JP2020097661A - Resin composition, and semiconductor device - Google Patents

Abstract

To provide a resin composition that can improve the reliability of a power semiconductor device, and is excellent in insulation, flexibility, and thick film deposition.SOLUTION: A resin composition contains (A) a resin component containing at least one selected from the group consisting of a polyimide resin, a polyamide resin, and a polyamide-imide resin, containing a structural unit represented by formula (Ia) and a structural unit represented by formula (IIa) and with a weight average molecular weight of 100,000 or more and (B) an organic solvent.SELECTED DRAWING: Figure 1

Description

One embodiment of the present disclosure relates to a resin composition having excellent insulating properties, flexibility, and thick film forming properties. Another embodiment of the present disclosure relates to a highly reliable semiconductor device using the resin composition.

Polyimide resins, polyamide resins and polyamide-imide resins are known as typical heat resistant resins and are used in various applications. Polyimide resins, polyamide resins, and polyamide-imide resins have excellent chemical resistance and mechanical properties in addition to heat resistance. Therefore, these resins are widely used in the field of electronics, for example, as a material for a surface protective film of a semiconductor element or an interlayer insulating film.

In recent years, the size of power semiconductor devices has been reduced, and at the same time, the current has been increased. It is widely known that a leak current may be generated from a circuit or an element when the current is increased, and the leak current causes a failure of the power semiconductor device. Therefore, from the viewpoint of the reliability of the semiconductor device, improvement in insulation in the power semiconductor device is strongly desired.

To improve insulation in power semiconductor devices, a resin such as polyimide resin, polyamide resin, and polyamide-imide resin is used to form an insulating film, and the insulating property is partially ensured at a required location, thereby improving the semiconductor property. A method for preventing the generation of a leak current between each member during the operation of the device has been studied.

In the above method, the insulating film is formed by applying a solvent solution (varnish) of the above resin to the power module before sealing and then drying the obtained coating film. As a method of applying the solvent solution of the above resin, general methods such as dispensing, dipping, potting, spray coating, spin coating and the like are used.

JP-A-2-173073

However, in recent years, the current handled by the power semiconductor device itself has increased due to an increase in the current flowing through the power semiconductor device or a change in the substrate material, for example, from Si to SiC. As a result, it has become difficult to obtain sufficiently satisfactory insulating properties and flexibility with conventional resins, and improvements in resins are desired. Above all, a resin capable of forming an insulating film having a sufficient thickness at a required portion is required from the viewpoint of ensuring sufficient insulation.

If the thickness of the resin coating film forming the insulating film is not sufficient, it becomes difficult to secure the insulation between the members. As a result, for example, a leak current is generated in the power semiconductor device, which causes malfunction. Generally, a method of dispersing an inorganic filler in a resin paste in order to secure a sufficient film thickness is known (Patent Document 1). However, when the above method is applied, an electric current passes through the interface of the inorganic filler, so that the insulating property of the coating film tends to be lowered. Therefore, in order to obtain excellent insulating properties, it is necessary to balance the insulating properties of the resin itself with the thick film formability that makes it possible to easily obtain a desired film thickness during film formation. Further, from the viewpoint of obtaining excellent reliability in the semiconductor device, it is also necessary that the coating film obtained from the resin has excellent flexibility.

From the above, the present disclosure provides a resin composition having excellent insulating properties, flexibility, and thick film forming properties. Further, the present disclosure provides a highly reliable semiconductor device using the above resin composition.

The inventors have conducted various studies on resin compositions containing polyimide resins, polyamide resins, and polyamideimide resins as resins, and resins containing specific structural units have high insulating properties and are excellent in flexibility. It has been found that the present invention has properties and can easily form a thick film having a desired thickness, and thus completed the present invention.
Embodiments of the present invention relate to: However, the present invention is not limited to the embodiments described below.

［式中、Ｒ_１〜Ｒ_４は、それぞれ独立して、水素原子、又は、炭素数１〜９のアルキル基、炭素数１〜９のアルコキシ基、及びハロゲン原子からなる群から選択される１種以上の置換基を表し、Ｘは、単結合、又は以下から選択される２価の有機基である。

（式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子、又は、炭素数１〜９のアルキル基、トリフルオロメチル基、トリクロロメチル基、及びフェニル基からなる群から選択される１種以上の置換基である。）]

［式中、Ｒ_７〜Ｒ_１０は、それぞれ独立して、水素原子、又は置換基を表し、Ｒ_１１及びＲ_１２は、それぞれ独立して、２価の炭化水素基を表し、ｍは１以上の整数である。］ One embodiment is (A) a polyimide resin containing a structural unit represented by the following formula (Ia) and a structural unit represented by the following formula (IIa), and having a weight average molecular weight of 100,000 or more, The present invention relates to a resin composition containing a resin component containing at least one selected from the group consisting of a polyamide resin and a polyamide-imide resin, and (B) an organic solvent.

[Wherein, R _{1 to} R ₄ are each independently 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. Representing one or more substituents, X is a single bond or a divalent organic group selected from the following.

(In the formula, R ₅ and R ₆ are each independently 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. There are at least one kind of substituent.)]

[Wherein, R _{7 to} R ₁₀ each independently represent a hydrogen atom or a substituent, R ₁₁ and R ₁₂ each independently represent a divalent hydrocarbon group, and m is 1 or more. Is an integer. ]

In the above embodiment, the polyimide resin, the polyamide resin and the polyamideimide resin are based on the total number of moles of the structural unit represented by the formula (Ia) and the structural unit represented by the formula (IIa). It is preferable to contain 3 to 7 mol% of the structural unit represented by the above formula (IIa).

In the above-mentioned embodiment, the polyamide-imide resin preferably further contains a structural unit represented by the following formula (IIIa).

In the above embodiment, the dielectric breakdown voltage of the film obtained by drying is preferably 150 kV/mm or more.

In the above embodiment, the glass transition temperature of each of the polyimide resin, the polyamide resin and the polyamideimide resin is preferably 200° C. or higher.

In the above embodiment, the elastic modulus at 35° C. of the film obtained by drying is preferably 0.5 to 3.0 GPa.

One embodiment relates to a semiconductor device having a film formed by using the resin composition of the above embodiment on the surface of a component.

According to the present invention, it is possible to provide a resin composition having excellent insulating properties, flexibility, and thick film forming properties. Further, according to the present invention, a highly reliable semiconductor device can be provided using the resin composition.

FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor device according to an embodiment. FIG. 2 is a schematic cross-sectional view showing an example of the semiconductor device according to the embodiment.

