JP5655885B2 - Adhesive composition, film adhesive, adhesive sheet and semiconductor device using the same - Google Patents

Description

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

  Conventionally, a silver paste has been mainly used for joining a semiconductor element and a semiconductor element mounting support member. However, with the recent increase in the size of semiconductor elements and the reduction in size and performance of semiconductor packages, the support members used are also required to be reduced in size and density. In response to these demands, silver paste can cope with such problems as wetting and spreading, defects in wire bonding caused by protrusions and inclination of semiconductor elements, difficulty in controlling the thickness of silver paste, and voids in silver paste. It's getting out of place. Therefore, in order to cope with the above requirements, in recent years, a film-like adhesive has been used (see, for example, Patent Documents 1 and 2).

  This film adhesive is used in manufacturing methods of semiconductor devices such as an individual sticking method and a wafer back surface sticking method. When manufacturing a semiconductor device by the former piece pasting method, first, a reel-like film adhesive is cut into pieces by cutting or punching, and then bonded to a support member. Then, the semiconductor elements separated by the dicing process are joined to produce a support member with a semiconductor element. Thereafter, a semiconductor device is obtained through a wire bonding process, a sealing process, and the like (see, for example, Patent Document 3). However, in the case of the individual sticking method, a dedicated assembly device that cuts out the film adhesive and adheres it to the support member is necessary, so that there is a problem that the manufacturing cost is higher than the method using the silver paste. It was.

  On the other hand, when a semiconductor device is manufactured by a wafer back surface attaching method, first, one surface of a film adhesive is attached to the back surface of the semiconductor wafer, and a dicing sheet is attached to the other surface of the film adhesive. Thereafter, the semiconductor element is separated into pieces from the semiconductor wafer by dicing, and the separated semiconductor element with a film adhesive is picked up and joined to the support member. Then, a semiconductor device is obtained through processes such as wire bonding and sealing. This wafer backside pasting method does not require a dedicated assembly device that cuts out the film adhesive and adheres it to the support member, and the conventional silver paste assembly device is used as it is, or a heating plate is added thereto. It can be used by improving a part of. Therefore, the wafer back surface attaching method is attracting attention as a method in which the manufacturing cost can be kept relatively low among the assembling methods using the film adhesive (see, for example, 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 are being further thinned. In connection with this, the wafer crack at the time of conveyance and the wafer crack at the time of sticking a film adhesive on the wafer back surface have become obvious. In order to prevent this problem, a technique of attaching a soft protective tape (commonly referred to as a back grind tape) to the wafer surface is being adopted.

  A film adhesive that can be attached to the backside of the wafer at a temperature lower than 100 ° C. due to circumstances such as the softening temperature of the back grind tape being 100 ° C. or lower and the suppression of wafer warpage due to thermal stress during bonding. The demand for is getting stronger. In addition, from the viewpoint of process characteristics at the time of assembling a semiconductor device, it is required that the pickup property after dicing is good, that is, the film-like adhesive once bonded and the dicing sheet are easily peeled.

  In addition, for the purpose of simplifying the bonding process on the wafer back surface, a film adhesive 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, a method using a “dicing / die bonding integrated film” may be proposed. The softening temperature of the dicing tape is usually 100 ° C. or lower as in the case of the back grind tape. Therefore, also in the form of the above-mentioned integral film, in addition to having good process characteristics such as the above-mentioned easy peelability, the dicing tape softening temperature and the suppression of the wafer warp are considered from 100 ° C. In addition, it is required for a film adhesive that it can be attached at a low temperature.

  On the other hand, reliability, that is, heat resistance, moisture resistance, reflow resistance, and the like are also required for a semiconductor device manufactured using a film adhesive. 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. As described above, there is an increasing demand for a film-like adhesive that can achieve high compatibility between process characteristics including low-temperature laminating properties and reliability of semiconductor devices including reflow resistance.

  Furthermore, when the support 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, which means that the moisture resistance reliability of the semiconductor device and between the wirings This is important for ensuring insulation reliability. If the adhesive is not sufficiently embedded, there is a high possibility that the moisture resistance reliability and the reflow resistance are lowered due to the voids in the unfilled portion. The adhesive embedding property has also been ensured by utilizing heat and pressure during transfer molding in the sealing process of the semiconductor device assembly process. However, as described above, as the stacking of a plurality of semiconductor elements proceeds, the thermal history process (such as die bonding and wire bonding) required for bonding and stacking individual semiconductor elements increases the number of stacked semiconductor elements. It tends to be longer with the time. When manufacturing a semiconductor device in which a plurality of semiconductor elements are stacked, the die bonding film used for bonding between the lowermost semiconductor element and the organic substrate with a stepped wiring has an upper stage between the die bonding and the transfer molding process. The thermal history for laminating the semiconductor elements is received. When the fluidity of the adhesive is lowered by heat curing, it becomes difficult to ensure the embeddability with respect to the wiring step on the substrate surface even by heat and pressure during transfer molding.

  Therefore, in a die bonding film used for bonding between a semiconductor element located at the bottom of such a semiconductor device and an organic substrate having a wiring step, the substrate is formed at the time of bonding the semiconductor composition to the organic substrate, that is, at the time of die bonding. It is desirable to be able to ensure sufficient embedding in the wiring step on the surface. However, the heat and pressure conditions at the time of die bonding are lower and lower than the heat and pressure at the time of transfer molding, from the warpage of the semiconductor element due to thermal stress and the suppression of damage to the circuit surface on the semiconductor element. It becomes a condition for a short time. Therefore, it is desirable that the die bonding film described above has a fluidity during heating that can ensure embedding in the wiring step on the substrate surface even under these conditions, and can sufficiently suppress the generation of foaming and voids. It is.

  Until now, in order to achieve both low-temperature workability and heat resistance, a film adhesive that combines a thermoplastic resin having a relatively low Tg and a thermosetting resin has been proposed (see, for example, Patent Document 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, the above-mentioned prior art has the heat resistance at the high temperature including the reflow resistance and the securing of the fluidity at the time of heating which makes it possible to embed the wiring on the wiring step on the substrate surface under the low temperature, low pressure and short time conditions described above. It is still not enough to provide materials that are compatible with the properties. In addition, as the demand for characteristics that can ensure good pick-up properties after dicing is increasing as the wafer becomes extremely thin, more detailed or precise material design is required to develop materials that combine these characteristics. is necessary.

  That is, in the conventional film-like adhesives including those described in Patent Documents 4 and 5, the ratio of a polyimide resin or acrylic rubber having a relatively low Tg or a low molecular weight and low viscosity epoxy resin is used. Due to the increased amount of blending, both the hot fluidity in the B stage and the heat resistance in the C stage have been achieved. However, the design to lower the Tg of the base resin and the design to increase the amount of low-viscosity epoxy resin increase the adhesiveness (tack) of the film surface, increase the die bond layer burr during dicing (decrease in breakability due to film ductility), In addition, problems such as rebonding of the die bond layer cut surface after dicing are caused, and the pick-up property after dicing becomes difficult to secure.

  In view of the above-described problems of the prior art, the present invention provides process characteristics such as filling property (embedding property) to an adherend, low-temperature laminating property and pick-up property after dicing, and reliability of a semiconductor device including reflow resistance. It aims at providing the adhesive agent composition which enables the realization | achievement of the film-like adhesive agent and adhesive sheet which have the characteristic which contributes to improvement enough. Another object of the present invention is to provide a semiconductor device obtained by using them.

（式中、Ｑ_１、Ｑ_２及びＱ_３は、直鎖状の炭素数１〜１０のアルキレン基を示し、Ｐは０〜１０の整数を示す。）

（式中、ｍは０〜８０の整数を示す。） In order to achieve the above object, the present invention is an adhesive composition containing a polyimide resin obtained by reacting a tetracarboxylic dianhydride and a diamine, wherein the total amount of the tetracarboxylic dianhydride is a tetracarboxylic dianhydride represented by the following formula (I), said diamine comprises 30 mol% or more diamines represented by the following general formula (II) with respect to the diamine component based on the total amount of the polyimide resin Has a glass transition temperature of 10 ° C. to 100 ° C., a melt viscosity at 100 ° C. of 6000 Pa · s or less, and a film surface tack force at 40 ° C. of the film of 200 gf or less when formed into a film. Ah is, diamine, or 10 mol% of a diamine represented by the following formula (V) with respect to the diamine component total amount further comprising, providing an adhesive composition.

_(Wherein, Q 1, _{Q 2} and _{Q 3} are a straight-chain alkylene group having 1 to 10 carbon atoms, P is an integer of 0.)

(In the formula, m represents an integer of 0 to 80.)

