JP2003147299A - Adhesive sheet, semiconductor device and method of manufacturing the same - Google Patents

Abstract

(57) [Problem] To provide an adhesive sheet which functions as a dicing tape in a dicing step and which functions as an adhesive sheet having excellent connection reliability in a bonding step between a semiconductor element and a support member. A thermopolymerizable and radiation-polymerizable adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive layer comprises (A) an epoxy resin and an epoxy resin curing agent; B) The weight average molecular weight containing the functional monomer is 10
The base material layer has a surface tension of more than 40 mN / cm; and an interface between the adhesive layer and the base material layer. Is 200 mN / cm before irradiation.
An adhesive sheet characterized by the above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet, a semiconductor device using the same, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, silver paste has been mainly used for joining a semiconductor element and a semiconductor element mounting support member.
However, with the recent miniaturization and high performance of semiconductor elements, the supporting members used are also required to be miniaturized and made finer. Occurrence of defects during wire bonding due to, difficulty in controlling the thickness of the adhesive layer,
Also, it has become difficult to meet the above requirements due to the occurrence of voids in the adhesive layer. Therefore, in recent years, a film adhesive has been used.

This film-like adhesive is roughly classified into an individual sticking method and a wafer back surface sticking method, depending on the method of use. Here, in order to clarify the difference between the two, the respective usages in manufacturing a semiconductor device will be outlined as an example.

In order to manufacture a semiconductor device by using the former individual film sticking type film adhesive, a reel-shaped adhesive film is cut out into individual pieces by cutting or punching, and then the individual pieces are adhered to a supporting member. Then, the semiconductor element separated into pieces by the dicing step is joined to the supporting member with the film adhesive to produce a supporting member with a semiconductor element; thereafter, a wire bonding step, a sealing step, etc. are carried out if necessary. As a result, a semiconductor device can be obtained.

However, in order to use the film adhesive of the individual sticking type, a dedicated assembling device for cutting out the adhesive film and adhering it to the supporting member is required.
There is a problem that the manufacturing cost is higher than that of the method using the silver paste.

On the other hand, in the latter case, in order to manufacture a semiconductor device by using a film adhesive of the wafer back surface sticking system, first, the film adhesive is stuck to the back surface of the semiconductor wafer, and then the dicing is applied to the other surface of the film adhesive. Then, a tape is attached; thereafter, the semiconductor element is diced from the wafer by dicing; the diced semiconductor element with a film adhesive is picked up and joined to a supporting member;
The semiconductor device can be obtained by subsequent steps such as heating, curing, and wire bonding.

[0007] This wafer backside sticking type film adhesive does not require a device for separating the film adhesive into pieces because it bonds the semiconductor element with the film adhesive to the supporting member, and is used for conventional silver pastes. As-is assembly device
Alternatively, since it can be used by improving a part of the device such as adding a heating plate, it is attracting attention as a method that can suppress the manufacturing cost relatively low among the assembling methods using the film adhesive.

The dicing tape used with this wafer back surface pasting type film adhesive is a pressure sensitive type or U type.
Broadly divided into V-type dicing tape.

The former pressure-sensitive dicing tape is usually
It is an adhesive coated on a polyvinyl chloride-based or polyolefin-based base film. This dicing tape is required to have sufficient adhesive force so that each element does not scatter due to rotation by the dicing saw when cutting in the dicing process, and when picking up, no adhesive is attached to each element and the element is not damaged. In order to achieve this, it is necessary to have a low adhesive strength that allows pickup.

However, since there is no pressure-sensitive dicing tape having the two contradictory performances as described above, the work of switching the dicing tape is performed in each process. In addition, inventory management of adhesive sheets has become complicated because a wide variety of dicing tapes having various adhesive strengths suited to the size of elements and processing conditions are required.

Furthermore, in recent years, especially as the capacity of CPUs and memories has increased, semiconductor elements have tended to increase in size.
Further, in products such as IC cards and memory cards, the memory used is becoming thinner. With the increase in size and thickness of these semiconductor elements, the pressure-sensitive dicing tape has a fixing force (high adhesive force) during dicing.
It is becoming difficult to satisfy the contradictory requirements of peeling strength (low adhesive strength) during pickup.

On the other hand, the UV type dicing tape has a high adhesive force at the time of dicing, but it has a low adhesive force by being irradiated with ultraviolet rays (UV) before being picked up.

Therefore, the problems of the pressure-sensitive tape have been improved, and it has been widely adopted as a dicing tape.

[0014]

However, although the problem of the pressure-sensitive dicing tape is improved by using the UV-type dicing tape, there remains a problem to be further improved in the film-like adhesive of the wafer back surface sticking system. It had been.

That is, in the method of using the film-like adhesive of the wafer back surface sticking system, two sticking steps such as sticking the film-like adhesive and the dicing tape are required before the dicing step. There was a problem that the work became complicated. Therefore, simplification of the working process has been demanded.

In view of the above-mentioned problems of the prior art, the present invention provides an adhesive sheet which acts as a dicing tape in the dicing step and acts as an adhesive sheet having excellent connection reliability in the step of joining a semiconductor element and a supporting member. The purpose is to Further, the present invention provides an adhesive sheet having heat resistance and moisture resistance required when mounting a semiconductor element having a large difference in thermal expansion coefficient on a semiconductor element mounting support member, and having excellent workability. With the goal. It is another object of the present invention to provide a method for manufacturing a semiconductor device that can simplify the manufacturing process.

[0017]

The present invention relates to the following inventions. <1> A heat-polymerizable and radiation-polymerizable adhesive sheet comprising a tacky adhesive layer and a base material layer, wherein the tacky adhesive layer comprises (A) an epoxy resin and an epoxy resin curing agent,
(B) a high molecular weight component having a weight average molecular weight of 100,000 or more including a functional monomer, and (C) a radiation-polymerizable compound, wherein the substrate layer has a surface tension of more than 40 mN / m, An adhesive sheet, characterized in that the adhesive strength at the interface between the adhesive layer and the substrate layer before irradiation with radiation is 200 mN / cm or more.

<2> In the adhesive sheet, the adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) at the interface between the adhesive layer and the base material layer before and after irradiation with radiation is 0.5 or less. > Adhesive sheet described.

