KR101304798B1 - Adhesive Composition and Sheet Having an Adhesive Layer of the Composition - Google Patents

Abstract

Provided are an adhesive composition which is excellent in chip taking out property, does not cause chip flow, and provides a low elastic modulus adhesive layer between a chip and a substrate, and a dicing die bond adhesive sheet provided with the adhesive layer.

(A) 5 to 60% by weight of polyimide silicone resin

(B) 5 to 60% by weight of an epoxy resin having a softening temperature of 80 ° C. or less

(C) 0.001 to 20% by weight of at least one epoxy resin curing catalyst selected from imidazole compounds and dicyandiamides

(D) 20 to 70% by weight of spherical silica having an average particle diameter of 0.1 to 10 microns

(E) 5 to 30% by weight of composite silicone rubber spherical fine particles

Adhesive composition comprising a.

Adhesive composition, dicing die bond sheet

Description

Adhesive Composition and Sheet Having an Adhesive Layer of the Composition

1 is a cross-sectional view of a dicing die bond sheet according to a first aspect of the present invention.

2 is a cross-sectional view of a dicing die bond sheet according to a second aspect of the present invention.

It is sectional drawing which shows the state which fixed the silicon wafer to the dicing die bond sheet of the 1st aspect of this invention.

4 is a cross-sectional view showing a state in which a silicon wafer is fixed to a dicing die-bonding tape according to a second aspect of the present invention.

<Explanation of symbols for the main parts of the drawings>

1: adhesive film base material

2: adhesive layer

3: adhesive layer

4: adhesive film base material

5: silicon wafer

[Document 1] Japanese Unexamined Patent Publication No. 3-189127

[Document 2] Japanese Unexamined Patent Publication No. 4-264003

[Document 3] Japanese Unexamined Patent Publication No. 10-60111

[Document 4] Japanese Unexamined Patent Publication No. 7-224259

[Document 5] Japanese Unexamined Patent Publication No. 8-27427

[Document 6] Japanese Patent No. 3221756

[Document 7] Japanese Unexamined Patent Publication No. 9-67558

[Document 8] Japanese Unexamined Patent Publication No. 2002-256236

[Document 9] Japanese Patent No. 2984549

TECHNICAL FIELD The present invention relates to an adhesive composition, and in particular, to a sheet having an adhesive composition which is significantly improved in terms of minimum melt viscosity and elastic modulus and an adhesive layer obtained from the composition.

With the recent miniaturization of electronic devices, miniaturization is also required for semiconductor chip mounting substrates. The adhesive film used to mount the semiconductor chip is required to be compressed at low temperature and low pressure in order to prevent the occurrence of warping or cracking when bonding to the wafer due to the thinning of the wafer and the chip or to prevent the occurrence of cracking when thermally pressing the chip onto the substrate. have.

Further, in the BGA structure, the semiconductor chip is adhesively fixed on the resin wiring board and resin-sealed thereon, but the chip mounting surface of these resin substrates has irregularities on the wiring pattern, and voids during chip mounting by the adhesive film. This may occur. It is conceivable to lower the melt viscosity of the adhesive film as a method of preventing voids, but for the rationalization of the process, batch curing is performed after resin sealing without curing the adhesive film at the time of mounting the chip, and sealing is performed due to the request for miniaturization of the semiconductor device. Since the resin thickness is required to be thin, when the melt viscosity is lowered, there is a possibility that the chip flows together with the sealing resin during sealing molding. Therefore, improvement of an adhesive film is calculated | required from the point of low temperature, low pressure bonding, and minimum melt viscosity.

On the other hand, a semiconductor device generally fixes a large diameter silicon wafer with an adhesive tape (dicing tape), peels off the chip cut by dicing (cutting separation) from the dicing tape, and takes it out (pick-up). ), And the chips taken out were manufactured by thermocompression bonding and adhesive fixing to a lead frame with a curable liquid adhesive (manufactured by a die bond). In recent years, a dicing die-bonding tape which functions as a dicing tape and a die-bonding agent has been developed. In other words, the tape is fixed so that the chip does not scatter during dicing, and after dicing, the tape can be easily taken out with the adhesive attached to the chip (pick-up). Adhere to the lead frame. This tape required the same improvement as the adhesive film.

As an adhesive, siloxane modified polyamideimide which introduce | transduced the siloxane structure into the polyimide and polyamideimide which are resins excellent in heat resistance conventionally is proposed (document 1, document 2). However, these resins did not have sufficient adhesive strength and heat resistance.

Moreover, although it was proposed to mix | blend the compound which has 2 or more maleimide groups with siloxane modified polyamideimide, and to improve high temperature characteristic (document 3), this resin composition was inferior to adhesiveness with respect to copper foil especially.

Although a heat resistant adhesive film containing polyimide silicone and an epoxy resin has been proposed (documents 4 and 5), since the polyimide silicone does not have a functional group which hardens, the adhesion and its reliability are poor.

 Although a heat resistant adhesive film containing polyimide silicone having an phenolic hydroxyl group and an epoxy resin has been proposed (Document 6), it was not sufficient in the generation of voids after low temperature, low pressure compression and packaging (PKG), and suppression of chip flow.

Moreover, the sheet | seat which formed thermoplastic polyimide-type resin as a dicing die-bonding layer on the plastic film base material as a dicing die-bonding tape is known (document 7). However, since the polyimide resin layer and the wafer were firmly adhered by thermocompression bonding, the chip takeout (pickup) properties could not be easily controlled. In addition, since the adhesive layer is a thermoplastic polyimide-based resin, adhesiveness, in particular, the adhesion after humidification required in the wire bonding, sealing, and solder reflow process, which is a manufacturing process of a semiconductor device, insufficient adhesion and strength at high temperatures, and the like. There was a flaw.

Moreover, (A) polyimide-type resin which improved the adhesiveness after humidification and the adhesiveness at high temperature on the film base material which provided the radiation polymeric adhesive layer which can control adhesiveness, (B) epoxy resin, (C) Dicing die-bonding tape which provided the resin layer which consists of a phenol resin and (D) hardening accelerator was proposed (document 8, document 9).

Since the die bond layer of the said die bond tape contains curable epoxy resin composition, it is excellent in adhesiveness after humidification, adhesiveness at high temperature, and strength. However, the die-bonding tape may be difficult to take out chips after dicing. This is because the radiation polymerizable adhesive layer for controlling adhesion is composed of a (meth) acrylate copolymer polymer, a (meth) acryl group-containing polymer or a polyfunctional acrylic compound and a photopolymerization initiator, and is easily compatible with an epoxy resin. It is considered that the adhesive force with the epoxy resin increases due to the reaction caused by, or fusion with the epoxy resin softened by thermocompression bonding of wafers in the dicing step. In addition, the adhesion (adhesive force) between the die bond layer and the radiation-polymerizable adhesive layer may change (increase) with time, and chip extraction (pickup) may not be possible in the same manner.

