), cyclopentanone (CPN), and cyclohexanone (CHN).

[0040] Although not particularly limited, examples of preferred combinations of solvent A / solvent B include GBL / CPN, GBL / CHN, and GBL / BuCA.

[0041] Although not restricted by theory, for example, GBL, which is an example of solvent A, is a polar solvent like NMP, but tends to be inferior to NMP in terms of the solubility of the resin. For this reason, it is considered that whitening is likely to occur after coating in a resin composition using GBL. On the other hand, solvent B is a solvent with low water absorption, for example, a solvent whose water content becomes 2% by mass or less after being stored for 3 hours in an environment of 30°C and 60% RH. Therefore, it is presumed that by using solvent A and solvent B with low water absorption in combination, the water absorption of solvent A can be suppressed. Also, it is presumed that by using solvent A and solvent B in combination, the coating film properties can be improved. The mass ratio of solvent A / solvent B can be appropriately adjusted from viewpoints such as the solubility of the resin and water absorption. In one embodiment, the mass ratio of solvent A / solvent B may be 90 / 10 to 10 / 90. Hereinafter, the case where the resin is resin (A) or resin (B) described later will be described in more detail.

[0042] 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 above mass ratio is more preferably 70 / 30 to 30 / 70, and even more preferably 60 / 40 to 40 / 60. By being such a combination, the surface roughness of the coating film after drying tends to be good, and it tends to be easy to prevent the drying of the nozzle when performing dispensing coating.

[0043] 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 above mass ratio is even more preferably 85 / 15 to 75 / 25. Also, it is preferable that the mass ratio of solvent A / solvent B1 is 90 / 10 to 75 / 25. By being such a combination, the water absorption rate decreases, and it tends to be easy to suppress the precipitation of the resin during coating film formation.

[0044] In one embodiment, the resin composition may further contain a solvent different from the above solvent A and solvent B, as long as the desired properties are not degraded. Based on the total mass of the solvents, the total amount of solvent A and solvent B is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99.7% by mass or more.

[0045] In one embodiment, from the viewpoint of drying properties during film formation, etc., the boiling points of solvent A and solvent B are each preferably 100 to 250°C. The above boiling points are more preferably 130 to 220°C, and even more preferably 150 to 210°C. Among the solvents exemplified above, from the viewpoint of boiling point, solvent A is preferably γ-butyrolactone (GBL, boiling point 204°C). On the other hand, as solvent B, cyclopentanone (CPN, boiling point 131°C), cyclohexanone (CHN, boiling point 156°C), and butyl cellosolve acetate (BuCA, boiling point 192°C) are preferred. When these solvents are used, since the boiling point is the same as or lower than that of NMP, excellent drying properties during film formation can be easily obtained in the same manner as when NMP is used.

[0046] (Resin) In the resin composition of the above embodiment, the resin may be a resin well-known in the art, but preferably contains at least one resin selected from the group consisting of at least polyamideimide, polyimide, polyamide, and polyamic acid. These resins are excellent in heat resistance, tough, and excellent in flexibility. Therefore, a resin composition using these resins can easily form a coating film having preferable properties, for example, as an insulating layer or a primer layer of a semiconductor element.

[0047] Polyamide-imide, polyimide, polyamide, and polyamic acid can be synthesized according to methods well known in the art. In the resin composition of the above embodiment, at least one resin selected from the group consisting of polyamide-imide, polyimide, polyamide, and polyamic acid may contain, for example, a structural unit represented by the following formula (Ia). Further, it may contain a structural unit represented by the following formula (IIa).

[0048]

Chemical formula

[0049] In the formula, R 1 ~R 4 each independently represents a hydrogen atom or one or more substituents 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 above alkyl group or alkoxy group may have any of a linear structure, a branched structure, and a cyclic structure. The above alkyl group and the above alkoxy group more preferably have 1 to 6 carbon atoms, and even more preferably have 1 to 3 carbon atoms. The above halogen atom may be any of a fluorine atom, a chlorine atom, and a bromine atom.

[0050] X is a single bond or a divalent organic group selected from the following. In one embodiment, X is preferably -CR 5 R 6 -.

Chemical formula

[0051] In the formula, R 5 and R 6 each independently represents a hydrogen atom or one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group. The above alkyl group may have any of a linear structure, a branched structure, and a cyclic structure. In one embodiment, in the formula, R5 and R 6 is 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.

[0052] [Chemical formula]

[0053] In the formula, R 7 ~R 10 each independently represents a hydrogen atom or a substituent, and R 11 and R 12 each independently represents a divalent hydrocarbon group, and m is an integer of 1 or more.

[0054] In one embodiment, the above R 7 ~R 10 are each independently preferably 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 any of a linear structure, a branched structure, and a cyclic structure. R 7 ~R 10 are more preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. The hydrogen atom in the phenyl group may be substituted with an alkyl group having 1 to 6 carbon atoms. In one embodiment, R 7 ~R 10 are each preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0055] The above R 11 and R 12 may each independently be an alkylene group having 1 to 9 carbon atoms or a phenylene group. The hydrogen atom in the phenylene group may be substituted with an alkyl group having 1 to 3 carbon atoms. The alkylene group may have any of a linear structure, a branched structure, and a cyclic structure. In one embodiment, R 11 and R12 Each is preferably an alkylene group having 1 to 6 carbon atoms in a straight chain, more preferably an alkylene group having 2 to 5 carbon atoms, and even more preferably an alkylene group having 3 or 4 carbon atoms, independently of one another. In the above formula, m is preferably 1 to 100, more preferably 1 to 40, and even more preferably 1 to 10.

