JP2010265338A - Adhesive composition, adhesive sheet and dicing die attach film - Google Patents

Abstract

An adhesive composition that provides a cured adhesive layer having high adhesive strength to various substrates and is useful for stably producing a highly reliable semiconductor device, and the composition. An adhesive sheet and a dicing die attach film to be used are provided.
(A) A glycidyl group-containing (meth) acrylic resin having a weight average molecular weight of 100,000 to 1,500,000 and (B) an organopolysiloxane structure, having a weight average molecular weight of 500 to 20,000, An adhesive composition comprising a polyimide resin having an amino group and a proportion of structural units having an organopolysiloxane structure in the total structural unit of 50 to 100 mol%; provided on the base material An adhesive sheet comprising an adhesive layer made of the above composition; a dicing film having a substrate and a pressure-sensitive adhesive layer provided thereon; and the above-mentioned provided on the pressure-sensitive adhesive layer of the dicing film A dicing die attach film comprising an adhesive layer made of the composition.
[Selection figure] None

Description

  The present invention relates to an adhesive composition suitable for adhering a semiconductor chip to a substrate, and in particular, by including a specific polyimide resin containing an organopolysiloxane structure, the semiconductor chip can be attached to the substrate with high adhesive force. The present invention relates to an adhesive composition that can be bonded, an adhesive sheet using the adhesive composition, and a dicing die attach film.

  For example, (i) a large-diameter silicon wafer on which an IC circuit is formed is cut into semiconductor chips by a dicing (cutting) process, and (ii) the semiconductor is made with a curable liquid adhesive using the chip as a die bond material. It is manufactured by thermocompression bonding to the device substrate (mounting), (iii) after wire bonding between the electrodes, and (iv) sealing for improving handling and protection from the external environment.

  Since the liquid adhesive tends to cause problems such as protrusion of the chip from the end of the chip and wire bonding due to the occurrence of tilt of the chip due to uneven thickness, a die bond film having an adhesive layer provided on the film in recent years has been developed. in use.

  The adhesive transferred to the semiconductor device substrate is cured after the mounting process and exposed to heat in processes such as wire bonding and resin sealing. On the other hand, semiconductor packages are becoming more and more compact year by year as seen in packaging structures (CSP) of the same size as chips, packaging structures in which chips are stacked (stacked CSP, SiP), and the like. Therefore, such adhesives are required to have extremely high adhesive strength as well as excellent heat stress.

  Conventionally, as the adhesive for die bonding, specifically, adhesive materials including a plastic resin, an epoxy resin, a curing agent, and a catalyst have been developed (for example, Patent Documents 1 to 5). Moreover, the adhesive composition containing an acrylic resin, an epoxy resin, and an aromatic diamine compound is also disclosed (for example, patent document 6). However, these adhesive materials and adhesive compositions have insufficient adhesiveness and cannot stably provide a highly reliable semiconductor device.

Japanese Patent Laid-Open No. 7-224259 JP-A-8-27427 JP-A-10-163391 Japanese Patent Laid-Open No. 11-12545 JP 2000-154361 A JP 2008-166958 A

  The present invention provides an adhesive composition having a high adhesive strength to various substrates, and is useful for stably producing a highly reliable semiconductor device, and the adhesive. It is an object of the present invention to provide an adhesive sheet and a dicing die attach film using the composition.

  The present inventors have found that the above object can be achieved by an adhesive composition containing a specific polyimide resin containing an organopolysiloxane structure.

That is, the present invention firstly
(A) The weight average molecular weight is 100,000 to 1,500,000, a (meth) acrylic resin containing a glycidyl group, and (B) an organopolysiloxane structure, and the weight average molecular weight is 500 to 20 There is provided an adhesive composition comprising a polyimide resin having an amino group at a terminal and a proportion of a structural unit having an organopolysiloxane structure of 50 to 100 mol% in all structural units.

  The present invention secondly provides an adhesive sheet comprising a base material and an adhesive layer made of the adhesive composition provided on the base material. In addition, the adhesive bond layer which consists of this adhesive composition maintains a film shape at room temperature even in the state peeled from the base material, and corresponds to what is called an adhesive film.

  Thirdly, the present invention provides a dicing film having a base material and a pressure-sensitive adhesive layer provided thereon, and an adhesive layer comprising the above-mentioned adhesive composition provided on the pressure-sensitive adhesive layer of the dicing film. Provided with a dicing die attach film.

  The adhesive composition of the present invention gives a cured adhesive layer having high adhesive strength to various substrates by heat curing. Therefore, the adhesive composition is useful for stably manufacturing a highly reliable semiconductor device.

  The present invention will be described in detail below. In the present specification, “weight average molecular weight” refers to a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).

[(A) (Meth) acrylic resin]
The component (A) is a (meth) acrylic resin having a weight average molecular weight of 100,000 to 1,500,000 and containing a glycidyl group. In this specification, the (meth) acrylic resin refers to a polymer containing a structural unit derived from a (meth) acrylic monomer composed of acrylic acid, an acrylic acid derivative, methacrylic acid and a methacrylic acid derivative. (A) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  The component (A) is, for example, a homopolymer or copolymer of the above (meth) acrylic monomer or a copolymer of the (meth) acrylic monomer and other monomers. And a polymer having a weight average molecular weight of 100,000 to 1,500,000 and containing a glycidyl group. In the copolymer of the (meth) acrylic monomer and the other monomer, the content of the structural unit derived from the other monomer is preferably 5 to 50 mol% in all the structural units. Preferably it is 10-30 mol%. In the copolymer of (meth) acrylic monomers and other monomers, these monomers may be used alone or in combination of two or more.

