JP4586966B2 - Adhesive composition and adhesive film - Google Patents

Description

  The present invention relates to an adhesive composition having a high adhesive force and a low elastic modulus, which is used for manufacturing a semiconductor device, and particularly suitable for a resin mold type semiconductor package, and an adhesive film using the same.

  In the manufacturing process of semiconductor devices, a large-diameter silicon wafer on which an IC circuit is formed is cut into semiconductor chips in a dicing process, and the lead frame is thermocompression-bonded and fixed with a curable liquid adhesive (die-bonding material). It is manufactured by (mounting) and sealing after wire bonding between electrodes for handling and protection from the external environment. As this sealing form, there are a hermetic sealing type such as metal sealing and ceramic sealing, and a non-hermetic sealing type using a resin. However, the transfer molding method using the latter resin is currently excellent in mass productivity and inexpensive. , The most commonly used. However, while this resin mold package has the above-mentioned advantages, it has disadvantages inferior in moisture resistance / heat resistance, thermal stress relaxation, heat dissipation, and the like.

  In addition, due to the recent demand for higher functionality of electronic components with the downsizing and multi-functionalization of electrical and electronic equipment, the wiring of semiconductor devices has been further miniaturized and increased in density. Since the semiconductor device has a structure (CSP) having the same size as an area array bonded chip without a lead frame or a lead frame, or a stacked structure of chips (stacked CSP, SiP), the heat in these packaging (PKG) Impact (stress) has also become severe.

  Furthermore, in the process of mounting and mounting these semiconductor devices on a printed circuit board, the reflow resistance corresponding to lead-free solder has become high (265 ° C.), which is becoming severe. For this reason, there has been a demand for optimization and high performance of materials used. In particular, in a packaging component material, the die bond material can be controlled over a relatively wide range of characteristics, so that it is possible to easily meet these requirements, and therefore it is possible to cope with severe thermal shock (stress) against the die bond material. Materials with high adhesion, low elastic modulus, and high heat resistance have been demanded.

  In addition, miniaturization is also required for the support substrate on which the semiconductor chip is mounted, and in the case of a liquid adhesive, wire bonding occurs due to contamination of the electrode due to protrusion from the end of the chip at the time of mounting the semiconductor chip or inclination of the chip due to uneven thickness of the adhesive layer. Therefore, it is also desired to form an adhesive film that can improve these disadvantages.

  As these adhesives, conventionally, low elastic modulus materials in which a siloxane structure is introduced into polyimide or polyamideimide, which are resins having excellent heat resistance, have been developed. JP-A-3-189127 (Patent Document 1), JP-A-4-264003 (Patent Document 2) and the like all propose siloxane-modified polyamideimide, but the adhesion to the substrate is not sufficient. .

  Japanese Patent Laid-Open No. 10-60111 (Patent Document 3) proposes that a compound having two or more maleimide groups is added to a siloxane-modified polyamideimide to improve high temperature characteristics. Is inferior in adhesive strength.

  JP-A-7-224259 (Patent Document 4) and JP-A-8-27427 (Patent Document 5) describe a heat-resistant adhesive composed of a polyimide silicone and an epoxy resin excellent in adhesiveness, low elasticity and heat resistance. Films have been proposed, but as a property based on packaging (PKG) process steps, the adhesion of the sealing resin to the die bond adhesive layer after adhesive cure is very poor.

Japanese Patent Laid-Open No. 3-189127 JP-A-4-264003 Japanese Patent Laid-Open No. 10-60111 Japanese Patent Laid-Open No. 7-224259 JP-A-8-27427

  The present invention has been made in view of the above circumstances, and in order to eliminate the above disadvantages, an adhesive composition that is excellent in adhesion and heat resistance and can be a cured product having a low elastic modulus, and an adhesive film using the same The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventor, as an adhesive composition containing a polyimide resin, an epoxy resin, and an epoxy resin curing catalyst, as the polyimide resin, a diorgano containing an epoxy group By using a polyimide resin having a polysiloxane bond, it was found that this adhesive composition can be a cured product having high adhesive strength, low elastic modulus, and high heat resistance, and has led to the present invention. .

（式中、Ｒ ¹ は炭素原子数３〜９の二価の有機基、Ｒ ² 〜Ｒ ⁶ はビニル基以外の炭素原子数１〜８の非置換又は置換の一価炭化水素基であり、ｎは０又は１以上の整数、ｍは１以上の整数、ｎ＋ｍは１〜１００の整数である。）

（式中、Ｒ ⁷ は独立に水素原子、ハロゲン原子、又は炭素原子数１〜８の非置換又は置換の一価炭化水素基である。）
上記（ｉｉ）オルガノハイドロジェンポリシロキサンが、下記構造式（１）及び／又は（２）

で示されるオルガノハイドロジェンポリシロキサンであり、
上記（Ａ）ポリイミド樹脂が、ポリイミド樹脂のポリマー骨格にフェノール性の水酸基を有する、エポキシ基含有ジオルガノポリシロキサン結合を有するポリイミド樹脂であることを特徴とする接着剤組成物。 That is, the present invention provides the following adhesive composition and an adhesive film obtained using the same.
(A) (i) a polyimide resin containing a diorganopolysiloxane bond having a vinyl group as an organic substituent in the main chain;
(Ii) (iii) a polyimide resin having an epoxy group-containing diorganopolysiloxane bond obtained by addition reaction of an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group with a platinum-based catalyst in the molecule;
An adhesive composition containing (B) an epoxy resin and (C) an epoxy resin curing catalyst as an essential component,
The (i) polyimide resin is
(I-1) tetracarboxylic dianhydride;
(I-2) Diaminopolysiloxane represented by the following structural formula (3), wherein at least one of all organic groups bonded to the silicon atom is a vinyl group, and a diamine containing a diamine represented by the following formula (4) Compound and
Obtained by dehydrating and ring-closing the polyamic acid resin obtained by the reaction,

(In the formula, R ¹ is a divalent organic group having 3 to 9 carbon atoms, R ^{2 to} R ⁶ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms other than vinyl group, n is 0 or an integer of 1 or more, m is an integer of 1 or more, and n + m is an integer of 1 to 100.)

