JP2011042730A - Adhesive composition, film-shaped adhesive, adhesive sheet, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition that is sufficiently good in any of low-temperature adhesiveness, fluidity when heated, and reliability after heat curing, and a film-shaped adhesive, an adhesive sheet, and a semiconductor device using the same. <P>SOLUTION: The adhesive composition contains (A) a polycondensation polymer having a Tg of 150°C or lower and (B) a thermosetting resin, wherein (A) the polycondensation polymer is obtained by performing polycondensation of an acid including a dimer acid which is a dimer of a 20-50C unsaturated fatty acid and a diamine and/or a diisocyanate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an adhesive composition, a film adhesive, an adhesive sheet, and a semiconductor device.

  Conventionally, a silver paste has been mainly used for joining a semiconductor element and a semiconductor element mounting support member. However, with the progress of miniaturization and high performance of semiconductor packages, silver paste has wettability, defects during wire bonding caused by protrusion and inclination of semiconductor elements, and difficulty in controlling thickness of silver paste. There was a problem such as property and void generation. Therefore, in order to cope with the above problem, in recent years, a film-like adhesive (film-like adhesive) has been used as an alternative to the silver paste (see Patent Documents 1 and 2).

  Semiconductor device manufacturing methods using a film-like adhesive include an individual piece attaching method and a wafer back surface attaching method. In the piece pasting method, after a reel-like film adhesive is cut into pieces, it is bonded to a support member, and a semiconductor element separated by a dicing process is attached to the obtained support member with a film adhesive. The support member with a semiconductor element is produced by bonding. Thereafter, a semiconductor device is obtained through a wire bonding process, a sealing process, and the like (see Patent Document 3). However, the individual piece pasting method requires an assembly device for cutting out the film-like adhesive and bonding it to the support member, so that there is a problem that the manufacturing cost is higher than when silver paste is used. .

  On the other hand, in the wafer back surface attaching method, one surface of the film adhesive is attached to the back surface of the semiconductor wafer, and then a dicing sheet is attached to the other surface of the film adhesive. And the obtained laminated body is separated into pieces by dicing, a semiconductor element with a film adhesive is picked up, and it is joined to a support member. Thereafter, a semiconductor device is obtained through a wire bonding process, a sealing process, and the like.

  The wafer back surface pasting method does not require an assembling apparatus for cutting out the film-like adhesive and adhering it to the support member, and can be used by simply or partially improving the conventional assembling apparatus for silver paste. For this reason, the wafer back surface pasting method has attracted attention as a method that can suppress the manufacturing cost relatively low among the methods for manufacturing a semiconductor device using a film adhesive (see Patent Document 4).

  Recently, in addition to downsizing, thinning and high performance of semiconductor elements, multi-functionalization has progressed, and semiconductor devices in which a plurality of semiconductor elements are stacked are rapidly increasing. Further, the thickness of the semiconductor device is also progressing in the direction of thinning. For this reason, semiconductor wafers have become extremely thin, and the risk of wafer warpage and wafer cracking has become a problem.

  Therefore, by using an adhesive sheet in which a dicing sheet is bonded to one surface of the film adhesive, that is, a film in which a dicing sheet and a die bond film are integrated (hereinafter referred to as a “dicing / die bond integrated film”). A method for simplifying the bonding process on the back surface of the wafer has been proposed. According to this method, the process of attaching the film to the back surface of the wafer can be simplified, so that the risk of wafer warpage and wafer cracking can be reduced.

  In addition, the softening temperature of a dicing tape is 100 degrees C or less normally. Therefore, it is desirable that the film adhesive in the dicing / die-bonding integrated film has a good sticking property (low temperature sticking property or low temperature laminating property) at a temperature lower than 100 ° C. Having good low-temperature sticking properties also leads to reduction of wafer warpage.

  In addition, semiconductor devices manufactured using film adhesives have good reliability such as wire bond resistance (heat resistance), reflow resistance (heat resistance and humidity resistance), and PCT resistance (heat resistance, humidity resistance, and pressure resistance). It is required to be. In order to ensure reflow resistance, it is required to have a high adhesive strength that can suppress the peeling or breaking of the die bond layer at a reflow heating temperature of around 260 ° C.

  Further, when the supporting member is an organic substrate having wiring on the surface, the film adhesive has sufficient filling property (embedding property) with respect to the wiring step, so that the moisture resistance reliability of the semiconductor device and the insulation reliability between the wirings are ensured. It has become important in securing sex. Therefore, there is a demand for a film-like adhesive having sufficient heat fluidity that can ensure sufficient filling (embedding property) for such an adherend.

  To date, resin compositions combining a thermoplastic resin having a relatively low Tg and a thermosetting resin have been proposed in order to obtain a film adhesive having both moldability and heat resistance (patent) Reference 5).

Japanese Patent Laid-Open No. 3-192178 JP-A-4-234472 Japanese Patent Laid-Open No. 9-17810 Japanese Patent Laid-Open No. 4-196246 Japanese Patent No. 3014578

  However, a sufficiently good adhesive composition has not been developed so far in terms of low temperature sticking property, fluidity during heat, and reliability after heat curing, and such an adhesive composition has not been developed. It was strongly desired.

  Accordingly, the present invention provides an adhesive composition that is sufficiently good in terms of low temperature sticking property, fluidity during heat, and reliability after heat curing, and a film-like adhesive, an adhesive sheet, and a semiconductor using the same. An object is to provide an apparatus.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors are sufficiently good in any of the above points by using a polycondensation polymer having a specific dimer acid as a polycondensation component and a specific Tg. It has been found that an adhesive composition can be obtained, and the present invention has been completed.

  That is, the present invention is an adhesive composition containing (A) a polycondensation polymer having a Tg of 150 ° C. or less and (B) a thermosetting resin, wherein (A) the polycondensation polymer is a carbon atom. The present invention relates to an adhesive composition obtained by polycondensation of an acid containing dimer acid, which is a dimer of unsaturated fatty acids having a number of 20 to 50, and diamine and / or diisocyanate.

  Since the adhesive composition of the present invention has the above-described configuration, it can obtain good low-temperature stickability and is excellent in thermal fluidity in the B stage, so that it can be used under conditions of low temperature, low pressure and short time during die bonding. It is possible to sufficiently satisfy the filling property (embedding property) with respect to the unevenness of the adherend surface and to highly satisfy the reliability of the semiconductor device such as reflow resistance and insulation durability including PCT resistance. it can.

  (A) It is preferable that a polycondensation polymer does not have an ester bond. That is, although the dimer acid has a long-chain flexible skeleton, it does not have a structure that is easily hydrolyzed, such as an ester bond, and therefore can be designed with hydrolysis resistance.

  (A) The polycondensation polymer is preferably a polyamide resin or a polyamideimide resin.

  (B) It is preferable that a thermosetting resin contains an epoxy resin. As a result, a network formation effect is obtained by thermal reaction with the reactive group contained in the amide group and the oligomer end group of the polyamide resin or polyamideimide resin which is the polycondensation polymer (A). The reflow property can be more fully satisfied.

