JPH0762324A - Heat-resistant adhesive, film with heat-resistant adhesive layer and production of thermoplastic resin - Google Patents

Abstract

PURPOSE:To improve heat resistance and adhesive force by incorporating a thermoplastic resin obtained by reacting a given thermo-plastic resin and a coupling agent. CONSTITUTION:An aromatic diamine and/or bisphenol is polycondensed with a di-, tri- or tetra-carboxylic acid or an aromatic chloride to obtain a thermoplastic resin of formula I [wherein R1 to R4 are each H, a lower alkyl, lower alkoxy or halogen; X is bond, -O-, -S-, -C(=)-, -SO2-, -S(=O)-, formula II to IV (where R5 and R6 are each H, a lower alkyl, trifluoromethyl, trichloromethyl or phenyl); Y is formula V or VI (where Ar is a divalent aromatic group; and Ar' is a trivalent group)] which is obtained in reactions for forming amide, ester, imide or ether groups. The resin in an amount of 80-99.9 pts.wt. is reacted with 20-0.1 pts.wt. of a coupling agent having functional group(s) capable of bonding chemically with the resin to obtain another thermoplastic resin, which is incorporated in the objective adhesive.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a heat-resistant adhesive, a film with a heat-resistant adhesive layer formed by laminating layers containing the heat-resistant adhesive, and a thermoplastic resin as a main component of the heat-resistant adhesive. Manufacturing method.

[0002]

2. Description of the Related Art Currently, an adhesive used in the field of electronics, for example, an adhesive between a metal foil in a printed circuit board and a supporting material such as a polyimide film, or a lead frame and a semiconductor in a resin-sealed semiconductor device. Materials having excellent high-temperature characteristics, purity, and workability are required for adhesives for elements (chips) and adhesives for so-called TAB tape metal foils and polyimide films.

Thermosetting resins such as epoxy type, rubber-modified epoxy type, phenol type, acrylic type, etc. which have been conventionally used as these adhesives show excellent adhesive strength, but they are inferior in heat resistance and purity and harden. There is a drawback that the adherend is sometimes contaminated by the outgas produced as a by-product.

On the other hand, it has been studied to use a thermoplastic resin having high heat resistance by melting and pressure bonding as an adhesive having excellent heat resistance and less outgassing because curing is unnecessary (for example, JP-A-61). -143479, Japanese Patent Laid-Open No. 1-268778).

However, when these thermoplastic resins are used as a melt-adhesive type adhesive, the viscosity at the time of melt-adhesion is low, and therefore the adhesive caused by foaming at the time of adhesion due to moisture absorption and the flow of the adhesive too much. There is a problem that the thickness reduction is large. In order to improve these, it is also possible to dry the hygroscopic moisture of the adhesive before bonding, or to adjust the bonding temperature and bonding pressure, but it is difficult to obtain a certain bonding strength and bonding state by these methods, Improvement is required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and provide a heat resistant adhesive having excellent heat resistance and adhesive strength, and a film with a heat resistant adhesive layer.

[0007]

The heat-resistant adhesive in the present invention is a thermoplastic resin obtained by a reaction that forms an amide group, an ester group, an imide group or an ether group (hereinafter referred to as "raw material thermoplastic resin"). A novel thermoplastic resin obtained by reacting 80 to 99.9 parts by weight of a coupling agent having a functional group capable of chemically bonding with the thermoplastic resin is added in an amount of 0.1 to 20 parts by weight. It is contained.

The heat-resistant adhesive can be used as a film with a heat-resistant adhesive layer obtained by laminating a layer containing the heat-resistant adhesive on one side or both sides of a support film.

The thermoplastic resin obtained by the reaction for forming the above-mentioned amide group, ester group, imide group or ether group, that is, the raw material thermoplastic resin, is aromatic polyamide, aromatic polyester, aromatic polyimide,
Aromatic polyethers, aromatic polyamideimides, aromatic polyesterimides, aromatic polyetherimides and the like are included. Each of these resins is produced by polycondensing an aromatic diamine and / or bisphenol which is a base component and a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid or an aromatic chloride which is an acid component or a reactive derivative thereof. be able to. Among these raw material thermoplastic resins, the functional groups that react with the coupling agent include amino groups, hydroxyl groups, and carboxyl groups at the terminal of the molecular chain. Therefore, the structure of the raw material thermoplastic resin in the present invention is not particularly limited as long as it is a resin having these functional groups.

As an example of the raw material thermoplastic resin in the present invention, a resin having a repeating unit as shown in the following chemical formula 4 can be mentioned.

