JP2003041206A - Adhesive sheet, its using method, and semiconductor device - 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) a polyimide resin, (B) an epoxy resin and its curing agent, and (C) a radiation-polymerizable copolymer having ethylenically unsaturated groups on the side chains.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive sheet, a method of using the same, and a semiconductor device.

[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) Polyimide resin, (B) Epoxy resin and epoxy resin curing agent (C) Adhesive layer comprising radiation-polymerizable copolymer having ethylenically unsaturated group in side chain, and base material layer A heat-polymerizable and radiation-polymerizable adhesive sheet comprising: 2. The pressure-sensitive adhesive layer contains the (A) polyimide resin 1
(1) containing 100 parts by weight, 1 to 200 parts by weight of the epoxy resin and the epoxy resin curing agent, and 5 to 400 parts by weight of the radiation polymerizable compound having an ethylenically unsaturated group in the side chain (C). Adhesive sheet. 3. (C) a radiation-polymerizable compound having an ethylenically unsaturated group in the side chain, a vinyl copolymer containing a functional group, at least one ethylenically unsaturated group, an oxirane ring, an isocyanate group, a hydroxyl group, a carboxyl group, Item 1 or Item 2 which is obtained by addition reaction with a compound having one functional group selected from the group consisting of an amino group and an acid anhydride.
The adhesive sheet described. 4. Item 4. The adhesive sheet according to any one of Items 1 to 3, which is irradiated with radiation to control the adhesive force between the adhesive layer and the substrate. 5. (I) The adhesive sheet according to any one of Items 1 to 4,
A step of adhering to the semiconductor wafer via the adhesive layer, (II) a step of irradiating the adhesive sheet with radiation to cure the adhesive layer and peeling the base material, and (III) dicing the semiconductor wafer And (IV) a step of adhering the semiconductor element with an adhesive layer and the semiconductor element mounting support member via the adhesive sheet. How to use adhesive sheet. 6. A semiconductor device comprising a structure in which a semiconductor element and a support member are bonded by using the adhesive sheet according to any one of Items 1 to 4 or by the method of using the adhesive sheet according to Item 5.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive sheet of the present invention comprises (A) 100 parts by weight of a polyimide resin, 1 to 200 parts by weight of the epoxy resin and the epoxy resin curing agent, and (C).
And a pressure-sensitive adhesive layer containing 5 to 400 parts by weight of a radiation-polymerizable copolymer having an ethylenically unsaturated group in its side chain.
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 so as not to damage each element at the time of picking up. Each process of dicing can be completed with one film.

The polyimide resin of the present invention can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in an organic solvent,
Using tetracarboxylic dianhydride and diamine in equimolar or almost equimolar amounts (addition order of each component is arbitrary), reaction temperature 80
The addition reaction is conducted at a temperature of not higher than 0 ° C, preferably 0 to 60 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid that is a precursor of polyimide is produced. The polyamic acid can be adjusted in molecular weight by heating at a temperature of 50 to 80 ° C. for depolymerization.
The polyimide resin can be obtained by subjecting the above reaction product (polyamic acid) to dehydration ring closure. The dehydration ring closure can be carried out by a thermal ring closure method in which heat treatment is carried out and a chemical ring closure method using a dehydrating agent.

The tetracarboxylic dianhydride used as a raw material for the polyimide resin is not particularly limited, and examples thereof include 1,2- (ethylene) bis (trimellitate anhydride) and 1,3- (trimethylene) bis (trimellitate anhydride). ), 1,4- (tetramethylene) bis (trimellitate anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride), 1,6- (hexamethylene) bis (trimellitate anhydride), 1, 7- (Heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitate anhydride), 1,9-
(Nonamethylene) bis (trimellitate anhydride), 1,
10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadeca) Methylene) bis (trimellitate anhydride), pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride Substance, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propan dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride , Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3 , 4-dicarboxyphenyl) ether dianhydride, benzene-1,
2,3,4-tetracarboxylic dianhydride, 3,4
3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic dianhydride, 3,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, Phenanthrene-1,8,9,10-tetracarboxylic dianhydride Thing, pyrazine-2 3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3 4,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,2 ′,
3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4- Dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1, 3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis (trimellitate anhydride), ethylene tetracarboxylic dianhydride, 1,2,
3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexa Hydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic acid) dianhydride, bicyclo- [2,2 , 2] -Oct-7-ene-
2,3,5,6-tetracarboxylic dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2
-Hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2 , 3,4,5-Tetracarboxylic acid dianhydride and the like can be used, and one kind or two or more kinds thereof can be used in combination.

