JP2008308618A - Adhesive composition and adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition providing a cured product having a low modulus and excellent adhesiveness, and to provide an adhesive film having the adhesive layer. <P>SOLUTION: The adhesive composition comprises (A) 100 pts.mass of a polyimide resin having a diorganopolysiloxane residue having a vinyl group and a phenyl group bound to silicon atoms, (B) 5-200 pts.mass of an epoxy resin, and (C) an epoxy resin-curing catalyst. The adhesive film is obtained by using the adhesive composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

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.

  The semiconductor device divides a large-diameter silicon wafer on which an IC circuit is formed into semiconductor chips in a dicing (cutting) process, and thermocompression-bonds the chips to a lead frame with a curable liquid adhesive (die bond material), The adhesive is hardened and fixed (mounted), and after wire bonding between the electrodes, it is sealed and packaged for improved handling and protection from the external environment. As sealing forms, there are hermetic sealing types such as metal sealing and ceramic sealing, and non-hermetic sealing types using resin. Currently, the latter method, particularly the transfer molding method using resin, is excellent in mass productivity. And because it is inexpensive, it is most commonly used. However, while sealing with resin has the above-mentioned advantages, there is a drawback that the resulting package is inferior in moisture resistance / heat resistance, thermal stress relaxation, heat dissipation, and the like.

  Also, in recent years, due to the demand for higher functionality of electronic components due to the downsizing and multi-functionalization of electrical and electronic equipment, the wiring of semiconductor devices has been miniaturized and increased in density. It has come to have a complicated structure such as a compact structure such as a package (CSP) of the same size or a package in which chips are stacked (stacked CSP, SiP). In such a package, it is difficult to disperse stress (thermal shock), or the stress tends to concentrate locally, and the demand for heat resistance stress in the package has become severe.

  Furthermore, due to the use of lead-free solder in the process of mounting and mounting these semiconductor devices on a printed circuit board, the reflow resistance has become high (265 ° C.), which is becoming severe. For this reason, there is a demand for optimization and high performance of materials used in semiconductor manufacturing. In particular, since the die bond material can control characteristics in a relatively wide range, it can easily meet these requirements. Therefore, there is a demand for a die bond material that can cope with severe thermal shock (stress) and has high adhesion, low elastic modulus, and high heat resistance.

  In addition, there is a demand for miniaturization of the support base (base material) for mounting a semiconductor chip, but if a liquid adhesive is used as a die bond material, contamination and adhesion of electrodes due to protrusion from the chip end when the semiconductor chip is mounted The chip tilt due to the non-uniform thickness of the layer causes a wire bond defect and impairs the reliability of the semiconductor device. Therefore, it is also desired to form an adhesive film so that these defects can be improved.

  As these adhesives, conventionally, siloxane-modified polyamideimide in which a siloxane structure is introduced into polyimide or polyamideimide, which are resins having excellent heat resistance, has been developed as a low elastic modulus material. None of these materials have sufficient adhesion to the substrate.

  Although it has been proposed to improve the high temperature characteristics by blending a siloxane-modified polyamideimide with a compound having two or more maleimide groups (Patent Document 1), this resin composition is inferior in adhesion to a substrate.

  In addition, although heat-resistant adhesive films composed of polyimide silicone and epoxy resin excellent in adhesiveness, low elasticity and heat resistance have been proposed (Patent Documents 2 and 3), characteristics required in packaging (PKG) process steps, That is, the adhesion of the die bond adhesive layer after the adhesive curing to the sealing resin is very poor.

  As an improvement, a heat-resistant adhesive film containing a polyimide silicone in which a vinyl group is introduced as a substituent in a polysiloxane skeleton and an epoxy resin has been proposed (Patent Document 4), but this film is also bonded to a sealing resin. Power is not enough.

In addition, the present inventors previously proposed an adhesive film comprising a polyimide silicone having a specific amount of diorganopolysiloxane residue and the residue having a phenyl silicone as a substituent together with an epoxy resin. (Japanese Patent Application No. 2006-327394). This film is excellent in adhesiveness to the substrate and gives a cured product having a low elastic modulus and heat resistance, but the adhesive strength with the sealing resin is not sufficient.
Japanese Patent Laid-Open No. 10-60111 Japanese Patent Laid-Open No. 7-224259 JP-A-8-27427 JP 2005-89678 A

  The present invention has been made in view of the above circumstances, and in order to eliminate the above-described drawbacks, the present invention is excellent in adhesiveness with a substrate, has low elasticity, excellent heat resistance, and excellent adhesiveness with a sealing resin. It aims at providing the adhesive composition which can become hardened | cured material, and an adhesive film using the same.

