JP4577895B2 - Adhesive composition and adhesive film - Google Patents

Description

  The present invention relates to an adhesive composition, and in particular, a polyimide silicone adhesive having a significantly improved elastic modulus by including a hydrogenated 1,2-polybutadiene resin and / or a hydrogenated 1,2-polybutadiene derivative resin. The present invention relates to an agent composition and an adhesive film obtained using the composition.

  The semiconductor device (i) divides a large-diameter silicon wafer on which an IC circuit is formed into semiconductor chips in a dicing (cutting) process, and (ii) leads the chip with a curable liquid adhesive (die bond material) or the like. It is manufactured by thermocompression bonding to a frame (mounting), (iii) after wire bonding between electrodes, and (iv) sealing to improve 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 resin. At present, the latter method, particularly the transfer molding method using a resin, is most commonly used because it is excellent in mass productivity and inexpensive.

  As the semiconductor package becomes more compact year by year, such as a packaging structure (CSP) of the same size as the chip and a packaging structure in which chips are stacked (stacked CSP, SiP), the thermal stress resistance in packaging is severe. It has become to.

  Furthermore, lead-free solder is used in the process of mounting and mounting these semiconductor devices on a printed circuit board, and high-temperature (265 ° C.) reflow resistance corresponding to the solder is also required.

  In the packaging constituent material, the die bond material can control the characteristics in a relatively wide range, and therefore, low elastic modulus, high adhesion, and high heat resistance that can cope with severe thermal stress are required. With the miniaturization of semiconductor circuits, a film-like adhesive or an adhesive film is desired as a die bond material instead of a conventional liquid adhesive. This is because the adhesive film can be used to prevent problems caused by the liquid adhesive, such as protrusion from the end of the chip, tilting of the chip due to uneven thickness, and wire bond defects. is there.

  As an adhesive, a low elastic modulus material in which a siloxane structure is introduced into polyimide or polyamideimide which is a resin having excellent heat resistance is known (for example, Patent Document 1 and Patent Document 2). However, these resins need improvement in terms of elastic modulus and adhesion to the substrate.

  Moreover, the composition which mix | blended the compound which has two or more maleimide groups with a siloxane modified polyamide imide, and improved the high temperature characteristic is known (patent document 3). However, this composition has poor adhesion.

  A heat-resistant adhesive film made of polyimide silicone and epoxy resin is also known (Patent Document 4, Patent Document 5). The film is excellent in adhesiveness but has a problem in terms of elastic modulus.

An adhesive in which a butadiene-acrylonitrile copolymer is added to a composition of a polyimide silicone resin and an epoxy resin in order to lower the elastic modulus is known (Patent Document 6), but the compatibility between the resins is poor. For this reason, when applied to a film, the surface is uneven, and the rubbery high molecular weight component is separated over time.
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 JP-A-2003-193016

  The present invention has been made in view of the above circumstances, and provides an adhesive composition that provides a cured product having excellent adhesiveness, low elastic modulus, and excellent heat resistance, and an adhesive film including the adhesive layer. For the purpose.

  As a result of intensive studies to achieve the above object, the present inventors blended a hydrogenated 1,2-polybutadiene derivative resin with an adhesive composition containing a polyimide resin, an epoxy resin, and an epoxy resin curing catalyst. As a result, the inventors have found that the above object can be achieved, and have made the present invention.

That is, the present invention
(A) 100 parts by mass of a polyimide resin having a diorganopolysiloxane residue in the main chain,
(B) 5 to 200 parts by mass of epoxy resin,
(C) an effective amount of an epoxy resin curing catalyst,
And (D) hydrogenated 1,2-polybutadiene resin and / or hydrogenated 1,2-polybutadiene derivative resin (A), (B) and (C) in a total amount of 100 to 100 parts by mass,
And an adhesive film provided with an adhesive layer made of the composition.

  The adhesive composition of the present invention is excellent in stability over time, and is coated on a base film to form a smooth surface coating film. The adhesive exhibits high adhesion to the chip and various substrates, and gives a cured product having a low elastic modulus and high heat resistance by heating.

