JPH05117621A - High thermal conductivity film adhesive that can be thermocompression bonded - Google Patents

Abstract

(57) [Summary] [Structure] An acid component containing 4,4'-oxydiphthalic acid dianhydride (A mole) and another acid dianhydride component (B mole), and a silicone diamine C mole represented by the formula (1): 1] And an amine component containing D moles of another diamine component, silicone diamine or this and 4,4′-oxydiphthalic dianhydride as essential components, and (A + C) / (A + B + C +
D) is reacted in the range of 0.5 to 1.0 and (A + B) / (C + D) is in the range of 0.8 to 1.2, and at least 80% or more of the polyimide siloxane is imidized, and 30 to 900 wt% of thermal conductivity to the polyimide siloxane. A thermo-compression-bondable highly heat-conductive film-like adhesive consisting of a filler having a rate of 5.0 [W / (m · K)] or more. [Effect] Excellent heat resistance, good workability in thermocompression bonding at low temperature, low pressure, and short time, excellent adhesion to metals such as copper and silicon, ceramics, and solder melting not only at room temperature but at 260 ° C It is possible to obtain a film adhesive having sufficient adhesive strength even at a temperature and having excellent heat dissipation property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film adhesive which has excellent thermal conductivity and heat resistance and can be used by thermocompression bonding.

[0002]

2. Description of the Related Art Heretofore, some heat-resistant thermocompression-bondable film adhesives have been known. For example, Japanese Patent Laid-Open No. 1-2822
No. 83, a polyamide-imide or polyamide hot-melt adhesive, JP-A-58-157190, JP-A-58-157190, a method for manufacturing a flexible printed circuit board using a polyimide adhesive, JP-A-62-235382 and JP-A-62-235383 describes a thermosetting polyimide film adhesive. However, polyamide-based and polyamide-imide-based resins have a drawback that the water absorption rate becomes large due to the hydrophilicity of the amide group, and there is a limit in using them as adhesives for electronic applications requiring reliability. .. The standard conditions for thermocompression bonding of film adhesives described in other publications are 275 ° C, 50kgf / cm ² and 30 minutes, which require electronic components sensitive to heat and pressure and mass productivity. It could not be said that it is necessarily advantageous as a film adhesive for other applications.

In recent years, as the degree of integration of semiconductor integrated circuits has increased, the use of heat sinks or heat radiating fins has been studied as a method for heat dissipation of ICs. There is a need for adhesives with high thermal conductivity. These high thermal conductivity adhesives have a film-like shape that can be thermocompression bonded than liquid adhesives that easily cause voids and bubbles to get inside because voids such as voids are present in the bonded area. Adhesives are said to be preferred. However, until now, no film-like adhesive has satisfied all of high thermal conductivity, high adhesiveness, heat resistance, workability and the like.

On the other hand, conventionally used epoxy resins,
Phenolic and acrylic adhesives can be used at relatively low temperatures,
Although it has an advantage that it can be thermocompression-bonded at a low pressure, it needs to be cured to some extent because it is a thermosetting type. Although a thermoplastic resin is often used as a hot melt adhesive, it has a drawback of poor heat resistance.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have earnestly studied to obtain a highly heat-conductive film adhesive having excellent heat resistance and capable of thermocompression bonding at low temperature, low pressure and short time, and as a result,
It has been found that an adhesive obtained by uniformly dispersing a filler having a certain thermal conductivity or more into a polyimide siloxane having a specific structure to form a film can achieve the above-mentioned target, and thus completed the present invention. The purpose is to
It is intended to provide a film-like adhesive having both thermal conductivity, heat resistance, and thermocompression bonding workability.

[0006]

The present invention provides an acid component containing A moles of 4,4'-oxydiphthalic acid dianhydride and other moles of an acid dianhydride component B;

[0007]

[Chemical 1]

An amine component containing C mole of silicone diamine represented by and D mole of other diamine component is
-At least one of oxydiphthalic dianhydride or silicone diamine is an essential component, and (A + C) /
(A + B + C + D) is 0.5 to 1.0, (A + B) / (C +
D) is reacted in the range of 0.8 to 1.2, and at least 80% or more of it is imidized with polyimide siloxane, and 30 to 900 wt% of the polyimide siloxane has a thermal conductivity of 5.0 [W /
(m · K)] or more, and a thermocompression-bondable film adhesive.