  In the adhesive composition containing a polyimide resin, an epoxy resin, and an epoxy resin curing catalyst, the present inventors have used a diorganopolysiloxane residue having a vinyl group and a phenyl group bonded to a silicon atom as the polyimide resin. It has been found that the above object can be obtained by using a resin having a group.

That is, the present invention
(A) 100 parts by mass of a polyimide resin having a diorganopolysiloxane residue having a vinyl group and a phenyl group bonded to a silicon atom,
(B) Epoxy resin The adhesive composition containing 5-200 mass parts and (C) epoxy resin curing catalyst, and an adhesive film using the same are provided.

  The adhesive composition of the present invention is excellent in adhesiveness with a base material, and can give a cured product having a low elastic modulus, excellent heat resistance and excellent adhesiveness with a sealing resin. The obtained adhesive film is useful as a die bond material for producing a highly reliable semiconductor.

  The adhesive composition of the present invention comprises the above components (A) to (C) as essential components, maintains a shape at room temperature, forms a film-like thin film, and cures through a plastic state by heating. The composition exhibits excellent adhesion to the substrate, and the cured product has low elasticity and high adhesion to the sealing resin.

  Each component will be described below.

The component (A) is a polyimide resin having a diorganopolysiloxane residue having a vinyl group and a phenyl group bonded to a silicon atom. As the polyimide resin, a polyamic acid resin represented by the following general formula (3), which is a precursor thereof, can be used, but water is a by-product due to imidization (dehydration ring closure) during heat curing in the die bonding process. However, since peeling of the adhesive surface may occur, it is preferable to use a polyimide resin represented by the following general formula (4) that has been imidized (dehydrated and closed) in advance.

（式中、Ｘは芳香族環又は脂肪族環を含む四価の有機基であり、Ｙは二価の有機基であり、ｋは１〜３００、好ましくは２〜３００の整数、特には５〜３００の整数であり、Ｙの少なくとも１は、ケイ素原子に結合しているビニル基及びフェニル基を有するジオルガノポリシロキサン残基である。）

Wherein X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, Y is a divalent organic group, k is an integer of 1 to 300, preferably 2 to 300, particularly 5 An integer of ˜300, and at least one of Y is a diorganopolysiloxane residue having a vinyl group and a phenyl group bonded to a silicon atom.

（式中、Ｘ、Ｙおよびｋは上記で定義した通りである。）

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

（式中、Ｘは上記で定義した通りである。）
で表されるテトラカルボン酸二無水物と、下記式（６）
Ｈ₂Ｎ−Ｙ−ＮＨ₂ （６）
（式中、Ｙは上記で定義した通りである。）
で表されるジアミンとを常法に従って、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) is represented by the following formula (5).

(Wherein X is as defined above.)
And a tetracarboxylic dianhydride represented by the following formula (6)
H ₂ N—Y—NH ₂ (6)
(Where Y is as defined above.)
It can obtain by making it react in the organic solvent in accordance with a conventional method.

  The polyimide resin represented by the general formula (4) can be obtained by dehydrating and ring-closing the polyamic acid resin represented by the general formula (3) by a conventional method.

The following are mentioned as a preferable example of the tetracarboxylic dianhydride represented by the said Formula (5), These can be used individually or in combination of 2 or more types.

  The diamine represented by the above formula (6) may include various diamines. In order to obtain the component (A) in the present invention, a diaminopolysiloxane having a vinyl group and a phenyl group bonded to a silicon atom. It is essential to include. From the viewpoint of solubility in an organic solvent, adhesion to a substrate, low elasticity, and flexibility, the amount of the diaminopolysiloxane is preferably 1 to 95 mol% of the total amount of diamine, more preferably 1 to 80 mol%. In addition, from the viewpoint of adhesiveness with the sealing resin, the diaminopolysiloxane is preferably a compound represented by the following formula (1).

