JP2003041209A - Adhesive sheet, semiconductor device, and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet which works as a dicing tape in the stage of dicing and exhibits an excellent connection reliability in the stage of bonding a semiconductor element to a support member; and a production method whereby the stage of producing a semiconductor device can be simplified. SOLUTION: This adhesive sheet, which is thermally polymerizable and radiation-polymerizable, comprises a substrate layer and a hardenable pressure- sensitive adhesive layer containing (A) an epoxy resin, (B) a modified polyamideimide resin prepared by reacting a mixture of (a) an aromatic polyisocyanate, (b) a tricarboxylic acid having an acid anhydride group, and (c) a dicarboxylic acid represented by formula (I) in a polar solvent, and (C) a radiation-polymerizable compound.

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 devices,
The supporting members used are also required to be smaller and more compact. In response to these requirements, the silver paste has various problems such as occurrence of defects during wire bonding due to protrusion and inclination of the semiconductor element, difficulty in controlling the thickness of the adhesive layer, and occurrence of voids in the adhesive layer. was there. In order to solve these problems, a film-shaped adhesive has been used in recent years. The film adhesive is used in an individual sticking method or a wafer back surface sticking method.

In the individual piece attaching method, a reel-shaped adhesive film is cut into individual pieces by cutting or punching, and then adhered to a supporting member. The semiconductor element separated into pieces by the dicing process is joined to the supporting member with the adhesive film to produce a supporting member with a semiconductor element, and then the semiconductor element is completed through a wire bonding step, a sealing step and the like. However. The individual sticking method requires a dedicated assembling device for cutting out the adhesive film and adhering it to the supporting member, and there is a problem that the assembling cost is higher than that of the method using the silver paste.

On the other hand, in the wafer back surface sticking method, an adhesive film is stuck to a semiconductor wafer, and after being stuck to a dicing tape, it is separated into individual pieces by a dicing process. The semiconductor element with an adhesive, which has been separated into individual pieces, is joined to a support member, and the semiconductor device is completed through subsequent steps such as heating, curing, and wire bonding. The wafer backside attachment method does not require a device for separating the adhesive film into individual pieces because the semiconductor element with adhesive is bonded to the supporting member, and the conventional assembly device for silver paste is used as it is or a heating plate is added. Since it can be used by improving a part of the device, it has attracted attention as a method which can suppress the assembling cost relatively low among the assembling methods using the film adhesive.

The individualization of the semiconductor elements in this wafer back surface attachment method is performed in a dicing step after attaching a dicing tape to the film adhesive side. At that time, the dicing tape used is a pressure sensitive type or a UV type.
It is roughly divided into types. The pressure-sensitive tape is usually a polyvinyl chloride-based or polyolefin-based base film coated with an adhesive. This dicing tape needs to have a sufficient adhesive force at the time of cutting so that each element is not scattered by the rotation by the dicing saw. On the other hand, at the time of picking up, it is necessary to satisfy the contradictory performance such as low adhesive strength for picking up in order to prevent the adhesive from adhering to each element and to prevent the element from being damaged. Therefore, in the case of the pressure-sensitive dicing tape, many kinds of adhesive sheets having various adhesive strengths which have a small tolerance of the adhesive strength and which are suitable for the size of the element and processing conditions are prepared and switched for each process. Therefore, it is necessary to stock many types of products, which complicates inventory management. Further, it is necessary to change the adhesive sheet for each process. Recently, a dicing tape called UV type, which has a high adhesive force during dicing and has a low adhesive force by being irradiated with ultraviolet rays (UV) before being picked up, has been widely adopted.

In recent years, semiconductor devices, especially CPUs and memories, have increased in capacity, and as a result, semiconductor devices tend 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,
With the pressure-sensitive type, it is becoming difficult to satisfy the contradictory requirements of a fixing force (high adhesive force) during dicing and a peeling force (low adhesive force) during pickup.

On the other hand, in the wafer back surface sticking method using the UV type, there is a problem that the film sticking step up to the dicing step has to be performed twice, which makes the work complicated.

[0008]

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 process and is excellent in connection reliability in the process of joining a semiconductor element and a supporting member. The purpose is to do. Further, this adhesive sheet is an adhesive sheet which has heat resistance and moisture resistance required when a semiconductor element having a large difference in thermal expansion coefficient is mounted on a semiconductor element mounting support member and is excellent in workability. Another object of the present invention is to provide a manufacturing method capable of simplifying the manufacturing process of a semiconductor device.

[0009]

The present invention relates to the following. 1. (A) Epoxy resin (B) (a) Aromatic polyisocyanate (b) Trivalent polycarboxylic acid having an acid anhydride group and (c) the following general formula (I)

[0010]

[Chemical 2]