The diamine used as the raw material for the polyimide is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether methane, bis (4
-Amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane,
3,4'-diaminodiphenyldifluoromethane, 4,
4'-diaminodiphenyldifluoromethane, 3,3 '
-Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2
-Bis (3-aminophenyl) propane, 2,2'-
(3,4'-diaminodiphenyl) propane, 2,2-
Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,
2- (3,4′-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3 -Aminophenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-
Phenylene bis (1-methylethylidene)) bisaniline, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3
-Aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2- Bis (4-
(4-Aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl)
Such as sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, 3,5-diaminobenzoic acid Aromatic diamine, 1,2-diaminoethane, 1,3
-Diaminopropane, 1,4-diaminobutane, 1,5
-Diaminopentane, 1,6-diaminohexane, 1,
7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminodecane,
1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, the following general formula (I)

[0014]

[Chemical 1]

(In the formula, R ₁ and R ₂ have 1 to 3 carbon atoms.
0 represents a divalent hydrocarbon group, which may be the same or different, R ₃ and R ₄ represent a monovalent hydrocarbon group, which may be the same or different, and m is an integer of 1 or more. Is a diaminopolysiloxane represented by
1,3-bis (aminomethyl) cyclohexane, sun
Techno Chemical Co., Ltd. Jeffamine D-23
0, D-400, D-2000, D-4000, ED-
600, ED-900, ED-2001, EDR-14
Aliphatic diamines such as polyoxyalkylene diamines such as 8 can be used, and one kind or two or more kinds thereof can be used together.

The epoxy resin used in the present invention is not particularly limited as long as it cures and exhibits an adhesive action. For example, Epicoat 807 manufactured by Yuka Shell Epoxy Co.,
815, 825, 827, 828, 834, 1001,
1004, 1007, 1009, Dow Chemical Company D
ER-330, 301, 361, YD manufactured by Tohto Kasei Co., Ltd.
8125, YDF8170 and other bisphenol A type epoxy resins, manufactured by Yuka Shell Epoxy Co., Ltd. Epicoat 1
52,154, Nippon Kayaku Co., Ltd. EPPN-201,
Phenol novolac type epoxy resin such as DEN-438 manufactured by Dow Chemical Co., Ltd., EOCN- manufactured by Nippon Kayaku Co., Ltd.
102S, 103S, 104S, 1012, 1025
1027, YDCN701, 70 manufactured by Tohto Kasei Co., Ltd.
2,703,704 and other o-cresol novolac type epoxy resins, manufactured by Yuka Shell Epoxy Co., Ltd. Epon
1031S, Ciba Specialty Chemicals Araldite 0163, Nagase Kasei Denacol EX-611, 614, 614B, 622, 512, 5
Polyfunctional epoxy resins such as 21,421,411,321, Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd.,
Tohkasei Co., Ltd. YH-434, Mitsubishi Gas Chemical Co., Inc.
Amine type epoxy resins such as TETRAD-X and TETRAD-C manufactured by Sumitomo Chemical Co., Ltd. ELM-120,
Ciba Specialty Chemicals Araldite P
Heterocycle-containing epoxy resin such as T810, E manufactured by UCC
An alicyclic epoxy resin such as RL4234, 4299, 4221, 4206 can be used.
It is also possible to use one species or a combination of two or more species.

As the curing agent for the epoxy resin, those generally used as a curing agent for the epoxy resin can be used, and amine, polyamide, acid anhydride, polysulfide, boron trifluoride and phenolic hydroxyl group are contained in one molecule. Bisphenol A, bisphenol F, which is a compound having two or more
Examples include phenols such as bisphenol S, polyfunctional phenols and phenol novolac resins, bisphenol A novolac resins, naphthol novolac resins, and cresol novolac resins, etc. Preference is given to using.

The radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain (C) used in the present invention is, for example,
(C ′) at least one ethylenically unsaturated group and a vinyl copolymer containing a functional group, an oxirane ring, an isocyanate group, a hydroxyl group, a carboxyl group, an amino group,
It can be obtained by addition reaction of a compound having a functional group selected from acid anhydrides and the like.

Examples of the functional group in the vinyl copolymer containing the above-mentioned (C ') functional group include a carboxyl group,
Examples thereof include a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride. Examples of the vinyl monomer used in the production of the vinyl copolymer include a compound having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride. Specifically, for example, , Acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide,
Examples thereof include methacrylamide, ethyl isocyanic acid methacrylate, glycidyl acrylate, and glycidyl methacrylate. These monomers can be used alone or in combination of two or more kinds.

In the production of the above vinyl copolymer, other vinyl monomers can be copolymerized if necessary. Examples of such a monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, -n-propyl acrylate, -n-propyl methacrylate, -iso-propyl acrylate, and methacrylic acid. -Iso-propyl, acrylic acid-n
-Butyl, methacrylic acid-n-butyl, acrylic acid-i
So-butyl, methacrylate-iso-butyl, acrylate-sec-butyl, methacrylate-sec-butyl, acrylate-tert-butyl, methacrylate-t
ert-butyl, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate,
Heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate,
Nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, acrylic acid Eicosyl, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylate Phenyl, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, acrylic acid Toxydiethylene glycol, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylic acid Diethylaminoethyl, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-methylstyrene, vinyl Nyltoluene,
Examples thereof include vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more.

At least one ethylenically unsaturated group (C ″), an oxirane ring, an isocyanate group,
Examples of the compound having one functional group such as a hydroxyl group, a carboxyl group, an amino group, and an acid anhydride include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-ethylacrylglycidyl, crotonyl glycidyl ether, and glycidyl crotonic acid. , Glycidyl isocrotate, ethyl methacrylate isocyanato, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, acrylamide, methacrylamide, Examples thereof include maleic anhydride, and these may be used alone or in combination of two or more.

The amount used is preferably set so that the ethylenically unsaturated group concentration is 3.0 × 10 ^{−4 to} 6.0 × 10 ⁻³ mol / g, and 6.0 × 1
0 ^{- 4,} more preferably to to 5.5 × ^{10 -3} mol / g, and particularly preferably to 9 × ¹⁰ -4 ~5.0 × ^{10 -3} mol / g. The ethylenically unsaturated group concentration is 3.
If it is less than 0 × 10 ⁻⁴ mol / g, the strength of the adhesive layer tends to be reduced, and if it exceeds 6.0 × 10 ⁻³ mol / g, a radiation-polymerizable copolymer having an ethylenically unsaturated group in its side chain is used. There is a tendency to cause gelation during the production of coalescence. Here, the ethylenically unsaturated group concentration indicates the number of moles of the ethylenically unsaturated group contained in 1 g of the radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain (C), and It is a value calculated by an expression.

[0023]

[Equation 1]

(In the formula, (C ″) _x represents the number of moles of the (C ″) component, and a _x represents the number of ethylenically unsaturated groups contained in one molecule of the (C ″) _x component). Further, a hardening accelerator can be further added to the tacky 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 and the like can be used. It is also possible to use one type or two or more types 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 0.1 to 5 relative to 100 parts by weight of the epoxy resin (B) and the epoxy curing agent.
Part by weight is preferable, and 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.

Further, a photopolymerization initiator which produces free radicals upon irradiation with active 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-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 above-mentioned photopolymerization initiator to be used is not particularly limited, but is usually 0.1% with respect to 100 parts by mass of the radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain (C).
It is from 01 to 30 parts by weight.

A high molecular weight resin compatible with an epoxy resin can be added to the adhesive layer forming the adhesive sheet of the present invention for the purpose of improving flexibility and reflow crack resistance. The high molecular weight resin is not particularly limited, and for example, a phenoxy resin, a high molecular weight epoxy resin, an ultra high molecular weight epoxy resin, or the like can be used, and one or more of these may be used in combination. it can. The amount of the high molecular weight resin compatible with the epoxy resin is preferably 40 parts by weight or less with respect to 100 parts by weight of the epoxy resin. If it exceeds 40 parts by weight, the Tg of the epoxy resin layer tends to decrease.