  Examples of the acrylic acid derivative include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, acrylic acid alkyl esters such as 2-ethylhexyl acrylate, lauryl acrylate; hydroxylethyl acrylate, hydroxylpropyl acrylate Acrylic acid hydroxyl alkyl esters such as benzyl acrylate, etc .; Acrylic esters containing aromatic hydrocarbon groups such as benzyl acrylate; Acrylic amides such as dimethyl acrylate amide; Imides such as imide acrylate TO-1492 (trade name, manufactured by Toagosei Co., Ltd.) Group-containing acrylic ester; epoxy group-containing acrylic ester such as glycidyl acrylate, and acrylonitrile.

  Examples of the methacrylic acid derivative include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid alkyl ester such as lauryl methacrylate; hydroxylethyl methacrylate, hydroxylpropyl methacrylate. Methacrylic acid hydroxyl alkyl ester such as benzyl methacrylate, aromatic hydrocarbon group-containing methacrylic acid ester, dimethyl methacrylate methacrylic acid amide, etc., imide methacrylate etc. imide group-containing methacrylic acid ester, glycidyl methacrylate epoxies, etc. Examples thereof include group-containing methacrylic acid esters.

  Examples of the other monomer include styrene, butadiene, and allyl derivatives (such as allyl alcohol, allyl acetate, allyl phenyl ether, allyl benzyl ether, and allyl benzoic acid).

  In a preferred embodiment of the present invention, the component (A) has the following formula:

で表される構造単位（即ち、アクリロニトリル由来の構造単位）を含む共重合体である。この共重合体は、単量体としてアクリロニトリルを用いることにより製造することができる。

A copolymer containing a structural unit represented by the formula (namely, a structural unit derived from acrylonitrile). This copolymer can be produced by using acrylonitrile as a monomer.

  The glycidyl group in the component (A) is synthesized by, for example, synthesizing the component (A) using a monomer containing a glycidyl group as at least a part of the monomer used as the raw material of the component (A). It can be introduced into the component (A). Examples of the monomer containing a glycidyl group include an acrylic acid derivative containing a glycidyl group (for example, glycidyl acrylate) and a methacrylic acid derivative containing a glycidyl group (for example, glycidyl methacrylate). A body may be used individually by 1 type, or may be used in combination of 2 or more types.

  The content of the glycidyl group in the component (A) is preferably 0.002 to 0.1 mol, more preferably 0.005 to 0.05 mol, per 100 g of the component (A). When the content is within this range, a composition having sufficient embedding performance and a cured adhesive layer having sufficient adhesive strength can be easily obtained.

  The weight average molecular weight of the component (A) is usually 100,000 to 1,500,000, preferably 500,000 to 1,500,000. If the molecular weight is less than 100,000, the adhesiveness and strength of the resulting cured adhesive layer may be reduced. If the molecular weight exceeds 1,500,000, the resulting composition may be too viscous to be handled.

  In addition, the (meth) acrylic resin of component (A) preferably has a glass transition point (Tg) measured by thermomechanical analysis (TMA) of −40 ° C. to 100 ° C., more preferably −10 to 70. ° C.

[(B) Polyimide resin]
The component (B) contains an organopolysiloxane structure, has a weight average molecular weight of 500 to 20,000, has an amino group at the terminal, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is a polyimide resin which is 50-100 mol%. When this amino group reacts with the glycidyl group in the component (A) and the epoxy group in the component (C) that is optionally blended, the adhesive composition of the present invention is cured. (B) A component may be used individually by 1 type, or may be used in combination of 2 or more type. The composition of this invention gives the adhesive hardened | cured material layer which has high adhesive force with respect to various base materials by containing (B) component. The organopolysiloxane structure may be linear, branched or cyclic, and examples thereof include a structure represented by the following formula. The organopolysiloxane structure present in component (B) may be a single type or a combination of two or more types.

（式中、Ｒは、１価の有機基であり、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基などのアルキル基；シクロブチル基、シクロペンチル基、シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基などのアリール基；ベンジル基、フェネチル基などのアラルキル基；およびこれらの基の炭素原子に結合した水素原子の少なくとも一部がハロゲン原子等で置換されてなる１価炭化水素基（例えば、クロロメチル基、3-クロロプロピル基、3,3,3-トリフルオロプロピル基等のハロゲン化アルキル基）等の、非置換または置換の炭素原子数が好ましくは１〜１２、より好ましくは１〜６の１価炭化水素基等が挙げられ、中でも、メチル基、フェニル基等が好ましく、ｎは１以上の整数であり、好ましくは１〜１０の整数である。）

(In the formula, R is a monovalent organic group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, or an octyl group; a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or the like; An alkyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenethyl group; and at least a part of hydrogen atoms bonded to carbon atoms of these groups; Unsubstituted or substituted, such as monovalent hydrocarbon groups substituted with halogen atoms (eg, halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group) The monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and the like are preferable. Among them, a methyl group, a phenyl group, and the like are preferable. , N is an integer of 1 or more, preferably an integer of 1 to 10.)

  The proportion of structural units having an organopolysiloxane structure in all structural units in component (B) is 50 to 100 mol%, preferably 70 to 100 mol%. When the proportion is less than 50 mol%, the resulting polyimide resin tends to have poor compatibility and dispersibility with the component (A), and the resulting adhesive composition can easily separate components. The structural unit in the component (B) is the following formula:

（式中、Ｖは四価の有機基であり、Ｗは二価の有機基である。）
で表されるものをいう。上記式で表される構造単位がオルガノポリシロキサン構造を有する場合、オルガノポリシロキサン構造はＶおよびＷのいずれか一方にのみ存在しても両方に存在してもよい。

(In the formula, V is a tetravalent organic group, and W is a divalent organic group.)
The one represented by When the structural unit represented by the above formula has an organopolysiloxane structure, the organopolysiloxane structure may exist only in one or both of V and W.