[Chemical 4]

As an example of the raw material thermoplastic resin,
There is a resin having a repeating unit represented by the following chemical formula 5 [general formula (I)].

[Chemical 5] [However, in the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or halogen, and X represents a bond, —O—, —S— ,
-C (C = 0) -, - SO 2 -, - S (= 0) -, of 6

[Chemical 6] (Wherein R ₅ and R ₆ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group), and X is different for each repeating unit. Good, Y is

[Chemical 7] (Wherein Ar represents an aromatic divalent group and Ar ′ represents a trivalent group), and Y may be different for each repeating unit. ]

Examples of the repeating unit represented by the general formula (I) include the following chemical formulas 8 and 9.

[Chemical 8]

[Chemical 9]

The polymer having a repeating unit represented by the general formula (I) is, for example, a compound having an aromatic dicarboxylic acid, an aromatic tricarboxylic acid or a reactive derivative thereof.
[General formula (II)]

[Chemical 10] Produced by polycondensing an aromatic diamine represented by the formula [wherein R ₁ , R ₂ , R ₃ , R ₄ and X in the general formula (II) have the same meaning as in the general formula (I)]. can do.

The aromatic dicarboxylic acid has two carboxyl groups bonded to the aromatic nucleus. Of course, this aromatic ring may have a hetero ring introduced,
Further, the aromatic rings may be bonded to alkylene, oxygen, carbonyl group and the like. Further on the aromatic ring, for example,
Substituents such as alkoxy, allyloxy, alkylamino and halogen which do not participate in the condensation reaction may be introduced. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenyldicarboxylic acid and 1,5-
Although naphthalene dicarboxylic acid etc. can be mentioned, terephthalic acid and isophthalic acid are easily available and preferable. Examples of the reactive derivative of aromatic dicarboxylic acid include dichloride, dibromide and diester of the aromatic dicarboxylic acid. Terephthalic acid dichloride and isophthalic acid dichloride are preferred. The aromatic tricarboxylic acid in the present invention has an aromatic nucleus bonded to two adjacent carbon atoms among three carboxyl groups. Of course, this aromatic ring may be one in which a hetero ring is introduced, or the aromatic rings may be bonded to alkylene, oxygen, a carbonyl group or the like. Further, a substituent which does not participate in the condensation reaction, such as alkoxy, allyloxy, alkylamino and halogen, may be introduced into the aromatic ring.

Examples of the aromatic tricarboxylic acid include trimellitic acid, 3,3,4'-benzophenone tricarboxylic acid, 2,3,4'-diphenyltricarboxylic acid 2,3,6-pyridinetricarboxylic acid and 3,4. , 4 '
-Benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2'-methoxy-3,4,4'-
Examples thereof include diphenyl ether tricarboxylic acid and 2'-chlorobenzanilide-3,4,4'-tricarboxylic acid. Further, the reactive derivative of the aromatic tricarboxylic acid, an acid anhydride of the aromatic tricarboxylic acid,
It means halide, ester, amide, ammonium salt and the like. Examples of these include trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-N, N-dimethylcarbamoylbenzene,
1,4-dicarbomethoxy-3-carboxybenzene,
1,4-dicarboxy-3-carbophenoxybenzene, 2,6-dicarboxy-3-carbomethoxypyridine, 1,6-dicarboxy-5-carbamoylnaphthalene, the above aromatic tricarboxylic acid and ammonia, dimethylamine, triethylamine Examples thereof include ammonium salts. Of these, trimellitic anhydride and trimellitic anhydride monochloride are preferable.

Examples of the aromatic diamine represented by the general formula (II) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [3-methyl-
4- (4-aminophenoxy) phenyl] propane,
2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5- Dimethyl-4- (4-aminophenoxy) phenylbutane, 2,2-bis [3,5-dibromo-4-
(4-Aminophenoxy) phenyl] butane, 1,1,
1,3,3,3-hexafluoro-2,2-bis [4-
(4-Aminophenoxy) phenyl] propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl ] Cyclohexane, 1,1-bis [4-
(4-aminophenoxy) phenyl] cyclopentane,
Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 4,4 ′ carbonylbis (p-phenyleneoxy) dianiline, 4,4′-bis (4 -Aminophenoxy) biphenyl and the like. Of these, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane is preferred. Mixtures of the above diamines can be used if desired.

Furthermore, known diamines other than the above-mentioned aromatic diamines, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 4,4'-
Diaminodiphenyl sulfone, metaphenylenediamine, piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylylenedimine, m-xylylenediamine, 3-methylheptamethylenediamine, 1,3-bis (3-amino) Propyl) tetramethyldisiloxane etc. can be used together. The ratio of these diamines to the total diamines is preferably 40 mol% or less. If this ratio exceeds 40 mol%, the thermal stability or adhesiveness tends to deteriorate.

