JP5589285B2 - Thermosetting adhesive composition and semiconductor device - Google Patents

Description

  The present invention relates to a thermosetting adhesive composition and a semiconductor device.

  As a method of adhering a semiconductor element such as an IC and a support such as a metal frame or an organic substrate, a method of mounting a semiconductor element on a support via an adhesive resin composition and curing and bonding is widely used. Yes. In recent years, solder containing no lead component is often used for mounting a semiconductor device on a substrate as part of environmental measures. In order to use such solder, it is necessary to increase the solder reflow temperature from the conventional temperature range of 220 to 245 ° C. to a temperature range of 260 to 70 ° C. For this reason, the adhesive resin composition has been increasingly required to reduce defects such as cracks in the semiconductor device due to an increase in thermal stress generated with an increase in solder reflow temperature.

  In response to such a demand, by increasing the adhesive strength between the adhesive resin composition, the semiconductor element, and the support, it is possible to reduce problems such as peeling of the semiconductor element even when the stress inside the semiconductor device increases. A technique has been studied (for example, see Patent Document 1). However, even such an adhesive resin composition does not provide a sufficient effect in a high temperature environment, and particularly during solder reflow at a high temperature of 260 to 270 ° C. However, it has not been possible to reduce problems such as peeling of the semiconductor device and internal cracks in the semiconductor device.

JP2002-212267

  An object of the present invention is to use a thermosetting adhesive composition capable of imparting excellent reliability to a semiconductor device without causing defects such as cracks in the semiconductor device even under a high temperature environment of 260 ° C. or higher, and the same. It is to provide a semiconductor device.

Such an object is achieved by the present invention described in [1] to [13] below.
[1] A step (A1) in which a metal support and a semiconductor element are bonded under a predetermined heating condition A using a thermosetting adhesive composition, and the metal support bonded in the step (A1). A semiconductor device having a step (A2) of sealing the semiconductor element and the semiconductor element with a sealing resin, and a step (A3) of heat-treating under a predetermined heating condition B after being sealed in the step (A2). A thermosetting adhesive composition used in the method, wherein the warpage amount 1 and the warpage amount 2 in the following warpage evaluation test A satisfy the conditional expressions A1 and A2.
[Curve Evaluation Test A: Silicon chip (size: 5 × 5 mm, thickness: 350 μm), support (made of copper with silver plating on the joint with the silicon chip, size: 8.5 × 8.5 mm, thickness: 0.18 The thermosetting adhesive composition is disposed on the heating condition A, and the silicon chip and the support are adhered (thermosetting adhesion). Cured layer thickness of the agent composition: 20 μm or more and 30 μm or less), the warpage amount of the silicon chip after bonding is defined as a warpage amount 1. Further, after the warpage amount 1 is measured, the warpage amount of the silicon chip after the heat treatment is performed under the heating condition B is set as the warpage amount 2.
Warpage amount: The difference in height between the end portion of the silicon chip and the highest portion of the silicon chip is defined as the warpage amount.
Conditional expression A1: 0.1 ≦ warping amount 1 ≦ 20 (μm), 0.1 ≦ warping amount 2 ≦ 20 (μm)
Conditional expression A2: 0.1 ≦ warping amount 1 / warping amount 2 ≦ 0.8]

[2] A step (B1) of adhering a resin support obtained by impregnating a thermosetting resin to a fibrous support substrate and a semiconductor element under a predetermined heating condition C using a thermosetting adhesive composition; After the step (B2) of sealing the resin support and the semiconductor element bonded in the step (B1) with a sealing resin, and after the sealing in the step (B2), a predetermined heating condition D A heat-curable adhesive composition used in a method for manufacturing a semiconductor device having a heat treatment step (B3), wherein a warpage amount 3 and a warpage amount 4 in the following warpage evaluation test B are conditional expressions B1 and B2. A thermosetting adhesive composition that satisfies the requirements.
[Curve evaluation test B: Silicon chip (size: 10 × 10 mm, thickness: 200 μm) on a thermosetting adhesive composition on a support (made of glass / epoxy laminate, size: 15 × 15 mm, thickness: 0.18 μm) Curing and bonding are performed under the heating condition C (cured layer thickness of the thermosetting adhesive composition: 20 μm or more and 30 μm or less), and the warpage amount of the silicon chip after bonding is set to 3 as the warpage amount. Further, after the warpage amount 3 is measured, the warpage amount of the silicon chip after the heat treatment is performed under the heating condition D is set as the warpage amount 4.
Warpage amount: The difference in height between the end portion of the silicon chip and the highest portion of the silicon chip is defined as the warpage amount.
Conditional expression B1: 0.1 ≦ warping amount 3 ≦ 90 (μm), 0.1 ≦ warping amount 4 ≦ 90 (μm)
Conditional expression B2: 0.1 ≦ warping amount 3 / warping amount 4 ≦ 0.8]

[3] The thermosetting adhesive composition according to the above [1] or [2], comprising a compound having a radical polymerizable functional group.

[4] The thermosetting adhesive composition according to the above [3], wherein the radical polymerizable functional group is an unsaturated carbon-carbon bond.

[5] The thermosetting adhesive composition according to the above [3] or [4], wherein the radical polymerizable functional group is a (meth) acryloyl group.

[6] The thermosetting adhesive composition according to any one of [3] to [5], wherein the compound having a radical polymerizable functional group is a compound having a maleimide ring.

[7] The thermosetting adhesive composition according to [6], wherein the compound having a maleimide ring is a bismaleimide compound having no aromatic ring.

[8] The thermosetting adhesive composition according to [3] or [4], wherein the compound having a radical polymerizable functional group is a polymer or copolymer of a butadiene compound.

[9] The thermosetting adhesive composition according to [8], wherein the polymer or copolymer of the butadiene compound has at least one functional group in the molecule.

[10] The functional group of the polymer or copolymer of the butadiene compound is at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a carboxy group, a hydroxyl group, or a maleic acid group. Thermosetting adhesive composition.

[11] The heat according to [1] or [2], comprising at least two or more compounds selected from the group consisting of a compound having a (meth) acryloyl group, a compound having a maleimide ring, a butadiene compound and an allyl ester compound. Curable adhesive composition.

[12] The thermosetting adhesive composition according to [11], wherein the allyl ester compound is an allyl ester compound having no aromatic ring.

[13] A semiconductor device having a semiconductor, a support, and a thermosetting layer for bonding them, wherein the thermosetting layer is the thermosetting resin composition according to any one of [1] to [12]. A semiconductor device comprising:

  By using the thermosetting adhesive composition according to the present invention, no defects such as cracks occur in the semiconductor device even under a high temperature environment of 260 ° C. or higher, and excellent reliability is imparted to the semiconductor device under a high temperature environment. can do.

It is a schematic sectional drawing which shows an example of the semiconductor device for a test.