Further, the tacky adhesive layer forming the adhesive sheet of the present invention, for the purpose of improving its handleability, improving 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 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 (A) Polyimide resin 1 in terms of its effect, heat resistance and cost.
It is preferably 0.01 to 10 parts by weight with respect to 00 parts by weight.

An ion scavenger may be further added to the adhesive layer for 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 to be used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the (A) polyimide resin from the viewpoints of the effect of addition, heat resistance and cost.

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 as long as it has a surface tension of more than 40 dyne / cm, and examples thereof include polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film and polypropylene. the film,
Examples thereof include plastic films such as polymethylpentene film and polyimide film.

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 raider 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,
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.

In the adhesive sheet of the present invention, in order to obtain a desired thickness, two or more separately prepared adhesive / adhesive agents may 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 significantly reduced after the irradiation, and the base material film of the adhesive sheet can be easily held with the adhesive layer 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.

[0051]

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. The temperature was raised to 80 ° C under the conditions below, while maintaining the reaction temperature at 80 ° C ± 2 ° C, 45.0 parts by mass of ethyl methacrylate, 35.0 parts by mass of 2-ethylhexyl acrylate, methacrylic acid.
A mixed liquid of 20.0 parts by mass and 1.0 part by mass of 2,2′-azobis (isobutyronitrile) 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 dropwise addition, the mixture was stirred at 100 ° C. for 20 hours and then cooled to room temperature to obtain a radiation-polymerizable copolymer having a weight average molecular weight of 25,000 and a glass transition temperature of about 10 ° C. and an ethylenically unsaturated group in its side chain. A polymer (A-1) was obtained.

(Synthesis Example 2) The same reaction as in Synthesis Example 1 was carried out except that the various formulations were changed as shown in Table 1, and the weight average molecular weight was 28,000 and the glass transition temperature was A radiation-polymerizable copolymer (A-2) having an ethylenically unsaturated group in its side chain at about 5 ° C was obtained.

[0054]

[Table 1]

(Example 1) 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to a 500 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube.
41.05 g (0.1 mol) and 150 g of N-methyl-2-pyrrolidone were charged and stirred. After dissolution of the diamine,
While cooling the flask in an ice bath, 52.2 g of 1,10- (decamethylene) bis (trimellitate anhydrous)
(0.1 mol) was added in small portions. After reacting for 3 hours at room temperature, 30 g of xylene was added, and the mixture was heated at 150 ° C. while blowing nitrogen gas, and xylene was removed azeotropically with water. The reaction solution was poured into water, the precipitated polymer was filtered off and dried to obtain a polyimide resin.

50 g of this polyimide resin, 10 g of o-cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: ESCN-195), phenol novolac resin (manufactured by Meiwa Kasei Co., Ltd., trade name: H-1) ) 5.3 g,
0.2 g of tetraphenylfosiphonium tetraphenylborate (trade name: TPPK, manufactured by Kitako Chemical Co., Ltd.), a radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain obtained in Synthesis Example 1 ( A-1) 13.1 g and 1-hydroxycyclohexyl phenyl ketone 0.2 g are added and dissolved in 200 g of N-methyl-2-pyrrolidone which is a solvent. This was well stirred and uniformly dispersed to obtain an adhesive varnish. A polyethylene terephthalate (manufactured by Teijin Ltd., Teijin Tetron film: G2-50, surface tension 50 dyne) having a thickness of 50 μm was applied to this adhesive varnish.
/ Cm) and heat-dried at 150 ° C. for 20 minutes to form an adhesive sheet with a substrate (polyethylene terephthalate film) having a thickness of 50 μm (adhesive sheet excluding the substrate has a thickness of 50 μm) (adhesion) Sheet 1) was prepared.

Using the adhesive sheet 1 thus obtained, a semiconductor device sample (a solder ball is formed on one side) is prepared 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. The results of these evaluations are summarized in Table 2.