(Wherein R ⁷ is independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.)
The above (ii) organohydrogenpolysiloxane has the following structural formula (1) and / or (2)

An organohydrogenpolysiloxane represented by:
The adhesive composition, wherein the (A) polyimide resin is a polyimide resin having an epoxy group-containing diorganopolysiloxane bond having a phenolic hydroxyl group in the polymer skeleton of the polyimide resin.

  The adhesive film obtained from the adhesive composition of the present invention gives high adhesion to various substrates by thermocompression bonding and heat curing, and also has high adhesion to the sealing resin, and also has a low elastic modulus and high heat resistance. A highly reliable resin packaging semiconductor device can be manufactured.

  The adhesive composition of the present invention comprises an adhesive composition containing (A) a polyimide resin having an epoxy group-containing diorganopolysiloxane bond, (B) an epoxy resin, and (C) an epoxy resin curing catalyst as essential components. It keeps its shape at room temperature, forms a film-like thin film, cures through a plastic state by heating, shows excellent adhesion to the substrate, and the cured product has a low elastic modulus. The adhesive strength to the sealing resin is high.

The polyimide resin having an epoxy group-containing diorganopolysiloxane bond as the component (A) of the present invention,
(I) a polyimide resin containing a diorganopolysiloxane bond having a vinyl group as an organic substituent in the main chain;
(Ii) An organohydrogenpolysiloxane having a silicon-bonded hydrogen atom and an epoxy group in the molecule can be obtained by (iii) addition reaction with a platinum-based catalyst.

  The polyimide resin containing a diorganopolysiloxane bond having a vinyl group as an organic substituent in the main chain of the reaction raw material component (i) of the component (A) is a precursor represented by the following general formula (5). Polyamic acid resin can also be used, but water may be produced as a by-product due to imidization (dehydration ring closure) during heat curing in the die-bonding process, and the adhesion surface may be peeled off. It is preferable to use a polyimide resin represented by the general formula (6). In this invention, it is necessary to contain the diorganopolysiloxane bond which has an epoxy group, and it is preferable to have a phenolic hydroxyl group in frame | skeleton from an adhesive point.

（式中、Ｘは芳香族環又は脂肪族環を含む四価の有機基、Ｙは二価の有機基、ｑは１〜３００の整数である。）

(In the formula, X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, Y is a divalent organic group, and q is an integer of 1 to 300.)

（式中、Ｘは芳香族環又は脂肪族環を含む四価の有機基、Ｙは二価の有機基、ｑは１〜３００の整数である。）

(In the formula, X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, Y is a divalent organic group, and q is an integer of 1 to 300.)

  In the general formula (5), q is an integer of 1 to 300, preferably an integer of 2 to 300, particularly an integer of 5 to 300. The polyamic acid resin having such a repeating number is obtained by the following method. Can be obtained more easily. Moreover, about the polyimide resin represented by the said General formula (6), it can obtain by dehydrating and ring-closing the polyamic acid resin represented by the said General formula (5) by a conventional method.

（但し、Ｘは上記と同様の意味を示す。）
で表されるテトラカルボン酸二無水物と、下記構造式（８）
Ｈ₂Ｎ−Ｙ−ＮＨ₂ （８）
（但し、Ｙは上記と同様の意味を示す。）
で表されるジアミンとを常法に従って、ほぼ等モルで有機溶剤中で反応させることによって得ることができる。 The polyamic acid resin represented by the general formula (5) has the following structural formula (7).

(However, X has the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following structural formula (8)
_{H 2 N-Y-NH 2} (8)
(However, Y has the same meaning as described above.)
According to a conventional method, the diamine can be obtained by reacting in a substantially equimolar amount in an organic solvent.

Here, specific examples of the tetracarboxylic dianhydride represented by the structural formula (7) include the following, but are not limited thereto.

  In addition, the tetracarboxylic dianhydride shown by the said Structural formula (7) may use 1 type (s) or 2 or more types depending on necessity.

  Of the diamine represented by the structural formula (8), preferably 1 to 80 mol%, more preferably 1 to 60 mol% is a diaminopolysiloxane compound represented by the following structural formula (3). From the viewpoints of solubility in organic solvents, adhesion to substrates, low elasticity, and flexibility. Since this diaminopolysiloxane compound contains a diorganopolysiloxane bond having an epoxy group in the polyimide resin of the present invention from the viewpoint of adhesiveness, at least one of all organic substituents bonded to the silicon atom is a vinyl group. It is necessary.

（式中、Ｒ¹は炭素原子数３〜９の二価の有機基、Ｒ²〜Ｒ⁶はビニル基以外の炭素原子数１〜８の非置換又は置換の一価炭化水素基であり、ｎは０又は１以上の整数、ｍは１以上の整数、ｎ＋ｍは１〜１００の整数である。）

(In the formula, R ¹ is a divalent organic group having 3 to 9 carbon atoms, R ^{2 to} R ⁶ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms other than vinyl group, n is 0 or an integer of 1 or more, m is an integer of 1 or more, and n + m is an integer of 1 to 100.)