(In the formula, a is 0 to 20, b is 0 to 70, and c
Is an integer of 1 to 90, R1 and R2 are hydrogen or C
1 to C3 alkyl group) represented by a reaction of a mixture of dicarboxylic acids in a polar solvent, a modified polyamideimide resin, (C) a radiation-polymerizable compound-containing adhesive layer, A heat-polymerizable and radiation-polymerizable adhesive sheet comprising a base material layer. 2. (A) epoxy resin and (B) modified polyamide-imide resin are 5/95 to 90/10 (parts by weight), and (C)
Item 2. The adhesive sheet according to Item 1, wherein the radiation-polymerizable compound is 1 to 400 parts by weight based on 100 parts by weight of the total amount of the (A) epoxy resin and the (B) modified polyamideimide resin. 3. Item 3. The adhesive sheet according to Item 1 or 2, which has a tensile modulus of elasticity of 2 GPa or less at 25 ° C in a tensile test when the modified polyamideimide resin is formed into a film. 4. The glass transition temperature of the modified polyamide-imide resin is 30.
It is 0 degreeC or less, The adhesive sheet in any one of the items 1-3 characterized by the above-mentioned. 5. The elastic modulus of the cured product of the adhesive composition is 20 at -60 ° C.
Item 5. The adhesive sheet according to any one of Items 1 to 4, which has a pressure of 00 MPa or less. 6. Item 6. The adhesive sheet according to any one of Items 1 to 5, which controls the adhesive force between the adhesive layer and the substrate by irradiating with radiation. 7. Using the adhesive sheet according to any one of Items 1 to 4,
Semiconductor device A semiconductor device in which a semiconductor and a device mounting support member are bonded together. 8. (1) A step of sticking an adhesive sheet comprising the adhesive / adhesive layer according to any one of Items 1 to 4 and a base material onto a semiconductor wafer via the adhesive / adhesive layer, and (2) Before or after dicing, a step of irradiating the adhesive sheet with radiation to cure the adhesive layer to form a semiconductor element, and then peeling the base material, and (3) dicing the semiconductor wafer Then, a semiconductor device including a step of attaching an adhesive layer and (4) a step of adhering the semiconductor element with an adhesive layer and a supporting member for mounting a semiconductor element via the adhesive sheet. Manufacturing method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive sheet of the present invention comprises (A) an epoxy resin and (B) a modified polyamideimide resin in a ratio of 5/9.
5 to 90/10 (parts by weight), and (C) the radiation-polymerizable compound is 1 to 400 per 100 parts by weight of the total amount of the (A) epoxy resin and (B) modified polyamideimide resin.
It has an adhesive layer which is a part by weight, and a base material layer. This makes it possible to obtain an adhesive sheet having both heat-polymerizable and radiation-polymerizable properties.

This adhesive sheet satisfies the contradictory requirements of having a sufficient adhesive force so that the semiconductor elements do not scatter during dicing and having a low adhesive force at the time of pickup so as not to damage each element. The steps of die bonding and dicing can be completed with a single film.

The (A) epoxy resin used in the present invention is
There is no particular limitation as long as it cures and exhibits an adhesive action. For example, Epicoat 807, 815, 825, 827, 828, 834, 1 manufactured by Yuka Shell Epoxy Co., Ltd.
001, 1004, 1007, 1009, DER-330, 301, 361 manufactured by Dow Chemical Co., YD8125, YDF8170 manufactured by Tohto Kasei Co., Ltd., bisphenol A type epoxy resin, Epicat 152,154 manufactured by Yuka Shell Epoxy Co., Ltd. EP manufactured by Nippon Kayaku Co., Ltd.
PN-201, phenol novolac type epoxy resin such as DEN-438 manufactured by Dow Chemical Co., Nippon Kayaku Co., Ltd.
EOCN-102S, 103S, 104S, 101
2,1025,1027, YDCN manufactured by Tohto Kasei Co., Ltd.
O-cresol novolac type epoxy resins such as 701, 702, 703 and 704, Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., Araldite 0163 manufactured by Ciba Specialty Chemicals, manufactured by Nagase Kasei Co., Ltd.
Denacol EX-611, 614, 614B, 622
Polyfunctional epoxy resins such as 512, 521, 421, 411 and 321; Yuka Shell Epoxy Co., Ltd. Epicoat 604; Tohto Kasei Co., Ltd. YH-434; Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, TETRAD- C, amine type epoxy resin such as ELM-120 manufactured by Sumitomo Chemical Co., Ltd., heterocyclic ring-containing epoxy resin such as Araldite PT810 manufactured by Ciba Specialty Chemicals, and alicyclic epoxy such as ERL4234, 4299, 4221, 4206 manufactured by UCC. A resin or the like can be used, and one kind or two or more kinds of these can be used in combination.

Examples of the aromatic polyisocyanate as the component (a) used in the present invention include 4,4'-diphenylmethane diisocyanate, tricylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate and 4,4 '. -[2,2-
Bis (4-phenoxyphenyl) propane] diisocyanate, biphenyl-4,4′-diisocyanate, biphenyl-3,3′-diisocyanate, biphenyl-
3,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,
3'-diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,
4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,4'-diisocyanate, naphthalene-1,
Examples thereof include 5-diisocyanate and naphthalene-2,6-diisocyanate. These can be used alone or in combination. If necessary, a portion of this may be added to hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-
It may be used by replacing it with an aliphatic, alicyclic isocyanate such as diisocyanate, hydrogenated m-xylene diisocyanate, lysine diisocyanate or the like, and polyisocyanate having 3 or more functional groups, and is stabilized with an appropriate blocking agent in order to avoid aging. You may use what was done.

As the (b) component trivalent carboxylic acid derivative having an acid anhydride group used in the present invention, for example, compounds represented by the following general formulas (II) and (III) are preferably used. There is no particular limitation as long as it is a trivalent carboxylic acid derivative having an acid anhydride group, but heat resistance,
Considering cost and the like, trimellitic anhydride is particularly preferable.