The adhesive composition of the present invention comprises (D) a hydrogenated 1,2-polybutadiene resin and / or a hydrogenated 1,2-polybutadiene derivative resin (hereinafter referred to as “resin (D)”). Resin (D) is mixed with (A) polyimide resin and (B) epoxy resin to form a uniform composition and to have an effect of reducing the elastic modulus of the cured product. As the resin (D), hydrogenated 1,2-polybutadiene resin (trade names BI-2000, BI-3000, manufactured by Nippon Soda Co., Ltd.), hydrogenated 1,2-polybutadiene derivative resin having a reactive functional group For example, those having epoxy groups at both ends (trade name EPB-13, manufactured by Nippon Soda Co., Ltd.), those having carboxyl groups at both ends (C-1000, manufactured by Nippon Soda Co., Ltd.), alcoholic hydroxyl groups (GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.)) and groups reactive with resins having these functional groups, such as isocyanate groups, amino groups, and A hydrogenated 1,2-polybutadiene derivative obtained by reacting with a compound having an alcoholic hydroxyl group, etc., can also be used. Functional group that reacts with, for example, hydrogenated 1,2-polybutadiene derivative resins containing epoxy groups and / or carboxyl groups, are preferred.

The compounding quantity of resin (D) is 5-100 mass parts with respect to 100 mass parts of (A), (B), (C) component total amount of this invention, Preferably it is 10-50 mass parts. The composition containing the resin (D) less than the lower limit value may have an excessively high elastic modulus of the cured product. On the other hand, the composition containing the resin (D) exceeding the upper limit may have low adhesion.

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の整数であり、Ｙの少なくとも1つがジオルガノポリシロキサン残基である。 In the present invention, as the (A) polyimide resin having a diorganopolysiloxane residue in the main chain, a polyamic acid resin represented by the following general formula (3), which is a precursor thereof, can also be used.

In the formula, X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, Y is a divalent organic group, q is an integer of 1 to 300, and at least one of Y is a diorganopolysiloxane residue. is there.

（式中、Ｘ、Ｙ及びｑは上で定義したとおりである。） However, since water may be generated as a by-product due to imidization (dehydration ring closure) during heat-curing in the die bonding step, peeling of the adhesive surface may occur, and therefore, it is represented by the following general formula (4) that has been imidized (dehydration ring closure) in advance. It is preferable to use a polyimide resin.

(Wherein X, Y and q are as defined above.)

  In the general formula (3), 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 can be prepared by the following method. A polyimide resin represented by the above general formula (4) can be obtained by dehydrating and ring-closing the resulting polyamic resin by a conventional method.

（但し、Ｘは上で定義したとおりである。）
で表されるテトラカルボン酸二無水物と、下記構造式（６）
Ｈ₂Ｎ−Ｙ−ＮＨ₂ （６）
（但し、Ｙは上で定義したとおりである。）
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 (3) has the following structural formula (5).

(However, X is as defined above.)
A tetracarboxylic dianhydride represented by the following structural formula (6)
H ₂ N—Y—NH ₂ (6)
(However, Y is as defined above.)
According to a conventional method, the diamine can be obtained by reacting in a substantially equimolar amount in an organic solvent.

Here, although the example of the tetracarboxylic dianhydride represented by the said Formula (5) is shown, it is not limited to these. Moreover, you may use 2 or more types of these tetracarboxylic dianhydrides as a mixture.

  The diorganopolysiloxane residue in the main chain of the polyimide resin (A) is preferably derived from a diaminosiloxane compound represented by the following formula (1). More preferably, from the viewpoint of solubility in an organic solvent, adhesion to a substrate, low elasticity, and flexibility, 1 to 80 mol%, more preferably 1 to 60 mol% of the total diamine amount is represented by the following structural formula. It is a diaminosiloxane compound (or α, ω-diaminopolysiloxane) represented by (1).

（式中、Ｒ³は炭素原子数３〜９の二価の有機基、Ｒ⁴及びＲ⁵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り、ｍは１〜２００の整数である。）

Wherein R ³ is a divalent organic group having 3 to 9 carbon atoms, R ⁴ and R ⁵ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and m is 1 to (It is an integer of 200.)