等のアリーレン基、これらを組み合わせたアルキレン・アリーレン基、−（ＣＨ₂）₃−Ｏ−，−（ＣＨ₂）₄−Ｏ−等のオキシアルキレン基、

等のオキシアリーレン基やこれらを組み合わせた

等のオキシアルキレン・アリーレン基などの、エーテル酸素原子を含んでもよい二価炭化水素基が挙げられる。 In the siloxane diamine (or α, ω-diaminopolysiloxane) represented by the structural formula (3), examples of the divalent organic group having 3 to 9 carbon atoms represented by R ¹ include — (CH ₂ ) an alkylene group such as _3— , — (CH ₂ ) ₄ —, —CH ₂ CH (CH ₃ ) —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —,

Arylene groups such as, alkylene / arylene groups combining these, oxyalkylene groups such as — (CH ₂ ) ₃ —O—, — (CH ₂ ) ₄ —O—,

Oxyarylene groups such as

And a divalent hydrocarbon group which may contain an ether oxygen atom, such as an oxyalkylene / arylene group.

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ^{2 to} R ⁶ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert. -Alkyl groups such as butyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, aryl groups such as phenyl group, tolyl group, xylyl group, aralkyl groups such as benzyl group, phenylethyl group, etc. Groups in which some or all of the hydrogen atoms bonded to the carbon atom are substituted with halogen atoms such as fluorine, bromine, and chlorine, such as chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc. Examples thereof include a halogen-substituted alkyl group, and among them, a methyl group and a phenyl group are preferable.

  m and n are 0.1 ≦ m / (m + n) ≦ 1, preferably 0.2 ≦ m / (m + n) ≦ 0.6. m + n is 1 to 100, preferably 5 to 50.

  These diaminopolysiloxane compounds represented by the structural formula (3) can be used singly or in combination of two or more as desired.

  Further, among the diamines represented by the structural formula (8), examples of diamines other than the diaminopolysiloxane compound represented by the structural formula (3) include p-phenylenediamine, m-phenylenediamine, and 4,4. '-Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1 , 4-bis (p-aminophenylthioether) benzene, 1,4-bis (m-aminophenyl) Oether) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-amino) Phenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] Ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-amino) Enoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4 -Aminophenoxy) phenyl] aromatic ring-containing diamine such as perfluoropropane and the like, preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1 , 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3 -Methyl-4- (4-aminophenoxy) phenyl] propane.

  In the present invention, from the viewpoint of adhesiveness, the polymer skeleton of the polyimide resin preferably has a phenolic hydroxyl group. The introduction of this hydroxyl group is a diamine compound having a phenolic hydroxyl group having high reactivity with an epoxy group. As such a diamine, those having the following structure can be exemplified.

（式中、Ｒ⁷は独立に水素原子又はフッ素、臭素、よう素等のハロゲン原子、あるいは炭素原子数１〜８のアルキル基、アルケニル基、アルキニル基、トリフルオロメチル基、フェニル基等の非置換又は置換の一価炭化水素基であり、各芳香族環についている置換基は全て同じでも構わないし、全て異なっていても構わない。ここでｐは０〜５の整数である。Ａ，Ｂはそれぞれ１種でもよく、２種以上であってもよい。Ｒは水素原子、ハロゲン原子又は非置換もしくは置換の一価炭化水素基である。）

(In the formula, R ⁷ is independently a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group, a trifluoromethyl group, a phenyl group, etc. A substituted or substituted monovalent hydrocarbon group, and the substituents on each aromatic ring may be all the same or different, where p is an integer of 0 to 5. A, B May be one kind or two kinds or more, and R is a hydrogen atom, a halogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)

Here, the substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms of R ⁷ is the same as those exemplified for the above R ^{2 to} R ⁶ , vinyl group, allyl group, propenyl group. Alkenyl groups such as isopropenyl group, butenyl group, isobutenyl group and hexenyl group, and alkynyl groups such as ethynyl group, propynyl group, butynyl group and hexynyl group. Further, examples of the unsubstituted or substituted monovalent hydrocarbon group for R include the same as those exemplified for R ⁷ above.

（式中、Ｒ⁷は上記と同じである。） In the present invention, among the diamine compounds having a phenolic hydroxyl group, a diamine compound represented by the following formula (4) is particularly preferable.

(Wherein R ⁷ is the same as above)

  In addition, in this invention, as a compounding quantity of the diamine compound which has a phenolic hydroxyl group, it is preferable that it is 5-60 mass% of the whole diamine compound, and especially 10-40 mass%. If the amount is too small, the adhesive strength may be low, and if it is too large, the flexibility of the adhesive layer may be insufficient.

（式中、Ｒ⁷は独立に水素原子又はフッ素、臭素、よう素等のハロゲン原子、あるいは炭素原子数１〜８のアルキル基、アルケニル基、アルキニル基、トリフルオロメチル基、フェニル基等の非置換又は置換の一価炭化水素基であり、上記Ｒ⁷と同様のものが例示され、各芳香族環についている置換基は全て同じでも構わないし、全て異なっていても構わない。Ｄは１種でも２種を併用してもよい。また、ｒは１〜３の整数である。） Moreover, the monoamine which has a phenolic hydroxyl group can also be used for introduction | transduction of a phenolic hydroxyl group, and the following structure can be illustrated.

(In the formula, R ⁷ is independently a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group, a trifluoromethyl group, a phenyl group, etc. Examples of the substituted or substituted monovalent hydrocarbon group include the same as those described above for R ^7, and all the substituents attached to each aromatic ring may be the same or different from each other. However, two may be used in combination, and r is an integer of 1 to 3.)

  When a monoamine having a phenolic hydroxyl group is used, the blending amount is 1 to 10 mol% with respect to the entire diamine compound.

  The amine compounds are not limited to these, and these amine compounds can be used alone or in combination of two or more as desired.