[0017]

[Chemical 3]

[0018]

[Chemical 4]

(However, in both formulas, R is hydrogen and has 1 to 1 carbon atoms.
0 represents an alkyl group or a phenyl group, and Y is —CH
₂ -, - CO -, - shows or -O-) - SO ₂

In addition to these, tetracarboxylic dianhydrides (pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4, 4'-sulfonyldiphthalic dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4-oxydiphthalic dianhydride, 1,1,1,3 , 3,3-hexafluoro-2,
2-bis (2,3-, or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride,
2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,
1,3,3,3-hexafluoro-2,2-bis [4-
(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride , Butanetetracarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene-
2: 3: 5: 6-tetracarboxylic dianhydride), aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid) , Aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid) and the like can be used. The amount of these used is preferably less than 50 mol% with respect to the total amount of the components (b) and (c).

The dicarboxylic acid represented by the above general formula (I) of the component (c) used in the present invention is represented by the following general formula (I)
V)

[0022]

[Chemical 5]

(In the formula, a, b, c, R ₁ and R ₂ have the same meanings as in the general formula (I).) A diamine and trimellitic anhydride are solvent-free or in an organic solvent. After reaction, the following general formula (V)

[0024]

[Chemical 6]

(Wherein a, b, c, R ₁ and R ₂ have the same meanings as in formula (I)), the compound can be obtained by subjecting it to a heat dehydration ring closure. it can.

The reaction for obtaining the compound represented by the above general formula (V) is preferably carried out at 0 to 150 ° C., and the reaction time is appropriately selected depending on the scale of the batch, the reaction conditions adopted and the like. You can

Examples of the diamine represented by the above general formula (IV) include Jeffamine D-230, D-400, D-2000 manufactured by San Techno Chemical Co., Ltd.
D-4000, ED-600, ED-900, ED-2
001, EDR-148 and the like. These are used alone or in combination of two or more. The use ratio of the diamine represented by the general formula (IV) and trimellitic anhydride is preferably 2: 1 (molar ratio).

The reaction of the compound represented by the general formula (V) by heat dehydration and ring closure to form the dicarboxylic acid represented by the general formula (I) is preferably carried out at 50 to 250 ° C., which facilitates dehydration and ring closure. In order to do so, a reduced pressure reaction can also be used.
The reaction for obtaining the compound represented by the general formula (V) and the reaction for obtaining the dicarboxylic acid represented by the general formula (I) can be carried out stepwise or continuously.
Considering the cost, it is preferable to carry out continuously.

Examples of usable organic solvents include ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester solvents (ethyl acetate, butyl acetate, γ-butyrolactone, etc.), ether solvents (diethylene glycol dimethyl ether, triethylene glycol, triethyl ether, etc.). Ethylene glycol dimethyl ether etc.), cellosolve solvent (butyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve acetate etc.), aromatic hydrocarbon solvent (toluene, xylene, p-cymene etc.), tetrahydrofuran, dioxane, N-methyl-
2-pyrrolidone, N, N-dimethylformamide, N,
Examples thereof include N-dimethylacetamide, dimethylsulfoxide, and sulfolane, but in view of solubility, boiling point, and cost, it is preferable to use a non-nitrogen-containing polar solvent used in the subsequent production of the modified polyamideimide resin. More preferably, the reaction is carried out without solvent.

In the present invention, the reaction ratio between the derivative of the trivalent carboxylic acid having an acid anhydride group as the component (b) and the dicarboxylic acid represented by the general formula (I) as the component (c) is the same as that of the component (b). / (C) component (molar ratio) 0.1 / 0.9 to 0.9 /
0.1 is preferable and 0.2 / 0.8 to 0.8
/0.2 is more preferable, and 0.3 / 0.7 to
The ratio of 0.7 / 0.3 is particularly preferable. 0.1 /
If it is less than 0.9, the heat resistance tends to decrease, and 0.9
If it exceeds /0.1, the adhesiveness tends to decrease.

The amounts of the components (a), (b) and (c) used in the present invention are such that the ratio of the number of moles of isocyanate groups to the total number of moles of carboxyl groups and acid anhydride groups is 0. 7 to 1.5 is preferable,
More preferably, it is around 1.0. If it is less than 0.7 or exceeds 1.5, it tends to be difficult to increase the molecular weight of the resin.

The reaction in the method for producing the modified polyamide-imide resin of the present invention is carried out by heating and condensing in a non-nitrogen-containing polar solvent while removing carbon dioxide which is liberated from the reaction system. The reaction temperature is preferably 80 to 200 ° C, more preferably 100 to 180 ° C. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions adopted. As the non-nitrogen-containing polar solvent used in the reaction, for example, cyclohexanone, dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, sulfolane, etc. are preferably used, but are highly volatile and low temperature curability. Most preferred is γ-butyrolactone capable of imparting

The amount of the non-nitrogen-containing polar solvent used is preferably 1.0 to 5.0 times (weight ratio) of the modified polyamideimide resin produced. If it is less than 1.0 times, the viscosity at the time of synthesis is too high, and the stirring tends to make it difficult to synthesize, and if it exceeds 5.0 times, the reaction rate tends to decrease.

The number average molecular weight of the modified polyamideimide resin of the present invention (measured by the GPC method and calculated using a calibration curve based on standard polystyrene) is preferably 4,000 to 30,000, and preferably 5,000 to 30,000. It is more preferably 28,000. When the number average molecular weight is less than 4,000, heat resistance and the like tend to decrease, and when it exceeds 30,000, it becomes difficult to dissolve in a non-nitrogen-containing solvent and easily insolubilizes during synthesis. The acid value (KOHmg / g) of the modified polyamideimide resin of the present invention is preferably 1-60, more preferably 3-50.
It is especially preferable that it is ˜50. When the acid value is less than 1,
The heat resistance tends to decrease, and if it exceeds 60, the viscosity stability tends to deteriorate. Further, after the synthesis is completed, the isocyanate group at the resin end is changed to alcohols, lactams,
It is also possible to block with a blocking agent such as oximes.