Hereinafter, embodiments of the present invention will be described more specifically, but the present invention is not limited to the following, and includes various embodiments.
1. Resin composition One embodiment is (A) a resin component containing at least one selected from the group consisting of a polyimide resin, a polyamide resin, and a polyamideimide resin, which has two specific structural units, and (B) The present invention relates to a resin composition containing an organic solvent. Hereinafter, each component will be specifically described.

(A) Resin Component The resin component constituting the resin composition contains a structural unit represented by the following formula (Ia) and a structural unit represented by the following formula (IIa), and has a weight average molecular weight of 100, At least one selected from the group consisting of a polyimide resin, a polyamide resin, and a polyamide-imide resin, which is 000 or more.

In the formula, R _{1 to} R ₄ are each independently a hydrogen atom or a substituent. The substituent is 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.
In one embodiment, each of R _{1 to} R ₄ is preferably a hydrogen atom. In other embodiments, it is preferable that R _{1 to} R ₄ are each independently an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a halogen atom. The alkyl group and the alkoxy group may have any of a linear structure, a branched structure and a cyclic structure. The alkyl group and the alkoxy group preferably have 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.
The halogen atom may be any of a fluorine atom, a chlorine atom and a bromine atom.

式中、Ｒ_５及びＲ_６は、それぞれ独立して、水素原子、又は置換基である。置換基は、炭素数１〜９のアルキル基、トリフルオロメチル基、トリクロロメチル基、及びフェニル基からなる群から選択される１種以上であってよい。上記アルキル基は、直鎖構造、分岐構造、及び環状構造のいずれであってもよい。一実施形態において、式中、Ｒ_５及びＲ_６は、それぞれ独立して、炭素数１〜６のアルキル基であることが好ましく、炭素数１〜３のアルキル基であることがより好ましく、炭素数１又は２のアルキル基であることがさらに好ましい。 X is a single bond or a divalent organic group selected from the following.

In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a substituent. The substituent may be one or more 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 alkyl group may have a linear structure, a branched structure, or a cyclic structure. In one embodiment, in the formula, R ₅ and R ₆ 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 carbon More preferably, it is an alkyl group of the number 1 or 2.

式中、Ｒ_７〜Ｒ_１０は、それぞれ独立して、水素原子、又は置換基である。置換基は、互いに同一であっても、異なっていてもよい。Ｒ_１１及びＲ_１２は、それぞれ独立して、２価の炭化水素基を表し、互いに同一であっても、異なっていてもよい。ｍは１以上の整数である。

In the formula, R _{7 to} R ₁₀ are each independently a hydrogen atom or a substituent. The substituents may be the same or different from each other. R ₁₁ and R ₁₂ each independently represent a divalent hydrocarbon group, and may be the same as or different from each other. m is an integer of 1 or more.

In one embodiment, R _{7 to} R ₁₀ are preferably each 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 any of a linear structure, a branched structure and a cyclic structure. R _{7 to} 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, each of R _{7 to} R ₁₀ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

R ₁₁ and R ₁₂ may be each independently 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 a linear structure, a branched structure or a cyclic structure. In one embodiment, R ₁₁ and R ₁₂ are each independently preferably a linear alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, and carbon. More preferably, it is an alkylene group of the formula 3 or 4.
In the above formula, m is preferably 1 to 100, more preferably 1 to 40, and further preferably 1 to 10.

In the resin composition, a structural unit represented by the above formula (Ia) (hereinafter referred to as structural unit (Ia)) and a structural unit represented by the following formula (IIa) (hereinafter referred to as structural unit (IIa)) It is possible to obtain excellent insulating properties and excellent flexibility by using a resin component containing (). In one embodiment, the resin composition preferably contains at least a polyamide-imide resin among the above resin components. When a polyamide-imide resin is used, it becomes easy to obtain more excellent heat resistance. Hereinafter, the polyimide resin, the polyamide resin, and the polyamideimide resin may be collectively referred to as “resin”.

The above resin can be produced using at least the compounds represented by the following formula (I) and the following formula (II). In the formula, R _{1 to} R ₁₂ , X, and m are as described in the formula (Ia) and the formula (IIa), and Y is an amino group or an isocyanate group. That is, in one embodiment, the structural units (Ia) and (IIa) correspond to a residue obtained by removing an amino group or an isocyanate group from a compound represented by the following formulas (I) and (II), In the structure of, it may be directly bonded to the amide bond site or the imide bond site.

In one embodiment, the resin is preferably produced using at least a compound represented by the following formula (I-1) and the following formula (II-1). In the formula, R _{1 to} R ₆ and R _{7 to} R ₁₀ are as described in the formula (Ia) and the formula (IIa), and Y is an amino group or an isocyanate group. n is an integer of 1 to 6, preferably 2 to 4, and more preferably 3 or 4.

In the above resin, the polyimide resin is, for example, a resin having an imide bond formed by the reaction of an acid component and a diamine component, and as the diamine component, at least the compounds represented by (I) and (II) above. It may be a resin produced without any particular limitation except that it is used. For example, in the production of the above resin, as the acid component, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, or the like is used. Aromatic carboxylic acid anhydrides can be preferably used.

In the above resin, the polyamide resin is, for example, a resin having an amide bond formed by the reaction of an acid component and a diamine component, and as the diamine component, at least the compounds represented by (I) and (II) above are used. It may be a resin produced without any particular limitation except that it is used. For example, in the production of the above resin, an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid can be preferably used as an acid component.

In the above resin, the polyamide-imide resin is a resin having an amide bond and an imide bond in the molecular skeleton, for example, by reacting a diamine component with an acid component containing a tricarboxylic acid anhydride or an acid halide thereof, and precursor It is obtained by forming a body (polyamic acid) and then dehydrating and ring-closing the precursor. The polyamideimide resin may be a resin produced without any particular limitation, except that at least the compounds represented by (I) and (II) are used as the diamine component or diisocyanate component.

Hereinafter, the resin will be described more specifically by taking a polyamide-imide resin as an example. In the following description, the polyimide resin, the polyamide resin, and the polyamideimide resin may be collectively referred to as a resin.
In one embodiment, the polyamide-imide resin contains at least a tricarboxylic acid anhydride or an acid halide thereof as an acid component. The tricarboxylic acid anhydride may be a derivative of an aromatic compound, an aliphatic compound, or an alicyclic compound having 3 or more carboxyl groups in the molecule. Examples of tricarboxylic acid anhydrides include trimellitic acid anhydride and cyclohexane tricarboxylic acid anhydride. Among the tricarboxylic acid anhydrides, trimellitic acid anhydride is preferable from the viewpoint of cost, reactivity, solubility and the like. Acid halides of trimellitic anhydride are also preferred. The tricarboxylic acid anhydride or its acid halide may be used alone or in combination of two or more kinds.