（式中、Ｒ^１は炭素原子数３〜９の二価の有機基であり、ｎは０又は１以上の整数、ｍは１以上の整数、ｐ、ｑは０又は１以上の整数で同時には０でない。ｎ＋ｍ＋ｐ＋ｑは２〜１００の整数であり、（ｍ＋ｐ＋ｑ）／（ｍ＋ｎ＋ｐ＋ｑ＋１）≧０．３かつ０．４≧（ｐ＋ｑ）／（ｍ＋ｎ＋ｐ＋ｑ＋１）≧０．１５である。）

(In the formula, R ¹ is a divalent organic group having 3 to 9 carbon atoms, n is 0 or an integer of 1 or more, m is an integer of 1 or more, and p and q are 0 or an integer of 1 or more at the same time. Is not 0. n + m + p + q is an integer from 2 to 100, (m + p + q) / (m + n + p + q + 1) ≧ 0.3 and 0.4 ≧ (p + q) / (m + n + p + q + 1) ≧ 0.15.

In the diaminopolysiloxane (or α, ω-diaminopolysiloxane) represented by the general formula (1), examples of the divalent organic group having 3 to 9 carbon atoms represented by R ¹ include — (CH ₂ ) _3— , — (CH ₂ ) ₄ —, —CH ₂ CH (CH ₃ ) —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ — and the like, an alkylene group, an arylene group, such as the following groups

これらを組み合わせたアルキレン・アリーレン基、−（ＣＨ_２）_３−Ｏ−，−（ＣＨ_２）_４−Ｏ−等のオキシアルキレン基、オキシアリーレン基、例えば下記の基

An alkylene / arylene group combining these, an oxyalkylene group such as — (CH ₂ ) ₃ —O—, — (CH ₂ ) ₄ —O—, an oxyarylene group, such as the following groups

、およびこれらを組み合わせたオキシアルキレン・アリーレン基、例えば下記の基

And oxyalkylene / arylene groups combining these, such as

などの二価炭化水素基が挙げられる。

And divalent hydrocarbon groups.

  In the formula (1), the total molar amount (m + p + q) of the diorganosiloxane unit containing a vinyl group and a phenyl group satisfies (m + p + q) / (m + n + p + q + 1) ≧ 0.3. If it is smaller than this, the adhesive force with the sealing resin is not sufficient. Preferably, (m + p + q) / (m + n + p + q + 1) ≧ 0.4.

Further, in the formula (1), the total molar amount (p + q) of the diorganosiloxane unit containing a phenyl group is an amount satisfying 0.4 ≧ (p + q) / (m + n + p + q + 1) ≧ 0.15. If it is smaller than the above range, the adhesive strength with the sealing resin may be inferior. When the above range is exceeded, the elastic modulus of the cured product may increase at low temperatures, and it may be difficult to produce diaminopolysiloxane. Preferably, 0.3 ≧ (p + q) / (m + n + p + q + 1) ≧ 0.2.

The diaminopolysiloxane of the above formula (1) is prepared by a known method according to the following formula: diaminodisiloxane (i), dimethylcyclopolysiloxane (ii), methylvinylcyclopolysiloxane (iii), methylphenylcyclopolysiloxane ( It can be produced by subjecting a compound appropriately selected from iv) and diphenylcyclopolysiloxane to equilibration polymerization using a catalyst such as potassium siliconate or phosphorus siliconate. The m, n, p and q of the diaminopolysiloxane thus obtained can be determined from the raw material charge ratio and the amine equivalent of the diaminopolysiloxane obtained.

  These diaminopolysiloxanes represented by the general formula (1) can be used alone or in combination of two or more as desired.

  The diamine represented by the above formula (6) may further contain a diaminopolysiloxane other than the diaminopolysiloxane represented by the above formula (1), for example, a diaminopolysiloxane having no vinyl group and no phenyl group. Alternatively, diaminodisiloxane may be included.

  Furthermore, the diamine represented by the above formula (6) can include the following compounds. For example, p-phenylenediamine, m-phenylenediamine, 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-aminophenylthioether) benzene, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-a Nophenoxy) 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 [4- (4-aminophen) Aromatic ring-containing diamines such as noxy) 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.

  Moreover, (A) polyimide resin of this invention may further contain the aromatic compound residue which has a phenolic hydroxyl group. The residue can be derived from a diamine compound having a phenolic hydroxyl group, and examples thereof include the following.

