JP2006005159A - Cohesive tape for dicing/die bonding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive tape for dicing/die bonding for stably carrying out a dicing/die bonding process in a semiconductor manufacturing process, and for forming a highly reliable semiconductor device with high adhesiveness after humidification and high adhesiveness and high strength in high temperature. <P>SOLUTION: An adhesive layer is laminated on an adhesive layer formed on a substrate so that an adhesive tape for dicing/die bonding can be formed. In this case, the adhesive layer contains (A) polyimide resin having siloxane coupling, (B) epoxy resin and (C) epoxy resin hardening catalyst as indispensable components, and consists of adhesive composition whose Young's modulus is 10 MPa or more, and the adhesion of the adhesive layer and the adhesive layer is 0.2 to 2.0 N/25 mm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive tape for dicing and die bonding, which has a function of fixing a wafer used in a wafer dicing process for manufacturing a semiconductor device and bonding a chip processed by dicing to a lead frame.

  In general, a semiconductor device has a large-diameter silicon wafer fixed with an adhesive tape (dicing tape), processed into a semiconductor chip in a dicing (cutting and separating) process, and then the chip is peeled off and taken out from the dicing tape (pickup). The lead frame is manufactured by thermocompression bonding and fixing with a curable liquid adhesive (die bond agent) or the like. Recently, the dicing and die bonding processes can be performed in succession to achieve rationalization of the process, and it is possible to avoid contamination of semiconductor parts due to the flow component of the liquid adhesive and protrusion from the chip fixing part. There has been a demand for a dicing die-bonding tape made of an adhesive sheet having an adhesive layer made of the above and having both the wafer fixing function of the dicing tape and the bonding function of the die-bonding material. That is, this tape has a fixing force so that the chip cut by dicing does not fly at the time of dicing, and can be easily taken out with the adhesive layer attached to the chip at the time of die bonding (pickup). It has a function of firmly bonding to the lead frame.

  As this dicing die-bonding tape, JP-A-9-67558 (Patent Document 1) proposes a sheet in which a thermoplastic polyimide resin is formed as a dicing die-bonding layer on a plastic film substrate. In this embodiment, at the time of dicing, the wafer is fixed by thermocompression bonding onto a polyimide resin layer that is in close contact with the base material, dicing is performed, the chip with the polyimide resin layer attached (pickup), thermocompression fixing to the lead frame, and heat bonding are performed. Is.

  Wafer fixing and chip pick-up (pickup) properties depend on the adhesion between the base material and the polyimide resin layer and cannot be easily controlled because the polyimide resin layer and the wafer are firmly adhered by thermocompression bonding. In addition, since the adhesive layer is a thermoplastic polyimide-based resin, the adhesiveness, particularly the adhesiveness after humidification required in the wire bonding, sealing, and solder reflow processes, which are semiconductor device manufacturing processes, at high temperatures There are drawbacks such as insufficient adhesion and strength.

  Further, in JP-A No. 2002-256236 (Patent Document 2), a radiation-polymerizable pressure-sensitive adhesive layer capable of controlling adhesion (adhesiveness) as reported in Japanese Patent No. 2984549 (Patent Document 3) is formed. A resin layer comprising (A) a polyimide resin, (B) an epoxy resin, (C) a phenol resin, and (D) a curing accelerator with improved adhesion after humidification and high temperature adhesion on a film substrate. There has been proposed a dicing die-bonding tape in which the film is formed.

  When a soft resin (particularly fluid resin) is used as the adhesive layer component (B) epoxy resin or (C) phenolic resin, the adhesive layer becomes soft depending on the composition, and chip cracks occur in the dicing process. To do.

  Furthermore, since this die bond layer contains a curable epoxy resin composition, adhesion after humidification, adhesion at high temperatures, and strength are improved, but chip pick-up (pickup) properties after dicing are improved. It can be difficult. That is, the radiation-polymerizable pressure-sensitive adhesive layer that controls adhesion between the substrate and the die bond layer reported in Japanese Patent No. 2984549 is a (meth) acrylate copolymer polymer, a (meth) acryl group-containing polymer, or a multifunctional product. A composition composed of an acrylic compound and a photopolymerization initiator, which is easily compatible with the die bond layer. The reaction between the ultraviolet ray irradiation or the fusion between the die bond layer and the adhesive layer softened by wafer-fixing thermocompression in the dicing process. Adhesion increases due to wearing and chip removal (pickup) cannot be easily performed. In addition, the adhesive force (adhesive force) between the die bond layer and the radiation-polymerizable adhesive layer changes (increases) with time, and similarly, there is a problem that the chip cannot be taken out (pickup).