From such a viewpoint, in one embodiment, the polyamideimide resin preferably uses at least a tricarboxylic acid anhydride represented by the following formula (III) or an acid halide thereof as an acid component.

In the formula, R is a hydroxyl group or a halogen atom. The halogen atom may be preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.
In one embodiment, when a diamine is used, an acid halide of trimellitic anhydride is preferably used as an acid component, and among them, trimellitic anhydride chloride represented by the following formula (III-1) is used. Is particularly preferable.

From the viewpoint described above, the polyamide-imide resin preferably contains a structural unit represented by the following formula (IIIa) (hereinafter, referred to as a structural unit (IIIa)).

The structural unit (IIIa) can be derived by using trimellitic anhydride represented by the above formula (III) or an acid halide thereof as an acid component and reacting with a diamine component or a diisocyanate component. it can.

In one embodiment, the polyamide-imide resin uses a compound represented by the above formula (I) and the above formula (II) as a diamine component or a diisocyanate component, and an acid component represented by the above formula (III). It may be a resin obtained by using the compound described above. In another embodiment, the polyamide-imide resin is obtained by further using a diamine component or a diisocyanate component and/or an acid component other than the compound represented by the formulas (I) to (III). It may be a resin that can be used.

The above-mentioned polyamide-imide resin is, for example, if necessary, in addition to the compound represented by the above formula (I) and the above formula (II), other than that, aromatic diamine or aromatic diisocyanate, aliphatic diamine or fat. It may be a resin obtained by further using a group diisocyanate, or an alicyclic diamine or an alicyclic diisocyanate.
Further, in addition to the compound represented by the above formula (III), a resin obtained by further using other acid component may be used. The acid component that can be used may include, for example, the above-mentioned tricarboxylic acid anhydride or acid halide thereof other than the compound represented by the above formula (III), and tricarboxylic acid such as trimellitic acid. Further, tetracarboxylic dianhydrides such as pyromellitic dianhydride and biphenyltetracarboxylic dianhydride, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and adipic acid. And an aliphatic dicarboxylic acid such as sebacic acid.

As represented by a polyamide-imide resin, in the resin, the structural unit (Ia) derived from the compound represented by the formula (I) and the formula (I The proportion of the structural unit (IIa) derived from the compound represented by II) is preferably 93 to 97 mol%, more preferably 94 to 96 mol%. In one embodiment, the resin is represented by a structural unit (Ia) derived from a compound represented by formula (I) and a formula (II) based on the total amount of structural units derived from a diamine component and/or a diisocyanate component. The ratio of the structural unit (IIa) derived from the compound may be 100 mol %. Here, the ratio (mol %) of the structural unit is calculated from the number of moles of the charged amount of the monomer compound with respect to each structural unit.

In one embodiment, as represented by a polyamide-imide resin, the ratio of the structural unit (IIa) is 3 to 7 mol based on the total number of moles of the structural unit (Ia) and the structural unit (IIa) in the resin. %, more preferably 4 to 6 mol %. In this embodiment, the structural unit (Ia) and the structural unit (IIa) in the resin are derived from a compound having a structure represented by the formula (I-1) and the formula (II-1) shown above. The structural units (I-1a) and (II-1a) are preferred. By adjusting the ratio of the structural unit (IIa) within the above range as described above, it becomes possible to improve the insulating property and flexibility in a well-balanced manner.

In one embodiment, the polyamide-imide resin preferably contains the following structures (1A) and/or (1B) and structures (2A) and/or (2B). Such a polyamide-imide resin is obtained by, for example, reacting trimellitic anhydride represented by the formula (III) or an acid halide thereof with two compounds represented by the formulas (I) and (II). Can be obtained through. In each formula, R _{1 to} R _4, R _{7 to} R _10, X and n are as described above.

The polyamide-imide resin of the above embodiment more preferably contains the following structures (1A-1) and/or (1B-1) and structures (2A-1) and/or (2B-1).

The polyamide-imide resin can be manufactured according to a known method and is not particularly limited. The polyamide-imide resin can be produced, for example, by reacting 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 without 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 depending on the scale of the batch, the reaction conditions adopted, and the like.

The organic solvent (reaction solvent) used during the production of the polyamide-imide 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, triethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate (ethylene glycol monoethyl ether acetate), dimethyl sulfoxide, Sulfur-containing solvents such as diethyl sulfoxide, dimethyl sulfone and sulfolane, cyclic ester (lactone) solvents such as γ-butyrolactone, ketone solvents such as cyclohexanone and methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethylacetamide, 1, Examples thereof include nitrogen-containing solvents such as 3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, and aromatic hydrocarbon solvents such as toluene and xylene. One of these organic solvents may be used alone, or two or more thereof may be used in combination. In one embodiment, it is preferable to select and use an organic solvent capable of dissolving the resulting resin, and it is preferable to use a polar solvent. Although the polar solvent will be described later, for example, a nitrogen-containing solvent is preferable.

In one embodiment, the polyamide-imide resin is produced by first reacting an acid component with a diamine component to produce a polyamide-imide resin precursor, and then dehydrating and ring-closing the precursor to obtain a polyamide-imide resin. be able to. However, the method for ring closure of the precursor is not particularly limited, and a method known in the art can be used. For example, a thermal ring-closing method of dehydrating and ring-closing by heating under normal pressure or reduced pressure, a chemical ring-closing method of using a dehydrating agent such as acetic anhydride in the presence or absence of a catalyst, and the like can be used.

In the case of the thermal ring closure method, it is preferable to carry out while removing the water generated by the dehydration reaction to the outside of the system. During the dehydration reaction, the reaction solution may be heated to a temperature of 80°C to 400°C, preferably 100°C to 250°C. Further, water may be removed azeotropically by using an organic solvent which is azeotropic with water, such as benzene, toluene, xylene and the like.