（式中、Ｒ^７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の炭素原子数１〜８の一価炭化水素基であり、各芳香環に付いている置換基は全てまたは一部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ｒは０〜５の整数である。Ａ，Ｂはおのおの１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。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。）

Wherein R ⁷ is independently a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an unsubstituted or substituted carbon atom such as an alkyl group, alkenyl group, alkynyl group, trifluoromethyl group or phenyl group. 1 to 8 monovalent hydrocarbon groups, and all or some of the substituents attached to each aromatic ring may be the same or different, where r is an integer of 0 to 5. A and B may be used alone or in combination of two or more, and R is a hydrogen atom, a halogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)

Here, examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms of R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. , Hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group and other alkyl groups, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group and other alkenyl groups, ethynyl group, propynyl group, butynyl group , Alkynyl groups such as hexynyl groups, aryl groups such as phenyl groups, tolyl groups and xylyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine. Groups substituted with halogen atoms such as bromine and chlorine, such as chloromethyl, trifluoromethyl, Examples thereof include halogen-substituted alkyl groups such as lomoethyl group and 3,3,3-trifluoropropyl group. When R is an unsubstituted or substituted monovalent hydrocarbon group, examples of R include the same as those exemplified for R ⁷ above.

  Moreover, the following are mentioned as another diamine which has a phenolic hydroxyl group.

（式中、Ｒは水素原子、フッ素、臭素、よう素などのハロゲン原子、又は炭素数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ハロゲン置換の１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構わない。Ｚは単結合、メチレン、プロピレンである。ｒは０〜５の整数である。）

(In the formula, R is a halogen atom such as a hydrogen atom, fluorine, bromine or iodine, or an unsubstituted or halogenated alkyl group, alkenyl group, alkynyl group, trifluoromethyl group, phenyl group or the like having 1 to 8 carbon atoms. It is a substituted monovalent hydrocarbon group, and the substituents attached to each aromatic ring may be the same or different, Z is a single bond, methylene or propylene, and r is an integer of 0 to 5. is there.)

  In the present invention, among the diamines having the phenolic hydroxyl group, a diamine represented by the following formula (2) is particularly preferable.

（式中、Ｒ^７は上記と同じである。）

(Wherein R ⁷ is the same as above)

  As a compounding quantity of the diamine compound which has a phenolic hydroxyl group, when mix | blending, it is 5-60 mass% of the whole diamine compound, It is preferable that it is especially 10-40 mass%. If the amount is too small, the adhesive force to the substrate may be low, and if too large, the flexibility of the adhesive layer may be insufficient.

  Moreover, the monoamine which has a phenolic hydroxyl group can also be used for introduction | transduction of a phenolic hydroxyl group, for example, the following structure can be illustrated.

（式中、Ｒ^７は上記と同じである。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。）

(In the formula, R ⁷ is the same as above. D may be used alone or in combination of two. P is an integer of 1 to 3)

  When using the monoamine which has a phenolic hydroxyl group, the compounding quantity is 1-10 mol% with respect to the whole diamine.

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

  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 resin. 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 , Polyphenol or poly Epoxy novolac obtained by condensing novolak type phenol resin (or halogenated novolak type phenol resin) such as epoxy glycidyl ether or polyglycidyl ester, phenol novolak, cresol novolak and the like obtained by condensing alcohol and epichlorohydrin and epichlorohydrin ( In other words, novolac type 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 epoxy Resin etc. are mentioned.
Among these, an epoxy compound having an aromatic compound residue is preferable because it is easily compatible with the component (A).

  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.

Furthermore, when the adhesive composition of the present invention is applied as an adhesive film, particularly when the silicon wafer to be attached is thin, the adhesive film can be pressure-bonded at low temperature and low pressure in order to prevent cracking and warping. (B) The epoxy resin preferably has a liquid or softening temperature of 80 ° C. or lower.

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

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

（式中、Ｒ^８〜Ｒ^１５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。）

(Wherein R ^{8 to} R ¹⁵ are a hydrogen atom, a halogen atom such as fluorine, bromine, iodine, or the like, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group, or an 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, examples of the monovalent hydrocarbon group of R ^{8 to} R ¹⁵ include the same groups as those exemplified above for R ⁷ , and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. An alkoxy 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.

Among these catalysts, particularly preferred catalysts are dicyandiamide and 2-phenyl-4,5-dihydroxymethylimidazole having a high melting point because of the storage stability of the adhesive composition of the present invention.

  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 0.01 to 10 parts by mass, preferably 0.1 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 phenol resins or Super Be ckcite 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 under a trade name such as 9 (made by Scado Zwoll, the Netherlands) and Methylon 75108 (made by General Electric, USA); . 138 (manufactured by Nihon Reichhold Chemical Co., Ltd.), Melan (manufactured by Hitachi, Ltd.), U-Van 10R (manufactured by Toyo Kodan Kogyo Co., Ltd.), etc. , Amino resins such as aniline resins; 1 as shown by the 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 to an integer of 1 to 10) Polysulfide resins having at least two mercapto groups in the molecule; organics such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl nadic acid, dodecyl succinic anhydride, chlorendic anhydride An acid or an anhydride thereof (an acid anhydride) may be used. 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, when using, 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. If 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 lowered.