  The adhesive composition of the present invention preferably further contains (C) a filler. This makes it easy to cut during dicing, easy peeling from the dicing tape during pickup due to suppression of film surface adhesion, and high elasticity during semiconductor device assembly heat history, as well as low moisture absorption, during reflow heating The reflow resistance can be further improved by improving the elastic modulus and breaking strength.

  The adhesive composition of the present invention is preferably used for bonding a semiconductor element to another semiconductor element or a semiconductor element mounting support member. Since the adhesive composition of the present invention exhibits the effects described above, it is suitable for applications in which a semiconductor element is bonded to another semiconductor element or a semiconductor element mounting support member. In addition, since the adhesive composition of the present invention has excellent thermal fluidity that enables embedding in a wiring step on a substrate surface under conditions of low temperature, low pressure, and short time during die bonding, a semiconductor element and a semiconductor It is particularly suitable for use in connecting an organic substrate with a wiring step as an element mounting support member.

  Moreover, this invention relates to the film adhesive formed by shape | molding the said adhesive composition in a film form. Since the film adhesive is composed of the adhesive composition of the present invention described above, it is sufficient for a semiconductor device such as a fluidity at the time of heat and a low temperature sticking property that can secure a filling property (embedding property) to an adherend. The process characteristics required at the time of manufacture and the reliability of the semiconductor device such as reflow resistance can be made excellent, and since it is in the form of a film, it is easy to handle, and the efficiency of the semiconductor device assembly process is improved. Contribute. In particular, the film adhesive can simplify the pasting process up to the dicing process, and can secure stable characteristics against heat history during package assembly.

  Moreover, this invention relates to an adhesive sheet provided with a support base material and the said film adhesive formed on the main surface of this support base material. Since such an adhesive sheet is obtained by laminating the film adhesive of the present invention on a support substrate, the same effect as the film adhesive can be obtained, and handling such as workability at the time of bonding can be achieved. It becomes easier.

  The support substrate is preferably a dicing sheet. Since such an adhesive sheet has both functions of a dicing sheet and a die bonding film, the manufacturing process of the semiconductor device can be further simplified. Here, the dicing sheet preferably has a base film and an adhesive layer provided on the base film.

  Furthermore, the present invention relates to a semiconductor device having a structure in which a semiconductor element and a semiconductor element mounting support member are bonded by the adhesive composition and / or a structure in which adjacent semiconductor elements are bonded to each other. According to such a semiconductor device, the semiconductor element and the semiconductor element mounting support member and / or the adjacent semiconductor elements are bonded to each other by the adhesive composition of the present invention. To obtain a semiconductor device that has excellent embeddability, is sufficiently suppressed from warping of the semiconductor element and damage to the circuit surface, and has high performance, high functionality, and reliability (such as reflow resistance). Can do. Further, such a semiconductor device is excellent in productivity and excellent in adhesive strength and moisture resistance during heating.

  ADVANTAGE OF THE INVENTION According to this invention, adhesive composition which is sufficiently favorable in any point of low temperature sticking property, fluidity | liquidity at the time of heat, and the reliability after heat-hardening, and a film adhesive using the same, an adhesive sheet, and a semiconductor An apparatus can be provided.

  Moreover, according to this invention, the adhesive composition and film adhesive of a wafer back surface attachment system which can respond | correspond to the semiconductor device which laminated | stacked the ultra-thin wafer and the several semiconductor element can be provided. When a film adhesive is attached to the wafer back surface, it is usually heated to a temperature at which the film adhesive melts. However, if the film adhesive of the present invention is used, the wafer back surface can be suppressed at a low temperature that can suppress the warpage of the wafer. It becomes possible to paste on. As a result, thermal stress is also reduced, and problems such as warpage of the wafer that becomes thinner and thinner can be solved.

  In addition, it is possible to ensure thermal fluidity that enables satisfactory embedding in a wiring step on the substrate surface, and it is possible to suitably cope with a manufacturing process of a semiconductor device in which a plurality of semiconductor elements are stacked. In addition, since high adhesive strength at high temperatures can be ensured, heat resistance and moisture resistance reliability can be improved, and the manufacturing process of the semiconductor device can be simplified.

  In addition, by optimizing the adhesive composition, thermal stress can be further reduced by suppressing wafer warpage and chip warpage due to curing shrinkage of film adhesives, etc. Performance, workability at the time of manufacturing a semiconductor device, and low outgassing property.

  Moreover, according to this invention, the adhesive sheet which bonded the said film adhesive and the dicing sheet can be provided. According to the adhesive sheet of the present invention, it is possible to provide a material that can simplify the pasting process up to the dicing process and secure stable characteristics against the assembly heat history of the package.

  Moreover, according to this invention, the adhesive sheet which consists of an adhesive layer and a base material which have both the function of the dicing sheet and the die-bonding film can be provided.

  Furthermore, according to this invention, the semiconductor device using the said film adhesive can be provided. The semiconductor device of the present invention is a highly reliable semiconductor device with a simplified manufacturing process. The semiconductor device of the present invention has heat resistance and moisture resistance required when a semiconductor element having a large difference in thermal expansion coefficient is mounted on a semiconductor element mounting support member.

It is a schematic cross section which shows one Embodiment of the film adhesive which concerns on this invention. It is a schematic cross section which shows one Embodiment of the adhesive sheet which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet which concerns on this invention. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device according to the present invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device which concerns on this invention. It is the schematic which shows a peel strength measuring apparatus.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  The adhesive composition of the present invention contains (A) a polycondensation polymer having a Tg of 150 ° C. or less and (B) a thermosetting resin.

  The temperature at which the film adhesive of the present invention can be applied to the backside of the semiconductor wafer is preferably not more than the softening temperature of the protective tape and dicing tape of the semiconductor wafer. In terms of suppressing warpage of the semiconductor wafer, the attaching temperature is preferably 10 to 150 ° C, more preferably 20 to 100 ° C, and still more preferably 20 to 80 ° C. In order to enable attachment at such a temperature, it is preferable to set the Tg of the film adhesive to 150 ° C. or lower, and for that purpose, the Tg of the polycondensation polymer (A) is set to 150 ° C. or lower. It is desirable to set it to −20 to 100 ° C., more preferably 20 to 80 ° C. When the Tg exceeds 150 ° C., there is a high possibility that the bonding temperature to the back surface of the semiconductor wafer exceeds 150 ° C., and when the Tg is less than −20 ° C., the tack of the film adhesive surface in the B stage state These properties are not preferable because the property tends to be strong and the handleability tends to deteriorate gradually.

  The above Tg is (A) the main dispersion peak temperature when the polycondensation polymer is formed into a film, and using a viscoelasticity analyzer (trade name: RSA-2) manufactured by Rheometrics Co., Ltd., the film size is 35 mm. The measurement was performed under the conditions of × 10 mm × 40 μm thickness, temperature rising rate 5 ° C./min, frequency 1 Hz, measurement temperature −150 to 300 ° C., the tan δ peak temperature in the vicinity of Tg was measured, and this was defined as the main dispersion temperature.