<3> In the adhesive sheet, the difference in adhesive strength (adhesive strength before irradiation-adhesive strength after irradiation) at the adhesive / adhesive layer / base material layer interface before and after irradiation with radiation is 100 mN / cm or more. > Adhesive sheet described.

<4> Epoxy group-containing (meth) containing 0.5 to 6 wt% of epoxy group-containing repeating units in the high-molecular-weight component having a weight average molecular weight of 100,000 or more containing the (B) functional monomer. <1> which is an acrylic copolymer
~ The adhesive sheet according to any one of <3>.

<5> The adhesive layer comprises 100 parts by weight of the epoxy resin (A) and an epoxy resin curing agent,
The weight average molecular weight including the functional monomer (B) is 10
The adhesive sheet according to any one of <1> to <4>, which contains 10 to 400 parts by weight of a high molecular weight component of 10,000 or more and 5 to 400 parts by weight of the radiation-curable compound (C).

<6> The adhesive layer is 10 at 25 ° C.
<2000> and <1> to <5> having a storage elastic modulus after heat curing of 3 to 50 MPa at 260 ° C.
The adhesive sheet according to any one of 1.

<7> The adhesive sheet according to any one of <1> to <6>, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiating radiation. .

<8> The adhesive strength after irradiation with radiation is 100
The adhesive sheet according to <1> to <7>, which has an mN / cm or less.

<9> A semiconductor device in which a semiconductor element and a semiconductor mounting support member are bonded to each other using the adhesive sheet according to any one of <1> to <8>.

<10> (a) An adhesive sheet comprising the adhesive layer according to any one of <1> to <8> and a base material layer is sandwiched between the adhesive layers. And a step of obtaining a semiconductor wafer with an adhesive sheet by providing the semiconductor wafer with an adhesive sheet on the semiconductor wafer, and (b) a step of dicing the semiconductor wafer with an adhesive sheet to obtain a semiconductor element with an adhesive sheet, (c)
A step of irradiating the adhesive sheet with radiation to reduce the adhesive force of the adhesive layer to the base layer, and peeling the base layer to obtain a semiconductor element with an adhesive layer; d)
And a step of adhering the semiconductor element with the adhesive layer and the supporting member for mounting the semiconductor element via the pressure-sensitive adhesive layer.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION First, the adhesive sheet of the present invention will be described. As a preferred embodiment, the adhesive sheet of the present invention has a weight average molecular weight of 1 including (A) epoxy resin and epoxy resin curing agent, and (B) functional monomer.
A tacky adhesive layer containing a high molecular weight component of at least 0,000 and (C) a radiation-polymerizable compound, and a surface tension of 40 mN / m
And a base material layer exceeding. This makes it possible to obtain an adhesive sheet having both heat-polymerizable and radiation-polymerizable properties.

The adhesive sheet of the present invention has a sufficient adhesive force so that the semiconductor element does not scatter during dicing, and then is irradiated with radiation to control the adhesive force between the adhesive layer and the base material layer. By satisfying the conflicting requirements of having a low adhesive strength so as not to damage each element at the time of pickup, each process of dicing and die bonding can be completed with one film. . The adhesive force during dicing (before radiation irradiation) is
For example, after the adhesive sheet is pressure-bonded to a semiconductor wafer to be diced at room temperature or while heating, only the base material layer is stretched at a pulling angle of 90 ° and a pulling speed of 50 m.
The peeling force (adhesive strength) when pulled at m / min is 300 mN / cm or more, more preferably 350 mN / cm or more, and further preferably 400 mN / cm or more. If this value is less than 300 mN / cm, the semiconductor element may scatter during dicing.

In the present invention, the adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) due to the 90 ° peeling force at the interface between the adhesive layer / base material layer before and after irradiation with radiation is 0.5.
Or less, more preferably 0.4 or less,
It is more preferably 0.3 or less. If this value is 0.
If it is larger than 5, each element tends to be damaged during pickup. On the other hand, the adhesive strength ratio (adhesive strength after irradiation /
The lower limit of (adhesion strength before irradiation) is not particularly limited, but from the viewpoint of workability, it is preferably 0.0001 or more.

In the present invention, the difference in adhesive strength (adhesive strength before irradiation-adhesive strength after irradiation) due to the 90 ° peeling force at the interface between the adhesive layer and the base material layer before and after irradiation with radiation is 20.
It is 0 mN / cm or more, more preferably 250 mN / cm or more, and further preferably 300 mN / cm. If this value is less than 200 mN / cm, each element tends to be damaged during pickup.

The (A) epoxy resin used in the present invention is
There is no particular limitation as long as it is cured and has an adhesive action. A bifunctional epoxy resin such as bisphenol A type epoxy, a novolac type epoxy resin such as a phenol novolac type epoxy resin or a cresol novolac type epoxy resin can be used. Further, generally known ones such as polyfunctional epoxy resin, glycidylamine type epoxy resin, heterocycle-containing epoxy resin or alicyclic epoxy resin can be applied.

As such an epoxy resin, a bisphenol A type epoxy resin is available from Yuka Shell Epoxy Co., Ltd., Epicoat 807, 815, 825, 82.
7,828,834,1001,1004,1007,
1009, Dow Chemical Co., DER-330, 30
1,361, Toto Kasei Co., Ltd., YD8125, YDF
8170 and the like. Examples of the phenol novolac type epoxy resin include Yuka Shell Epoxy Co., Ltd., Epicoat 152 and 154, Nippon Kayaku Co., Ltd., EPPN.
-201, Dow Chemical Co., DEN-438, etc.
In addition, as the o-cresol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EOCN-102S, 103.
S, 104S, 1012, 1025, 1027, manufactured by Tohto Kasei Co., Ltd., YDCN701, 702, 703, 704
And so on. As the polyfunctional epoxy resin, Yuka Shell Epoxy Co., Ltd., Epon 1031S, Ciba Specialty Chemicals, Araldite 016
3, Nagase Kasei Co., Ltd., Denacol EX-611,6
14,614B, 622,512,521,421,4
11, 321 and the like. The amine type epoxy resin is manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 6
04, Tohto Kasei Co., Ltd., YH-434, Mitsubishi Gas Chemical Co., Inc., TETRAD-X, TETRAD-C, Sumitomo Chemical Co., Ltd., ELM-120. Examples of the heterocycle-containing epoxy resin include ERL4234, 4299, 4221, 4206 manufactured by UCC, such as Araldite PT810 manufactured by Ciba Specialty Chemicals. These epoxy resins can be used alone or in combination of two or more.