In the case of the chemical ring closure method, the reaction is 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, and carbodiimide compounds such as dicyclohexylcarbodiimide. At the time of the reaction, it is preferable to use a substance which promotes the cyclization reaction such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine and imidazole together. The chemical dehydrating agent is used in an amount of 90 to 600 mol% with respect to the total amount of the diamine component, and the substance that promotes the cyclization reaction is used in a ratio of 40 to 300 mol% with respect to the total amount of the diamine component. In addition, a dehydration catalyst such as triphenyl phosphite, tricyclohexyl phosphite, triphenyl phosphate, phosphoric acid, a phosphorus compound such as phosphorus pentoxide, or a boron compound such as boric acid or boric anhydride may be used.

In the production of the polyamide-imide resin, the use ratio (molar ratio) of the acid component and the diamine component (diisocyanate component) is not particularly limited, and can be adjusted so that the reaction proceeds without excess or deficiency. In one embodiment, it is preferable that the total amount of the diamine component is 0.80 to 1.10 mol with respect to the total amount of the acid component of 1.00 mol, from the viewpoint of the molecular weight and the degree of crosslinking of the polyamideimide resin to be produced, The amount is more preferably 0.95 to 1.08 mol, further preferably 0.95 to 1.03 mol.

As represented by the polyamide-imide resin described above, the weight average molecular weight (Mw) of the resin constituting the resin composition is preferably 100,000 or more. On the other hand, although not particularly limited, the Mw is preferably 160,000 or less from the viewpoint of solubility. In one embodiment, the Mw of the resin is preferably in the range of 110,000 to 160,000. When the Mw of the resin is within the above range, a coating film having an optimum thickness can be easily formed during the coating operation. The Mw of the above resin is more preferably in the range of 120,000 to 160,000, and further preferably in the range of 130,000 to 150,000. “Mw” described in the present specification is a value measured by gel permeation chromatography in terms of standard polystyrene.

In one embodiment, a film can be obtained by drying the resin composition. In forming the film, a step of applying the resin composition may be included before drying the resin composition. Here, drying means evaporating the organic solvent contained in the resin composition by, for example, natural drying or heat drying. The film formation by drying can be carried out, for example, according to the method described in Examples described later. From the viewpoint of performing the drying more sufficiently, the drying step may be performed plural times (twice or more).

In one embodiment, the thick film formability of a coating film obtained by using the above resin composition can be evaluated from the aspect ratio (=coating thickness/coating width) of a dried coating film obtained by dispensing coating. .. The aspect ratio is preferably 0.05 or more, more preferably 0.06 or more, still more preferably 0.07 or more, from the viewpoint of obtaining a film thickness with which sufficient insulation can be easily obtained. The measurement of the aspect ratio can be performed using, for example, a Dektak 6M surface profiler manufactured by ULVAC, Inc.

In one embodiment, as represented by the polyamide-imide resin described above, the resin used to form the resin composition preferably has a glass transition temperature (Tg) of 180° C. or higher. The "glass transition temperature (Tg)" described in the present specification is a value obtained by carrying out a dynamic viscoelasticity test using a film obtained by applying and drying a resin dissolved in a solvent. More preferably, the resin has a Tg of 200° C. or higher. When the resin has a Tg of 200° C. or higher, excellent reliability can be obtained even in a heat cycle test generally performed at a high temperature of 200° C. or higher. Further, when the power semiconductor device is configured by using the above resin, it is possible to prevent the resin from being softened by the heat generated during driving and the adhesiveness from being deteriorated.

In the resin composition, the resin is preferably soluble in an organic solvent at room temperature from the viewpoint of workability during film formation. In the present specification, "soluble in an organic solvent at room temperature" means that at room temperature, when a solution obtained by adding an organic solvent to a resin and stirring is visually confirmed, there is no precipitate and no turbidity. , Means that the entire solution becomes transparent. Here, the “room temperature” may be in the range of approximately 10° C. to 40° C., and is preferably in the range of 20 to 30° C. In one embodiment, the “solution” means, for example, a solution obtained by adding 1 to 30 mg of the resin powder to 100 mL of an organic solvent. The organic solvent will be described later.

(B) Organic Solvent The resin composition contains the resin component described above and an organic solvent. In this specification, the resin composition may be referred to as a varnish.
The organic solvent is not particularly limited as long as it can dissolve the resin component such as the polyamide-imide resin. In one embodiment, the organic solvent may be a solvent composed of polar molecules (sometimes referred to as polar solvent). In one embodiment, the organic solvent forming the resin composition may be the same as the reaction solvent used in the production of the resin.

As an example of an organic solvent,
Nitrogen-containing compounds such as N-methylpyrrolidone, dimethylacedamide, dimethylformamide, 1,3-dimethyltetrahydro-2(1H)-pyrimidinone Sulfur-containing compounds such as sulfolane and dimethylsulfoxide,
Lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone and ε-caprolactone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone,
Polyhydric alcohols such as ethylene glycol and glycerin, and
Ethers, i.e.
Diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether,
Diethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, and triethylene glycol dibutyl ether,
Tetraethylene glycol dialkyl ether such as tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, and tetraethylene glycol dibutyl ether,
Diethylene glycol monomethyl ether, and diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether,
Triethylene glycol monomethyl ether such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and tetraethylene glycol monoalkyl ether such as tetraethylene glycol monomethyl ether and tetraethylene glycol monoethyl ether, and ethylene glycol monomethyl ether Ethers such as ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), and the like including ethylene glycol monoalkyl ether acetate are included.

These organic solvents may be used alone or in combination of two or more. In one embodiment, the organic solvent preferably contains a nitrogen-containing compound, and more preferably N-methylpyrrolidone. In another embodiment, the organic solvent preferably contains ethers, and more preferably diethylene glycol dialkyl ether and ethylene glycol monoalkyl ether acetate. In still another embodiment, the organic solvent may be a mixed solvent containing a nitrogen-containing compound and ethers. For example, the organic solvent is preferably a mixed solvent of N-methylpyrrolidone and butyl cellosolve acetate, and the mixing ratio thereof is not particularly limited.

The blending amount of the organic solvent in the resin composition can be appropriately adjusted in consideration of the storage elastic modulus or the viscosity. In one embodiment, the compounding amount of the organic solvent is preferably 350 to 550 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition. The organic solvent is more preferably added in a proportion of 400 to 500 parts by weight with respect to 100 parts by weight of the total amount of the polyamide-imide resin. By adjusting the blending amount of the organic solvent with respect to the resin within the above range, the resin can be easily dissolved and a viscosity suitable for thickening the film can be easily obtained.