(Semiconductor device manufacturing process)
Hereinafter, the thermosetting adhesive composition and the semiconductor device according to the present invention will be described in detail.
The thermosetting adhesive composition according to the present invention includes a step (1) for bonding a support and a semiconductor element, and a step (2) for sealing the support and the semiconductor element bonded from the step (1). And a thermosetting adhesive composition used in a method for manufacturing a semiconductor device having a heat treatment step (3), wherein a warpage amount obtained in a predetermined warpage evaluation test satisfies a predetermined conditional expression. It is characterized by.

  The manufacturing method of the semiconductor device in which the thermosetting adhesive composition according to the present invention is used includes a step (step (1)) of bonding the support and the semiconductor element using the thermosetting adhesive composition. . Specifically, a thermosetting adhesive composition is applied to a support or a semiconductor element, the semiconductor element is arranged on the support via the applied thermosetting adhesive composition, and further, thermosetting adhesion is performed. The support and the semiconductor element are bonded together by heat-curing the agent composition.

  The manufacturing method of the semiconductor device using the thermosetting adhesive composition according to the present invention is a step of sealing the support and the semiconductor element bonded in the step (1) with a sealing resin (step 2). ). The sealing resin used in this step is often a thermosetting resin, and is often cured by heating after sealing.

  The method for manufacturing a semiconductor device using the thermosetting adhesive composition according to the present invention includes a step (step 3) of performing a heat treatment (heating) after sealing the semiconductor element in the step (2). . This process is a process aimed at promoting the curing reaction of the sealing material, and is called a post-cure mold or the like.

(Process for heating semiconductor device and warpage of semiconductor device)
The semiconductor device manufactured through the above steps is soldered by a process called IR reflow for further mounting on a mother board. As described above, all steps after the curing and bonding step (step 1) of the thermosetting adhesive composition are steps for heating the semiconductor device. Furthermore, since the heating temperature differs depending on each process, a difference also occurs in deformation of each member due to a difference in linear expansion coefficient between the respective members, and as a result, stress is generated in the semiconductor device.

  For example, the temperature at which the support and the semiconductor element are bonded in Step 1 is often about 175 ° C. In this case, the support and the semiconductor element are almost flat at the end of curing. When this is returned to room temperature, the semiconductor element is up, the support is down, and it warps in a convex shape. Thereafter, the support to which the semiconductor element is bonded in the sealing step (step 2) is heated to about 175 ° C., and is again flattened and sealed.

  Further, after sealing the semiconductor element or the like in the step 2, post mold cure is performed in the step 3 at 175 ° C. As described above, this is because the curing reaction of the sealing resin is not sufficient at the end of sealing, and this process completes the curing of the sealing resin and imparts mechanical strength and dimensional stability. In the post mold curing process, the entire semiconductor device is warped due to the volume shrinkage of the sealing resin.

  More specifically, a ball grid array (hereinafter referred to as MAPBGA) by a mold array packaging method (body size: 10 × 12 mm, PKG thickness: 1.0 mm, die size: 7 × 7 mm, die thickness: 0.35 mm, substrate: A description will be given using an example of a bismaleimide triazine resin (thickness: 0.3 mm). When the above semiconductor device is measured with a shadow moiré or a temperature variable laser three-dimensional measuring machine, the semiconductor device is warped in a concave shape with the sealing material side up and the support side down at room temperature. Further, the semiconductor device warps in a convex shape in an environment of 260 ° C. corresponding to the IR reflow temperature. Compared to the warpage of the semiconductor device in a room temperature environment immediately after the sealing, the warpage of the semiconductor device after the post mold cure (step 3) is greatly warped in a concave shape with the semiconductor element facing upward. Further, the warpage in the 260 ° C. environment of the semiconductor device that has undergone the post mold cure (step 3) tends to be smaller than the warp in the convex mold as compared with the case that has not undergone the post mold cure (step 3). This is due to the fact that the curing reaction of the sealing resin is promoted by the post mold cure (step 3).

(Influence on reliability evaluation test by warpage of semiconductor device)
Due to the deformation (warp) of the entire semiconductor device as described above, stress is generated in the cured layer of the thermosetting adhesive composition that bonds the support and the semiconductor element in the semiconductor device. At the heating temperature (about 175 ° C.) in the step of bonding the support and the semiconductor element via the thermosetting adhesive composition (step 1), the support and the semiconductor element are flat. Further, since the sealing temperature is also around 175 ° C., it is considered that the stress generated in the semiconductor device is relatively small at the stage of the sealing step (step 2). However, the volume change as described above occurs in the sealing resin by the post mold cure (step 3). This volume change increases the stress generated in the semiconductor device. Furthermore, if the deformation of the die attach part (support / resin composition / semiconductor element) inside the semiconductor device is small with respect to the volume change of the sealing resin, the sealing resin and the die attach are determined from the difference in deformation. As a result, a larger stress is generated in the semiconductor including the interface.

  It is considered that the problems such as peeling of the die attach portion and cracking of the sealing resin in the semiconductor device are caused when the sum of the stresses generated in the semiconductor device exceeds a certain range. For this reason, as the stress generated by the post mold cure increases as described above, the allowable range of stress due to heat, water absorption, etc. in the reliability evaluation of the semiconductor device decreases, and the reliability in a high temperature environment such as a reflow process decreases. It becomes.

  On the other hand, if the die attach part in the semiconductor device is deformed to some extent in response to the volume change of the sealing resin during the post mold cure (step 3), the sealing resin part and the die attach The difference in deformation from the portion can be reduced, and the stress generated in the semiconductor can be reduced.

  As a specific means for reducing the stress generated inside the semiconductor device as described above, a cured layer of a thermosetting adhesive composition that bonds the support and the semiconductor element is sealed (step 2). As an example, the curing reaction may be in a state in which the curing reaction has not completely progressed at the stage where) is completed. As a result, the die attach portion can be deformed to some extent in accordance with the deformation of the sealing resin during heating in the post mold cure (step 3), and the stress generated in the semiconductor device can be reduced.

  In the post mold cure (step 3), whether or not the die attach part is deformed to some extent according to the deformation of the sealing resin, that is, as described above, after the bonding step (step 1), the thermosetting adhesive composition Whether or not the progress of the curing reaction can be controlled can be evaluated by a predetermined warpage evaluation test of the die attach part itself. In this evaluation, the ratio between the silicon chip warpage after bonding the support and the semiconductor device via the thermosetting adhesive composition and the silicon chip warpage after heat treatment at a temperature equivalent to mold cure after bonding By using a thermosetting adhesive composition in which the warpage ratio falls within a predetermined range, the die attach portion can be deformed to some extent according to the deformation of the sealing resin.