[0056] In one embodiment, the resin may be a polyamideimide resin further containing a structural unit represented by the following formula (IIIa).

Chemical formula

[0057] In one embodiment, at least one resin selected from the group consisting of polyamideimide, polyimide, polyamide, and polyamic acid may contain, for example, a structural unit having a cardo-structured fluorene skeleton represented by the following formula (IVa). Further, it may contain at least one selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc).

Chemical formula

[0058]

Chemical formula

[0059] In the above formula (IVa), each X independently represents a hydrogen atom or at least one substituent selected from the group consisting of 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. 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 have any of a straight-chain structure, a branched structure, and a cyclic structure.

[0060] In one embodiment, X is preferably, independently of each other, a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a halogen atom. 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. In one embodiment, X is preferably a hydrogen atom for each.

[0061] In the above formulas (Va), (Vb), and (Vc), S independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 3, and c represents an integer of 0 to 4.

[0062] In one embodiment, the resin may further contain a structural unit (VIa) represented by the following formula.

Chemical formula

[0063] In the formula, R independently represents at least one substituent selected from the group consisting of a hydrogen atom, 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 of 1 to 6. The halogen atom may be a fluorine atom, a chlorine atom, or a bromine atom. The alkyl group and the alkoxy group may have any of a linear structure, a branched structure, and a cyclic structure. In one embodiment, R is preferably, independently of each other, 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. n is preferably an integer of 2 to 4, and more preferably 3 or 4.

[0064] In the above embodiment, the resin is preferably a resin containing a structural unit represented by the above formula (Ia) and a structural unit represented by the above formula (IIa) or (VIa). The resin is more preferably a polyamide-imide resin containing a structural unit represented by the above formula (Ia) and a structural unit represented by the above formula (IIa) or (VIa). The resin is even more preferably a polyamide-imide resin containing a structural unit represented by the above formula (Ia), a structural unit represented by the above formula (IIa) or (VIa), and a structural unit represented by the following formula (IIIa).

[0065] In the above embodiment, the resin is preferably a resin containing a structural unit represented by the above formula (IVa) and a structural unit represented by any one of the above formulas (Va), (Vb), and (Vc). The resin is more preferably a resin containing a structural unit represented by the above formula (IVa), a structural unit represented by any one of the above formulas (Va), (Vb), and (Vc), and a structural unit represented by the above formula (IIa) or (VIa). The resin is more preferably a polyamide-imide resin containing a structural unit represented by the above formula (IVa), a structural unit represented by any one of the above formulas (Va), (Vb), and (Vc), and, if necessary, a structural unit represented by (IIa) or (VIa), and even more preferably a polyamide-imide resin further containing a structural unit represented by the following formula (IIIa).

[0066]

Chemical formula

[0067] As another embodiment of the polyamide-imide resin (B) having the above cald structure type fluorene skeleton, instead of the structural unit represented by any one of the above formulas (Va), (Vb), and (Vc), it may have a structural unit represented by the following formula (Vd).

Chemical formula

[0068] 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 diphenylketone 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.

[0069] B each independently represents a hydrogen atom or at least one substituent selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a trifluoromethyl group, a carboxylic acid group, a hydroxy group, and a halogen atom. The halogen atom may be a fluorine atom, a chlorine atom, or a bromine atom. In one embodiment, B is preferably each 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.

[0070] (Polyamideimide) Hereinafter, polyamideimide will be described more specifically as an example of the resin. Polyamideimide is a resin obtained by reacting a diamine compound or a diisocyanate compound with an acid component containing a tribasic acid anhydride or a tribasic acid halide. Here, each raw material compound may be used by arbitrarily combining a plurality of types thereof.

[0071] The diamine compound or the diisocyanate compound may be, for example, an aromatic diamine or an aromatic diisocyanate, an aliphatic diamine or an aliphatic diisocyanate. An aromatic diamine or an aromatic diisocyanate is preferred. 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'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 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, naphthalenediamine, naphthalenediisocyanate.

[0072] 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, hexamethylenediisocyanate.

[0073] In one embodiment, it is preferable to use a diamine compound or a diisocyanate compound from which the structural units represented by the formulas (Ia), (IIa), (IVa), (Va) to (Vd), and (VIa) described above can be derived. For example, a diamine compound or a diisocyanate compound from which the structural unit represented by the formula (IVa) can be derived is represented by the following formula (IV). In the formula, X is as described above, and Y represents an amino group (-NH 2 ), or an isocyanate group (-NCO).

[0074]

Chemical formula

[0075] 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, and the like. These can be suitably used as diamine compounds from which the structural unit (IVa) can be derived.

[0076] In addition, specific examples of the compound from which the structural unit represented by the formula (VIa) can be derived include 1,3-bis(3-aminopropyl)1,1,1,3,3,3-hexamethyldisiloxane, 1,3-bis(2-aminoethyl)1,1,1,3,3,3-hexamethyldisiloxane, 1,3-bis(aminomethyl)1,1,1,3,3,3-hexamethyldisiloxane, 1,3-bis(4-aminobutyl)1,1,1,3,3,3-hexamethyldisiloxane, 1,3-bis(5-aminopentyl)1,1,1,3,3,3-hexamethyldisiloxane, 1,3-bis(6-aminohexyl)1,1,1,3,3,3-hexamethyldisiloxane, and the like.