The above-mentioned film surface tack force is the method described in JISZ0237-1991 (probe diameter 5.1 mm, peeling speed 10 mm on the surface of a film in which a polyimide resin is formed into a film shape, using a probe tacking tester manufactured by Reska. / S, contact load 100 gf / cm ² , contact time 1 s), and the tack strength (adhesive strength) at 40 ° C. is measured.

  According to the adhesive composition of the present invention, by having the above-described configuration, the filling property (embedding property) to the adherend, the low-temperature laminating property, the pick-up property after dicing, the reflow resistance, etc. It is possible to form a film-like adhesive layer having sufficient characteristics that contribute to improving the reliability of the semiconductor device.

  If the glass transition temperature of the polyimide resin is less than 10 ° C., the adhesive force on the surface of the adhesive layer becomes too strong and the handleability in the B-stage state is deteriorated, so it is difficult to form and use it in a film form. It becomes. On the other hand, when the glass transition temperature exceeds 100 ° C., it becomes difficult to set the temperature of application to the back surface of the wafer to 100 ° C. or lower when it is formed into a film.

  When the melt viscosity at 100 ° C. of the polyimide resin exceeds 6000 Pa · s, when formed into a film shape, it is not possible to sufficiently ensure the fluidity at the time of low temperature, low pressure and short time, The filling property (embedding property) to the adherend is impaired.

  When the film surface tack force at 40 ° C. of the polyimide resin exceeds 200 gf, the film surface adhesiveness of the obtained film-like adhesive becomes strong, and the film handling property tends to deteriorate, Burrs tend to remain due to a decrease in breakability due to film ductility. On the other hand, when the tack force exceeds 200 gf, the peelability from the dicing tape after dicing is lowered, and the pickup property tends to be lowered due to re-bonding of the cut surface of the film after dicing. In addition, the room temperature in this specification means 5-30 degreeC.

（式中、Ｒ_１及びＲ_２はそれぞれ独立に炭素数１〜５のアルキレン基又はフェニレン基を示し、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６はそれぞれ独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示す。） The said diamine can further contain 10 mol% or more of diamine represented by the following general formula (III) with respect to the diamine component whole quantity.

(In the formula, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms. Represents a phenyl group or a phenoxy group.)

  Good adhesiveness can be obtained by using the diamine represented by the above formula (III) in the above ratio as the diamine.

（式中、ｑは１〜２０の整数を示す。） Moreover, the said diamine can further contain 10 mol% or more of diamine represented with the following general formula (IV) with respect to the diamine component whole quantity.

(In the formula, q represents an integer of 1 to 20.)

  By using the diamine represented by the formula (IV) in the above ratio as the diamine, it becomes easy to impart low moisture absorption at the same time as lowering the Tg.

It said diamine is 10 mol% or more including the diamine represented by the formula (V) with respect to the diamine component total amount.

  By using the diamine represented by the above formula (V) in the above ratio as the diamine, it becomes easy to impart high fluidity when heated.

  The adhesive composition of the present invention can further contain a thermosetting resin. Thereby, good reflow resistance can be obtained.

  The adhesive composition of the present invention can be used for bonding a semiconductor element to another semiconductor element or a semiconductor element mounting support member.

  When the adhesive composition of the present invention is used for bonding a semiconductor element to a semiconductor element mounting support member, the semiconductor element mounting support member is preferably an organic substrate with a wiring step.

  The present invention also provides a film adhesive obtained by forming the adhesive composition of the present invention into a film.

  The film-like adhesive of the present invention is composed of the adhesive composition of the present invention, so that process characteristics such as filling property (embedding property), low-temperature laminating property and pick-up property after dicing, Further, it is possible to sufficiently combine characteristics that contribute to improving the reliability of the semiconductor device including reflow resistance.

  The film adhesive of this invention can be used in order to adhere | attach a semiconductor element on another semiconductor element or a semiconductor element mounting support member.

  Moreover, when the film adhesive of this invention is used in order to adhere | attach a semiconductor element on the supporting member for semiconductor element mounting, it is preferable that the supporting member for semiconductor element mounting is an organic substrate with a wiring level | step difference.

  The present invention also provides an adhesive sheet comprising a base film and an adhesive layer formed by forming the adhesive composition of the present invention provided on at least one surface of the base film into a film shape. The adhesive sheet of the present invention is provided with an adhesive layer made of the adhesive composition of the present invention, so that process properties such as filling property (embedding property) to the adherend, low-temperature laminating property, and pick-up property after dicing, In addition, the semiconductor device can sufficiently have characteristics that contribute to improving the reliability of the semiconductor device including reflow resistance. Further, the adhesive layer provided in the adhesive sheet of the present invention can function as an adhesive layer having both functions of a dicing sheet and a die bond film.

  The present invention also provides an adhesive sheet obtained by laminating an adhesive layer formed by forming the adhesive composition of the present invention into a film and a dicing sheet.

  In the adhesive sheet of the present invention, the dicing sheet may have a base film and a pressure-sensitive adhesive layer provided on the base film.

  The adhesive sheet of the present invention can be used for bonding a semiconductor element to another semiconductor element or a semiconductor element mounting support member.

  When the adhesive sheet of the present invention is used for bonding a semiconductor element to a semiconductor element mounting support member, the semiconductor element mounting support member is preferably an organic substrate with a wiring step.

  The present invention also provides a semiconductor device having a structure in which a semiconductor element and another semiconductor element and / or a semiconductor element and a semiconductor element mounting support member are bonded to each other by the adhesive composition of the present invention.

  The present invention also provides a semiconductor device having a structure in which a semiconductor element and another semiconductor element and / or a semiconductor element and a support member for mounting a semiconductor element are bonded by the film adhesive of the present invention.

  The present invention also provides a semiconductor device having a structure in which a semiconductor element and another semiconductor element and / or a semiconductor element and a semiconductor element mounting support member are bonded together by the adhesive sheet of the present invention.

  According to the present invention, process characteristics such as filling property (embedding property) to an adherend, low-temperature laminating property and pick-up property after dicing, and characteristics that contribute to improving the reliability of a semiconductor device including reflow resistance are provided. It is possible to provide a film-like adhesive, an adhesive sheet, and an adhesive composition that can realize the film adhesive sufficiently. In addition, the present invention can provide a semiconductor device obtained using them.

  Moreover, according to this invention, the film-like adhesive for semiconductor element fixation 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 affixing the film adhesive on the back of the wafer, it is usually heated to a temperature at which the film adhesive melts, but if the film adhesive of the present invention is used as a semiconductor element fixing film adhesive, It becomes possible to affix on the back surface of the wafer at a temperature lower than the softening temperature of the protective tape of the ultra-thin wafer or the dicing tape to be bonded. Thereby, thermal stress is also reduced, and problems such as warpage of the wafer that becomes thinner and thinner can be solved.

  In addition, the film adhesive of the present invention can have fluidity at the time of heat that enables good embedding in a wiring step on the surface of a substrate by heat and pressure at the time of die bonding, so that a plurality of semiconductor elements are laminated. It can respond suitably to the manufacturing process of the semiconductor device. Moreover, since the film adhesive of this invention can have high adhesive strength at the time of high temperature, it is excellent in heat resistance and can simplify the manufacturing process of a semiconductor device. Furthermore, since the film-like adhesive of the present invention can be attached at a low temperature, chip jump during dicing can be suppressed while reducing thermal stress such as warpage of the wafer. In addition, since good cutting performance at the time of dicing and good pickup performance after dicing can be ensured, workability at the time of manufacturing the semiconductor device can be improved.

  Moreover, according to the adhesive sheet of this invention, the sticking process to a dicing process can be simplified and the characteristic stable also with respect to the assembly heat history of a package can be exhibited.

It is a schematic cross section which shows one Embodiment of the film adhesive of this invention. It is a schematic cross section which shows one Embodiment of the adhesive sheet of this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet of this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet of this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet of this invention. It is a schematic cross section showing one embodiment of a semiconductor device of the present invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device of this invention.

  The adhesive composition of the present invention is an adhesive composition containing a polyimide resin obtained by reacting a tetracarboxylic dianhydride and a diamine, and the tetracarboxylic dianhydride has the following formula (I): 30 mol% or more of the tetracarboxylic dianhydride represented by the formula (II) is included with respect to the total amount of the tetracarboxylic dianhydride component, and the diamine is represented by the following formula (II) with respect to the total amount of the diamine component. The polyimide resin has a glass transition temperature of 10 ° C. to 100 ° C., a melt viscosity at 100 ° C. of 6000 Pa · s or less, and a film at 40 ° C. when formed into a film. The surface tack force is 200 gf or less.