(Other ingredients)
If necessary, additives such as a colorant and a coupling agent, and additional components such as a resin modifier may be added to the resin composition (varnish). When the resin composition contains an additional component, the amount of the additional component is preferably 50 parts by weight or less based on 100 parts by weight of the total amount of the resin (solid component) in the resin composition. By setting the amount of the additional component to be 50 parts by weight or less, it becomes easy to suppress deterioration of the physical properties of the obtained coating film.

In one embodiment, the resin composition preferably further contains a coupling agent. When a coupling agent is used, it becomes easy to improve the adhesion to each member. The coupling agent that can be used is not particularly limited and may be any of silane-based, titanium-based, and aluminum-based coupling agents, but silane-based coupling agents are most preferred.
The silane-based coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryllane. Roxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Silane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyl-tris[2-(2-methoxyethoxy)ethoxy]silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3-4,5-dihydroimidazole-1 -Yl-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3-cyanopropyl-tri Ethoxysilane, hexamethyldisilazane, N,O-bis(trimethylsilyl)acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichlorosilane, octyltri Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri(methacryloyloxyethoxy)silane, methyltri(glycidyloxy)silane, N-β(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, octadecyldimethyl [3-(trimethoxysilyl)propyl]ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloro It may be lopropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, trimethylsilylisocyanate, dimethylsilylisocyanate, methylsilyltriisocyanate, vinylsilyltriisocyanate, phenylsilyltriisocyanate, tetraisocyanatesilane, ethoxysilaneisocyanate and the like. One of these may be used alone, or two or more may be used in combination.

The titanium-based coupling agent is not particularly limited, and includes, for example, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri(dioctyl phosphate) titanate, Isopropyl tricumyl phenyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(n-aminoethyl) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2) 2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, dicumylphenyloxyacetate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra( 2-Ethylhexyl) titanate, titanium acetylacetonate, polytitanium aethylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium chiliethanolaminate, polyhydroxytitanium stearate, tetra. Methyl orthotitanate, tetraethyl orthotitanate, tetarapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, cresyl titanate monomer, cresyl titanate polymer, diisopropoxy-bis(2,4-pentadionate) titanium (IV), It may be diisopropyl-bis-triethanolaminotitanate, octyleneglycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer, tri-n-butoxytitanium monostearate and the like. These 1 type may be used individually or may be used in combination of 2 or more type.

The aluminum-based coupling agent is not particularly limited, and examples thereof include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), Such as aluminum tris(acetylacetonate), aluminum-monoisopropoxymonooleoxyethylacetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate. It may be an aluminum chelate compound, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, aluminum alcoholate such as aluminum ethylate.

In one embodiment, the resin composition preferably has a dielectric breakdown voltage of 150 kV/mm or more at room temperature after drying. The dielectric breakdown voltage is more preferably 180 kV/mm or more, further preferably 200 kV/mm or more. When the breakdown voltage is 150 kV/mm or more, even a leak current of the power semiconductor device can be sufficiently prevented, and excellent reliability of the semiconductor device can be easily obtained.
In one embodiment, a dielectric breakdown voltage of 200 kV/mm or more can be achieved only with a resin component such as a polyamide-imide resin used in the resin composition. Therefore, the resin composition can be formed without using an inorganic filler or the like. From such a viewpoint, in one embodiment, the resin composition can be composed only of the resin component and the organic solvent.

The “dielectric breakdown voltage (kV/mm)” described in the present specification is a value obtained by conducting a dielectric breakdown test using a resin composition or a resin film dissolved in a solvent. More specifically, for example, the measurement is performed using a sample in which a resin composition (varnish) is applied and dried on an Al substrate to form a film. The conditions at the time of measurement may typically be a pressure rising rate: 0.5 kV/sec (AC 50 Hz), electrode dimensions: high pressure side; φ20 mm ball, low pressure side; metal plate, test atmosphere: in oil.

In one embodiment, the viscosity of the resin composition is preferably in the range of 7,000 to 15,000 mPa·s, and more preferably in the range of 8,000 to 13,000 mPa·s. Here, as for the viscosity, a varnish obtained by dissolving a resin in a solvent so that a nonvolatile component (solid component) is 15 to 20% is obtained by using an E-type viscometer at 25° C. It is a value obtained by measuring at 10 rpm. If the viscosity measured at 10 rpm is less than 7,000 mPa·s, it becomes difficult to secure a sufficient film thickness during coating. Further, if the viscosity exceeds 15,000 mPa·s, it becomes difficult to form a uniform film during coating. In the above resin composition, a desired viscosity can be easily obtained by using a resin containing a specific structural unit and having a weight average molecular weight of 100,000 or more.

The viscosity can be measured using, for example, 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 the resin composition solution is put into the viscometer, and the viscosity 10 minutes after the start of the measurement is recorded.

In one embodiment, the elastic modulus at 35° C. of the film obtained by applying and drying the resin composition (varnish) is preferably in the range of 0.5 to 3.0 GPa, and 1.0 to 3.0 GPa. The range is more preferably. The elastic modulus is a value measured by a dynamic viscoelasticity measuring device. If the elastic modulus is less than 0.5 GPa, the film becomes too soft, and the reliability of the power semiconductor device may be reduced. On the other hand, if the elastic modulus exceeds 3.0 GPa, the stress relaxation property of the film decreases, which may reduce the reliability of the power semiconductor device. From the viewpoint of obtaining good flexibility in order to further enhance the reliability of the power semiconductor device, the elastic modulus is more preferably in the range of 2.2 GPa to 3.0 GPa, most preferably in the range of 2.2 GPa to 2.8 GPa. preferable.

For the measurement of the elastic modulus, for example, a dynamic viscoelasticity measuring device “Rheogel-E4000 type” manufactured by UBM Co., Ltd. can be used. A film obtained by applying and drying a resin composition (varnish) is cut to have a width of 4 mm to prepare a sample, and using this sample, a chuck distance of 20 mm, a measurement frequency of 10 MHz, and a measurement temperature of 35° C. It is performed under measurement conditions.

2. Semiconductor Device The resin composition of the above embodiment is excellent in heat resistance, and also excellent in insulating property, flexibility, and thick film forming property, and thus can be suitably used as a constituent material of a semiconductor device. One embodiment relates to a semiconductor device having a film using the resin composition of the above embodiment on the surface of a constituent member. For example, the film may form an insulating film in a semiconductor device. In addition, the film may form an adhesive layer, a protective layer, or the like. The semiconductor device having the above film has excellent adhesion between each member and excellent reliability. In one embodiment, the above resin composition can be preferably used as a constituent material of a power semiconductor device using a silicon carbide (SiC) substrate or a gallium nitride (GaN) substrate.