[0077] As one embodiment, the polyamide-imide resin (A) preferably has a structural unit represented by the formula (Ia) and a structural unit represented by the formula (IIa). In this polyamide-imide resin (A), the total amount of the proportion of the structural unit represented by the formula (Ia) and the proportion of the structural unit represented by the formula (IIa) may exceed 80 mol% with respect to the total amount of the structural units derived from the diamine compound or the diisocyanate compound, and may be 100 mol%. Also, as another embodiment, the polyamide-imide resin (B) may be a resin having a structural unit represented by the formula (IIa) and a structural unit represented by the formula (IVa), and preferably further has at least one structural unit selected from the group consisting of the structural units represented by the formulas (Va), (Vb), and (Vc). In this polyamide-imide resin (B), the total amount of the proportion of the structural unit represented by the formula (IIa), the proportion of the structural unit represented by the formula (IVa), and the proportion of at least one structural unit selected from the group consisting of the structural units represented by the formulas (Va), (Vb), and (Vc) may exceed 80 mol% with respect to the total amount of the structural units derived from the diamine compound or the diisocyanate compound, and may be 100 mol%. Here, the proportion of the structural unit represented by the formula (IVa) may preferably be 10 to 90 mol%, more preferably 30 to 70 mol%, and still more preferably 40 to 60 mol% with respect to the total amount of the structural units derived from the diamine compound or the diisocyanate compound. By adjusting the proportion of the structural unit represented by the formula (IVa) within the above range, it becomes easy to balance solubility while enhancing the heat resistance of the resin. In any of the polyamide-imide resins (A) and (B) of the above embodiments, the proportion of the structural unit represented by the formula (IIa) may preferably be 1 to 50 mol%, more preferably 3 to 30 mol%, and still more preferably 5 to 10 mol% with respect to the total amount of the structural units derived from the diamine compound or the diisocyanate compound. In one embodiment, in order to produce a polyamideimide resin, other diamine compounds or diisocyanate compounds capable of deriving structural units other than the structural units represented by formulas (Ia), (IIa), (IVa), (Va) to (Vd), and (VIa) may be used in combination. The proportion of the structural units derived from other diamine compounds or diisocyanate compounds is preferably 20 mol% or less based on the total amount of the structural units derived from the diamine compounds or diisocyanate compounds. The proportion of the structural units derived from the above other compounds is more preferably 10 mol% or less, and even more preferably 5 mol% or less.

[0078] The tribasic acid anhydride is not particularly limited, but preferably an aromatic tribasic acid anhydride is used, and among them, trimellitic anhydride is preferable. The tribasic acid halide is not particularly limited, but tribasic acid chloride is used, and more preferably an aromatic tribasic acid chloride is used. For example, trimellitic anhydride chloride (trimellitic anhydride chloride) and the like can be mentioned. From the viewpoint of reducing the environmental load, it is preferable to use trimellitic anhydride or the like. From such a viewpoint, in one embodiment, the polyamideimide resins (A) and (B) preferably further contain the above formula (IIIa) derived from trimellitic anhydride as a structural unit derived from a tribasic acid anhydride. Based on the total amount of the structural units derived from the acid component, the proportion of the structural unit represented by the above 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 the structural units derived from the acid component, the proportion of the structural unit represented by the above formula (IIIa) may be 100 mol%.

[0079] As 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 dianhydrides can be used within a range that does not impair the properties of the polyamideimide. The dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, etc. The tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, etc. These may be used alone or in any combination of multiple types. From the viewpoint of maintaining the properties of the polyamideimide, 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% in all carboxylic acids, and more preferably in the range of 0 to 30 mol%.

[0080] The usage ratio of the diamine compound (or diisocyanate compound) to the acid component (the total amount of the tribasic acid anhydride or tribasic acid anhydride halide and the dicarboxylic acid and tetracarboxylic dianhydride used as required) is preferably adjusted from the viewpoints of the molecular weight and crosslinking degree of the resulting polyamideimide. For example, with respect to 1.0 mol of the total amount of the acid component, it is preferable to use 0.8 to 1.1 mol of the diamine compound (or diisocyanate compound), more preferably 0.95 to 1.08 mol, and particularly preferably 1.0 to 1.05 mol.

[0081] Polyamideimide is a resin having an amide bond and an imide bond in its molecular skeleton, 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, the polyamideimide preferably has a structural unit represented by the following formula (1).

Chemical formula

[0082] In one embodiment, R may be a structural unit represented by the formula (Ia) described above and a structural unit represented by the formula (IIa). The polyamideimide (A) having such a structure can be obtained, for example, by reacting 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminopropyl)1,1,3,3-tetramethyldisiloxane, and trimellitic anhydride chloride.

[0083] In another embodiment, R may be a structural unit represented by the formula (IVa) described above, a structural unit represented by any one of the formulas (Va), (Vb), and (Vc), and a structural unit represented by the formula (VIa). The polyamideimide (B) having such a structure can be obtained, for example, by reacting 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylenebis[2,6-bis(1-methylethyl)benzenamine], and trimellitic anhydride chloride.

[0084] (Method for producing polyamideimide resin) The polyamideimide resin can be produced according to a known method and is not particularly limited. The polyamideimide resin can be produced, for example, through the reaction of a diamine component and / or a diisocyanate component with an acid component. The diamine component, diisocyanate component, and acid component are as described above. The above reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. The reaction temperature is preferably in the range of 25°C to 250°C. The reaction time can be appropriately adjusted according to the batch scale, the reaction conditions employed, and the like.

[0085] The organic solvent (synthetic solvent) used in the production of polyamideimide resin is not particularly limited. Examples of usable organic solvents include ether 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 (lactone) solvents such as γ-butyrolactone; acyclic ester solvents such as cellosolve acetate; ketone 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 solvents such as toluene and xylene. These organic solvents may be used alone or in combination of two or more.

[0086] In one embodiment, it is preferable to select and use an organic solvent capable of dissolving the resin to be 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'-dimethylpropyleneurea [1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one]; dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, sulfolane, etc. Among them, nitrogen-containing solvents are preferred.