In said formula (II), Q < ₁ >, Q < ₂ > and Q < ₃ > show a C1-C10 alkylene group each independently, and P shows the integer of 0-10. Q ₁ , Q ₂ and Q ₃ are preferably each independently a linear alkylene group having 1 to 10 carbon atoms, and more preferably a linear alkylene group having 2 to 4 carbon atoms. preferable.

  The polyimide resin according to the present invention can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. Specifically, in an organic solvent, tetracarboxylic dianhydride and diamine are equimolar, or if necessary, the total of diamine components with respect to a total of 1.0 mol of tetracarboxylic dianhydride components. In the range of 0.5 to 2.0 mol, preferably 0.8 to 1.0 mol (addition order of each component is arbitrary), and the addition reaction is performed at a reaction temperature of 80 ° C. or lower, preferably 0 to 60 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The tetracarboxylic dianhydride is preferably recrystallized and purified with acetic anhydride in order to suppress deterioration of various properties of the adhesive composition.

  In addition, about the composition ratio of the tetracarboxylic dianhydride and diamine in said condensation reaction, when the total of a diamine component exceeds 2.0 mol with respect to the total 1.0 mol of a tetracarboxylic dianhydride component, In the resulting polyimide resin, the amount of amine-terminated polyimide oligomer tends to increase. On the other hand, when the total of diamine components is less than 0.5 mol, the amount of acid-terminated polyimide oligomer tends to increase. In any case, the weight average molecular weight of the polyimide resin becomes excessively low, and the properties such as the heat resistance of the adhesive formed into a film tend to be lowered.

  The molecular weight of the polyimide resin can be adjusted by adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range.

  The acid dianhydride to be used is preferably dried by heating at a temperature lower than the melting point of the monomer by 10 to 20 ° C. for 12 hours or more, or subjected to recrystallization purification treatment with acetic anhydride. As an index, the difference between the endothermic start temperature and the endothermic peak temperature by a differential scanning calorimeter (DSC) is preferably within 10 ° C. The endothermic start temperature and the endothermic peak temperature are measured using DSC (DSC-7 model, manufactured by Perkin Elmer) under the conditions of a sample amount of 5 mg, a heating rate of 5 ° C./min, and a measurement atmosphere: nitrogen. Use the value when

  In addition, the said polyamic acid can also adjust the molecular weight by heating at the temperature of 50-80 degreeC, and making it depolymerize. The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed and a chemical ring closure method using a dehydrating agent.

  The tetracarboxylic dianhydride that is a raw material of the polyimide resin contains the tetracarboxylic dianhydride represented by the above formula (I) in an amount of 30 mol% or more based on the total amount of the tetracarboxylic dianhydride component. It is preferable to contain 50 mol% or more, more preferably 70 mol% or more. In addition, when the content of the tetracarboxylic dianhydride represented by the above formula (I) is less than 30 mol%, the reactivity with the diamine to be reacted is impaired, and a film adhesive at normal temperature described later It is difficult to ensure low surface tackiness. Further, it tends to be difficult to ensure moisture resistance reliability such as hydrolysis resistance.

  The tetracarboxylic dianhydride used in combination is not particularly limited. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3, 3′-biphenyltetracarboxylic 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, -Dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2 ', 3'-benzophenone tetracarboxylic dianhydride, 3,3,3', 4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4 , 5,8-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloro Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene -1 4,5,8-tetracarboxylic 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-dicarbo Xylphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid bis Anhydride, 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, -Tetracarboxylic 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- Hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-si Lohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the following general formula (VII), And tetracarboxylic dianhydrides represented by the following general formula (VIII) are preferable in view of providing excellent moisture resistance reliability. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

（式中、ｎは２〜２０の整数を示す）

(In the formula, n represents an integer of 2 to 20)

  As a diamine used as a raw material for the polyimide resin according to the present invention, the diamine represented by the general formula (II) is contained in an amount of 30 mol% or more, preferably 35 mol% or more, more preferably, based on the total amount of the diamine component. It is preferable to contain 40 mol% or more. Specific examples of the diamine represented by the general formula (II) include aliphatic diamines having the following structural formula.

  In addition, when the content of the diamine represented by the general formula (II) is less than 30 mol%, it tends to be difficult to simultaneously achieve low Tg, thermal fluidity and low film surface adhesion, Absent.

  The diamine used in combination is not particularly limited. For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino Diphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethermethane, 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 ′ -Diaminodiphenyl Ruphone, 4,4'-diaminodiphenylsulfone, 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, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-a Nophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylene) Bis (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-aminoenoxy) phenyl) Sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) phenyl) sulfone , Aromatic diamines such as bis (4- (4-aminoenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) In addition to cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, and the like, siloxane diamines represented by the following general formula (III) are exemplified.

（式中、Ｒ_１及びＲ_２はそれぞれ独立に炭素数１〜５のアルキレン基又はフェニレン基を示し、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６はそれぞれ独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示す。）

(In the formula, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms. Represents a phenyl group or a phenoxy group.)

  Examples of the siloxane diamine represented by the above formula (III) include 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy- 1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl- 1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl- 1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy -1,3-bis (4-aminobuty ) Disiloxane and the like.

  In addition, other aliphatic diamines represented by the following general formula (IV), specifically 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-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1, Examples include aliphatic diamines such as 2-diaminocyclohexane.

（ｑは１〜２０の整数を示す。）

(Q represents an integer of 1 to 20)

  Other examples include propylene glycol-based diamines represented by the following general formula (V), specifically, Jeffermin ED-230, ED-400, ED-2000, ED-4000 manufactured by Sun Techno Chemical Co., Ltd. , ED-600, ED-900, ED-2001, EDR-148, and BASF (manufactured) polyetheramine D-230, D-400, and aliphatic diamines such as D-2000.

（式中、ｍは０〜８０の整数を示す）

(In the formula, m represents an integer of 0 to 80)

  Among them, the siloxane diamine represented by the above formula (III) in that it can impart good adhesiveness, and the aliphatic represented by the above formula (IV) in that it can impart low hygroscopicity at the same time as lowering Tg. The diamine is preferably used in combination with the propylene glycol-based diamine represented by the above (V) in that it can impart high fluidity when heated. Moreover, it is preferable that all the usage-amounts are 10 mol% or more of all the diamine, and 10-70 mol% is more preferable. When the amount used is less than 10 mol%, the above-mentioned effects tend to be difficult to obtain, and when it exceeds 70 mol%, the stability of the varnish is deteriorated, which is not preferable. These diamines may be used alone or in combination of two or more. Moreover, the said polyimide resin may mix (blend) 2 or more types individually or as needed.

  The temperature at which the film adhesive of the present invention can be applied to the back surface of the wafer is preferably not higher than the softening temperature of the protective tape and dicing tape of the wafer, and also from the viewpoint of suppressing warpage of the semiconductor wafer. The attaching temperature is preferably 20 to 120 ° C, more preferably 20 to 100 ° C, and particularly preferably 20 to 80 ° C. In order to enable attachment at such a temperature, it is necessary that the Tg of the polyimide resin according to the present invention to be contained is 10 to 100 ° C. When the Tg of the polyimide resin according to the present invention exceeds 100 ° C., there is a high possibility that the bonding temperature to the wafer back surface exceeds 100 ° C., and when the Tg is less than 10 ° C., the adhesion of the film surface in the B stage state The strength tends to be strong and the handling property tends to be poor. Furthermore, Tg of the polyimide resin according to the present invention is preferably 10 to 80 ° C, and more preferably 20 to 80 ° C.

  Moreover, it is preferable that the weight average molecular weight of the polyimide resin which concerns on this invention is controlled within the range of 20000-100,000, 30000-80000 is more preferable, and 30000-60000 is especially preferable. When the weight average molecular weight is in this range, the film formability, flexibility, and breakability when it is in the form of a sheet or film are appropriate, and the fluidity during heating is appropriate, so that the dicing property It is possible to achieve both good embeddability in the substrate surface wiring step. If the weight average molecular weight is less than 20000, the film formability tends to be poor and the toughness of the film tends to be small. If it exceeds 100,000, the breakability and the hot fluidity tend to decrease, and the dicing property Since there is a tendency to decrease, that is, the uncutness due to the film ductility at the time of dicing, and the embedding property with respect to the unevenness on the substrate tends to decrease, neither is preferable.