  In the polycondensation polymer (A) constituting the adhesive composition of the present invention, an acid containing dimer acid, which is a dimer of unsaturated fatty acid having 20 to 50 carbon atoms, and diamine and / or diisocyanate are polymerized. It is obtained by condensation. Examples of the dimer acid include those obtained by dimerizing unsaturated fatty acids such as palmitic acid, oleic acid, linoleic acid, and linolenic acid. Among them, dimer acid obtained from an unsaturated fatty acid having 36 carbon atoms is more preferable. In addition, these dimer acids may partially contain monomeric acids and trimer acids. In this case, the dimer acid content is preferably 60% by weight or more. Two or more of these dimer acids may be used.

  (A) Polycondensation polymers include polyamide resins and polyamideimide resins. In addition, it is preferable that a hydrolysable ester bond is not contained in the structure of the (A) polycondensation polymer in order to ensure moisture resistance reliability.

  The polyamide resin can be obtained by using a carboxylic acid compound containing dimer acid as an acid component, combining diamine and / or diisocyanate, and subjecting these raw materials to a condensation reaction. As an acid component as a raw material, in addition to dimer acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids such as terephthalic acid may be used in combination. In this case, the content of the dimer acid is preferably 3 mol% or more of the total acid component, more preferably 10 mol% or more, and even more preferably 30 mol% or more.

  The polyamide-imide resin can be obtained by combining dimer acid, trimellitic anhydride and / or tetracarboxylic dianhydride as an acid component, combining diamine and / or diisocyanate, and subjecting these raw materials to a condensation reaction. it can. In this case, the content of the dimer acid is preferably 3 mol% or more of the total acid component, more preferably 10 mol% or more, and even more preferably 30 mol% or more.

  Although there is no restriction | limiting in particular as diamine used as a raw material of the said polyamide resin or a polyamideimide resin, It is preferable to select the compound which does not contain an ester bond in a molecule | numerator. Examples of such diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3, 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) Methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4 ' Diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 4 , 4′-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis 3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene) )) Bisaniline, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2- Bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) Hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfur Bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,5- Aromatic diamines such as diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, 5,5′-methylene-bis (anthranilic acid), 4,4 '-Diaminobenzanilide, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,7,10-trioxatridecane-1,13-diamine, 4,9-dioxadodecane-1,12- In addition to diamine, Jeffermin D-230, D-400, D-2000, D-4000, ED-600, ED- manufactured by Sun Techno Chemical Co., Ltd. 00, ED-2001, EDR-148, aliphatic amines such as polyoxyalkylene diamines such as polyetheramine D-230, D-400, D-2000 manufactured by BASF Corporation, 1,2-diaminoethane, 1, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Aliphatic diamines such as diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, and 1,1,3,3-tetramethyl-1,3-bis (4- Aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxy Sun, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) di Siloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane Siloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) Disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1, 5-bis (3-aminopropyl) trisiloxane, , 1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5 -Bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5- Tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) ) Trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5- Bis (3-aminopropyl) trichiro Sun, 1,1,3,3,5,5 hexapropylphosphorustriamide 1,5-bis (3-aminopropyl) include siloxane diamine such as trisiloxane. These diamines can be used alone or in combination of two or more.

  The diisocyanate used as a raw material for the polyamide resin or polyamideimide resin is not particularly limited, and examples thereof include diphenylmethane-4, 4′-diisocyanate, diphenylmethane-2, 4′-diisocyanate, and toluene-2,4-diisocyanate. , Toluene-2,6-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,1′-methylenebis (4-isocyanatocyclohexane), 1,3-bis (isocyanatomethyl) benzene And diisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane, and the like can be used alone or in combination. In addition, these diisocyanates can be used individually by 1 type or in combination of 2 or more types.

  Although there is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of the said polyamidoimide resin, The compound which does not contain an ester bond in a molecule | numerator is preferable. Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyl. Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis ( 3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4- Dikarboki Phenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3,2 ′, 3 '-Benzophenonetetracarboxylic dianhydride, 3,3,3', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1 , 4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1, 4,5,8- Tracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6 -Tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,2 ' , 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4 -Dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitate anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride Decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6- Tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4- Cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene-2, 3,5,6-tetracar Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 4,4 ′ -Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexa) Fluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- , 2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4 '-(4,4'-isopropylidene Dendiphenoxy) bis (phthalic dianhydride) and the like. These tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  The polyamide resin or polyamideimide resin can be obtained by reacting an acid component containing at least dimer acid with a diamine and / or diisocyanate by a known method. That is, in an organic solvent, an acid component containing dimer acid and diamine and / or diisocyanate are equimolar, or if necessary, a total of 0 mol of diamine and / or diisocyanate with respect to a total of 1.0 mol of acid components. It is obtained by adjusting the composition ratio in the range of 0.5 to 2.0 mol, preferably 0.8 to 1.0 mol (addition order of each component is arbitrary).

  In addition, about the composition ratio of the acid component and diamine and / or diisocyanate in the said condensation reaction, when the total of a diamine and / or diisocyanate exceeds 2.0 mol with respect to 1.0 mol of total of an acid component, the polyamide resin obtained Or, in the polyamide-imide resin, the amount of amine or isocyanate-terminated oligomer tends to increase. On the other hand, when the total amount of diamine and / or diisocyanate is less than 0.5 mol, the amount of acid-terminated oligomer tends to increase. In any case, the weight average molecular weight of the obtained polyamide resin or polyamideimide resin is lowered, and various properties including the heat resistance of the adhesive composition tend to be lowered. Further, when an epoxy resin having reactivity with these terminals is blended, as the amount of the above oligomer increases, the storage stability of the adhesive composition deteriorates, and the tendency thereof is amine or isocyanate. It becomes more prominent as the amount of the terminal oligomer increases. Therefore, it is not preferable to deviate from the above composition ratio. The composition ratio between the acid component and the diamine and / or diisocyanate is appropriately determined in consideration of the required properties of the adhesive composition.

  In addition to the above condensation reaction, the polyamide-imide resin of the present invention is obtained by previously reacting trimellitic anhydride with a diamine to form a carboxylic acid-terminated imide oligomer, followed by additional polycondensation of dimer acid and diisocyanate. You can also. The carboxylic acid-terminated imide oligomer can be obtained by adjusting the composition in the range of 0.1 to 1.9 mol, preferably 0.5 to 1.0 mol of diamine with respect to 2.0 mol of trimellitic anhydride. Thereafter, a carboxylic acid-terminated imide oligomer and a dimer acid can be used as an acid component and a diisocyanate can be subjected to a condensation reaction to obtain a dimer acid polyamideimide resin. The composition ratio of the acid component to the diisocyanate in this condensation reaction is When the total of diisocyanate exceeds 2.0 mol relative to the total of 1.0 mol, the amount of isocyanate-terminated oligomer tends to increase in the resulting polyamideimide resin, while the total diisocyanate is less than 0.5 mol If so, the amount of the acid-terminated oligomer tends to increase, and in any case, the weight average molecular weight of the resulting polyamideimide resin is lowered, and various properties including the heat resistance of the adhesive composition are lowered. Tend. In addition, when an epoxy resin having reactivity with these ends is blended, the storage stability of the adhesive composition is worsened as the amount of the oligomer increases, and the tendency is It becomes more prominent as the amount of oligomer increases. Therefore, it is not preferable to deviate from the above composition ratio. The composition ratio between the acid component and the diisocyanate is appropriately determined in consideration of the required characteristics of the adhesive composition.