The ratio of the epoxy resin to the modified polyamideimide resin is 5/95 to 90/10 (parts by mass), preferably 10/90 to 90/10 (parts by mass), and more preferably 10/90. ˜85 / 15 (parts by mass). If the ratio of the epoxy resin to the modified polyamide-imide resin is outside this range, the heat resistance tends to be poor.

When the modified polyamideimide resin used in the present invention is formed into a film, the tensile modulus in a tensile test is 2 GPa or less at 25 ° C., preferably 0.2 G.
Pa to 1.8 GPa. When the tensile modulus exceeds 2 GPa, the effect of lowering the modulus of elasticity of the obtained adhesive sheet near room temperature is not sufficient, and the deterioration tends to be large when the temperature cycle test is performed. Further, the glass transition temperature (Tg) in thermomechanical analysis when the modified polyamideimide resin used in the present invention is formed into a film is 300 ° C. or lower, preferably 50 ° C. to 300 ° C., more preferably 50 ° C. ~ 250 ° C. If Tg exceeds 300 ° C, the adhesion tends to be poor.

The (C) radiation-polymerizable compound 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 , Triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane Trimethacrylate, 1,4-pig 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-di Chill acrylamide, N- methylol acrylamide, tris (beta-hydroxyethyl)
Isocyanurate triacrylate, the following general formula (V
I)

[0038]

[Chemical 7]

(In the formula, R represents hydrogen or a methyl group, and q
And r are integers of 1 or more), diols, and general formula (VII)

[0040]

[Chemical 8]

(Wherein n is an integer of 0 to 1 and R is a divalent or trivalent organic group having 1 to 30 carbon atoms), and an isocyanate compound represented by the general formula ( V
III)

[0042]

[Chemical 9]

(Wherein R ₁ is hydrogen or a methyl group,
R ₂ is an ethylene group or a propylene group), a urethane acrylate or urethane methacrylate comprising a compound represented by the general formula (IX)

[0044]

[Chemical 10]

(Wherein R represents a divalent organic group having 2 to 30 carbon atoms), and a general formula (X)

[0046]

[Chemical 11]

(In the formula, n is an integer of 0 to 1) Urea methacrylate consisting of a compound, a vinyl copolymer containing a functional group, at least one ethylenically unsaturated group, and an oxirane ring, A radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain obtained by the addition reaction of a compound having one functional group such as an isocyanate group, a hydroxyl group and a carboxyl group can be used. 1
It is also possible to use one species or a combination of two or more species.

The amount of the radiation-polymerizable compound (C) used in the present invention is 1 to 400 parts by weight per 100 parts by weight of the total amount of the epoxy resin (A) and the modified polyamideimide resin (B), but preferably 1 to 400 parts by weight. It is 3 to 350 parts by weight, and more preferably 5 to 300 parts by weight. If the amount of the (C) radiation-polymerizable compound used is less than 1 part by weight, it tends to be difficult to control the adhesive force between the adhesive layer and the substrate when irradiated with radiation, and the amount is 400 parts by weight. When it exceeds the amount, the heat resistance of the obtained adhesive sheet tends to be lowered.

The storage elastic modulus of the cured adhesive obtained by curing the tacky adhesive layer forming the adhesive sheet of the present invention is 20 at -60 ° C.
The pressure is 00 MPa or less, and preferably 100 to 2000 MPa. The storage elastic modulus was measured using a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheology Co., Ltd.), a tensile load was applied to the cured adhesive, and the frequency was 10 Hz and the temperature rising rate was 5 to 10 ° C./min. The measurement was performed in the temperature dependence measurement mode in which the temperature was measured from 70 ° C to 250 ° C. Storage elastic modulus is -60
If it exceeds 2000 MPa at ° C, the effect of alleviating the thermal stress caused by the difference in the thermal expansion coefficient between the semiconductor element and the supporting member becomes small, and the tendency of peeling or cracking increases.

The tacky-adhesive layer forming the adhesive sheet of the present invention has the purpose of improving its strength, flexibility and heat resistance.
It is also possible to incorporate a high molecular weight component containing a functional group. The high molecular weight component containing a functional group is preferably an epoxy group-containing acrylic copolymer containing 0.5 to 6% by weight of glycidyl acrylate or glycidyl methacrylate, which is incompatible with the epoxy resin.

The epoxy group-containing acrylic copolymer containing 0.5 to 6 parts by weight of glycidyl acrylate or glycidyl methacrylate is not particularly limited, and HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd. can be used. . When the functional group monomer is carboxylic acid type acrylic acid or hydroxyl group type hydroxymethyl (meth) acrylate, the crosslinking reaction easily proceeds, gelation in varnish state and increase in curing degree in B stage state It is not preferable because there is a problem such as a decrease in adhesive strength due to the above. The amount of glycidyl (meth) acrylate used as the functional group monomer is a copolymer ratio of 2 to 6% by weight.
If it is 2% by weight or less, the adhesive force may be lowered, and if it is 6% by weight or more, gelation may occur. The balance may be ethyl (meth) acrylate, butyl (meth) acrylate, or a mixture of both, but the mixing ratio is determined in consideration of the glass transition temperature (hereinafter abbreviated as Tg) of the copolymer, and Tg is It is preferably −10 ° C. or higher. If the Tg is less than -10 ° C, the tackiness of the adhesive layer in the B stage state becomes large, and the handleability may deteriorate. The polymerization method is not particularly limited, and pearl polymerization, solution polymerization and the like can be used.