  By setting the Tg and the weight average molecular weight of the polyimide resin within the above ranges, not only can the temperature for attaching to the backside of the wafer be kept low, but also die bonding at a low temperature can be secured. An increase in warpage can be suppressed. Moreover, the favorable cut property at the time of dicing is securable. Furthermore, the fluidity at the time of die bonding, which is a feature of the present invention, can be effectively imparted. Moreover, when the said semiconductor element mounting support member is an organic substrate, the vaporization of the moisture absorption of the organic substrate by the heating temperature at the time of die bonding can be suppressed, and the foaming of the die bonding material layer by vaporization can be suppressed. In addition, said Tg is the main dispersion peak temperature of a polyimide, The film which formed the polyimide resin in the film shape on the parallel disk (diameter 8mm) using the rheometric scientific make and rotation type rheometer ARES. The sample was sandwiched with a gap width 2 to 5 μm smaller than the sample thickness, and the tan δ peak temperature was measured when measured at a frequency of 1 Hz, a strain of 1%, a heating rate of 5 ° C./min, and a measurement temperature of 30 ° C. to 300 ° C. This was designated as Tg. Moreover, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (C-R4A by Shimadzu Corporation).

  Furthermore, the polyimide resin according to the present invention has a melt viscosity at 100 ° C. of 6000 Pa · s or less. Here, melt viscosity refers to a rotational rheometer made by rheometric scientific, sandwiching a film sample in which a polyimide resin is formed into a film shape on a parallel disk (diameter 8 mm) with a gap width 2 to 5 μm smaller than the sample thickness. It is the value of complex viscosity at 100 ° C. when measured using ARES under the conditions of a frequency of 1 Hz, a strain of 1%, a heating rate of 5 / min, and a measurement temperature of 30 ° C. to 300 ° C. By setting the melt viscosity at 100 ° C. within the above range, a semiconductor element can be formed on a support member having surface irregularities such as an organic substrate on which wiring is formed using the obtained film adhesive. When pressure bonding is performed at a temperature of 80 to 150 ° C. at a pressure of 1 MPa or less, it is possible to ensure good step embedding in the surface irregularities of the support member. The polyimide resin according to the present invention preferably has a melt viscosity at 100 ° C. of 100 to 6000 Pa · s, and more preferably 500 to 3000 Pa · s. When the melt viscosity is less than 100 Pa · s, the heat flow at the time of thermocompression bonding at 80 to 150 ° C. when using the obtained film adhesive becomes too large, and air entrainment remaining at the support member interface Alternatively, voids tend to remain inside the film adhesive due to foaming or the like, and when the melt viscosity exceeds 6000 Pa · s, the heat flow due to the above-described thermocompression bonding when using the obtained film adhesive Is difficult to secure, and it tends to be difficult to ensure the embedding of a step in a substrate having irregularities. The melt viscosity of the polyimide resin according to the present invention is such that, for example, 30 mol% or more of the acid anhydride of the general formula (I) is used and 30 mol% or more of the diamine of the general formula (II) is used. It becomes possible to introduce a diamine having a long-chain alkyl group in between, and thereby the rigidity of the polymer is lowered, so that the range can be adjusted to 6000 Pa · s or less.

Moreover, when the polyimide resin which concerns on this invention is formed in a film form, the film surface tack strength in 40 degreeC of the said film will be 200 gf or less. Here, the film surface tack strength refers to the method described in JISZ0237-1991 (probe diameter 5.1 mm, peeling speed 10 mm / s, contact with respect to the top surface coated with the film, using a probe tacking tester manufactured by Reska. This is a value when the tack strength (adhesive strength) at 40 ° C. is measured with a load of 100 gf / cm ² and a contact time of 1 s. When the film surface tack strength exceeds 200 gf, the film-like adhesive obtained has a tendency to increase the film surface tackiness at room temperature, resulting in poor film handleability, and a decrease in breakability due to film ductility during dicing. This is not preferable because burrs tend to remain, the peelability from the dicing tape after dicing tends to decrease, and the pick-up property tends to decrease due to re-bonding of the cut surface of the film after dicing. In addition, in this invention, room temperature is 5-30 degreeC. The polyimide resin according to the present invention preferably has a film surface tack strength at 40 ° C. of 100 gf or less, more preferably 50 gf or less when formed into a film. The film surface tack strength of the polyimide resin according to the present invention is, for example, by using 30 mol% or more of the acid anhydride of the general formula (I) and using 30 mol% or more of the diamine of the general formula (II), By introducing a diamine having a long-chain alkyl group between the imide skeletons, the rigidity of the polymer is lowered and the Tg can be reduced, and at the same time, the ether skeleton of the diamine of the general formula (II) is reduced in tack. Can contribute to the range of 200 gf or less.

  The adhesive composition of the present invention can further contain (B) a thermosetting resin. This (B) thermosetting resin is not particularly limited as long as it is a component composed of a reactive compound that causes a crosslinking reaction by heat. For example, epoxy resin, cyanate ester resin, maleimide resin, allyl nadiimide resin, Phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, poly Isocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, thermosetting resin synthesized from cyclopentadiene, thermosetting resin by trimerization of aromatic dicyanamide Etc. It is below. Among these, an epoxy resin, a maleimide resin, and an allyl nadiimide resin are preferable in that an excellent adhesive force at a high temperature can be imparted in combination with the polyimide resin according to the present invention. In addition, these thermosetting resins can be used individually or in combination of 2 or more types.

  When the above thermosetting resin is used, its content is low outgassing property, film forming property (toughness), fluidity during heating, and high adhesive force at high temperature due to thermosetting. 1-200 mass parts is preferable with respect to 100 mass parts of polyimide resins according to the invention, and 10-100 mass parts is more preferable.

  Further, the adhesive composition of the present embodiment can contain a curing agent and a catalyst for curing the thermosetting resin, and if necessary, a curing agent and a curing accelerator, or a catalyst and a promoter. Can be used in combination. About the addition amount of the said hardening | curing agent and a hardening accelerator, and the presence or absence of addition, it judges and adjusts in the range which can ensure the fluidity | liquidity at the time of the desirable heat mentioned later and the heat resistance after hardening.

  As an epoxy resin which is one of the preferred thermosetting resins, those containing at least two epoxy groups in the molecule are more preferable, and phenol glycidyl ether type epoxy resins are extremely preferable in terms of curability and cured product characteristics. preferable. 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. 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, trifunctional (or tetrafunctional) glycidyl ether, dicyclo Examples include glycidyl ether of pentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. It is. These can be used alone or in combination of two or more. In addition, it is preferable to use high-purity products 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 prevention of corrosion 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 them, 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, dicyclopentagen cresol novolak resins, dicyclopentagen phenol novolak resins, xylylene-modified phenol novolak resins, naphthol compounds, tris Examples include phenolic compounds, tetrakisphenol novolac resins, bisphenol A novolac resins, poly-p-vinylphenol resins, phenol aralkyl resins, and the like. These compounds preferably have a number average molecular weight in the range of 400-1500. Thereby, at the time of assembling and heating the semiconductor device, it is possible to effectively reduce outgas which causes contamination of the semiconductor element or the device.

  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.

  As a maleimide resin which is one of preferable thermosetting resins, a compound containing two or more maleimide groups in a molecule, a bismaleimide resin represented by the following general formula (1), and a general formula ( Novolak type maleimide resin represented by 2) and the like.

［式中、Ｒ^１１は芳香族環及び／又は直鎖、分岐若しくは環状脂肪族炭化水素を含む２価の有機基を示す。］

[Wherein R ¹¹ represents a divalent organic group containing an aromatic ring and / or a linear, branched or cyclic aliphatic hydrocarbon. ]

［式中、ｎは０〜２０の整数を示す。］

[In formula, n shows the integer of 0-20. ]

R ¹¹ in the general formula (1) is not particularly limited as long as it is a divalent organic group containing an aromatic ring and / or a linear, branched or cyclic aliphatic hydrocarbon, but preferably benzene Examples include a residue, a toluene residue, a xylene residue, a naphthalene residue, a linear, branched, or cyclic alkyl group, or a mixed group thereof, more preferably a divalent organic group having the following structure.

［式中、ｔは１〜１０の整数を示す。］

[Wherein t represents an integer of 1 to 10. ]

  Among them, a bismaleimide resin having a structure represented by the following formula (3) and / or a structure represented by the above general formula (2) in that heat resistance and high-temperature adhesive force after curing of the adhesive film can be imparted. The novolac maleimide resin is preferably used.

  For curing the maleimide resin, allylated bisphenol A, a cyanate ester compound, or the like can be used in combination, or a catalyst such as a peroxide can be used. About the addition amount of the said compound and a catalyst, and the presence or absence of addition, it adjusts suitably in the range which can ensure the target characteristic.

  As an allyl nadiimide resin which is one of the preferable thermosetting resins, a bisallyl nadiimide resin represented by the following general formula (4) is a compound containing two or more allyl nadimide groups in the molecule. .