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、及び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二価炭化水素基が包含される。 In the formula (1), as R ³ , for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ CH (CH ₃ ) —, — (CH ₂ ) ₆ —, — (CH _{2) 8} - such as an alkylene group,

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 combinations thereof

And other divalent hydrocarbon groups such as oxyalkylene and arylene groups.

Examples of R ⁴ and R ⁵ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, and octyl group. Allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, alkenyl group such as hexenyl group, aryl group such as phenyl group, tolyl group, xylyl group, aralkyl group such as benzyl group, phenylethyl group, etc. Groups in which some or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., for example, chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group And halogen-substituted alkyl groups such as methyl group and phenyl group are preferable.

Examples of other diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2′-bis (4-aminophenyl) propane, 4 , 4′-diaminodiphenyl sulfone, 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-aminophenylthioether) 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-aminophenoxy) 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-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis Aromatic ring-containing diamines such as [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] 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, and the like.
These diamino compounds can be used alone or in combination of two or more.

From the viewpoint of adhesiveness, the (A) polyimide resin preferably further contains an aromatic compound residue having a phenolic hydroxyl group in the main chain. The residue can be derived from a diamine compound having a phenolic hydroxyl group, and examples thereof include the following.

（式中、Ｒ⁷は独立に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、トリフルオロメチル基、フェニル基などの非置換又は置換一価炭化水素基であり、各芳香族環に付いている置換基は全て同じでも、異なっていてもよい。ここでｎは０〜５の整数である。Ａ、Ｂはそれぞれ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, or the like. It is a substituted or substituted monovalent hydrocarbon group, and all the substituents attached to each aromatic ring may be the same or different, where n is an integer of 0 to 5. A and B are each 2 And R may be 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 R ⁴ and R ⁵ above, and also an ethynyl group, propynyl group, butynyl group. And alkynyl groups such as a hexynyl group. Further, the unsubstituted or substituted monovalent hydrocarbon group for R can be exemplified by the same groups as those exemplified for R ⁷ above.

（式中、Ｒ⁷は上記と同じである。） Among the diamine compounds having a phenolic hydroxyl group, a diamine compound represented by the following formula (2) is particularly preferable.

(Wherein R ⁷ is the same as above)

  The amount of the diamine compound having a phenolic hydroxyl group is preferably 5 to 80 mol%, particularly 10 to 60 mol% of the entire diamine compound. When the amount is less than the lower limit, the effect of improving the adhesive strength of the composition may be insufficient. When the amount exceeds the upper limit, the coating film, that is, the flexibility of the adhesive layer is insufficient. There is.

（式中、Ｒ⁷は上記のとおりであり、各芳香族環に付いている置換基は全て同じでも異なっていてもよい。Ｄは１種でも２種を併用してもよい。また、ｐは１〜３の整数である。） A monoamine having a phenolic hydroxyl group can be used for introducing a phenolic hydroxyl group, and the following structures can be exemplified.

(In the formula, R ⁷ is as described above, and the substituents attached to each aromatic ring may be the same or different. D may be used alone or in combination of two. Is an integer from 1 to 3.)

  The monoamine having a phenolic hydroxyl group is used in an amount of 1 to 10 mol% based on the entire diamine compound. Moreover, you may use it as a mixture of 2 or more types.

  As an example of the formation reaction of the polyamic acid resin and the polyimide resin, 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. Synthesize the resin. 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 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 addition, in order to adjust the molecular weight of polyamic acid and polyimide resin, dicarboxylic acid anhydrides such as maleic anhydride and phthalic anhydride and / or aniline, n-butylamine, and monoamines having the above-mentioned phenolic hydroxyl groups 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.

  As the (B) epoxy resin used in the present invention, one having at least two epoxy groups in one molecule is preferable. Examples of such epoxy resins include, for example, bis (4-hydroxyphenyl) methane, 2,2′-bis (4-hydroxyphenyl) propane, or halides thereof, diglycidyl ethers and polycondensates thereof ( So-called bisphenol F type epoxy resin, bisphenol A type epoxy resin), 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 , Polyphenols or Epoxy novolaks obtained by condensing epoxy glycidyl ether or polyglycidyl ester, phenol novolak, cresol novolak and other novolak type phenol resins (or halogenated novolak type phenol resins) 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.