As the epoxy resin curing agent (A) used in the present invention, a commonly used known curing agent can be used. For example, bisphenols having two or more phenolic hydroxyl groups in one molecule such as amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F and bisphenol S, phenol novolac resins, bisphenol A. Examples thereof include phenolic resins such as novolac resins and cresol novolac resins. Particularly, a phenol resin such as a phenol novolac resin, a bisphenol A novolac resin, or a cresol novolac resin is preferable because it has excellent electrolytic corrosion resistance when absorbing moisture.

As a preferable phenol resin curing agent,
For example, manufactured by Dainippon Ink and Chemicals, Inc., trade names: Phenolite LF2882, Phenolite LF2822,
Phenolite TD-2090, Phenolite TD-21
49, Phenolite VH-4150, Phenolite VH
4170 and the like.

The high molecular weight component having a weight average molecular weight of 100,000 or more containing the functional monomer (B) used in the present invention contains a functional monomer such as glycidyl acrylate or glycidyl methacrylate and has a weight average molecular weight of An epoxy group-containing (meth) acrylic copolymer having a molecular weight of 100,000 or more is preferable, and it is preferable that it is incompatible with the epoxy resin.

As the epoxy group-containing (meth) acrylic copolymer, for example, (meth) acrylic ester copolymer, acrylic rubber and the like can be used, and acrylic rubber is more preferable. Acrylic rubber is a rubber containing acrylic acid ester as a main component and mainly composed of a copolymer such as butyl acrylate and acrylonitrile, or a copolymer such as ethyl acrylate and acrylonitrile.

In the present invention, the functional monomer means a monomer having a functional group. As the functional group,
Examples thereof include a glycidyl group, an acryloyl group, a methacryloyl group, a hydroxyl group and a carboxyl group.

It is preferable to use glycidyl acrylate or glycidyl methacrylate as the functional monomer. As such an epoxy group-containing (meth) acrylic copolymer having a weight average molecular weight of 100,000 or more, for example, HTR-8 manufactured by Teikoku Chemical Industry Co., Ltd.
60P-3 and the like.

The amount of the epoxy resin-containing repeating unit such as glycidyl acrylate or glycidyl methacrylate is preferably 0.5 to 6.0% by weight, and 0.5 to 5.0% by weight.
Weight% is more preferable, and 0.8 to 5.0 weight% is particularly preferable. When the amount of the epoxy group-containing repeating unit is within this range, the adhesive force can be secured and gelation can be prevented.

Examples of the functional monomer include glycidyl acrylate and glycidyl methacrylate as well as ethyl (meth) acrylate and butyl (meth) acrylate. These are used alone or in combination of two or more kinds. You can also In addition, in this invention, ethyl (meth) acrylate shows both ethyl acrylate and ethyl methacrylate.
The mixing ratio when the functional monomers are used in combination is determined in consideration of the glass transition temperature (hereinafter referred to as “Tg”) of the epoxy group-containing (meth) acrylic copolymer,
It is preferable that g is -10 ° C or higher. Tg is -10
This is because when the temperature is not lower than 0 ° C, the tackiness of the adhesive layer in the B-stage state is appropriate and the handling property does not occur.

When a high molecular weight component containing a functional monomer (B) and having a weight average molecular weight of 100,000 or more is produced by polymerizing the above monomers, the polymerization method is not particularly limited. For example, pearl polymerization, A method such as solution polymerization can be used.

In the present invention, the weight average molecular weight of the high molecular weight component containing the (B) functional monomer is 100,000 or more, preferably 300,000 to 3,000,000, and preferably 500,000 to 2,000,000. Is more preferable. When the weight average molecular weight is within this range, the strength, flexibility and tackiness when formed into a sheet or film are appropriate,
Further, since the flow property is appropriate, the circuit filling property of the wiring can be secured. In addition, in this invention, a weight average molecular weight shows the value measured by gel permeation chromatography and converted using the standard polystyrene calibration curve.

The amount of the high molecular weight component (B) containing a functional monomer and having a weight average molecular weight of 100,000 or more is
10 to 400 parts by weight is preferable with respect to 100 parts by weight of the epoxy resin and the epoxy resin curing agent (A). Within this range, it is possible to secure the elastic modulus and the suppression of the flowability during molding, and it is possible to obtain sufficient handleability at high temperatures. The amount of the high molecular weight component used is more preferably 15 to 350 parts by weight, and particularly preferably 20 to 300 parts by weight.

The radiation-polymerizable compound (C) used in the present invention is not particularly limited, and examples thereof include methyl acrylate and
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, tri Ethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate ,
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2
-Hydroxypropane, methylenebisacrylamide,
N, N-dimethylacrylamide, N-methylolacrylamide, triacrylate of tris (β-hydroxyethyl) isocyanurate, the following general formula (I)

[Chemical 1] (Wherein, R ₁ and R ₂ represent hydrogen or a methyl group, and q and r are integers of 1 or more), diols, and general formula (II)

[Chemical 2] (In the formula, n is an integer of 0 to 1 and R ₃ is a divalent or trivalent organic group having 1 to 30 carbon atoms), and the general formula (III)

[Chemical 3] (Wherein, R ₄ is hydrogen or a methyl group, and R ₅ is an ethylene group or a propylene group), a urethane acrylate or urethane methacrylate comprising a compound represented by the general formula (IV)

[Chemical 4] (In the formula, R ₆ represents a divalent organic group having 2 to 30 carbon atoms), and a general formula (V)

[Chemical 5] (Wherein, n is an integer of 0 to 1 and R ₇ is a divalent or trivalent organic group having 1 to 30 carbon atoms), and the general formula (VI).

[Chemical 6] (Wherein, n is an integer of 0 to 1), a urea methacrylate composed of a compound represented by the formula, at least one ethylenically unsaturated group in a vinyl copolymer containing a functional group, an oxirane ring, an isocyanate group, Examples thereof include radiation-polymerizable copolymerization having an ethylenically unsaturated group in the side chain obtained by the addition reaction of a compound having one functional group such as a hydroxyl group and a carboxyl group. These radiation-polymerized compounds can be used alone or in combination of two or more.