[0087] The amount of the synthetic solvent used is not particularly limited, but it is preferably 300 to 3,500 parts by weight, more preferably 400 to 2,000 parts by weight, based on 100 parts by weight of the total amount of the acid component and the diamine compound or diisocyanate compound. Generally, the synthetic solvent is removed according to well-known techniques after the synthesis of the resin, and the resin is recovered. For example, water is added to the reaction solution containing the resin to precipitate the resin, and the resin is obtained by separating and recovering this precipitate. If necessary, a step of heating and drying the recovered resin may be provided. The heating and drying may be carried out in two or more steps, or may be carried out by heating to a temperature within a range that does not cause phase transition or decomposition of the resin.

[0088] In one embodiment, the polyamideimide resin can be produced by first producing a precursor of the polyamideimide resin by the reaction of an acid component and a diamine component, and then dehydrating and ring-closing this precursor to obtain the polyamideimide resin. However, the method for ring-closing the above precursor is not particularly limited, and methods well-known in the art can be used. For example, a thermal ring-closing method in which dehydration and ring-closing are carried out by heating under normal pressure or reduced pressure, a chemical ring-closing method in which a dehydrating agent such as acetic anhydride is used in the presence or absence of a catalyst, etc. can be used.

[0089] In the case of the thermal ring-closing method, it is preferably carried out while removing the water generated in the dehydration reaction outside the system. During the dehydration reaction, the reaction solution may be heated to 80°C to 400°C, preferably 100°C to 250°C. Further, an organic solvent capable of azeotroping with water such as benzene, toluene, xylene, etc. may be used in combination to remove water by azeotropic distillation.

[0090] 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, for example, acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, etc., carbodiimide compounds such as dicyclohexylcarbodiimide, etc. are preferably used. During the reaction, it is preferable to use in combination a substance that promotes the cyclization reaction such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine, imidazole, etc.

[0091] The chemical dehydrating agent may be used in a proportion of 90 to 600 mol% based on the total amount of the diamine component, and the substance that promotes the cyclization reaction may be used in a proportion of 40 to 300 mol% based on the total amount of the diamine component. Further, a dehydration catalyst such as a phosphorus compound such as triphenyl phosphite, tricyclohexyl phosphite, triphenyl phosphate, phosphoric acid, phosphorus pentoxide, a boron compound such as boric acid, boric anhydride, etc. may be used.

[0092] In one embodiment, from the viewpoint of ensuring the strength of the coating film, 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. On the other hand, from the viewpoint of ensuring solubility in an organic solvent, 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. "Mw" described in this specification is a value measured by gel permeation chromatography in terms of standard polystyrene.

[0093] In one embodiment, the Mw of the polyamideimide is preferably in the range of 30,000 to 150,000. The above 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, the change in viscosity of the resin composition can be suppressed, and good storage stability can be easily obtained.

[0094] The Mw of the polyamideimide can be measured by sampling a sample ring during resin synthesis and using a calibration curve of standard polystyrene by gel permeation chromatography (GPC). By continuing the synthesis of the polyamideimide until the target number average molecular weight is reached, it can be controlled within the above preferred range. The measurement conditions of GPC will be described later in the examples.

[0095] 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. On the other hand, from the perspective of solubility, the Tg is preferably 400°C or lower, more preferably 380°C or lower, and even more preferably 350°C or lower. 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. The Tg is preferably 120 to 400°C, more preferably 150 to 380°C, and even more preferably 200 to 350°C.

[0096] When the polyamideimide has a Tg of 150°C or higher, excellent reliability can be obtained, for example, even in a heat cycle test. Also, when the resin composition is applied to form a primer layer of a power semiconductor device, it is possible to easily suppress the softening of the coating film due to heat generation during driving and the resulting decrease in adhesion.

[0097] By designing the resin with a backbone such that the Tg of the polyamideimide is 350°C or lower, solubility in a solvent can be ensured, thus improving film-forming processability.

[0098] The content of the resin in the resin composition can be appropriately set according to its use. Although not particularly limited, in one embodiment, from the perspective of balance with other components, the content of the resin is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total mass of the resin composition.

[0099] By setting the content of the resin in the resin composition to 5% by mass or more, the coating amount required to achieve the target film thickness after applying and drying the resin composition is reduced, so that the processability can be easily improved. On the other hand, by setting the content of the resin in the resin composition to 25% by mass or less, the viscosity stability when the resin composition is stored for a long time can be easily improved.

[0100] In one embodiment, the viscosity of the resin composition is not particularly limited, and may be, for example, in the range of 10 to 400 mPa·s. The viscosity of the resin composition can be adjusted according to the coating method. From such a perspective, 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 other embodiments, 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. Here, the above viscosity is a value obtained by measuring a varnish dissolved in a solvent so that the non-volatile component (solid component) is 1 to 20% using an E-type viscometer under the condition of 25°C at 10 rpm. When the viscosity measured at 10 rpm is 10 mPa·s or more, it is easy to ensure a sufficient film thickness during coating. Also, when the above viscosity is 400 mPa·s or less, it tends to be easy to ensure a uniform film thickness during coating. The above viscosity can be measured, for example, using a viscometer (RE type) manufactured by Toki Sangyo Co., Ltd. In the measurement, the measurement temperature is set to 25°C ± 0.5°C, then 1 mL to 1.5 mL of a solution of the resin composition is put into the viscometer, and the viscosity 10 minutes after the start of measurement is recorded.