  Furthermore, in the composition of the present invention, silica fine powder, alumina, titanium oxide, carbon black, fillers such as conductive particles, inorganic or organic fillers, pigments, dyes, etc. are colored to the extent that the properties are not impaired. Additives such as an agent, a wetting improver, an antioxidant, and a heat stabilizer can be blended.

In particular, silica particles and silicone fine particles having a particle size of 10 μm or less are preferable.

The silica particles moderately increase the melt viscosity of the adhesive layer, suppress the chip flow in the resin sealing step, and decrease the moisture absorption rate and the linear expansion rate of the cured product. The silica particles preferably have an average particle size of 10 μm, more preferably 5 μm or less, and a maximum particle size of 20 μm or less. If the average particle size exceeds this range, the smoothness of the surface of the adhesive film of the present invention may be impaired. The silica particles are preferably surface-treated with an organosilicon compound from the viewpoint of fluidity of the composition.

Silica particles include reinforcing properties such as fumed silica and precipitated silica, and crystalline silica such as silica quartz. Specifically, Aerosil R972, R974, R976, manufactured by Nippon Aerosil Co., Ltd., SE-2050, SC-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO- from Admatechs Co., Ltd. Examples include E2, SO-C2, SO-E3, SO-C3, SO-E5, SO-C5, Musil 120A and Musil 130A manufactured by Shin-Etsu Chemical Co., Ltd., and a mixture thereof.

The blending amount of the silica particles is preferably 5 to 80% by mass, particularly 10 to 60% by mass, based on the total mass of the composition. If it is less than these ranges, the effect of lowering the moisture absorption rate and the linear expansion coefficient is lost, and if it exceeds, the elastic modulus may increase.

  As the silicone fine particles, composite silicone rubber fine particles are preferable. The composite silicone fine particles are particles in which microorganisms of a polyorganosilsesquioxane resin produced by polymerization on the surface are present on at least a part of the surface of the silicone rubber particles. By blending the composite silicone fine particles, it is possible to achieve a decrease in the elastic modulus and water absorption rate of the cured product in combination with the silica particles.

The composite silicone fine particles preferably have an average particle size of 0.1 to 10 μm, more preferably 0.5 to 5 μm. If the average particle size exceeds this range, the smoothness of the surface state of the adhesive film of the present invention may be impaired. Moreover, it is preferable that a maximum particle size is 20 micrometers or less, More preferably, it is 10 micrometers or less.

The compounding quantity of a composite silicone particle is 5-30 mass% of a composition total mass, Preferably it is 10-20 mass%. Outside these ranges, effects on the elastic modulus and water absorption of the cured product cannot be obtained, and the linear expansion coefficient of the cured product may increase and the strength may decrease.

The composite silicone fine particles can be prepared according to a method described in, for example, JP-A-7-196815. That is, an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane are added to an aqueous dispersion of spherical silicone rubber fine particles having an average particle size of 0.1 to 10 μm, and the organotrialkoxysilane is added on the surface of the spherical silicone rubber fine particles. Hydrolyze and polymerize, then dry it. The amount of the polyorganosilsesquioxane resin is preferably 1 to 500 parts by mass, more preferably 2 to 100 parts by mass with respect to 100 parts by mass of the silicone rubber spherical fine particles. If the amount is less than the lower limit, the dispersibility of the composite silicone fine particles in the adhesive composition may be deteriorated, and the film composition may be nonuniform. On the other hand, when it exceeds the said upper limit, there exists a tendency for the elasticity modulus of adhesive hardened | cured material to become high.

As the composite silicone fine particles, for example, KMP-600, KMP-605, X-52-7030 and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be used. A mixture of two or more of these can also be used.

The adhesive composition of the present invention can be prepared by mixing the above components (A) to (C) and optionally other components at room temperature by conventional mixing means.

  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). The substrate and the adherend may be sandwiched and pressure-bonded, and then heat-cured and bonded. 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. The adhesive layer is cured by pressure bonding at a pressure of 0.01 to 10 MPa, particularly 0.1 to 2 MPa, and then at a temperature of 100 to 200 ° C., particularly 120 to 180 ° C. for 30 minutes to 5 hours, particularly 1 to 5 hours. This can be done by curing.

