JP2005139393A - Resin composition, resin varnish, heat-resistant adhesive, heat-resistant adhesive material using the adhesive, lead-frame with the adhesive material, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition, resin varnish, heat-resistant adhesive, heat-resistant adhesive material using the adhesive, and lead-frame with the adhesive material that can be bonded at a low temperature and is excellent in heat resistance, compared with those by conventional techniques, and a semiconductor device. <P>SOLUTION: This resin composition comprises a polymer having a structure unit represented by formula (I) wherein n is an integer of 3-7; Y is a group represented by formula (II); and Y's in the structure units may be different from each other. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition, a resin varnish, a heat-resistant adhesive, a heat-resistant adhesive material using the same, a lead frame with an adhesive material, and a semiconductor device, and in particular, bonding at a relatively low temperature such as in the manufacture of a semiconductor device. The present invention relates to a resin composition, a resin varnish, a heat-resistant adhesive, a heat-resistant adhesive material using the same, a lead frame with an adhesive material, and a semiconductor device, which are suitable for applications that require both heat resistance and heat resistance.

  Adhesive materials currently used in the field of electronics, such as adhesive materials between metal foils on printed circuit boards and support materials such as polyimide films, and lead frames and semiconductor elements (chips) in resin-encapsulated semiconductor devices A material excellent in high temperature characteristics, purity, and workability is required for an adhesive material or an adhesive material between a metal foil of a so-called TAB tape and a polyimide film.

  Conventionally, thermosetting resins such as epoxy-based, rubber-modified epoxy-based, phenol-based, and acrylic-based materials that have been used as these adhesive materials show excellent adhesiveness, but are inferior in heat resistance and purity, and have a secondary effect during curing. There is a drawback that the adherend is contaminated by the generated outgas.

  On the other hand, studies have been made to use a thermoplastic resin having a high heat resistance after being melt-bonded as an adhesive material (for example, Patent Document 1, Patent Document 2, etc.).

  Adhesive materials using the above thermoplastic resins are widely used in LOC (lead on chip) packages and the like because they have excellent heat resistance, do not require curing, and generate little outgas.

However, since the above-mentioned thermoplastic adhesive material has a high bonding temperature of 300 to 400 ° C., a thermoplastic adhesive material that can be bonded at a lower temperature (for example, 200 to 300 ° C.) has been demanded.
JP-A-1-268778 JP-A-1-282283

  An object of the present invention is to provide a resin composition, a resin varnish, a heat-resistant adhesive, a heat-resistant adhesive material using the same, and a lead frame with an adhesive material that can be bonded at a low temperature as compared with the prior art and has excellent heat resistance. And providing a semiconductor device.

  The present invention is characterized by the following items (1) to (8).

(1) A resin composition comprising a polymer having a structural unit represented by the following general formula (I).

(2) A resin varnish obtained by dissolving a resin composition containing a polymer having a structural unit represented by the following general formula (I) in an organic solvent.

  (3) The organic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, diethylene glycol dimethyl ether, tetrahydrofuran, cyclohexanone, cyclopentanone, and methyl ethyl ketone. (2) The resin varnish as described.

(4) A heat-resistant adhesive comprising a polymer having a structural unit represented by the following general formula (I).

  (5) The heat-resistant adhesive according to (4), further comprising a silane coupling agent.

  (6) A support film, and an adhesive layer formed by applying the heat-resistant adhesive according to (4) or (5) on one side or both sides of the support film. Heat resistant adhesive material.

  (7) A lead frame with an adhesive material, wherein the heat resistant adhesive material according to (6) is used.

  (8) A semiconductor device obtained by bonding the lead frame with an adhesive material according to (7) above and a semiconductor element.

  According to the present invention, a resin composition, a resin varnish, a heat-resistant adhesive, a heat-resistant adhesive material using the same, and a lead frame with an adhesive material that can be bonded at a low temperature as compared with the prior art and have excellent heat resistance And a semiconductor device can be provided.

The resin composition or heat-resistant adhesive of the present invention is characterized by containing a polymer having a structural unit represented by the following general formula (I).