The acid component of the aromatic dicarboxylic acid, aromatic tricarboxylic acid or reactive derivative thereof is preferably used in an amount of 80 to 120 mol%, particularly preferably 95 to 105 mol% based on the total amount of the diamine. .
The highest molecular weight is obtained when these are used in equimolar amounts. If the amount of the acid component is too large or too small with respect to the diamine, the molecular weight tends to decrease, and mechanical strength, heat resistance, etc. tend to decrease.

In such a reaction, a known method used for a reaction between an amine and an acid can be directly employed, and various conditions are not particularly limited. A known method can be used for the polycondensation reaction of the aromatic dicarboxylic acid, the aromatic tricarboxylic acid or the reactive derivative thereof and the diamine. By using two or more kinds of aromatic diamines, or using two or more kinds of aromatic dicarboxylic acids or reactive derivatives thereof, two or more kinds of aromatic tricarboxylic acids or reactive derivatives thereof, Polymers having different repeating units represented by the formula (1) can be obtained. Further, by using an aromatic dicarboxylic acid or a reactive derivative thereof in combination with an aromatic tricarboxylic acid or a reactive derivative thereof, a polymer having different repeating units represented by the general formula (I) can be obtained. The polymer preferably has a reduced viscosity in a 0.2% by weight dimethylformamide solution at 30 ° C. of 0.2 to 2.0 dl / g. If this reduced viscosity is too small, heat resistance and mechanical strength decrease,
If it is too large, the adhesiveness tends to decrease.

The coupling agent used in the present invention has two or more functional groups in its compound molecule, at least one of which reacts with the raw material thermoplastic resin, and the remaining functional groups have the remaining functional groups. It is necessary to react with the thermoplastic resin or between the functional groups. There are no particular restrictions on the molecular structure, molecular weight, etc., as long as it has two or more functional groups. Examples of such coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like. As the functional group of the raw material thermoplastic resin, an amino group at the terminal of the molecule, a hydroxy group,
Since a carboxy group and the like can be considered, the functional group reactive with the raw material thermoplastic resin in the coupling agent includes an epoxy group, an amino group, a vinyl group, a methacryloyl group, and the like. Examples of the self-reactive functional group in the coupling agent include methoxy group and ethoxy group.

Preferred as the coupling agent in the present invention is a silane coupling agent, for example, γ-
(2-Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltri Methoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ- Methacryloxypropyl methylenedimethoxysilane and the like can be mentioned.

In the present invention, the blending ratio of the raw material thermoplastic resin and the coupling agent is preferably 0.1 to 20% by weight based on the total solid content of the two. . More preferably 0.5 to 1
It is 0% by weight. When the amount of the coupling agent is less than 0.1% by weight, the effect of preventing foaming at the time of adhesion and the flow of the adhesive too much is low, and when it exceeds 20% by weight, the adhesive strength tends to decrease.

The novel thermoplastic resin in the present invention is prepared by previously reacting the raw material thermoplastic resin with the coupling agent, but the method is not particularly limited. For example, the raw material thermoplastic resin and the coupling agent are N-
It is effective to dissolve in a polar solvent such as methyl-2-pyrrolidone, dimethylacetamide, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc., and heat the solvent to dry the solvent and simultaneously react. The temperature at this time is 150 ° C. or higher, preferably 200 ° C.
It is preferable to dry for 5 minutes or more. By sufficiently reacting in this manner, a novel thermoplastic resin becomes a resin that is insoluble in the polar organic solvent but can be melted.

An adhesive containing a novel thermoplastic resin is
A varnish prepared by dissolving the raw material thermoplastic resin, coupling agent, etc. in a solvent in advance is cast on a glass plate, stainless steel plate, etc., dried and peeled to form a film, which is then heated to react and insoluble in polar organic solvents. However, a film adhesive can be obtained by forming a meltable resin. Further, such a varnish is applied to one side or both sides of a polyimide film, a polyester film, or a Teflon film, and then heat-reacted to form a resin that is insoluble in a polar organic solvent but is meltable, thereby forming a heat-resistant adhesive film. A film with a heat resistant adhesive layer formed by laminating agent layers can be obtained. This varnish is impregnated into a thin cloth mat of fibers having excellent heat resistance such as glass fibers, and then heated and reacted to form a resin that is insoluble in a polar organic solvent but is meltable to obtain a fiber-reinforced sheet form. be able to. Also, after applying this varnish to the adherend as it is, it is heated and reacted to form a resin that is insoluble in the polar organic solvent but softens by heating, and then it can be thermocompression-bonded with another adherend.