  To give specific examples of the polyamic acid resin and polyimide resin formation reaction, the above starting materials are dissolved in a solvent under an inert atmosphere, and are usually reacted at 80 ° C. or lower, preferably 0 to 40 ° C. A polyamic acid resin is synthesized. Further, by heating the obtained polyamic acid resin to 100 to 200 ° C., preferably 150 to 200 ° C., the acid amide portion of the polyamic acid resin is dehydrated and cyclized to synthesize the target polyimide resin. Can do.

  The organic solvent used for the reaction may not be one that can completely dissolve the starting material as long as it is inert to the resulting polyamic acid. Examples include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide, preferably aprotic Polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

  In order to facilitate the above dehydration ring closure, it is desirable to use an azeotropic dehydrating agent such as toluene or xylene. Further, dehydration ring closure can be performed at a low temperature using an acetic anhydride / pyridine mixed solution.

  In order to adjust the molecular weight of polyamic acid and polyimide resin, maleic anhydride, dicarboxylic acid anhydride such as phthalic anhydride and / or aniline, n-butylamine, monoamine having phenolic hydroxyl group mentioned above are added. You can also However, the addition amount of dicarboxylic anhydride is usually 0 to 2 parts by mass per 100 parts by mass of tetracarboxylic dianhydride, and the addition amount of monoamine is usually 0 to 2 parts by mass per 100 parts by mass of diamine. Part.

  The polyimide resin thus obtained is preferably purified by precipitating in a solvent that does not dissolve the polyimide resin for epoxy group introduction reaction. As these solvents, water, methanol, ethanol and the like can be used.

  Next, the reaction raw material component (ii) is an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group in the molecule, and may be either chain-like or cyclic, and the structure is not particularly limited. However, in terms of synthesis, those having one silicon-bonded hydrogen atom in the molecule are preferred. The following compounds can be exemplified.

（式中、Ｒ²〜Ｒ⁶はビニル基以外の炭素原子数１〜８の非置換又は置換の一価炭化水素基であり、ｓ，ｕは１以上の整数、ｓ＋ｔ＋ｕは３〜１０の整数である。）

(Wherein R ^{2 to} R ⁶ are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms other than a vinyl group, s and u are integers of 1 or more, and s + t + u is an integer of 3 to 10) .)

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ^{2 to} R ⁶ include the same ones as described above. Among them, a methyl group is preferable, and examples of the component (ii) include organohydrogenpolysiloxanes represented by the following structural formulas (1) and (2).

  The reaction raw material component (iii) is a platinum-based catalyst, and examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complexes, and the like.

  The compounding amount of the platinum-based catalyst is 0.1 to 1,000 ppm, preferably 1 to 500 ppm as platinum metal in the platinum-based catalyst with respect to the total amount of (i) and (ii) raw material components.

  The addition reaction of (i) and (ii) raw material components is achieved by heating in a suitable solvent. Any solvent may be used as long as it is inactive to the component (ii) and dissolves the components (i) and (ii). Toluene, xylene, hexane, heptane, ethanol, methyl ethyl ketone, methyl isobutyl ketone, And cyclohexanone. Moreover, as heating conditions, it is 40 to 120 degreeC, and is 2 to 6 hours.

  As the epoxy resin of component (B) used in the present invention, a compound having at least two epoxy groups in one molecule is preferable, and the molecular structure, molecular weight and the like are not particularly limited. As such an epoxy compound, for example, bis (4-hydroxyphenyl) methane, 2,2′-bis (4-hydroxyphenyl) propane or a diglycidyl ether of this halide and a condensation polymer thereof (so-called bisphenol F) Type epoxy resin, bisphenol A type epoxy resin, etc.), butadiene diepoxide, vinylcyclohexene dioxide, diglycidyl ether of resorcin, 1,4-bis (2,3-epoxypropoxy) benzene, 4,4′-bis (2 , 3-epoxypropoxy) diphenyl ether, 1,4-bis (2,3-epoxypropoxy) cyclohexene, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 1,2-dioxybenzene or resorcinol, many Hydric phenol or Epoxy novolaks obtained by condensing novolac type phenol resins (or halogenated novolac type phenol resins) such as epoxy glycidyl ethers or polyglycidyl esters, phenol novolacs, cresol novolacs, etc., obtained by condensing monohydric alcohol and epichlorohydrin with epichlorohydrin (Ie, novolac epoxy resin), epoxidized polyolefin epoxidized by peroxidation method, epoxidized polybutadiene, naphthalene ring-containing epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, cyclopentadiene type An epoxy resin etc. are mentioned.

  (B) The compounding quantity of the epoxy resin of a component is 5-200 mass parts with respect to 100 mass parts of (A) component polyimide resin, It is preferable that it is especially 10-100 mass parts. If the amount of the epoxy resin is too small, the adhesive strength may be inferior, and if too large, the flexibility of the adhesive layer may be insufficient.

  It should be noted that a monoepoxy compound may be appropriately used in combination with an epoxy compound having at least two epoxy groups in one molecule. Examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, Examples include ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide and the like. Moreover, the epoxy resin to be used is not necessarily limited to only one type, and two or more types can be used in combination.

  There is no restriction | limiting in particular in the epoxy resin curing catalyst of (C) component used by this invention, For example, a phosphorus catalyst, an amine catalyst, etc. are illustrated.

  Here, examples of the phosphorus-based catalyst include triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate, and compounds shown below.