[0101] (Other components) In one embodiment, the above resin composition can contain arbitrary components according to its intended use in addition to the resin and the organic solvent. For example, the resin composition can be preferably used as a paint. When the resin composition is used as a paint, arbitrary components such as pigments, fillers, defoamers, preservatives, and surfactants may be added as necessary. Also, it may further contain a resin other than the above resin.

[0102] The above resin composition can be used for film formation. A method for manufacturing a 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 containing polyamide, polyamideimide, or polyimide. When such a resin composition is used, the drying is preferably carried out in two steps 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 a coating film, a coating film can be obtained at a lower heating temperature as compared with the case where polyamic acid is applied and imidized. 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 containing the solvent A and the solvent B, and a silane coupling agent. Such a paint (resin composition) can be suitably used as a coating film material for manufacturing a semiconductor device. From such a viewpoint, one embodiment of the present invention relates to a semiconductor device having a coating film formed using the paint of the above embodiment.

[0103] A semiconductor device according to one embodiment of the present invention can be obtained by a manufacturing method including 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 on a constituent member of the semiconductor device and heating and drying it. Conditions such as the heating temperature and heating time during coating film formation (heating and drying) can be adjusted as appropriate. In one embodiment, it is preferable that the heating and drying are carried out in two steps. In this embodiment, the heating and drying temperature in the first step may preferably be in the range of 30 to 120 °C, more preferably in the range of 50 to 100 °C. The heating and drying temperature in the second step 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.

[0104] One embodiment of the present invention relates to a method for manufacturing a semiconductor device, which includes forming a coating film on the surface of a substrate on which at least a semiconductor element is mounted, using the coating material (resin composition) of the above embodiment. The above coating material can be used, for example, to form a coating film such as a protective layer of a semiconductor device, a primer layer for improving the adhesion between a sealing material and a substrate, and an insulating layer of a semiconductor device. The method for manufacturing the above semiconductor device may include the step of forming the above coating film and a sealing step. The step of forming the above coating film is as described above and may be carried out, for example, before the sealing step. Since the above coating material substantially does not contain NMP, it not only has excellent working safety, but also suppresses the deterioration of characteristics in comparison with a coating material using NMP by a specific combination of solvents, and it becomes possible to easily obtain the desired characteristics. Also, it becomes easy to lower the drying temperature during coating film formation.

[0105] In one embodiment, the method for manufacturing a semiconductor device includes at least applying the coating material (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 sealing layer on the above insulating layer. In the above manufacturing method, from the viewpoint of workability, it is preferable that the resin composition contains a polyamideimide resin as a resin component. The formation of the above insulating layer can be carried out by applying the resin composition to a predetermined location and drying the coating film. The application of the resin composition can be carried out by applying various coating methods. The method of applying is not particularly limited, and examples include a spray coating method, a potting method, a dipping method, a dispensing method, etc. Considering workability and the like, the potting method or dispensing coating is preferable.

[0106] In one embodiment, the film thickness of the coating film obtained by forming a film of the resin composition is not particularly limited, but may be in the range of 0.5 to 10 μm. When the coating film has a film thickness within the above range, for example, it tends to be easy to ensure sufficient adhesion to the substrate. From this viewpoint, the film thickness is preferably in the range of 1 to 10 μm, and more preferably in the range of 3 to 10 μm.

[0107] 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, the die pad material is preferably at least one selected from the group consisting of Ni, Cu, and Ag plating formed thereon. The lead material of the lead frame is preferably selected from the group consisting of Ni and Cu. The material of the semiconductor element is not particularly limited and may be, for example, a silicon wafer, a silicon carbide wafer, or the like.

[0108] The resin encapsulation layer can be composed of a cured product of a resin well-known as an encapsulation material in the art. As the encapsulation material, for example, a liquid or solid epoxy resin composition can be used. The resin encapsulation layer can be formed, for example, by performing transfer molding using the encapsulation material.

[0109] In another embodiment, the method for manufacturing a semiconductor device includes, for example, applying and drying the resin composition of the above embodiment on a semiconductor substrate having a plurality of wirings of the same structure to form a resin layer, and forming, if necessary, rewiring that is electrically conductive with the electrodes on the semiconductor substrate on the resin layer. In addition to these steps, a protective layer (resin layer) may be formed using the resin composition on the rewiring or the resin layer, if necessary. Further, in addition to the above steps, forming external electrode terminals on the resin layer, if necessary, and then dicing, if necessary, may also be included.

[0110] In the above semiconductor device, the semiconductor element is not particularly limited, and may be, for example, a silicon wafer, a silicon carbide wafer, or the like. The method of applying the resin layer is not particularly limited, but spin coating, spray coating, or dispense coating is preferably used. The drying method of the resin layer can be performed by a method known in the art. Since the resin composition of the above embodiment is also excellent in characteristics such as sputter resistance, plating resistance, and alkali resistance required in the process of forming rewiring, it is not limited to the configuration of the semiconductor device described above, and can be suitably used as a constituent material of any semiconductor device.

[0111] Exemplary embodiments of the present invention are summarized below. [1] At least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, at least one solvent A having a lactone structure, and at least one glycol ester-based solvent B1 compatible with the solvent A and the mass ratio of the solvent A / the solvent B1 is 90 / 10 to 75 / 25, The resin composition includes 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). [Chemical formula] (In the formula, R 1 ~ R 4 each independently represents a hydrogen atom, or one or more substituents 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, X is a single bond or a divalent organic group selected from the following, [Chemical formula] In the formula, R 5 and R 6is, independently of each other, a hydrogen atom or one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group.)