  A monoepoxy compound may be appropriately used in combination, for example, styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide, etc. Can be mentioned. These epoxy resins may be used alone or in combination of two or more.

  (B) As for the compounding quantity of an epoxy resin, 5-200 mass parts is preferable with respect to 100 mass parts of (A) polyimide resin, and it is especially preferable that it is 10-100 mass parts. When the blending amount of the epoxy resin is less than the lower limit value, the adhesive strength of the composition may be inferior, and when the upper limit value is exceeded, the flexibility of the adhesive layer may be insufficient.

  A well-known thing can be used as an epoxy resin curing catalyst (C) used by this invention, For example, a phosphorus catalyst, an amine catalyst, etc. are illustrated.

（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。） Examples of the phosphorus catalyst include triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate, and compounds as shown below.

(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) A non-substituted or substituted monovalent hydrocarbon group such as a group, a trifluoromethyl group or 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 dicyandiamide, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. It is done.

  These epoxy resin curing catalysts can be used alone or in combination of two or more. The compounding amount of the epoxy resin curing catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin. It is.

The composition of this invention may mix | blend the hardening | curing agent for epoxy resins. As the curing agent, various conventionally known ones can be used, such as diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, Amine compounds such as metaxylylenediamine, menthanediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; epoxy resin-diethylenetriamine adduct, amine -Modified aliphatic polyamines such as ethylene oxide adducts, cyanoethylated polyamines; bisphenol A, trimethylol allyloxyphenol, low polymerization degree phenol novolac resins, epoxidized or butylated phenolic resins or "Super B" eckcite "1001 (manufactured by Nippon Reichhold Chemical Co., Ltd.)," Hitanol "4010 (manufactured by Hitachi, Ltd.), Scadoform 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, a phenolic resin (phenol novolac resin) is desirable because it provides good molding workability, provides excellent moisture resistance, is non-toxic and is relatively inexpensive. 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.

Although the usage-amount of this hardening | curing agent is suitably adjusted, generally it is 1-100 mass parts with respect to 100 mass parts of said epoxy resins, More typically, it is the range of 5-50 mass parts. 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.

  Furthermore, the composition of the present invention includes fillers such as silica fine powder, alumina, titanium oxide, carbon black, conductive particles, inorganic or organic pigments, and the like within a range not impairing the effects of the present invention. Additives such as coloring agents such as dyes, wetting improvers, antioxidants and heat stabilizers can be added according to the purpose.

  The adhesive composition of the present invention comprises the above (A) polyimide resin, (B) epoxy resin, (C) epoxy resin curing catalyst, (D) hydrogenated 1,2-polybutadiene resin, and other components as desired. It can be prepared by mixing according to a conventional method.

  The adhesive composition of the present invention can be used, for example, by dissolving the adhesive composition in an aprotic polar solvent such as toluene, cyclohexanone, or NMP at an appropriate concentration, coating the substrate, drying it, and applying the adhesive composition. Crimp the body and heat cure. 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. It is also possible to bond by adhering to the adherend and heat curing. As the support substrate, polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil or the like, or those obtained by releasing the surface can be used. .

  As drying conditions after apply | coating an adhesive composition, it is preferable to set it as normal temperature -200 degreeC, especially 80-150 degreeC for 1 minute-1 hour, especially 3-10 minutes. There is no restriction | limiting in particular in the film thickness of an adhesive bond layer, It can select according to the objective, Usually, it is 10-100 micrometers, Preferably it is 15-50 micrometers. 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 can be cured 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 including an adhesion process.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these Examples.

Synthesis of polyimide resin [Synthesis Example 1]
Into a 1 L separable flask equipped with a 25 ml water quantitative receiver with a cock connected to a reflux condenser, a thermometer, and a stirrer, diaminosiloxane having the following structure: KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 421) 44 0.03 part by mass and 100 parts by mass of 2-methylpyrrolidone as a reaction solvent were added and stirred at 80 ° C. to disperse diaminosiloxane. A solution of 38.72 parts by mass of 6FDA (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 100 parts by mass of 2-methylpyrrolidone as an acid anhydride was added dropwise thereto at room temperature. An acid anhydride-rich amic acid oligomer was synthesized by performing a time stirring reaction.