（式中、Ｒ⁸〜Ｒ¹⁵は水素原子又はフッ素、臭素、よう素などのハロゲン原子、あるいは炭素原子数１〜８のアルキル基、アルケニル基、アルキニル基、又は炭素原子数１〜８のアルコキシ基、トリフルオロメチル基、フェニル基などの非置換もしくは置換の一価炭化水素基であり、総ての置換基が同一でも、おのおの異なっていても構わない。）

(Wherein R ^{8 to} R ¹⁵ are a hydrogen atom or a halogen atom such as fluorine, bromine, iodine, or an alkyl group, alkenyl group, alkynyl group, or alkoxy having 1 to 8 carbon atoms) An unsubstituted or substituted monovalent hydrocarbon group such as a group, a trifluoromethyl group, and a phenyl group, and all the substituents may be the same or different.)

Here, as monovalent hydrocarbon groups for R ^{8 to} R ¹⁵ , those similar to those exemplified for R ⁷ above, and alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, etc. Can be mentioned.

  Examples of the amine catalyst include imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. .

  The epoxy resin curing catalyst in the present invention can be used singly or in combination of two or more. In addition, the compounding quantity of the epoxy resin curing catalyst of (C) component can be made into a catalyst amount, and is 0.1-10 mass parts normally with respect to 100 mass parts of epoxy resin of (B) component, Especially 0.5- 5.0 parts by mass.

If necessary, an epoxy resin curing agent can be used in the adhesive composition of the present invention. As this curing agent, conventionally known various curing agents for epoxy resins can be used, for example, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpiperazine, bis (4-amino). Amine compounds such as -3-methylcyclohexyl) methane, metaxylylenediamine, menthanediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane Epoxy resins-modified aliphatic polyamines such as diethylenetriamine adducts, amine-ethylene oxide adducts, cyanoethylated polyamines; bisphenol A, trimethylolallyloxyphenol, low polymerization degree phenol novolac resins, epoxidized or butylated pheno Le resin or "Super Beckcite" 1001 [manufactured by Nippon Reichhold Chemical Co. (Ltd.)], "Hitanol" 4010 [(Ltd.) manufactured by Hitachi, Ltd.], Scado form L. A phenolic resin containing at least two phenolic hydroxyl groups in the molecule, such as a phenolic resin known by a trade name such as 9 (made by Scado Zwoll, the Netherlands) and Methylon 75108 (made by General Electric, USA); “Beckamine "P. 138 [manufactured by Nippon Reichhold Chemical Co., Ltd.], “Melan” [manufactured by Hitachi, Ltd.], “U-Van” 10R [manufactured by Toyo Kodan Kogyo Co., Ltd.], etc. resin; formula _{HS (C 2 H 4 OCH 2} OC 2 H 4 SS) n C 2 H 4 OCH 2 OC 2 H 4 SH (n = 1~10 integer); melamine resins, amino resins such as aniline resins Polysulfide resin having at least two mercapto groups in one molecule; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl nadic acid, dodecyl succinic anhydride, chlorendic anhydride Examples thereof include organic acids such as acids or anhydrides (acid anhydrides) thereof. Among the curing agents described above, the phenolic resin (phenol novolac resin) gives good molding workability to the composition of the present invention, gives excellent moisture resistance, has no toxicity, and is relatively inexpensive. Is desirable. The above-mentioned curing agents are not necessarily limited to one type in use, and two or more types may be used in combination depending on the curing performance of the curing agents.

  The amount used in the case of blending this curing agent is an effective amount for curing the epoxy resin, and the suitable blending amount varies depending on the specific type, but generally 100 parts by mass of the epoxy resin of the component (B) 1 to 100 parts by mass, preferably 5 to 50 parts by mass. When the amount of the curing agent used is less than 1 part by mass, it may be difficult to cure the composition of the present invention satisfactorily. May be diluted to require a long time for curing, and there may be a disadvantage that the physical properties of the cured product are deteriorated.

  Moreover, when using the polyimide resin which has a phenolic hydroxyl group in frame | skeleton as (A) component, the compounding ratio with an epoxy resin and a phenol-type resin hardening | curing agent is important. In this case, the curing reaction is carried out by utilizing the reaction between the phenolic hydroxyl group and the epoxy group. However, if the epoxy group is too small, the adhesive force with the adherend may not be sufficient. Since the elastic modulus may be increased by the resin, it is unsuitable for producing a flexible adhesive film. Therefore, the blending amount of the epoxy resin and the phenolic resin curing agent is 1 to 900 parts by mass, preferably 5 to 400 parts by mass with respect to 100 parts by mass of the polyimide resin.

  Here, the total chemical equivalent ratio of the phenolic resin curing agent to the epoxy resin and the polyimide resin having a phenolic hydroxyl group in the skeleton is not particularly limited, but is preferably in the range of 0.7 to 1.3, More preferably, it is 0.8-1.2. If this range is exceeded, the characteristics may change over time.

  In addition, also when not using a phenol-type resin as an epoxy resin hardening | curing agent, the compounding quantity and equivalent ratio of a polyimide resin and an epoxy resin can be made the same as the above.

  Furthermore, the adhesive composition of the present invention includes fillers such as silica fine powder, alumina, titanium oxide, carbon black, and conductive particles, inorganic or organic, within a range not impairing the effects of the present invention. Colorants such as pigments and dyes, additives such as wetting improvers, antioxidants and heat stabilizers can be added depending on the purpose.

  The adhesive composition of the present invention can be prepared by mixing the above (A) polyimide resin, (B) epoxy resin, (C) epoxy resin curing catalyst, and other components according to a conventional method.

  The method of using the adhesive composition of the present invention obtained above is, for example, dissolving the adhesive composition in an aprotic polar solvent such as toluene, cyclohexanone, NMP, and the like, and applying the solution on a substrate. After drying, the adherend is pressed and cured by heating. In addition, an adhesive composition dissolved in an appropriate concentration in a solvent is applied onto a support substrate and dried to obtain a film in which an adhesive layer is formed (hereinafter referred to as an adhesive film), and this adhesive film is used as a substrate. Can be attached by adhering to the adherend by pressure bonding and heat curing. As this film-forming support substrate, polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil, etc., or those whose surfaces have been subjected to mold release treatment should be used. Can do.