JP-A-9-67558 JP 2002-256236 A Japanese Patent No. 2998449

  The present invention has been made in view of the above circumstances, and does not cause a wafer to withstand dicing, does not generate chip cracks during dicing, and has a stable adhesion (adhesive strength) with a die bond layer that can be easily taken out (pickup). Another object of the present invention is to provide an adhesive tape for dicing and die bonding that has excellent properties and has excellent adhesion to lead foam.

  As a result of diligent studies to achieve the above object, the present inventor, as a die-adhesive layer capable of thermocompression bonding of a wafer, has excellent adhesiveness and a polyimide / epoxy resin curable composition having a certain Young's modulus value or more. Stable dicing performance by using a dicing die-bonding tape with a structure consisting of a silicone adhesive layer that is incompatible with the die adhesive layer as the adhesive layer between the adhesive layer and the die adhesive layer and the substrate. The present inventors have found that good chip pick-up property (pickup property) and excellent die adhesion without occurrence of chip cracking and adhesive force change with time can be obtained, and the present invention has been made.

  That is, the present invention comprises an adhesive layer laminated on an adhesive layer formed on a substrate, and the adhesive layer comprises (A) a polyimide resin having a siloxane bond, (B) an epoxy resin, (C) It contains an epoxy resin curing catalyst as an essential component and is composed of an adhesive composition having a Young's modulus of 10 MPa or more, and the adhesive strength between the adhesive layer and the adhesive layer is 0.2 to 2.0 N / 25 mm. An adhesive tape for dicing and die bonding is provided.

  According to the adhesive tape for dicing and die bonding of the present invention, by using this, dicing in the semiconductor manufacturing process, the die bonding process can be stably performed, high adhesiveness after humidification, high adhesiveness at high temperature, By having high strength, a highly reliable semiconductor device can be formed.

  The adhesive tape for dicing and die bonding of the present invention is an adhesive comprising (A) a polyimide resin, (B) an epoxy resin, and (C) an epoxy resin curing catalyst as an essential component on an adhesive layer formed on a substrate. The adhesive layer which consists of an agent composition is provided.

  Specific examples of the adhesive layer substrate in the adhesive tape for dicing and die bonding of the present invention include polyethylene film, polypropylene film, polybutadiene film, polybutene film, polymethylpentene film, polyvinyl chloride film, and copolymer films thereof. Polyolefin film, polyethylene terephthalate film, polyester film such as polybutylene terephthalate film, (meth) acrylic acid copolymer film, vinyl acetate copolymer film, polyether ketone, polyether ether ketone, polyether sulfone film, polyamide Film, polyimide film, polyetherimide film, polycarbonate film, polystyrene film, etc. are mentioned, but after dicing process In order to facilitate the removal of the film, it is necessary to isolate the cut chips by expanding the base material (expanding), so that a stretchable film, specifically, a polyethylene film, a polypropylene film, etc. General purpose film. Further, those obtained by crosslinking these, those obtained by plasma or corona treatment on the surface, or those obtained by laminating these films or different films may be used.

  The film thickness of the substrate film is usually 20 to 400 μm, preferably 30 to 150 μm, although it depends on the kind of film and the desired stretchability.

  Examples of the pressure-sensitive adhesive layer formed on the substrate include rubber-based pressure-sensitive adhesives made of natural rubber and synthetic rubber, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, etc., but pressure-sensitive adhesives that are not compatible with the adhesive layer. A silicone pressure-sensitive adhesive is particularly preferable. As the silicone pressure-sensitive adhesive, there can be used a pressure-sensitive adhesive composed of a thermosetting chain-like organopolysiloxane and a solid silicone resin. There are two types of thermosetting silicone adhesives: organic peroxide curing type and platinum addition curing type. When stretchable polyethylene film or polypropylene film is used as the base material, it may be deformed by heat. It is particularly preferable to use a platinum addition-curable silicone pressure-sensitive adhesive that can be cured at a low temperature.

Here, the organic peroxide curing type silicone pressure sensitive adhesive is composed of a chain organopolysiloxane, a (R ¹ ₃ SiO _1/2 ) unit, and a (SiO ₂ ) unit (R ¹ is a substituted or unsubstituted monovalent carbonization. Organopolysiloxane copolymer resin comprising (hydrogen groups) (organopolysiloxane mixture with (R ¹ ₃ SiO _1/2 ) molar ratio of 0.5 to 1.5 units to (SiO ₂ ) units) and crosslinking It contains an organic peroxide such as benzoyl peroxide, bis (4-methylbenzoyl) peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane as a curing agent. The platinum addition type silicone pressure sensitive adhesive is composed of a chain-like vinyl group-containing organopolysiloxane, the organopolysiloxane copolymer resin, an organohydrogenpolysiloxane containing silicon-bonded hydrogen atoms as a crosslinking curing agent, and a chlorination as a catalyst. It contains a platinum group metal catalyst such as platinum acid, alcohol-modified chloroplatinic acid, platinum olefin complex, platinum and vinylsiloxane complex.