［式中、Ｒ^１２は芳香族環及び／又は直鎖、分岐若しくは環状脂肪族炭化水素を含む２価の有機基を示す。］

[Wherein, R ¹² represents a divalent organic group containing an aromatic ring and / or a linear, branched or cyclic aliphatic hydrocarbon. ]

R ¹² in the general formula (4) is a divalent organic group containing an aromatic ring and / or a linear, branched or cyclic aliphatic hydrocarbon, preferably a benzene residue, a toluene residue, xylene Examples thereof include a residue, a naphthalene residue, a linear, branched, or cyclic alkyl group, or a mixed group thereof, more preferably a divalent organic group having the following structure.

［式中、ｔは１〜１０の整数を示す。］

[Wherein t represents an integer of 1 to 10. ]

  Among them, liquid hexamethylene bisallyldiimide represented by the following formula (5), low melting point (melting point: 40 ° C.) solid xylylene bisallyldiimide represented by the following formula (6) It acts as a compatibilizing agent between different components constituting the agent composition, and can impart good thermal fluidity at the B stage of the adhesive film, and the solid xylylene-type bisallylnadiimide is In addition to good thermal fluidity, it can suppress an increase in film surface tackiness at room temperature, handleability, easy peeling from the dicing tape during pick-up, and suppression of re-bonding of the cut surface after dicing. This is more preferable. In addition, these bisallyl nadiimide can be used individually by 1 type or in combination of 2 or more types.

  The allyl nadiimide resin described above requires a curing temperature of 250 ° C. or more when singly cured in the absence of a catalyst, which is a major obstacle to practical use. In addition, in a system using a catalyst, only a metal corrosive catalyst such as a strong acid or an onium salt, which is a serious drawback in an electronic material, can be used, and a temperature of about 250 ° C. is required for final curing. However, it is possible to cure at a low temperature of 200 ° C. or lower by using any one of the above allyl nadiimide resin and a bifunctional or higher acrylate compound, a methacrylate compound, or a maleimide resin (reference: A.A. Renner, A. Kramer, “Allylnadic-Imides: A New Class of Heat-Resistant Thermosets”, J. Polym. Sci., Part A Polym. Chem., 27, 1301 (1989)).

  The acrylate compound is not particularly limited as long as the number of acrylic functional groups contained in one molecule is 2 or more. For example, pentenyl acrylate, tetrahydrofurfuryl acrylate, diethylene glycol diacrylate, triethylene Ethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, ethylene oxide modified neopentyl Glycol acrylate, polypropylene glycol diacrylate, phenoxyethyl acrylate, tricyclodecane dimethylol diacrylate, Trimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tri acrylate tris (beta-hydroxyethyl) isocyanurate. The bifunctional or higher methacrylate compound is not particularly limited as long as the number of methacrylic functional groups in one molecule is 2 or more. For example, pentenyl methacrylate, tetrahydrofurfuryl methacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene oxide modified neo Pentyl glycol methacrylate, polypropylene glycol dimethacrylate, phenoxyethyl methacrylate, tricyclo Kanji methylol dimethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexa methacrylate, trimethacrylate of tris (beta-hydroxyethyl) isocyanurate. These acrylate compounds or methacrylate compounds can be used alone or in combination of two or more.

  The adhesive composition of the present invention can further contain an inorganic filler. Examples of the inorganic filler include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, and amorphous. Examples include fillers such as crystalline silica, boron nitride, titania, glass, iron oxide, and ceramic, and these inorganic fillers can be used in combination of two or more. Among these, silica is preferable because it can provide high adhesive force and can reduce impurities that cause metal corrosion, thereby improving the reliability of the semiconductor device. Moreover, it is preferable that the shape of the inorganic filler to be used is spherical in terms of thermal fluidity in the film thickness direction and high adhesive strength, as will be described later. The spherical shape includes shapes such as a true spherical shape, a circular granular shape, and an elliptical shape.

  The amount of the filler used is determined according to the characteristics or functions to be imparted, but is preferably 10 to 40% by volume, more preferably 10 to 30% by volume, particularly based on the total volume of the resin component and the filler. Preferably it is 10-20 volume%. By appropriately increasing the amount of filler, the film surface can be reduced in adhesiveness and elastic modulus can be increased, and dicing properties (cutability with a dicer blade), pickup properties (easy peeling from dicing tape), wire bonding properties (super Sonic efficiency) and adhesive strength during heat can be effectively improved. When the filler is increased more than necessary, the low temperature sticking property, the interfacial adhesion with the adherend, and the fluidity during heat are characteristic of the present invention, and the reliability including reflow resistance is reduced. The amount of filler used is preferably within the above range. The optimal filler content is determined to balance the required properties. 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 three-roller, and a ball mill.

  The inorganic filler preferably has a maximum particle size of 25.0 μm or less, and more preferably 20.0 μm or less. A lower limit value of the minimum particle size is not particularly provided, but is preferably 0.001 μm or more. When the particle size is less than 0.001 μm, the interfacial area with the resin is increased, the dispersibility in the resin varnish is decreased, and the fluidity during heating tends to decrease due to the increase in hot melt viscosity. Yes, when the above particle diameter exceeds 25.0 μm, there is a tendency that high adhesive force cannot be obtained, and when processing into a thin film form, the surface becomes rough and the film formability tends to be impaired. Yes, neither is preferred.

  Further, the inorganic filler preferably has at least two particle size distributions in a range where the maximum particle size is 25.0 μm or less, and the difference in particle size at which the frequency of each particle size distribution peaks is preferably 1 μm or more. More preferably. Thus, the combined use of large and small inorganic fillers with different particle size distributions increases the packing density of the inorganic filler in the adhesive film, reduces the film surface tack at the B stage, improves the film cutting property during dicing, and after dicing Effects such as suppression of re-bonding of the film cut surface can be obtained. Further, by using fillers having different particle diameters in combination, it is possible to effectively suppress an increase in hot melt viscosity at the B stage due to an increase in filler filling amount. That is, it is considered that the stress transmission effect in the thickness direction of the adhesive film is increased when the resin is in a fluid state by thermocompression bonding. Furthermore, the use of a spherical filler is considered to provide a sliding effect when the fillers are brought into contact with each other by pressure. With the above design, the filler blending system can effectively achieve both low adhesion and hot fluidity, which are usually in a reciprocal relationship. Furthermore, this design also has the effect of increasing the packing density of the filler, and since the area occupied by the apparent resin can be reduced on the cut surface of the adhesive film after dicing, the effect of suppressing rebonding of the cut surface after dicing can be obtained. . In addition, the filler density is increased by using fillers with different particle diameters in combination, and the filler is a polishing agent against the dicing blade at the time of dicing due to the synergistic effect of the shape factor due to the mixture of different particle diameter fillers. It is considered that the polishing efficiency for the cut surface of the adhesive film during dicing is improved. If the difference between the particle sizes at which the frequency of each particle size distribution described above is a peak is less than 1 μm, it tends to be difficult to obtain the above effect, which is not preferable.

  As a method of giving two particle size distributions to the inorganic filler to be used, there is a method of using two kinds of inorganic fillers having different average particle sizes in addition to using a single inorganic filler designed to have two particle size distributions. is there. In this case, it is preferable that the difference of the average particle diameter of each filler is 1 micrometer or more. Moreover, when using together 2 types of inorganic fillers, the average particle diameter of one filler may be 0.01-2.0 micrometers, and the average particle diameter of the other filler may be 2.0-10.0 micrometers. Preferably, a filler is selected and combined so that the difference between the average particle diameters of both is 1 μm or more. When the average particle diameter of the filler is less than 0.01 μm, or the average particle diameter of the filler exceeds 10.0 μm, neither is preferable for the same reason as described above.

  When two types of fillers having different average particle diameters are used in combination, the ratio of fillers having a small average particle diameter is 10 to 70% by mass based on the total amount of filler, and the ratio of fillers having a large average particle diameter is 30 based on the total amount of filler. By adjusting in the range of -90 mass%, the above-mentioned effect can be effectively secured. The particle size or average particle size of the filler is a value obtained when measuring the particle size distribution. Regarding the particle size distribution, particle size, and average particle size of the inorganic filler filled in the adhesive film, the adhesive film is heated in an oven at 600 ° C. for 2 hours to decompose and volatilize the resin component, and the remaining inorganic filler is observed by SEM. Or by calculating from the particle size distribution measurement.

  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 the said coupling agent shall be 0.01-20 mass parts with respect to 100 mass parts of polyimide resins from the surface of the effect, heat resistance, and cost.

  In the adhesive composition of the present invention, in addition to the above-mentioned components, if necessary, a thermoplastic polymer component, a thermosetting resin other than an epoxy resin, a coupling agent, a filler, and the like are appropriately blended. Also good.