  In addition, although only the suppression of the curing reaction of the thermosetting adhesive composition after the bonding step (step 1) can solve the problem caused by the stress generated in the semiconductor device as described above, Other problems in the actual semiconductor device production process cannot be solved. For example, there are problems such as peeling of the semiconductor element from the support in the wire bonding step performed after the curing is completed, and poor bonding between the wire and the semiconductor element. These problems arise because sufficient adhesive force and elastic modulus cannot be obtained because the curing reaction of the thermosetting adhesive composition is insufficient. Therefore, even if it is a thermosetting adhesive composition that suppresses the progress of the curing reaction after the bonding step (step 1) according to the present invention, it does not cause problems on the production step as described above. The adhesive strength (adhesion with a 4 × 4 mm silicon chip, measurement temperature 250 ° C.) after the adhesion step (step 1) is 4N or more, and the elastic modulus at 250 ° C. (measurement conditions: JIS K7244, tensile mode, temperature increase rate 5 ° C.) / Min, frequency 10 Hz, sample size 4 × 15 mm × thickness 200 μm, measuring device Seiko Instruments Inc. DMS6100) is preferably 50 to 1000 MPa.

(Measurement method of adhesive strength)
A method for evaluating the adhesive strength required for the thermosetting adhesive composition used for manufacturing a semiconductor device will be described in detail. The adhesive strength between the support bonded through the thermosetting adhesive composition and the silicon chip is such that a silicon chip of 5 × 5 mm □ (thickness: 350 μm) is bonded to the support through the thermosetting adhesive composition. It can be evaluated by measuring the shear strength at 250 ° C. Usually, if an adhesive strength of 40N or more is obtained, it does not peel off at the time of wire bonding or sealing, so whether or not it exceeds 40N is used as a criterion.

  When the support 3 and the silicon chip 4 shown in FIG. 1 are cured and bonded with a thermosetting adhesive composition, the cured layer 2 of the thermosetting adhesive composition after bonding has a thickness of 20 μm to 30 μm. It is preferable to adjust the coating amount so as to adhere and measure.

(Warpage evaluation method)
As the test semiconductor device 1 for performing the warpage evaluation, a device in which the support 3 and the silicon chip 4 are cured and bonded via a thermosetting adhesive composition as illustrated in FIG. 1 is used. Hereinafter, a case where the support is a metal frame and an organic substrate will be described.

(When using a metal frame as a support)
When a metal frame is used as a support, the measurement condition is that a 9 mm-square joint is coated with a thermosetting adhesive composition on a copper frame and a cured layer of the thermosetting adhesive composition. A silicon chip (5 mm □, thickness 350 μm) is arranged so that the thickness of the substrate becomes 20 μm or more and 30 μm or less. Thereafter, the thermosetting adhesive composition is cured by heating condition A (heating condition in the step (1)) to bond the copper frame and the silicon chip. The warpage amount of the silicon chip after bonding is defined as warpage amount 1. Further, after the warpage amount 1 is measured, the bonded copper frame and the silicon chip are heat-treated under the heating condition B (heating condition in the mold cure (step 3)), and the warpage amount of the silicon chip after the heat treatment is set as the warpage amount 2.

The warpage amount 1 and the warpage amount 2 defined as described above were measured by the following methods, respectively.
Warpage amount 1: Measured using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Engineering & Service, LSI-150).
Warpage amount 2: After measurement of warpage 1, treatment is performed at 175 ° C. for 4 hours, which is a post mold curing condition, and measurement is performed using a temperature variable laser three-dimensional measuring machine or the like.
Specifically, the difference in height between the height of the most protruded portion of the silicon chip surface and the height of the end portion of the silicon chip is measured as each warp amount.

  Both warpage amounts 1 and 2 are preferably 0.1 μm or more and 20 μm or less. If the warpage amounts 1 and 2 are not less than the lower limit of the above range, sufficient adhesive strength and elastic modulus required for the semiconductor device manufacturing process of the adhesive composition can be obtained. Moreover, if it is below the upper limit of the above range, the force applied to the chip in the semiconductor device does not become excessive, and the occurrence of chip cracking can be reduced.

  The ratio of the warpage amount 1 and the warpage amount 2 (warpage amount 1 / warpage amount 2) is preferably 0.1 or more and 0.8 or less, more preferably 0.2 or more and 0.8 or less, particularly 0.3. More than 0.8 is preferable. By setting it to the range lower limit value or more, it is possible to reduce the stress generated due to excessive deformation of the die attach portion in the post mold cure (step 3). In addition, by setting the upper limit of the range or less, the warp change (deformation) amount of the die attach part after the post mold cure after the sealing (step 3) occurs appropriately according to the deformation of the sealing resin, Stress generated inside the semiconductor can be suppressed.

(When using an organic substrate as a support)
When using a resin support formed by impregnating a fibrous support base material with a thermosetting resin as a support, the measurement conditions are glass-epoxy laminate (FR-4, glass cloth two layers, surface solar ink PSR-4000AUS308, A thermosetting adhesive composition is applied onto a support having a glass transition temperature (120-140 ° C.), a size: 15 × 15 mm, and a thickness: 0.18 microns, and the thickness of the cured layer of the thermosetting adhesive composition A silicon chip (10 mm □, thickness 200 μm) is arranged so that becomes 20 to 30 microns. Thereafter, the thermosetting adhesive composition is cured by the heating condition C (the heating condition in the step (1)) to bond the copper frame and the silicon chip. The warpage amount of the semiconductor element after bonding is defined as a warpage amount 3. In addition, after the warpage amount 3 is measured, the bonded resin support and the silicon chip are subjected to heat treatment under the heating condition D (heating condition in mold cure (step 3)). To do.

  A specific measurement method for the warpage amounts 3 and 4 can be measured by the same method as the method for measuring the warpage amounts 1 and 2, respectively.

  The warpage amounts 3 and 4 are preferably 0.1 μm or more and 90 μm or less. If the warpage amounts 3 and 4 are not less than the lower limit of the above range, sufficient adhesive strength and elastic modulus required in the semiconductor device manufacturing process of the adhesive composition can be obtained. Moreover, if it is below the said range upper limit, the force added to the chip | tip in a semiconductor device can be suppressed and generation | occurrence | production of the crack of a chip | tip can be reduced.

  The ratio of the warpage amount 3 and the warpage amount 4 (warpage amount 3 / warpage amount 4) is preferably 0.1 or more and 0.8 or less, more preferably 0.2 or more and 0.8 or less, and particularly 0.3. More than 0.8 is preferable. By setting it to the range lower limit value or more, it is possible to reduce the stress generated due to excessive deformation of the die attach portion in the post mold cure (step 3). In addition, by setting the upper limit of the range or less, the warpage change (deformation) amount of the die attach portion after the post mold cure after the sealing (step 3) occurs according to the deformation of the sealing resin. The stress generated inside can be suppressed.