Accordingly, an object of the present invention is to provide an adhesive composition which is excellent in chip takeout property and does not cause chip flow, and provides an adhesive layer having a low elastic modulus between the chip and the substrate, and a dicing die bond adhesive sheet having the adhesive layer. It is done.

That is, the present invention is as follows.

(A) 5 to 60% by weight of polyimide silicone resin

(B) 5 to 60% by weight of an epoxy resin having a softening temperature of 80 ° C. or less

(C) 0.001 to 20% by weight of at least one epoxy resin curing catalyst selected from imidazole compounds and dicyandiamides

(D) 20 to 70% by weight of spherical silica having an average particle diameter of 0.1 to 10 microns

(E) 5 to 30% by weight of composite silicone rubber spherical fine particles

Adhesive composition comprising a.

BEST MODE FOR CARRYING OUT THE INVENTION [

(A) polyimide silicone resin in the composition of this invention is represented by following General formula (2).

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

(A) Polyimide silicone resin contains the polyimide resin containing a siloxane bond. That is, at least one of X and Y in Formula 2 may include the siloxane bond. (A) The polyimide silicone resin is contained at 5 to 60% by weight, preferably 20 to 50% by weight of the total weight of the composition of the present invention.

(A) The polyimide silicone resin may be a polyamic acid resin which is a precursor of the compound of formula (2) represented by the following formula (3). However, it is preferable to use the polyimide resin of the general formula (2), because water may be generated by imidization (dehydration ring closure) during heat curing in the die bonding step, and peeling of the adhesive surface may occur.

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

In Chemical Formulas 2 and 3, q is an integer of 1 to 300, preferably an integer of 2 to 300, in particular an integer of 5 to 300. If q is less than the said lower limit, adhesive strength will run short, and if it exceeds the said upper limit, heat | fever crimpability will run short. More preferably, q is a number in which the glass transition point of (A) polyimide silicone resin becomes 100-200 degreeC, Preferably it is the range of 120-190 degreeC.

The polyimide resin represented by the formula (2) can be obtained by dehydrating and closing the polyamic acid resin represented by the formula (3) by a conventional method. The polyamic acid resin can be easily obtained by the following method. In other words, the tetracarboxylic dianhydride represented by the following general formula (4) and the diamine represented by the following general formula (5) are reacted in the organic solvent in almost equimolar amounts according to a conventional method.

(Where X represents the same meaning as above).

H ₂ NY-NH ₂

(Y represents the same meaning as above.)

Examples of the tetracarboxylic dianhydride represented by the general formula (4) are shown below. It is also possible to use a mixture of two or more kinds of these tetracarboxylic dianhydrides.

Among the diamines represented by the formula (5), preferably 1 to 80 mol%, more preferably 1 to 60 mol% is a diaminosiloxane compound represented by the following formula (1) solubility in the organic solvent of the polyimide resin, It is preferable at the point of adhesiveness with respect to a base material, the low elastic modulus of hardened | cured material, and a softness | flexibility.

In the formula, R ³ is a divalent organic group having 3 to 9 carbon atoms, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms independently of each other, and m is an integer of 1 to 200.

As R ³ , for example, alkyl such as-(CH ₂ ) ₃ -,-(CH ₂ ) _4- , -CH ₂ CH (CH ₃ )-,-(CH ₂ ) ₆ -,-(CH ₂ ) _8- An arylene group, an arylene group exemplified below,

Benzyl alkyl groups, such as alkylene and _{arylene, - (CH 2) 3 -O-} , - oxy-arylene group, which illustrated in the (CH _{2) 4} oxyalkylene group, such as -O-,,

 And oxyalkylene arylene groups exemplified below;

The divalent hydrocarbon group which may contain an ether structure, such as these, is mentioned.

Examples of R ⁴ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group and octyl group, and vinyl group , Alkenyl groups such as allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, aryl groups such as phenyl group, tolyl group and xylyl group, aralkyl groups such as benzyl group and phenylethyl group, these A group in which part or all of the hydrogen atoms bonded to carbon atoms of the group are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., for example, chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc. The halogen substituted alkyl group etc. are mentioned, Especially, a methyl group and a phenyl group are preferable. m is an integer of 1-200, Preferably it is an integer of 1-100, More preferably, it is an integer of 1-80.

What is shown below as an example of the siloxane diamine represented by the said General formula (1) is mentioned, These 2 or more types combination may be sufficient.

Examples of diamines represented by the formula (5) other than the siloxydiamine include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 1,4-bis (3-aminophenoxy) benzene , 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthioether) benzene, 1,4-bis (m-aminophenylthioether) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4 -Aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy ) Phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] Tan, 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-aminophenoxy) phenyl] sulphone, 2,2-bis [4- ( Aromatic ring-containing diamines such as 4-aminophenoxy) phenyl] perfluoropropane; and the like, preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 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.

A phenolic hydroxyl group can be introduce | transduced into (A) polyimide resin, and can also be made to react with (B) epoxy resin. The said hydroxyl group can be introduce | transduced by using the diamine compound which has a phenolic hydroxyl group, and the thing of the following structure can be illustrated as said diamine compound.

A is a single bond and any of the groups exemplified below.

B is a single bond and any of the groups exemplified below

Wherein R ² is independently a hydrogen atom or a halogen atom such as fluorine, bromine or iodine or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, alkenyl group, alkynyl group, trifluoromethyl group or phenyl group It is a monovalent hydrocarbon group. n is an integer of 1 to 5; A and B may be 2 or more types, respectively. R is a hydrogen atom, a halogen atom or an unsubstituted or substituted monovalent hydrocarbon group.

Here, as R <^2> , the same thing as what was illustrated about said R <^4> , and alkynyl groups, such as an ethynyl group, a propynyl group, butynyl group, hexynyl group, etc. can be illustrated. In addition, R may be the same as those exemplified in the above R ² .

In this invention, the diamine compound especially represented by following formula (6) among the diamine compound which has the said phenolic hydroxyl group is preferable.

(In formula, R <^2> is the same as the above.)