The weight average molecular weight of the epoxy group-containing acrylic copolymer is preferably 300,000 to 3,000,000,
It is more preferably 500,000 to 2,000,000. If the weight average molecular weight is less than 300,000, the strength and flexibility of the sheet or film may decrease and the tackiness may increase, and if it exceeds 3 million, the flowability is small and the circuit filling property of the wiring is low. May decrease.

The compounding amount of the epoxy group-containing acrylic copolymer is preferably 10 to 400 parts by weight. If the content is less than 10 parts by mass, the effect of reducing the elastic modulus and the suppression of the flowability during molding tends to be small, and if it exceeds 400 parts by mass, the handleability at high temperature tends to be deteriorated.

Further, a hardening accelerator can be further added to the adhesive layer forming the adhesive sheet of the present invention.
The curing accelerator is not particularly limited, and examples thereof include imidazoles. Specifically, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1
-Cyanoethyl-2-phenylimidazolium trimellitate or the like can be used, and one kind or two or more kinds of these can be used in combination. Etc. can be used, and these 1 type (s) or 2 or more types can also be used together.

The amount of the curing accelerator added is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (A) epoxy resin,
0.2 to 3 parts by weight is more preferable. If the addition amount is less than 0.1 parts by weight, curability tends to be poor, and if it exceeds 5 parts by weight, storage stability tends to decrease.

A photopolymerization initiator which produces free radicals upon irradiation with actinic light may 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-cyclohexylphenylketone , 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-
Diethylthioxanthone, 2-ethylanthraquinone,
Aromatic ketones such as phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ethers, methylbenzoin, ethylbenzoin and other benzoins, benzyl dimethyl ketal and other benzyl derivatives, 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, 2,4-di (p-
2,4,5-triarylimidazole dimer such as methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenyl Acridine,
An acridine derivative such as 1,7-bis (9,9′-acridinyl) heptane can be used, and one or more of these can be used in combination. The amount of the photopolymerization initiator used is not particularly limited, but is usually 0.01 to 100 parts by mass of the radiation-polymerizable compound (C).
30 parts by weight.

Further, the tacky adhesive layer forming the adhesive sheet of the present invention is used for the purpose of improving its handleability, thermal conductivity, adjusting melt viscosity and imparting thixotropic property.
It is also possible to add an inorganic filler. The inorganic filler is not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, Boron nitride,
Examples thereof include 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 100.
It is preferably 1 to 20 parts by volume with respect to parts by volume. If it is less than 1 part by volume, the effect of addition tends not to be obtained, and if it exceeds 20 parts by volume, 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 are caused. Tend.

Further, various coupling agents may be added to the adhesive layer forming the adhesive sheet of the present invention in order to improve the interfacial bonding between different materials. 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 these 1 type, or 2 or more types can also be used together.

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, etc. can be used, and these 1 type (s) or 2 or more types can also be used together.

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 Etc. can be used bets may be used in combination one or more of them. The amount of the coupling agent used is 100 parts by weight of the epoxy resin (A) in terms of its effect, heat resistance and cost.
It is preferably 0.01 to 10 parts by weight.

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 above-mentioned ion scavenger used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A) 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 substrate used for the adhesive sheet of the present invention is not particularly limited, and examples thereof include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. To be

The solvent is not particularly limited, and examples thereof include methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, xylene, butyl cellosolve, methanol, ethanol, 2-.
Methoxyethanol dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone, etc. can be used, and these 1 type (s) or 2 or more types can also be used together.

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 base film, a known method can be used, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. .

The thickness of the adhesive sheet is not particularly limited,
Both the adhesive layer and the substrate preferably have a thickness of 5 to 250 μm. 5μ
If it is thinner than m, the stress relaxation effect tends to be poor, and 2
If it is thicker than 50 μm, it is not economical and it cannot meet the demand for miniaturization of semiconductor devices. Further, in the adhesive sheet of the present invention, in order to obtain a desired thickness, two or more separately prepared adhesive / adhesive agents can be attached to the adhesive / adhesive layer side of the adhesive sheet. In this case, the bonding conditions are required so that the adhesive layers do not separate from each other.

When the adhesive sheet having the above-described structure is irradiated with radiation, the adhesive force of the base material is greatly reduced after the irradiation, and the base material film of the adhesive sheet can be easily held while the adhesive layer is held on the semiconductor element. You can pick up from.

The method of using the adhesive sheet according to the present invention will be described below. A semiconductor wafer to be subjected to dicing processing is pressure-bonded onto the adhesive sheet at room temperature or while heating, and the steps of dicing, washing and drying are added. At this time, since the semiconductor element is sufficiently adhered and held on the adhesive sheet, the semiconductor element does not drop out during the above steps.

Next, ultraviolet rays (UV) or electron beams (E
Radiation such as B) is applied to the adhesive sheet to polymerize and cure the radiation-polymerizable adhesive sheet. As a result, the adhesive force between the radiation-polymerizable adhesive sheet and the base material film of the adhesive sheet is reduced to such an extent that the semiconductor element can be picked up, and the desired adhesiveness can be easily obtained by providing the expandability. The space is obtained and the pickup becomes easy.

Radiation is applied to the adhesive sheet from the surface of the adhesive sheet having a radiation-polymerizable property. 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.