  In particular, the polyimide compound as the component (B) includes tetracarboxylic dianhydride containing at least one compound represented by the following formulas (1) to (4), 4,4′-diaminodiphenylsulfone, and 3, It is preferable to contain a polyimide resin obtained by reacting a diamine compound containing at least one of 3′-diaminodiphenylsulfone with an excess of the diamine compound.

  The polyimide resin of (B) component manufactured using the tetracarboxylic dianhydride containing at least 1 sort (s) of the compound represented by said Formula (1)-(4) is (meth) acryl of (A) component. The compatibility and dispersibility with respect to the resin are likely to be better. In such an adhesive composition containing a polyimide resin, each component is more difficult to separate, and when applied as a film adhesive, it is easy to obtain a smooth coating film, and the adhesive force to various substrates tends to be higher. .

  (B) The total content of the compounds represented by the above formulas (1) to (4) is 50 to 100 mol% in all tetracarboxylic dianhydrides used to produce the component polyimide resin. It is preferable that it is 70-100 mol%, and it is more preferable. When the content is 50 to 100 mol%, the obtained component (B) tends to have better compatibility and dispersibility with respect to the component (A), and each component is further separated in the resulting adhesive composition. Hard to do.

  The adhesive composition containing the polyimide resin as the component (B) produced by using a diamine compound containing at least one of 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone has further storage stability. It will be excellent. In addition, a semiconductor device manufactured by forming such an adhesive composition into a film shape and applying it as a bonding material for a semiconductor chip has an adhesive hardened material layer in which the remaining amount of voids is further reduced, and the reliability is further improved. It will be excellent. In particular, the total content of 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone in the total diamine compound used for producing the polyimide resin of component (B) is 50 to 100 mol%. It is preferable that it is 70 to 100 mol%.

  (B) As a polyimide resin of a component, it represents with the following general formula (6) formed by imidating (dehydration ring closure) the polyamic acid resin represented with the following general formula (5) which is the precursor, for example. A polyimide resin can be used.

（式中、Ｘはオルガノポリシロキサン構造、芳香族環および脂肪族環の少なくとも１種を含む四価の有機基であり、ただし、全Ｘの５０〜１００モル％、好ましくは７０〜１００モル％がオルガノポリシロキサン構造を含み、Ｙは二価の有機基であり、ｐは１〜５０の整数である。）

(In the formula, X is a tetravalent organic group containing at least one of an organopolysiloxane structure, an aromatic ring and an aliphatic ring, provided that 50 to 100 mol%, preferably 70 to 100 mol% of the total X Includes an organopolysiloxane structure, Y is a divalent organic group, and p is an integer of 1 to 50.)

（式中、Ｘ、Ｙおよびｐは前記のとおりである。）

(In the formula, X, Y and p are as defined above.)

  In the general formula (5), p is an integer of 1 to 50, preferably an integer of 2 to 30. A polyamic acid resin having such a repeating number can be easily obtained by, for example, the following method. it can. The polyimide resin represented by the general formula (6) can be obtained, for example, by dehydrating and ring-closing the polyamic acid resin represented by the general formula (5) by a conventional method.

  The polyamic acid resin represented by the general formula (5) is, for example, the following structural formula (7):

（式中、Ｘは上記と同様の意味を表す。）
で表されるテトラカルボン酸二無水物と、下記一般式（８）：
Ｈ₂Ｎ−Ｙ−ＮＨ₂ （８）
（式中、Ｙは上記と同様の意味を表す。）
で表されるジアミン化合物とを、常法に従って、該ジアミン化合物過剰で、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。ジアミン化合物過剰で上記の反応を行うことによって、末端にアミノ基を有するポリイミド樹脂を得ることができ、このアミノ基を（Ａ）成分のグリシジル基を含有する（メタ）アクリル系樹脂および場合により配合される（Ｃ）成分のエポキシ樹脂と反応させることにより、本発明の接着剤組成物を硬化させることができる。

(In the formula, X represents the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following general formula (8):
_{H 2 N-Y-NH 2} (8)
(In the formula, Y represents the same meaning as described above.)
Can be obtained by reacting in an organic solvent with an excess of the diamine compound according to a conventional method. By performing the above reaction with an excess of diamine compound, a polyimide resin having an amino group at the terminal can be obtained, and this amino group is blended with a (meth) acrylic resin containing the glycidyl group of the component (A) and optionally. The adhesive composition of the present invention can be cured by reacting with the component (C) epoxy resin.

  Here, when the specific example of the tetracarboxylic dianhydride represented by the said General formula (7) is shown, the following will be mentioned, but 50-100 mol% of all the X in the said General formula (5) Is not limited to these as long as it contains an organopolysiloxane structure. In order to make 50-100 mol% of all X in the general formula (5) contain an organopolysiloxane structure, in particular, compounds represented by the following formulas (1) to (4) should be used. it can.

  In addition, the tetracarboxylic dianhydride shown by the said General formula (7) may be used individually by 1 type or in combination of 2 or more type depending on necessity. In addition, in the total tetracarboxylic dianhydride represented by the general formula (7), the total content of the compounds represented by the above formulas (1) to (4) is 50 to 100 mol as described above. %, And more preferably 70 to 100 mol%.

  Furthermore, specific examples of the diamine compound represented by the general formula (8) include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 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-aminophenyl) Nylthioether) 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-a) Minophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- ( Aromatic ring-containing diamine compounds such as 4-aminophenoxy) phenyl] perfluoropropane and the like, and 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone are preferred. Among the above specific examples, those other than 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone are 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.

  In addition, you may use the diamine compound shown by the said General formula (8) individually by 1 type or in combination of 2 or more type depending on necessity. In the total diamine compound represented by the general formula (8), the total content of 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone is 50 to 100 mol% in the same manner as described above. It is preferable that it is 70-100 mol%.