  The pressure-sensitive adhesive layer using the silicone pressure-sensitive adhesive has a pressure-sensitive adhesive force of 0.2 to 2.0 N / 25 mm with respect to the adhesive layer of the present invention. If the adhesive strength is less than 0.2 N / 25 mm, the chip may be peeled off together with the adhesive layer during dicing and may fly. On the other hand, if the adhesive force is larger than 2.0 N / 25 mm, it is difficult to take out the chip (pickup), and preferably 0.3 to 1.5 N / 25 mm. In addition, this adhesive force can be easily changed by the crosslinking density of the adhesive and the content of the silicone resin component.

  Next, the adhesive layer (die adhesive layer) of the present invention is composed of an adhesive composition containing (A) a polyimide resin, (B) an epoxy resin, and (C) an epoxy resin curing catalyst as essential components. It maintains its shape at room temperature, forms a film-like thin film, cures through a plastic state by heating, and has excellent adhesion to a substrate.

  Although the polyamic acid resin which is the precursor represented by the general formula (1) can be used as the component (A) polyimide resin, water is by-produced by imidization (dehydration ring closure) at the time of heat curing in the die bonding process. In some cases, peeling of the adhesive surface may occur, and a polyimide resin represented by the following general formula (2) that has been imidized (dehydrated and closed) in advance is preferable. Moreover, it is preferable to have a phenolic hydroxyl group in the skeleton from the viewpoint of adhesiveness.

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

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

The polyamic acid resin represented by the general formula (1) has the following structural formula (3)

(However, X has the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following structural formula (4)
_{H 2 N-Y-NH 2} (4)
(However, Y has the same meaning as described above.)
It is obtained by reacting the diamine represented by the formula (1) with an approximately equimolar amount in an organic solvent according to a conventional method.

  In the above formula (1), n is an integer of 1 to 300, preferably an integer of 2 to 300, particularly an integer of 5 to 300. The polyamic acid resin having such a repeating number is the above-mentioned method. Can be obtained more easily. Furthermore, the polyimide resin represented by the general formula (2) can be obtained by dehydrating and ring-closing the polyamic acid resin represented by the general formula (1) by a conventional method.

  Here, specific examples of the tetracarboxylic dianhydride represented by the above formula (3) include the following, but are not limited thereto.

  In addition, as the tetracarboxylic dianhydride of the above formula (3), one or more of the above may be used as desired.

Among the diamines represented by the above formula (4), preferably 1 to 80 mol%, more preferably 1 to 50 mol% is the following structural formula (5).

Wherein R ² is a divalent organic group having 3 to 9 carbon atoms, R ³ and R ⁴ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and m is 1 to 200. (It is an integer.)
It is preferable from the point of the solubility to an organic solvent, the adhesiveness with respect to a base material, and a softness | flexibility to be represented by these.

In the siloxane diamine compound (or α, ω-diaminosiloxane) represented by the general formula (5), examples of the divalent organic group having 3 to 9 carbon atoms represented by R ² include — (CH _{2 ) 3 -, - (CH 2} ) 4 -, - CH 2 CH (CH 3) -, - (CH 2) 6 -, - (CH 2) 8 - such as an alkylene group,

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

Oxyarylene groups such as

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

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert group. -Alkyl groups such as butyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, etc., phenyl group Aryl groups such as tolyl group and xylyl group, aralkyl groups such as benzyl group and phenylethyl group, and part or all of hydrogen atoms bonded to carbon atoms of these groups are halogen atoms such as fluorine, bromine and chlorine A substituted group, for example, a halogen-substituted alkyl group such as a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, etc. . Among them methyl and phenyl groups are preferred. m is an integer of 1 to 200, preferably an integer of 1 to 100, more preferably an integer of 1 to 80.

Specific examples of the siloxane diamine compound represented by the general formula (5) include, but are not limited to, those shown below.

  These diaminosiloxane compounds represented by the above formula (5) can be used alone or in combination of two or more as desired.