The diamine compound having the phenolic hydroxyl group is preferably used at 5 to 90 mol% with respect to 100 mol of the diamine compound, and is typically used at 5 to 60 mass%, particularly 10 to 40 mass% of the total amount of the diamine compound. When the ratio is too small, the adhesive force may be lowered, and when too large, the flexibility of the adhesive layer may be insufficient.

Moreover, the monoamine which has a phenolic hydroxyl group can also be used, and the following structure can be illustrated.

In the formula, R ² is the same as described above. D may use 2 types together. In addition, p is an integer of 1-3.

When using the monoamine which has a phenolic hydroxyl group, it is 0.5-5 mol% with respect to the whole diamine compound.

Two or more kinds of the amine compound may be used in combination.

The production reaction of the polyamic acid resin and the polyimide resin dissolves the starting material described above in a solvent under an inert atmosphere, and usually reacts at 80 ° C. or lower, preferably 0 to 40 ° C. to synthesize a polyamic acid resin. By heating the obtained polyamic acid resin to 100-200 degreeC normally, Preferably it is 150-200 degreeC, the acidamide part of polyamic-acid resin can be dehydrated-closed and the polyimide resin made into the objective can be synthesize | combined.

As long as the organic solvent used for the said reaction is inert to the polyamic acid obtained, the starting material may not be completely dissolved. For example, tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylform Amides and dimethylsulfoxides, and are preferably aprotic polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvent can be used individually by 1 type or in combination of 2 or more types.

In order to facilitate said dehydration ring closure, it is preferable to use an azeotropic dehydrating agent, such as toluene and xylene. Furthermore, dehydration ring closure can also be performed at low temperature using the acetic anhydride / pyridine mixed solution.

In addition, in order to adjust the molecular weight of polyamic acid and a polyimide resin, dicarboxylic acid anhydrides, such as maleic anhydride and phthalic anhydride, and / or aniline, n-butylamine, the monoamine which has the phenolic hydroxyl group exemplified above are used. It can also be added. However, the addition amount of dicarboxylic anhydride is 5 mol or less normally per 100 mol of tetracarboxylic dianhydride, and the addition amount of monoamine is also 5 mol or less normally per 100 mol of diamines.

It is preferable that the glass transition temperature of the obtained polyimide resin is 200 degrees C or less. When the said temperature is exceeded, the thermal bonding property of the adhesive film of this invention may be inferior.

 The epoxy compound (B) used by this invention needs to have a softening temperature of 80 degrees C or less so that the adhesive film of this invention can be crimped | bonded by low temperature and low pressure. Moreover, the epoxy compound which has two or more epoxy groups in 1 molecule is preferable. Examples of epoxy compounds include bis (4-hydroxyphenyl) methane, 2,2'-bis (4-hydroxyphenyl) propane or diglycidyl ethers of these halides and their polycondensates (so-called bisphenol F type epoxy resins). , Bisphenol A type epoxy resin, etc.); Diglycidyl ethers such as resorcin, hydroquinone and methylresorcin; 1,4-bis (2,3-epoxypropoxy) benzene, 4,4'-bis (2,3-epoxypropoxy) diphenyl ether and hydrides thereof, butadiene diepoxide, vinylcyclohexene dioxide , 1,4-bis (2,3-epoxypropoxy) cyclohexene, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 1,2-dioxybenzene or resorcinol, polyhydric phenol Or novolac phenol resins (or halogenated novolac phenol resins) and epichloro, such as epoxyglycidyl ethers or polyglycidyl esters obtained by condensation of polyhydric alcohols with epichlorohydrin, phenol novolacs and cresol novolacs The liquid epoxy novolak (namely, novolak-type epoxy resin) obtained by condensing hydrin, and mixtures thereof are mentioned.

Moreover, use of a monoepoxy compound suitably does not interfere, As this monoepoxy compound, styrene oxide, cyclohexene oxide, propylene oxide, methylglycidyl ether, ethylglycidyl ether, phenylglycidyl ether , Allylglycidyl ether, octylene oxide, dodecene oxide and mixtures thereof are exemplified.

Moreover, the epoxy compound whose softening temperature exceeds 80 degreeC can also be used together in the grade which does not impair the characteristic of the adhesive film of this invention. Examples of such epoxy compounds include 1,2-dioxybenzene or resorcinol, polyhydric phenol or polyhydric alcohol, and epoxy glycidyl ether or polyglycidyl ester obtained by condensation of epichlorohydrin, phenol novolac, Epoxy phenols obtained by condensation of novolak-type phenolic resins (or halogenated novolak-type phenolic resins) such as cresol novolac and epichlorohydrin (i.e., novolak-type epoxy resins), and epoxidation by epoxidation. Solid epoxy compounds such as polyvalent epoxy compounds such as polyolefins, epoxidized polybutadienes, naphthalene ring-containing epoxy resins, biphenyl epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins and cyclopentadiene type epoxy resins. Can be mentioned.

(B) The epoxy compound is contained at 5 to 60% by weight, preferably 10 to 50% by weight of the total weight of the composition. When the compounding quantity of an epoxy compound is less than the said lower limit, the adhesiveness of a film may fall, and the thermal crimping property of the film in low temperature and low pressure may become inferior, and when the said upper limit is exceeded, the elasticity modulus and moisture absorption rate of hardened | cured material will rise, There exists a tendency for the reliability of an adhesive part to become low.

Moreover, the hardening | curing agent of epoxy resin can also be added to the adhesive composition of this invention to the extent which does not impair the characteristic. As this curing agent, various curing agents for conventionally known epoxy resins can be used, and for example, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpiperazine, bis (4-amino -3-methylcyclohexyl) methane, methaxylyleneamine, mentandiamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane Amine compound; Modified aliphatic polyamines such as epoxy resin-diethylenetriamine adduct, amine-ethylene oxide adduct and cyanoethylated polyamine; Bisphenol A, trimethylolallyloxyphenol, low-polymerization phenol novolac resins, epoxidized or butylated phenolic resins or "Super Beckcite" 1001 [manufactured by Nippon Reich Hold Kagaku Kogyo Co., Ltd.], "Hitanol" 4010 Two or more phenolic hydroxyl groups in the molecule, such as a phenol resin known under the trade names such as Hitachi Seisakusho Co., Ltd., Scado form L.9 (manufactured by Scado Zwoll, Netherlands), and Methylon 75108 (manufactured by General Electric, Inc. of the United States). Phenolic resin containing; "Beckamine" P.138 [manufactured by Nippon Reich Hold Kagaku Kogyo Co., Ltd.], "Meran" [manufactured by Hitachi Seisakusho Co., Ltd.], "U-Van" 10R [manufactured by Toyo Koatsu Kogyo Co., Ltd.] Carbon resins known under such trade names; Amino resins such as melamine resins and aniline resins; Two or more mercapto groups in one molecule such as represented 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 (an integer from n = 1 to 10) Polysulfide resin having; Organic acids such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methylnamic acid, dodecyl succinic anhydride, chloric anhydride, or anhydrides thereof (acid anhydrides). Among the above-mentioned curing agents, phenolic resins (phenol novolak resins) are preferred because they provide good molding workability to the composition of the present invention, provide excellent moisture resistance, and are nontoxic and relatively inexpensive. The hardening | curing agent mentioned above is not necessarily limited to one type in its use, According to the hardening performance of these hardening | curing agents, etc., you may use 2 or more types together. About a compounding quantity, if the target physical property is obtained, it will not specifically limit.