  The polymer having the structural unit represented by the general formula (I) is 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, bis (3- (3- (3-aminophenoxy) phenoxy). Phenyl) ether, 1,3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, bis (3- (3- (3- (3-aminophenoxy) phenoxy) phenoxy) phenyl) ether 1, at least one aromatic diamine selected from the group consisting of 1,3-bis (3- (3- (3- (3- (3-aminophenoxy) phenoxy) phenoxy) phenoxy) benzene, isophthalic acid and / or terephthalic acid Alternatively, it can be obtained by polycondensing a reactive derivative thereof or an acid component such as trimellitic acid or a reactive derivative thereof.

  As the aromatic diamine, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1, in order to sufficiently increase the adhesiveness of the resin composition and sufficiently increase the molecular weight of the polymer. 3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene is more preferable, and 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene is particularly preferable. .

  Examples of the derivatives of isophthalic acid and / or terephthalic acid include dichloride, dibromide, and diester. Preferably, terephthalic acid dichloride and isophthalic acid dichloride are used to sufficiently increase the molecular weight of the polymer.

  The reactive derivative of trimellitic acid in the present invention means its acid anhydride, halide, ester, amide, ammonium salt and the like. Examples of these include trimellitic anhydride, trimellitic anhydride monochloride, and ammonium salts thereof composed of ammonia, dimethylamine, triethylamine, and the like. Among these, trimellitic anhydride and trimellitic anhydride monochloride are preferable, and trimellitic anhydride monochloride is more preferable in order to sufficiently increase the molecular weight of the polymer.

The structural unit represented by the general formula (I) may be present in a part of the polymer structure, and does not necessarily represent a repeating unit. That is, when only one of the aromatic diamines listed above as a monomer and an acid component are polymerized, the polymer structure can be shown by a repeating unit represented by the following general formula (II). When other diamines are further included as a monomer, the structural unit represented by the above general formula (I) may be included in a part of the polymer structure.

  In the present invention, examples of other diamines that can be used in combination with the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-bis- (3- Aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- ( 4-Aminophenoxy)] hexafluoropropane, 4,4'-methylenebis (2,6-diisopropylamine) and other known aromatic diamines. Among these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis- (3-aminophenoxy) benzene, and the like are preferable in order to improve adhesiveness. Further, the ratio of the known aromatic diamine to the whole aromatic diamine is not particularly limited, but is preferably 0 to 95 mol%, more preferably 10 to 90 mol%, and more preferably 20 to 80 mol%. It is particularly preferred. If the ratio of the known aromatic diamine exceeds 95 mol%, the adhesiveness tends to be lowered, and the molecular weight of the resin composition obtained is not easily lowered unless it is added at all.

  Also, α, ω-bis (3-aminopropyl) -polydimethylsiloxane such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, 1,12-diaminododecane, 1,6-diaminohexane, etc. A diamine such as α, ω-diaminoalkane can be used in combination, and the adhesiveness of the resin composition can be enhanced by using these diamines. The ratio of such diamines to the total diamines including aromatic diamines is not particularly limited, but is preferably 0 to 60 mol% or less, more preferably 10 to 50 mol% or less, and more preferably 20 to 40 mol%. It is particularly preferable that the amount is not more than mol%.

  In the present invention, an acid component such as isophthalic acid and / or terephthalic acid or a reactive derivative thereof, or trimellitic acid or a reactive derivative thereof is preferably used in an amount of 80 to 120 mol% based on the total amount of diamines. In particular, 95 to 105 mol% is preferable. When these are used in equimolar amounts, the highest molecular weight resin can be obtained. By making the acid component within the above numerical range relative to the diamine, the molecular weight of the polymer can be increased, and the mechanical strength, heat resistance and the like are improved.

  In the present invention, when a polycondensation reaction between the diamine and the acid component as described above can be employed as it is, a method used in a known reaction can be employed as it is, and various conditions are not particularly limited.

  Moreover, the weight average molecular weight of the polymer is preferably 10,000 to 200,000, and more preferably 20,000 to 100,000. Moreover, it is preferable that it is 50-200 degreeC, and, as for the glass transition temperature (Tg) of a polymer, it is more preferable that it is 75-150 degreeC.