  Moreover, when determining the composition of the polyamide resin or the polyamideimide resin, it is necessary to design the Tg to be 150 ° C. or less, and the dimer acid as a raw material is 3 mol% or more in the total acid component, Preferably it is 10 mol% or more, More preferably, it is 30 mol% or more. If the amount of dimer acid used is less than 3 mol%, it tends to be difficult to impart low temperature adhesiveness and hot fluidity, which is not preferable.

  The weight average molecular weight of the polyamide resin or polyamideimide resin is preferably controlled within a range of 5,000 to 100,000, more preferably 10,000 to 80,000, and still more preferably 10,000 to 50,000. If the weight average molecular weight is within this range, the strength, flexibility, and tackiness when sheet-like or film-like are appropriate, and the fluidity during heating is appropriate, leading to wiring differences on the substrate surface. The satisfactory embedding property can be more sufficiently ensured. When the weight average molecular weight is less than 5,000, the film formability gradually deteriorates and the strength of the film tends to decrease. When the weight average molecular weight exceeds 100,000, the heat fluidity gradually deteriorates and the unevenness on the substrate is reduced. Since the embedding property tends to decrease, neither is preferable.

  By setting the Tg and the weight average molecular weight of the polyamide resin or polyamideimide resin within the above ranges, not only can the temperature applied to the back surface of the semiconductor wafer be kept low, but also the semiconductor element can be used as a semiconductor element mounting support member. The heating temperature (die bonding temperature) at the time of bonding and fixing can also be lowered, and an increase in warpage of the semiconductor element can be suppressed. In addition, fluidity can be effectively imparted under conditions of low temperature, low pressure, and short time during die bonding, which is a feature of the present invention. In addition, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation make, brand name: C-R4A).

  Moreover, (B) thermosetting resin used by this invention can use the component which consists of a reactive compound which raise | generates a crosslinking reaction with heat, without being specifically limited. Examples of reactive compounds that cause a crosslinking reaction by heat include epoxy resins, bismaleimide resins, cyanate ester resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, silicone resins, and resorcinol formaldehyde. Resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, cyclohexane In addition to thermosetting resins synthesized from pentadiene, thermosetting resins by trimerization of aromatic dicyanamide, polyfunctional acrylate and / or methacrylate compounds, compounds having a styryl group, diallyl bisphenol , Bisallylnadimide, diallyl phthalate or diallyl phthalate prepolymer, diallyl melamine, triallyl isocyanurate, allyl-modified phenol novolac, 1,3-diallyl-5-glycidyl isocyanurate. Among these, an epoxy resin is preferable because it can have an excellent adhesive force at high temperatures. In addition, these thermosetting resins can be used individually by 1 type or in combination of 2 or more types.

  In the adhesive composition, the content of the (B) thermosetting resin is preferably 1 to 200 parts by mass, and preferably 5 to 100 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin. More preferably, it is 5-50 mass parts. If this content exceeds 200 parts by mass, outgassing during heating increases, and film formability (toughness) tends to be gradually impaired. If the content is less than 1 part by mass, The possibility of being unable to effectively impart heat fluidity, heat resistance at the C-stage and high-temperature adhesiveness gradually increases, and neither is preferable.

  In the adhesive composition, an organic peroxide, a curing agent, or a catalyst can be used for curing the thermosetting resin (B), and a curing agent, a curing accelerator, or a catalyst is used as necessary. And a cocatalyst can be used in combination. About the addition amount of the said hardening | curing agent, hardening accelerator, a catalyst, a co-catalyst, and an organic peroxide, and the presence or absence of addition, the fluidity | liquidity at the time of heat, sclerosis | hardenability mentioned later, and heat resistance after hardening can be ensured. Judge and adjust by range.

  As an epoxy resin that is one of the preferred (B) thermosetting resins, those containing at least two epoxy groups in the molecule are more preferable, and phenol glycidyl ether type epoxy in terms of curability and cured product characteristics. Resins are highly preferred. Examples of such resins include bisphenol A type (or AD type, S type, and F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct. Trifunctional type (or tetrafunctional type) such as bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolac resin glycidyl ether, naphthalene resin glycidyl ether, trisphenolmethane type Glycidyl ether, glycidyl ether of dicyclopentadiene phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, naphthalene Glycidyl amine resin, diallyl bisphenol A diglycidyl ether or its polycondensate, such as monoallyldiglycidylisocyanuric acid. These can be used individually by 1 type or in combination of 2 or more types.

  In addition, it is preferable to use a high-purity product in which the impurity ions, alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less for these epoxy resins. This is preferable for preventing migration and corrosion of metal conductor circuits.

  When using the said epoxy resin, a hardening | curing agent can also be used as needed. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, and organic acid dihydrazides. , Boron trifluoride amine complexes, imidazoles, tertiary amines and the like. Among these, phenol compounds are preferable, and phenol compounds having at least two phenolic hydroxyl groups in the molecule are more preferable. Examples of such compounds include phenol novolak resins, cresol novolak resins, t-butylphenol novolak resins, dicyclopentagencresol novolak resins, dicyclopentagen phenol novolak resins, xylylene-modified phenol novolak resins, naphthol compounds, trisphenols. Examples thereof include tetrakisphenol novolac resin, bisphenol A novolac resin, poly-p-vinylphenol resin, and phenol aralkyl resin. Among these, those having a number average molecular weight in the range of 400 to 1500 are preferable. By using these curing agents, it is possible to effectively reduce the outgas that causes contamination of the semiconductor element or the device during the assembly heating of the semiconductor device. In order to secure the heat resistance of the cured product, the compounding amount of these phenolic compounds is such that the equivalent ratio of the epoxy equivalent of the epoxy resin and the OH equivalent of the phenolic compound is 0.95: 1.05. It is preferable to adjust so that it may become -1.05: 0.95.

  Moreover, a hardening accelerator can also be used as needed. The curing accelerator is not particularly limited as long as it cures a thermosetting resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate and the like.

  The adhesive composition of the present invention preferably further contains (C) a filler. (C) As filler, for example, metal filler such as silver powder, gold powder, copper powder, nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, Examples include magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, ceramic and other inorganic fillers, carbon, rubber filler, and other organic fillers. Regardless of the shape, it can be used without particular limitation.

  (C) The filler can be properly used according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy, etc. to the adhesive composition, and the nonmetallic inorganic filler is thermally conductive, low thermal expansion, low hygroscopicity to the adhesive layer. The organic filler is added for the purpose of imparting toughness to the adhesive layer. These metal fillers, inorganic fillers or organic fillers can be used singly or in combination of two or more. Among these, metal fillers, inorganic fillers, or insulating fillers are preferable in terms of being able to impart conductivity, thermal conductivity, low moisture absorption characteristics, insulation, and the like required for adhesive materials for semiconductor devices, and inorganic fillers, Alternatively, among the insulating fillers, a boron nitride filler or a silica filler is more preferable in that the dispersibility with respect to the resin varnish is good and a high adhesive force during heating can be imparted.