The (C) epoxy resin curing catalyst used in the present invention is an imidazole compound and / or dicyandiamide.

As imidazole compound catalyst, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethyl imida Imidazole derivatives, such as a sol, etc. are mentioned.

The epoxy resin curing catalyst in this invention can be used individually by 1 type or in mixture of 2 or more types. An imidazole compound and dicyandiamide can also be used together. In addition, (C) the epoxy resin curing catalyst is contained in an amount of 0.001 to 20% by weight, preferably 0.01 to 10% by weight of the total weight of the composition.

In the composition of the present invention, the silica particles (D) increase the melt viscosity of the adhesive layer to suppress chip flow in the resin encapsulation step, and exhibit an effect of decreasing the moisture absorption rate and the linear expansion rate of the cured product. The silica particles are spherical and have an average particle diameter of 0.1 µm to 10 µm, preferably 5 µm to 0.5 µm, and a maximum particle diameter of 20 µm or less. When average particle diameter exceeds this range, the smoothness of the surface of the adhesive film of this invention may be impaired. It is preferable that the said silica particle was surface-treated with the organosilicon compound which has an epoxy group.

(D) As silica particles, SE-2050, SC-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO-E2, SO-C2, SO-E3, SO -C3, SO-E5, SO-C5, etc. are illustrated and a mixture thereof may be sufficient.

(D) It is preferable that the compounding quantity of a silica particle shall be 20 to 70 weight%, especially 30 to 65 weight% of the total weight of a composition. If it exceeds these ranges, a moisture absorption may increase rather, or adhesive may become unable to crimp | bond at low temperature and low pressure.

The composition of this invention is characterized by including (E) composite silicone rubber microparticles | fine-particles. (E) Composite silicone microparticles | fine-particles are particle | grains in which the microorganism of the polyorgano silsesquioxane resin produced | generated by superposing | polymerizing on the said surface exists in at least one part on the surface of a silicone rubber particle. By mix | blending (E) composite silicone microparticles | fine-particles, the increase of the minimum melt viscosity of an adhesive agent and the fall of the elasticity modulus of hardened | cured material can be achieved with said (D) silica particle.

The composite silicon fine particles (E) have an average particle diameter of 0.1 to 10 m, preferably 0.5 to 5 m. When average particle diameter exceeds this range, the smoothness of the surface state of the adhesive film of this invention may be impaired. Moreover, it is preferable that a maximum particle diameter is 20 micrometers or less, More preferably, it is 10 micrometers or less. In addition, in this invention, the measurement of an average particle diameter is based on the laser diffraction scattering method.

The compounding quantity of (E) composite silicone particle is 5-30 weight%, Preferably it is 10-20 weight% of the total weight of a composition. Outside of these ranges, the adhesive is difficult to be crimped at low temperature and low pressure, and the linear expansion coefficient of the cured product may increase.

(E) Composite silicone microparticles | fine-particles can be produced according to the method described, for example in Unexamined-Japanese-Patent No. 7-196815. That is, an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane are added to the water dispersion of the spherical silicone rubber fine particles having an average particle diameter of 0.1 to 10 µm to hydrolyze and polymerize the organotrialkoxysilane on the surface of the spherical silicone rubber fine particles, This is then dried. The amount of the polyorganosilsesquioxane resin is preferably 1 to 500 parts by weight, more preferably 2 to 100 parts by weight based on 100 parts by weight of the silicone rubber spherical fine particles. If it is less than the said lower limit, the dispersibility in resin powder (A) and (B) of composite silicone microparticles | fine-particles worsens, and there exists a possibility that the composition of a film may become nonuniform. On the other hand, when more than the said upper limit, there exists a tendency for the elasticity modulus of adhesive hardened | cured material to become high.

As (E) composite silicon microparticles | fine-particles, KMP-600, KMP-605, X-52-7030 by Shin-Etsu Chemical Co., Ltd., etc. can be used, for example. Moreover, these 2 or more types of mixture can also be used.

In addition to the components described above, the resin composition of the present invention includes fillers such as alumina, titanium oxide, carbon black, conductive particles, coloring agents such as inorganic or organic pigments, dyes, wetting enhancers, and oxidation, within the range of not impairing the effects of the present invention. Additives, such as an inhibitor and a heat stabilizer, can be added.

The adhesive composition of the present invention comprises the above-mentioned (A) polyimide resin, (B) epoxy compound, (C) epoxy resin curing catalyst, (D) silica particles and (E) composite silicon fine particles, according to the conventional method, according to the conventional method. It can manufacture by mixing.

The adhesive composition of this invention obtained above can be used as an adhesive agent as an adhesive film and an adhesive layer of a dicing die-bonding sheet | seat. An adhesive is prepared by dissolving the composition in an appropriate concentration in an aprotic polar solvent such as toluene, cyclohexanone, NMP, and the like. After apply | coating the obtained adhesive on the pad of a circuit board and drying, a to-be-adhered body is crimped | bonded and heat-hardened. An adhesive film can be prepared by dissolving the composition in a suitable concentration in a solvent, applying it on a supporting substrate, and drying it. This adhesive film is adhered to a substrate, and then the supporting substrate is peeled off and the adherend is pressed thereon, followed by heat curing. As this support base material, polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil, or the like or a release treatment of these surfaces can be used.

As dry conditions of the adhesive composition apply | coated on a base material, it is preferable to set it as normal for 1 minute-1 hour, especially 3 to 20 minutes at normal temperature-200 degreeC, especially 80-150 degreeC. There is no restriction | limiting in particular in the film thickness of the obtained adhesive bond layer, Although it can select according to the objective, it is preferable that it is 10-100 micrometers, especially 15-50 micrometers. In addition, the curing conditions of the adhesive layer, after pressing at a pressure of 0.01 to 10 MPa, in particular 0.1 to 2 MPa, the temperature of 100 to 200 ℃, especially 120 to 180 ℃ 30 minutes to 5 hours, in particular 1 to 2 hours desirable.