  The adhesive composition of the present invention can be used not only in the production of electronic parts such as semiconductor devices but also in various productions including an adhesion process, for example, in the production of LED parts, sensors, liquid crystal parts and the like.

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

Synthesis of polyimide resin [Synthesis Example 1]
To 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, 35.8 parts by mass of bis (3,4-dicarboxyphenyl) sulfone dianhydride and Then, 250 parts by mass of a solvent cyclohexanone was charged and stirred to disperse the acid anhydride.
In the dispersion, the following formula

で示され、かつ（ｍ＋ｐ＋ｑ）／（ｍ＋ｎ＋ｐ＋ｑ＋１）＝０．４および（ｐ＋ｑ）／（ｍ＋ｎ＋ｐ＋ｑ＋１）＝０．２０である、ビニル基およびフェニル基を含有するビニルフェニルメチルジアミノポリシロキサン（以後、「ジアミノシロキサン−１」という。）６３．２８質量部（上式においてｎ、ｍおよびｑは各々ある範囲の整数であり、それらの平均が、ジアミノポリシロキサン−１のアミン当量が５９７となるような大きさである）をシクロヘキサノン６０質量部に分散させた溶液を滴下して、室温にて１時間撹拌反応させた後、更に２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン２１．３５質量部をシクロヘキサノン５０質量部に分散させた溶液を滴下して、室温にて１６時間撹拌反応させたることにより、アミック酸オリゴマーを合成した。該アミック酸オリゴマー溶液に、トルエン８０ｍｌを投入してから温度を上げ、約１７０℃で６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、１７０℃でトルエンを除去した。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、減圧乾燥してポリイミドシリコーン樹脂−１を得た。

And (m + p + q) / (m + n + p + q + 1) = 0.4 and (p + q) / (m + n + p + q + 1) = 0.20, a vinyl phenylmethyldiaminopolysiloxane containing a vinyl group and a phenyl group (hereinafter “diamino”) 63.28 parts by mass (in the above formula, n, m and q are each an integer within a certain range, and the average thereof is such that the amine equivalent of diaminopolysiloxane-1 is 597. Is added dropwise in 60 parts by mass of cyclohexanone, followed by stirring at room temperature for 1 hour, and then further 2,2-bis (4- (4-aminophenoxy) phenyl) propane 21. A solution in which 35 parts by mass is dispersed in 50 parts by mass of cyclohexanone is dropped, and the mixture is stirred at room temperature for 16 hours. It was synthesized Mick acid oligomer. The amic acid oligomer solution was charged with 80 ml of toluene and then heated to reflux at about 170 ° C. for 6 hours. After confirming that a predetermined amount of water has accumulated in the moisture meter and that no water has flowed out, remove the effluent accumulated in the moisture meter and remove toluene at 170 ° C. 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 polyimide silicone resin-1.

When the infrared absorption spectrum of the obtained resin was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on an imide group was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It was 21,000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent.
[Synthesis Example 2]
In Synthesis Example 1, instead of diaminosiloxane-1, a vinyl group represented by the formula in Synthesis Example 1 and (m + p + q) / (m + n + p + q + 1) = 0.545 and (p + q) / (m + n + p + q + 1) = 0.272 And phenylphenyl-containing vinylphenylmethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-2”, amine equivalent 723) is used in an amount of 62.18 parts by mass, and 2,2-bis (4- (4-aminophenoxy) A polyimide silicone resin-2 was obtained in the same manner as in Synthesis Example 1 except that 25.45 parts by mass of phenyl) propane and 370 parts by mass of cyclohexanone were used in total. The molecular weight was 23,000.

[Synthesis Example 3]
In Synthesis Example 1, instead of diaminosiloxane-1, a vinyl group and a phenyl group represented by the following formula and having (m + p + q) / (m + n + p + q + 1) = 0.585 and (p + q) / (m + n + p + q + 1) = 0.333 Of 2,2-bis (4- (4-aminophenoxy) phenyl) propane using 59.60 parts by mass of vinylphenylmethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-3”; amine equivalent 693). Was obtained in accordance with Synthesis Example 1 except that 25.45 parts by mass and 360 parts by mass of cyclohexanone were used in total. The molecular weight was 23,000.