  The thermosetting adhesive composition according to the present invention preferably contains a thermosetting resin and a filler. Examples of the thermosetting resin include a liquid cyanate resin, a liquid epoxy resin, a compound having a (meth) acryloyl group, a compound having a maleimide ring, a compound having a radical polymerizable functional group such as an allyl ester compound, and an allyl group. Examples include triallyl isocyanurate and phenol resin. Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, glycidylamine type liquid epoxy resin, and the like. In order to obtain sufficient properties for assembly of semiconductor devices such as adhesiveness and elastic modulus after curing, and to cause suitable deformation during post mold curing, it may contain a thermosetting resin having a functional group capable of radical polymerization preferable. From the viewpoint of moldability, it is preferable that the radically polymerizable functional group having good curability contains a thermosetting resin having an unsaturated carbon-carbon bond. In addition, a compound having a radically polymerizable functional group within a range in which the object of the present invention can be achieved, and in a range that does not affect the curability, workability, reliability, etc., is used in combination with, for example, an epoxy resin. It is also possible.

  Examples of the compound having a (meth) acryloyl group which is one of thermosetting resins that can be used in the present invention include 2- (meth) acryloyloxyethyl succinic acid and 2- (meth) acryloyloxypropyl succinic acid. Acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl methyl hexahydrophthalic acid, 2- (meth) Acryloyloxypropylmethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) Acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxye Rumethyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylmethyltetrahydrophthalic acid, 2-hydroxy 1,3 di (meth) acryloxypropane, tetramethylolmethane tri (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 1,4-cyclohexanedi Methanol mono (meth) acrylate, ethyl-α- (hydroxymethyl) (meth) acrylate, 4-hydroxybutyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, Sobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, Isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylates, cyclohexyl (meth) acrylates, tertiary butylcyclohexyl (meth) acrylates, tetrahydrofurfuryl (meth) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, Methylolpropane tri (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, neopentyl glycol (meth) acrylate, trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorooctylethyl ( (Meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, Nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyalkylene glycol mono (meth) acrylate, octoxy polyalkylene glycol mono (meth) acrylate, lauroxy polyalkylene glycol mono (meth) acrylate, stearoxy polyalkylene glycol Mono (meth) acrylate, Allyloxy polyalkylene glycol mono (meth) acrylate, Nonylphenoxy polyalkylene glycol mono (meth) acrelane N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, 1,2-di (meth) acrylamide ethylene glycol, di (meth) acryloyloxymethyltricyclodecane, 2 -(Meth) acryloyloxyethyl, N- (meth) acryloyloxyethyl maleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxyethyl phthalimide, n-vinyl-2- Although there are pyrrolidone, styrene derivatives, α-methylstyrene derivatives, (meth) acryl-modified polybutadiene, etc., there is no particular limitation.

  Moreover, the compound which has the said (meth) acryloyl group may use together the compound which has 2 or more types of (meth) acryloyl group from points, such as sclerosis | hardenability, workability | operativity, adhesiveness, reliability. The compound having a (meth) acryloyl group may be a compound having a polyfunctional (meth) acryloyl group containing two or more functional groups in one molecule.

  Examples of the compound having a maleimide ring, which is one of thermosetting resins that can be used in the present invention, include 1,2-bis (maleimide) ethane, 1,6-bismaleimide hexane, and 4,4′-bis. Maleimide diphenylmethane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N , N′-1,4-phenylenedimaleimide, N- (1-phenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4- Nitrophenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-cyclohexylmaleimi N-ethylmaleimide, N-methylmaleimide, N-phenylmaleimide, N-succinimidyl 3-maleimide benzoate, N-succinimidyl 3-maleimide propyrate, N-succinimidyl 3-maleimide butyrate, N-succinimidyl 3-maleimidohexano Art, N- [4- (2-benzimidyl) phenyl] maleimide, 9-fluorenylmethyl carbonate N-succinimidyl, 2-bromobenzylsuccinimidyl carbonate, 3,3′-dithiodipropionic acid di ( N-succinimidyl), di (N-succinimidyl) carbonate, N, N, N ′, N′-tetramethyl-O- (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2 -Tetrachloroethoxycarbonyloxy) succinimide, N- (2-chloroca) Bobenzoxyoxy) succinimide, N- (tert-butoxycarbonyl) -O-benzyl-L-serine N-succinimidyl, N-aminosuccinimide hydrochloride, N-bromosuccinimide, N-carbobenzoxy Oxysuccinimide, N-chlorosuccinimide, N-ethylsuccinimide, N-hydroxysuccinimide, N-eusuccinimide, N-phenylsuccinimide, N-succinimidyl 6- (2,4- Dinitroanilino) hexanoate, N-succinimidyl 6-maleimidohexanoate and the like are mentioned, but bismaleimide having two maleimide rings in one molecule is preferred from the viewpoint of curing. The two maleimide rings may be bonded via aliphatic or aromatic hydrocarbons or alkylene groups comprising these hydrocarbons via ethers or esters.

  The content of the compound having a maleimide ring is not particularly limited, but is preferably 0.5 to 25% by weight, particularly preferably 1 to 18% by weight, based on the whole liquid resin composition. By setting the content to be equal to or higher than the lower limit value, it is possible to obtain a suitable adhesion force to the support of the semiconductor element. Moreover, the elastic modulus of the hardened | cured material after hardening | curing adhesive composition is made suitable by setting it as the said upper limit or less, and the crack generation | occurrence | production to the semiconductor element resulting from the brittleness of the said hardened | cured material can be suppressed. .

  In the present invention, as described above, a polymer or copolymer of a butadiene compound capable of radical polymerization can be used. By using a polymer or copolymer of a butadiene compound, low stress can be imparted to the cured product of the thermosetting adhesive composition. By applying this low stress property, the adhesion between the semiconductor element and the support is improved, and peeling does not easily occur. The influence of the main chain skeleton structure of the polymer or copolymer of the butadiene compound on the low stress property imparted to the cured product of the thermosetting adhesive composition is large. When attention is paid to the microstructure of the butadiene polymer or copolymer, 1.8 to 2.2 ppm (1,4 vinyl bond) and 4.8 in 1H-NMR (400 MHz) using deuterated chloroform as a solvent. It is preferable that the ratio of 1,4 vinyl bonds is 50% or more with respect to the total of 1,4 vinyl bonds and 1,2 vinyl bonds calculated from the peak area ratio of ˜5.1 ppm (1,2 vinyl bonds). The higher the 1,4 vinyl bond ratio, the lower the viscosity of the butadiene compound as a polymer or copolymer, the better the workability such as application of the resulting resin composition to the support, and the low temperature of the cured product. It is because it is excellent in low-stress property. More preferably, the ratio of 1,4 vinyl bonds is 60% or more and 85% or less.

  When a polymer or copolymer of a butadiene compound is used in the thermosetting adhesive composition according to the present invention, the preferred blending amount is 1% by weight or more and 15% by weight or less in the resin composition. By making it within the above range, suitable workability and low stress can be obtained.