The adhesive sheet for dicing die-bonding is equipped with the adhesive bond layer which consists of said adhesive composition on the silicone adhesion layer formed on the base material, For example, it can be set as the structure shown in FIGS. In the same drawing, (1) is an adhesive film substrate, (2) is an adhesive layer, (3) is an adhesive layer, (4) is an adhesive film substrate, and the tape of FIG. It is formed smaller than an adhesion layer according to the magnitude | size. In the present invention, the sheet also includes a tape-shaped one.

As the base material 1, the same thing as the base material of the adhesive film mentioned above can be used. Namely, polyolefin films such as polyethylene, polypropylene, polybutadiene film, polybutene film, polymethylpentene film, polyvinyl chloride film, and copolymer films thereof; Polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; (Meth) acrylic acid copolymer film, vinyl acetate copolymer film, polyether ketone film, polyether ether ketone film, polyether sulfone film, polyamide film, polyimide film, polyetherimide film, polycarbonate film, Polystyrene films and the like can be used. Moreover, what bridge | crosslinked these, the thing which carried out the plasma or corona treatment, and laminated | stacked these films or another film may be sufficient. Among them, polyethylene films and polypropylene films are preferred in view of having elongation that can easily isolate the chip which is cut by expanding the substrate (expanding) after the dicing step.

Although the film thickness of this base film is adjusted suitably according to the kind of film and desired stretchability, it is typically 20-400 micrometers, Preferably it is 30-150 micrometers.

The silicone adhesive layer 2 is formed from a silicone adhesive which is not compatible with the adhesive layer. For example, the adhesive containing the heat-hardening type | mold chain organopolysiloxane and solid silicone resin generally used can be used. The heat-curable silicone pressure-sensitive adhesives include organic peroxide curable and platinum addition-curable, but when an extensible polyethylene film and a polypropylene film are used as the substrate, they may be deformed by heat. It is preferable to use a silicone adhesive.

Silicone pressure-sensitive adhesive of the organic peroxide curing type is (i) a chain _{^{organopolysiloxane, (ii) (R 14 3}} SiO 1/2) units and (SiO ₂₎ organopolysiloxane copolymer resin (but consisting of units, R ¹⁴ is a substituted or Unsubstituted monovalent hydrocarbon group, the molar ratio of (R ¹⁴ ₃ SiO _1/2 ) units to (SiO ₂ ) units is from 0.5 to 1.5), and (iii) crosslinking agents such as benzoylperoxide, bis (4 -Methylbenzoyl) peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and the like.

Platinum addition-curable silicone pressure-sensitive adhesives (i) organopolysiloxane containing a linear vinyl group, (ii) the organopolysiloxane copolymer resin and (iii) a organohydrogenpolysiloxane containing a crosslinking agent such as a silicon-bonded hydrogen atom, (iv) A catalyst, for example, a platinum group metal catalyst such as platinum chloride, alcohol-modified platinum chloride, olefin complex of platinum, and complex of vinylsiloxane with platinum.

The adhesive layer using the silicone adhesive has an adhesive force of 0.05 to 1.0 N / 25 mm, preferably 0.1 to 0.7 N / 25 mm with respect to the adhesive layer obtained from the composition of the present invention. When adhesive force is smaller than the said lower limit, the chip | tip may peel and scatter with an adhesive bond layer at the time of dicing. Moreover, when adhesive force is larger than the said upper limit, chip taking out (pickup) will become difficult. By adjusting the crosslinking density of an adhesive and content of a silicone resin component, adhesive force can be adjusted in the said range.

The manufacturing method of the adhesive sheet for dicing die bonds of this invention is demonstrated. First, the said silicone adhesive is apply | coated on the plastic film base material 1, it hardens by heat, and forms the adhesion layer 2 (it calls this an adhesive film hereafter). It is preferable that the thickness of this adhesion layer is 5-100 micrometers, More preferably, it is 10-50 micrometers. Although it also depends on the heat resistance of a plastic film base material as hardening conditions, it is 60-120 degreeC normally.

Thus, the adhesive tape for dicing die-bonding of this invention can be obtained by opposing and crimping | bonding the silicone adhesion layer 2 surface of the adhesive film obtained and the adhesive bond layer surface of the adhesive film obtained by the said method. Here, as conditions for crimping | bonding an adhesive film and an adhesive film, it is preferable to set it as 0.01-2 MPa, especially 0.1-1 MPa at normal temperature.

The use method of the dicing die bond sheet of this invention is demonstrated, referring FIGS. 1 is a cross-sectional view of an example of a dicing die bond sheet. 2 is a cross-sectional view of a sheet in which the adhesive layer is smaller than the adhesive layer by the dicing frame. In FIG.1 and 2, the base film 4 of the adhesive bond layer side is peeled off, and a wafer is thermally crimped and fixed to the adhesive bond layer 3. 3 and 4 show a state where the adhesive film base material 4 of the sheets of FIGS. 1 and 2 is peeled off and adhered to the silicon wafer 5, respectively. Although thermocompression bonding conditions can be suitably selected according to the composition of an adhesive bond layer, Usually, they are 0.01-0.2 MPa at 40-120 degreeC. Subsequently, after dicing the wafer, the adhesive layer is peeled off from the pressure-sensitive adhesive layer to take out the chips with the adhesive layer attached thereto (pick up), and the chips are thermocompression-bonded to the resin substrate or the lead frame through the adhesive to be heat cured. . Alternatively, the chip with the adhesive layer may be temporarily fixed on the substrate by thermal compression, and then the chip may be sealed with a mold material to be cured and bonded simultaneously with the heat curing of the mold material. The former thermal compression and heat curing conditions can be appropriately selected depending on the composition of the adhesive layer, but usually 120 to 250 ° C, and the latter thermal compression temporary fixing is 0.01 to 0.2 MPa at 40 to 200 ° C.

The adhesive sheet for dicing die-bonding of this invention can be used not only for manufacture of a semiconductor device but also in the manufacturing process of various apparatuses with adhesion and dicing.

<Examples>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited to the following Example.