で示されるフェノール性水酸基を有する芳香族ジアミン１７．２５質量部と１００質量部の２−メチルピロリドンを環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、攪拌器を備えた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時間攪拌し、ポリアミック酸溶液を合成した。その後、キシレン２５ｍｌを投入してから温度を上げ、約１８０℃で２時間環流させた。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、得られた反応液を大過剰のメタノール中に滴下し、ポリマーを析出させ、減圧乾燥してポリイミド樹脂を得た。 Next, the following formula

A 25 ml water quantitative receiver, thermometer, and stirrer with 17.25 parts by mass of an aromatic diamine having a phenolic hydroxyl group represented by formula (1) and 100 parts by mass of 2-methylpyrrolidone connected to a reflux condenser were provided. A 1 L separable flask was charged and dispersed, and the above 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, 25 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 obtained reaction solution was dropped into a large excess of methanol to precipitate a polymer and dried under reduced pressure to obtain a polyimide resin.

When obtained was measured infrared absorption spectrum of the polyimide resin, the absorption based on polyamic acid does not appear, check the absorption based on imide group in 1780 cm ^-1 and 1720 cm ^-1, due to phenolic hydroxyl 3500 cm ^-1 Absorption was confirmed.

Examples 1-5, Comparative Examples 1-2
50 parts by mass of (A) polyimide resin obtained in Synthesis Example 1 was dissolved in 50 parts by mass of cyclohexanone, and (B) epoxy resin (bisphenol A type epoxy resin, RE310S (trade name), Nippon Kayaku Co., Ltd. or Epicoat 834 (trade name), Japan Epoxy Resin Co., Ltd.), (C) Epoxy curing catalyst (Dicyandiamide (DICY), Shikoku Kasei Co., Ltd.), (D) Hydrogenation Polybutadiene resin (hydrogenated 1,2-polybutadiene derivative resin having epoxy groups at both ends, EPB-13 (trade name), manufactured by Nippon Soda Co., Ltd. or hydrogenated 1,2-polybutadiene derivatives having carboxy groups at both ends Resin, C-1000 (trade name), 70 mass% cyclohexanone solution manufactured by Nippon Soda Co., Ltd.) are mixed in the mass part (solid content) shown in the table, and an adhesive The Narubutsu was prepared.
As a comparative example, a composition containing no hydrogenated polybutadiene resin and a 70% by mass cyclohexanone solution of a butadiene-acrylonitrile copolymer (CTBN 1300 × 31, carboxyl group-containing polymer, manufactured by Ube Industries) instead of the hydrogenated polybutadiene resin are included. A composition was prepared.

Stability of resin composition with time Stability of each composition obtained was evaluated. Each composition was allowed to stand for 4 hours, and visually observed whether or not there was any separation, etc., G was evaluated when no phase separation was observed, and NG was evaluated when phase separation was observed.

  Next, each composition was applied onto a PET film having a thickness of 50 μm coated with a fluorine-based silicone release agent, and dried by heating at 120 ° C. for 10 minutes to form an adhesive film having an adhesive layer having a thickness of about 50 μm. Produced.

Surface state of adhesive layer The surface of the adhesive layer on each of the obtained films was visually observed, and the surface having a smooth surface was evaluated as G, and the surface with unevenness was observed as NG.

  Furthermore, for each adhesive film, the properties of the cured adhesive film (Young's modulus, glass transition point, reduced heating weight, adhesiveness of the sealing resin to the cured adhesive resin, adhesiveness to the substrate, adhesiveness after wet heat) are described below. It was evaluated by.

Young's modulus Each adhesive film was cured by heating at 175 ° C. for 1 hour. A 20 mm × 5 mm × 50 μm film was cut out, and the Young's modulus was measured using a dynamic viscoelasticity measuring device under the conditions of tension mode, distance between chucks of 15 mm, measurement temperature of 25 ° C., and measurement frequency of 30 Hz.