After the expanding step, the semiconductor element is picked up together with the radiation-cured adhesive sheet, and pressure-bonded to the supporting member at room temperature or while heating, and then heated. By heating, the adhesive sheet develops an adhesive force that withstands reliability, and the adhesion between the semiconductor element and the supporting member is completed.

[0074]

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) In a 100 ml flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a cooling tube with an oil / water separator, Jeffamine D-400 (trade name of San Techno Chemical Co., aliphatic diamine, amine) was used. Value 4.4
(Meq / g)) 31.82 g (0.07 mol) and trimellitic anhydride 26.88 g (0.14 mol) are charged, and the temperature is raised to 80 ° C. and stirred for 30 minutes. Then, the temperature was raised to 160 ° C., and the mixture was stirred under reduced pressure (pressure inside the flask: about 8.8 × 10 ⁴ Pa) for 2 hours to give an acid value of 140.
KOH mg / g of dicarboxylic acid was obtained.

(Synthesis Example 2) In a flask exactly the same as in Synthesis Example 1, Jeffamine D-2000 (trade name of San Techno Chemical Co., aliphatic diamine, amine value 1.
0 (meq / g)) 60 g (0.03 mol) and trimellitic anhydride 11.52 g (0.06 mol) were charged, and the same operation as in Synthesis Example 1 was carried out to obtain an acid value of 47K.
OH mg / g of dicarboxylic acid was obtained. Infrared absorption spectra (JIR-100, JIR-100, manufactured by JEOL Ltd.) of the dicarboxylic acids obtained in Synthesis Example 1 and Synthesis Example 2 were measured by the KBr method.
The characteristic absorption of the imide group was confirmed around 1780 cm ⁻¹ .

(Synthesis Example 3) 4,4'-in a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a cooling tube.
Diphenylmethane diisocyanate 32.5 g (0.
13 mol), 12.48 g of trimellitic anhydride (0.
065 mol), the dicarboxylic acid 5 obtained in Synthesis Example 1
After charging 2.16 g (0.065 mol) and γ-butyrolactone 204.0 g and heating to 160 ° C.,
The reaction was carried out for 2.5 hours to obtain a resin having a number average molecular weight of 13,100. The obtained resin was diluted with γ-butyrolactone to have a nonvolatile content of 25% by mass and an acid value of 16.7 KOHmg.
/ G of modified polyamideimide resin solution (PAI-1) was obtained.

(Synthesis Example 4) 4,4'-diphenylmethane diisocyanate 1 was placed in the same flask as in Synthesis Example 3.
5.75 g (0.063 mol), trimellitic anhydride
6.048 g (0.0315 mol), dicarboxylic acid obtained in Synthesis Example 2 73.962 g (0.0315 mol)
And γ-butyrolactone 203.48 g were charged, and 1
After the temperature was raised to 60 ° C., the reaction was carried out for 3.5 hours to obtain a resin having a number average molecular weight of 22,000. The obtained resin is γ
-Diluted with butyrolactone to obtain a modified polyamideimide resin solution (PAI-2) having a nonvolatile content of 25 mass% and an acid value of 14.1 KOHmg / g.

(Synthesis Example 5) 4,4'-diphenylmethane diisocyanate 5 was placed in the same flask as in Synthesis Example 3.
1.0 g (0.204 mol), trimellitic anhydride 3
After charging 8.4 g (0.2 mol) and N-methyl-2-pyrrolidone 187.74 g and heating up to 130,
After reacting for 4 hours, a resin having a number average molecular weight of 17,000 was obtained. The obtained resin was diluted with N, N-dimethylformamide to give a nonvolatile content of 25% by mass and an acid value of 32.0KO.
Hmg / g polyamide-imide resin solution (PAI-3)
Got

The modified polyamideimide solution and the polyamideimide solution thus obtained were coated on a glass plate and the mixture was heated at 90 ° C. for 4 hours.
After drying for 80 seconds, the glass transition temperature (Tg) and the tensile elastic modulus of the coating film (film thickness: 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere were measured under the following conditions.
The results are shown in Table 1.

(1) Glass transition temperature (Tg) Thermomechanical analyzer (Seiko Denshi Co., Ltd. TMA-12)
It was measured in 0). Measurement mode: Extension measurement span: 10 mm Load: 10 g Temperature increase rate: 5 ° C / min Atmosphere: Air (2) Tensile modulus universal testing machine (Tensilon UCT- manufactured by Orientec Co., Ltd.)
5T type). Measurement temperature: 25 ° C Tensile speed: 5 mm / min

[0082]

[Table 1]

Example 1 20 parts by mass of YD8125 (trade name, manufactured by Tohto Kasei Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 175), modified polyamideimide resin solution (PAI-1) obtained in Synthesis Example 3 153.8
5. 5 parts by mass (80 parts by mass as a resin alone), 0.2 parts by mass of Curezol 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd.), dipentaerythritol hexaacrylate 13.
1 g and 0.2 g of 1-hydroxycyclohexyl phenyl ketone were mixed with stirring and deaerated under vacuum. A polyethylene terephthalate having a thickness of 50 μm (made by Teijin Ltd., Teijin Tetron film: G2-50) was prepared using this adhesive varnish.
It was coated on the surface and dried by heating at 140 ° C for 5 minutes, and the film thickness with the substrate (polyethylene terephthalate film) was 5
A 0 μm adhesive sheet (the thickness of the adhesive sheet excluding the base material is 50 μm) (adhesive sheet 1) was produced.

The storage elastic modulus when the 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., Ltd.) (sample size:
Length 20 mm, width 4 mm, film thickness 80 μm, heating rate 5 ° C
/ Min, tensile mode, 10 Hz, automatic static load), and the result was 580 MPa at -60 ° C.