The heat-resistant adhesive containing the novel thermoplastic resin is laminated on an adherend and then heat-pressed at a temperature equal to or higher than the softening point for adhesion. At this time, even when used in a hygroscopic state, there is little or no foaming at the time of adhesion, and there is little or no thickness reduction due to excessive flow of the adhesive. Excellent heat resistance and adhesive strength after bonding.

Further, the heat resistant adhesive of the present invention includes
In addition to the novel thermoplastic resin described above, antimony trioxide,
Difficult inorganic compounds such as aluminum hydroxide and barium borate, silica, alumina, mica, titanium oxide, zirconia, calcium silicate, magnesium hydroxide, magnesium oxide, iron oxide, calcium carbonate, silicon carbide, boron nitride, silver powder, An inorganic filler such as gold powder, copper powder or nickel powder may be contained in a ratio of 70% by weight or less based on the total amount of the adhesive. If the amount of these inorganic fillers exceeds 70% by weight, the adhesive strength tends to decrease. Further, other fillers, stabilizers, surfactants, solvents and the like may be included depending on the purpose.

A printed circuit board obtained by adhering a supporting material and a metal foil using the heat-resistant adhesive of the present invention (for example, via a sheet-like adhesive made of a heat-resistant adhesive) is useful. For example, a printed circuit board is manufactured by sandwiching a sheet-like adhesive between a support material and a metal foil, heating and melting at 300 ° C. to 400 ° C. and 5 to 100 Kg / cm ² for 1 second to 10 minutes and pressurizing. it can. At this time, a film with a heat-resistant adhesive layer (where the supporting film is a polyimide film)
By using, it is possible to manufacture the flexible printed circuit board with high productivity.

Examples of the support material include paper phenol-based support material, epoxy-based support material, and polyimide-based support material.

By using the heat-resistant adhesive or the film with a heat-resistant adhesive layer of the present invention, a high-capacity semiconductor having excellent reliability can be easily manufactured with good workability and yield. For example, a polyimide film (with a double-sided adhesive layer) as a support film is punched out or cut into pieces (film pieces) and sandwiched between a lead frame and a semiconductor element at 300 ° C to 400 ° C.
A semiconductor device is manufactured by heating and melting at 100 Kg / cm ² for 1 second to 10 minutes, pressurizing and pressing, then joining a lead frame and a semiconductor element with a gold wire, etc., transfer molding with a molding material such as epoxy resin, and sealing. Can be manufactured.

[0030]

The heat-resistant adhesive in the present invention is obtained by blending a specific raw material thermoplastic resin with a specific amount of a specific coupling agent and reacting them with each other until they become insoluble in a polar organic solvent. When an adherend such as a substrate is thermocompression-bonded using an agent, neither foaming nor excessive flow of the adhesive at the time of adhesion and excellent adhesive strength are exhibited. A so-called coupling agent represented by a silane coupling agent has a functional group that reacts with an organic substance and a functional group that reacts with an inorganic substance, and has a property of chemically bonding the organic substance and the inorganic substance by utilizing these reactions. Until now, it has been common to use this property to improve the adhesiveness with inorganic adherends by incorporating a coupling agent into various adhesives. The functional group for reacts with the inorganic adherend to improve the adhesiveness when bonded to the adherend, and it is not expected to prevent foaming or excessive flow of the adhesive at the time of bonding. However, in the present invention, prior to bonding, not only the functional group for the organic substance of these coupling agents but also the functional group for the inorganic substance are reacted in advance to make them insoluble in a polar organic solvent. Even when used in a moisture-absorbed state, there is no foaming at the time of bonding, it is possible to prevent the adhesive from flowing too much, and it is possible to obtain excellent bonding strength. The above insolubilization is considered to be because a polymer having a crosslinked structure is produced as a result of the reaction between the raw material thermoplastic resin and the coupling agent.

[0031]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto.