  (B) Although the weight average molecular weight of the polyimide resin of a component is 500-20,000, Preferably it is 1000-15000. If the weight average molecular weight is outside this range, at least the dispersibility of the adhesive composition may be deteriorated or the adhesive force may be reduced. The weight average molecular weight can be appropriately adjusted. For example, the weight average molecular weight of the polyimide resin produced by the above method from the tetracarboxylic dianhydride represented by the structural formula (7) and the diamine compound represented by the general formula (8) It can adjust by changing the molar ratio of an acid dianhydride and a diamine compound. That is, it can be adjusted by the excess amount of the diamine compound relative to tetracarboxylic dianhydride. When the excess amount is large, the molecular weight decreases, and when the excess amount is small, the molecular weight increases.

  More specifically, the polyamic acid resin is synthesized by dissolving the above-mentioned starting materials in a solvent under an inert atmosphere, and usually reacting at 80 ° C. or lower, preferably 0 to 40 ° C. More specifically, the target polyamide resin is obtained by heating the obtained polyamic acid resin to 100 to 200 ° C., preferably 150 to 200 ° C., and dehydrating and ring-closing the acid amide portion of the polyamic acid resin. Can be synthesized.

  The organic solvent used in the above reaction may not be one that can completely dissolve the starting material as long as it is inert to the resulting polyamic acid resin and polyimide resin. Examples of the organic solvent include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and dimethyl sulfoxide. Preferred are aprotic polar solvents, particularly preferred are N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These organic 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.

[(C) Epoxy resin]
Although the epoxy resin of (C) component is not specifically limited, What has at least 2 epoxy group in 1 molecule is preferable. Moreover, when using the adhesive composition of this invention as an adhesive film, (C) component is an epoxy resin whose softening temperature is 100 degrees C or less at the point which can pressure-bond the obtained adhesive film at lower temperature and lower pressure. Is preferable, and a liquid epoxy resin may be used. The softening temperature can be measured by, for example, the ring and ball method (JIS K 7234). (C) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the component (C) include bis (4-hydroxyphenyl) methane, 2,2′-bis (4-hydroxyphenyl) propane, diglycidyl ethers of halides thereof, and polycondensates thereof (so-called bisphenol F). Type epoxy resin, bisphenol A type epoxy resin, etc.); butadiene diepoxide; vinylcyclohexene dioxide; 1,2-dihydroxybenzene diglycidyl ether, resorcinol diglycidyl ether, 1,4-bis (2,3-epoxypropoxy) ) Diglycidyl ethers such as benzene, 4,4′-bis (2,3-epoxypropoxy) diphenyl ether, 1,4-bis (2,3-epoxypropoxy) cyclohexene; bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate Polyglycidyl ether obtained by condensing polyphenol or polyhydric alcohol and epichlorohydrin; epoxy novolac obtained by condensing novolac phenol resin such as phenol novolak or cresol novolac or halogenated novolac phenol resin and epichlorohydrin (That is, novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin); epoxidized polyolefin or epoxidized polybutadiene epoxidized by peroxidation method; naphthalene ring-containing epoxy resin; biphenyl type epoxy resin; phenol aralkyl Type epoxy resin; biphenyl aralkyl type epoxy resin; cyclopentadiene type epoxy resin; dicyclopentadiene type epoxy resin, etc. And the like. Silicone modified epoxy resin may also be used. Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin or a combination thereof is preferable.

  Moreover, you may use an epoxy resin hardening | curing agent to such an extent that the characteristic of the adhesive composition of this invention is not impaired. The epoxy resin curing agent is not particularly limited, and various conventionally known ones can be used. An epoxy resin hardening | curing agent may be used individually by 1 type, or may be used in combination of 2 or more type according to hardening performance.

Examples of the epoxy resin curing agent include aliphatic amines such as diethylenetriamine, triethylenetetramine, and diethylaminopropylamine; N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, menthanediamine, 3,9- Alicyclic amines such as bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; meta-phenylenediamine, para-phenylenediamine, 1,2-diaminebenzene, 4 , 4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 4, 4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl Sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, bis (3-aminophenyl) diethylsilane, 4,4'-diaminodiphenyldiethylsilane, benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, 4,4'- Diaminobenzophenone, N, N-bis (4-aminophenyl) -n-butylamine, N, N-bis (4-aminophenyl) methylamine, 1,5-diaminonaphthalene, 3,3′-dimethyl-4, 4′-diaminobiphenyl, 4-aminophenyl-3-aminobenzoate, N, N-bis (4-amino Nophenyl) aniline, bis (p-beta-amino-t-butylphenyl) ether, p-bis-2- (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-amino) Pentyl) benzene, (1,3-bis (4-aminophenoxy)) benzene, m-xylylenediamine, p-xylylenediamine, 4,4′-diaminodiphenyl ether phosphine oxide, 4,4′-diaminodiphenyl N— Aromatic amines such as methylamine and 4,4′-diaminodiphenyl N-phenylamine; epoxy resins—modified aliphatic polyamines such as diethylenetriamine adduct, amine-ethylene oxide adduct, cyanoethylated polyamine; bisphenol A, trimethylolallyloxyphenol , Low polymerization degree phenol novo Click resin, epoxidized or butylated phenolic resin or Super Beckcite1001 (manufactured by Nippon Reichhold Chemical Co. (Ltd.)), Hitanol 4010 ((Ltd.) manufactured by Hitachi, Ltd.), Scado form L. Phenolic resins containing at least two phenolic hydroxyl groups in the molecule, such as phenolic resins known by trade names such as 9 (manufactured by Scado Zwoll, the Netherlands) and Methylon 75108 (manufactured by General Electric, USA); P. 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 resin such as aniline resin; represented by formula: HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ SS) _L C ₂ H ₄ OCH ₂ OC ₂ H ₄ SH (wherein L is an integer of 1 to 10) Polysulfide resins having at least two mercapto groups in one molecule, such as polysulfide resin; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl nadic acid, dodecyl succinic anhydride, anhydrous Examples thereof include organic acids such as chlorendic acid or anhydrides thereof (acid anhydrides); dicyandiamide and the like.