  In the present invention, for the purpose of increasing the compatibility with other resins, it is more preferable to use polybutadiene having a functional group. Specific functional groups possessed by polybutadiene include vinyl groups, epoxy groups, carboxy groups, hydroxyl groups or maleic acid groups. Among these functional groups, it is more preferable to use a polybutadiene having a maleic acid group in terms of obtaining a resin composition having high compatibility and excellent coating workability.

  Moreover, as a thermosetting resin used for this invention, an allyl ester type compound can be used. Examples of the allyl ester compounds include diallyl phthalate, diallyl terephthalate, diallyl isophthalate, triallyl trimerate, diallyl malate, allyl methacrylate, and allyl acetoacetate.

  The number average molecular weight of the allyl ester compound is not particularly limited, but is preferably 500 to 10,000, and particularly preferably 500 to 8,000. When the number average molecular weight is within the above range, curing shrinkage can be particularly reduced, and deterioration of adhesion can be prevented.

  Examples of the allyl ester compounds having the number average molecular weight as described above include terephthalic acid, isophthalic acid, phthalic acid, 5-norbornene-endo-2,3-dicarboxylic acid, 1,4-dicyclodicarboxylic acid, and adipic acid. And both terminal allyl ester compounds obtained by adding allyl alcohol by esterification to the terminal of a polyester synthesized from a dicarboxylic acid such as the above or a methyl ester derivative thereof and an alkylene diol having 2 to 8 carbon atoms.

  When using an allyl ester type compound as this invention, the content is not specifically limited, However, 0.01-15 weight% of the whole said resin composition is preferable, and 1-11 weight% is especially preferable. By setting the content to be equal to or higher than the lower limit value, brittleness of the cured product can be suppressed, and by setting the content to be equal to or lower than the upper limit value, occurrence of bleeding can be suppressed.

  The thermosetting resin used in the present invention may contain at least two or more selected from a compound having a (meth) acryloyl group, a compound having a maleimide ring, a butadiene compound, and an allyl ester compound. Thereby, the thermosetting adhesive composition excellent in especially the balance of adhesiveness and heat resistance can be obtained.

  The compound having a maleimide ring or an allyl ester compound preferably has no aromatic ring. This is because the aromatic ring has a rigid structure, and the presence of the aromatic ring increases the rigidity of the cured product so that the cured product becomes brittle, and as a result, cracks are likely to occur in the semiconductor device. From the viewpoint of solving such problems, it is preferable to have a polyalkylene oxide in the main skeleton. By using polyalkylene oxide, it is considered that an adhesive composition having a high elastic modulus at 260 ° C. ambient temperature and having reduced brittleness is suppressed, and the occurrence of cracks and the like in the semiconductor device is suppressed.

  The number of carbon atoms in the alkylene group contained in the repeating unit in the polyalkylene oxide is preferably 3 or more and 6 or less. When carbon number is more than the said lower limit, the fall of the water absorption characteristic of hardened | cured material can be suppressed and the adhesiveness required for the reliability in IR reflow process can be maintained. Moreover, the adhesiveness with respect to a metal which can suppress the raise of the hydrophobicity of thermosetting adhesive composition itself by making carbon number below the said upper limit can be obtained.

The thermosetting adhesive composition according to the present invention preferably contains a filler. As a result, adjustment of viscosity and thixotropy, thermal elastic modulus, and the like can be improved, and handling such as application work to a support or a semiconductor element becomes easy.

  The filler can be made of metal powder such as silver, gold, nickel and iron in order to impart conductivity. In order to impart insulating properties, for example, ceramic particles such as silica and alumina, or thermosetting resin or thermoplastic resin particles can be used. The shape of particles generally used as a filler includes various shapes such as a scale, a sphere, a resin, and a powder, but the shape is not particularly limited in the present invention.

  The content of the filler is preferably 60 to 90% by weight, and particularly preferably 70 to 85% by weight, based on the entire thermosetting adhesive composition according to the present invention. By setting the content within the above range, viscosity and thixotropy can be made suitable, and workability can be improved.

  The average particle size of the filler is preferably 1 to 10 μm, particularly preferably 2 to 7 μm. By setting the average particle diameter to be equal to or larger than the lower limit, the viscosity of the adhesive composition can be made suitable. Moreover, the problem at the time of shaping | molding of a nozzle etc. can be reduced by setting it as the said upper limit or less. In addition, the said average particle diameter can be measured using the particle size distribution measuring apparatus which used the laser diffraction / scattering method, for example.

  When the thermosetting adhesive composition according to the present application contains a compound having a radical polymerizable functional group in the thermosetting resin, it is preferable to use a radical initiator in combination.

  Examples of the radical initiator include methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, 1,1-di (tert-hexylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) -2-methyl. Cyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, 2,2-di (tert-butylperoxy) butane, n-butyl-4,4-di (tert-butylperoxy) valerate, 2,2 -Di (4,4-di (tert-butylperoxy) cyclohexane) propane, p-methane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroper Oxide, te t-Butyl hydroperoxide, di (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide , Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne, diisobutyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauryl peroxide Di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicar Nate, di (2-ethylhexyl) peroxydicarbonate, disec-butylperoxydicarbonate, cumylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxyneodecanate, tert-hexylper Oxyneodecanate, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, 2,5-dimethyl-2, 5, -di (2-diethylhexinoylperoxy) hexane, tert-butylperoxy-2-ethylhexanate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy 3,5,5-trimethylhexa Tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyacetonate, tert-peroxy-3-methylbenzoate, tert-butylperoxybenzoate, tert-butylperoxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (tert-butylperoxyacetate) Oxycarbonyl) benzophenone and the like, and a plurality of these may be used as necessary. Of these, those having a decomposition start temperature of 90 to 160 ° C. are preferred from the viewpoint of curability. By setting the decomposition start temperature to be equal to or higher than the lower limit of the range, the storage stability is excellent, and when the decomposition start temperature is lower than the upper limit of the range, the curability is excellent. The decomposition start temperature is determined by differential thermal scanning analysis (DSC). About 1 mg of the initiator is put in a stainless steel sealed container, the sample is heated at a heating rate of 10 ° C./min, and the decomposition start temperature can be measured from the required exothermic peak.

  The thermosetting adhesive composition according to the present application may contain other additives such as a coupling agent, an antifoaming agent, and a surfactant as necessary.

(How to use thermosetting adhesive composition)
The usage method of the thermosetting adhesive composition according to the present invention will be described using specific examples. When the thermosetting adhesive composition according to the present invention is a liquid adhesive, after premixing various components as described above, kneading is performed using three rolls, and further vacuum defoaming is performed, thereby liquid adhesion. An agent can be obtained. The obtained liquid adhesive is dispense-applied to, for example, a predetermined portion of a support (especially a lead frame) using a commercially available die bonder, and then a semiconductor element is mounted and heat-cured. Then, a semiconductor device can be obtained by wire bonding and transfer molding using a sealing resin whose main component is an epoxy resin or the like.