  Moreover, in the resin composition or heat-resistant adhesive of the present invention, a thermosetting resin such as an epoxy resin, a phenol resin, or a bismaleimide resin may be further added to the polymer obtained as described above. When adding a thermosetting resin, the thermosetting resin is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and more preferably 0 to 15 parts by weight with respect to 100 parts by weight of the polymer. It is particularly preferable that

  Moreover, the resin composition or heat-resistant adhesive of the present invention may further contain a filler such as ceramic powder, glass powder, silver powder, copper powder, resin particles, rubber particles, etc., added to the polymer obtained as described above. When adding a filler, the addition amount is preferably 1 to 30 parts by weight and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the polymer.

  Moreover, it is preferable that the coupling agent is added to the polymer obtained by the above in order for the resin composition or heat resistant adhesive of this invention to improve adhesiveness with a base material and to improve heat resistance.

  As the coupling agent, for example, a coupling agent such as vinyl silane, epoxy silane, amino silane, mercapto silane, titanate, aluminum chelate, zirco aluminate and the like can be used, and a silane coupling agent is preferably used. Although it does not specifically limit as a silane coupling agent, For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ((beta) -methoxyethoxy) silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, (gamma)- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ- Examples thereof include silane coupling agents having an organic reactive group at the terminal, such as aminopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane. Among these, epoxysilane coupling agents having an epoxy group are preferred. Here, the organic reactive group is a functional group such as an epoxy group, a vinyl group, an amino group, or a mercapto group. The addition amount of the coupling agent is preferably 1 to 10 parts by weight and more preferably 2 to 7 parts by weight with respect to 100 parts by weight of the polymer.

  Moreover, the resin composition or heat-resistant adhesive of the present invention containing the above components can be dissolved in an organic solvent to obtain a resin varnish. The type of organic solvent is not particularly limited, but in terms of solubility of the resin composition, an aprotic polar solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, and dimethylformamide, and an ether such as diethylene glycol dimethyl ether and tetrahydrofuran. It is preferably selected from the group consisting of ketone solvents such as system solvents, cyclohexanone, cyclopentanone, methyl ethyl ketone, more preferably N-methyl-2-pyrrolidone, diethylene glycol dimethyl ether, and cyclohexanone, and particularly N-methyl-2-pyrrolidone. preferable.

  The heat-resistant adhesive material of the present invention has a support film and an adhesive layer formed by applying the heat-resistant adhesive on one or both surfaces of the support film. Of course, it is good also as a single layer film form which consists of the said heat resistant adhesive, However, It is more preferable to form an adhesive bond layer on a support film in terms of heat resistance or intensity | strength. In the present invention, an adhesive layer can be provided on one or both sides of the support film, but when used as an adhesive material for a LOC (Lead On Chip) package, an adhesive layer is provided on both sides of the support film. Is preferred.

  The support film is not particularly limited, but is preferably a film made of a resin that can withstand heat during the semiconductor device assembly process. For example, an aromatic polyimide film, an aromatic polyamide film, an aromatic polyamideimide film, an aromatic polysulfone Examples include films, aromatic polyethersulfone films, polyphenylene sulfide films, aromatic polyetherketone films, polyarylate films, aromatic polyetheretherketone films, and polyethylene naphthalate films. An aromatic polyimide film is particularly preferable in terms of heat resistance. The thickness of the support film is not particularly limited, but is preferably 5 to 100 μm and more preferably 10 to 50 μm in order to achieve both a reduction in thickness and strength of the semiconductor package.

  Moreover, it is preferable to treat the surface of the support film in order to sufficiently enhance the adhesion to the adhesive layer. The surface treatment method for the support film is not particularly limited, and examples thereof include chemical treatment such as alkali treatment and silane coupling treatment, physical treatment such as sand mat treatment, plasma treatment, and corona treatment.

  The thickness of the adhesive layer is not particularly limited, but the adhesive layer on one side is preferably 5 to 40 μm and preferably 10 to 30 μm in order to achieve both a thin semiconductor package and sufficient adhesive strength. Is more preferable.

  The method for forming the adhesive layer on one side or both sides of the support film is not particularly limited. Usually, a varnish produced by dissolving the heat-resistant adhesive in the organic solvent as described above is formed on the support film. After coating, it can be formed by heat treatment to remove the solvent.

  In the above, the coating method of the resin varnish is not particularly limited, and for example, roll coating, reverse roll coating, gravure coating, bar coating, comma coating, and the like are performed. Moreover, you may apply through a support film in resin varnish. The heat treatment temperature and time for heat treatment for removing the organic solvent, imidization and the like are not particularly limited, but are preferably a temperature and time at which the amount of the remaining organic solvent can be 10% by weight or less.