  (C) Although the usage-amount of a filler is decided according to the characteristic or function to provide, it is preferable that it is 1-40 volume% on the basis of the sum total of the resin component of an adhesive composition, and a filler, More preferably, it is 30 volume%, and it is still more preferable that it is 5-20 volume%. (C) By appropriately increasing the amount of filler, the film surface can be reduced in adhesion and increased in elastic modulus, dicing (cutting with a dicer blade), pick-up (easily peelable from the dicing tape), wire bonding Property (ultrasound efficiency) and adhesive strength during heating can be effectively improved. (C) When the filler is increased more than necessary, the low temperature sticking property, interfacial adhesion with the adherend, and hot fluidity, which are the characteristics of the present invention, are impaired, and the reliability including reflow resistance is lowered. Therefore, the amount of filler used is preferably within the above range. In order to balance the required characteristics, it is preferable to determine an optimum filler content. (C) Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill.

  Various coupling agents can be added to the adhesive composition of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective. It is preferable that the usage-amount of a coupling agent shall be 0.01-20 mass parts with respect to 100 mass parts of (A) thermoplastic resins from the surface of the effect, heat resistance, and cost.

  In addition, an ion scavenger can be further added to the adhesive composition of the present invention in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, a triazine thiol compound, a compound known as a copper damage preventer for preventing copper from being ionized and dissolved, such as a bisphenol-based reducing agent, a zirconium-based compound And inorganic ion adsorbents such as antimony bismuth-based magnesium aluminum compounds. The amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A) from the viewpoint of the effect of addition, heat resistance, cost, and the like.

  You may add tackifiers, such as a softening agent, anti-aging agent, a coloring agent, a flame retardant, and a terpene-type resin, to the adhesive composition of this invention suitably.

  By using the adhesive composition, the film adhesive, the adhesive sheet and the semiconductor device of the present invention can be obtained.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive according to the present invention. The film adhesive 1 of FIG. 1 is formed by forming the adhesive composition of the present invention into a film. The thickness of the film adhesive 1 is preferably 1 to 200 μm. As a form of the film adhesive 1, as shown in FIG. 1, a single-layer film adhesive 1 is mentioned. In the case of this form, the film adhesive 1 is preferably transported in a tape shape with a width of about 1 to 20 mm or a sheet shape with a width of about 10 to 50 cm and wound around a winding core. Thereby, storage and conveyance of the film adhesive 1 become easy. The film adhesive 1 may be a film in which single-layer films are stacked and bonded for the purpose of increasing the film thickness.

  As a manufacturing method of the film adhesive 1, first, each said component ((A) polycondensation polymer which contains a dimer acid as a condensation component, (B) thermosetting resin, and necessity are comprised. Accordingly, (C) filler and other components) are mixed in an organic solvent, and the mixture is kneaded as necessary to prepare a varnish (varnish for forming an adhesive layer). Mixing and kneading for preparing the varnish can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill. Next, the film adhesive 1 can be obtained by coating the varnish on a base film, heating and drying to form an adhesive layer, and removing the base film. The heating and drying conditions are not particularly limited as long as the organic solvent in the varnish is sufficiently volatilized, but it is usually performed by heating at 50 to 200 ° C. for 0.1 to 90 minutes.

  The organic solvent used in the production of the adhesive layer, that is, the organic solvent in the varnish is not particularly limited as long as each component can be uniformly dissolved, kneaded, or dispersed. For example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, ethyl acetate and the like.

  The base film used in the production of the film adhesive 1 is not particularly limited as long as it can withstand the above heating and drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, Examples include an etherimide film, a polyether naphthalate film, and a methyl pentene film. These base films may be a combination of two or more types to form a multilayer film, or the surface may be treated with a release agent such as silicone or silica.

  Application of the varnish to the base film may be performed on only one main surface of the base film, or may be performed on both main surfaces. After the film adhesive 1 is formed, the substrate film removed may be used as the film adhesive 1 or may be used as an adhesive sheet without removing the substrate film.

  FIG. 2 is a schematic cross-sectional view showing an embodiment of an adhesive sheet according to the present invention. An adhesive sheet 100 shown in FIG. 2 includes a base film 2 that is a supporting base and a film adhesive 1 as an adhesive layer provided on both main surfaces thereof.

  FIG. 3 is a schematic cross-sectional view showing another embodiment of the adhesive sheet according to the present invention. The adhesive sheet 110 shown in FIG. 3 is obtained by laminating a film adhesive 1 and a protective film (cover film) 3 in this order on one main surface of a base film 2. The protective film 3 is provided so as to cover the film adhesive 1 in order to prevent damage and contamination of the film adhesive 1. In this case, the film adhesive 1 is used for die bonding after peeling off the protective film 3.

  FIG. 4 is a schematic cross-sectional view showing another embodiment of the adhesive sheet according to the present invention. The adhesive sheet 120 has a configuration in which the film adhesive 1 is laminated on the pressure-sensitive adhesive layer 6 of the dicing sheet 5 in which the pressure-sensitive adhesive layer 6 is provided on one main surface of the base film 7 as a support base material. have. The base film 7 may be the same as the base film 2 described above. Moreover, it is preferable that the film adhesive 1 in the adhesive sheet 120 is preliminarily formed in a shape close to a semiconductor wafer to which the adhesive is attached (pre-cut). The adhesive sheet according to the present invention may be a sheet provided with a dicing sheet made of only the base film 7 instead of the dicing sheet 5 in the adhesive sheet 120. Here, FIG. 5 is a schematic cross-sectional view showing another embodiment of the adhesive sheet according to the present invention. In the adhesive sheet 130, the film adhesive 1 is laminated on one main surface of the base film 7. It has a configuration. These adhesive sheets 120 and 130 are a base film 7 that can ensure elongation (common name, expanded) when a film adhesive 1 and a dicing sheet 5 or tensile tension are applied for the purpose of simplifying the semiconductor device manufacturing process. And a dicing / die bonding integrated film adhesive. That is, these adhesive sheets have characteristics required for both the dicing sheet and the die bonding film.

  Thus, the adhesive layer 6 that functions as a dicing sheet is provided on the base film 7, and the film adhesive 1 of the present invention that functions as a die bonding film is further formed on the adhesive layer 6. A laminated structure or a structure in which the expandable base film 7 and the film-like adhesive 1 are bonded to each other so that it functions as a dicing sheet during dicing and as a die bonding film during die bonding. To do. Therefore, the adhesive sheets 120 and 130 can be picked up and used as a semiconductor element with a film adhesive after laminating and dicing the film adhesive 1 on the back surface of the semiconductor wafer.