Chemical formula

Chemical formula

[0112] [2] At least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, and polyamic acid, at least one solvent A having a lactone structure, and at least one cyclic ketone-based solvent B2 compatible with the solvent A and contains, the mass ratio of the solvent A / the solvent B2 is 70 / 30 to 30 / 70, the resin contains 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), a resin composition.)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0113] [3] The resin composition according to [1] or [2], wherein the boiling point of the solvent A is 100 to 250 °C.

[0114] [4] The resin composition according to any one of [1] to [3], wherein the boiling point of the solvent B1 or solvent B2 is 100 to 250 °C.

[0115] [5] The resin composition according to [1], wherein the solvent A contains γ-butyrolactone and the solvent B1 contains ethylene glycol monomethyl ether acetate.

[0116] [6] The resin composition according to [2], wherein the solvent A contains γ-butyrolactone and the solvent B2 contains cyclopentanone or cyclohexanone.

[0117] [7] The resin (A) and the resin (B) each contain a polyamideimide further having a structural unit represented by the following formula (1), and the resin composition according to any one of [1] to [6] above. [Chemical formula] (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 of 1 or more.)

[0118] [8] The resin (B) is a resin further containing at least one structural unit selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc), and the resin composition according to any one of [1] to [7] above. [Chemical formula] (In the formula, S each independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 3, and c represents an integer of 0 to 4.)

[0119] [9] A semiconductor device provided with a coating film formed using the resin composition according to any one of [1] to [8] above.

[0120]

[10] A method for manufacturing a semiconductor device, including forming a coating film using the resin composition according to any one of [1] to [8] above.

[0121]

[11] In the method for manufacturing a semiconductor device according to

[10] above, the formation of the coating film is performed before the sealing step.

[0122]

[12] In the method for manufacturing a semiconductor device according to

[11] or

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

[0123] Next, various examples will be described. It goes without saying that the preferred embodiments of the present invention are not limited to these examples, but include many other embodiments based on the gist of the invention. 1. Synthesis of polyamideimide (Synthesis Example 1) Into a 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser with an oil-water separator, under a nitrogen stream, 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 placed, and further 310.1 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and dissolved to obtain a solution. Next, while cooling the above solution so that the temperature does not exceed 20°C, 26.1 g of trimellitic anhydride chloride (hereinafter referred to as TAC) was added. 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. The obtained polyamic acid solution was further treated at 180°C for 6 hours to obtain a polyamideimide resin solution. This polyamideimide resin solution was poured into water, and the obtained precipitate was separated, pulverized, and dried by heating to obtain powdered polyamideimide (A). Regarding the weight average molecular weight (Mw) of the obtained polyamideimide (A), when measured in terms of standard polystyrene using gel permeation chromatography (hereinafter referred to as GPC), Mw was 98,000. Also, the glass transition temperature (Tg) was 220°C.

[0124] (Synthesis Example 2) Into a 1-liter four-necked 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 placed under a nitrogen stream. Further, 298 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and dissolved to obtain a solution. Next, 21.1 g of trimellitic anhydride chloride (hereinafter referred to as TAC) was added to the above solution while cooling so as not to exceed 20°C. After stirring at room temperature for 2 hours, 12.1 g of triethylamine (hereinafter referred to as TEA) was added, and the reaction was carried out at room temperature for at least 15 hours to obtain a polyamic acid solution. The obtained polyamic acid solution was further carried out at 180°C for 6 hours to obtain a polyamideimide resin solution. This polyamideimide resin solution was poured into water, and the obtained precipitate was separated, pulverized, and heat-dried to obtain a powdery polyamideimide (B). Regarding the weight average molecular weight (Mw) of the obtained polyamideimide (B), when measured in terms of standard polystyrene using gel permeation chromatography (hereinafter referred to as GPC), Mw was 67,000. Also, the glass transition temperature (Tg) was 330°C.

[0125] The measurement conditions of GPC for the polyamideimides obtained in Synthesis Examples 1 and 2 are as follows. Liquid delivery pump: LC-20AD UV-Vis detector: SPD-20A Flow rate: 1 mL / min Column temperature: 40°C Molecular weight standard substance: Standard polystyrene Eluent: NMP

[0126] Also, the measurement method of the glass transition temperature (Tg) of the polyamideimides obtained in Synthesis Examples 1 and 2 is as follows. The polyamide-imides obtained in Synthesis Example 1 and Synthesis Example 2 were each dissolved in a mixed solvent of GBL / BuCA = 8 / 2 to prepare varnishes. The prepared varnishes were applied onto a substrate using a bar coater and heat-dried to obtain dry films with a thickness of 10 μm. The heat-drying for forming the above dry films was carried out under the conditions of heating at 100 °C for 10 minutes and then drying at 200 °C for 1 hour. Using the dry film obtained as described above as a measurement sample, the following measurements were carried out. The measurement sample was placed in a dynamic viscoelasticity measuring apparatus (Rheogel-E4000) manufactured by UBM Co., Ltd., and the glass transition temperature of the polyamide-imide resin was measured. The measurement was carried out under the conditions of a chuck distance of 20 mm and a heating rate of 3 °C / min, and the glass transition temperature (Tg) was obtained from the peak position of tanδ.

[0127] 2. Preparation of polyamide-imide resin composition (Example 1) Into a 0.5-liter four-necked flask equipped with an anchor blade having a diameter of 100 mm, under a nitrogen stream, 11.8 g of the polyamide-imide 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 a silane coupling agent (product name "KBM-403 (3-glycidoxypropylmethyldimethoxysilane)" manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the mixture was stirred at 100 rpm for 12 hours to obtain a yellow solution. The obtained yellow solution was filled into a filter KST-47 (manufactured by Advantec Co., Ltd.) and pressure-filtered at a pressure of 0.3 MPa to obtain a resin composition (1) (solid content: 12.4% by mass).