Using the adhesive sheet 1 thus obtained, a semiconductor device sample (a solder ball is formed on one surface) is produced by bonding a semiconductor chip and a wiring board using a polyimide film having a thickness of 25 μm as a base material with the adhesive sheet. The heat resistance and humidity resistance were examined. The reflow crack resistance and the temperature cycle test were applied to the heat resistance evaluation method. The maximum temperature of the sample surface is 240 ° C for the evaluation of reflow crack resistance.
IR set to keep this temperature for 20 seconds
The sample was passed through a reflow furnace and cooled by leaving it at room temperature twice. The crack in the sample was visually inspected and observed with an ultrasonic microscope. The case where no cracks were generated was marked with ◯, and the one where cracks were generated was marked with x. The temperature cycle resistance is determined by leaving the sample in an atmosphere of −55 ° C. for 30 minutes and then in an atmosphere of 125 ° C. for 30 minutes as one cycle, and after 1000 cycles, destroying peeling, cracks, etc. using an ultrasonic microscope. The one in which no occurrence was indicated as ◯, and the one in which occurred was indicated as x. Moreover, the humidity resistance is evaluated as follows: temperature 121 ° C., humidity 100%, 2.03 ×
Atmosphere of 10 ⁵ Pa (pressure cooker test: P
It was performed by observing peeling after 72 hours of CT treatment). 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, after fixing the semiconductor wafer on a dicing device and dicing it into 5 mm × 5 mm, UV-330 H manufactured by Oak Manufacturing Co., Ltd.
Using a QP-2 type exposure machine, exposing from the support film side of the adhesive sheet with an exposure amount of 500 mJ / cm ² , and picking up the dicing chips with a pickup device, the chip fly and the picking up property at the time of dicing evaluated.

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

Example 2 25 parts by mass of Epicoat 828 (trade name of Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 190), modified polyamideimide resin solution (PAI) obtained in Synthesis Example 3 -1)
144.23 parts by mass (75 parts by mass as a resin simple substance) and Curezol 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd.)
0.2 parts by mass, 13.1 g of dipentaerythritol hexaacrylate and 0.2 g of 1-hydroxycyclohexyl phenyl ketone were stirred and mixed, and degassed in vacuum. This adhesive varnish was coated with polyethylene terephthalate (manufactured by Teijin Ltd., Teijin Tetron Film: G) having a thickness of 50 μm.
2-50), and heat-dried at 140 ° C. for 5 minutes to obtain an adhesive sheet having a substrate (polyethylene terephthalate film) and a thickness of 50 μm (the adhesive sheet excluding the substrate has a thickness of 50 μm) ( An adhesive sheet 2) was produced.
A dynamic viscoelasticity measuring device (DVE 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.
-V4) (Sample size: Length 20m
m, width 4 mm, film thickness 80 μm, heating rate 5 ° C./min,
As a result of pulling mode, 10 Hz, automatic static load), -6
It was 420 MPa at 0 ° C. Table 2 shows the results of evaluating the obtained adhesive sheet 2 under the same conditions as in Example 1.

Example 3 Synthesis Example 3 in Example 1
The modified polyamideimide resin solution (PAI-
The same operation was performed except that 1) was changed to the modified polyamideimide resin solution (PAI-2) obtained in Synthesis Example 4,
(Adhesive sheet 3) was produced. This adhesive sheet 3 17
The storage elastic modulus when cured at 0 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (Rheology Co., DVE-V4) (sample size: length 20 mm, width 4 mm, film thickness 80).
μm, heating rate 5 ° C / min, tension mode, 10H
z, automatic static load), as a result, it was 500 MPa at −60 ° C. Table 2 shows the results of evaluation of the obtained adhesive sheet 3 under the same conditions as in Example 1.

Example 4 Synthesis Example 3 in Example 2
The modified polyamideimide resin solution (PAI-
The same operation was performed except that 1) was changed to the modified polyamideimide resin solution (PAI-2) obtained in Synthesis Example 4,
(Adhesive sheet 4) was produced. 17 this adhesive sheet 4
The storage elastic modulus when cured at 0 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (Rheology Co., DVE-V4) (sample size: length 20 mm, width 4 mm, film thickness 80).
μm, heating rate 5 ° C / min, tension mode, 10H
z, automatic static load), and the result was 380 MPa at -60 ° C. Table 2 shows the results of evaluation of the obtained adhesive sheet 4 under the same conditions as in Example 1.

Comparative Example 1 Synthesis Example 3 in Example 1
The modified polyamideimide resin solution (PAI-
The same operation was performed except that 1) was changed to the polyamideimide resin solution (PAI-3) obtained in Synthesis Example 5,
(Adhesive sheet 5) was produced. 17 this adhesive sheet 5
The storage elastic modulus when cured at 0 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (Rheology Co., DVE-V4) (sample size: length 20 mm, width 4 mm, film thickness 80).
μm, heating rate 5 ° C / min, tension mode, 10H
z, automatic static load), 2200 MPa at -60 ° C
Met. Table 2 shows the results of evaluation of the obtained adhesive sheet 5 under the same conditions as in Example 1.