Glass transition point Each adhesive film was cured by heating at 175 ° C. for 1 hour. A 20 mm × 5 mm × 50 μm film was cut out, and using a thermomechanical property measuring device TMA-2000 (manufactured by ULVAC-RIKO), a tension mode, a distance between chucks of 15 mm, a measuring temperature of 25 to 300 ° C., and a heating rate of 10 ° C./min. The glass transition point was measured under the condition of a measurement load of 10 g.

Heat Weight Reduction Temperature Each adhesive film was cured by heating at 175 ° C. for 1 hour. The film was measured for weight loss by heating under nitrogen using a TGA measuring device (manufactured by Rigaku Denki Co., Ltd., differential type differential thermal balance, TG8120) to determine the temperature at which the weight loss was 5% by mass.

Adhesion test (initial)
Each adhesive film is cut into 5 mm × 5 mm, and the adhesive layer side is heated for 18 seconds to 18 alloy × 18 mm 42 alloy (KAKU-42, 42 alloy test piece manufactured by Toppan Printing Co., Ltd.) at 80 ° C. and 0.01 MPa. After fixing by pressure bonding, the PET film was peeled off, and again a test piece of 18 mm × 18 mm 42 alloy was laminated with an adhesive layer so that the overlap with the test piece was 5 mm × 5 mm, It was fixed by thermocompression bonding under the same conditions as described above. The pressure-bonded laminate was heat-treated at 175 ° C. for 4 hours to cure the adhesive layer, thereby preparing an adhesive test piece. Thereafter, shear adhesive strength (MPa) was measured at a speed of 2.0 mm / min using an autograph tensile tester manufactured by Shimadzu Corporation.

Adhesion test after wet heat After holding an adhesive test piece prepared in the same manner as described above for 168 hours under the condition of 85 ° C./85% RH, the above test was performed using an autograph tensile tester manufactured by Shimadzu Corporation. In the same manner, the shear adhesive strength was measured.

The evaluation results are shown in Table 1.

   As can be seen from Table 1, the cured product obtained from the composition of the present invention has substantially the same heat resistance as the composition containing no hydrogenated polybutadiene resin (Comparative Example 1) and has a remarkable Young's modulus. Very low. Moreover, compared with the composition (Comparative Example 2) containing a butadiene-acrylonitrile copolymer, it is excellent in stability over time and gives a coating film with a smooth surface.

   The adhesive composition of the present invention is suitably used for semiconductor die bonding. In addition, it is suitable as an adhesive in applications requiring low elastic modulus and high heat resistance.

Claims (6)

(A) 100 parts by mass of a polyimide resin having a diorganopolysiloxane residue in the main chain,
(B) 5 to 200 parts by mass of epoxy resin,
(C) an effective amount of an epoxy resin curing catalyst,
And (D) hydrogenated 1,2-polybutadiene resin and / or hydrogenated 1,2-polybutadiene derivative resin (A), (B) and (C) in a total amount of 100 to 100 parts by mass,
An adhesive composition comprising: (D) A hydrogenated 1,2-polybutadiene resin and / or a hydrogenated 1,2-polybutadiene derivative resin is contained in an amount of 10 to 50 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C). The adhesive composition according to claim 1. The adhesive composition according to claim 1 or 2, wherein the (D) hydrogenated 1,2-polybutadiene derivative resin has an epoxy group and / or a carboxyl group. The adhesive composition according to any one of claims 1 to 3, wherein the diorganopolysiloxane residue is derived from a diamine compound represented by the following formula (1).

(In the formula, R ³ is a divalent organic group having 3 to 9 carbon atoms, R ⁴ and R ⁵ are monovalent hydrocarbon groups having 1 to 8 carbon atoms which may be substituted; (It is an integer of 200.) The polyimide resin (A) further has an aromatic compound residue having a phenolic hydroxyl group, and the residue is derived from a diamine compound represented by the following formula (2). 5. The adhesive composition according to any one of 4 above.

(In the formula, R ^{7 s} are each independently a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.)   The adhesive film provided with the contact bonding layer which consists of an adhesive composition of any one of Claims 1-5.