[(D) Filler]
In order to reduce the elastic modulus, water absorption, and linear expansion coefficient of the resulting cured adhesive layer, a filler of component (D) may be blended as an optional component in the composition of the present invention. There is no restriction | limiting in particular in the filler of (D) component, A well-known thing can be used. (D) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  (D) The average particle diameter of a component becomes like this. Preferably it is 10 micrometers or less (for example, 0.1-10 micrometers), More preferably, it is 5 micrometers or less (for example, 0.5-5 micrometers). When the average particle diameter exceeds 10 μm, the smoothness of the surface of the adhesive film made of the adhesive composition of the present invention may be impaired. Moreover, it is preferable that the maximum particle diameter of (D) component is 20 micrometers or less, More preferably, it is 10 micrometers or less. In the present specification, the “average particle size” means a volume-based average particle size corresponding to 50% of the cumulative distribution obtained by a particle size distribution measuring apparatus using a laser light diffraction method. The “maximum particle size” is the maximum value of the particle size in the cumulative distribution measured when the average particle size is obtained as described above.

  Examples of the component (D) include inorganic fillers such as silica fine powder, conductive metal particles such as alumina, titanium oxide, carbon black, and silver particles; and organic fillers such as silicone fine particles. Among these, silica fine powder and silicone fine particles are preferable. Hereinafter, the silica fine powder and the silicone fine particles will be described in more detail.

-Silica fine powder There is no restriction | limiting in particular in a silica fine powder, A well-known thing can be used. Silica fine powder may be used individually by 1 type, or may be used in combination of 2 or more types. The average particle size and the maximum particle size of the silica fine powder are the same as those generally described for the component (D). The silica fine powder is preferably surface-treated with an organosilicon compound such as organoalkoxysilane, organochlorosilane, organosilazane, and low molecular weight siloxane from the viewpoint of fluidity of the resulting composition.

  Examples of the silica fine powder include reinforcing silica such as fumed silica and precipitated silica; and crystalline silica such as 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 manufactured by Admatechs Co., Ltd. -E2, SO-C2, SO-E3, SO-C3, SO-E5, SO-C5; Musil 120A and Musil 130A manufactured by Shin-Etsu Chemical Co., Ltd. are exemplified.

-Silicone fine particles There is no restriction | limiting in particular in a silicone fine particle, A well-known thing can be used, For example, a silicone rubber fine particle, a silicone resin fine particle, etc. are mentioned. Silicone fine particles may be used alone or in combination of two or more. Although only silicone fine particles may be used as the component (D), since the elastic modulus and water absorption of the obtained cured product layer can be more effectively reduced, the silicone fine particles are used in combination with the silica fine powder. Is preferred. The average particle size and the maximum particle size of the silicone fine particles are the same as those generally described for the component (D).

  As the silicone fine particles, composite silicone rubber fine particles are preferable. The composite silicone rubber fine particles are particles in which the microorganism of polyorganosilsesquioxane resin produced by a polymerization reaction on the surface is present on at least a part of the surface of the silicone rubber fine particles. The composite silicone rubber fine particles can be prepared, for example, according to the method described in JP-A-7-196815. That is, an alkaline substance itself or an alkaline aqueous solution thereof and 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. The alkoxysilane is hydrolyzed and polymerized, and then dried to obtain composite silicone rubber fine particles. The content 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 spherical silicone rubber fine particles. If the content is less than 1 part by mass, the composite silicone rubber fine particles have poor dispersibility in the resulting adhesive composition, and the resulting adhesive film may have a non-uniform composition. On the other hand, when this content exceeds 500 mass parts, there exists a tendency for the elasticity modulus of the hardened | cured material layer obtained to become high.

  As the composite silicone rubber fine particles, for example, KMP-600, KMP-605, X-52-7030 and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

[Other ingredients]
Furthermore, the composition of the present invention includes various components as components (A) and (B), and in some cases, in addition to the components (C) and (D), as well as other components as long as the object of the present invention is not impaired. Additives may be blended. Examples of the additive include a wettability improver, an antioxidant, and a heat stabilizer.

[Preparation of composition]
The adhesive composition of the present invention is prepared by mixing the components (A) and (B) and, if necessary, the components (C) and (D) and other components with a mixer or the like according to a conventional method. can do. The blending amounts of the components (A) to (D) are as follows.

  (B) The compounding quantity of a component becomes like this. Preferably it is 5-500 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 10-200 mass parts. When the blending amount is within the above range, it is preferable in terms of stress relaxation due to adhesive strength and flexibility of the cured adhesive.

  (C) The compounding quantity of a component becomes like this. Preferably it is 5-300 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 10-100 mass parts. When the blending amount is within the above range, it is preferable from the viewpoint of adhesiveness and flexibility of the cured product.

  (D) The compounding quantity of a component is 5-80 mass% in the adhesive composition of this invention, It is preferable that it is 10-60 mass% especially. When the blending amount is less than 5% by mass, at least one of the water absorption coefficient and the linear expansion coefficient of the obtained cured adhesive layer may be difficult to decrease. If the blending amount exceeds 80% by mass, the resulting cured adhesive layer may have an increased elastic modulus. In particular, when silicone fine particles are blended as the component (D), the blending amount is preferably 5 to 30% by mass, more preferably 10 to 20% by mass in the adhesive composition of the present invention. When the blending amount is in the range of 5 to 30% by mass, it is possible to effectively suppress an increase in the elastic modulus, water absorption rate, and linear expansion coefficient of the obtained cured adhesive layer.