Comparative Example 2 Synthesis Example 3 in Example 2
The modified polyamideimide resin solution (PAI-
The same operation was performed except that 1) was changed to the polyamideimide resin solution (PAI-3) obtained in Synthesis Example 5,
(Adhesive sheet 6) was produced. 17 this adhesive sheet 6
The storage elastic modulus when cured at 0 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (Rheology Co., DVE-V4) (sample size: length 20 mm, width 4 mm, film thickness 80).
μm, heating rate 5 ° C / min, tension mode, 10H
z, automatic static load), as a result, 3200 MPa at -60 ℃
Met. The results of evaluation of the obtained adhesive sheet 6 under the same conditions as in Example 1 are shown in Table 2.

Comparative Example 3 20 parts by mass of YD8125 (trade name of Tohto Kasei Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 175), modified polyamideimide resin solution (PAI-1) obtained in Synthesis Example 3 153.8
5 parts by mass (80 parts by mass as a resin simple substance) and 0.2 parts by mass of Curezol 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd.) were stirred and mixed, and degassed in vacuum. . A 50 μm thick polyethylene terephthalate (Teijin Co., Ltd.)
Manufactured by Teijin Tetoron Film: G2-50), dried by heating at 140 ° C. for 5 minutes, and an adhesive sheet having a base material (polyethylene terephthalate film) and having a thickness of 50 μm (adhesive sheet excluding the base material). Thickness is 50μ
m) (Adhesive sheet 7) was produced. The storage elastic modulus when this adhesive sheet 7 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). 8
0 μm, heating rate 5 ° C / min, tension mode, 10H
z, automatic static load), as a result, it was 600 MPa at −60 ° C. Table 2 shows the results of evaluation of the obtained adhesive sheet 7 under the same conditions as in Example 1.

[0094]

[Table 2]

From Table 2, the adhesive sheet of the present invention is excellent in heat resistance and moisture resistance, has no chip fly during dicing,
The pick-up property is also good. Furthermore, since the difference in adhesive strength before and after exposure is large, the tolerance of work conditions is large,
It has a high degree of workability tolerance and excellent workability.

[0096]

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

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 4/00 C09J 4/00 179/08 179/08 B H01L 21/52 H01L 21/52 CE F term (Reference) 4J004 AA11 AA13 AB06 FA05 4J034 BA08 CA25 CB02 CB04 CB05 CB07 CC03 CC12 CC22 CC33 CC54 CC61 CC65 CC66 CC67 CC68 CC69 CD04 CD05 CD06 CD09 CD12 DA05 DB04 DB07 DG03 DG04 DG25 HA01 HA07 HC03 HC65 HC67 HC71 HC13 HC13 HC13 HC46 HC52 HC71 HC13 HC13 HC46 HC52 HC71 HC13 HC13 HC46 HC73 RA08 RA14 4J040 EC001 EH032 FA132 JA09 JB07 NA20 4J043 PA01 QB58 RA05 RA34 SA11 SA43 SA72 SB01 SB02 TA11 TA13 TA14 TA21 TA22 TB01 TB02 UA011 UA121 UA122 UA131 UA132 UA151 UA261 UA432 UA662 UA672 UA761 UB011 UB012 UB121 UB122 UB142 UB152 UB302 UB401 VA011 VA021 VA031 VA041 VA051 VA061 VA081 WA05 WA22 ZB01 5F047 AA11 AA13 AA17 BA23 BA26 BA39 BB03 BB19

Claims (8)

[Claims] 1. (A) Epoxy resin (B) (a) Aromatic polyisocyanate (b) Trivalent polycarboxylic acid having an acid anhydride group and (c) The following general formula (I): (In the formula, a is 0 to 20, b is 0 to 70, c is an integer of 1 to 90, and R1 and R2 are hydrogen or a C1 to C3 alkyl group). Thermopolymerizable and radiation-polymerized, characterized by comprising a modified polyamide-imide resin characterized by reacting in a polar solvent, an adhesive / adhesive layer containing (C) a radiation-polymerizable compound, and a substrate layer. Adhesive sheet. 2. The (A) epoxy resin and the (B) modified polyamide-imide resin are 5/95 to 90/10 (parts by weight), and the (C) radiation-polymerizable compound is the (A) epoxy resin and (B). The adhesive sheet according to claim 1, wherein the modified polyamideimide resin is 1 to 400 parts by weight with respect to 100 parts by weight as a total amount. 3. The tensile modulus of elasticity in a tensile test when the modified polyamide-imide resin is formed into a film is 2 G at 25 ° C.
It is below Pa, Claim 1 or Claim 2 characterized by the above-mentioned.
The adhesive sheet described. 4. The glass transition temperature of the modified polyamide-imide resin is 300 ° C. or lower.
3. The adhesive sheet according to any one of 3 above. 5. The elastic modulus of the cured product of the adhesive composition is -6.
The adhesive sheet according to any one of claims 1 to 4, which has a pressure of 2000 MPa or less at 0 ° C. 6. The adhesive sheet according to claim 1, wherein the adhesive force between the adhesive layer and the substrate is controlled by irradiating with radiation. 7. A semiconductor device in which a semiconductor element semiconductor and an element mounting support member are adhered using the adhesive sheet according to any one of claims 1 to 4. 8. (1) An adhesive sheet comprising the adhesive / adhesive layer according to claim 1 and a base material is attached to a semiconductor wafer via the adhesive / adhesive layer. Process,
(2) Before or after dicing, a step of irradiating the adhesive sheet with radiation to cure the adhesive layer to form a semiconductor element, and then peeling the base material, and (3) the semiconductor Dicing the wafer,
A method of manufacturing a semiconductor device, comprising: a step of attaching a tacky adhesive layer; and (4) a step of adhering the semiconductor element with the tacky adhesive layer and a supporting member for mounting a semiconductor element via the adhesive sheet. .