  Drying conditions when the adhesive composition is used as an adhesive layer are preferably from room temperature to 200 ° C., particularly 80 to 150 ° C., for 1 minute to 1 hour, particularly 3 to 10 minutes.

  The film thickness of this adhesive layer is not particularly limited and can be selected according to the purpose, and is preferably 10 to 100 μm, particularly preferably 15 to 50 μm. Moreover, as the curing conditions of the adhesive layer, after pressure bonding at a pressure of 0.01 to 10 MPa, particularly 0.1 to 2 MPa, the temperature is 100 to 200 ° C., particularly 120 to 180 ° C. for 30 minutes to 5 hours, especially 1 to It is preferable to cure in 2 hours.

  The adhesive composition of the present invention can be used not only in the production of electronic components but also in various processes involving adhesion.

EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Synthesis of polyimide resin containing epoxy group [Synthesis Example 1]
A 1-L separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer, and a stirrer contains 18.2 mol% of vinyl groups based on the total organic groups bonded to silicon atoms. Following formula

で示されるビニルメチルジアミノポリシロキサン５４．４８質量部（アミン当量４５４）、反応溶媒として２−メチルピロリドン６０質量部を仕込み、撹拌し、ジアミンを分散させた。酸無水物として６ＦＤＡ（２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン）４４．４２質量部を２−メチルピロリドン１４０質量部に溶解した溶液を滴下して室温にて２時間撹拌反応を行うことにより、酸無水物リッチのアミック酸オリゴマーを合成した。

Was charged with 54.48 parts by mass of vinylmethyldiaminopolysiloxane (amine equivalent 454) and 60 parts by mass of 2-methylpyrrolidone as a reaction solvent, and the diamine was dispersed. A solution prepared by dissolving 44.42 parts by mass of 6FDA (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane) in 140 parts by mass of 2-methylpyrrolidone as an acid anhydride was added dropwise at room temperature for 2 hours. By carrying out a stirring reaction, an acid anhydride-rich amic acid oligomer was synthesized.

に示すフェノール性水酸基を有する芳香族ジアミン（ジアミン−１）１９．７９質量部と２−メチルピロリドン１５６質量部を還流冷却器が連結されたコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１Ｌのセパラブルフラスコに仕込み、分散させ、前出の酸無水物リッチのアミック酸オリゴマーを滴下した後、室温で１６時間撹拌し、ポリアミック酸溶液を合成した。その後、キシレン５０ｍｌを投入してから温度を上げ、約１８０℃で２時間還流させた。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、１８０℃でキシレンを除去した。反応終了後、大過剰のメタノール中に得られた反応液を滴下してポリマーを析出させ、減圧乾燥して骨格中にフェノール性の水酸基を有するポリイミド樹脂を得た。 Next, the following formula

A 25 ml water quantitative receiver, thermometer, and stirrer with a reflux condenser connected to 19.79 parts by mass of an aromatic diamine (diamine-1) having a phenolic hydroxyl group and 156 parts by mass of 2-methylpyrrolidone Was added to a 1 L separable flask and dispersed, and the above-mentioned acid anhydride-rich amic acid oligomer was added dropwise, followed by stirring at room temperature for 16 hours to synthesize a polyamic acid solution. Thereafter, 50 ml of xylene was added, the temperature was raised, and the mixture was refluxed at about 180 ° C. for 2 hours. Confirm that the specified amount of water has accumulated in the moisture meter and that no water has flowed out, and remove xylene at 180 ° C while removing the effluent collected in the meter. did. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer and dried under reduced pressure to obtain a polyimide resin having a phenolic hydroxyl group in the skeleton.

When an infrared absorption spectrum of the obtained polyimide resin was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and based on imide groups at 1,780 cm ⁻¹ and 1,720 cm ^−1. Absorption was confirmed, and absorption based on a phenolic hydroxyl group was confirmed at 3,500 cm ⁻¹ .

で示される分子中にケイ素原子結合水素原子とエポキシ基を有するオルガノハイドロジェンポリシロキサン４１．２１質量部、白金量が２５ｐｐｍとなるような塩化白金酸の２−エチルヘキサノール変性溶液を添加し、８０℃で３時間撹拌し、付加反応させた。反応終了後、大過剰のメタノール中に得られた反応液を滴下してポリマーを析出させ、減圧乾燥してエポキシ基を含有するポリイミド樹脂−Ｉを得た。 100 parts by mass of this polyimide resin is dissolved in 565 parts by mass of cyclohexanone, and the following structural formula

41.21 parts by mass of an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group in the molecule represented by the above, and a 2-ethylhexanol-modified solution of chloroplatinic acid so that the platinum amount is 25 ppm, The mixture was stirred at 0 ° C. for 3 hours to cause addition reaction. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer and dried under reduced pressure to obtain a polyimide resin-I containing an epoxy group.

  A small amount of the obtained polyimide resin solution was dropped into a large excess of methanol to precipitate a polymer, dried under reduced pressure, and measured for an NMR spectrum. Absorption based on the vinyl group was reduced to 18% before the reaction, It was confirmed that an epoxy group was introduced by the addition reaction.

[Synthesis Example 2]
In Synthesis Example 1, 54.72 parts by mass (amine equivalent) of vinylmethyldiaminopolysiloxane having the structure of Synthesis Example 1 containing 9.1 mol% of vinyl groups of all organic groups bonded to silicon atoms as vinylmethyldiaminopolysiloxane. 456) and 2-methylpyrrolidone as a reaction solvent were used in the same manner as in Synthesis Example 1 except that 357 parts by mass (total amount) was used.