  The pressure-sensitive adhesive layer 6 is formed of a pressure-sensitive or radiation-curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer 6 is particularly limited as long as it has a sufficient adhesive strength that prevents the semiconductor element from scattering during dicing, and has a low adhesive strength that does not damage the semiconductor element in the subsequent semiconductor element pick-up process. A conventionally well-known thing can be used without this. For example, radiation curable adhesives have high adhesive strength when dicing, and low adhesive strength due to radiation irradiation before pick-up when picking up after dicing. is there.

  Further, the base film 7 is not particularly limited as long as it can ensure elongation (common name, expanded) when a tensile tension is applied, but a film made of polyolefin is preferably used.

  The adhesive composition and film adhesive of the present invention described above are used for semiconductor elements such as IC and LSI, lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resins and epoxy resins; glass Die bonding adhesive material for bonding substrates such as non-woven fabrics with polyimide resin, epoxy resin, or other plastic; Can be used as Especially, it is suitably used as an adhesive material for die bonding for adhering an organic substrate having an uneven surface to a semiconductor element, such as an organic substrate having an organic resist layer on the surface and an organic substrate having wiring on the surface.

  The adhesive composition and film adhesive of the present invention are also suitable as an adhesive material for bonding adjacent semiconductor elements in a semiconductor device (Stacked-PKG) having a structure in which a plurality of semiconductor elements are stacked. Used.

  Next, the use of the film adhesive of the present invention will be specifically described with reference to the drawings for a semiconductor device provided with the film adhesive of the present invention. In recent years, semiconductor devices having various structures have been proposed, and the use of the film adhesive of the present invention is not limited to the semiconductor devices having the structure described below.

  FIG. 6 is a schematic cross-sectional view showing an embodiment of a semiconductor device according to the present invention. In the semiconductor device 200 shown in FIG. 6, the semiconductor element 9 is bonded to the support member 10 via the die bonding layer 1 formed of the above-mentioned film adhesive, and the connection terminal (not shown) of the semiconductor element 9 is provided. It has a configuration in which it is electrically connected to an external connection terminal (not shown) via a wire 11 and further sealed with a sealing material 12.

  FIG. 7 is a schematic cross-sectional view showing another embodiment of the semiconductor device according to the present invention. In the semiconductor device 210 shown in FIG. 7, the first-stage semiconductor element 9a is bonded to the support member 10 on which the terminals 13 are formed via the die bonding layer 1 formed by the film adhesive, and the upper surface of the semiconductor element 9a. The semiconductor element 9b is bonded through the die bonding layer 1 formed of the film adhesive, and the whole is sealed with the sealing material 12. Connection terminals (not shown) of the semiconductor element 9a and the semiconductor element 9b are electrically connected to external connection terminals via wires 11, respectively.

  The semiconductor device (semiconductor package) shown in FIGS. 6 and 7 has the film adhesive of the present invention sandwiched between a semiconductor element and a semiconductor element mounting support member, and bonded by thermocompression bonding, and then wire bonding. It can manufacture by passing through processes, such as a sealing process with a sealing material, as needed. The heating temperature in the thermocompression bonding step is usually 20 to 250 ° C., the load is usually 0.01 to 20 kgf, and the heating time is usually 0.1 to 300 seconds.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of dimer acid polyamide resin>
(PA-1)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, dimer acid (manufactured by Harima Chemicals Co., Ltd., trade name: Haridimer 250, molecular weight: 580, carbon number: 36, dimer acid content: 80 wt%) 72.50 g, diphenylmethane-4,4′-diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) 31.28 g, and N-methyl-2-pyrrolidone 155.67 g as an organic solvent were charged, and the reaction solution was stirred. Then, reaction was carried out at 200 ° C. for 6 hours while blowing nitrogen gas to obtain a dimer acid polyamide resin (PA-1) varnish. When GPC of the obtained dimer acid polyamide resin (PA-1) was measured, it was number average molecular weight Mn = 10200 and weight average molecular weight Mw = 21600 in terms of polystyrene. Moreover, Tg of dimer acid polyamide resin (PA-1) was 57 degreeC.

(PA-2)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, dimer acid (manufactured by Harima Chemicals Co., Ltd., trade name: Haridimer 250, molecular weight: 580, carbon number: 36, dimer acid content: 80 wt%) 76.13 g, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (trade name: LP-7100, manufactured by Shin-Etsu Chemical Co., Ltd.) 15.53 g, 4,9-dioxadodecane- First, 12.75 g of 1,12-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 127.61 g of N-methyl-2-pyrrolidone as an organic solvent were added, and the reaction solution was stirred and then blown with nitrogen gas at 200 ° C. for 5 hours. It was made to react, the water produced | generated was removed, and the dimer acid polyamide resin (PA-2) varnish was obtained. When GPC of the obtained dimer acid polyamide resin (PA-2) was measured, it was number average molecular weight Mn = 10100 and weight average molecular weight Mw = 20700 in terms of polystyrene. Moreover, Tg of dimer acid polyamide resin (PA-2) was 5 degreeC.

<Synthesis of dimer acid polyamideimide resin>
(PAI-1)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, dimer acid (manufactured by Harima Chemicals Co., Ltd., trade name: Haridimer 250, molecular weight: 580, carbon number: 36, dimer acid content: 80 wt%) 36.25 g, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100) 15.53 g, 4,9-dioxadodecane- 12.12 g of 1,12-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 119.87 g of N-methyl-2-pyrrolidone as an organic solvent were charged, and the reaction solution was stirred. After the diamine is dissolved, 15.38 g of 4,4′-oxydiphthalic dianhydride recrystallized and purified in advance with acetic anhydride is added little by little, and the reaction is carried out at 200 ° C. for 5 hours while blowing nitrogen gas to produce water. Was removed to obtain a dimer acid polyamideimide resin (PAI-1) varnish. When GPC of the obtained dimer acid polyamideimide resin (PAI-1) was measured, it was number average molecular weight Mn = 11600 and weight average molecular weight Mw = 23800 in terms of polystyrene. The Tg of the dimer acid polyamideimide resin (PAI-1) was 30 ° C.

(PAI-2)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100) ) 6.21 g, 4.10 g of 4,9-dioxadodecane-1,12-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 154.26 g of N-methyl-2-pyrrolidone as an organic solvent were charged. Stir. After the diamine is dissolved, 24.00 g of trimellitic anhydride recrystallized and purified in advance with acetic anhydride is added little by little, and the reaction is carried out at 180 ° C. for 1 hour while blowing nitrogen gas. A terminal imide oligomer was produced. Dimer acid (manufactured by Harima Kasei Co., Ltd., trade name: Halidimer 250, molecular weight: 580, carbon number: 36, dimer acid content: 80% by weight), 36.25 g, and diphenylmethane-4, 4′- Diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) 31.28 g was charged and reacted at 200 ° C. for 5 hours to obtain a dimer acid polyamideimide resin (PAI-2) varnish. When GPC of the obtained dimer acid polyamideimide resin (PAI-2) was measured, it was number average molecular weight Mn = 16000 and weight average molecular weight Mw = 31900 in terms of polystyrene. Moreover, Tg of dimer acid polyamideimide resin (PAI-2) was 75 degreeC.