  The thickness of the film adhesive using the adhesive composition of the present invention is preferably 1 to 100 μm.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive according to the present invention. A film adhesive 1 shown in FIG. 1 is obtained by forming the adhesive composition of the present invention into a film. FIG. 2 is a schematic cross-sectional view showing an embodiment of an adhesive sheet according to the present invention. The adhesive sheet 100 shown in FIG. 2 includes a base film 2 and an adhesive layer 1 ′ formed by forming the adhesive composition of the present invention provided on one surface of the base film 2 into a film shape. 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 includes a base film 2 and an adhesive layer 1 ′ formed by forming the adhesive composition of the present invention provided on both surfaces of the base film 2 into a film shape. In addition, in order to prevent damage and contamination of the adhesive layer, a cover film can be provided on the adhesive layer as appropriate. For example, as shown in FIG. 4, an adhesive sheet having a structure in which a cover film 3 is further provided on the side surface opposite to the base film 2 of the adhesive layer 1 ′ provided on the base film 2. It may be 120.

  In the case of the form of a single-layer film adhesive 1 as shown in FIG. 1, it is preferable to carry it in the form of a tape having a width of about 1 to 20 mm or a sheet of about 10 to 50 cm and wound around a winding core. .

  The film adhesive according to the present invention can be produced by the following procedure. First, an adhesive layer forming varnish comprising the adhesive composition of the present invention is prepared. This varnish can be obtained, for example, by blending and kneading (B) a thermosetting resin, if necessary, a filler and other components to the polyimide resin varnish according to the present invention synthesized in an organic solvent. . Next, an adhesive layer forming varnish is applied on the base film to form a varnish layer. Next, a film adhesive can be obtained by removing the substrate film after the varnish layer is heated and dried.

  The organic solvent used for the preparation of the varnish, that is, the varnish solvent is not particularly limited as long as the material 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 of the present invention 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, A polyetherimide film, a polyether naphthalate film, a methylpentene film, etc. are mentioned. Two or more kinds of these base films may be combined to form a multilayer film, or the surface may be treated with a release agent such as silicone or silica.

  The above mixing and kneading can be carried out by appropriately combining dispersers such as ordinary stirrers, crackers, three rolls, and ball mills. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently volatilized, but the heating is usually performed at 50 to 200 ° C. for 0.1 to 90 minutes.

  Examples of the base film 2 constituting the adhesive sheets 100, 110, and 120 include PET and OPP.

  Examples of the cover film 3 include PET, PE, and OPP.

  The adhesive layer 1 ′ can be provided by laminating the base film 2 with the film adhesive according to the present invention obtained in advance. In addition, the adhesive layer 1 ′ is formed by coating the base film 2 with an adhesive layer forming varnish comprising the adhesive composition of the present invention, as in the case of producing the film adhesive according to the present invention. It can also be formed by heating and drying.

  Moreover, the adhesive sheet which has a structure which laminated | stacked the film adhesive of this invention and the dicing sheet as suitable embodiment of the adhesive sheet of this invention is mentioned. The film adhesive included in the adhesive sheet can function as a semiconductor element fixing film adhesive.

  Examples of the dicing sheet include a dicing sheet having a structure in which a pressure-sensitive adhesive layer is laminated on a base film, or a dicing sheet including only a base film. In the case of this aspect, it is preferable that the adhesive sheet is formed in a shape close to the wafer in advance (pre-cut).

  As an adhesive sheet of this embodiment, what has the composition shown in Drawing 2 and the composition shown in Drawing 5 is mentioned, for example. In the case of the adhesive sheet 100 shown in FIG. 2, an adhesive layer 1 'made of the film adhesive of the present invention is provided on the base film 2 as a dicing sheet. In the case of the adhesive sheet 130 shown in FIG. 5, an adhesive layer 6 and an adhesive film comprising the film-like adhesive of the present invention on the base film 7 that can ensure elongation when a tensile tension is applied (commonly called an expand). The agent layer 1 ′ is provided in this order. According to these adhesive sheets, it is possible to have both a function as a die bonding film and a function as a dicing sheet, and it is possible to simplify the semiconductor device manufacturing process.

  That is, as in the adhesive sheet shown in FIG. 5, the pressure-sensitive adhesive layer that functions as a dicing sheet is provided on the base film, and the function of the die-bonding film is further formed on the pressure-sensitive adhesive layer. As a dicing sheet at the time of dicing, by laminating a film adhesive, or by laminating the expandable base film and the film adhesive of the present invention like the adhesive sheet shown in FIG. At the time of die bonding, the function as a die bonding film can be exhibited. Such a dicing sheet / die bonding film-integrated adhesive sheet is laminated on the back surface of the semiconductor wafer while heating the film-like adhesive of the adhesive sheet, and after dicing the laminate, the film-like adhesive It can be used to pick up the attached semiconductor element.

  The pressure-sensitive adhesive layer 6 may be either a pressure-sensitive type or a radiation-curing type, has a sufficient adhesive strength that prevents the semiconductor element from scattering during dicing, and is low enough not to damage the semiconductor element in the subsequent pick-up process of the semiconductor element. As long as it has adhesive strength, it can be formed using a conventionally known material without any particular limitation.

  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, film-like adhesive and adhesive sheet of the present invention include 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; As an adhesive material for die bonding to bond substrates such as ceramics such as alumina, etc. to adhere to substrates such as ceramics such as alumina; Can be used. Among them, it is suitably used as an adhesive material for die bonding for bonding a semiconductor element to an organic substrate having an uneven surface on an organic substrate having an organic resist layer on the surface, an organic substrate having wiring on the surface, and the like. .

  The adhesive composition, film adhesive and adhesive sheet of the present invention are also suitable as an adhesive material for adhering a semiconductor element and a semiconductor element in a Stacked-PKG having a structure in which a plurality of semiconductor elements are stacked. Used for.

  As a use of the film adhesive of the present invention, a semiconductor device provided with a film adhesive will be specifically described with reference to the drawings. 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 the semiconductor device of the present invention. In the semiconductor device 200 shown in FIG. 6, the semiconductor element 9 is bonded to the semiconductor element mounting support member 10 via the film adhesive 1 of the present invention, and the connection terminal (not shown) of the semiconductor element 9 is connected to the wire 11. And is electrically connected to an external connection terminal (not shown) and sealed with a sealing material 12.

  FIG. 7 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. In the semiconductor device 210 shown in FIG. 7, the first-stage semiconductor element 9a is bonded to the semiconductor element mounting support member 10 on which the terminals 13 are formed via the film adhesive 1 of the present invention. A second-stage semiconductor element 9b is bonded onto 9a via a film adhesive 1 of the present invention. Connection terminals (not shown) of the first-stage semiconductor element 9 a and the second-stage semiconductor element 9 b are electrically connected to external connection terminals via wires 11 and are sealed with a sealing material 12. Thus, the film adhesive of the present invention can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

  The semiconductor device (semiconductor package) shown in FIGS. 6 and 7 has, for example, a film-like adhesive of the present invention sandwiched between a semiconductor element and a semiconductor mounting support member or a semiconductor element, and bonded by thermocompression bonding. Alternatively, the above-described semiconductor element with a film adhesive is bonded to the semiconductor element mounting support member or the semiconductor element by thermocompression bonding, and then a wire bonding process, a process such as a sealing process with a sealing material, if necessary. It can obtain by going through. The heating temperature in the thermocompression bonding 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 specifically described based on examples, but the present invention is not limited thereto.

The Tg and average molecular weight of the synthesized polyimide resin were determined by the following method.
<Tg of polyimide resin>
Using a rotational rheometer ARES manufactured by Rheometric Scientific, a film sample in which a polyimide resin is formed in a film shape on a parallel disk (diameter 8 mm) is sandwiched with a gap width 2 to 5 μm smaller than the sample thickness, and a frequency of 1 Hz, The tan δ peak temperature when measured under the conditions of 1% strain, a heating rate of 5 ° C./min, and a measurement temperature of 30 ° C. to 300 ° C. was measured and this was defined as Tg.
<Average molecular weight of polyimide resin>
Using high performance liquid chromatography (C-R4A, manufactured by Shimadzu Corporation), the weight average molecular weight and number average molecular weight in terms of polystyrene were determined.

<Synthesis of polyimide resin>
(Synthesis of polyimide PI-1)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, ether diamine (manufactured by Tokyo Chemical Industry, B13 (molecular weight: 220.31)) 11.01 g (0.05 mol), 1,3-bis A reaction solution charged with 12.42 g (0.05 mol) of (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical, LP-7100 (molecular weight: 248.51)) and 113 g of N-methyl-2-pyrrolidone Stir. After the diamine was dissolved, 32.62 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride previously purified by recrystallization from acetic anhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 75.5 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to form a polyimide resin (hereinafter referred to as “polyimide PI-1”). A varnish was obtained. When the average molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight Mn = 19000 and weight average molecular weight Mw = 31000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 53 degreeC.