Example 1 205 g (0.5 g) of 2,2-bis [4 (4-aminophenoxy) phenyl] propane under a nitrogen atmosphere in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube. Mol), propylene oxide 69.6 g (1.2 mol)
Was added and dissolved in 1200 g of N-methyl-2-pyrrolidone. This solution was cooled to -5 ° C, and 101.5 g (0.5 mol) of isophthalic acid dichloride was added at a temperature of 2
It was added so as not to exceed 0 ° C. Stirring was continued at room temperature for 3 hours. The obtained reaction solution was poured into methanol to isolate the polymer. This was dried, dissolved in dimethylformamide, poured into methanol, and dried under reduced pressure to obtain a purified aromatic polyamide powder. The reduced viscosity (η _{SP / C} ) (0.2% by weight solution of dimethylformamide, measured at 30 ° C., the same below) of this aromatic polyamide was 1.02 d1 / g. 60 g of the obtained aromatic polyamide powder and 1.8 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone, silane coupling agent SH-6040) were dissolved in 200 g of N-methyl-2-pyrrolidone. And got a varnish. This varnish was cast on a glass plate to a thickness of 90 μm,
After drying at 0 ° C for 10 minutes, it was peeled off from the glass plate, fixed on an iron frame and dried at 200 ° C for 10 minutes and 300 ° C for 10 minutes to obtain an adhesive film having a thickness of 25 µm. The resulting film was insoluble in N-methylpyrrolidone. Further, the obtained film was cut into a 5 mm square, left to stand in a thermo-hygrostat at 40 ° C. and 65% RH for 24 hours to absorb moisture, and then a thickness of 0.2
mm of iron-nickel alloy lead frame 0.2m
Place it on the inner lead of 0.2 mm width at m intervals, 35
A pressure of 20 Kg / cm ² was applied at a temperature of 0 ° C. for 3 seconds for pressure bonding. The adhesive film after adhesion was examined under a microscope and found to be free from foaming, and when visually observed, no deformation of the adhesive film was observed. Further, a 5 mm square silicon chip was pressure-bonded for 3 seconds at a temperature of 350 ° C. and a pressure of 20 Kg / cm ² on the adhesive film bonded to the lead frame. When it was attempted to measure the shear adhesive strength of the chip using a push-pull gauge, the silicon chip broke, and the strength at that time exceeded 10 kg.

Example 2 143.5 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane] under nitriding was placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube. 0.3
5 mol), 1,3-bis (aminopropyl) tetramethyldisiloxane 37.2 g (0.15 mol) and propylene oxide 69.6 g (1.2 mol) were added and dissolved in N-methyl-2-pyrrolidone 1200 g. did. The solution was cooled to −5 ° C. and 101.5 g (0.5 mol) of isophthalic acid dichloride was added at this temperature so that the temperature did not exceed 20 ° C. Stirring was continued at room temperature for 3 hours. The obtained reaction solution was poured into methanol to isolate the polymer.
This was dried, dissolved in dimethylformamide, poured into methanol, and dried under reduced pressure to obtain a purified aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 0.82 dl / g. 60 g of the obtained aromatic polyamide powder and 1.8 g of γ-glycidoxypropyltrimethoxysilane were added to 20 g of N-methyl-2-pyrrolidone.
It was dissolved in 0 g to obtain a varnish. This varnish was cast on both sides of a polyimide film (Upilex S manufactured by Ube Industries, Ltd.) having a thickness of 50 μm to a thickness of 90 μm, and the temperature was 1 ° C. at 1 ° C.
After drying at 0 ° C. and 300 ° C. for 10 minutes, a polyimide film having a 25 μm-thick adhesive layer on both sides was obtained. The adhesive layer of the obtained polyimide film with an adhesive layer was insoluble in N-methylpyrrolidone. In addition, the obtained polyimide film with an adhesive layer is cut into 5 mm squares and 40
After being left to stand in a thermo-hygrostat at 65 ° C. and 65% RH for 24 hours to absorb moisture, a 0.2-mm thick copper lead frame 0.2
Place it on the inner leads of 0.2 mm width at mm intervals,
Pressure was applied at a temperature of 300 ° C. and a pressure of 20 Kg / cm ² for 3 seconds for pressure bonding. The adhesive film after adhesion was examined under a microscope and found to be free from foaming, and when visually observed, no deformation of the adhesive film was observed. Furthermore, a 5 mm square silicon chip is placed on a polyimide film with an adhesive layer adhered to the lead frame at a temperature of 300 ° C. and 20 kg.
It was pressure-bonded for 3 seconds at a pressure of / cm ² . When I tried to measure the shear adhesive strength of the chip using a push-pull gauge, the silicon chip broke and the strength at that time was 10K.
It was over g.