The acid dianhydride used in the present invention is
4,4'-oxydiphthalic acid dianhydride (hereinafter abbreviated as ODPA) and other acid dianhydrides. Examples of acid dianhydrides other than ODPA include pyromellitic dianhydride, 3,3 ',
4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2 ',
3,3'-benzophenone tetracarboxylic dianhydride, 2,3,
3 ', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene- 1,
2,4,5-Tetracarboxylic acid dianhydride, naphthalene-1,4,5,8
-Tetracarboxylic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2 , 5,6-Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic acid dianhydride, 2 , 6-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7
-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4, 5,8-tetrachloronaphthalene
-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride Substance, 2,3,3 ', 4'-diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3" -p-terphenyl tetracarboxylic dianhydride, 2,3,3 ", 4" -p-terphenyl tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride Anhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1, 1-bis (2,3-dicarboxyphenyl) ethane dianhydride 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic acid Dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride,
Phenanthrene-1,2,7,8-tetracarboxylic dianhydride,
Phenanthrene-1,2,6,7-tetracarboxylic dianhydride,
Phenanthrene-1,2,9,10-tetracarboxylic dianhydride,
Cyclopentane-1,2,3,4-tetracarboxylic dianhydride,
Pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-
Examples thereof include, but are not limited to, 2,3,4,5-tetracarboxylic dianhydride.

The diamine components used in the present invention are silicone diamine and other diamines. Other diamines are not particularly limited, but specific examples include 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,6-dimethyl-m-phenylenediamine, and 2, 5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene,
4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-
Xylidine, 4,4'-methylene-2,6-diethylaniline, 2,
4-toluenediamine, m-phenylene-diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane, 3,3 '-Diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-
Diphenylmethane, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether , 3,3'-
Diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4,4 "-diamino-
p-terphenyl, 3,3 "-diamino-p-terphenyl, bis
(p-amino-cyclohexyl) methane, bis (p-β-amino-
t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino-pentyl) benzene, p-bis (1,1-dimethyl-5- Amino-pentyl) benzene, 1,5-diamino-naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diamino-toluene, m-xylene- 2,5-diamine, p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2,6-diamino-pyridine,
2,5-diamino-pyridine, 2,5-diamino-1,3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2- Dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2,5-dimethyl-hexamethylene
-Diamine, 3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene
-Diamine, 3-methyl-heptamethylene-diamine, 4,4-dimethyl-heptamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl-nonamethylene-
Diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino-1,10-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino-octadecane, 2,12- Diamino-octadecane, 2,17-diamino-
Examples include aicosane, 1,3-bis (3-aminophenoxy) benzene and the like.

The reaction between the acid dianhydride and the diamine in the present invention can be carried out by a known method. Either the acid dianhydride component or the diamine component is dissolved or suspended in an organic solvent in advance, and the other component is gradually added in a powder or liquid state or in a state of being dissolved in the organic solvent. Since the reaction is exothermic, the temperature of the reaction system is preferably maintained near room temperature while cooling.

The molar ratio (A + B) / (C + D) of the acid dianhydride component and the diamine component is preferably in the vicinity of the equivalent, particularly in the range of 0.8 to 1.2. If either one is too large, the molecular weight does not increase and heat resistance and mechanical properties deteriorate, which is not preferable. After reacting at around room temperature to synthesize polyamic acid, imidization can be carried out by a known method such as heating or using an acetic anhydride / pyridine catalyst. The imidization ratio is preferably at least 80% or more. If the imidization ratio is lower than 80%, imidization progresses when the film is formed later and thermocompression bonding is performed, water is generated, and voids are caused, resulting in a decrease in adhesive strength, which is not preferable.

The value of (A + C) / (A + B + C + D) is
It is necessary to be 0.5 to 1.0, and if it is 0.5 or less, the heat melting property will be reduced, and thermocompression bonding conditions of at least 300 ° C. or more or 50 kgf / cm ² or more are required, which is preferable in terms of mass productivity. Absent. When it is 0.5 or more, thermocompression bonding can be performed at a temperature of 250 ° C. or less and a pressure of 20 kgf / cm ² or less in a short time within 10 minutes, and good adhesive strength can be achieved.