(Synthesis of polyimide PI-2)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inlet tube, ether diamine (manufactured by Tokyo Chemical Industry, B13 (molecular weight: 220.31)) 11.01 g (0.05 mol), polyether diamine (BASF) Manufactured, D400 (molecular weight: 452.4)) 22.62 g (0.05 mol) and 133 g of N-methyl-2-pyrrolidone were stirred. After the diamine was dissolved, 32.62 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride previously purified by recrystallization from acetic anhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 78.5 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to form a polyimide resin (hereinafter referred to as “polyimide PI-2”). A varnish was obtained. When the average molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight Mn = 20000 and weight average molecular weight Mw = 39000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 40 degreeC.

(Synthesis of polyimide PI-3)
1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical, LP-7100 (molecular weight: 248.51)) in a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inflow pipe ) 9.94 g (0.04 mol), ether diamine (B-13 (molecular weight: 220.31)) 8.81 g (0.04 mol), 1,12-dodecanediamine (manufactured by Tokyo Chemical Industry: molecular weight 200.36) 4 The reaction solution charged with 0.0 g (0.02 mol) and N-methyl-2-pyrrolidone 140 g was stirred. After the diamine was dissolved, 32.62 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride previously purified by recrystallization from acetic anhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 80.5 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to form a polyimide resin (hereinafter referred to as “polyimide PI-3”). A varnish was obtained. When the average molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight Mn = 18000 and weight average molecular weight Mw = 30000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 62 degreeC.

(Synthesis of polyimide PI-4)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 2.12 g (0.035 mol) of 1,12-diaminododecane, polyether diamine (manufactured by BASF, D2000 (molecular weight: 1923)) 17 .31 g (0.03 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., LP-7100) 2.61 g (0.035 mol), and N-methyl-2-pyrrolidone 113 g The reaction solution charged with was stirred. After 1,12-diaminododecane and polyetherdiamine were dissolved, 4,4 ′-(4,4′-isopropylidenedidiene purified in advance by recrystallization from acetic anhydride while cooling the flask in an ice bath. 15.62 g (0.1 mol) of phenoxy) bis (phthalic dianhydride) was added in small portions. After reacting at room temperature for 8 hours, 75.5 g of xylene was added, and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to obtain a polyimide resin (hereinafter referred to as “polyimide PI-4”). A varnish was obtained. When the average molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight Mn = 12000 and weight average molecular weight Mw = 54000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 22 degreeC.

(Synthesis of polyimide PI-5)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 10.21 g (0.05 mol) of ether diamine (manufactured by Tokyo Chemical Industry, B-12 (molecular weight 204.31)) and N-methyl The reaction solution charged with 140 g of -2-pyrrolidone was stirred. After the diamine was dissolved, 52.2 g (0.1 mol) of decamethylene bistrimellitic dianhydride previously purified by recrystallization from acetic anhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 80.5 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to form a polyimide resin (hereinafter referred to as “polyimide PI-5”). A varnish was obtained. When the average molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight Mn = 28000 and weight average molecular weight Mw = 83000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 80 degreeC.

(Synthesis of polyimide PI-6)
In a 300 ml flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 41 g (0.1 mol) of 2,2-bis (4-aminophenoxyphenyl) propane (manufactured by Wakayama Seika: molecular weight 410.5), And 122 g of N-methyl-2-pyrrolidone were added and stirred. After dissolution of the diamine, 32.62 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride previously recrystallized and purified with acetic anhydride was added little by little while cooling the flask in an ice bath. After reacting at room temperature for 8 hours, 83 g of xylene was added, heated at 180 ° C. while blowing nitrogen gas, and azeotropic removal of xylene with water was performed to obtain a polyimide resin (hereinafter referred to as “polyimide PI-6”) varnish. . As a result of measuring the average molecular weight of the obtained polyimide resin by GPC, it was Mw = 72000 and Mn = 23000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 200 degreeC.

(Synthesis of polyimide PI-7)
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 17.62 g (0.08 mol) of ether diamine (manufactured by Tokyo Chemical Industry, B13 (molecular weight: 220.31)), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical, LP-7100 (molecular weight: 248.51)) 2.48 g (0.01 mol), polyether diamine (manufactured by BASF, D400 (molecular weight 452.4)) The reaction solution charged with 4.52 g (0.01 mol) and N-methyl-2-pyrrolidone 113 g was stirred. After the diamine was dissolved, 32.62 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride previously purified by recrystallization from acetic anhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 75.5 g of xylene was added, and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to form a polyimide resin (hereinafter referred to as “polyimide PI-7”). A varnish was obtained. When the average molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight Mn = 26000 and weight average molecular weight Mw = 43000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 60 degreeC.

  About the polyimide PI-1-7 synthesize | combined above, the film surface tack force (strength) in 100 degreeC melt viscosity and 40 degreeC was evaluated by the method shown below. The results are shown in Tables 1 and 2.

<100 ° C melt viscosity>
The polyimide resin varnish is applied onto a base film (release agent-treated PET film) so that the film thickness after drying is 40 μm, and heated in an oven at 80 ° C. for 30 minutes, and then at 120 ° C. for 30 minutes. The base film was peeled off to form a polyimide resin film having a thickness of 40 μm. 3-7 sheets of this film were stacked and bonded together to prepare a film sample adjusted to a thickness of 100-300 μm. The above film sample is sandwiched between parallel disks (diameter 8 mm) with a gap width 2 to 5 μm smaller than the sample thickness, and using a rotating rheometer ARES (manufactured by Rheometric Scientific), frequency 1 Hz, distortion 1% The viscosity of the sample was measured under conditions of a temperature rate of 5 / min and a measurement temperature of 30 ° C to 300 ° C. The value of the complex viscosity at 100 ° C. at this time was defined as 100 ° C. melt viscosity.

<Film surface tack force (strength) at 40 ° C.>
A polyimide resin film having a thickness of 40 μm was formed in the same manner as in the above <100 ° C. melt viscosity> measurement. The upper surface of this film is compliant with the method described in JISZ0237-1991 (probe diameter 5.1 mm, peeling speed 10 mm / s, contact load 100 gf / cm ² , contact time 1 s) using a Resca probe tacking tester. Then, tack force (adhesive force) at 40 ° C. was measured. The value at this time was taken as the film surface tack force (strength) at 40 ° C.

  It was confirmed that all of polyimides PI-1 to 3 and 7 have the characteristics that the melt viscosity at 100 ° C. is 6000 Pa · s or less and the film surface tack force at 40 ° C. is 200 gf or less.

<Preparation of adhesive composition and manufacture of semiconductor device>
(Examples 2 and 4, Reference Examples 1 and 3 and Comparative Examples 1 to 3)
Each of the above polyimide PI-1 to 7 was used, and each component was blended at a composition ratio (unit: part by mass) shown in Tables 3 to 4 below to obtain an adhesive composition (varnish for forming an adhesive layer). . In addition, the detail of each material in Tables 3-4 is as follows.

VG-3101: manufactured by Printec Co., Ltd., trifunctional epoxy resin YDF-8170: manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin NHN-100: manufactured by Nippon Kayaku Co., Ltd., cresol naphthol formaldehyde polycondensate SE6050: ad Co., Ltd. Matex SE2050: Admatechs Co., Ltd.

[Method for producing adhesive sheet]
The adhesive composition is applied onto a base film (peeling agent-treated PET film), heated in an oven at 80 ° C. for 30 minutes, and then at 120 ° C. for 30 minutes to peel off the base film. A 30 μm film adhesive was obtained. The produced film adhesive was cut out to a diameter of 210 mm and bonded onto T-80MW (80 μm) manufactured by Denki Kagaku Kogyo at room temperature (25 ° C.) using DM-300-H manufactured by JCM Corporation. As a result, an adhesive sheet in which the film adhesive and the dicing sheet were laminated was obtained.

[Confirmation of low temperature laminating properties]
A 200 μm-thick semiconductor wafer was laminated on the adhesive sheet at a hot plate setting temperature of 80 ° C., and the laminating property was evaluated. The laminate used DM-300-H manufactured by JCM Co., Ltd., and was “good” when pasting was possible, and “bad” when no film adhesive was stuck to the back side of the semiconductor wafer. The results are shown in Tables 3-4.

[Checking pickup properties]
A 100 μm-thick semiconductor wafer was laminated on the hot plate on the adhesive sheet to prepare a dicing sample. As for the hot plate surface temperature during lamination, Examples 2 and 4, Reference Examples 1 and 3 and Comparative Example 1 were performed at 80 ° C, and Comparative Examples 2 to 3 were performed at 180 ° C.