  100 parts by mass of this polyimide resin is dissolved in 510 parts by mass of cyclohexanone, 27.47 parts by mass of organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group in the molecule of Synthesis Example 1, and the platinum amount is 25 ppm. A 2-ethylhexanol-modified solution of chloroplatinic acid was added and stirred at 80 ° C. for 3 hours to cause addition reaction. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer and dried under reduced pressure to obtain a polyimide resin-II containing an epoxy group.

  As a result of measuring the NMR spectrum of the obtained polyimide resin in the same manner as in Synthesis Example 1, it was confirmed that the absorption based on the vinyl group was reduced to 20% before the reaction, and the epoxy group was introduced by the addition reaction.

[Synthesis Example 3]
In Synthesis Example 1, 66.01 parts by mass (amine equivalent) of vinylmethyldiaminopolysiloxane having the structure of Synthesis Example 1 containing 9.5 mol% of vinyl groups of all organic groups bonded to silicon atoms as vinylmethyldiaminopolysiloxane. 826), according to Synthesis Example 1 except that 29.68 parts by mass of aromatic diamine having a phenolic hydroxyl group (diamine-1) and 421 parts by mass (total amount) of 2-methylpyrrolidone as a reaction solvent were used. Thus, a polyimide resin was obtained.

で示される分子中にケイ素原子結合水素原子とエポキシ基を有するオルガノハイドロジェンポリシロキサン２９．０質量部、白金量が２５ｐｐｍとなるような塩化白金酸の２−エチルヘキサノール変性溶液を添加し、８０℃で３時間撹拌し、付加反応させた。反応終了後、大過剰のメタノール中に得られた反応液を滴下してポリマーを析出させ、減圧乾燥してエポキシ基を含有するポリイミド樹脂−ＩＩＩを得た。 100 parts by mass of this polyimide resin is dissolved in 514 parts by mass of cyclohexanone, and the following structural formula

29.0 parts of an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group in the molecule represented by formula (2), and a 2-ethylhexanol-modified solution of chloroplatinic acid so that the platinum amount is 25 ppm, The mixture was stirred at 0 ° C. for 3 hours to cause addition reaction. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer and dried under reduced pressure to obtain a polyimide resin-III containing an epoxy group.

  As a result of measuring the NMR spectrum of the obtained polyimide resin in the same manner as in Synthesis Example 1, it was confirmed that the absorption based on the vinyl group was reduced to 16% before the reaction, and the epoxy group was introduced by the addition reaction.

で示される分子中にケイ素原子結合水素原子とエポキシ基を有するオルガノハイドロジェンポリシロキサン６９．６８質量部、白金量が２５ｐｐｍとなるような塩化白金酸の２−エチルヘキサノール変性溶液を添加し、８０℃で４時間撹拌し、付加反応させた。反応終了後、大過剰のメタノール中に得られた反応液を滴下してポリマーを析出させ、減圧乾燥してエポキシ基を含有するポリイミド樹脂−ＩＶを得た。 [Synthesis Example 4]
In Synthesis Example 2, 100 parts by mass of the obtained polyimide resin was dissolved in 675 parts by mass of cyclohexanone, and the following structural formula

69.68 parts by mass of an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group in the molecule represented by the above, and a 2-ethylhexanol-modified solution of chloroplatinic acid so that the platinum amount is 25 ppm, The mixture was stirred at 4 ° C. for 4 hours to cause addition reaction. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer and dried under reduced pressure to obtain a polyimide resin-IV containing an epoxy group.

  As a result of measuring the NMR spectrum of the obtained polyimide resin in the same manner as in Synthesis Example 1, it was confirmed that the absorption based on the vinyl group was reduced to 15% before the reaction, and the epoxy group was introduced by the addition reaction.

[Synthesis Example 5]
In Synthesis Example 1, 51.8 parts by mass (amine equivalent 432) of diaminosiloxane having the following structure not containing a vinyl group as diaminosiloxane and 348 parts by mass (total amount) of 2-methylpyrrolidone as a reaction solvent were used. Except that, polyimide resin-V was obtained according to Synthesis Example 1.

[Synthesis Example 6]
In Synthesis Example 1, 64.32 parts by mass (amine equivalent 804) of diaminosiloxane having a structure used in Synthesis Example 5 that does not contain a vinyl group as diaminosiloxane, 29.68 of aromatic diamine (diamine-1) having a phenolic hydroxyl group A polyimide resin-VI was obtained in the same manner as in Synthesis Example 1 except that 415 parts by mass (total amount) was used as the part by mass and the amount of 2-methylpyrrolidone that is a reaction solvent.

[Examples 1 to 4 , Reference Example 1 , Comparative Examples 1 and 2]
50 parts by mass of the polyimide resins I to VI obtained in Synthesis Examples 1 to 6 were dissolved in 50 parts by mass of cyclohexanone, and liquid epoxy resin RE310S or NC3000 (manufactured by Nippon Kayaku Co., Ltd.) was added to these solutions shown in Table 1 below. Imidazole-based curing catalyst 2PHZ (manufactured by Shikoku Kasei Co., Ltd.) was mixed in the blending amounts shown in Table 1 below to prepare adhesive compositions-I to VII.

  The adhesive compositions-I to VII obtained above are applied onto a PET film having a thickness of 50 μm coated with a fluorosilicone release agent, and heated and dried at 80 ° C. for 30 minutes to form an adhesive layer of about 50 μm. An adhesive film was prepared. Let the film produced from each adhesive composition-I-VII be adhesive film-I-VII.