  In addition, it can use similarly to the above about a film adhesive. In this case, for example, after laminating a film adhesive on the support, a semiconductor device can be obtained by the same process.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

Example 1
(Preparation of thermosetting adhesive composition)
As a compound having a functional group capable of radical polymerization, 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., light ester HO-MS), 1,4-cyclohexanedimethanol monoacrylate (Nippon Kasei Chemical Co., Ltd.) , CHDMMA), polyalkylene maleimide acetate (manufactured by Dainippon Ink Industries, Ltd., LumiCure MIA-200), propyl dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 3PG), allyl ester Polyalkylene ester-containing allyl ester (all-ester resin DA101, manufactured by Showa Denko KK) as a system compound, 1,1-di (tert-butylperoxy) cyclohexane (manufactured by NOF Corporation, Perhexa CS as a radical initiator) ), Average grain as filler Flaky silver powder having a particle diameter of 3 μm and a maximum particle size of 20 μm, and γ-glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E) and tetrasulfide ditriethoxysilane (manufactured by Daiso Corporation, CABRUS4) as additives. It mix | blended with the mixing ratio of Table 1, mixed by 3 rolls, and also vacuum-defoamed, and obtained the thermosetting adhesive composition.

(Example 1 Adhesive strength)
About the obtained thermosetting adhesive composition, the adhesive strength in a 250 degreeC environment was measured after hardening by 175 degreeC 30 minute hardening conditions by making a support body into a copper frame according to the following measuring method of adhesive strength. The result was 62N.

(Example 1 Warpage evaluation)
The copper frame and the silicon chip were cured and bonded using the adhesive composition of Example 1, and the warpage amount 1 was measured. After measuring the amount of warpage 1, the amount of warpage 2 was measured by heating at 175 ° C. for 4 hours. The amount of warpage 1 is 3.4 μm. Warpage 2 was 5.6 μm. The value of conditional expression A2 (ratio of warpage 1 / warpage 2) was 0.61.

(Manufacture of semiconductor devices)
As a support, a semiconductor element (5 × 5 mm, thickness 350 μm) having a SiN layer on the surface of a copper frame (die pad size: 8 × 8 mm, thickness 160 μm) whose silver plate is plated on the die attach portion as a support is the thermosetting of Example 1. It arrange | positioned through adhesive composition, and it heat-cured in oven on the conditions of 175 degreeC and 30 minutes, and was adhere | attached. Next, sealing is performed using an epoxy resin composition for semiconductor sealing (manufactured by Sumitomo Bakelite Co., EME-G700), and then heating is performed at 175 ° C. for 4 hours to form a semiconductor device (80 p MQFP, size 14 × 20 mm). , Thickness 2 mm). In addition, the semiconductor device was obtained by the same method also about the adhesive composition which concerns on Examples 2 thru | or 4 and Comparative Examples 1 thru | or 4 below.

(Example 2)
The same procedure as in Example 1 was performed except that a thermosetting adhesive composition having the following composition was used. As a compound having a functional group capable of radical polymerization, UM-90 (1/1) DA (manufactured by Ube Industries, Ltd., 1,6-hexanediol / 1,4-dimethanolcyclohexane (= 1/1) and dimethyl carbonate Synthesized polycarbonate diol (polycarbonate diacrylate in which an acroyl group is introduced into a molecular weight of about 900), 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., light ester HO-MS), 1,4-cyclohexanedi Methanol monoacrylate (manufactured by Nippon Kasei Chemical Co., Ltd., CHDMMA), propyl dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 3PG), 1,1-di (tert-butylperoxy) cyclohexane (Japan) as radical initiator Fat and oil Co., Ltd., Perhexa CS), average grain as filler Flaky silver powder having a particle diameter of 3 μm and a maximum particle size of 20 μm, and γ-glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E) and tetrasulfide ditriethoxysilane (manufactured by Daiso Corporation, CABRUS4) as additives. Formulated as shown in Table 1.

(Example 2 adhesive strength)
The adhesive strength of the obtained adhesive was measured in the same manner as in Example 1. The result was 65N.

(Example 2 warpage evaluation)
As a result of warpage measured by the same method as in Example 1, warpage amount 1 was 3.8 μm and warpage amount 2 was 6.1 μm. The value of conditional expression A2 (ratio of warp 1 / warp 2) was 0.62.

(Examples 3 and 4)
The same procedure as in Example 1 was carried out except that the resin composition constituting the adhesive was as follows. Polyalkylene ester-containing allyl ester as an allyl ester compound as a compound having a functional group capable of radical polymerization (Showa Denko Co., Ltd., allyl ester resin DA101), propyl dimethacrylate (Kyoeisha Chemical Co., Ltd., light ester 3PG) 1,1-di (tert-butylperoxy) cyclohexane (manufactured by NOF Corporation, Perhexa CS) as a radical initiator, and diglycidyl bisphenol F (Nippon Kayaku Co., Ltd.) as an epoxy resin as a resin that does not undergo radical polymerization Manufactured by RE-303S), bisphenol F (Dainippon Ink Industries Co., Ltd., DIC-BPF), dicyandiamide (EH3636AS manufactured by Asahi Denka Co., Ltd.) as a curing agent for the above thermosetting resin, and 2- Phenyl-4-methyl-5-hydroxymethyl Imidazole (Cureazole 2P4MHZ: manufactured by Shikoku Kasei Kogyo Co., Ltd.), flake silver powder as filler, γ-glycidylpropyltrimethoxysilane (KBS-403E manufactured by Shin-Etsu Chemical Co., Ltd.) and tetrasulfide ditriethoxysilane as additives (Daiso Co., Ltd., CABRUS4) was blended as shown in Table 1, kneaded using three rolls, and defoamed to obtain a resin composition.

(Example 3 Adhesive strength)
The adhesive strength was measured in the same manner as in Example 1. The result was 43N.

(Example 3 Warpage evaluation)
As a result of warping measured by the same method as in Example 1, warp amount 1 was 1.6 μm and warp amount 2 was 3.0 μm. The value of conditional expression A2 (ratio of warpage 1 / warpage 2) was 0.54.

(Example 4 adhesive strength)
The adhesive strength measured by the same method as in Example 1 was 52N.

(Example 4 Warpage evaluation)
As a result of warping measured by the same method as in Example 1, the warpage amount 1 was 2.8 μm, and the warpage amount 2 was 3.9 μm. The value of conditional expression A2 (ratio of warp 1 / warp 2) was 0.72.