  Next, using a fully automatic dicer DFD-6361 manufactured by DISCO Corporation, the laminated product of the semiconductor wafer, the film adhesive, and the dicing sheet was cut into a 10 mm × 10 mm semiconductor chip. The cutting was performed by a single cut method in which the processing was completed with one blade. A dicing blade NBC-ZH104F-SE 27HEDD manufactured by DISCO Corporation was used as the blade, and the blade was rotated at 45000 rpm and the cutting speed was 50 mm / s. The blade height at the time of cutting was set to leave 10 μm of the adhesive sheet.

  The pick-up property of the semiconductor chip produced by the above method was evaluated using a flexible die bonder DB-730 manufactured by Renesas East Japan Semiconductor. The pickup collet used was RUBBER TIP 13-087E-33 (size: 10 × 10 mm) manufactured by Micromechanics, and the EJECTOR NEEDLE SEN2-83-05 manufactured by Micromechanics was used for the push-up pin (diameter: 0.7 mm, tip shape) : Semicircle with a diameter of 350 μm). Nine push-up pins were arranged at a pin center interval of 4.2 mm. The pick-up property was evaluated under the conditions of a pin push-up speed during pick-up: 10 mm / s and a push-up height: 1000 μm. When 100 consecutive chips were picked up and chip cracking, pickup mistakes, etc. did not occur, “good”, and even when one chip cracked, pickup mistakes, etc. occurred, “bad”. The results are shown in Tables 3-4.

[Check embedding]
A 100 μm-thick semiconductor wafer was laminated on the hot plate on the adhesive sheet to prepare a dicing sample. As for the hot plate surface temperature during lamination, Examples 2 and 4, Reference Examples 1 and 3 and Comparative Example 1 were performed at 80 ° C, and Comparative Examples 2 to 3 were performed at 180 ° C.

  Next, the laminated product of the said semiconductor wafer, the film adhesive, and the dicing sheet was cut | disconnected using the full auto dicer DFD-6361 by DISCO Corporation. The cutting was performed by a single cut method in which the processing was completed with one blade. A dicing blade NBC-ZH104F-SE 27HEDD manufactured by DISCO Corporation was used as the blade, and the blade was rotated at 45000 rpm and the cutting speed was 50 mm / s. The blade height at the time of cutting was set to leave 10 μm of the adhesive sheet. The size for cutting the semiconductor wafer was 7.5 × 7.5 mm.

  The film-adhesive semiconductor chip obtained in the above dicing step was pressure-bonded to a substrate with wiring, and the substrate step embedding property during pressure bonding was evaluated. The semiconductor chip was crimped to the substrate with wiring using a flexible die bonder DB-730 manufactured by Renesas East Japan Semiconductor Co., Ltd., with a hot plate surface temperature of 130 ° C., a crimping load of 5 N, and a crimping time of 2 s. The substrate with wiring uses E-679F (0.2 mm thickness) manufactured by Hitachi Chemical Co., Ltd. as the base material, and a solder resist AUS-308 manufactured by Taiyo Ink Co., Ltd. is used as the circuit protection layer. The thickness was about 10 μm. The sample after crimping is observed with an ultrasonic imaging device HYFOCUS manufactured by Hitachi Construction Machinery Finetech Co., “Good” when there is no void between the film adhesive and the substrate with wiring. “Bad”. The results are shown in Tables 3-4.

[reliability]
The sample obtained in the above embedding experiment was processed in an oven at 100 ° C., 110 ° C., 120 ° C. for 1 hour each to cure the film adhesive, and then sealed on the upper surface of the substrate with wiring using a general-purpose press The material was molded. CEL-9750ZHF10 made by Hitachi Chemical Co., Ltd. was used as the sealing material, and the molding conditions were 180 ° C./6.75 MPa / 90 s. The molded sample was cured at 175 ° C./5 h in an oven and then separated into pieces by a dicer to obtain a semiconductor package.

  The semiconductor package was dried in an oven at 125 ° C. for 12 hours, then subjected to JEDEC level 2 (85 ° C./85% RH / 168 hours), and then reflowed at a maximum temperature of 265 ° C. three times. For the reflow treatment, Furukawa Electric Co., Ltd. salamander XNA-645PC was used, and the reflow profile was set in accordance with JEDEC standard J-STD-020C. The semiconductor package after the reflow treatment was observed using an ultrasonic imaging apparatus, and “good” was obtained when there was no defect such as peeling, and “bad” when peeling or cracking occurred. The results are shown in Tables 3-4.

  As described above, according to the present invention, a film shape that sufficiently combines process characteristics such as low-temperature laminating properties and pick-up properties after dicing, and characteristics that contribute to improving the reliability of semiconductor devices including reflow resistance. An adhesive composition capable of forming an adhesive can be provided.

  DESCRIPTION OF SYMBOLS 1 ... Film adhesive, 1 '... Adhesive layer, 2 ... Base film, 3 ... Cover film, 6 ... Adhesive layer, 7 ... Base film, 9, 9a, 9b ... Semiconductor element, 10 ... Semiconductor mounting Support member, 11 ... wire, 12 ... sealing material, 100,110,120,130 ... adhesive sheet, 200,210 ... semiconductor device.

Claims (17)

An adhesive composition containing a polyimide resin obtained by reacting tetracarboxylic dianhydride and diamine,
The total amount of the tetracarboxylic acid dianhydride is a tetracarboxylic dianhydride represented by the following formula (I),
The diamine contains 30 mol% or more of a diamine represented by the following general formula (II) with respect to the total amount of the diamine component,
The polyimide resin has a glass transition temperature of 10 ° C. to 100 ° C., a melt viscosity at 100 ° C. of 6000 Pa · s or less, and a film surface tack force at 40 ° C. of the film when formed into a film shape. 200gf Ri der below,
The adhesive composition in which the diamine further contains 10 mol% or more of a diamine represented by the following formula (V) with respect to the total amount of the diamine component .

_(Wherein, Q 1, _{Q 2} and _{Q 3} are a straight-chain alkylene group having 1 to 10 carbon atoms, P is an integer of 0.)

(In the formula, m represents an integer of 0 to 80.) The adhesive composition according to claim 1, wherein the diamine further contains 10 mol% or more of a diamine represented by the following general formula (III) with respect to the total amount of the diamine component.

(In the formula, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms. Represents a phenyl group or a phenoxy group.) The adhesive composition according to claim 1 or 2, wherein the diamine further comprises 10 mol% or more of a diamine represented by the following general formula (IV) with respect to the total amount of the diamine component.

(In the formula, q represents an integer of 1 to 20.) The adhesive composition according to any one of claims 1 to 3 , further comprising a thermosetting resin. The adhesive composition according to any one of claims 1 to 4 , which is used for adhering a semiconductor element to another semiconductor element or a semiconductor element mounting support member. The adhesive composition according to claim 5 , wherein the semiconductor element mounting support member is an organic substrate with a wiring step. The film adhesive formed by forming the adhesive composition as described in any one of Claims 1-4 in a film form. The film adhesive of Claim 7 used in order to adhere | attach a semiconductor element on another semiconductor element or a semiconductor element mounting support member. The film adhesive according to claim 8 , wherein the semiconductor element mounting support member is an organic substrate with a wiring step. A base film, and an adhesive layer formed by forming the adhesive composition according to any one of claims 1 to 4 in a film shape on at least one surface of the base film, Adhesive sheet. An adhesive sheet obtained by laminating an adhesive layer formed by forming the adhesive composition according to any one of claims 1 to 4 into a film and a dicing sheet. The dicing sheet is one having a pressure-sensitive adhesive layer provided on the substrate film and the substrate film on the adhesive sheet according to claim 1 1. The semiconductor device, used to adhere to other semiconductor device or a semiconductor element-mounting supporting member, the adhesive sheet according to any one of claims 1 0 to 1 2. The semiconductor element-mounting support member is an organic substrate with wiring step, the adhesive sheet according to claim 1 3. A semiconductor having a structure in which a semiconductor element and another semiconductor element and / or a semiconductor element and a semiconductor element mounting support member are bonded by the adhesive composition according to any one of claims 1 to 4. apparatus. A semiconductor device having a structure in which a semiconductor element and another semiconductor element and / or a semiconductor element and a semiconductor element mounting support member are bonded by the film adhesive according to claim 7 . By an adhesive sheet according to any one of claims 1 0 to 1 2, the semiconductor device and other semiconductor devices, and / or has a structure in which a semiconductor element and a semiconductor element-mounting supporting member is formed by bonding, Semiconductor device.

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