A curing accelerator may be added to the adhesive layer forming the adhesive sheet of the present invention. The curing accelerator is not particularly limited and includes imidazoles, dicyandiamide derivative, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, 1,8-diazabicyclo ( 5,4,0) undecene-7-tetraphenylborate and the like can be used. These may be used alone or in combination of two or more.

The amount of the curing accelerator added is 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent.
0.1-5 parts by weight is preferable, and 0.2-3 parts by weight is more preferable. When the amount added is in this range, both curability and storage stability can be achieved.

Further, a photopolymerization initiator which produces free radicals upon irradiation with actinic light can be added to the adhesive layer forming the adhesive sheet of the present invention. Examples of such a photopolymerization initiator include benzophenone, N,
N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,
4'-diaminobenzophenone, 4-methoxy-4'-
Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,
Aromatic ketones such as 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, benzoin ether such as benzoin phenyl ether, benzoin such as methylbenzoin and ethylbenzoin, benzyldimethyl ketal, etc. Benzyl derivative, 2- (o
-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m
-Methoxyphenyl) imidazole dimer, 2- (o-
Fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Body, 2, 4
-Di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl)-
2,4,5-Diphenylimidazole dimers, etc.
-Triarylimidazole dimers, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane, and the like can be used,
These may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is not particularly limited, but is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the radiation-polymerizable compound (C).

The adhesive layer forming the adhesive sheet of the present invention has a storage elastic modulus of 10 to 10 at a temperature of 25 ° C. when it is cured by heating.
It is preferably 2000 MPa and 3 to 50 MPa at 260 ° C. Elastic modulus at 25 ° C is 20 to 190
0 MPa is more preferable, and 50 to 1800 MPa is particularly preferable. The elastic modulus at 260 ° C is 5 to 50MP.
a is more preferable, and 7 to 50 MPa is particularly preferable. When the storage elastic modulus is in this range, the effect of relaxing the thermal stress generated due to the difference in the thermal expansion coefficient between the semiconductor element and the supporting member is maintained, and it is possible to suppress the occurrence of peeling and cracks, and to handle the adhesive. The thickness accuracy of the adhesive layer and the occurrence of reflow cracks can be suppressed. This storage modulus is
For example, a dynamic viscoelasticity measuring device (DVE manufactured by Rheology Co., Ltd.
-V4), applying a tensile load to the cured adhesive,
The measurement can be performed in a temperature dependence measurement mode in which the temperature is measured from −50 ° C. to 300 ° C. under conditions of a frequency of 10 Hz and a heating rate of 5 to 10 ° C./min.

A high molecular weight resin compatible with an epoxy resin may be added to the adhesive layer forming the adhesive sheet of the present invention for the purpose of improving flexibility and reflow crack resistance. As such a high molecular weight resin,
It is not particularly limited, and examples thereof include phenoxy resin, high molecular weight epoxy resin, and ultrahigh molecular weight epoxy resin. These may be used alone or in combination of two or more.

The amount of the high molecular weight resin compatible with the epoxy resin is the same as that of the epoxy resin and the epoxy resin curing agent 1.
It is preferably 40 parts by weight or less with respect to 00 parts by weight. Within this range, the Tg of the epoxy resin layer can be secured.

Further, an inorganic filler is added to the adhesive layer forming the adhesive sheet of the present invention for the purpose of improving its handleability, thermal conductivity, adjusting melt viscosity and imparting thixotropic property. You can also The inorganic filler is not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate,
Examples thereof include calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, crystalline silica, and amorphous silica, and the shape of the filler is not particularly limited. These fillers can be used alone or in combination of two or more.

Among them, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable for improving thermal conductivity. Further, for the purpose of adjusting the melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystallinity Silica, amorphous silica and the like are preferable.

The amount of the inorganic filler used is the adhesive layer 10
1 to 20 parts by weight is preferable with respect to 0 parts by weight. If it is less than 1 part by weight, the effect of addition tends not to be obtained, and if it exceeds 20 parts by weight, problems such as an increase in the storage elastic modulus of the adhesive layer, a decrease in adhesiveness, and a decrease in electrical properties due to void remaining may occur. Tend.

Further, in the adhesive layer forming the adhesive sheet of the present invention, in order to improve interfacial bonding between different materials,
Various coupling agents can also be added. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based coupling agents, and among them, the silane-based coupling agent is preferable because of its high effect.

The silane coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane. , Γ-methacryloxypropylmethyldimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercapto Propyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl-tris (2- (Methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyltrimethoxysilane, 3-4,5-dihydroimidazole-1-
Ile-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethoxysilane, 3-cyanopropyltriethoxysilane, hexamethyl Disilazane, N, O-bis (trimethylsilyl)
Acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichlorosilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyl) Oxyethoxy) silane, methyltri (glycidyloxy) silane,
N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane , Γ−
Chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate,
Methyl silyl triisocyanate, vinyl silyl triisocyanate, phenyl silyl triisocyanate, tetraisocyanate silane, ethoxy silane isocyanate, etc. can be used, and they can be used individually or in combination of 2 or more types.

As the titanium-based coupling agent,
For example, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate,
Isopropyl tridodecyl benzene sulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Titanate, isopropyl tris (n-aminoethyl)
Titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl)
Phosphite titanate, dicumylphenyl oxyacetate titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium Ethyl acetonate, titanium octylene glycolate,
Titanium lactate ammonium salt, titanium lactate,
Titanium lactate ethyl ester, titanium chilliethanol aminate, polyhydroxytitanium stearate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetarapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, cresyl titanate monomer, cresyl titanate polymer, di Isopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolaminotitanate, octyleneglycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer , Tri-n-butoxytitanium monostearate and the like can be used, and can be used alone or in combination of two or more kinds.

As the aluminum-based coupling agent,
For example, ethyl acetoacetate aluminum diisopropylate, aluminum tooth (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum = monoisopropoxy. Aluminum chelate compounds such as monooleoxyethyl acetoacetate, aluminum-di-n-butoxide monoethyl acetoacetate, aluminum-di-iso-propoxide-monoethyl acetoacetate, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate. Rate, aluminum-sec-butyrate, aluminum ethylate and other aluminum alcohol Can be used bets like, alone or in combination of two or more kinds may be used. The amount of the coupling agent used is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent from the viewpoints of the effect, heat resistance and cost.

