JPH05117622A - Hot melt bondable filmy adhesive having high thermal conductivity - Google Patents

Abstract

PURPOSE:To obtain a filmy adhesive having not only thermal conductivity and heat resistance but also thermocompression bonding efficiency by incorporating a filler into a specific polyimidosiloxane. CONSTITUTION:An acid component comprising A mol of an acid-terminated silicone compound represented by formula I, as an essential reactant, and B mol of other acid dianhydride is reacted with an amine component comprising C mol of a diaminosilicone compound represented by formula II, as an essential reactant, and D mol of other diamine, provided that (A+C)/(A+B+C+D) is 0.3 to 1.0 and (A+B)/(C+D) is 0.8 to 1.2. Thus, a polyimidosiloxane having a degree of imidization of at least 80% is obtained. 100 pts.wt. this polymer is mixed with 30-900 pts.wt. filler having a thermal conductivity of 5.0W/(m.K) or higher. In formula I, R1 is, e.g. a trivalent aliphatic or aromatic group, R2 and R3 each is, e.g. a monovalent aliphatic group, and n is 1 to 100. In formula II, R1 and R2 each is, e.g. a 1-5C divalent aliphatic group, R3 and R4 each is, e.g. a monovalent aliphatic group, and n is 1 to 100.

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 is based on the formula (1)

[0007]

[Chemical 1]

An acid component containing A moles of the acid-terminated silicone compound represented by and B moles of another acid dianhydride component;

[0009]

[Chemical 2]

An amine component containing C moles of a diamino silicone compound represented by and D moles of another diamine component,
At least one of an acid-terminated silicone compound and a diaminosilicone compound as an essential component, (A + C)
/ (A + B + C + D) is 0.3 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
Acid-terminated silicone compounds and other acid dianhydrides, but examples of acid dianhydrides other than acid-terminated silicone compounds include pyromellitic dianhydride and 3,3 ′, 4,4′-benzophenone tetra Carboxylic acid dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, naphthalene-2,3,6, 7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic 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 acid dianhydride, 2,7-Dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4 , 5,8-Tetracarboxylic acid dianhydride, 1,4,5,8-Tetrachloronaphthalene-2,3,6,7-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl Tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyltetracarboxylic acid dianhydride, 3,3 ", 4, 4 "-p-terphenyltetracarboxylic dianhydride, 2,2", 3,3 "-p-terphenyltetracarboxylic dianhydride, 2,3,3", 4 "-p-terphenyltetra Carboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl)-
Propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 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 dianhydride Thing, perylene
-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,
11,12-Tetracarboxylic acid dianhydride, phenanthrene-1,
2,7,8-Tetracarboxylic acid dianhydride, phenanthrene-1,
2,6,7-Tetracarboxylic acid dianhydride, phenanthrene-1,
2,9,10-Tetracarboxylic acid dianhydride, cyclopentane-1,
2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-
Tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride However, the present invention is not limited to these.

The acid-terminated silicone compound used in the present invention is not particularly limited, but examples thereof include a phthalic anhydride-terminated silicone compound and a nadic acid anhydride-terminated silicone compound represented by the following formula.

[0013]

[Chemical 3]

The diamine component used in the present invention is a diamino silicone compound and another diamine.
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-1,1
0-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino-octadecane, 2,12-diamino-octadecane,
2,17-diamino-icosane, 1,3-bis (3-aminophenoxy) benzene and the like can be mentioned.

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 0.3 to 1.0, and if it is less than 0.3, 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 the acid terminal silicone compound and the diamino silicone compound is contained as an essential component.
Due to the structural characteristics of the acid-terminated silicone compound and the diaminosilicone compound, at least one of them is contained in the polyimide so as to satisfy the above-mentioned molar ratio, whereby the heat melting property is excellent and the adhesive strength is also good. Therefore, it is possible to obtain a film-like adhesive having excellent balance with heat resistance.

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 thermal conductive film adhesive of the present invention is not particularly limited, but usually a sufficiently imidized varnish is added with a filler, 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.

[0025]

【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) 17.54
g (0.06 mol), diamino silicone compound of the following formula 3
3.67 g (0.04 mol)

[0026]

[Chemical 4]

300 g of N-methyl-2-pyrrolidone (NM
P) and dissolved in 4,4'-oxydiphthalic acid dianhydride (O
DPA) 24.82 g (0.08 mol), acid-terminated silicone compound of the following formula 20.40 g (0.02 mol)

[0028]

[Chemical 5]

[0029] was gradually added as a solid over 30 minutes, and stirring was continued for 2 hours. Dry nitrogen gas was kept flowing all the time, and the system was kept at 20 ° C. for the whole reaction during the reaction by cooling with an ice bath before adding more acid anhydride.

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 the solid content was collected by filtration, and then dried in a vacuum dryer under reduced pressure at 120 ° C for 5 hours. Let The FT of the polyimide siloxane thus obtained
The -IR spectra measured were determined in 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, 100%
It was found to be imidized.