  The lead frame with an adhesive material of the present invention can be produced, for example, by bonding the heat-resistant adhesive material for semiconductors of the present invention in contact with one surface of the lead frame.

  The semiconductor device of the present invention can be manufactured, for example, by bonding the lead frame with an adhesive material of the present invention and a semiconductor element through an adhesive layer of the adhesive material.

  EXAMPLES Next, although an Example demonstrates this invention, this invention is not restrict | limited at all by these.

(Example 1)
In a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a fractionation tower, 300.2 g (0 of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene in a nitrogen atmosphere .63 mol), 67.0 g (0.27 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added and dissolved in 1470 g of N-methyl-2-pyrrolidone. Further, this solution was cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a glass transition point (hereinafter referred to as Tg) of 117 ° C. and a 5% weight loss temperature of 408 ° C. 120 g of this polyetheramideimide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 180 g of N-methyl-2-pyrrolidone, and an aromatic polyetheramideimide adhesive varnish. Got.

  Furthermore, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of this polyimide film to a thickness of 65 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90 ° peel strength (peeling speed: 300 mm per minute, the same applies hereinafter) between the adhesive layer and the lead frame was measured and found to be 1400 N / m. Further, a 5 mm square silicon chip was bonded on the adhesive material bonded to the lead frame at a temperature of 200 ° C., a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear adhesive strength of the chip was measured using a push-pull gauge. However, it was 700 gf. Thereafter, a wire bonding step and a sealing step were performed to produce the semiconductor device of FIG. 2, and no defects such as poor adhesion and outgassing occurred.

(Example 2)
In a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a fractionation tower, 300.2 g (0 of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene in a nitrogen atmosphere .63 mol), 54.0 g (0.27 mol) of 1,12-diaminododecane was added and dissolved in 1420 g of N-methyl-2-pyrrolidone. Further, this solution was once heated to 70 ° C. and then cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a Tg of 115 ° C. and a 5% weight loss temperature of 410 ° C. 120 g of this polyetheramideimide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 180 g of N-methyl-2-pyrrolidone, and an aromatic polyetheramideimide adhesive varnish. Got.

  Furthermore, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of this polyimide film to a thickness of 65 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90 ° peel strength (peeling speed: 300 mm per minute, the same applies hereinafter) between the adhesive layer and the lead frame was measured and found to be 1600 N / m. Further, a 5 mm square silicon chip was bonded on the adhesive material bonded to the lead frame at a temperature of 200 ° C., a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear adhesive strength of the chip was measured using a push-pull gauge. However, it was 800 gf. Thereafter, a wire bonding step and a sealing step were performed to produce the semiconductor device of FIG. 2, and no defects due to poor adhesion or outgassing occurred.

(Example 3)
In a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a fractionation column, 214.4 g (0 of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene in a nitrogen atmosphere .45 mole) 2,2-bis [4- (4-aminophenoxy) phenyl] propane 73.8 g (0.18 mole), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 67.0 g (0.27 mol) was added and dissolved in 1420 g of N-methyl-2-pyrrolidone. Further, this solution was cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a Tg of 133 ° C. and a 5% weight loss temperature of 411 ° C. 120 g of this polyetheramideimide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 180 g of N-methyl-2-pyrrolidone, and an aromatic polyetheramideimide adhesive varnish. Got.

  Furthermore, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of this polyimide film to a thickness of 65 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. 1 in which an adhesive layer having a thickness of 25 μm was formed on both surfaces of the support film. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90-degree peel strength between the adhesive layer and the lead frame (peeling speed: 300 mm per minute, the same applies hereinafter) was 1300 N / m. Further, a 5 mm square silicon chip was bonded on the adhesive material bonded to the lead frame at a temperature of 200 ° C., a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear adhesive strength of the chip was measured using a push-pull gauge. However, it was 400 gf. Thereafter, a wire bonding step and a sealing step were performed to produce the semiconductor device of FIG. 2, and no defects due to poor adhesion or outgassing occurred.