  Further, among the diamines represented by the above formula (4), examples of the diamine other than the diaminosiloxane compound represented by the above formula (5) include p-phenylenediamine, m-phenylenediamine, and 4,4′-diamino. Diphenylmethane, 4,4′-diaminodiphenyl ether, 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (3- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4- Bis (p-aminophenylthioether) benzene, 1,4-bis (m-aminophenylthioether) Benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- Chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) Phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, Bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) Enyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-amino) Aromatic ring-containing diamines such as phenoxy) phenyl] perfluoropropane, etc., 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, from the viewpoint of adhesiveness, the polymer skeleton of the polyimide component of the present invention preferably has a phenolic hydroxyl group, and the introduction of this hydroxyl group can be obtained by using a diamine compound having a phenolic hydroxyl group, and has the following structure: Can be illustrated.

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

Here, the substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms of R ⁵ is the same as those exemplified for the above R ³ and R ⁴ , and also an ethynyl group, a propynyl group, and a butynyl group. And alkynyl groups such as a hexynyl group. Further, the unsubstituted or substituted monovalent hydrocarbon group of R can be exemplified by the same groups as those exemplified for R ⁵ above.

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

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

(In the formula, R ⁵ is independently a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group, a trifluoromethyl group, a phenyl group, etc. A substituted or substituted monovalent hydrocarbon group, the same as R ⁵ described above is exemplified, and all the substituents attached to each aromatic ring may be the same or different from each other. However, two types may be used together, and p is an integer of 1 to 3.)

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

  To give specific examples of the polyamic acid resin and polyimide resin formation reaction, the above starting materials are dissolved in a solvent under an inert atmosphere, and are usually reacted at 80 ° C. or lower, preferably 0 to 40 ° C. A polyamic acid resin is synthesized. Further, a method of synthesizing a target polyimide resin by dehydrating and ring-closing the acid amide portion of the polyamic acid resin by raising the temperature of the obtained polyamic acid resin to 100 to 200 ° C., preferably 150 to 200 ° C. Is taken. The organic solvent used for the reaction may not be one that can completely dissolve the starting material as long as it is inert to the resulting polyamic acid. Examples include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide, preferably aprotic Polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

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

  In order to adjust the molecular weight of the resin, dicarboxylic anhydrides such as maleic anhydride and phthalic anhydride and / or aniline, n-butylamine, and monoamines having the above-described phenolic hydroxyl groups may be added. . However, the addition amount of dicarboxylic acid anhydride is usually 0 to 2 parts by mass per 100 parts by mass of dicarboxylic dianhydride, and the addition amount of monoamine is usually 0 to 2 parts by mass per 100 parts by mass of diamine. It is.

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

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

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

  The epoxy resin curing catalyst of component (C) used in the present invention is not particularly limited, and examples of the phosphorus catalyst include triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate and the compounds shown below. Can be mentioned.

(Wherein R ^{6 to} R ¹³ are a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an alkyl group, alkenyl group, alkynyl group, or alkoxy having 1 to 8 carbon atoms) An unsubstituted or substituted monovalent hydrocarbon group such as a group, a trifluoromethyl group, and a phenyl group, and all the substituents may be the same or different.)

Here, examples of the monovalent hydrocarbon group of R ^{6 to} R ¹³ are the same as those exemplified for R ⁵ above, and alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Can be mentioned.

  In addition, as an amine catalyst, imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like are blended. Can do.

  The epoxy resin curing catalyst in the present invention can be used singly or in combination of two or more. In addition, the compounding quantity of the epoxy resin curing catalyst of (C) component can be made into a catalytic amount, and is 0.1-10 mass parts normally with respect to 100 mass parts of (B) component, Preferably it is 0.5-5 mass. Part.

An epoxy resin curing agent can be used in the adhesive composition of the present invention. As this curing agent, conventionally known various curing agents for epoxy resins can be used, for example, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpiperazine, bis (4-amino). Amine compounds such as -3-methylcyclohexyl) methane, metaxylylenediamine, menthanediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane Epoxy resins-modified aliphatic polyamines such as diethylenetriamine adducts, amine-ethylene oxide adducts, cyanoethylated polyamines; bisphenol A, trimethylolallyloxyphenol, low polymerization degree phenol novolac resins, epoxidized or butylated pheno Le resin or "Super Beckcite" 1001 [manufactured by Nippon Reichhold Chemical Co. (Ltd.)], "Hitanol" 4010 [(Ltd.) manufactured by Hitachi, Ltd.], Scado form L. A phenolic resin containing at least two phenolic hydroxyl groups in the molecule, such as a phenolic resin known under the trade name of 9 (manufactured by Scado Zwoll, The Netherlands), Methylon 75108 (manufactured by General Electric, USA); and “Beckamine "P. 138 [manufactured by Nippon Reichhold Chemical Co., Ltd.], “Melan” [manufactured by Hitachi, Ltd.], “U-Van” 10R [manufactured by Toyo Kodan Kogyo Co., Ltd.], etc. resin; formula _{HS (C 2 H 4 OCH 2} OC 2 H 4 SS) n C 2 H 4 OCH 2 OC 2 H 4 SH (n = 1~10 integer); melamine resins, amino resins such as aniline resins Polysulfide resin having at least two mercapto groups in one molecule; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl nadic acid, dodecyl succinic anhydride, chlorendic anhydride Examples thereof include organic acids such as acids or anhydrides (acid anhydrides) thereof. Among the curing agents described above, the phenolic resin (phenol novolac resin) gives good molding workability to the composition of the present invention, provides excellent moisture resistance, is non-toxic and relatively inexpensive. Is desirable. The above-mentioned curing agents are not necessarily limited to one type in use, and two or more types may be used in combination depending on the curing performance of the curing agents.