[Use of composition]
The adhesive composition of the present invention can be used, for example, to bond two adherends. These adherends are not particularly limited. Examples of one adherend include a silicon chip and an LED chip, and examples of the other adherend include a resin substrate such as a BT substrate. .

  For example, the adhesive composition of the present invention is dissolved in a solvent at an appropriate concentration, applied onto one adherend, dried, and then applied to the adherend surface to which the adhesive composition has been applied. These two adherends can be bonded together by pressure-bonding the adherends and heat-curing the adhesive composition. Examples of the solvent include aprotic polar solvents such as toluene, cyclohexanone, and N-methylpyrrolidone (NMP). Drying is preferably performed at room temperature to 200 ° C., particularly 80 to 150 ° C. for 1 minute to 1 hour, particularly 3 to 10 minutes. The pressure bonding is preferably performed at a pressure of 0.01 to 10 MPa, particularly 0.1 to 2 MPa. The heat curing is preferably performed at a temperature of 100 to 200 ° C., particularly 120 to 180 ° C. for 30 minutes to 5 hours, particularly 1 to 5 hours.

  Moreover, the adhesive composition of this invention can also be used for adhere | attaching two to-be-adhered bodies in the state shape | molded in the film form. For example, the two adherends can be bonded using an adhesive sheet including a base material and an adhesive layer made of the adhesive composition of the present invention provided on the base material. More specifically, for example, the adhesive layer is peeled off from the adhesive sheet, and the adhesive layer is sandwiched between two adherends in a layered manner and heat-cured and heat-cured. The body can also be glued. The conditions for pressure bonding and heat curing are the same as described above.

  The adhesive sheet can be obtained by dissolving the adhesive composition of the present invention in a solvent at an appropriate concentration in the same manner as described above, applying the solution onto a substrate and drying it to form an adhesive layer. Examples of the solvent and drying conditions are the same as described above. There is no restriction | limiting in particular in the film thickness of an adhesive bond layer, Although it can select according to the objective, It is preferable that it is 10-100 micrometers, and it is especially preferable that it is 15-50 micrometers. The substrate is usually in the form of a film, for example, polyethylene film, polypropylene film, polyester film, polyamide film, polyimide film, polyamideimide film, polyetherimide film, polytetrafluoroethylene film, paper, metal foil, etc. The base material or the base material whose surface has been release-treated can be used, and the base material whose surface has been release-treated is particularly preferable. The thickness of the substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

  The adhesive composition of the present invention can be used for the dicing die attach film of the present invention. That is, the dicing die attach film of the present invention includes a dicing film having a base material and a pressure-sensitive adhesive layer provided thereon, and the adhesive composition of the present invention provided on the pressure-sensitive adhesive layer of the dicing film. A dicing die attach film provided with an adhesive layer comprising: The substrate is usually in the form of a film, and for example, polyethylene, polypropylene, polyvinyl chloride, and copolymers thereof can be used. The thickness of the substrate is preferably 50 to 200 μm, more preferably 70 to 150 μm. Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. The thickness of the pressure-sensitive adhesive layer is preferably 1 to 20 μm, more preferably 5 to 10 μm.

  The dicing die attach film of the present invention can be produced, for example, by laminating the adhesive layer in the adhesive sheet of the present invention on the adhesive layer of the dicing film. It can also be obtained by dissolving the adhesive composition of the present invention in a solvent at a suitable concentration similar to the above, applying the composition onto the pressure-sensitive adhesive layer of the dicing film, and drying to form an adhesive layer. Examples of the solvent, drying conditions, and the thickness of the adhesive layer are the same as described above. As the dicing film, for example, a pressure-sensitive dicing film or an ultraviolet curable dicing film can be used.

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

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

[(B) Synthesis of polyimide resin]
[Synthesis Example 1]
Into a 1 L separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer and a stirrer, 39.73 parts by mass of 4,4′-diaminodiphenylsulfone as a diamine compound, tetracarboxylic acid 62.1 parts by mass of a compound represented by the following formula (1) as a dianhydride and 305.49 parts by mass of γ-butyrolactone as a reaction solvent were charged (diamine compound: tetracarboxylic dianhydride (molar ratio) = 16: 15) Stirred at room temperature for 16 hours, then stirred at 80 ° C. for 2 hours to react the diamine compound with the tetracarboxylic dianhydride to synthesize a polyamic acid solution.

  Thereafter, 60 parts by mass of xylene was added to the polyamic acid solution, the temperature was raised, and the mixture was refluxed at about 200 ° C. for 6 hours. Reflux was stopped after confirming that a predetermined amount of water had accumulated in the moisture determination receiver and no outflow of water was observed, and a solution containing polyimide resin A was obtained. The weight average molecular weight of the polyimide resin A was 9,500. This polyimide resin contains a dimethylpolysiloxane structure represented by the following formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 100 mol%.

When the infrared absorption spectrum of the polyimide resin A was measured, absorption based on the unreacted functional group of the polyamic acid did not appear, and absorption based on the imide group was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ .

[Synthesis Example 2]
In Synthesis Example 1, instead of 62.1 parts by mass of the compound represented by the above formula (1) as tetracarboxylic dianhydride, 33.12 parts by mass of the compound represented by the above formula (1) and 6FDA (that is, 2, 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, the same shall apply hereinafter) 31.09 parts by mass (the ratio of the compound represented by the above formula (1) in the total tetracarboxylic dianhydride) = 53.33 mol%, diamine compound: tetracarboxylic dianhydride (molar ratio) = 16:15), except that the charged amount of γ-butyrolactone was changed from 305.49 parts by mass to 311.82 parts by mass In the same manner as in Example 1, a solution containing polyimide resin B was obtained. The weight average molecular weight of the polyimide resin B was 9,700. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 53.33 mol%.