[Synthesis Example 4]
In Synthesis Example 1, a vinyl group represented by the formula in Synthesis Example 1 and having (m + p + q) / (m + n + p + q + 1) = 0.571 and (p + q) / (m + n + p + q + 1) = 0.286 instead of diaminosiloxane-1. And phenyl group-containing vinylphenylmethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-4”, amine equivalent 1312) in an amount of 73.4 parts by mass, 2,2-bis (4- (4-aminophenoxy) Polyimide silicone resin-4 was obtained according to Synthesis Example 1 except that 31.61 parts by mass of phenyl) propane and 430 parts by mass of cyclohexanone were used. The molecular weight was 25,000.

[Synthesis Example 5]
In Synthesis Example 1, instead of di-2,2-bis (4- (4-aminophenoxy) phenyl) propane, an aromatic diamine (diamine-1) having a phenolic hydroxyl group represented by the following structural formula is 30.67. A polyimide silicone resin-5 was obtained in the same manner as in Synthesis Example 1 except that mass parts were used and 390 parts by mass of cyclohexanone was used in total. The molecular weight was 20,000.

[Comparative Synthesis Example 1]
In Synthesis Example 1, instead of diaminosiloxane-1, all organic groups bonded to silicon atoms represented by the following formula are all methyl groups except aminopropyl groups, (m + p + q) / (m + n + p + q + 1) = 0 and ( p-q) / (m + n + p + q + 1) = 0 dimethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-5”; amine equivalent 486) was used in an amount of 51.52 parts by mass, and 2,2-bis (4- (4 -Aminophenoxy) phenyl) propane, polyimide silicone resin-6 was obtained according to Synthesis Example 1 except that 21.35 parts by mass and cyclohexanone in total of 330 parts by mass were used. The molecular weight was 24,000.

[Comparative Synthesis Example 2]
In Synthesis Example 1, vinylmethyl containing a vinyl group represented by the following formula and having (m + p + q) / (m + n + p + q + 1) = 0.273 and (p + q) / (m + n + p + q + 1) = 0 instead of diaminosiloxane-1 55.97 parts by mass of diaminopolysiloxane (hereinafter referred to as “diaminosiloxane-6”, amine equivalent 528) and 21.35 parts by mass of 2,2-bis (4- (4-aminophenoxy) phenyl) propane Polyimide silicone resin-7 was obtained according to Synthesis Example 1 except that 340 parts by mass of cyclohexanone was used in total. The molecular weight was 23,000.

[Comparative Synthesis Example 3]
In Synthesis Example 1, instead of diaminosiloxane-1, a phenyl group represented by the following formula and containing (m + p + q) / (m + n + p + q + 1) = 0.273 and (p + q) / (m + n + p + q + 1) = 0.273 is contained. 60.03 parts by mass of phenylmethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-7”, amine equivalent 698) and 25.45 of 2,2-bis (4- (4-aminophenoxy) phenyl) propane were used. A polyimide silicone resin-8 was obtained in the same manner as in Synthesis Example 1 except that 370 parts by mass of mass parts and cyclohexanone were used in total. The molecular weight was 22,000.

Preparation of adhesive composition (Examples 1-6, Comparative Examples 1-3)
In each of the polyimide resin solutions obtained above, cyclohexanone so that the solid content concentration of the entire resin composition is 55 wt% together with the epoxy resin, catalyst, silica, and composite silicone rubber fine particles having the blending amounts shown in Table 1 below. The mixture was mixed with a rotating / revolving mixer (manufactured by Shinky Corporation) to prepare an adhesive composition.

  Next, each composition that was allowed to stand for 24 hours 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 layer having a thickness of about 25 μm. The provided adhesive film was produced.

    Furthermore, the following test was done about each adhesive film. The results are shown in Table 1.

Young's modulus after curing The adhesive film obtained above was cured by heating at 175 ° C. for 2 hours. A 40 mm × 10 mm × 200 μm film was cut out to make a test piece, using a dynamic viscoelasticity measuring device, in a tensile mode, with a chuck distance of 10 mm, a measurement temperature of −80 ° C. to 300 ° C., and a measurement frequency of 1 Hz. It was measured.

Glass transition point and coefficient of linear expansion The adhesive film was heat treated at 175 ° C. for 2 hours, dried and cured. A 20 mm × 5 mm × 200 μm film was cut out to form a test piece, and the glass transition point and the linear expansion coefficient were measured. For the measurement, a thermomechanical measuring device, TMA-2000 (manufactured by ULVAC-RIKO) is used, and in the tension mode, the distance between chucks is 15 mm, the measurement temperature is −60 to 300 ° C., the temperature rising rate is 5 ° C./min, and the measurement load is 3 g Measurements were made. In the linear expansion coefficient, α1 is a value in the temperature range below the glass transition point, and α2 is a value at a temperature above the glass transition point.