Example 3 205 g (0) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane under nitriding was placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a fractionating head. 0.5 mol) was added and dissolved in 1200 g of N-methyl-2-pyrrolidone. This solution was cooled to -10 ° C, and at this temperature, 105.3 g of trimellitic anhydride monochloride (0.5
Mol) was added so that the temperature did not exceed -5 ° C. After the trimellitic anhydride monochloride was dissolved, 76 g of triethylamine was added so that the temperature did not exceed 5 ° C. After stirring at room temperature for 1 hour, the mixture was reacted at 180 ° C. for 9 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. This was dried, dissolved in dimethylformamide, poured into methanol, and dried under reduced pressure to obtain a purified polyamideimide powder. The reduced viscosity of this polyamide-imide is 0.91 dl.
/ G. 60 g of the obtained polyamideimide powder and 1.8 g of γ-glycidoxypropyltrimethoxysilane
Was dissolved in 200 g of tetrahydrofuran to obtain a varnish. This varnish was cast on a glass plate to a thickness of 90 μm, dried at 50 ° C. for 10 minutes, peeled off from the glass plate, fixed on an iron frame, and dried at 300 ° C. for 10 minutes to obtain an adhesive film having a thickness of 25 μm. Got The resulting film was insoluble in tetrahydrofuran. Also, the obtained film is 5 m
Cut it into m squares, and place it in a thermo-hygrostat at 40 ° C and 65% RH for 2
After left to stand for 4 hours to absorb moisture, a 0.2 mm thick lead frame made of an iron-nickel alloy is used at 0.2 mm intervals.
Place it on the inner lead of mm width, and at the temperature of 350 ℃, 2
A pressure of 0 Kg / cm ² was applied for 3 seconds for pressure bonding. The adhesive film after adhesion was examined under a microscope and found to be free from foaming, and when visually observed, no deformation of the adhesive film was observed. Furthermore, a 5 mm square silicon chip is placed at 350 ° C. on the adhesive film adhered to the lead frame.
It was pressure-bonded for 3 seconds at a pressure of 20 Kg / cm ² at the temperature of. When the shear adhesive strength of the chip was measured with a push-pull gauge, the silicon chip broke, and the strength at that time exceeded 10 kg.

Example 4 143.5 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane under nitriding in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a fractionating head. (0.3
5 mol) and 37.2 g (0.15 mol) of 1,3-bis (aminopropyl) tetramethyldisiloxane were added and N-
It was dissolved in 1200 g of methyl-2-pyrrolidone. This solution was cooled to -10 ° C, and 105.3 g (0.5 mol) of trimetic anhydride monochloride was added at this temperature.
It was added so as not to exceed 5 ° C. After the trimet anhydride monochloride was dissolved, 76 g of triethylamine was added so that the temperature did not exceed 5 ° C. After stirring at room temperature for 1 hour, the mixture was reacted at 180 ° C. for 9 hours to complete imidization. The obtained reaction solution was poured into methanol to isolate the polymer. This was dried, dissolved in dimethylformamide, poured into methanol, and dried under reduced pressure to obtain a purified polyamideimide powder. The reduced viscosity of this polyamideimide was 0.78 dl / g. 60 g of the obtained polyamideimide powder and 1.8 g of γ-glycidoxypropyltrimethoxysilane were dissolved in 200 g of diethylene glycol dimethyl ether to obtain a varnish. This varnish was cast on both sides of a polyimide film (Upilex S manufactured by Ube Industries, Ltd.) with a thickness of 50 μm to a thickness of 90 μm and dried at 100 ° C. for 10 minutes and at 300 ° C. for 10 minutes to form an adhesive layer with a thickness of 25 μm. A polyimide film having both sides attached was obtained. The adhesive layer of the obtained polyimide film with an adhesive layer was insoluble in diethylene glycol dimethyl ether. Moreover, the obtained polyimide film with an adhesive layer was cut into a 5 mm square, and the temperature was 40 ° C. and 65 ° C.
After being left in a thermo-hygrostat of% RH for 24 hours to absorb moisture, it is placed on inner leads of 0.2 mm width at 0.2 mm intervals of 0.2 mm thick copper lead frames and 20 kg at 300 ° C. / Cm ² pressure was applied for 3 seconds for pressure bonding. The polyimide film with the adhesive layer after adhesion was examined under a microscope and found to be free from foaming, and visually, no deformation of the adhesive was observed. Furthermore, 5 on the polyimide film with the adhesive layer adhered to the lead frame.
20mm / mm square silicon chip at 300 ℃
It was pressure-bonded for 3 seconds with a pressure of cm ² . When I tried to measure the shear adhesive strength of the chip using a push-pull gauge, the silicon chip broke and the strength at that time was 10 kg.
Was exceeded.