1 and 2 are schematic cross-sectional views showing one embodiment of a semiconductor device. The semiconductor device shown in FIGS. 1 and 2 has a die pad 1a, a semiconductor element 2, an insulating film 3a, 3b, or 3, a lead 1b, a wire 4, and a resin sealing layer 5, and an insulating film. Are each formed from the resin composition of the above embodiment.
In the semiconductor device, the portion where the leak current is most likely to occur is the lower end portion of the wire connected to the semiconductor element. Therefore, as shown in FIG. 1, as one embodiment, it is preferable that the insulating film 3a is provided at least at the lower end portion of the wire connected to the semiconductor element. As another embodiment, in addition to the insulating film 3a, the insulating film 3b may be provided on the lower end portion of the wire connected to the lead 1b. As another embodiment, as shown in FIG. 2, in the semiconductor device, the insulating film 3 formed of the above resin composition may be provided on the upper surface, the side surface of the semiconductor element, and the upper surface of the die pad.
By thus providing the insulating film formed from the resin composition of the above-described embodiment, it is possible to more effectively prevent the leak current generated in the semiconductor device and improve the reliability of the semiconductor device. it can.

In one embodiment, a method for manufacturing a semiconductor device includes at least coating a resin composition of the above embodiment on a surface of a substrate on which a semiconductor element is mounted and drying the resin composition to form an insulating film, and And forming a resin encapsulating layer.
In the above production method, from the viewpoint of workability, the resin composition preferably contains a polyamide-imide resin as a resin component. The formation of the insulating film can be performed by applying the resin composition to a predetermined place and drying the coating film. The resin composition can be applied by applying various application methods. The coating method is not particularly limited, and examples thereof include a spray coating method, a potting method, a dipping method, and a dispensing method. In consideration of workability, the potting method or dispense coating is preferable.

The material of the substrate is not particularly limited and can be selected from the materials well known in the art. From the viewpoint 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.
The resin encapsulating layer can be composed of a cured product of a resin known in the art as an encapsulating material. As the sealing material, for example, a liquid or solid epoxy resin composition can be used. The resin sealing layer can be formed, for example, by transfer molding using a sealing material.

In another embodiment, a method for manufacturing a semiconductor device includes, for example, forming a resin layer by applying and drying the polyamideimide resin composition of the above embodiment on a semiconductor substrate on which a plurality of wirings having the same structure are formed, And, if necessary, forming a rewiring on the resin layer so as to be electrically connected to the electrode on the semiconductor substrate. In addition to these steps, a protective layer (resin layer) may be formed on the rewiring or the resin layer using the above resin composition, if necessary. Further, in addition to the above steps, it may include forming external electrode terminals on the resin layer if necessary, and then performing dicing if necessary.

In the above semiconductor device, the semiconductor element is not particularly limited, but may be, for example, a silicon wafer, a silicon carbide wafer, or the like. The method for applying the resin layer is not particularly limited, but spin coating, spray coating, or dispense coating is preferable. The resin layer can be dried by a method known in the art. The resin composition of the above embodiment is excellent in characteristics such as spatter resistance, plating resistance, and alkali resistance required in the step of forming rewirings, and therefore, is limited to the configuration of the semiconductor device described above. It can be suitably used as a constituent material of all semiconductor devices without being damaged.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

1. Synthesis of polyamide-imide resin (Synthesis example 1)
A 2-liter 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil/water separator was charged with 2,2-bis[4-(4-aminophenoxy)phenyl]propane under a nitrogen stream. 108.08 g, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane 3.45 g, respectively, and N-methyl-2-pyrrolidone (NMP) was further added. 700 g was added and dissolved.
Next, while cooling the reaction solution so as not to exceed 20° C., 59.00 g of trimellitic anhydride chloride (TAC) was added. After stirring at room temperature for 1 hour, while cooling the reaction solution so as not to exceed 20° C., 33.96 g of triethylamine (TEA) was added and reacted at room temperature for 3 hours to prepare a polyamic acid solution.
The resulting polyamic acid solution was further dehydrated at 190° C. for 6 hours to prepare a polyamideimide resin solution. A precipitate obtained by pouring this polyamideimide resin solution into water was separated, pulverized, and dried to obtain a powdery polyamideimide resin (PAI-1). The weight average molecular weight (Mw) of the obtained polyamideimide resin (PAI-1) was measured by gel permeation chromatography (GPC) in terms of standard polystyrene, and Mw was 140,000.

The detailed conditions for measuring Mw are as follows.
Liquid sending pump: LC-20AD manufactured by Shimadzu Corporation
UV-Vis detector: Shimadzu SPD-20A
Column: Shodex, KD-806M manufactured by Showa Denko KK
Eluent: NMP, manufactured by Mitsubishi Chemical Corporation Flow rate: 1 mL/min
Column temperature: 40°C
Molecular weight standard substance: Standard polystyrene

(Synthesis example 2)
A 2-liter 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil/water separator was charged with 2,2-bis[4-(4-aminophenoxy)phenyl]propane under a nitrogen stream. 110.35 g, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane 2.07 g, respectively, and N-methyl-2-pyrrolidone (NMP) was further added. 700 g was added and dissolved.
Next, while cooling the reaction solution so as not to exceed 20° C., 59.00 g of trimellitic anhydride chloride (TAC) was added. After stirring at room temperature for 1 hour, while cooling the reaction solution so as not to exceed 20° C., 33.96 g of triethylamine (TEA) was added and reacted at room temperature for 3 hours to prepare a polyamic acid solution.
The resulting polyamic acid solution was further dehydrated at 190° C. for 6 hours to prepare a polyamideimide resin solution. A precipitate obtained by pouring this polyamideimide resin solution into water was separated, pulverized, and dried to obtain a powdery polyamideimide resin (PAI-2). The weight average molecular weight (Mw) of the obtained polyamideimide resin (PAI-2) was measured by gel permeation chromatography (GPC) in terms of standard polystyrene, and Mw was 150,000.