An ion scavenger may be further added to the adhesive layer forming the adhesive sheet of the present invention in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited, and examples thereof include triazine thiol compounds, bisphenol-based reducing agents, and the like, compounds known as copper damage inhibitors for preventing copper from being ionized and dissolved, and zirconium-based compounds. Inorganic ion adsorbents such as antimony bismuth magnesium aluminum compounds. The amount of the ion scavenger used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent, from the viewpoints of the effect of addition, heat resistance, cost, and the like.

The adhesive sheet of the present invention can be obtained by dissolving or dispersing the composition forming the adhesive sheet in a solvent to form a varnish, applying the varnish on a base film and heating to remove the solvent.

The base material used in the adhesive sheet of the present invention is not particularly limited as long as it has a surface tension of more than 40 mN / m. For example, polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene. Examples thereof include films, polymethylpentene films, plastic films such as polyimide films, and the like.

The substrate used for the adhesive sheet of the present invention has a surface tension of more than 40 mN / m. It is preferably more than 40 mN / m and 80 mN / m or less, and more preferably more than 40 mN / m and 60 mN / m or less. The surface tension of the base material used for the adhesive sheet is 40 mN / m
The adhesive strength between the adhesive sheet and the base material is sufficient when the semiconductor wafer to be subjected to the dicing processing is pressure-bonded to the adhesive sheet, and the interface sheet peels between the adhesive sheet and the base material to perform the dicing process. This is because there is no risk of causing the semiconductor device to fall.

After completion of the dicing step, the adhesive sheet of the present invention is irradiated with radiation such as electron beams (EB) rather than ultraviolet rays (UV) to polymerize and cure the radiation-polymerizable adhesive sheet. The adhesive force at the interface between the base material and the base material is reduced to enable pickup of semiconductor elements. In the case of the conventional adhesive sheet, when the surface tension of the substrate exceeds 40 mN / m, the adhesive strength between the adhesive sheet and the substrate interface is not sufficiently reduced, and the pick-up property tends to be poor. However, even if the surface tension of the base material exceeds 40 mN / m, the adhesive sheet of the present invention has an adhesive force between the adhesive sheet and the base material interface after irradiation with radiation such as ultraviolet rays (UV) or electron beams (EB). It is sufficiently lowered, and the pickup of the semiconductor element becomes good. Therefore, conventionally, the substrate film to be used has been surface-treated so that the surface tension of the substrate is 40 mN / m or less. However, in the adhesive sheet of the present invention, the substrate film needs to be surface-treated. There is also no cost advantage.

The solvent for forming the above varnish is not particularly limited, but in consideration of volatility at the time of film production, for example, methanol, ethanol,
2-methoxyethanol, 2-ethoxyethanol, 2
It is preferred to use relatively low boiling solvents such as butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene. Also,
A solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or cyclohexanone can be used for the purpose of improving the coating property. These solvents can be used alone or in combination of two or more kinds.

In the production of the varnish when the inorganic filler is added, taking into consideration the dispersibility of the inorganic filler, a raisin machine,
It is preferable to use a triple roll, a ball mill, a bead mill, or the like, and these can be used in combination. Further, it is also possible to shorten the mixing time by mixing the inorganic filler and the low molecular weight raw material in advance and then blending the high molecular weight raw material. Also,
After forming the varnish, air bubbles in the varnish can be removed by vacuum deaeration or the like.

As a method for applying the varnish to the substrate film, a known method can be used, for example, knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, curtain coating method and the like. Is mentioned.

The thickness of the adhesive sheet is not particularly limited,
The thickness of both the adhesive layer and the base material layer is preferably 5 to 250 μm.
If it is thinner than 5 μm, the stress relaxation effect tends to be poor, and if it is thicker than 250 μm, it becomes uneconomical and it cannot meet the demand for miniaturization of the semiconductor device.

In the adhesive sheet of the present invention, one or more adhesive layers or adhesive layers are further sandwiched between the semiconductor wafer and the adhesive layer in order to obtain a desired sheet thickness. You may provide like this. In this case, as the adhesive layer provided as desired, those prepared by a conventionally known method can be used in addition to those prepared by the above method. A commercially available adhesive sheet, for example, a polyimide-based adhesive, a silicon oligomer-based adhesive, a rubber-epoxy adhesive, or an epoxy adhesive can be used as the adhesive layer provided as desired. However, it is necessary to consider a bonding condition based on a conventionally known technique so that the adhesive layers are not separated from each other. When the adhesive sheet having the above-described structure is irradiated with radiation, the adhesive force of the adhesive layer to the base material layer is significantly reduced after irradiation with radiation. Therefore, as described later, by using the adhesive sheet of the present invention in the dicing step when manufacturing a semiconductor device, as a result, the adhesive layer and the base material layer are easily separated,
The semiconductor element provided with the adhesive layer can be suitably picked up.

Next, a method of manufacturing a semiconductor device using the adhesive sheet of the present invention will be described as one embodiment of the method of using the adhesive sheet of the present invention. (A) First, a semiconductor wafer to be diced is pressure-bonded on the adhesive sheet at room temperature or while heating to provide the adhesive sheet on the semiconductor wafer. (B) Then, according to a conventionally known technique, dicing of a semiconductor wafer provided with the adhesive sheet on the surface, and washing and drying of a semiconductor element obtained after the dicing are performed. At this time, since the semiconductor wafer (element) is sufficiently adhered and held by the adhesive sheet, the semiconductor element does not scatter or fall off during the above steps.

(C) Next, the adhesive sheet is irradiated with radiation such as ultraviolet rays (UV) or electron beams (EB) to polymerize and cure the adhesive layer of the radiation-polymerizable adhesive sheet. Radiation irradiation to the adhesive sheet is not particularly limited as long as the radiation-polymerizable adhesive sheet is polymerized and cured, and is performed based on a conventional method. At that time, the irradiation of the semiconductor is performed from the viewpoint that the layout of the pickup device can be freely set and the work space can be widened in the subsequent pickup work, or that the adhesive layer of the adhesive sheet is suitably polymerized and cured. It is expedient to irradiate from below the work table on which the wafer is installed, upwards, that is so that the radiation passes through the substrate layer and reaches the adhesive layer. When EB is used as the radiation, the base film of the adhesive sheet does not need to be light transmissive, but when UV is used as the radiation, the base film of the adhesive sheet needs to be light transmissive.