(Example 5)
The composition of the resin composition constituting the adhesive was as follows, and the production method was the same as in Example 1. As a compound having a functional group capable of radical polymerization, UM-90 (1/1) DA (manufactured by Ube Industries, Ltd., 1,6-hexanediol / 1,4-dimethanolcyclohexane (= 1/1) and dimethyl carbonate Synthesized polycarbonate diol (polycarbonate diacrylate with an acroyl group introduced into the molecular weight of about 900), 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Kasei Chemical Co., Ltd., CHDMMA), propyl dimethacrylate (Kyoeisha Chemical Co., Ltd.) Made of light ester 3PG), polyalkylenemaleimide acetate as a compound having a maleimide ring (Dainippon Ink Industries, Ltd., LumiCure MIA-200), 1,4 vinyl bond as a butadiene compound polymer or copolymer 72% polybutadiene and none Maleic anhydride-modified polybutadiene obtained by reaction with maleic acid (number average molecular weight 3100, acid value 74 meq KOH / g, manufactured by Satomer, Ricobond 1731), 1,1-di (tert-butylperoxy) cyclohexane (as radical initiator) Nippon Oil & Fats Co., Ltd., Perhexa CS), flaky silver powder having an average particle size of 3 μm and a maximum particle size of 20 μm as a filler, and γ-glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E) as an additive ), Tetrasulfide ditriethoxysilane (Daiso Co., Ltd., CABRUS4) was blended as shown in Table 1.

(Example 5 adhesive strength)
The adhesive strength of the adhesive composition of Example 5 was measured by the following adhesive strength measurement method. The support was a glass-epoxy laminate (FR-4, glass cloth two layers, surface solar ink PSR-4000AUS308, glass transition temperature 120- 140 ° C.). The result was 56N.

(Example 5: Warpage evaluation)
A silicon chip is cured via the thermosetting adhesive composition of Example 5 on a glass-epoxy laminate (FR-4, glass cloth 2 layers, surface solar ink PSR-4000AUS308, glass transition temperature 120-140 ° C.). The amount of warpage 3 was measured after bonding. After measurement of the amount of warpage 3, the amount of warpage 4 was measured after post mold cure heating at 175 ° C. for 4 hours. The amount of warpage 3 was 39 μm. The amount of warpage 4 was 75 μm. The value of conditional expression B2 (ratio of warpage 3 / warpage 4) was 0.52.

(Manufacture of semiconductor devices)
Using the adhesive composition of Example 5, a BT substrate having a thickness of 0.3 mm is used as a support, and a silicon chip (7 × 7 mm, thickness 0.35 mm) is disposed. After that, using an epoxy resin composition for semiconductor encapsulation (EME-G760, manufactured by Sumitomo Bakelite Co., Ltd.), it is sealed in a 5.5 × 6.6 × 1.0 mm panel shape, and then subjected to post mold cure at 175 ° C. for 4 hours. Pass IR reflow once without water absorption. After that, a semiconductor device (MAPBGA) was obtained by dividing into pieces with a body size: 10 × 12 mm using a dicing saw.

(Comparative Example 1)
The same procedure as in Example 1 was carried out except that the resin composition constituting the adhesive was as follows. Diglycidyl bisphenol F (manufactured by Nippon Kayaku Co., Ltd., RE-303S), cresyl gresidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., CGE), a compound having no functional group capable of radical polymerization, Bisphenol F (manufactured by Dainippon Ink Industries, Ltd., DIC-BPF), dicyandiamide (Asahi Denka Co., Ltd., EH3636AS) as a curing agent, 2-phenyl-4-methyl-5-hydroxymethylimidazole (as a curing accelerator) Curesol 2P4MHZ: Shikoku Kasei Kogyo Co., Ltd., flaky silver powder as filler, γ-glycidylpropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403E) and tetrasulfide ditriethoxysilane (Daiso) 3 manufactured by CABRUS4) as shown in Table 1 It was kneaded with Lumpur, to obtain a resin composition by degassing.

(Comparative Example 1 Adhesive strength)
The adhesive strength of the adhesive composition of Comparative Example 1 was measured in the same manner as in Example 1. The result was 44N.

(Comparative Example 1 Warpage Evaluation)
The warpage of the adhesive composition of Comparative Example 1 was measured in the same manner as in Example 1. As a result, the warpage amount 1 was 2.0 μm, and the warpage amount 2 was 2.1 μm. The value of conditional expression A2 (the ratio of warpage 1 / warpage 2) was 0.95.

(Comparative Example 2)
The same procedure as in Example 1 was carried out except that the resin composition constituting the adhesive was as follows. Diglycidyl bisphenol F (manufactured by Nippon Kayaku Co., Ltd., RE-303S), cresyl glycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., CGE) as a compound having no radical polymerizable functional group, curing of the above thermosetting resin Aromatic amine (manufactured by Nippon Kayaku Co., Ltd., Kayahard A-A) as an agent, thiazole compound (manufactured by Ouchi Shinsei Kagaku Kogyo Co., Noxeller DM) as a curing accelerator, and flaky silver powder as shown in Table 1 Thus, it knead | mixed using 3 rolls and deaerated, and the resin composition was obtained.

(Comparative Example 2 Adhesive Strength)
The adhesive strength of the adhesive composition of Comparative Example 2 was measured by the same method as in Example 1. The result was 25N.

(Comparative Example 2 Warpage Evaluation)
The warpage of the adhesive composition of Comparative Example 2 was measured in the same manner as in Example 1. As a result, the warpage amount 1 was 1.6 μm and the warpage amount 2 was 1.7 μm. The value of conditional expression A2 (the ratio of warpage 1 / warpage 2) was 0.94.

(Comparative Example 3)
The same procedure as in Example 1 was carried out except that the resin composition constituting the adhesive was as follows. Diglycidyl bisphenol F (manufactured by Nippon Kayaku Co., Ltd., RE-303S), cresyl gresidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., CGE), a compound having no functional group capable of radical polymerization, A phenol compound (Maywa Kasei Co., Ltd., MEH-8010), dicyandiamide (Asahi Denka Co., Ltd., EH3636AS) as a curing agent, and flaky silver powder as a filler are blended as shown in Table 1, and three rolls are combined. The resin composition was obtained by kneading and defoaming. Comparative Example 3 corresponds to Example 1 described in Patent Document 1 (Japanese Patent Laid-Open No. 2002-212267).

(Comparative Example 3 Adhesive Strength)
The adhesive strength of the adhesive composition of Comparative Example 3 was measured in the same manner as in Example 1. The result was 45N.

(Comparative Example 3 Warpage Evaluation)
The warpage of the adhesive composition of Comparative Example 3 was measured in the same manner as in Example 1. As a result, the warpage amount 1 was 1.6 μm and the warpage amount 2 was 1.8 μm. The value of conditional expression A2 (ratio of warpage 1 / warpage 2) was 0.89.