Example 2 In Example 1, the radiation-polymerizable copolymer (A- having an ethylenically unsaturated group in the side chain) was used.
The same operation as in Example 1 was carried out except that 1) was replaced with the radiation-polymerizable copolymer (A-2) having an ethylenically unsaturated group in the side chain obtained in Synthesis Example 2, and the substrate (polyethylene) was used. Adhesive sheet having a thickness of 50 μm (terephthalate film) (thickness of the adhesive sheet excluding the base material is 50 μm)
(Adhesive sheet 2) was produced. Table 2 shows the results of evaluating the obtained adhesive sheet 2 under the same conditions as in Example 1.

Comparative Example 1 In Example 1, the radiation-polymerizable copolymer (A- having an ethylenically unsaturated group in the side chain)
The same operation as in Example 1 was carried out except that 1) and 1-hydroxycyclohexyl phenyl ketone were removed, and an adhesive sheet having a substrate (polyethylene terephthalate film) and having a thickness of 50 μm (adhesive sheet excluding the substrate). To have a thickness of 50 μm) (adhesive sheet 3). Table 2 shows the results of evaluation of the obtained adhesive sheet 3 under the same conditions as in Example 1.

(Comparative Example 2) In Example 1, a radiation-polymerizable copolymer (A- having an ethylenically unsaturated group in the side chain) was used.
Example 1 except that 1) was changed to 4G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., tetraethylene glycol dimethacrylate)
The same operation as above was performed to prepare an adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (the adhesive sheet excluding the base material has a thickness of 50 μm) (adhesive sheet 4). The obtained adhesive sheet 4 was used in Example 1.
The results of evaluation under the same conditions as in Table 2 are shown in Table 2.

[0062]

[Table 2]

Pickup property: Probability (% / 100 chip) of picking up a chip after dicing with a pickup die bonder was shown.

From Table 2, 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.

[0065]

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. Further, the semiconductor device using the adhesive sheet of the present invention has heat resistance, moisture resistance and workability necessary for mounting a semiconductor element having a large difference in thermal expansion coefficient on the semiconductor mounting support member.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J004 AA02 AA13 AA16 AA17 AB01                       AB05 AB06 CA04 CA05 CA06                       CC02 FA05 FA08                 4J040 EC041 EC061 EC071 EC161                       EH021 FA231 GA05 GA07                       GA13 GA20 HB36 HC01 JA09                       JB02 JB07 JB09 KA16 LA06                       LA07 LA08 NA20 PA23                 5F047 AA11 AA13 BA24 BA34 BA39                       BB03 BB19

Claims (6)

[Claims] 1. A tacky adhesive layer comprising (A) a polyimide resin, (B) an epoxy resin and an epoxy resin curing agent (C) a radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain. And a heat-polymerizable and radiation-polymerizable adhesive sheet having a base layer. 2. The adhesive layer comprises 100 parts by weight of the (A) polyimide resin, 1 to 200 parts by weight of the epoxy resin and an epoxy resin curing agent, and (C) an ethylenically unsaturated side chain. Radiation-polymerizable compound having a group of 5 to
The adhesive sheet according to claim 1, which contains 400 parts by weight. 3. A radiation-polymerizable compound having an ethylenically unsaturated group in the side chain (C) is a vinyl copolymer having a functional group, at least one ethylenically unsaturated group, an oxirane ring, an isocyanate group, The adhesive sheet according to claim 1 or 2, which is obtained by an addition reaction with a compound having one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and an acid anhydride. 4. The adhesive sheet according to claim 1, wherein the adhesive force between the adhesive layer and the substrate is controlled by irradiating with radiation. 5. (I) A step of attaching the adhesive sheet according to any one of claims 1 to 4 to a semiconductor wafer through the adhesive layer, (II) irradiating the adhesive sheet with radiation. Curing the adhesive layer to peel off the substrate, (II
I) a step of dicing a semiconductor wafer to obtain a semiconductor element with an adhesive layer, (IV) a step of adhering a semiconductor element with an adhesive layer and a semiconductor element mounting support member via the adhesive sheet A method of using the adhesive sheet, comprising: 6. A semiconductor comprising a structure in which a semiconductor element and a supporting member are bonded by using the adhesive sheet according to any one of claims 1 to 4 or by the method of using the adhesive sheet according to claim 5. apparatus.