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

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

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

  Even when no phenolic resin is used as the epoxy resin curing agent, the blending amount and equivalent ratio of the polyimide resin and the epoxy resin can be the same as described above.

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

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

  In this case, the uncured adhesive layer of the present invention needs to have a Young's modulus of 10 MPa or more in order to prevent chip cracks during dicing, and is combined with (A) a polyimide resin and (B) an epoxy resin. It is necessary to select the type and blending amount of the epoxy resin curing agent so that the Young's modulus is obtained. A more preferable range of Young's modulus is 15 MPa or more, particularly 20 MPa or more. The upper limit is not particularly limited, but is usually 3,000 MPa or less, particularly 2,000 MPa or less.

  The manufacturing method of the adhesive tape for dicing and die bonding of the present invention will be described. First, the above-mentioned silicone adhesive is applied on a plastic film substrate and cured by heat to form an adhesive layer (hereinafter referred to as an adhesive film). Called). Here, as the plastic film base material, those exemplified above can be used, but a stretchable film is preferable, and a general-purpose polyethylene film or polypropylene film is particularly preferable. Moreover, it is preferable that the thickness of this adhesion layer is 5-100 micrometers, More preferably, it is 10-50 micrometers. The curing condition is usually 60 to 120 ° C., although it depends on the heat resistance of the plastic film substrate.

  Next, the adhesive composition containing (A) a polyimide resin, (B) an epoxy resin, and (C) an epoxy resin curing catalyst of the present invention as essential components is suitable for an aprotic polar solvent such as toluene, cyclohexanone, or NMP. The film is dissolved in a proper concentration, applied onto a supporting substrate and dried to obtain a film having an adhesive layer (hereinafter referred to as an adhesive film). As the support substrate, polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil or the like, or those obtained by releasing the surface thereof can be used.

  The thickness of the adhesive layer is not limited and can be selected according to the purpose, and is usually 10 to 100 μm.

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

  The adhesive tape for dicing and die bonding of the present invention can be obtained by bonding the silicone pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive film thus obtained and the adhesive layer surface of the adhesive film by pressure bonding. Here, the pressure-bonding conditions for pressure-bonding the adhesive film and the adhesive film are preferably 0.01 to 2 MPa, particularly 0.1 to 1 MPa at room temperature.

  The method for using the adhesive tape for dicing / die bonding of the present invention is such that the substrate film on the adhesive layer side is peeled off, and the wafer is thermocompression bonded to the adhesive layer and fixed to the adhesive tape for dicing / die bonding. The thermocompression bonding conditions can be variously selected depending on the composition of the adhesive layer, but is usually 0.01 to 0.2 MPa at 40 to 120 ° C. Subsequently, after fixing to a dicing apparatus and dicing, the pressure-sensitive adhesive layer and the base material are peeled off, the chip with the adhesive layer attached is taken out (pickup), and this chip is bonded to the lead frame by thermocompression bonding and heat curing. The thermocompression bonding conditions can be the same as the thermocompression bonding conditions of the wafer and the adhesive layer, and the heat curing conditions can be variously selected depending on the composition of the adhesive layer. is there.

  The adhesive tape for dicing die bonding of the present invention can be configured as shown in FIGS. Here, in FIGS. 1 and 2, 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 the adhesive layer according to the shape and size of the silicon wafer to be bonded. 3 and 4 show a state in which the tape of FIGS. 1 and 2 is bonded to the silicon wafer 5 with the adhesive film substrate removed.

  The adhesive tape for dicing and die bonding of the present invention can be used not only in the production of semiconductor devices but also in the production processes of various devices involving adhesion and dicing.

  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.