Example 5 60 g of aromatic polyetherimide (Ultem 1000 manufactured by Nippon GE Plastics Co., Ltd.) and γ-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone, silane coupling agent SH-6040)
3.0 g was dissolved in 200 g of N, N-dimethylacetamide to obtain a varnish. 90 μm of this varnish on a glass plate
Cast to a thickness of 10 ° C, dried at 100 ° C for 10 minutes, peeled off from the glass plate, fixed on an iron frame, and kept at 200 ° C for 10 minutes at 300 ° C.
After drying for 10 minutes, an adhesive film having a thickness of 25 μm was obtained. The obtained film was insoluble in N, N-dimethylacetamide. Further, the obtained film was cut into a 5 mm square, left to stand in a thermo-hygrostat at 40 ° C. and 65% RH for 24 hours to absorb moisture, and then 0.2 mm thick of an iron-nickel alloy lead frame. 0.2mm at 2mm intervals
Place on the inner lead of width, 20K at the temperature of 350 ℃
Pressure was applied for 3 seconds at a pressure of g / cm ² for pressure bonding. The adhesive film after adhesion was examined under a microscope and found to be free from foaming, and when visually observed, no deformation of the adhesive film was observed. Further, a 5 mm square silicon chip was pressure-bonded for 3 seconds at a temperature of 350 ° C. and a pressure of 20 Kg / cm ² on the adhesive film bonded to the lead frame. When the shear adhesive strength of the chip was measured using a push-pull gauge, it was 7 kg.

Example 6 Polysulfone which is an aromatic polyether (Udel Polysulfone P-170 manufactured by Amoco Japan Limited)
0) 60 g and 6.0 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone Co., silane coupling agent SH-6040) were dissolved in 200 g of N-methyl-2-pyrrolidone to obtain a varnish. It was This varnish was cast on a glass plate to a thickness of 90 μm,
After drying at 0 ° C for 10 minutes, it was peeled off from the glass plate, fixed on an iron frame and dried at 200 ° C for 10 minutes and 300 ° C for 10 minutes to obtain an adhesive film having a thickness of 25 µm. The resulting film was insoluble in N-methyl-2-pyrrolidone. Moreover, the obtained film was cut into 5 mm square, and 40 ° C.
After allowing it to stand in a thermo-hygrostat of 65% RH for 24 hours to absorb moisture, it is placed on an inner lead of 0.2 mm width at 0.2 mm intervals of a lead frame made of an iron-nickel alloy having a thickness of 0.2 mm, 350 A pressure of 20 Kg / cm ² was applied at a temperature of ° C for 3 seconds for pressure bonding. The adhesive film after adhesion was examined under a microscope and found to be free from foaming, and when visually observed, no deformation of the adhesive film was observed. Furthermore,
5mm on the adhesive film adhered to the lead frame
20Kg / cm square silicon chip at 350 ℃
The pressure of ² was applied for 3 seconds. When the shear adhesive strength of the chip was measured with a push-pull gauge, it was 7 kg.

Example 7 In Example 4, 1.8 g of γ-glycidoxypropyltrimethoxysilane was added to γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent KBM90).
3) The adhesive state and adhesive strength of the polyimide film with an adhesive layer were evaluated in the same manner except that the amount was 0.06 g.
The polyimide film with the adhesive layer after adhesion was examined under a microscope and found to be free from foaming, and visually, no deformation of the adhesive was observed. The shear adhesive strength was 10 kg or more.

Example 8 In Example 4, 1.8 g of γ-glycidoxypropyltrimethoxysilane was added to γ-methacryloxypropylpropyldimethyoxysilane (Toray Dow Corning Silicone Co., Ltd. silane coupling agent AY43-060). 6.
The adhesive state and adhesive strength of the polyimide film with an adhesive layer were evaluated in the same manner except that the amount was 0 g. The polyimide film with the adhesive layer after adhesion was examined under a microscope and found to be free from foaming, and visually, no deformation of the adhesive was observed. The shear adhesive strength is 7 kg.
Met.

Example 9 In Example 4, 1.8 g of γ-glycidoxypropyltrimethoxysilane was added to γ-glycidoxypropylmethyldimethoxysilane (Toray Dow Corning Silicone Co., Ltd. silane coupling agent AY43-031). 15.0
The adhesive state and the adhesive strength of the polyimide film with the adhesive layer were evaluated in the same manner except that the value was g. The polyimide film with the adhesive layer after adhesion was examined under a microscope and found to be free from foaming, and visually, no deformation of the adhesive was observed. The shear adhesive strength was 8 kg.

Comparative Example 1 In the same manner as in Example 4 except that 1.8 g of γ-glycidoxypropyltrimethoxysilane was changed to 0 g, the adhesive state and adhesive strength of the polyimide film with an adhesive layer were measured. When evaluated, the shear adhesive strength is 10K
Although it showed a good adhesive strength of g or more, the state where it adhered to the lead of the lead frame after moisture absorption was examined by a microscope, and the entire surface of the adhesive foamed, and the lead was embedded in the adhesive layer and remained on the lead. The thickness of the adhesive is reduced by 7 μm,
It was μm.