(D) Then, the semiconductor element with the adhesive layer obtained by dicing is picked up, and the semiconductor element provided with the adhesive layer is heated at room temperature or on a supporting member for mounting a semiconductor element. While crimping. At this time, as described above, since the base material layer is easily peeled off due to the large decrease in the adhesive strength of the adhesive / bonding agent layer to the base material layer after irradiation with radiation, the adhesive / sticker layer is attached. A semiconductor element will be picked up suitably. In addition, the adhesive layer develops an adhesive force that withstands reliability by heating, and the semiconductor element and the supporting member are bonded to each other.

(E) Further, a semiconductor device can be obtained by performing predetermined steps such as bonding and sealing based on a conventionally known method.

[0072]

EXAMPLES The present invention will be described in more detail below with reference to examples. The present invention is not limited to these.

(Synthesis Example 1) 90.0 parts by mass of propylene glycol monomethyl ether and 60.0 parts by mass of toluene were charged into a four-necked flask equipped with a stirrer, a dropping funnel, a cooling tube and a nitrogen introducing tube, and a nitrogen gas atmosphere was prepared. Below 80
45.0 parts by mass of ethyl methacrylate, 35.0 parts by mass of 2-ethylhexyl acrylate, 20.0 parts by mass of methacrylic acid and 2,2 'while the reaction temperature is raised to 80 ° C ± 2 ° C. -Azobis (isobutyronitrile) 1.
0 parts by mass of the mixed solution was uniformly added dropwise over 4 hours. After the dropping, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and then 0.05 part by mass of hydroquinone was added. After the addition of hydroquinone, the temperature of the reaction system was raised to 100 ° C., and over 3 hours, 33.0 parts by mass of glycidyl methacrylate, 0.1 part by mass of benzyltrimethylammonium chloride, 30.0 parts by mass of propylene glycol monomethyl ether and toluene. 20.0 parts by mass of the mixed solution was added dropwise. After the dropping, the mixture was stirred at 100 ° C. for 20 hours and then cooled to room temperature to give a weight average molecular weight of 2
A radiation-polymerizable compound (A-1) having an ethylenically unsaturated group in the side chain of 8,000 and a glass transition temperature of about 5 ° C was obtained.

(Synthesis Example 2) VESTA was placed in a four-necked flask equipped with a stirrer, a dropping funnel, a cooling tube and a nitrogen introducing tube.
After charging 888 parts by mass of NAT IPDI (trade name, manufactured by Daicel Hurus Co., Ltd., isophorone diisocyanate) and 789 parts by mass of ethyl acetate, the temperature was raised to 70 ° C., and then 70
Insulated at ~ 75 ° C, 232 parts by mass of 2-hydroxyethyl acrylate, PTG650SN (Hodogaya Chemical Co., Ltd.)
Product name, polyoxytetramethylene glycol, number average molecular weight of about 650) 1950 parts by mass, hydroquinone monomethyl ether 1.53 parts by mass, L101 (Tokyo Fine Chemical Co., Ltd. product name, dibutyltin laurate)
A mixed liquid of 1.53 parts by mass and ethyl acetate 526 parts by mass was uniformly added dropwise over 3 hours to carry out a reaction. After completion of the dropping, the reaction was allowed to proceed for about 5 hours, the disappearance of the isocyanate group was confirmed by IR measurement, and the reaction was terminated to obtain a radiation-polymerizable compound (A-2).

(Synthesis Example 3) 197.06 g (0) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in a four-necked flask equipped with a stirrer, a dropping funnel, a condenser and a nitrogen inlet tube. .48 mol) and γ-butyrolactone (318.14 g) were charged, and the temperature was raised to 30 ° C.
While maintaining at ~ 40 ° C, 2,2,4-trimethylhexamethylene diisocyanate 50.4 g (0.24 mol)
Was dripped little by little. After dropping, after continuing the reaction for 1 hour at 30 ° C., Karenz MOI (Showa Denko KK, trade name, isocyanate ethyl methacrylate) 70.68 g
(0.456 mol) and 0.318 g of hydroquinone monomethyl ether were added dropwise little by little while maintaining the temperature at 30 ° C. After the dropping, the reaction was continued at 30 ° C. or lower for 2 hours to obtain a radiation-polymerized compound (A-3).

(Example 1) (Preparation of Adhesive Sheet 1) 42.3 parts by mass of YDCN-703 (trade name, manufactured by Tohto Kasei Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 210), Priofen LF2882 ( Dainippon Ink and Chemicals Co., Ltd. product name, bisphenol A novolac resin 23.9 parts by mass, HTR-860P-3 (Teikoku Chemical Industry Co., Ltd. product name, epoxy group-containing acrylic rubber, molecular weight 1 million,
Tg-7 ° C) 44.1 parts by mass, Cureazole 2PZ-C
N (trade name of Shikoku Chemicals Co., Ltd., 1-cyanoethyl-
2-phenylimidazole) 0.4 parts by mass, NUC A
-187 (trade name, manufactured by Nippon Unicar Co., Ltd., γ-glycidoxypropyltrimethoxysilane) 0.7 parts by mass, a radiation-polymerizable compound having an ethylenically unsaturated group in the side chain obtained in Synthesis Example 1 ( A-1) Methyl ethyl ketone was added to a composition consisting of 22.05 parts by mass and 0.5 part by mass of 1-hydroxycyclohexyl phenyl ketone, and the mixture was stirred and mixed, followed by vacuum deaeration. This adhesive varnish has a thickness of 50 μm
Polyethylene terephthalate (manufactured by Teijin Ltd., Teijin Tetron film: G2-50, surface tension 50 dyne /
cm) and heat-dried at 140 ° C. for 5 minutes to form an adhesive sheet having a substrate (polyethylene terephthalate film) and a thickness of 50 μm (adhesive sheet excluding the substrate has a thickness of 50 μm) (adhesive sheet) 1) was produced.