(PAI-3)
In a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet tube, 41.05 g of 2,2-bis (4-aminophenoxyphenyl) propane and N-methyl-2-pyrrolidone 195 as an organic solvent 0.000 g was charged and the reaction solution was stirred. After the diamine was dissolved, 38.45 g of trimellitic anhydride recrystallized and purified in advance with acetic anhydride was added little by little, and the mixture was stirred at 80 ° C. for 30 minutes while blowing nitrogen gas. Subsequently, 130 g of xylene was added and heated at 160 ° C. for 2 hours to azeotropically remove xylene together with water. Then, 25.00 g of diphenylmethane-4,4′-diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, Reaction was performed at 190 ° C. for 2 hours to obtain a polyamideimide resin (PAI-3) varnish. When GPC of the obtained polyamide-imide resin (PAI-3) was measured, it was number average molecular weight Mn = 21100 and weight average molecular weight Mw = 80000 in terms of polystyrene. Moreover, Tg of dimer acid polyamideimide resin (PAI-3) was 250 degreeC.

<Synthesis of polyimide resin>
(PI-1)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100) ) 9.94 g, polyoxypropylenediamine (manufactured by BASF Corporation, trade name: D400, molecular weight: 450), 27.00 g, and 94 g of N-methyl-2-pyrrolidone as an organic solvent were charged, and the reaction solution was stirred. After the diamine is dissolved, 25.83 g of 4,4′-oxydiphthalic dianhydride recrystallized and purified in advance with acetic anhydride is added little by little, and heated at 180 ° C. while blowing nitrogen gas, thereby generating water. Azeotropic removal was performed to obtain a polyimide resin (PI-1) varnish. When GPC of the obtained polyimide resin (PI-1) was measured, it was number average molecular weight Mn = 21200 and weight average molecular weight Mw = 35600 in terms of polystyrene. Moreover, Tg of polyimide resin (PI-1) was 33 degreeC.

(PI-2)
In a 500 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet tube, 20.52 g of 2,2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadodecane-1,12- 10.20 g of diamine and 331.68 g of N-methyl-2-pyrrolidone as an organic solvent were charged, and the reaction solution was stirred. After the diamine is dissolved, 52.20 g of decamethylene bistrimellitate dianhydride recrystallized and purified in advance with acetic anhydride is added in small portions and heated at 175 ° C. while blowing nitrogen gas to azeotrope the water produced. Removal of polyimide resin (PI-2) varnish was obtained. When the molecular weight of the obtained polyimide resin (PI-2) was measured by GPC, it was number average molecular weight Mn = 21900 and weight average molecular weight Mw = 58200 in terms of polystyrene. Moreover, Tg of polyimide resin (PI-2) was 67 degreeC.

(PI-3)
In a 500 ml flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inflow pipe, 41.05 g of 2,2-bis (4-aminophenoxyphenyl) propane and 373 g of N-methyl-2-pyrrolidone were charged. The reaction was stirred. After the diamine is dissolved, 52.20 g of decamethylene bistrimellitate dianhydride recrystallized and purified in advance with acetic anhydride is added little by little while cooling the flask in an ice bath, and at room temperature while blowing nitrogen gas. After the reaction for 250 hours, 250 g of xylene was added and heated at 175 ° C., and xylene was removed azeotropically with water to obtain a polyimide resin (PI-3) varnish. As a result of measuring GPC of the obtained polyimide resin (PI-3), it was number average molecular weight Mn = 22800 and weight average molecular weight Mw = 121800 in terms of polystyrene. Moreover, Tg of polyimide resin (PI-3) was 120 degreeC.

(PI-4)
In a 500 ml flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inflow pipe, 41.05 g of 2,2-bis (4-aminophenoxyphenyl) propane and 328 g of N-methyl-2-pyrrolidone were charged. The reaction was stirred. After the diamine is dissolved, while cooling the flask in an ice bath, 41.00 g of ethylene bistrimellitate dianhydride recrystallized and purified in advance with acetic anhydride is added little by little, and nitrogen gas is blown in at room temperature for 8 hours. After the reaction, 220 g of xylene was added and heated at 175 ° C., and xylene was removed azeotropically with water to obtain a polyimide resin (PI-4) varnish. As a result of measuring GPC of the obtained polyimide resin (PI-4), it was number average molecular weight Mn = 24500 and weight average molecular weight Mw = 133000 in terms of polystyrene. Moreover, Tg of the polyimide resin (PI-4) was 170 ° C.

<Preparation of adhesive composition>
Dimer acid polyamide resins (PA-1) and (PA-2) obtained above, dimer acid polyamide imide resins (PAI-1) to (PAI-3), and polyimide resins (PI-1) to (PI-4) ), Each component is blended at the composition ratio (unit: part by mass) shown in Table 1 below, and the adhesive compositions (varnish for forming an adhesive layer) of Examples 1 to 4 and Comparative Examples 1 to 6 are used. Prepared.

In addition, the symbol of each component in Table 1 means the following.
YDF-8170: Tohto Kasei, bisphenol F type liquid epoxy resin (epoxy equivalent: 160)
HP-850N: manufactured by Hitachi Chemical Co., Ltd., phenol novolak (OH equivalent: 106)
TPPK: manufactured by Tokyo Chemical Industry Co., Ltd., tetraphenylphosphonium tetraphenylborate HP-P1: manufactured by Mizushima Alloy Iron Co., Ltd., boron nitride filler NMP: manufactured by Kanto Chemical Co., Inc., N-methyl-2-pyrrolidone

<Preparation of adhesive sheet>
The obtained adhesive layer forming varnish was applied on a substrate (peeling agent-treated PET film, thickness 50 μm) so that the film thickness after drying would be 40 μm ± 5 μm, and then 80 ° C. in an oven. 30 minutes, followed by heating and drying at 120 ° C. for 30 minutes to obtain adhesive sheets of Examples 1 to 4 and Comparative Examples 1 to 6 in which film adhesives were formed on the substrate. The state of the film adhesive at the stage where the adhesive sheet is formed is referred to as “B stage”.

<Evaluation test>
(Evaluation of low temperature adhesiveness)
The adhesive sheets of Examples 1 to 4 and Comparative Examples 1 to 6 were cut into a width of 10 mm and a length of 40 mm to obtain a film-like adhesive with a substrate. This film-like adhesive with a substrate is placed on the back surface (surface opposite to the support table) of the silicon wafer (6 inch diameter, thickness 400 μm) placed on the support table. In this way, lamination was performed by pressurizing with a roll (temperature 100 ° C., linear pressure 4 kgf / cm, feed rate 0.5 m / min).

  The sample thus prepared was subjected to a 90 ° peel test at room temperature using a rheometer (manufactured by Toyo Seiki Seisakusho Co., Ltd., “Strograph ES” (trade name)). -The peel strength between silicon wafers was measured. Based on the measurement results, the samples having a peel strength of 2 N / cm or more were evaluated as “A”, and the samples having a peel strength of less than 2 N / cm were evaluated as “C”. “A” means that the low temperature sticking property is good, and “C” means that the low temperature sticking property is insufficient. The evaluation results are shown in Tables 1 and 2.