[Synthesis Example 3]
In Synthesis Example 1, 81.30 parts by mass of the compound represented by the following formula (2) was used as a tetracarboxylic dianhydride instead of 62.1 parts by mass of the compound represented by the above formula (1) (diamine compound: tetra Carboxylic acid dianhydride (molar ratio) = 16: 15), polyimide resin C was prepared in the same manner as in Synthesis Example 1 except that the charged amount of γ-butyrolactone was changed from 305.49 parts by mass to 363.09 parts by mass. A solution containing was obtained. The weight average molecular weight of the polyimide resin C was 10,800. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 100 mol%.

[Synthesis Example 4]
In Synthesis Example 1, 69.30 parts by mass of a compound represented by the following formula (3) was used as a tetracarboxylic dianhydride instead of 62.1 parts by mass of the compound represented by the above formula (1) (diamine compound: tetra Carboxylic dianhydride (molar ratio) = 16: 15), polyimide resin D was prepared in the same manner as in Synthesis Example 1 except that the charged amount of γ-butyrolactone was changed from 305.49 parts by mass to 327.09 parts by mass. A solution containing was obtained. The weight average molecular weight of the polyimide resin D was 9,900. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 100 mol%.

[Synthesis Example 5]
In Synthesis Example 1, 73.50 parts by mass of the compound represented by the following formula (4) was used as a tetracarboxylic dianhydride instead of 62.1 parts by mass of the compound represented by the above formula (1) (diamine compound: tetra Carboxylic acid dianhydride (molar ratio) = 16: 15), polyimide resin E was prepared in the same manner as in Synthesis Example 1 except that the charged amount of γ-butyrolactone was changed from 305.49 parts by mass to 339.69 parts by mass. A solution containing was obtained. The weight average molecular weight of the polyimide resin E was 10,100. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 100 mol%.

[Synthesis Example 6]
In Synthesis Example 1, 49.66 parts by mass of 3,3′-diaminodiphenylsulfone was used as the diamine compound instead of 39.73 parts by mass of 4,4′-diaminodiphenylsulfone, and the above formula ( The amount of the compound represented by 1) was changed from 62.1 parts by mass to 41.4 parts by mass (diamine compound: tetracarboxylic dianhydride (molar ratio) = 2: 1), and the amount of γ-butyrolactone was charged. Was changed from 305.49 parts by mass to 273.18 parts by mass in the same manner as in Synthesis Example 1 to obtain a solution containing polyimide resin F. The weight average molecular weight of the polyimide resin F was 820. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 100 mol%.

[Synthesis Example 7]
In Synthesis Example 1, 49.66 parts by mass of 3,3′-diaminodiphenylsulfone was used as a diamine compound instead of 39.73 parts by mass of 4,4′-diaminodiphenylsulfone (diamine compound: tetracarboxylic dianhydride ( Molar ratio) = 4: 3), and a solution containing polyimide resin G was obtained in the same manner as in Synthesis Example 1 except that the amount of γ-butyrolactone was changed from 305.49 parts by mass to 335.28 parts by mass. . The weight average molecular weight of the polyimide resin G was 2,050. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, has amino groups at both ends, and the proportion of structural units having an organopolysiloxane structure in all structural units is It is 100 mol%.

[Synthesis Example 8]
In Synthesis Example 1, instead of 62.1 parts by mass of the compound represented by the above formula (1) as a tetracarboxylic dianhydride, 16.56 parts by mass of the compound represented by the above formula (1) and 48.86 parts by mass of 6FDA (Ratio of the compound represented by the above formula (1) in all tetracarboxylic dianhydrides = 26.67 mol%, diamine compound: tetracarboxylic dianhydride (molar ratio) = 16: 15), γ -A solution containing polyimide resin H was obtained in the same manner as in Synthesis Example 1 except that the amount of butyrolactone was changed from 305.49 parts by mass to 315.45 parts by mass. The weight average molecular weight of the polyimide resin H was 9,700. This polyimide resin contains a dimethylpolysiloxane structure represented by the above formula (9) as an organopolysiloxane structure, and has amino groups at both ends. Among all structural units, the structural unit has an organopolysiloxane structure. The ratio is 26.67 mol%.

[Preparation of adhesive composition]
The following components (A) to (D) and other components are charged in a blending amount (parts by mass) shown in Table 1 into a rotating / revolving mixer (manufactured by Shinky Co., Ltd.). Methyl ethyl ketone was added so as to have a concentration of 20% by mass and mixed to prepare an adhesive composition.

(A) (Meth) acrylic resin (A) As component (A), the following three (meth) acrylic resins (all manufactured by Nagase ChemteX) having a glycidyl group and further having a structural unit derived from acrylonitrile are used. It was. The component (A) was blended as a resin solution obtained by dissolving the following resins separately in methyl ethyl ketone. In addition, the compounding quantity of (A) component shown in Table 1 is the value converted into the compounding quantity of resin itself instead of the compounding quantity of a resin solution.
SG-P3: containing 0.021 mol / 100 g of glycidyl group, weight average molecular weight = 850,000, Tg = 12 ° C., resin solution concentration = 15% by mass
SG-P3-42: 0.035 mol / 100 g of glycidyl group, weight average molecular weight = 750,000, Tg = 12 ° C., resin solution concentration = 15% by mass

(B) Polyimide resin Polyimide resins A to G synthesized in each of Synthesis Examples 1 to 7 above.

(Other components) Polyimide resins other than (B) component (for comparison)
Polyimide resin H synthesized in Synthesis Example 8

(Other components) Diamine compound (for comparison)
3,3′-DDS: 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.)
・ 4,4′-DDS: 4,4′-diaminodiphenylsulfone (manufactured by Wakayama Seika Co., Ltd.)