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 230 ° 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 the same adhesive sample was placed on a hot plate at 260 ° C for 10 seconds and the shear strength was measured, it was 1.0k.
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 3.1 [W / (m · K)] and 1 × 10 ¹⁵ [Ω-cm], respectively, indicating that they have high thermal conductivity and excellent insulation properties. Was confirmed.

(Example 2) As an acid anhydride component, 10.56 g (0.01 mol) of an acid-terminated silicone compound of the following formula,

[0033]

[Chemical 6]

ODPA 18.61 g (0.06 mol), 3,3 ', 4,4'
-Benzophenone tetracarboxylic dianhydride (BTD
A) 12.89 g (0.04 mol) and, as a diamine component, 58.92 g (0.07 mol) of a diamino silicone compound represented by the following formula,

[0035]

[Chemical 7]

2,4-diaminotoluene 3.67 g (0.03 mol)
Polyimide siloxane was obtained by the same method as in Example 1 except that was used, and the imidization ratio was measured.
%Met. This resin was dissolved in a 1: 1 mixed solvent of diglyme and butyl cellosolve acetate (BCA) to obtain a concentration
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 the mixture was mixed with a triple 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 size is cut out from this film, sandwiched between a copper lead frame and a 3mm x 3.5mm square size silicon chip, and a 500g load is applied for 10 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, 1.
It was 5 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 1.6 [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.

[0039]

[Table 1]

As in Examples 1 and 2 and Examples 3 to 5 in Table 1, the acid-terminated silicone compound and the diaminosilicone compound are contained in the total resin composition in an amount of 0.3 to 0.3 in terms of the number of moles.
1.0, the molar ratio of the acid anhydride and the diamine is in the range of 0.8 to 1.2, the imidization rate is 80% or more, using polyimide siloxane, the thermal conductivity of 5.0 [W / (m · K)] or more The film obtained by uniformly dispersing the filler can obtain a strong adhesive strength at a relatively low temperature of 250 ° C or less and a relatively low pressure of 5 kgf / cm ² under a thermocompression bonding condition of 10 seconds. The adhesive strength was 1 kgf or more even at a high temperature of 260 ° C. The obtained adhesive layer also had a thermal conductivity of 1.0 [W / (m · K)] or higher and high thermal conductivity, and had an insulating property of 10 ¹⁰ [Ω-cm] or higher in terms of volume resistivity.

On the other hand, when the molar ratio of the acid-terminated silicone compound and the diaminosilicone compound to the total resin composition is less than 0.3 as in Comparative Example 1, 250 ° C., 5 kgf /
Under the thermocompression bonding condition of cm ² for 10 seconds, sufficient adhesive strength 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. Comparative Example 4
As described above, when a filler having a thermal conductivity of 5.0 [W / (m · K)] or less was used, sufficient thermal conductivity could not be obtained. When the imidization ratio was less than 80% as in Comparative Example 5, voids were generated on the film surface after thermocompression bonding, and thus sufficient adhesive strength could not be obtained. As described above, good results could not be obtained except under the conditions of the present invention.

[0042]

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 resistance. The adhesive layer had high thermal conductivity and excellent heat dissipation. In addition, it is possible to obtain a highly heat-conductive film-like adhesive which is unprecedented and is advantageous in terms of mass productivity that enables thermocompression bonding at low temperature, low pressure, and short time.

[Procedure amendment]

[Submission date] November 13, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

[0035]

[Chemical 7]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039]

[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]

[Chemical 2]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

An amine component containing C moles of a diamino silicone compound represented by and D moles of another diamine component,
An acid-terminated silicone compound and a diamino silicone compound are essential components, and (A + C) / (A + B + C + D) is 0.
3 to 1.0, (A + B) / (C + D) are reacted in the range of 0.8 to 1.2, and at least 80% or more of polyimide siloxane imidized, and 30 to polyimide siloxane
A film-like adhesive capable of thermocompression bonding, which comprises a filler having a thermal conductivity of 5.0 [W / (m · K)] of 900 wt% or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the present invention, it is necessary that the acid terminal silicone compound and the diamino silicone compound are contained as essential components. Due to the structural characteristics of the acid-terminated silicone compound and the diaminosilicone compound, at least one of them is contained in the polyimide so as to satisfy the above-mentioned molar ratio, whereby the heat melting property is excellent and the adhesive strength is also good. Therefore, it is possible to obtain a film-like adhesive having excellent balance with heat resistance.

Claims (1)

[Claims] 1. An acid component containing A mole of the acid-terminated silicone compound represented by the formula (1) and another B mole of the acid dianhydride component, C mole of the diaminosilicone compound represented by the formula (2) and another diamine. An amine component containing component D moles,
At least one of an acid-terminated silicone compound and a diaminosilicone compound as an essential component, (A + C)
/ (A + B + C + D) is 0.3 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)] A thermocompression-bondable highly heat-conductive film adhesive, which is composed of a filler having the above content. [Chemical 1] [Chemical 2]