Synthesis Example 1. Polyimide Silicone Resin-1 Having Phenolic Hydroxyl Group

32.2 parts by mass of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in a 1-liter flask equipped with a coke-attached 25 ml water meter, thermometer, and stirrer connected to a reflux condenser; 150 parts by mass of solvent 2-methylpyrrolidone was added and stirred to disperse the acid anhydride. In the dispersion

51.28 parts by mass of dimethyldiaminopolysiloxane (hereinafter referred to as "diaminosiloxane-1") (wherein j is an integer in a range, and the average thereof is an amine equivalent of dimethyldiaminopolysiloxane of 641). A solution dispersed in 50 parts by mass of 2-methylpyrrolidone was added dropwise and stirred for 1 hour at room temperature to synthesize an acid anhydride-rich amic acid oligomer. The amic acid oligomer solution to the formula

29.68 parts by mass of aromatic diamine having a phenolic hydroxyl group (hereinafter referred to as "phenoldiamine-1") and 140 parts by mass of 2-methylpyrrolidone were added dropwise, followed by stirring at room temperature for 16 hours to synthesize a polyamic acid solution. It was. Thereafter, 80 ml of toluene was added and the temperature was raised to reflux at about 180 ° C. for 4 hours. It was confirmed that a predetermined amount of water accumulated in the water metering receiver and the outflow of water were not seen, and toluene was removed at 180 ° C while removing the effluent collected in the water metering receiver. After completion | finish of reaction, the reaction liquid obtained in the excess methanol was dripped, the polymer was precipitated, and it dried under reduced pressure, and obtained polyimide silicone resin-1 which has a phenolic hydroxyl group.

As a result of measuring the infrared absorption spectrum of the obtained resin, absorption based on a polyamic acid indicating that there was an unreacted functional group was not observed, and absorption based on an imide group at 1780 cm ^-1 and 1720 cm ^-1 , 3500 cm ^-1 The absorption based on the phenolic hydroxyl group was confirmed. It was 56,000 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. Polyimide Silicone Resin-2 Having Phenolic Hydroxyl Group

31.0 parts by mass of bis (3,4-dicarboxyphenyl) ether dianhydride and 64.1 parts by mass of diaminosiloxane in place of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in Synthesis Example 1 1, instead of phenoldiamine-1

Polyimide silicone resin having a phenolic hydroxyl group according to Synthesis Example 1, except that 12.9 parts by mass of aromatic diamine (phenoldiamine-2) having a phenolic hydroxyl group represented by -2 was obtained. The molecular weight was 63,000.

Synthesis Example 3. Polyimide Silicone Resin-3

44.4 parts by mass of 6 FDA (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane) instead of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in Synthesis Example 1 56.98 parts by mass of dimethyldiaminopolysiloxane (hereinafter referred to as `` diaminosiloxane-2 '') which differ only in diaminosiloxane-1 and amine equivalents instead of diaminosiloxane-1 (amine equivalent 407), instead of phenoldiamine-1 BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) Polyimide silicone resin-in accordance with Synthesis Example 1, except that 12.3 parts by mass and 340 parts by mass of 2-methylpyrrolidone in total were used. Got 3. The molecular weight was 72,000.

Synthesis Example 4. Polyimide Silicone Resin-4

44.4 parts by mass of 6FDA (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane) instead of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in Synthesis Example 1, 0.51 parts by mass of dimethyldiaminopolysiloxane-2 in place of diaminosiloxane-1 and 34.44 parts by mass of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) in place of phenoldiamine-1 Polyimide silicone resin -D was obtained according to Synthesis Example 1 except that 290 parts by mass of 2-methylpyrrolidone was used. The molecular weight was 74,000.

Preparation of Polyimide Resin Solution

40 mass parts of the polyimide resins 1-4 obtained by the synthesis examples 1-4 were melt | dissolved in 60 mass parts of cyclohexanone, and the polyimide resin solution was obtained.

Preparation of adhesive composition Example  1 to 6, Comparative example  1, 2, Reference Example  1, 2)

The epoxy composition, the catalyst, the silica, and the composite silicone rubber fine particles shown in the following Table 1 were mixed with each polyimide resin solution in a rotating and revolving mixer (manufactured by Shinki Co., Ltd.) at a compounding amount shown in the same table to prepare an adhesive composition. It was.

Preparation of Adhesive Films I to X

Each adhesive composition was applied onto a 50 μm thick PET film coated with a fluorine silicon release agent and heated to dry at 120 ° C. for 30 minutes to form a 50 μm thick and about 25 μm thick adhesive layer, respectively.

Silicone adhesive I to IV Manufacturing

[Production Example 1]

(CH _{3) 3} SiO _1/2 units of SiO ₂ units and 1.1 mol per 1 mol ratio methylpolysiloxane resin to a toluene solution containing 60% by mass 33.33 parts by mass of the terminal and side-chain vinyl groups having polymerization degree of 0.002 mole per 100 gr in consisting of 80 parts by mass of 2,000 raw rubber dimethylpolysiloxane and 172 parts by mass of toluene were dissolved until homogeneous, and then 0.68 parts by mass of the organopolysiloxane compound having silicon atom-bonded hydrogen atoms of the following structure in the mixed solution and 3- as a reaction inhibitor. 0.24 parts by mass of methyl-1-butyn-3-ol was mixed, and then, a mixture of 2-ethylhexanol of chloroplatinic acid having a platinum content of 40 ppm was mixed to prepare a silicone pressure-sensitive adhesive composition-I.

[Production Example 2]

According to Production Example _{9 (CH 3) 3 SiO 1} /2 units of 1.1 mole of SiO ₂ units of 50 parts by mass of 1 toluene containing 60 mass% of a methylpolysiloxane resin consisting of a ratio of the molar solution, a vinyl group 100 gr in the ends and side chains 70 parts by mass of a raw rubber-like dimethylpolysiloxane having a degree of polymerization of 0.002 mol per sugar, 165.7 parts by mass of toluene, 0.64 parts by mass of an organopolysiloxane compound having a silicon atom-bonded hydrogen atom of the above structure, and 3-methyl-1-butyne-3 as a reaction inhibitor Silicone pressure-sensitive adhesive composition -II was prepared from a 2-ethylhexanol modified solution of chloroplatinic acid having 0.24 parts by mass of -ol and a platinum content of 40 ppm.