(Comparative Example 4)
As a compound having a functional group capable of radical polymerization, 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., light ester HO-MS), 1,4-cyclohexanedimethanol monoacrylate (Nippon Kasei Chemical Co., Ltd.) , CHDMMA), polyalkylene maleimide acetate (manufactured by Dainippon Ink Industries, Ltd., LumiCure MIA-200), propyl dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 3PG), allyl ester Polyalkylene ester-containing allyl ester (all-ester resin DA101 manufactured by Showa Denko KK) as a base compound, flaky silver powder as a filler, and γ-glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) as an additive -403E) and Las sulfide blunder triethoxysilane (Daiso Co., CABRUS4) were compounded in the mixing ratio described in Table 1, were mixed by three rolls were further degassed to obtain a thermosetting adhesive composition.

(Comparative Example 4 Adhesive Strength)
The adhesive strength of the adhesive composition of Comparative Example 4 was measured in the same manner as in Example 1. The result was 13N.

(Comparative Example 4 Warpage Evaluation)
The warpage of the adhesive composition of Comparative Example 4 was measured in the same manner as in Example 1. As a result, the warpage amount 1 was 1.2 μm and the warpage amount 2 was 5.6 μm. The value of conditional expression A2 (ratio of warpage 1 / warpage 2) was 0.21.

(Measurement method of adhesive strength)
Details of the method for measuring the adhesive strength measured in each experimental example are as follows. A 5 × 5 mm silicon chip is mounted on the AUS using a silver-plated copper lead frame or glass / epoxy laminate as a support for the die attach part, and the lead frame in an oven set at a surface temperature of 175 ° C. It was cured by heating for 30 minutes when used and 15 minutes when using the substrate. Immediately after curing, the die shear strength during heating at 250 ° C. was measured (unit: N / chip). The measurement value at this time was 40 N / chip or more and was deemed acceptable.

  The following solder crack resistance was evaluated for the semiconductor devices obtained using the adhesive compositions of the examples and comparative examples. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.

(Solder crack resistance)
For each of the examples and comparative examples, the semiconductor device manufactured above was subjected to moisture absorption treatment for 168 hours at 85 ° C. and a relative humidity of 60%, and then IR reflow treatment (260 ° C., 10 seconds, 3 times reflow). The package after the treatment was measured for the degree of peeling with an ultrasonic deep wound device (transmission type). Each code is as follows.
○: No peeling of the semiconductor element inside the semiconductor device occurred.
X: Peeling of the semiconductor device inside the semiconductor device occurred.

  In Examples 1 to 5, the warpage amount in the warpage evaluation test satisfies a predetermined conditional expression, and the semiconductor element was not peeled even when the IR reflow process was performed after the semiconductor device was manufactured. On the other hand, the comparative examples did not satisfy the conditional expression of the warp amount, and all the semiconductor elements were peeled off.

  When the thermosetting adhesive composition obtained by the present invention is used, a semiconductor device having excellent solder crack resistance can be obtained even under a high temperature environment such as IR reflow treatment.

DESCRIPTION OF SYMBOLS 1 ... Test semiconductor device 2 ... Hardened layer 3 of thermosetting adhesive composition ... Support body 4 ... Silicon chip

Claims (11)

A thermosetting adhesive composition for bonding a metal support and a semiconductor element used in a semiconductor device sealed with a sealing resin,
The thermosetting adhesive composition contains a filler, and a compound having a radical polymerizable functional group, a radical initiator,
The filler content is 60 to 90% by weight of the entire thermosetting adhesive composition,
The content of the compound having a functional group capable of radical polymerization is 11.4 to 23.9 % by weight of the entire thermosetting adhesive composition,
2.4 / 23.9 % × 100% by weight or more of the compound having a functional group capable of radical polymerization is a compound having two or more (meth) acryloyl groups in one molecule,
The content of the radical initiator is such that the weight ratio of the radical initiator / radical polymerizable compound having a functional group satisfies 0.2 / 14.9 to 0.2 / 11.4,
A thermosetting adhesive composition in which the warpage amount 1 and the warpage amount 2 in the following warpage evaluation test A satisfy the conditional expressions A1 and A2.
[Warpage evaluation test A: Silicon chip (size: 5 × 5 mm, thickness: 350 μm) on a support (copper made by silver plating on the joint with the silicon chip, size: 8.5 × 8.5 mm, thickness: 160 μm) It arrange | positions through the said applied thermosetting adhesive composition, the said thermosetting adhesive composition is hardened by 175 degreeC for 30 minutes, and the said silicon chip and the said support body are adhere | attached (thermosetting adhesion) Cured layer thickness of the agent composition: 20 μm or more and 30 μm or less), the warpage amount of the silicon chip after bonding is defined as a warpage amount 1. Further, the warpage amount of the silicon chip after heat treatment is performed at 175 ° C. for 4 hours after the warpage amount 1 is measured is defined as a warpage amount 2.
Warpage amount: The difference in height between the end portion of the silicon chip and the highest portion of the silicon chip is defined as the warpage amount.
Conditional expression A1: 0.1 ≦ warping amount 1 ≦ 20 (μm), 0.1 ≦ warping amount 2 ≦ 20 (μm)
Conditional expression A2: 0.1 ≦ warping amount 1 / warping amount 2 ≦ 0.8]   The thermosetting adhesive according to claim 1, comprising a compound having an unsaturated carbon-carbon bond other than a compound containing two or more (meth) acryloyl groups as the compound having a functional group capable of radical polymerization. Agent composition.   The thermosetting according to claim 2, wherein the compound having an unsaturated carbon-carbon bond other than the compound containing two or more (meth) acryloyl groups is a compound having one (meth) acryloyl group in one molecule. Adhesive composition. The thermosetting adhesive composition according to claim 2, wherein the compound having an unsaturated carbon-carbon bond other than the compound containing two or more (meth) acryloyl groups is a compound having a maleimide ring.   The thermosetting adhesive composition according to claim 4, wherein the compound having a maleimide ring is a bismaleimide compound having no aromatic ring.   The thermosetting adhesive composition according to claim 2, wherein the compound having an unsaturated carbon-carbon bond other than the (meth) acryloyl group is a polymer or copolymer of a butadiene compound.   The thermosetting adhesive composition according to claim 6, which has at least one functional group in a molecule of the polymer or copolymer of the butadiene compound.   The thermosetting according to claim 7, wherein the functional group of the polymer or copolymer of the butadiene compound is at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a carboxy group, a hydroxyl group, and a maleic acid group. Adhesive composition.   A compound having an unsaturated carbon-carbon bond other than a compound containing two or more (meth) acryloyl groups, a compound having one (meth) acryloyl group in the molecule, a compound having a maleimide ring, a butadiene compound and allyl The thermosetting adhesive composition according to claim 2, comprising at least two compounds selected from the group consisting of ester compounds.   The thermosetting adhesive composition according to claim 9, wherein the allyl ester compound is an allyl ester compound having no aromatic ring.   It is a semiconductor device which has a semiconductor element, a metal support body, and the thermosetting layer which adhere | attaches them, Comprising: The said thermosetting layer consists of a thermosetting adhesive composition of any one of Claims 1 thru | or 10. Semiconductor device.