[Synthesis Example 1]
To a 1 L separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer, and a stirrer, the following formula
45.70 parts by mass of diaminosiloxane [KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.)] and 100 parts by mass of 2-methylpyrrolidone as a reaction solvent were stirred at 80 ° C. to disperse the diamine. . By adding dropwise a solution of benzophenone tetracarboxylic acid anhydride: BTDA 32.22 parts by mass and 2-methylpyrrolidone 100 parts by mass as an acid anhydride and stirring reaction at room temperature for 2 hours, acid anhydride-rich amic acid An oligomer was synthesized.

Next, the following formula
A 25 ml water quantitative receiver with a cock in which 22.60 parts by mass of an aromatic diamine having a phenolic hydroxyl group (diamine-1) represented by the formula (2) and 100 parts by mass of 2-methylpyrrolidone are connected to a reflux condenser, a thermometer, A 1 L separable flask equipped with a stirrer was charged and dispersed. The acid anhydride-rich amic acid oligomer described above was added dropwise, followed by stirring at room temperature for 16 hours to synthesize a polyamic acid solution. Thereafter, 25 ml of xylene was added, the temperature was raised, and the mixture was refluxed at about 180 ° C. for 2 hours. Confirm that the specified amount of water has accumulated in the moisture meter and that no water has flowed out, and remove xylene at 180 ° C while removing the effluent accumulated in the meter. did. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer, which was dried under reduced pressure to obtain a polyimide resin-I having a phenolic hydroxyl group in the skeleton.

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

Preparation of Adhesive Composition 40 parts by mass of the polyimide resin-I obtained in Synthesis Example 1 was dissolved in 60 parts by mass of cyclohexanone, and this solution was mixed with the epoxy resin and the blending amount shown in Table 1 below. Articles I-VI were prepared.
Preparation of adhesive film The adhesive composition obtained above was applied onto a 50 μm thick PET film coated with a fluorosilicone release agent, and dried by heating at 80 ° C. for 30 minutes to form an adhesive layer of about 50 μm. An adhesive film was prepared. The films prepared from the respective adhesive compositions-I to VI are referred to as adhesive films-I to VI.

Preparation of silicone pressure-sensitive adhesive composition and UV-curable pressure-sensitive adhesive composition [Preparation Example 1]
50 parts by mass of a toluene solution containing 60% by mass of a methylpolysiloxane resin having a ratio of 1.1 mol of (CH ₃ ) ₃ SiO _1/2 units and 1 mol of SiO ₂ units; 70 parts by weight of a raw rubber-like dimethylpolysiloxane having a degree of polymerization of 2,000 mol and 0.008 parts by weight of toluene are dissolved until uniform, and then, in this mixed solution, an organo group having silicon atom-bonded hydrogen atoms having the following structure 0.64 parts by mass of polysiloxane compound, 2-ethylhexanol-modified solution of chloroplatinic acid so that the platinum amount is 40 ppm and 0.15 parts by mass of 3-methyl-1-butyn-3-ol as a reaction inhibitor are mixed A silicone pressure-sensitive adhesive composition-I was prepared.

[Preparation Example 2]
According to Preparation Example 1, 66.66 parts by mass of a toluene solution containing 60% by mass of a methylpolysiloxane resin consisting of 1.1 mol of (CH ₃ ) ₃ SiO _1/2 units and 1 mol of SiO ₂ units, the terminal and Organopolysiloxane compound having 60 parts by mass of raw rubber-like dimethylpolysiloxane having a degree of polymerization of 2,000 having 0.002 mol of vinyl groups per side chain, 73.34 parts by mass of toluene, and silicon-bonded hydrogen atoms having the above structure From 0.55 parts by mass, 2-ethylhexanol modified solution of chloroplatinic acid such that the platinum amount is 40 ppm and 0.15 parts by mass of 3-methyl-1-butyn-3-ol as a reaction inhibitor, a silicone adhesive Composition-II was prepared.

[Preparation Example 3]
According to Preparation Example 1, 83.33 parts by mass of a toluene solution containing 60% by mass of a methylpolysiloxane resin consisting of 1.1 mol of (CH ₃ ) ₃ SiO _1/2 units and 1 mol of SiO ₂ units, the terminal and Organopolysiloxane compound having 50 parts by weight of raw rubber-like dimethylpolysiloxane having a polymerization degree of 2,000 having 0.002 mol of vinyl groups per side chain, 66.67 parts by weight of toluene, and silicon-bonded hydrogen atoms having the above structure 0.46 parts by mass, 2-ethylhexanol modified solution of chloroplatinic acid such that the amount of platinum is 40 ppm, and 0.15 parts by mass of 3-methyl-1-butyn-3-ol as a reaction inhibitor, a silicone adhesive Composition-III was prepared.