[0128] (Examples 2 to 8) In the preparation of the resin composition described in Example 1, except that the resin, Solvent A, Solvent B, and the silane coupling agent were respectively changed to the formulations shown in Table 1, resin compositions (2) to (8) were prepared in the same manner as in Example 1. Various properties of the obtained resin compositions (2) to (8) are shown in Table 1.

[0129] (Comparative Example 1) In the preparation of the resin composition described in Example 1, except that Solvent A was not used and the formulation was changed as shown in Table 1, the resin composition (C1) was prepared in the same manner as in Example 1. Various properties of the obtained resin composition (C1) are shown in Table 1.

[0130] (Comparative Example 2) In the preparation of the resin composition described in Example 1, except that Solvent B was not used and the formulation was changed as shown in Table 1, the resin composition (C2) was prepared in the same manner as in Example 1. Various properties of the obtained resin composition (C2) are shown in Table 1.

[0131] (Comparative Example 3) In the preparation of the resin composition described in Comparative Example 1, except that BuCA was used instead of CPN, the resin composition (C2) was prepared in the same manner as in Example 1. The resin was insoluble in BuCA.

[0132] (Reference Example) In the preparation of the resin composition described in Example 1, except that NMP was used instead of Solvent A and the formulation was changed as shown in Table 1, the resin composition was prepared in the same manner as in Example 1. Various properties of the obtained resin composition are shown in Table 1.

[0133] 3. Various Evaluation Results Regarding Solvent A and Solvent B used in the preparation of the resin composition, various properties were evaluated according to the methods described below.

[0134] <Compatibility between Solvent A and Solvent B> First, 10 ml of Solvent B is mixed into 10 ml of Solvent A in a colorless and transparent glass container. Then, the solution obtained by stirring (dispersing) these at 25°C is allowed to stand for 10 minutes. Thereafter, 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 they are incompatible. On the other hand, if no interface is observed in the solution, it is determined that they are compatible. The determination results for the solvents used in each example are shown in Table 1.

[0135] <Water Content in Solvent B> A cylindrical container with a radius of 2 cm was filled with 30 g of dried solvent B and stored for 3 hours in an environment of 30 °C and 60% RH. The water content in solvent B after storage was measured. The measurement was carried out at room temperature using a moisture meter CA-21 manufactured by Nitto Seiko Analytic Co., Ltd. The results are shown in Table 1.

[0136] <Viscosity of the resin composition> Using a viscometer (RE type) manufactured by Toki Sangyo Co., Ltd., the measurement temperature was set to 25 °C ± 0.5 °C. Then, 1 mL to 1.5 mL of the resin composition was put into the viscometer, and the viscosity 10 minutes after the start of measurement was measured.

[0137] For the resin compositions prepared in the examples and comparative examples, various properties were evaluated according to the methods described below.

[0138] <Evaluation of whitening (resin precipitation)> 20 mg of the resin composition was applied onto a glass plate. Then, the glass plate with the undried coating film was placed on a grid installed in a constant temperature bath at 30 °C and 50% RH, and the top was covered so that the wind did not directly hit it. The appearance of the coating film after standing still in this state for 5 minutes was visually evaluated. The evaluation results are shown in Table 1. (Evaluation criteria) A: There is no change in the appearance after 5 minutes. B: A white shadow was seen, but transparency was maintained. C: White precipitation occurred and it became opaque.

[0139] <Surface roughness> For the resin compositions obtained in the examples and comparative examples, the surface roughness after the spray coating process was measured. Specifically, first, using a spray coating apparatus manufactured by Sun Atec Co., Ltd. on a silicon mirror wafer, the resin compositions described in the examples and comparative examples were line-coated at equal intervals and applied to the entire wafer. The spray coating conditions are as follows. · Nozzle model number: SV-91 · Resin composition supply pressure: 0.1 MPa · Atomization pressure: 0.35 MPa · Nozzle movement speed: 300 mm / s · Line coating interval: 10 mm · Discharge amount: 1.2 g / 5 s

[0140] After that, the silicon mirror wafer coated with the resin composition was placed on a hot plate at 80°C and dried for 30 minutes. The average surface roughness Ra was measured using a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd. The measurement conditions for the surface roughness are as follows. · Apparatus: Surfcom NEX100 · Measurement range: 10 mm · Measurement speed: 1.5 mm / s From the values obtained in the above measurement, the surface roughness (undulation) was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. (Evaluation criteria) Good: Ra is less than 0.5 μm. Poor: Ra is 0.5 μm or more.

Table 1

[0141] As is clear from Table 1, the embodiments of the present invention that satisfy the requirements of the combination of the specific solvent A and solvent B, that is, the polyamide-imide resin compositions obtained in each example, can suppress resin precipitation and provide excellent coating film properties with a small surface roughness. On the other hand, the polyamide-imide resin compositions obtained in the comparative examples that do not satisfy the requirements of the combination of the specific solvent A and solvent B resulted in resin precipitation (Comparative Example 2) or the resin did not dissolve in the solvent in the first place (Comparative Example 3). Further, even when resin precipitation was suppressed, the surface roughness was large and the coating film properties were inferior (Comparative Example 1). This is presumably because CPN is excellent in the solubility of the resin, but CPN alone has too high volatility and the coating film dried rapidly after spray coating. From the above, it can be seen that the resin composition using a specific solvent in combination as an alternative solvent for NMP can provide a resin composition capable of realizing at least the same level of characteristics as when using NMP as shown in the reference example.