(Measurement of flow amount)
The adhesive sheets of Examples 1 to 4 and Comparative Examples 1 to 6 were cut into 10 mm × 10 mm sizes to obtain test pieces. This test piece was sandwiched between two slide glasses (manufactured by Matsunami Glass Industry Co., Ltd., 76 mm × 26 mm × 1.0 to 1.2 mm thickness), and 100 kgf / cm ² overall on a 150 ° C. hot platen. The pressure bonding was performed for 90 seconds while applying a load. The amount of protrusion of the film adhesive from the four sides of the PET base material after thermocompression bonding was measured with an optical microscope, and the average value thereof was defined as the flow amount (μm). The larger the value of this flow amount, the better the thermal fluidity at the B stage and the better the filling property (embedding property) with respect to the unevenness of the adherend surface. Tables 1 and 2 show the measurement results of the flow amount.

(Measurement of 260 ° C peel strength)
The adhesive sheets of Examples 1 to 4 and Comparative Examples 1 to 6 were cut to a size of 5 mm × 5 mm, and a silicon chip (42 mm lead frame) was used on the 42 alloy lead frame using the film adhesive (5 mm × 5 mm × 40 μm thickness). 5 mm × 5 mm × 400 μm thickness) was thermocompression bonded. The conditions of thermocompression bonding were 150 ° C. for the film-like adhesives of Examples 1 to 3 and Comparative Examples 1 and 3, and 180 ° C. for the film-like adhesives of Example 4 and Comparative Example 4. The film adhesives 2, 5, and 6 were set at 250 ° C., load: 1 kgf / chip, and time: 5 seconds. After thermocompression bonding, it was cured by heating in an oven at 180 ° C. for 5 hours.

  Then, after heating for 20 seconds on a heating plate at 260 ° C., the silicon chip 9 is peeled off at a measurement speed of 0.5 mm / second using an adhesive strength evaluation device (peel strength measuring device) shown in FIG. The strength was measured, and the value at this time was defined as 260 ° C. peel strength (N / chip).

  Also, after thermocompression bonding under the above conditions, after heat curing at 180 ° C. for 5 hours, left in a constant temperature and humidity chamber of 85 ° C. and 85% RH for 48 hours, and then the silicon chip 9 at 260 ° C. in the same manner as above. The value when the peel strength was measured was defined as the 260 ° C. peel strength after moisture absorption (N / chip). The greater the peel strength, the better the reflow resistance and the higher the reliability of the semiconductor device. The measurement results are shown in Tables 1 and 2.

  In the peel strength measuring device 300 shown in FIG. 8, a handle 32 is provided around the fulcrum 33 at a variable angle at the tip of a rod attached to the push-pull gauge 31. The 260 ° C. peel strength is measured by placing a laminated body in which a silicon wafer 34 having a protrusion and a 42 alloy lead frame 35 are bonded via a film adhesive 1 on a 260 ° C. hot platen 36. The peeling stress when the handle 32 was moved at 0.5 mm / second with the handle 32 hooked on the protrusion of the silicon wafer 34 was measured by the push-pull gauge 31.

(PCT resistance)
An adhesive sheet in which a B-stage film adhesive adjusted to a thickness of 40 μm on a 50 μm thick Upilex substrate (manufactured by Ube Industries) was cut into a size of 50 mm × 50 mm to obtain a test piece. In this evaluation, except that the boron nitride filler (HP-P1) was excluded, a film adhesive having the composition shown in the examples of Table 1 and the comparative examples of Table 2 was used (film adhesive without filler). . This test piece was cured by heating in an oven at 180 ° C. for 5 hours, and then put into a pressure cooker PCT305S manufactured by Hirayama Seisakusho, and subjected to a treatment for 300 hours under a heating and pressing condition of 121 ° C. and 100% RH 2 atm. The piece was visually observed. “A” indicates that the film-like adhesive portion has not changed before and after the test, “C” indicates that the film-like adhesive portion has become clouded or brittle after the test, or “C” indicates that the film-like adhesive has flowed out. The PCT resistance was evaluated. The evaluation results are shown in Tables 1 and 2.

  As shown in Table 1, the adhesive compositions of the examples are sufficiently good in all of the points of low temperature sticking property, fluidity during heat, and reliability after heat curing (reflow resistance and PCT resistance). Met. On the other hand, as shown in Table 2, the adhesive composition of the comparative example was insufficient in any of the above points.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition and film adhesive of a wafer back surface attachment system which can respond to the semiconductor device which laminated | stacked the ultra-thin wafer and the several semiconductor element can be provided. When a film adhesive is pasted on the wafer back surface, it is usually heated to a temperature at which the film adhesive melts. However, if the film adhesive of the present invention is used, the wafer back surface can be suppressed at a low temperature that can suppress the warpage of the wafer. It becomes possible to paste on. As a result, thermal stress is also reduced, and problems such as warpage of the wafer that becomes thinner and thinner can be solved.

  DESCRIPTION OF SYMBOLS 1 ... Film adhesive, 2 ... Base film, 3 ... Protective film, 5 ... Dicing sheet, 6 ... Adhesive layer, 7 ... Base film, 9, 9a, 9b ... Semiconductor element, 10 ... For semiconductor element mounting Support member, 11 ... wire, 12 ... sealing material, 13 ... terminal, 31 ... push-pull gauge, 34 ... silicon wafer, 35 ... 42 alloy lead frame, 36 ... hot plate, 100, 110, 120, 130 ... adhesive sheet , 200, 210... Semiconductor devices.

Claims (12)

(A) an adhesive composition containing a polycondensation polymer having a Tg of 150 ° C. or less, and (B) a thermosetting resin,
The (A) polycondensation polymer is obtained by polycondensation of an acid containing dimer acid, which is a dimer of unsaturated fatty acid having 20 to 50 carbon atoms, and diamine and / or diisocyanate. , Adhesive composition.   The adhesive composition according to claim 1, wherein the (A) polycondensation polymer does not have an ester bond.   The adhesive composition according to claim 1 or 2, wherein the (A) polycondensation polymer is a polyamide resin.   The adhesive composition according to any one of claims 1 to 3, wherein the (A) polycondensation polymer is a polyamideimide resin.   The adhesive composition according to any one of claims 1 to 4, wherein the (B) thermosetting resin contains an epoxy resin.   (C) The adhesive composition according to any one of claims 1 to 5, further comprising a filler.   The adhesive composition according to any one of claims 1 to 6, which is used for bonding a semiconductor element to another semiconductor element or a semiconductor element mounting support member.   The film adhesive formed by shape | molding the adhesive composition as described in any one of Claims 1-7 in a film form.   An adhesive sheet comprising: a support substrate; and the film adhesive according to claim 8 formed on a main surface of the support substrate.   The adhesive sheet according to claim 9, wherein the support substrate is a dicing sheet.   The adhesive sheet according to claim 10, wherein the dicing sheet has a base film and an adhesive layer provided on the base film.   A structure in which a semiconductor element and a semiconductor element mounting support member are bonded by the adhesive composition according to claim 1 and / or a structure in which adjacent semiconductor elements are bonded to each other. A semiconductor device.

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