Example 4
In a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a fractionation tower, 85.8 g (0) of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene in a nitrogen atmosphere .18 mol), 210.5 g (0.72 mol) of 1,3-bis- (3-aminophenoxy) benzene, and 67.0 g (0.27 of 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Mol) and was dissolved in 1420 g of N-methyl-2-pyrrolidone. Further, this solution was cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a Tg of 140 ° C. and a 5% weight loss temperature of 410 ° C. 120 g of the obtained polyetheramideimide powder and 6.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SH6040) are dissolved in 180 g of N-methyl-2-pyrrolidone, and aromatic polyetheramideimide is obtained. An adhesive varnish was obtained.

  Furthermore, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of this polyimide film to a thickness of 65 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90 ° peel strength (peeling speed: 300 mm per minute, the same applies hereinafter) between the adhesive layer and the lead frame was measured and found to be 1400 N / m. Further, a 5 mm square silicon chip was bonded on the adhesive material bonded to the lead frame at a temperature of 200 ° C., a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear adhesive strength of the chip was measured using a push-pull gauge. However, it was 400 gf. Thereafter, a wire bonding step and a sealing step were performed to produce the semiconductor device of FIG. 2, and no defects due to poor adhesion or outgassing occurred.

(Example 5)
1,3-bis (3- (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene in a 5-liter four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube and fractionation tower under nitrogen atmosphere 300.2 g (0.63 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 67.0 g (0.27 mol) was added and dissolved in 1470 g of N-methyl-2-pyrrolidone. Further, this solution was cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a Tg of 97 ° C. and a 5% weight loss temperature of 400 ° C. 120 g of this polyetheramideimide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 180 g of N-methyl-2-pyrrolidone, and an aromatic polyetheramideimide adhesive varnish. Got.

  Furthermore, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of this polyimide film to a thickness of 65 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. 1 in which an adhesive layer having a thickness of 25 μm was formed on both surfaces of the support film. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90 ° peel strength (peeling speed: 300 mm per minute, the same applies hereinafter) between the adhesive layer and the lead frame was measured and found to be 1600 N / m. Further, a 5 mm square silicon chip was bonded on the adhesive material bonded to the lead frame at a temperature of 200 ° C., a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear adhesive strength of the chip was measured using a push-pull gauge. However, it was 1000 gf. Thereafter, a wire bonding step and a sealing step were performed to produce the semiconductor device of FIG. 2, and no defects due to poor adhesion or outgassing occurred.

(Example 6)
In a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a fractionation tower, 300.2 g (0 of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene in a nitrogen atmosphere .63 mol), 67.0 g (0.27 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added and dissolved in 1470 g of N-methyl-2-pyrrolidone. The solution was further cooled to 0 ° C., and 182.9 g (0.9 mol) of isophthalic acid chloride at this temperature was added. When the isophthalic acid chloride was dissolved, 100 g of triethylamine was added. After stirring for 2 hours at room temperature, the resulting reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramide had a Tg of 107 ° C. and a 5% weight loss temperature of 400 ° C. 120 g of this polyetheramide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 180 g of N-methyl-2-pyrrolidone to obtain an aromatic polyetheramide adhesive varnish. It was.

  Furthermore, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of this polyimide film to a thickness of 65 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90 ° peel strength (peeling speed: 300 mm per minute, the same applies hereinafter) between the adhesive layer and the lead frame was measured and found to be 900 N / m. Further, a 5 mm square silicon chip was bonded on the adhesive material bonded to the lead frame at a temperature of 200 ° C., a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear adhesive strength of the chip was measured using a push-pull gauge. However, it was 400 gf. Thereafter, a wire bonding step and a sealing step were performed to produce the semiconductor device of FIG. 2, and no defects due to poor adhesion or outgassing occurred.

(Comparative Example 1)
Under a nitrogen atmosphere, 258.3 g (0) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a fractionation tower. .63 mol), 67.0 g (0.27 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added and dissolved in 1300 g of N-methyl-2-pyrrolidone. Further, this solution was cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a Tg of 179 ° C. and a 5% weight loss temperature of 412 ° C. 120 g of this polyetheramideimide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 360 g of N-methyl-2-pyrrolidone, and an aromatic polyetheramideimide adhesive varnish Got.