The storage elastic modulus when this adhesive sheet 1 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology Co.) (sample size:
Length 20 mm, width 4 mm, film thickness 80 μm, heating rate 5 ° C
/ Min, tensile mode, 10 Hz, automatic static load), the result was 360 MPa at 25 ° C. and 4 MPa at 260 ° C.

(Preparation of Semiconductor Device Sample) A semiconductor device sample (single-sided) in which a semiconductor chip and a wiring board using a polyimide film having a thickness of 25 μm as a base material are bonded together by using the obtained adhesive sheet 1 Solder balls were formed). That is, 10 mm x 10 mm obtained by dicing a silicon wafer with a surface oxide film
10 mm x 1 in advance on a chip of x 0.33 mmt
After temporarily bonding the adhesive sheet 1 cut into a size of 0 mm to a polyimide substrate with wiring, at 160 ° C. and 0.02 MPa.
At 5 seconds, thermocompression bonding was performed. Then, using Hitachi Chemical Co., Ltd. sealing material (CEL-9200), 180
The semiconductor device (12 mm × 12 mm × 0.7) was sealed under the conditions of 20 ° C. and 20 sec, and post-cured at 180 ° C. for 5 hours.
9 mmt) was obtained.

(Evaluation) With respect to the semiconductor device sample, heat resistance and moisture resistance were examined as follows. The reflow crack resistance and the temperature cycle test were applied to the heat resistance evaluation method. To evaluate the resistance to reflow cracking, the sample was passed through an IR reflow furnace where the maximum temperature of the sample surface was 240 ° C and the temperature was set to maintain this temperature for 20 seconds, and the sample was allowed to stand at room temperature and cooled twice. The cracks in the sample were visually inspected and observed with an ultrasonic microscope. If there are no cracks, mark ○
What was occurring was marked as x. The temperature cycle resistance is determined by leaving the sample in a -55 ° C atmosphere for 30 minutes, and then
The step of leaving it in an atmosphere of 5 ° C. for 30 minutes was set as one cycle, and after 1000 cycles, the one in which no breakage such as peeling or cracking occurred using an ultrasonic microscope was marked with ◯, and the one in which it occurred was marked with x. Also, the humidity resistance is evaluated at a temperature of 12
It was carried out by observing peeling after 72 hours of treatment in an atmosphere (pressure cooker test: PCT treatment) of 1 ° C., 100% humidity and 2.03 × 10 ⁵ Pa. The case where peeling was not recognized was marked with ◯, and the case where peeling occurred was marked with x.

On the other hand, the adhesive sheet 1 was attached to a silicon wafer having a thickness of 150 μm, and the silicon wafer with the adhesive sheet was placed on the dicing machine. Next, the semiconductor wafer is fixed on a dicing device and 100 mm / sec.
After dicing to 5 mm × 5 mm at a speed of 5 mm × 5 mm, the product was exposed from the support film side of the adhesive sheet with an exposure amount of 500 mJ / cm ² using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd. The dicing chip was picked up by a pick-up device, and the chip fly during dicing and the pick-up property were evaluated.

Further, the above-mentioned silicon wafer with an adhesive sheet was exposed to light from the support film side of the adhesive sheet at an exposure dose of 500 mJ / cm ² , and the adhesive strength of the adhesive sheet / base material interface before and after exposure was 90 ° C. peel strength. It was measured (pulling speed: 50 mm / min). The results of these evaluations are summarized in Table 1.

Example 2 In Example 1, a radiation-polymerizable compound (A- having an ethylenically unsaturated group in its side chain) was used.
1) is a radiation-polymerizable compound (A-) obtained in Synthesis Example 2.
The same operation as in Example 1 was carried out except for 2), and an adhesive sheet having a substrate (polyethylene terephthalate film) and having a film thickness of 50 μm (the adhesive sheet excluding the substrate has a thickness of 50 μm) (adhesive sheet). 2) was produced. A dynamic viscoelasticity measuring device (DVE-V manufactured by Rheology Co., Ltd.) was used to measure the storage elastic modulus when the adhesive sheet 2 was cured at 170 ° C. for 1 hour.
4) (sample size: length 20 mm, width 4 mm, film thickness 80 μm, temperature rising rate 5 ° C./min, tensile mode, 10 Hz, automatic static load).
It was 2 MPa at 50 MPa and 260 ° C. Table 1 shows the results of evaluation of the obtained adhesive sheet 2 under the same conditions as in Example 1.

Example 3 In Example 1, the radiation-polymerizable compound (A- having an ethylenically unsaturated group in the side chain) was used.
1) is a radiation-polymerizable compound (A-) obtained in Synthesis Example 3.
The same operation as in Example 1 was carried out except that 3), and an adhesive sheet having a base material (polyethylene terephthalate film) and having a film thickness of 50 μm (adhesive sheet thickness excluding the base material was 50 μm) (adhesive sheet). 3) was produced. A dynamic viscoelasticity measuring device (DVE-V manufactured by Rheology Co., Ltd.) was used to measure the storage elastic modulus when the adhesive sheet 3 was cured at 170 ° C. for 1 hour.
4) (sample size: length 20 mm, width 4 mm, film thickness 80 μm, temperature rising rate 5 ° C./min, tensile mode, 10 Hz, automatic static load).
It was 5 MPa at 80 MPa and 260 ° C. Table 1 shows the results of evaluation of the obtained adhesive sheet 3 under the same conditions as in Example 1.

Comparative Example 1 In Example 1, the substrate to which the adhesive composition was applied was polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin Ltd., Teijin Tetron film: G2-50, surface tension 50 dyne / cm). ), Single-sided release-treated polyethylene terephthalate (manufactured by Teijin Ltd., Purex S-31, thickness 50 μm, surface tension 25 dy)
ne / cm), and the same operation as in Example 1 was carried out except that the release-treated surface was coated to obtain an adhesive sheet 4. Table 1 shows the results of evaluation of the obtained adhesive sheet 4 under the same conditions as in Example 1.