In the present invention, it is necessary that at least one of ODPA and silicone diamine is contained as an essential component. Due to the structural characteristics of ODPA and silicone diamine, at least one of them is contained in the polyimide so as to satisfy the above-mentioned molar ratio, so that it has excellent heat melting property, good adhesive strength, and heat resistance. It is possible to obtain a film-like adhesive having an excellent balance with

The organic solvent used in the present invention is not particularly limited, but one solvent or a mixed solvent of two or more solvents may be used as long as it can be uniformly dissolved. Typical solvents of this type are N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, Hexamethylphosphoramide, N-methyl
-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethyl sulfone, dimethyl tetramethylene sulfone, γ
-Butyrolactone, diglyme, tetrahydrofuran,
There are methylene chloride, dioxane, cyclohexanone, and the like, and a poor solvent can be used as a volatilization regulator, a film smoothing agent, etc. within a range in which it can be uniformly dissolved.

If the high thermal conductivity filler used in the present invention has a thermal conductivity of 5.0 [W / (m · K)] or more, sufficient thermal conductivity can be obtained by uniformly dispersing it in the film adhesive. Therefore, the type is not particularly limited, but when conductivity is not required, insulating and semiconducting ceramics mainly having phonon conduction are preferable. When the thermal conductivity is less than 5.0 [W / (m · K)], sufficient thermal conductivity cannot be obtained when uniformly dispersed in the film-like adhesive layer, which is not preferable.

Examples of the high thermal conductive filler used in the present invention include Al ₂ O ₃ , BeO, MgO, SiC, TiC, TiN and Si ₃ N.
₄ , AlN, BN, ZrB ₂ , MoSi ₂ , diamond and the like, which may be used alone or in combination of two or more, but are not particularly limited thereto. As the shape, a flake shape, a dendritic shape, a spherical shape, or the like is used. You may mix and use the thing of a different particle size. The particle size for obtaining the required characteristics is preferably 0.01 to 50 μm. The amount of filler in the film adhesive of the present invention is 30 to 900w with respect to the resin.
A ratio of t% is desirable. If it is less than 30 wt%, sufficient thermal conductivity cannot be obtained, which is not preferable, and if it exceeds 900 wt%, the adhesive strength is lowered, which is not preferable.

The method of using the thermocompression-bondable high-heat-conductive film adhesive of the present invention is not particularly limited, but a filler is usually added to a sufficiently imidized varnish, and a mixer, three After uniformly dispersing using a roll, etc., dilute it if necessary and adjust the viscosity, apply it to a substrate with excellent releasability such as Teflon, then volatilize the solvent by heat treatment to form a film Then, it is peeled from the base material to obtain a film containing a high thermal conductive filler. This is sandwiched between the adherends and then thermocompression bonded. Alternatively, it may be applied on the adherend in advance and then subjected to heat treatment to sufficiently volatilize the solvent, and then thermocompression bonding is performed together with one of the adherends.

If desired, various additives can be added to the polyimide siloxane which is the base resin of the adhesive of the present invention. For example, surface smoothing agents when applied to substrates, leveling agents and various surfactants to enhance wettability, silane coupling agents, and various cross-linking agents to enhance heat resistance after thermocompression bonding of adhesives, etc. Is an additive.
These additives can be used in an amount that does not impair the properties of the film adhesive.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0021]

【Example】

(Example 1) In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material charging port, and a dry nitrogen gas inlet tube, 1,
3-bis (3-aminophenoxy) benzene (APB) 8.77g
(0.03 mol) and 58.94 g of silicone diamine of the following formula
(0.07 mol)

[0022]

[Chemical 2]

300 g of N-methyl-2-pyrrolidone (NM
P) and dissolved in 4,4'-oxydiphthalic acid dianhydride (O
31.02 g (0.1 mol) of DPA was gradually added in powder form over 30 minutes, and stirring was continued for 2 hours. Dry nitrogen gas was kept flowing during this time, and the system was kept at 20 ° C. for the whole reaction during the reaction by cooling with an ice bath before adding ODPA.