  Furthermore, using a polyimide film (Upilex SGA manufactured by Ube Industries Co., Ltd.) having a chemical treatment on the surface having a thickness of 50 μm as a support film, the varnish was cast on both sides of this polyimide film to a thickness of 100 μm, Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. 1 in which an adhesive layer having a thickness of 25 μm was formed on both surfaces of the support film. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to the lead frame with the adhesive material, the 90-degree peel strength between the adhesive layer and the lead frame (peeling speed: 300 mm per minute, the same applies hereinafter) was 1000 N / m. In addition, a 5 mm square silicon chip was bonded onto the adhesive material bonded to the lead frame at a temperature of 200 ° C, a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear bond strength of the chip was measured using a push-pull gauge. As a result, since it was 0 gf, the subsequent manufacture of the semiconductor device could not be performed.

(Comparative Example 2)
Under a nitrogen atmosphere, 258.3 g (0) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a fractionation tower. .54 mol), 67.0 g (0.36 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added and dissolved in 1300 g of N-methyl-2-pyrrolidone. Further, this solution was cooled to 0 ° C., and 189.5 g (0.9 mol) of trimellitic anhydride chloride was added at this temperature. When the trimellitic anhydride chloride was dissolved, 100 g of triethylamine was added. After stirring at room temperature for 2 hours, the temperature was raised to 180 ° C. and reacted for 5 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N-methyl-2-pyrrolidone and poured into methanol to isolate the polymer again. Then, the polyetheramide imide powder refine | purified by drying under reduced pressure was obtained. The obtained polyetheramideimide had a Tg of 168 ° C. and a 5% weight loss temperature of 403 ° C. 120 g of this polyetheramideimide powder and 6.0 g of a silane coupling agent (trade name: SH6040, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 360 g of N-methyl-2-pyrrolidone, and an aromatic polyetheramideimide adhesive varnish Got.

  Further, a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) having a chemical treatment applied to the surface having a thickness of 50 μm was used as a support film, and the varnish was cast on both sides of the polyimide film to a thickness of 100 μm. Drying was carried out at 5 ° C. for 5 minutes and at 180 ° C. for 5 minutes to obtain an adhesive material having the structure of FIG. Next, this was bonded to a lead frame (material 42 alloy) at a temperature of 280 ° C., a pressure of 3 MPa, and a time of 0.5 seconds. With respect to this lead frame with an adhesive material, the 90-degree peel strength (peeling speed: 300 mm per minute, the same applies hereinafter) between the adhesive layer and the lead frame was measured to be 400 N / m. In addition, a 5 mm square silicon chip was bonded onto the adhesive material bonded to the lead frame at a temperature of 200 ° C, a pressure of 0.015 MPa, and a time of 0.5 seconds, and the shear bond strength of the chip was measured using a push-pull gauge. As a result, it was 200 gf. After that, the wire bonding process and the sealing process were performed to produce the semiconductor device of FIG. 2. As a result, no outgas was generated, but there was a problem that the lead frame and the adhesive material were peeled off during transportation or wire bonding.

  From the results of Examples 1 to 5 and Comparative Examples 1 and 2, it is shown that the heat resistant adhesive of the present invention is excellent in heat resistance and can be bonded at a low temperature of about 200 to 300 ° C.

It is sectional drawing of the adhesive material for semiconductors of this invention. It is sectional drawing of the semiconductor device using the adhesive material for semiconductors of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support film 2 Adhesive layer 3 Adhesive material 4 Semiconductor element 5 Lead frame 6 Sealing material 7 Bonding wire 8 Bus bar

Claims (8)

A resin composition comprising a polymer having a structural unit represented by the following general formula (I).

A resin varnish obtained by dissolving a resin composition containing a polymer having a structural unit represented by the following general formula (I) in an organic solvent.

  3. The organic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, diethylene glycol dimethyl ether, tetrahydrofuran, cyclohexanone, cyclopentanone, and methyl ethyl ketone. Resin varnish. A heat-resistant adhesive comprising a polymer having a structural unit represented by the following general formula (I):

  Furthermore, a silane coupling agent is included, The heat resistant adhesive agent of Claim 4 characterized by the above-mentioned.   A heat-resistant adhesive material, comprising: a support film; and an adhesive layer formed by applying the heat-resistant adhesive according to claim 4 on one or both surfaces of the support film.   A lead frame with an adhesive material, wherein the heat resistant adhesive material according to claim 6 is used.   A semiconductor device comprising the lead frame with an adhesive material according to claim 7 and a semiconductor element.

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