[Preparation Example 4]
According to Preparation Example 1, 25 parts by mass of a toluene solution containing 60% by mass of a methylpolysiloxane resin consisting of 1.1 mol of (CH ₃ ) ₃ SiO _1/2 units and 1 mol of SiO ₂ units, terminal and side chains 85 parts by weight of a raw rubber-like dimethylpolysiloxane having a degree of polymerization of 2,000 having a vinyl group of 0.002 mole per 100 gr, 0.78 parts by weight of toluene, and 0.78 parts by weight of an organopolysiloxane compound having silicon-bonded hydrogen atoms having the above structure From 0.15 parts by weight of 2-methylhexanol-modified solution of chloroplatinic acid such that the platinum amount is 40 ppm and 3-methyl-1-butyn-3-ol as a reaction inhibitor, silicone adhesive composition-IV Was prepared.

[Preparation Example 5]
Add and mix 0.05 parts by weight of dibutyltin dilaurate to 100 parts by weight of a 25% by weight ethyl acetate solution of a copolymer having a weight average molecular weight of 290,000 consisting of 75 parts by weight of butyl acrylate and 25 parts by weight of 2-hydroxyethyl acrylate, To this mixed solution, a mixed solution of 6.7 parts by mass of methacryloyloxyethyl isocyanate and 7 parts by mass of ethyl acetate was added dropwise. After completion of dropping, the mixture was heated and stirred at 60 ° C. until the absorption of isocyanate disappeared by infrared absorption spectrum measurement to obtain an acrylate polymer having a methacryl group. 71.4 parts by weight of this solution, 75 parts by weight of butyl acrylate and 25 parts by weight of 2-hydroxyethyl acrylate, 33 parts by weight of a 25% by weight ethyl acetate solution of a copolymer having a weight average molecular weight of 290,000, a polyvalent isocyanate compound coronate L (manufactured by Nippon Polyurethane Co., Ltd.) 0.5 parts by mass, photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, Ciba Geigy) 1 part by mass is mixed, and ultraviolet light whose adhesiveness is reduced by UV irradiation Curable adhesive composition-V was prepared.

Preparation of Adhesive Film Silicone adhesive compositions-I to IV were applied on unstretched polyethylene (LLDP) having a thickness of 100 μm and heated at 100 ° C. for 10 minutes to form a 15 μm silicone adhesive layer. Adhesive films I to IV were prepared.
The UV curable pressure sensitive adhesive composition-V was coated on 100 μm thick unstretched polypropylene whose surface was corona-treated, and heated at 100 ° C. for 1 minute to form a 15 μm pressure sensitive adhesive layer. Was made.

Preparation of dicing die-bonding tape The adhesive layer surface of the silicone adhesive film obtained above and the adhesive layer surface of the adhesive film are pressure-bonded with a roll of 2 kg and a width of 300 mm in the combination shown in Table 1, and dicing die-bonding tapes I to X Was made.

Using the adhesive films I to VI and dicing die bond tapes I to X obtained above, the glass transition point, Young's modulus, adhesiveness test, adhesiveness test after wet heat, adhesive strength by the following test methods Measurement, dicing and chip removal test were conducted. Table 1 shows these results.
Glass transition point The adhesive film obtained above was cured by heat treatment at 175 ° C. for 1 hour. The glass transition point was measured for a 20 mm × 5 mm × 50 μm film. For the measurement, TMA-2000 (manufactured by ULVAC-RIKO), a measuring device for thermomechanical properties, was used under the conditions of tension mode, distance between chucks of 15 mm, measuring temperature of 25 to 300 ° C., heating rate of 10 ° C./min, and measuring load of 10 g. The glass transition point was measured.
Young's modulus The adhesive film obtained above was heat-treated at 175 ° C. for 1 hour to be cured. The dynamic viscoelastic modulus was measured for a 20 mm × 5 mm × 50 μm film. A dynamic viscoelasticity measuring device was used for the measurement, and the Young's modulus was measured under the conditions of a tension mode, a distance between chucks of 15 mm, a measurement temperature of 25 ° C., and a measurement frequency of 30 Hz.
Adhesion test The dicing die-bonding tape obtained above was cut into 5 mm × 5 mm, and the base film on the adhesive layer side was peeled off, and this was cut into a 42 alloy of 18 mm × 18 mm (KAKU-42, 42 manufactured by Toppan Printing Co., Ltd.). After thermobonding to an alloy test piece) at 80 ° C. and 0.01 MPa for 30 seconds and fixing, the adhesive layer and the substrate film were peeled off, and a 18 alloy × 18 mm 42 alloy test piece was again used. It was fixed by thermocompression bonding under conditions. The pressure-bonded laminate was heat-treated at 175 ° C. for 1 hour to cure the adhesive layer, and an adhesive test piece was produced. Thereafter, the shear adhesive force was measured at a speed of 2.0 mm / min using an autograph tensile tester manufactured by Shimadzu Corporation.
Adhesion test after wet heat After holding the above-mentioned adhesion test piece under the condition of 85 ° C / 85% RH for 168 hours, using an autograph tensile tester manufactured by Shimadzu Corporation, the speed is 2.0 mm / Shear adhesion was measured in minutes.
Measurement of adhesive strength The dicing die-bonding tape obtained above was cut into a tape having a width of 25 mm, the base film on the adhesive layer side was peeled off, and the stainless steel plate of SUS27CP (thickness 1.0 mm) was peeled off from the adhesive layer side. , 30 mm in width) was fixed by thermocompression bonding at 80 ° C. and 0.01 MPa for 60 seconds. After leaving this test body for 30 minutes or more under constant temperature and humidity of 25 ± 2 ° C. and 50 ± 5% RH, the end of the adhesive film was folded back to 180 ° from the adhesive layer and peeled off at a speed of 300 mm / min. The peel force was measured.