[Production Example 3]

According to Production Example _{1 (CH 3) 3 SiO 1} /2 units of 1.1 mole of SiO ₂ units 1 toluene containing 60 mass% of a methylpolysiloxane resin consisting of a ratio of the molar solution of 16.66 parts by weight, 100 gr vinyl group at ends and side chains 90 parts by mass of a raw rubber-like dimethylpolysiloxane having a degree of polymerization of 2,000 per mole per 2,000, 180 parts by mass of toluene, 0.77 parts by mass of an organopolysiloxane compound having a silicon atom-bonded hydrogen atom of the above structure, 3-methyl-1-butyne-3 as a reaction inhibitor Silicone pressure-sensitive adhesive composition -III was prepared from a 2-ethylhexanol modified solution of chloroplatinic acid having 0.24 parts by mass of -ol and a platinum content of 40 ppm.

[Production Example 4]

According to Production Example _{9 (CH 3) 3 SiO 1} /2 units of 1.1 mol as SiO ₂ unit 1 of a toluene solution containing 60 mass% of a methylpolysiloxane resin consisting of a ratio of moles 83.33 parts by weight, a vinyl group 100 gr in the ends and side chains 50 parts by mass of raw rubber dimethylpolysiloxane having a degree of polymerization of 2,000, having 0.002 moles per sugar, 152.4 parts by mass of toluene, 0.46 parts by mass of an organopolysiloxane compound having a silicon atom-bonded hydrogen atom of the above structure, and 3-methyl-1-butyne-3 as a reaction inhibitor Silicone pressure-sensitive adhesive composition -IV was prepared from a 2-ethylhexanol modified solution of chloroplatinic acid having 0.24 parts by mass of -ol and a platinum content of 40 ppm.

Preparation of Adhesive Film

Silicone adhesive films I to IV were prepared by applying the silicone adhesive compositions I to IV on 100 탆 thick unstretched polyethylene (LDP) and heating at 100 ° C. for 10 minutes to form a 15 탆 silicone adhesive layer. .

Dicing ㆍ die  Production of bond sheet Example  7 to 13, Comparative example  3, 4, Reference Example  3 to 6)

The adhesion layer surface of the silicone adhesive film obtained above and the adhesive bond layer surface of an adhesive film were crimped | bonded by the load of 2 kg and width 300mm roll by the combination shown in Table 2, and dicing die bond sheets I-XIII were manufactured.

Measurement of the minimum melt viscosity using each uncured adhesive film was carried out by measuring the glass transition point, the linear expansion coefficient, Young's Modulus, and the moisture absorption rate of the cured product obtained from each adhesive, using each dicing die bond sheet. The adhesiveness, adhesiveness after wet heat, adhesive force, thermocompression property, dicing and chip taking out property, the generation | occurrence | production of the space | gap after resin sealing, the presence or absence of chip | tip movement, and the reliability evaluation of the package were performed according to the method shown below, respectively. Table 1 and Table 2 show these results.

Dispersibility of Silicone Rubber Powder

The surface state (unevenness due to poor dispersibility) of the cured film having a thickness of 25 μm was observed. A without irregularities was referred to as A, and B with irregularities.

Glass transition point, linear expansion coefficient

The adhesive film was heat treated at 175 ° C. for 2 hours to dry and cure. A film of 20 mm × 5 mm × 50 μm was cut out and the glass transition point was measured. The measurement was carried out using a thermomechanical measuring device, TMA-2000 (manufactured by Albag Ricoh), in a tensioning mode with a distance of 15 mm, a measurement temperature of 25 to 300 ° C., a temperature increase rate of 5 ° C./min, and a measurement load of 3 g. The glass transition point and the coefficient of linear expansion were measured at.

Young's modulus

The adhesive film obtained above was heated and hardened at 175 degreeC for 2 hours. The film of 40 mm x 10 mm x 50 micrometers was cut out, and the Young's modulus was measured on the conditions of 10 mm of chuck | zipper distances, the measurement temperature of 25 degreeC, and the measurement frequency of 1 Hz using the dynamic viscoelasticity measuring apparatus.

Moisture absorption rate

The adhesive film obtained above was heat-hardened at 175 degreeC for 2 hours. The film of 150 mmx150 mmx50 micrometers was cut out, and it hold | maintained for 168 hours under 85 degreeC / 85% RH conditions, and the moisture absorption rate was measured by weight change.

Lowest melt viscosity

Each uncured adhesive film was thermally laminated at 80 ° C. to prepare a test piece having a thickness of about 1 mm. Using this sample, the melt viscosity of the film-like adhesive composition was measured in a parallel plate type viscoelasticity measuring device (MR-300, manufactured by Rheology Corporation).

Adhesive test

The dicing die-bonding tape was thermocompression-bonded to the 450-micrometer 6-inch silicon wafer, and then diced into 2 mm x 2 mm. The silicon chip with the adhesive layer on the back side was cut out and thermally pressed onto a BT substrate and a silicon substrate coated with a 10 mm x 10 mm resist AUS303 (manufactured by Unitechno Co., Ltd.) for 2 seconds at 150 ° C and 0.1 MPa, respectively. Fixed The obtained test body was heated at 175 degreeC for 2 hours, hardening an adhesive layer, and the adhesive test piece was produced. The shear adhesive force in 240 degreeC was measured by the bond tester (4000PXY by DAGE Co., Ltd.).

Adhesive test after moist heat

The adhesive test piece was kept for 168 hours under the condition of 85 ° C / 60% RH, and then passed through a reflow furnace at 260 ° C three times, and the shear adhesion at 240 ° C was measured in the same manner as above.

Measurement of adhesion

The dicing die bond sheet obtained above was cut out in the shape of a tape having a width of 25 mm, the base film on the adhesive layer side was peeled off, and the adhesive layer side was placed on a glass plate (thickness 2.0 mm, width 50 mm) at 80 ° C and 0.01 MPa. It was thermally pressed for 10 seconds under the conditions. After leaving this test body at 25 ± 2 ° C for 50 hours at a constant temperature of 50 ± 5% RH for 24 hours, the end of the adhesive film was peeled off from the adhesive layer, folded at 180 °, and peeled off at a rate of 300 mm / min. Force was measured.

Dicing  And chips Blowout  exam

The base film on the adhesive bond layer side of the dicing die bond sheet obtained above was peeled, and it thermocompression-bonded at 80 degreeC to the 150-micrometer 8-inch wafer by the film bonding apparatus (FM-114) by Technovision Corporation (roll pressure) , 2 kg). This was diced with the chip of a 10 mm side, and chip extraction was performed by the die bonder apparatus (BESTEM-D02-Type C) by NEC Machinery. In the table, A means that the chip did not scatter during dicing, B that scattered, and A that the chip could be taken out without a problem were indicated by A and B that the chip was not possible.