Adhesiveness of sealing resin to cured adhesive The adhesive layer surface of the adhesive film obtained above was fixed by thermocompression bonding to a Cu test piece of 18 mm × 18 mm for 10 seconds at 70 ° C. and 0.01 MPa, and then 175 The adhesive layer was cured by heat treatment at 0 ° 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. 1 and then heat-treated at 175 ° C. for 4 hours. The sealing resin layer was cured. This sample was measured for shear adhesive force between the sealing resin and the adhesive using a bond tester (4000 PXY, manufactured by DAGE).

Adhesion test 450μm silicon wafer is diced into 2mm x 2mm chips, then the created adhesive film is thermocompression bonded to the backside of this silicon chip at 100 ° C, cut into chip shape, and silicon chip with adhesive film is attached The chip was placed on a BT substrate and a silicon substrate on which a 10 mm × 10 mm resist AUS303 (manufactured by Unitechno Co., Ltd.) was applied and cured so that the surface to which the adhesive film was attached was in contact with the substrate at 150 ° C., 0 ° C. It was fixed by thermocompression bonding for 2 seconds under the condition of 1 MPa. The obtained test body was heated at 175 ° C. for 2 hours to cure the adhesive layer, thereby preparing an adhesive test piece. The shear adhesive strength at 260 ° C. was measured with a bond tester (manufactured by DAGE, 4000PXY).

In Table 1, all compounding amounts are solid contents. The materials used are as follows.
Materials Epoxy resin 1: RE-310S (manufactured by Nippon Kayaku Co., Ltd.), liquid epoxy resin epoxy resin 2: Epicoat 834 (manufactured by Japan Epoxy Resin Co., Ltd.), semi-solid, softening temperature 64 ° C.
Epoxy resin curing catalyst: Dicyandiamide (Japan Epoxy Resin)
Epoxy resin curing agent: OCN-3 (manufactured by Asahi Organic Materials Co., Ltd.), phenolic silica particles: SE-2050 (manufactured by Admatechs), spherical silica, average particle size of 0.5 μm
Composite silicone rubber powder: X-52-7030 (manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.7 μm

   As can be seen from Table 1, the cured product obtained from the composition of the present invention has a low elastic modulus and excellent heat resistance, and also has high adhesive force with the sealing 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 of the sealing resin, and further has a low elastic modulus and high heat resistance, This is useful for manufacturing a highly reliable resin packaging semiconductor device.

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 (9)

(A) 100 parts by mass of a polyimide resin having a diorganopolysiloxane residue having a vinyl group and a phenyl group bonded to a silicon atom,
(B) Epoxy resin 5 to 200 parts by mass, and (C) an adhesive composition containing an epoxy resin curing catalyst. (A) A component is obtained by reaction of tetracarboxylic dianhydride and diamine, 1-95 mol% of the total amount of this diamine is diorganopolysiloxane represented by following formula (1). The adhesive composition according to claim 1.

(In the formula, R ¹ is a divalent organic group having 3 to 9 carbon atoms, n is an integer of 0 or 1 or more, m is an integer of 1 or more, and p and q are 0 or an integer of 1 or more at the same time. Is not 0. n + m + p + q is an integer from 2 to 100 and (m + p + q) / (m + n + p + q + 1) ≧ 0.3 and 0.4 ≧ (p + q) / (m + n + p + q + 1) ≧ 0.15. The adhesive composition according to claim 1 or 2, wherein the component (A) has an aromatic compound residue having a phenolic hydroxyl group. The adhesive composition according to any one of claims 1 to 3, wherein the component (B) has an aromatic compound residue. The adhesive composition according to any one of claims 1 to 4, comprising an inorganic filler. The adhesive composition according to any one of claims 1 to 5, comprising composite silicone rubber fine particles. The adhesive composition according to any one of claims 1 to 6, wherein the component (B) comprises an epoxy resin having a softening point of 80 ° C or less as measured by the ring and ball method JIS-K7234. (B) Adhesive composition of any one of Claims 1-7 in which a component contains a liquid epoxy resin at 25 degreeC. The adhesive film provided with the contact bonding layer which consists of an adhesive composition of any one of Claims 1-8.

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