Comparative Example 2 In Example 2, the substrate to which the adhesive composition was applied was polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin Ltd., Teijin Tetron film: G2-50, surface tension 50 dyne / cm). ), Single-sided release-treated polyethylene terephthalate (Teijin Co., Ltd.)
Manufactured by Purex S-31, thickness 50 μm, surface tension 25 dyne / cm), and the same operation as in Example 1 was performed except that the release-treated surface was coated to obtain an adhesive sheet 5. Table 1 shows the results of evaluation of the obtained adhesive sheet 5 under the same conditions as in Example 1.

Comparative Example 3 In Example 3, the substrate to which the adhesive composition was applied was polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin Ltd., Teijin Tetron film: G2-50, surface tension 50 dyne / cm). ), Single-sided release-treated polyethylene terephthalate (Teijin Co., Ltd.)
Manufactured by Purex S-31, thickness 50 μm, surface tension 25 dyne / cm), and the same operation as in Example 1 was performed except that the release-treated surface was coated to obtain an adhesive sheet 6. The results of evaluation of the obtained adhesive sheet 6 under the same conditions as in Example 1 are shown in Table 1.

(Comparative Example 4) In Example 1, the radiation-polymerizable compound (A- having an ethylenically unsaturated group in the side chain) was used.
Except for 1) and 1-hydroxycyclohexyl phenyl ketone, the same operation as in Example 1 was carried out.
The storage modulus when cured at 0 ° C for 1 hour is 3 at 25 ° C.
An adhesive sheet 7 having a pressure of 80 MPa and a pressure of 5 MPa at 260 ° C. was obtained. Table 1 shows the results of evaluation of the obtained adhesive sheet 7 under the same conditions as in Example 1.

[0088]

[Table 1] From Table 1, the adhesive sheet of the present invention is excellent in heat resistance and moisture resistance, has no chip fly during dicing, and has good pickup property. Furthermore, since the difference in the adhesive strength before and after the exposure is large, the working condition margin is large and the workability is excellent.

[0089]

INDUSTRIAL APPLICABILITY The adhesive sheet of the present invention can be used as a dicing tape in the dicing process and as an adhesive having excellent connection reliability in the bonding process of the semiconductor element and the supporting member. Further, the adhesive sheet of the present invention has heat resistance and moisture resistance necessary for mounting a semiconductor element having a large difference in thermal expansion coefficient on a semiconductor mounting support member, and is excellent in workability. Further, the method for manufacturing a semiconductor device using the adhesive sheet of the present invention can simplify the manufacturing process,
Moreover, the manufactured semiconductor device has heat resistance, moisture resistance, and workability required when a semiconductor element having a large difference in thermal expansion coefficient is mounted on the semiconductor mounting support member.

Continued front page    (72) Inventor Keisuke Okubo             48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.             Company Research Institute F-term (reference) 4J004 AA10 AA11 AA13 AB01 AB05                       AB06 BA02 CA04 CA06 CB03                       FA05 FA08                 4J040 EB032 EC061 EC062 EC071                       EC072 FA131 FA231 GA01                       GA05 GA11 GA19 GA20 HA196                       HA306 HA316 HA326 HB19                       HB22 HB36 HC03 HC12 HC22                       HD30 HD41 JA02 JA09 JB02                       JB07 JB09 KA16 KA17 KA25                       LA01 LA06 LA09 MA10 MA11                       NA20 PA23 PA30 PA32                 5F047 BA34 BB03 BB19

Claims (10)

[Claims] 1. A heat-polymerizable and radiation-polymerizable adhesive sheet comprising a tacky adhesive layer and a base material layer, wherein the tacky adhesive layer comprises (A) an epoxy resin and an epoxy resin curing agent, (B) a high molecular weight component having a weight average molecular weight of 100,000 or more including a functional monomer, and (C) a radiation-polymerizable compound, wherein the substrate layer has a surface tension of more than 40 mN / cm, An adhesive sheet, characterized in that the adhesive strength at the interface between the adhesive layer and the substrate layer before irradiation with radiation is 200 mN / cm or more. 2. The adhesive sheet, wherein the adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) at the interface between the adhesive layer and the base material layer before and after irradiation with radiation is 0.5 or less. Adhesive sheet. 3. The adhesive sheet, wherein the difference in adhesive strength (adhesive strength before irradiation-adhesive strength after irradiation) at the interface between the adhesive layer and the base material layer before and after irradiation with radiation is 100 mN / cm or more. Adhesive sheet. 4. An epoxy group-containing (meth) acrylic in which the high-molecular-weight component having a weight average molecular weight of 100,000 or more containing the functional monomer (B) contains an epoxy group-containing repeating unit in an amount of 0.5 to 6% by weight. The adhesive sheet according to claim 1, which is a copolymer. 5. A high molecular weight component in which the adhesive layer contains 100 parts by weight of the (A) epoxy resin and epoxy resin curing agent and the (B) functional monomer and has a weight average molecular weight of 100,000 or more. 10 to 400 parts by weight, and (C) the radiation-polymerizable compound are contained in 5 to 400 parts by weight, the adhesive sheet according to any one of claims 1 to 4. 6. The adhesive layer is 10 to 20 at 25 ° C.
The storage elastic modulus after heat curing of 00 MPa and 3 to 50 MPa at 260 ° C., and the storage elastic modulus according to claim 1.
The adhesive sheet according to the item. 7. The adhesive force between the adhesive layer and the base material layer is controlled by irradiating with radiation.
The adhesive sheet according to claim 1. 8. The adhesive strength after irradiation with radiation is 100 mN /
The adhesive sheet according to claim 1, which has a size of not more than cm. 9. A semiconductor device in which a semiconductor element and a semiconductor mounting support member are bonded together by using the adhesive sheet according to claim 1. Description: 10. (a) An adhesive sheet comprising the adhesive layer according to any one of claims 1 to 8 and a base material layer,
A step of obtaining a semiconductor wafer with an adhesive sheet by providing the adhesive layer on the semiconductor wafer with the adhesive layer sandwiched therebetween;
Dicing the semiconductor wafer with an adhesive sheet to obtain a semiconductor element with an adhesive sheet, and (c) irradiating the adhesive sheet with radiation to reduce the adhesive force of the adhesive layer to the base layer, And a step of peeling the base material layer to obtain a semiconductor element with an adhesive layer, and (d) the semiconductor element with an adhesive layer and a supporting member for mounting a semiconductor element via the adhesive layer. And a step of adhering the semiconductor device.