Comparative Example 2 The adhesive state and adhesive strength of a polyimide film with an adhesive layer were measured in the same manner as in Example 4 except that 1.8 g of γ-glycidoxypropyltrimethoxysilane was changed to 20 g. As a result of evaluation, the polyimide film with an adhesive layer after adhesion was examined by a microscope and found that no foaming was observed, and no deformation of the adhesive was visually observed. However, the shear adhesive strength was as low as 1 Kg.

Comparative Example 3 An adhesive film was prepared in the same manner as in Example 3 except that the drying and reaction conditions were 300 ° C. for 10 minutes and 50 ° C. for 24 hours under reduced pressure. The obtained adhesive film was dissolved in tetrahydrofuran, and it was found that the adhesive resin and the silane coupling agent did not react three-dimensionally. Moreover, when the adhesive state and the adhesive strength of the adhesive film were evaluated, the shear adhesive strength was 10K.
Although it showed a good adhesive strength of g or more, the state where it adhered to the lead of the lead frame after moisture absorption, the entire surface of the adhesive foamed when examined with a microscope, and the lead got stuck in the adhesive and the adhesion on the lead The thickness of the agent becomes 9μm thinner, 16μ
It was m.

As can be seen from the results of Comparative Examples 1 and 3,
A thermoplastic resin adhesive to which a coupling agent is not added or which is not sufficiently reacted even if added is foamed at the time of heat fusion bonding, and the adhesive flows too much to change the film thickness. On the other hand, as can be seen from Examples 1 to 9, the coupling agent was added in an amount of 0.1% to 20% and the
The three-dimensionally reacted thermoplastic adhesive does not foam at the time of adhesion, the adhesive does not deform and the thickness does not change, and exhibits good adhesive strength. As shown in Comparative Example 2, when the coupling agent is added in an amount of more than 20% and reacted, no foaming or deformation at the time of adhesion is observed, but the adhesive strength is lowered.

[0045]

EFFECTS OF THE INVENTION The heat-resistant adhesives according to claims 1 to 3 and the films with heat-resistant adhesive layers according to claims 4 to 5 do not foam during thermocompression bonding even when used in a hygroscopic state, and also deform during thermocompression bonding. There is no change in thickness due to, and it has excellent adhesive strength. The novel thermoplastic resin according to claims 6 to 7 is useful as a material for such an adhesive.

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Claims (7)

[Claims] 1. A functional group capable of chemically bonding to a thermoplastic resin is added to 80 to 99.9 parts by weight of a thermoplastic resin obtained by a reaction for forming an amide group, an ester group, an imide group or an ether group. Having a coupling agent of 0.1
A heat resistant adhesive containing a thermoplastic resin obtained by mixing 20 parts by weight and reacting. 2. A thermoplastic resin obtained by a reaction for forming an amide group, an ester group, an imide group or an ether group has a repeating unit represented by the following chemical formula 1 [general formula (I)]. The heat resistant adhesive according to claim 1. [Chemical 1] [However, in the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or halogen, and X represents a bond, —O—, —S— ,
-C (=) -, - SO 2 -, - S (= O) -, Formula 2 [Formula 2] (Wherein R ₅ and R ₆ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group), and X is different for each repeating unit. Well, Y is (Wherein Ar represents an aromatic divalent group and Ar ′ represents a trivalent group), and Y may be different for each repeating unit. ]. 3. The heat resistant adhesive according to claim 1, wherein the coupling agent is a silane coupling agent. 4. The heat-resistant adhesive according to claim 1, wherein the thermoplastic resin obtained by the reaction for forming an amide group, an ester group, an imide group or an ether group is insoluble in a polar organic solvent. 5. A film with a heat-resistant adhesive containing the heat-resistant adhesive according to claim 1, claim 2, claim 3 or claim 4 on one side or both sides of a support film. 6. 80 to 99.9 parts by weight of a thermoplastic resin obtained by a reaction for forming an amide group, an ester group, an imide group or an ether group is added with a functional group capable of chemically bonding with the thermoplastic resin. Having a coupling agent of 0.1
A novel method for producing a thermoplastic resin, which comprises mixing 20 to 20 parts by weight and reacting them. 7. A coupling agent having a functional group capable of chemically bonding with a thermoplastic resin obtained by a reaction forming an amide group, an ester group, an imide group or an ether group is reacted until it becomes insoluble in a polar organic solvent. A method for producing a novel thermoplastic resin according to claim 6.