Heat Compressibility

The dicing die-bonding tape obtained above was cut | disconnected to width 25mm * 200mm, and this was thermally crimped on the mirror surface side of the wafer at the temperature of 50-80 degreeC. Next, the adhesive layer was peeled off and the presence or absence of the adhesive layer in the wafer surface was confirmed. When peeling an adhesive layer, the tape which also peels an adhesive bond layer means that the thermocompression property to a wafer is bad. This is indicated by B in Table 1. When peeling an adhesive layer, the tape peeled from an interface with an adhesive bond layer can take out in the state which an adhesive bond layer adhered to a chip at the time of taking out a chip | tip, and it means that it is preferable as a dicing die-bonding tape. This is indicated as A in Table 2.

Generation of voids and chip movement after resin sealing

The dicing die-bonding tape was thermocompression-bonded to a 150-micrometer 8 inch silicon wafer, and then diced to cut the silicon wafer into 8 mm x 8 mm. The silicon chip was thermally pressed for 1 second at 150 MPC at 0.1 MPa onto a map on a 250 μm resin substrate (a BT substrate coated with a resist AUS303), and then molded into a thickness of 600 μm from the resin substrate. After resin sealing (175 degreeC, sealing pressure 6.9 MPa, 90 second) with KMC2500VA-T1 (made by Shin-Etsu Chemical Co., Ltd.), it heat-hardened at 175 degreeC and 4 hours. The sealed portion was observed with an ultrasonic image measuring device to investigate the occurrence of voids and the presence of chip movement.

Package Reliability

The total 20 packages in which the resin-sealed chip was separated were held for 192 hours under the conditions of 30 ° C./60%RH, and then passed through a reflow furnace at 260 ° C. three times, followed by voids and peeling in the ultrasonic image measuring apparatus. The presence or absence was observed.

In the said Table 1, all the compounding quantities are solid content. In addition, resin used etc. are as follows.

In the example  Used resin, etc.

B1: RE-310S: liquid epoxy resin, manufactured by Nippon Kayaku Co., Ltd.

B2: RE-600N: epoxy resin, liquefaction temperature 60 ℃, manufactured by Nippon Kayaku Co., Ltd.

B3: EOCN-102S: Epoxy resin, softening temperature 55-77 degreeC, Nisborne Kayaku Co., Ltd. dicyandiamide: Japan epoxy resin company

2PHZ: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Co., Ltd.)

D1: SE-2050: spherical silica, manufactured by Admatex Co., Ltd., average particle size: 0.5 μm

D2: SE-1050: spherical silica, manufactured by Admatex Co., Ltd., average particle size: 0.1 μm

E1: X-52-7030: Silicone rubber composite powder, average particle diameter of 0.7 µm, manufactured by Shin-Etsu Chemical Co., Ltd.

E2: KMP-600: Silicone rubber composite powder, average particle diameter of 5 µm, manufactured by Shin-Etsu Chemical Co., Ltd.

Resin used in reference example

Epicoat M1003: epoxy resin, softening temperature 89 ° C, manufactured by Japan Epoxy Resin Co., Ltd.

KMP-597: Silicone rubber powder, average particle diameter of 5 µm, manufactured by Shin-Etsu Chemical Co., Ltd.

Comparative Example 1 is a composition containing no fine particles. From Table 1, the low melt viscosity and the tape including the layer of the same adhesive (Comparative Example 3) resulted in chip flow.

Comparative Example 2 contains spherical silica and has a higher melt viscosity than Comparative Example 1. However, in the die-bonding film (comparative example 4), chip | tip movement was seen and the Young's modulus was high.

Reference Example 1 is a composition containing an epoxy resin having a high softening point. This cannot be thermally pressed (Reference Example 3) and evaluation of adhesiveness and the like could not be performed.

Reference Example 2 is a composition containing silicone rubber fine particles that do not have a polyorganosilsesquioxane resin microstructure on its surface. The powder could not be used as an adhesive film because of poor dispersibility to the resin system.

Reference Examples 5 and 6 include a layer made of the adhesive of the present invention. However, since the adhesive force is outside the scope of the present invention, there is a chip scattering and there is a problem in chip taking out.

On the other hand, the die-bonding film containing the adhesive agent of the Example and the layer of the said adhesive was favorable in any performance.

The adhesive composition of the present invention provides an adhesive having low elastic modulus, low linear expansion, and low water absorption, and is suitable for bonding various electronic components. Moreover, the adhesive sheet for dicing die bonds of this invention is equipped with the favorable chip taking out property. Moreover, this chip can be adhered firmly by thermocompression bonding and heat-curing on a substrate or the like, and can be suitably used for the manufacture of semiconductor devices.

Claims (7)

materials, A pressure-sensitive silicone pressure sensitive adhesive layer formed on the substrate, and Adhesive layer formed on the pressure-sensitive silicone pressure-sensitive adhesive layer / RTI &gt; The adhesive layer is (A) 5 to 60% by weight of polyimide silicone resin (B) 5 to 60% by weight of an epoxy resin having a softening temperature of 80 ° C. or less (C) 0.001 to 20% by weight of dicyandiamide (D) 20 to 70% by weight of spherical silica having an average particle diameter of 0.1 to 10 microns, and (E) 5 to 30% by weight of silicone rubber spherical fine particles having an average particle diameter of 0.1 to 10 microns and comprising a polyorganosilsesquioxane resin microstructure on its surface It is prepared from an adhesive composition comprising a, 180 ° peel force measured by peeling the pressure-sensitive adhesive layer from the adhesive layer formed on the pressure-sensitive silicone pressure-sensitive adhesive layer is 0.05 to 1.0 N / 25 mm, Adhesive sheet for dicing die-bonding. The adhesive sheet for dicing die-bonding according to claim 1, wherein the pressure-sensitive silicone pressure-sensitive adhesive layer is made of a platinum addition-curable silicone pressure-sensitive adhesive. The adhesive sheet for dicing die bonds of Claim 1 whose minimum melt viscosity measured by the parallel plate type viscoelasticity measuring apparatus is 1000 Pa.s or more. The adhesive sheet for dicing die bond according to claim 1, wherein (A) the polyimide silicone resin has a phenolic hydroxyl group. The adhesive for dicing and diebonding of Claim 1 in which (A) polyimide silicone resin contains the polyimide resin obtained by making tetracarboxylic dianhydride and the diamine compound of the structure represented by following formula (1) react. Sheet. &Lt; Formula 1 >

(Wherein R ³ is a divalent organic group having 3 to 9 carbon atoms, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms independently of each other, and m is an integer of 1 to 200) .) delete delete

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