Then, 60 g of xylene was added to this system,
Remove the dry nitrogen inlet tube and replace it with a Dean Starch reflux condenser, remove the ice bath and heat in an oil bath to raise the system temperature. Continue heating while removing water generated by imidization from the system by azeotropic distillation with toluene.
The reaction was terminated 5 hours after the imidization proceeded at 0 to 160 ° C. and no more water was generated. This polyimide varnish was added dropwise to 30 liters of methanol with stirring for 1 hour to precipitate the resin, and only solid content was collected by filtration, and then dried in a vacuum dryer under reduced pressure at 50 ° C. for 5 hours. Let
FT-IR of the polyimide siloxane thus obtained
The spectrum was measured, was determined and the absorption based on imide before amide bond appearing at 1650 cm ^-1, the imidization ratio from absorption based on imide rings appearing at 1780 cm ^-1, found that it is 100% imidated It was

This polyimide siloxane was dissolved in diethylene glycol dimethyl ether (diglyme),
The concentration was adjusted to 10%. 120 wt% of boron nitride having an average particle size of 2 μm was added to this varnish with respect to the resin content and mixed using a three-roll to obtain a paste. This paste is cast on a Teflon plate whose surface has been polished using an applicator, and the solvent is volatilized by heat treatment at 120 ° C for 5 hours in a dryer, and peeled off from the Teflon substrate to form a film with a thickness of 25 μm. It was created. A 3mm x 3.5mm square piece is cut out from this film, sandwiched between a copper lead frame and a 3mm x 3.5mm square silicon chip, and a load of 500g is applied on a 250 ° C hot plate ( Approximately 4.76kgf / cm ² ) After thermocompression bonding for 10 seconds, cool to room temperature and measure the shear strength with a push-pull gauge. At a value of 10kgf or more, the silicon chip breaks and accurate shear strength is obtained. It was so strong that I couldn't do it. Next, when a similar adhesive sample was placed on a 260 ° C hot plate for 10 seconds and the shear strength was measured, it was 0.8k.
The gf intensity was obtained. The mode of destruction is cohesive failure,
Part of the film was left on the lead frame and the chip. No void was observed in the film. The thermal conductivity and volume resistivity of this film were measured to be 3.2 [W / (m · K)] and 1 × 10 ¹⁵ [Ω-cm], respectively, indicating high thermal conductivity and excellent insulation. Was confirmed.

(Example 2) ODP was used as an acid anhydride component.
A 18.61 g (0.06 mol), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) 12.89 g (0.04 mol) and 33.68 g of the silicone diamine used in Example 1 as a diamine component ( 0.04 mol), 2,4-diaminotoluene 6.11 g (0.05 mol), 1,3-bis (3-aminopropyl)
A polyimidesiloxane was obtained by the same method as in Example 1 except that 2.49 g (0.01 mol) of tetramethyldisiloxane (APDS) was used, and the imidization ratio was measured.
It was 100%. This resin was dissolved in a 1: 1 mixed solvent of diglyme and butyl cellosolve acetate (BCA),
The concentration was adjusted to 15%.

To this varnish, 150 wt% of Al ₂ O ₃ having an average particle size of 3 μm was added with respect to the resin content and mixed by a three-roll to obtain a paste. This paste is cast on a Teflon plate whose surface has been polished using an applicator, and then 120
The solvent was volatilized by heating at 5 ° C. for 5 hours and peeled off from the Teflon substrate to form a film having a thickness of 25 μm. A 3mm x 3.5mm square piece is cut out from this film, sandwiched between a copper lead frame and a 3mm x 3.5mm square silicon chip, and a 500g load is applied for 20 seconds on a 250 ° C hot plate to bond it. did. When the shear strength was measured at room temperature, the silicon chip broke at 10 kgf or more. Next, when a similar adhesive sample was placed on a hot plate at 260 ° C for 10 seconds and shear strength was measured, 2.
It was 1 kgf. No void was observed on the surface of the adhesive film. The thermal conductivity and volume resistivity of this film were measured to be 1.7 [W / (m · K)] and 1 × 10 ¹⁶ [Ω-c, respectively]
m], and it was confirmed that it has high thermal conductivity and excellent insulation.

(Examples 3 to 5 and Comparative Examples 1 to 5) Except for the composition of polyimide siloxane, imidization time, type of high thermal conductive filler, and addition amount, the same procedure as in Example 1 was carried out. I got the result.