Dicing and chip removal test The substrate film on the adhesive layer side of the dicing die-bonding tape obtained above was peeled off and fixed by thermocompression bonding to a 6-inch wafer at 80 ° C. and 0.01 MPa for 10 seconds. This was diced into 2 mm square chips, observed for the presence or absence of chip cracks, taken out with a suction collet with a diameter of 1.5 mm, and evaluated according to the following criteria.
Dicing condition equipment DAD341 (manufactured by DISCO Corporation)
Blade ZHT445 2050SE 27EEE
30,000 rpm
Feeding speed 30mm / sec
Observation of Chip Crack Generation Five chips (25 in total) were taken out from the diced wafer positions 1 to 5 shown in FIG. 5, and the cut surface was observed with a microscope to confirm the generation of cracks.
Chip removal (chip skipping during dicing)
○: None ×: Available (chip removal)
○: Possible ×: Impossible

Epicoat 834: EOCN-1020-55 manufactured by Japan Epoxy Dilen Co., Ltd .: o-cresol novolac type epoxy resin (epoxy equivalent 200), NC-3000 manufactured by Nippon Kayaku Co., Ltd .: biphenyl aralkyl type epoxy resin, RE-310S manufactured by Nippon Kayaku Co., Ltd. : Bisphenol A type epoxy resin, Nippon Kayaku Co., Ltd. 2PHZ: 2-Phenyl-4,5-dihydroxymethylimidazole, Shikoku Kasei Co., Ltd. * Cannot be measured due to problems with dicing and chip removal ** (Number of cracked chips) / (Total number of observation chips)
*** Irradiates ultraviolet rays with an energy amount of 500 mJ / cm ²

It is a schematic sectional drawing which shows an example of the dicing die-bonding tape of this invention. It is a schematic sectional drawing which shows the other example of the dicing die-bonding tape of this invention. It is a schematic sectional drawing explaining an example of the state which fixed the silicon wafer to the dicing die-bonding tape of this invention. It is a schematic sectional drawing explaining the other example of the state which fixed the silicon wafer to the dicing die-bonding tape of this invention. It is explanatory drawing which shows a chip crack generation | occurrence | production observation position.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adhesive film base material 2 Adhesive layer 3 Adhesive layer 4 Adhesive film base material 5 Silicon wafer

Claims (5)

  An adhesive layer is laminated on the adhesive layer formed on the substrate, and the adhesive layer is (A) a polyimide resin having a siloxane bond, (B) an epoxy resin, and (C) an epoxy resin cured. A dicing and comprising a catalyst as an essential component and comprising an adhesive composition having a Young's modulus of 10 MPa or more and an adhesive strength between the adhesive layer and the adhesive layer of 0.2 to 2.0 N / 25 mm. Adhesive tape for die bonding.   The adhesive tape for dicing and die bonding according to claim 1, wherein the adhesive layer is a silicone-based adhesive.   The adhesive tape for dicing and die bonding according to claim 1 or 2, wherein the substrate is a stretchable film.   4. The adhesive tape for dicing and die bonding according to claim 3, wherein the stretchable film is polyethylene or polypropylene.   The adhesive tape for dicing and die bonding according to any one of claims 1 to 4, wherein the polymer skeleton of the polyimide resin as the component (A) of the adhesive layer has a phenolic hydroxyl group.