Claims

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 the solvent A, the resin composition not containing a resin filler having an average particle diameter of 0.1 to 5.0 μm, wherein the mass ratio of the solvent A / the solvent B1 is 90 / 10 to 75 / 25, the resin is 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 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). 【Chemical 1】 (wherein, R １ ~ R ４ each independently represents one or more substituents selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom, X is a single bond or a divalent organic group selected from the following: [Chemical Formula 2] In the formula, R ５ and R ６ are each independently one or more substituents selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group. 【Chemical Formula 3】 (wherein R ７ to R １０ each independently represents a hydrogen atom or a substituent, R １１ and R １２ each independently represents a divalent hydrocarbon group, and m is an integer of 1 or more.) [Chemical Formula 4] (In the formula, X independently represents a hydrogen atom or at least one substituent selected from the group consisting of 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.) [Chemical Formula 5] (In the formula, R represents the residue obtained by removing an amino group from a diamine compound or the residue obtained by removing an isocyanate group from a diisocyanate compound, and n represents an integer of 1 or more.)

2. 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 the solvent A, the resin composition having a viscosity of 10 to 400 mPa·s measured at 25°C and 10 rpm, wherein the mass ratio of the solvent A / the solvent B1 is 90 / 10 to 75 / 25, the resin is 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 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). 【Chemical Formula 6】 (In the formula, R1 to R4 each independently represent a hydrogen atom or one or more substituents 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, X is a single bond or a divalent organic group selected from the following: [Chemical Formula 7] In the formula, R5 and R6 are each independently a hydrogen atom or one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group. 【Chemical Formula 8】 (In the formula, R7 to R10 each independently represent a hydrogen atom or a substituent, R11 and R12 each independently represent a divalent hydrocarbon group, and m is an integer of 1 or more.) [Chemical Formula 9] (In the formula, each X independently represents a hydrogen atom or at least one substituent selected from the group consisting of 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.) 【Chemical Formula 10】 (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 of 1 or more.)

3. A resin composition comprising a polyamideimide, at least one solvent A having a lactone structure, and at least one cyclic ketone solvent B2 compatible with the solvent A, which does not contain a resin filler having an average particle diameter of 0.1 to 5.0 μm, wherein the mass ratio of the solvent A / the solvent B2 is 70 / 30 to 30 / 70, wherein the resin is 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 structural unit represented by the following formula (IIa), a structural unit represented by the following formula (IVa), and a resin composition containing a polyamideimide (B) having a structural unit represented by the following formula (1). 【Chemical Formula 11】 (wherein, R １ ~ R ４ each independently represents one or more substituents selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and a halogen atom, X is a single bond or a divalent organic group selected from the following: 【Chemical 12】 wherein, R ５ and R ６ are each independently a hydrogen atom, or one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group.) 【Chemical Formula 13】 (wherein R ７ to R １０ each independently represents a hydrogen atom or a substituent, R １１ and R １２ each independently represents a divalent hydrocarbon group, and m is an integer of 1 or more.) 【Chemical Formula 14】 (In the formula, each X independently represents a hydrogen atom or at least one substituent selected from the group consisting of 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.) 【Chemical Formula 15】 (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 of 1 or more.)

4. A resin composition comprising a polyamideimide, at least one solvent A having a lactone structure, and at least one cyclic ketone solvent B2 compatible with the solvent A, which has a viscosity of 10 to 400 mPa·s measured at 25°C and 10 rpm. The mass ratio of the solvent A to the solvent B2 is from 70 / 30 to 30 / 70, The resin composition includes 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). 【Chemical 16】 (In the formula, R1 to R4 each independently represent a hydrogen atom, or one or more substituents 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, X is a single bond or a divalent organic group selected from the following, 【Chemical 17】 (In the formula, R5 and R6 each independently represent a hydrogen atom, or one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, a trifluoromethyl group, a trichloromethyl group, and a phenyl group.) 【Chemical Formula 18】 (In the formula, R7 to R10 each independently represent a hydrogen atom or a substituent, R11 and R12 each independently represent a divalent hydrocarbon group, and m is an integer of 1 or more.) 【Chemical Formula 19】 (In the formula, X each independently represents a hydrogen atom, or at least one substituent selected from the group consisting of 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.) 【Chemical 20】 (In the formula, R represents the residue obtained by removing an amino group from a diamine compound, or the residue obtained by removing an isocyanate group from a diisocyanate compound, and n represents an integer of 1 or more.)

5. The resin composition according to any one of claims 1 to 4, wherein the boiling point of the solvent A is 100 to 250 °C.

6. The resin composition according to any one of claims 1 to 5, wherein the boiling point of the solvent B1 or the solvent B2 is 100 to 250 °C.

7. The resin composition according to claim 1 or 2, wherein the solvent A contains γ-butyrolactone and the solvent B1 contains ethylene glycol monomethyl ether acetate.

8. The resin composition according to claim 3 or 4, wherein the solvent A contains γ-butyrolactone and the solvent B2 contains cyclopentanone or cyclohexanone.

9. The polyamideimide (B) in the resin composition according to any one of claims 1 to 8 is a resin further containing at least one structural unit selected from the group consisting of structural units represented by the following formulas (Va), (Vb), and (Vc). 【Chemical 21】 (In the formula, each S independently represents an alkyl group having 1 to 3 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 3, and c represents an integer of 0 to 4.)

10. A semiconductor device including a coating film formed using the resin composition according to any one of claims 1 to 9.

11. A method for manufacturing a semiconductor device, including forming a coating film using the resin composition according to any one of claims 1 to 9.

12. The method for manufacturing a semiconductor device according to claim 11, wherein the formation of the coating film is performed before a sealing step.

13. The method for manufacturing a semiconductor device according to claim 11 or 12, wherein the coating film is a primer layer or an insulating layer.

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