  Using the adhesive films -I to VII, the properties of the cured adhesive film (Young's modulus, adhesiveness of the sealing resin to the cured adhesive resin, adhesiveness with the Ag substrate, adhesiveness after wet heat) were evaluated by the following methods. These results are also shown in Table 1.

Young's modulus The adhesive film obtained above was heat-treated at 175 ° C for 1 hour and cured. The dynamic viscoelastic modulus was measured for a 20 mm × 5 mm × 50 μm film. A dynamic viscoelasticity measuring device was used for the measurement, and the Young's modulus was measured under the conditions of a tension mode, a distance between chucks of 15 mm, a measurement temperature of 25 ° C., and a measurement frequency of 30 Hz.

Adhesiveness of sealing resin to cured adhesive The adhesive layer surface of the adhesive film obtained above was fixed by thermocompression bonding to an 18 mm × 18 mm Cu test piece at 80 ° C. and 0.01 MPa for 10 seconds, and then 175 The heat resistant resin layer was cured by heat treatment at 1 ° C. for 1 hour. Next, sealing resin KMC-2520VA-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) was molded into a truncated cone shape at 175 ° C. using a transfer molding machine as shown in FIG. The sealing resin layer was cured by heat treatment. This sample was measured for shear adhesive force between the sealing resin and the adhesive using a bond tester (manufactured by Daisy, UK). Here, in FIG. 1, 1 is sealing resin, 2 is an adhesive agent, 3 is Cu board.

Adhesion with Ag substrate The adhesive film obtained above was cut into 5 mm x 5 mm, and the adhesive layer surface was thermocompression bonded on an 18 mm x 18 mm Ag-plated Cu plate at 80 ° C and 0.01 MPa for 10 seconds. After fixing, the PET film substrate was peeled off, and an 18 mm × 18 mm Ag-plated Cu plate was again thermocompression bonded under the same conditions as described above and fixed. The pressure-bonded laminate was heat-treated at 175 ° C. for 1 hour to cure the heat-resistant resin layer, thereby preparing an adhesive test piece. Thereafter, the shear adhesive force was measured at a speed of 2.0 mm / min using an autograph tensile tester manufactured by Shimadzu Corporation.

Adhesiveness after wet heat After holding the above-mentioned test piece for adhesion under the conditions of 85 ° C./85% RH for 168 hours, using an autograph tensile tester manufactured by Shimadzu Corporation at a speed of 2.0 mm / min. Shear adhesion was measured.

ＲＥ−３１０Ｓ：ビスフェノールＡ型エポキシ樹脂、日本化薬社製
ＮＣ−３０００：ビフェニルアラルキル型エポキシ樹脂、日本化薬社製
２ＰＨＺ：２−フェニル−４，５−ジヒドロキシメチルイミダゾール、四国化成社製
＊試験試料を作製時（封止樹脂モールド時）に封止樹脂が剥離し、測定不能。

RE-310S: Bisphenol A type epoxy resin, Nippon Kayaku Co., Ltd. NC-3000: Biphenyl aralkyl type epoxy resin, Nippon Kayaku Co., Ltd. 2PHZ: 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Kasei Co., Ltd. * Test The sealing resin peels off when the sample is manufactured (sealing resin mold), and measurement is impossible.

In the Example of this invention, it is a schematic perspective view of the sample which measures the adhesiveness of an adhesive agent and sealing resin.

Explanation of symbols

1 Sealing resin 2 Adhesive 3 Cu plate

Claims (5)

(A) (i) a polyimide resin containing a diorganopolysiloxane bond having a vinyl group as an organic substituent in the main chain;
(Ii) (iii) a polyimide resin having an epoxy group-containing diorganopolysiloxane bond obtained by addition reaction of an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom and an epoxy group with a platinum-based catalyst in the molecule;
An adhesive composition containing (B) an epoxy resin and (C) an epoxy resin curing catalyst as an essential component,
The (i) polyimide resin is
(I-1) tetracarboxylic dianhydride;
(I-2) Diaminopolysiloxane represented by the following structural formula (3), wherein at least one of all organic groups bonded to the silicon atom is a vinyl group, and a diamine containing a diamine represented by the following formula (4) Compound and
Obtained by dehydrating and ring-closing the polyamic acid resin obtained by the reaction,

(In the formula, R ¹ is a divalent organic group having 3 to 9 carbon atoms, R ^{2 to} R ⁶ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms other than vinyl group, n is 0 or an integer of 1 or more, m is an integer of 1 or more, and n + m is an integer of 1 to 100.)

(In the formula, R ⁷ is independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.)
The above (ii) organohydrogenpolysiloxane has the following structural formula (1) and / or (2)

An organohydrogenpolysiloxane represented by:
The above-mentioned (A) polyimide resin is a polyimide resin having an epoxy group-containing diorganopolysiloxane bond having a phenolic hydroxyl group in the polymer skeleton of the polyimide resin. The blending amount of the (B) component epoxy resin is 5 to 400 parts by weight with respect to 100 parts by weight of the (A) component polyimide resin, and the blending amount of the (C) component epoxy resin curing catalyst is (B). The adhesive composition according to claim 1, which is 0.1 to 10 parts by mass with respect to 100 parts by mass of the component epoxy resin. (I-2) The proportion of diaminopolysiloxane represented by the structural formula (3) in the diamine compound and having at least one of all organic groups bonded to the silicon atom is a vinyl group is 1 to 80 mol%. The adhesive composition according to claim 1 or 2. (I-2) The adhesive composition according to claim 1, 2 or 3, wherein the ratio of the diamine represented by the formula (4) in the diamine compound is 5 to 60% by mass. The adhesive film obtained using the adhesive composition of any one of Claims 1-4 .

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