(C) Epoxy resin Epoxy resin 1: EOCN-1020-55 (manufactured by Nippon Kayaku Co., Ltd.), softening temperature 55 ° C
Epoxy resin 2: HP-7200 (Dainippon Ink Chemical Co., Ltd.), softening temperature 59-63 ° C

(D) Filler ・ Silica fine powder: SC-2050, spherical silica, average particle size 0.5 μm, manufactured by Admatechs ・ Composite silicone rubber fine particles: X-52-7030, average particle size 0.7 μm, Shin-Etsu Chemical Co., Ltd. Made by company

(Other components) Adhesion aid Coupling agent: X-12-414 (manufactured by Shin-Etsu Chemical Co., Ltd.), mercapto silane coupling agent

[Preparation of adhesive sheet]
Next, the adhesive composition was applied onto a 50 μm thick PET film coated with a fluorine-based silicone release agent, dried by heating at 110 ° C. for 10 minutes, and provided with an adhesive layer having a thickness of about 25 μm. A sheet was produced.

[test]
The obtained adhesive composition or adhesive sheet was subjected to the following test. The results are shown in Table 1.

(1) Dispersion stability of adhesive composition The prepared adhesive composition was allowed to stand for 24 hours, and the state of phase separation was visually observed. In Table 1, the case where phase separation occurs is indicated by “x”, and the case where phase separation does not occur is indicated by “◯”.

(2) Initial adhesiveness A silicon wafer having a thickness of 500 μm and a resin substrate (BT substrate on which resist AUS303 (manufactured by Unitechno Co., Ltd.) has been applied and cured) are diced into 3 mm × 3 mm chips, and thus obtained silicon The adhesive sheet was thermocompression bonded at 70 ° C. so that the adhesive layer was in contact with the back surface of the chip or resin chip. Next, the adhesive sheet was cut into the same shape as the chip, and the chip with the adhesive sheet was taken out. The PET film was peeled from these chips to obtain chips with an adhesive layer. Next, on the 10 mm × 10 mm silicon substrate or the 10 mm × 10 mm BT substrate on which the resist AUS303 is applied and cured, the obtained chip with the adhesive layer is brought into contact with the surface to which the adhesive layer is attached. It was mounted and fixed by thermocompression bonding for 1 second under conditions of 170 ° C. and 0.1 MPa. Thus, the board | substrate with which the chip | tip was fixed was heated at 175 degreeC for 4 hours, the adhesive bond layer was hardened, and the test piece (adhesion test piece) was produced. Using this adhesion test piece, the shear adhesive force between the adhesive cured product layer and the substrate was measured at 260 ° C. with a bond tester (manufactured by DAGE, 4000PXY).

(3) Adhesiveness after moist heat After holding the adhesive test piece of (2) above for 168 hours under the condition of 85 ° C./60% RH and then passing it through a reflow furnace at 260 ° C. three times, Similarly, the shear adhesive strength was measured at 260 ° C.

^＊比較例１では、接着剤組成物の分散安定性が不良であったため、接着用シートを作製することができなかったことから、接着性試験は行わなかった。

^{* In} Comparative Example 1, since the dispersion stability of the adhesive composition was poor, an adhesive sheet could not be prepared, and thus the adhesion test was not performed.

  The composition of Examples 1-7 contains (B) component, ie, the specific polyimide resin in which the ratio of the structural unit which has an organopolysiloxane structure exists in a predetermined range. On the other hand, the composition of Comparative Example 1 contains a polyimide resin in which the proportion of structural units having an organopolysiloxane structure is lower than a predetermined range instead of the polyimide resin of component (B). A composition contains the diamine compound different from (B) component instead of the polyimide resin of (B) component. As shown in Table 1, the composition of the present invention has good dispersibility unlike the composition of Comparative Example 1, and the cured product layer obtained from the composition of the present invention is the composition of Comparative Examples 2 and 3. Compared with the cured product layer obtained from the above, the adhesive strength is remarkably high.

  The adhesive composition of the present invention is useful as an adhesive for these substrates because it has good dispersion stability and gives a cured adhesive layer having high adhesion to various substrates. The adhesive composition is also useful as an adhesive layer in an adhesive sheet and a dicing die attach film for stably manufacturing a highly reliable semiconductor device.

Claims (9)

(A) The weight average molecular weight is 100,000 to 1,500,000, a (meth) acrylic resin containing a glycidyl group, and (B) an organopolysiloxane structure, and the weight average molecular weight is 500 to 20 An adhesive composition comprising a polyimide resin having an amino group at the end and a proportion of structural units having an organopolysiloxane structure of 50 to 100 mol% in all structural units. (B) component polyimide resin, tetracarboxylic dianhydride containing at least one compound represented by the following formulas (1) to (4), 4,4′-diaminodiphenylsulfone and 3,3 ′ The adhesive composition according to claim 1, comprising a polyimide resin obtained by reacting a diamine compound containing at least one of diaminodiphenylsulfone with an excess of the diamine compound.

  The adhesive composition according to claim 1 or 2, further comprising (C) an epoxy resin. The component (A) has the following formula:

The adhesive composition which concerns on any one of Claims 1-3 containing the structural unit represented by these.   Furthermore, (D) Adhesive composition which concerns on any one of Claims 1-4 which contains 5-80 mass% of fillers in this adhesive composition.   The adhesive composition according to claim 5, wherein the component (D) is fine silica powder, fine silicone particles, or a combination thereof.   The adhesive composition according to any one of claims 1 to 6, which is formed into a film.   The adhesive sheet provided with the base material and the adhesive bond layer which consists of an adhesive composition of any one of Claims 1-6 provided on this base material.   A dicing film having a base material and a pressure-sensitive adhesive layer provided thereon, and an adhesive composition according to any one of claims 1 to 6 provided on the pressure-sensitive adhesive layer of the dicing film. Dicing die attach film with an adhesive layer.