(Synthesis example 3)
A 2-liter 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil/water separator was charged with 2,2-bis[4-(4-aminophenoxy)phenyl]propane under a nitrogen stream. 105.80 g, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (4.82 g), respectively, and N-methyl-2-pyrrolidone (NMP) was further added. 700 g was added and dissolved.
Next, while cooling the reaction solution so as not to exceed 20° C., 59.00 g of trimellitic anhydride chloride (TAC) was added. After stirring at room temperature for 1 hour, while cooling the reaction solution so as not to exceed 20° C., 33.96 g of triethylamine (TEA) was added and reacted at room temperature for 3 hours to prepare a polyamic acid solution.
The resulting polyamic acid solution was further dehydrated at 190° C. for 6 hours to prepare a polyamideimide resin solution. A precipitate obtained by pouring this polyamideimide resin solution into water was separated, pulverized, and dried to obtain a powdery polyamideimide resin (PAI-3). The weight average molecular weight (Mw) of the obtained polyamideimide resin (PAI-3) was measured by gel permeation chromatography (GPC) in terms of standard polystyrene, and the Mw was 130,000.

(Synthesis example 4)
A 2-liter 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil/water separator was charged with 2,2-bis[4-(4-aminophenoxy)phenyl]propane under a nitrogen stream. 102.389 g, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane 6.89 g, respectively, and N-methyl-2-pyrrolidone (NMP) was added. 700 g was added and dissolved.
Next, while cooling the reaction solution so as not to exceed 20° C., 59.00 g of trimellitic anhydride chloride (TAC) was added. After stirring at room temperature for 1 hour, while cooling the reaction solution so as not to exceed 20° C., 33.96 g of triethylamine (TEA) was added and reacted at room temperature for 3 hours to prepare a polyamic acid solution.
The resulting polyamic acid solution was further dehydrated at 190° C. for 6 hours to prepare a polyamideimide resin solution. A precipitate obtained by pouring this polyamideimide resin solution into water was separated, pulverized, and dried to obtain a powdery polyamideimide resin (PAI-4). The weight average molecular weight (Mw) of the obtained polyamideimide resin (PAI-4) was measured by gel permeation chromatography (GPC) in terms of standard polystyrene, and the Mw was 85,000.

(Synthesis example 5)
A 2-liter 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil/water separator was charged with 2,2-bis[4-(4-aminophenoxy)phenyl]propane under a nitrogen stream. 113.77 g was added, and 700 g of N-methyl-2-pyrrolidone (NMP) was further added and dissolved.
Next, while cooling the reaction solution so as not to exceed 20° C., 59.00 g of trimellitic anhydride chloride (TAC) was added. After stirring at room temperature for 1 hour, while cooling the reaction solution so as not to exceed 20° C., 33.96 g of triethylamine (TEA) was added and reacted at room temperature for 3 hours to prepare a polyamic acid solution.
The resulting polyamic acid solution was further dehydrated at 190° C. for 6 hours to prepare a polyamideimide resin solution. A precipitate obtained by pouring this polyamideimide resin solution into water was separated, pulverized, and dried to obtain a powdery polyamideimide resin (PAI-5). The weight average molecular weight (Mw) of the obtained polyamideimide resin (PAI-5) was measured by gel permeation chromatography (GPC) in terms of standard polystyrene, and Mw was 180,000.

2. Preparation of polyamide-imide resin composition (Example 1)
In a 0.5 liter four-necked flask at room temperature (25° C.), 18 g of the polyamide-imide resin (PAI-1) obtained in Synthesis Example 1 and 32. 8 g and 49.2 g of butyl cellosolve acetate were added and stirred for 12 hours to obtain a polyamideimide resin composition. When the obtained resin composition was visually confirmed at room temperature (25° C.), it was yellow and transparent. The above resin composition was filled in a filter (KST-47 manufactured by Advantech Co., Ltd.), and pressure filtration was performed at a pressure of 0.3 MPa to obtain a polyamideimide resin composition (P-1).

(Example 2)
A polyamideimide resin composition (P-2) was prepared in the same manner as in Example 1 except that the polyamideimide resin (PAI-2) obtained in Synthesis Example 2 was used as the polyamideimide resin. When the obtained resin composition was visually confirmed at room temperature (25° C.), it was yellow and transparent.

(Example 3)
A polyamideimide resin composition (P-3) was prepared in the same manner as in Example 1 except that the polyamideimide resin (PAI-3) obtained in Synthesis Example 3 was used as the polyamideimide resin. When the obtained resin composition was visually confirmed at room temperature (25° C.), it was yellow and transparent.

(Comparative Example 1)
A polyamideimide resin composition (P-4) was prepared in the same manner as in Example 1 except that the polyamideimide resin (PAI-4) obtained in Synthesis Example 4 was used as the polyamideimide resin. When the obtained resin composition was visually confirmed at room temperature (25° C.), it was yellow and transparent.

(Comparative example 2)
At room temperature (25° C.), in a 0.5 liter four-necked flask, under a nitrogen stream, 18 g of the polyamideimide resin (PAI-4) obtained in Synthesis Example 4 and 32. 8 g and 49.2 g of butyl cellosolve acetate were added and stirred for 12 hours to obtain a polyamideimide resin composition. When the obtained resin composition was visually confirmed at room temperature (25° C.), it was yellow and transparent.
10 g of silica filler (SC2050/manufactured by Admatechs Co., Ltd.) was added to the above resin composition, and the mixture was stirred at a dispa (5,000 rpm/10 minutes). Then, it was filled in a filter (KST-47 manufactured by Advantech Co., Ltd.) and pressure filtration was performed at a pressure of 0.3 MPa to obtain a polyamideimide resin composition (P-5).

(Comparative example 3)
A polyamideimide resin composition (P-6) was prepared in the same manner as in Example 1 except that the polyamideimide resin (PAI-5) obtained in Synthesis Example 5 was used as the polyamideimide resin. When the obtained resin composition was visually confirmed at room temperature (25° C.), it was yellow and transparent.

3. Characteristic Evaluation of Polyamideimide Resin Composition Using the polyamideimide resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3, various characteristics were evaluated as follows. The results are shown in Table 1.

(viscosity)
The viscosity of each polyamideimide resin composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was measured under the following conditions using a viscometer (RE type) manufactured by Toki Sangyo Co., Ltd.
Sampling volume: 1.2mL
Measurement temperature: 25°C
Cone rotation speed: 10 rpm
Measurement time: 10 minutes.

(Elastic modulus)
The polyamideimide resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were applied onto a substrate using a bar coater and dried to obtain a film having a thickness of 10 μm. The main drying of the membrane was then carried out at 230° C. for 2 hours. The coating film thus obtained was cut to a width of 4 mm and used as a measurement sample.
The measurement sample was installed in a dynamic viscoelasticity measuring device “Rheogel-E4000 type” manufactured by UBM Co., Ltd., and the elastic modulus of the polyamide-imide resin was measured. The measurement was carried out under the condition that the distance between chucks was 20 mm, and the elastic modulus was obtained by reading the value at 35°C.