[0029]

[Table 1]

As in Examples 1 and 2 and Examples 3 to 5 in Table 1, ODPA and silicone diamine were 0.5 to 1.0 in terms of mole ratio in the total resin composition, and acid anhydride and diamine were mixed. Using polyimide siloxane with a molar ratio in the range of 0.8 to 1.2 and an imidization ratio of 80% or more, the thermal conductivity is
A film in which a filler of 5.0 [W / (mK)] or more is evenly dispersed is formed into a film at a relatively low temperature of 250 ° C or less and 5 kg.
With a relatively low pressure of f / cm ² or less, strong adhesive strength can be obtained under thermocompression bonding conditions of 10 seconds or less.
The adhesive strength was 0.5 kgf or higher even at a high temperature of 260 ° C. Also, the thermal conductivity of the obtained adhesive layer is 1.0 [W / (m ・
K)] or higher, it has high thermal conductivity, and its insulating property is 10 in volume resistivity.
^It was over ¹⁰ [Ω-cm].

On the other hand, as in Comparative Example 1, the ratio of ODPA and silicone diamine in the total resin composition is a molar ratio.
When it was less than 0.5, sufficient adhesive strength could not be obtained under the thermocompression bonding conditions of 250 ° C., 5 kgf / cm ² , and 10 seconds. Also, 300
Even at 30 ° C., 50 kgf / cm ² and 30 seconds, sufficient adhesive strength at high temperature could not be obtained. As in Comparative Example 2, when the amount of the filler added was less than 30 wt% with respect to the resin content, sufficient thermal conductivity could not be obtained. On the contrary, as in Comparative Example 3,
When the amount of the filler added exceeded 900 wt%, the relative amount of the resin as the adhesive component decreased, and sufficient adhesive strength could not be obtained. When a filler having a thermal conductivity of 5.0 [W / (m · K)] or less was used as in Comparative Example 4, sufficient thermal conductivity could not be obtained. When the imidization ratio is less than 80% as in Comparative Example 5,
Since voids occur on the film surface after thermocompression bonding,
Sufficient adhesive strength was not obtained. As described above, good results could not be obtained except under the conditions of the present invention.

[0032]

EFFECTS OF THE INVENTION The thermocompression-bondable film adhesive of the present invention has excellent adhesiveness to metals such as copper and silicon and ceramics, and is sufficient not only at room temperature but also at solder melting temperature such as 260 ° C. It has excellent adhesive strength and excellent heat dissipation. Moreover, low temperature, low pressure,
It is possible to obtain a heat-resistant film adhesive which is advantageous in terms of mass productivity that can be thermocompression bonded in a short time.

[Procedure amendment]

[Submission date] November 13, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

[Chemical 2]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

[0029]

[Table 1] ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 19, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

An amine component containing C moles of silicone diamine represented by and D moles of other diamine components, silicone diamine or this and 4,4'-oxydiphthalic dianhydride as essential components, and (A + C) / ( A + B + C +
D) is reacted in the range of 0.5 to 1.0 and (A + B) / (C + D) is in the range of 0.8 to 1.2, and at least 80% or more of the polyimide siloxane is imidized, and 30 to 900 wt% of thermal conductivity to the polyimide siloxane. A thermocompression-bondable film-like adhesive comprising a filler having a rate of 5.0 [W / (m · K)] or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

In the present invention, it is necessary that silicone diamine or ODPA and silicone diamine are contained as essential components. Due to the structural characteristics of silicone diamine and ODPA, when at least one of them is contained in the polyimide so as to satisfy the above-mentioned molar ratio, it has excellent heat melting property, good adhesive strength, and heat resistance. It is possible to obtain a film-like adhesive having an excellent balance with

Claims (1)

[Claims] 1. An acid component containing A mol of 4,4′-oxydiphthalic dianhydride and B mol of another acid dianhydride component, C mol of a silicone diamine represented by the formula (1) and another diamine component D. An amine component containing a mole of at least one of 4,4'-oxydiphthalic dianhydride or silicone diamine as an essential component, and (A + C) / (A +
B + C + D) is 0.5 to 1.0, (A + B) / (C + D) is 0.
Polyimide siloxane that is reacted in the range of 8 to 1.2, at least 80% or more of which is imidized, and a filler having a thermal conductivity of 5.0 [W / (mK)] of 30 to 900 wt% with respect to the polyimide siloxane. A highly heat-conductive film adhesive that can be thermocompression bonded. [Chemical 1]