(Dielectric breakdown voltage)
The polyamideimide resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were applied onto an Al metal substrate using a bar coater and dried to obtain a film having a thickness of 10 μm. The main drying of the membrane was then carried out at 230° C. for 2 hours. The dielectric breakdown voltage of the obtained coating film was measured under the following conditions.
Test temperature: 25°C
Step-up speed: 0.5kV/sec (AC 50Hz)
Electrode dimensions: High pressure side; φ20 mm ball, low pressure side; Metal plate Test atmosphere: In oil

(Measurement of aspect ratio)
Using each of the polyamideimide resin compositions (varnish) obtained in Examples 1 to 3 and Comparative Examples 1 to 3, coating was performed under the following conditions.
Nozzle diameter: φ0.29 mm
Nozzle speed: 10 mm/sec Discharge pressure: 0.3 MPa
Then, after drying, main drying was performed at 230° C. for 2 hours. The shape of the coating film after drying was measured with a Dektak 6M surface profiler (manufactured by ULVAC, Inc.) to calculate the aspect ratio of the coating film (=coating thickness/coating width).

As can be seen from Table 1, in each of the resin compositions of Examples 1 to 3 which are the embodiments of the present invention, the dielectric breakdown voltage is 150 kV/mm or more, and the dry coating film aspect ratio after dispensing is 0. It was 0.05 or more. The elastic modulus was within the range of 0.5 to 3.0 GPa. From these facts, a resin composition containing a structural unit (Ia) and a structural unit (IIa) and having excellent Mw of 100,000 or more has excellent insulating properties, flexibility, and thick film forming properties. You can see that you can provide.

On the other hand, the resin composition of Comparative Example 1 uses a resin having an Mw of less than 100,000, and has a low viscosity and a poor thick film forming property in comparison with Examples 1 to 3. In the resin composition of Comparative Example 2, an inorganic filler (silica) is added for the purpose of improving the viscosity of the resin composition of Comparative Example 1. However, in Comparative Example 2, in comparison with Examples 1 to 3, the values of the viscosity and the aspect ratio were similar, but the result was that the dielectric breakdown voltage was significantly lowered. The resin composition of Comparative Example 3 uses a resin containing the structural unit (Ia) but not the structural unit (IIa). Comparative Example 3 has the same viscosity and the same aspect ratio as those of Examples 1 to 3 but has a high elastic modulus, and therefore the reliability of the power semiconductor device is considered to be deteriorated.

From the above, the resin composition according to the present invention can be suitably used as a constituent material of a power semiconductor device that partially needs high insulation, and it is possible to secure sufficient insulation. You can see.

1: lead frame 1a: die pad 1b: lead 2: semiconductor elements 3a, 3b, 3: insulating film (cured film of resin composition)
4 wire 5 resin sealing layer

As an example of an organic solvent,
N- methylpyrrolidone, Jimechiruase DOO, dimethylformamide, 1,3-dimethyl-tetrahydropyran -2 (IH) - nitrogen-containing compounds such as pyrimidinone sulfolane, sulfur-containing compounds such as dimethyl sulfoxide,
Lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone and ε-caprolactone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone,
Polyhydric alcohols such as ethylene glycol and glycerin, and
Ethers, i.e.
Diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether,
Triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, and triethylene glycol dibutyl ether,
Tetraethylene glycol dialkyl ether such as tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, and tetraethylene glycol dibutyl ether,
Diethylene glycol monomethyl ether, and diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether,
Triethylene glycol monomethyl ether such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and tetraethylene glycol monoalkyl ether such as tetraethylene glycol monomethyl ether and tetraethylene glycol monoethyl ether, and ethylene glycol monomethyl ether ether acetate, ethylene glycol monoethyl ether acetate, ethers including ethylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), and the like.

The titanium-based coupling agent is not particularly limited, and includes, for example, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri(dioctyl phosphate) titanate, Isopropyl tricumyl phenyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(n-aminoethyl) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2) 2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, dicumylphenyloxyacetate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra( 2-ethylhexyl) titanate, titanium acetyl acetonate, Porichitan'a cell chill acetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium dust aminate, polyhydroxy titanium stearate, tetramethyl orthotitanate, tetraethyl orthotitanate, Te preparative La propyl orthotitanate, tetra-isobutyl orthotitanate, stearyl titanate, cresyl titanate monomers, cresyl titanate polymer, diisopropoxy - bis (2,4-penta dionate) titanium (IV) , Diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxy titanium monostearate polymer, tri-n-butoxy titanium monostearate polymer, tri-n-butoxy titanium monostearate and the like. These 1 type may be used individually or may be used in combination of 2 or more type.

Claims (7)

(A) A polyimide resin, a polyamide resin, and a polyamide containing a structural unit represented by the following formula (Ia) and a structural unit represented by the following formula (IIa) and having a weight average molecular weight of 100,000 or more. A resin composition comprising a resin component containing at least one selected from the group consisting of imide resins and (B) an organic solvent.

[Wherein, R _{1 to} R ₄ are each independently 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. Representing one or more substituents, X is a single bond or a divalent organic group selected from the following.

(In the formula, R ₅ and R ₆ are each independently 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. There are at least one kind of substituent.)]

[Wherein, R _{7 to} R ₁₀ each independently represent a hydrogen atom or a substituent, R ₁₁ and R ₁₂ each independently represent a divalent hydrocarbon group, and m is 1 or more. Is an integer. ] The polyimide resin, the polyamide resin, and the polyamideimide resin have the formula (IIa) based on the total number of moles of the structural unit represented by the formula (Ia) and the structural unit represented by the formula (IIa). ) The resin composition according to claim 1, containing 3 to 7 mol% of the structural unit represented by the formula (1). The resin composition according to claim 1, wherein the polyamide-imide resin further contains a structural unit represented by the following formula (IIIa).

The resin composition according to claim 1, wherein the film obtained by drying has a dielectric breakdown voltage of 150 kV/mm or more. The resin composition according to any one of claims 1 to 4, wherein the glass transition temperature of each of the polyimide resin, the polyamide resin, and the polyamide-imide resin is 200°C or higher. The resin composition according to claim 1, wherein the film obtained by drying has an elastic modulus at 35° C. of 0.5 to 3.0 GPa. A semiconductor device having a film formed by using the resin composition according to claim 1 on the surface of a component.

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